Composite antibacterial toothpaste

Abstract

The invention discloses a composite antibacterial toothpaste, which comprises a friction agent, a humectant, a thickening agent, a foaming agent, a sweetening agent, water and a bacteriostatic agent, the bacteriostatic agent comprises nano silver particles and povidone iodine, and the friction agent comprises hydrated silica, medium particle size bamboo charcoal and small particle size bamboo charcoal according to a mass ratio of 8: 0.5: 1.5. The nano-silver particles are loaded in the medium-particle-size bamboo charcoal and the small-particle-size bamboo charcoal. The two bacteriostatic agents povidone iodine and nano-silver particles are combined for use, so that the growth of microorganisms can be inhibited through different mechanisms, the povidone iodine and the nano-silver particles cover different bacteria to form a synergistic effect, and lasting antibacterial protection is provided. In addition, the friction agent with specific composition can provide a better cleaning effect, reduces potential damage to teeth and gingiva, realizes a slow release effect of a bacteriostatic agent, has an excellent antibacterial effect and good safety, and can effectively solve the problem that the antibacterial effect is reduced due to the fact that silver ions react in an iodine solution to generate precipitates.

Description

Technical Field

[0001] The present invention relates to the field of toothpaste, in particular to the field of antibacterial toothpaste, and in particular to a toothpaste with a composite antibacterial agent. The toothpaste has excellent antibacterial effect and good safety, and can effectively solve the problem that silver ions react in an iodine solution to generate precipitation and reduce the antibacterial effect. Background Art

[0002] In recent years, as people pay more attention to oral health, the demand for antibacterial toothpaste has increased. In order to improve the antibacterial effect of toothpaste, people have tried to combine multiple antibacterial ingredients. On the basis of improving the antibacterial performance of the product, it can also avoid to a certain extent the inability of toothpaste with a single antibacterial ingredient to effectively inhibit bacteria when targeting drug-resistant bacteria. Among them, nanosilver particles and povidone iodine are two common antibacterial agents, each of which has a unique antibacterial mechanism and antibacterial performance. Nanosilver particles destroy bacterial cell membranes, produce reactive oxygen species (ROS) and release silver ions (Ag +) to kill bacteria, and has significant inhibitory effect on a variety of gram-positive and gram-negative bacteria, fungi and viruses. Povidone-iodine releases free iodine (I2) to destroy proteins, enzymes and nucleic acids in bacterial cells, leading to cell death, and has broad antibacterial activity on a variety of bacteria, fungi and viruses. The two antibacterial ingredients are widely used in toothpaste, mouthwash and other oral care products. For example, CN110037940A discloses an oral bactericidal disinfectant mouthwash, and specifically discloses the weight percentage of each component as follows: povidone-iodine 4.5%~5.5%; potassium iodate 0~0.05%; potassium iodide 0.1%~0.15%; polyvinylpyrrolidone 0.5%~0.8%; sodium dodecyl sulfate 0.05%~0.1%; glycerol 1%~3%; polyethylene glycol 4000 0.4%~0.6%; citric acid 0.15%~0.25%; adjuvant 0%~0.1%; freshener 0.5%~1.2%; purified water balance. The mouthwash has good bactericidal and disinfectant effect, low irritation, no harm to human body, good stability, long storage time and other characteristics. CN103385804A discloses a nano-silver mouthwash for preventing and treating oral diseases, which contains 0.1ppm~1000ppm nano-silver and the following components (mass percentage): hemostatic agent: 0.01%~5%; local anesthetic: 0.01%~5%; bacteriostatic agent: 0.01%~10%; dispersing agent: 0.1%~25%; thickening agent: 0.1%~25%; wetting agent: 0.1%~15%; cooling agent: 0.1%~10%; adhesion agent: 0.1%~35%; flavoring agent: 0.01%~5%; coloring agent: 0.01%~5%. Silver particles with a diameter of 10~50 nanometers can be adsorbed on the cell membrane of harmful microorganisms, interfere with their metabolism, damage protein shells and DNA molecules, and cause death. It has broad-spectrum bactericidal and bacteriostatic effect, is durable and effective, has no toxic side effects, does not produce drug resistance, is safe and reliable, easy to use, and simple to produce and prepare.

[0003] However, when nano-silver particles and povidone-iodine are present in the same preparation at the same time, silver ions (Ag + ) and iodine ions (I -) will react to form an insoluble silver iodide (AgI) precipitate. This precipitate not only affects the physical stability of the toothpaste, but also reduces the antibacterial effect of nanosilver particles and povidone iodine. Although silver iodide also has a certain antibacterial effect, the antibacterial effect is significantly lower than the effect of using silver nanoparticles or povidone iodine antibacterial agents alone. For example, CN112512486A discloses an iodine-containing aqueous oral care composition, which contains: silver cations; iodide anions; fluoride anions; and water. When in contact with additional water or saliva in the oral environment, the oral care single-piece composition forms a precipitate, which can provide a fluoride effect similar to a coating. The composition can reduce the incidence of caries, reduce dentin sensitivity and root sensitivity, and can treat the patient's tooth surface. JP7142574B2 discloses a tooth surface treatment material that can inhibit the development of caries or suppress hypersensitivity without damaging the aesthetic surface of the treatment site. The tooth surface treatment material is composed of complex ions of silver ions and iodide ions and water. CN112512485A discloses an aqueous oral care composition containing thiocyanate, comprising: silver cations; thiocyanate anions; fluoride anions; and water, wherein the source of silver cations is selected from silver fluoride, silver chloride, silver nitrate, silver iodide, silver ammonium fluoride, and combinations thereof. When in contact with additional water or saliva in an oral environment, the oral care one-part composition forms a precipitate comprising AgSCN, which provides an antibacterial effect.

[0004] Therefore, when using nanosilver particles and povidone-iodine as two antibacterial agents at the same time, how to avoid the reaction between silver and iodine while maintaining the antibacterial properties of both has become a technical problem that needs to be solved urgently. Summary of the Invention

[0005] To address the deficiencies in the prior art, the present invention provides a composite antibacterial toothpaste comprising an abrasive, a moisturizer, a thickener, a foaming agent, a sweetener, water, and an antibacterial agent, wherein the antibacterial agent is nanosilver particles and povidone iodine. The abrasive comprises hydrated silica, medium-sized bamboo charcoal, and small-sized bamboo charcoal in a mass ratio of 8:0.5:1.5, and the nanosilver particles are loaded into the medium-sized bamboo charcoal and small-sized bamboo charcoal. The present invention employs the combined use of povidone iodine and nanosilver particles, two antibacterial agents, to inhibit the growth of microorganisms through different mechanisms, thereby increasing the difficulty of microorganisms developing drug resistance. At the same time, the two antibacterial agents cover different bacterial genera, forming a synergistic effect. The simultaneous use of the two antibacterial agents can rapidly reduce the number of bacteria in the oral cavity in a short period of time and maintain a low bacterial level for a longer period of time, providing long-lasting antibacterial protection and a synergistic antibacterial effect. Furthermore, the abrasive composition of the present invention provides superior cleaning performance. The hydrated silica exhibits excellent abrasiveness and mildness, effectively removing stains from tooth surfaces without damaging tooth enamel. Its fine particle structure helps form a uniform friction layer. The inclusion of medium-sized bamboo charcoal increases the abrasive's overall adsorption capacity, helping to remove even more stubborn stains and odors. The small-sized bamboo charcoal further enhances the abrasive's fineness, making the toothpaste gentler during use and reducing potential damage to teeth and gums. The small-sized bamboo charcoal can also penetrate deep into subtle depressions on the tooth surface for cleaning. Loading nanosilver onto the bamboo charcoal not only improves its stability but also utilizes the charcoal's porous structure to achieve a sustained-release effect, allowing the nanosilver to be continuously released during brushing, extending its release time and providing long-lasting antibacterial protection, thereby enhancing its antibacterial effectiveness.

[0006] In order to achieve the above-mentioned purpose of the invention, the present invention provides a composite antibacterial toothpaste, which contains an abrasive, a moisturizer, a thickener, a foaming agent, a sweetener, water and an antibacterial agent, wherein the antibacterial agent is nanosilver particles and povidone iodine, and the abrasive is composed of hydrated silica, medium-particle bamboo charcoal and small-particle bamboo charcoal in a mass ratio of 8:0.5:1.5, and the nanosilver particles are loaded in the medium-particle bamboo charcoal and small-particle bamboo charcoal.

[0007] Furthermore, the medium-sized bamboo charcoal has a particle size of 10μm-50μm, the small-sized bamboo charcoal has a particle size of 0.2μm-5μm, the hydrated silica has a particle size of 10-80μm, and the mass ratio of nanosilver particles to povidone-iodine in the antibacterial agent is 0.02-1:1-5. The medium-sized bamboo charcoal (10μm-50μm) has a targeted physical cleaning effect. This particle size matches tooth stains (such as tea and smoke stains, which typically have a particle size of 10-50μm). It directly removes stubborn stains adhering to the enamel surface through mechanical friction, and is particularly effective in cleaning areas prone to accumulation, such as pits and fissures and interproximal surfaces. The internal pore size of the medium-sized bamboo charcoal is mostly mesopores of 2-50nm, providing a stable "skeleton-type" carrier for the nanosilver. This pore size gradually breaks down with friction during brushing, releasing the nanosilver in a targeted manner to deeply clean areas such as the gingival sulcus and periodontal pockets, thereby prolonging the duration of the local antibacterial effect. Small particle size bamboo charcoal (0.2μm-5μm) has a specific surface area of ​​800-1500m 2 / g, can fill the gaps between hydrated silica particles, forming a "fine-rough" compound friction system, without increasing the overall friction value (RDA value), it improves the cleaning ability of tooth surface micropores (such as early enamel demineralization areas), while reducing mechanical stimulation to the gums. At the same time, the extremely small bamboo charcoal micropores can also chemically adsorb nanosilver particles to prevent them from agglomerating in the paste. In addition, the natural porous structure of hydrated silica (mainly pore size 10-50nm) is highly consistent with the molecular size of povidone iodine, forming a "pore-molecular level" precise embedding, avoiding the precipitation of PVP-I due to water migration during storage. At the same time, the shear force during brushing destroys the pore surface, and the iodine molecules (I2) are controllably released to achieve "contact sterilization + continuous antibacterial". When the toothpaste is used, the nanosilver loaded on the small-particle bamboo charcoal has a large specific surface area, and initially releases a small amount of Ag quickly. + , quickly inhibiting oral surface bacteria; nanosilver wrapped in medium-sized bamboo charcoal is gradually released with friction, forming a long-lasting antibacterial effect; PVP-I in the hydrated silica pores is released through a swelling-diffusion mechanism, and the speed matches the brushing time (2-3 minutes), ensuring that while effectively removing plaque, it avoids excessive free iodine concentration that causes the active metal silver precipitation to fail.

[0008] Furthermore, the nano silver particles are evenly distributed on the surface and in the internal pores of the medium-sized bamboo charcoal and the small-sized bamboo charcoal, and the povidone iodine is distributed in the internal pores of the hydrated silica.

[0009] Furthermore, the humectant is at least one of polyethylene glycol, glycerin, and sorbitol; the thickener is at least one of hydroxyethyl cellulose, xanthan gum, and carrageenan; the foaming agent is at least one of sodium lauryl sulfate and sodium lauryl sulfate; and the sweetener is at least one of sodium saccharin and stevia. The humectant component in the composite antibacterial toothpaste forms a protective film on the oral surface after brushing, keeping the mouth moist. The sweetener in the toothpaste provides a pleasant taste, while the bamboo charcoal molecules can absorb odor molecules, reducing unpleasant oral odor.

[0010] Furthermore, the toothpaste further comprises a pH adjuster, which is sodium hydrogen phosphate and sodium dihydrogen phosphate. The pH of the toothpaste is 6 to 7. At this pH, nanosilver and povidone iodine are both highly stable and can remain stable in the toothpaste for a long time, thereby extending the life of the toothpaste product. Other pH adjusters can also be used to adjust the pH range of the toothpaste, such as sodium dihydrogen phosphate, dilute sodium hydroxide solution, dilute acetic acid, etc.

[0011] Furthermore, the amounts of the components in the toothpaste are as follows, by weight percentage: 16-32% of hydrated silica, 1-2% of medium-sized bamboo charcoal, 3-6% of small-sized bamboo charcoal, 15-25% of moisturizing agent, 1-5% of thickener, 0.5-1% of foaming agent, 0.05-0.5% of sweetener, 0.02-1% of nano-silver particles, 1-5% of povidone-iodine, and the balance is water.

[0012] Preferably, the amounts of the components in the toothpaste are as follows, by weight percentage: 25.6% hydrated silica, 1.6% medium-particle bamboo charcoal, 4.8% small-particle bamboo charcoal, 20% moisturizer, 2% thickener, 1% foaming agent, 0.5% sweetener, 0.05% nano-silver particles, 3% povidone iodine, and the balance is water.

[0013] Another aspect of the present invention provides a method for preparing a composite antibacterial toothpaste, comprising the following steps:

[0014] (1) Prepare nanosilver-bamboo charcoal composite material, prepare 10mM / L AgNO3 aqueous solution and 5mM / L polyvinyl pyrrolidone solution, take 10mL of the prepared AgNO3 solution and 5mL of polyvinyl pyrrolidone solution in a beaker and stir at room temperature for half an hour to allow the silver ions to be fully dispersed, weigh bamboo charcoal according to the mass ratio of silver to bamboo charcoal of 0.02~1:4~8 and add it to the mixed solution, wherein the bamboo charcoal consists of medium-sized bamboo charcoal and small-sized bamboo charcoal in a mass ratio of 1:3, stir at room temperature for 4h under ultraviolet light, then filter, wash and filter the obtained solid repeatedly with deionized water, then wash and dehydrate with 85% ethanol and anhydrous ethanol in turn, filter, and finally dry the obtained solid at 50℃ in vacuum for 8h. Nanosilver particles are loaded on bamboo charcoal by chemical reduction under ultraviolet light, thereby enhancing the stability and release efficiency of nanosilver.

[0015] (2) Weighing raw materials of hydrated silica, moisturizing agent, thickener, foaming agent, sweetener, water, povidone iodine, and nanosilver-bamboo charcoal composite material according to mass ratio, mixing hydrated silica and povidone iodine and ball milling them so that povidone iodine is completely dispersed into the pores inside the hydrated silica, rinsing with deionized water and drying to obtain the povidone iodine-hydrated silica composite material; the povidone iodine is dispersed into the pores inside the hydrated silica by ball milling, thereby improving the distribution uniformity and stability of the povidone iodine.

[0016] (3) Preparation of toothpaste: The weighed moisturizer, thickener, foaming agent, sweetener and water are mixed and stirred evenly, and then the nanosilver-bamboo charcoal composite material is added and stirred until uniformly dispersed. After adjusting the pH, the povidone iodine-hydrated silica composite material is added and stirred until uniformly dispersed. After further adjusting the pH, stirring is continued for 1 to 5 hours to obtain a uniform paste. The paste is vacuum degassed and canned.

[0017] Furthermore, the particle size of the medium-sized bamboo charcoal is 10 μm-50 μm, the particle size of the small-sized bamboo charcoal is 0.2 μm-5 μm, the particle size of the hydrated silica is 10-80 μm, and the mass ratio of the nanosilver particles to povidone iodine in the antibacterial agent is 0.02-1:1-5.

[0018] Furthermore, the pH is 6-7.

[0019] Compared with the prior art, the present invention provides a composite antibacterial toothpaste and a preparation method thereof. The beneficial effects of this technical solution are as follows:

[0020] 1. The toothpaste prepared by the present invention has better antibacterial effect. Nanosilver particles and povidone iodine produce a synergistic antibacterial effect. The combined use of nanosilver and povidone iodine can inhibit the growth of microorganisms through different mechanisms, increasing the difficulty for microorganisms to develop drug resistance. The porous structure of bamboo charcoal can fix nanosilver particles through physical adsorption or chemical bonding, prevent their agglomeration and ineffectiveness, ensure that the antibacterial ingredients are evenly distributed in the paste, achieve a sustained release effect, prolong its action time, and thus provide more lasting antibacterial protection; the pores of hydrated silica are a hydrophilic environment, which can be filled with povidone iodine (PVP-I), which can achieve a more uniform release and ensure that the antibacterial effect is continuously exerted throughout the entire brushing process. The combined use of nanosilver and povidone iodine can produce a synergistic antibacterial effect, enhance the penetration and removal ability of dental plaque biofilm, provide more comprehensive antibacterial protection and improve stability; at the same time, nanosilver is loaded on bamboo charcoal, and povidone iodine is distributed on hydrated silica to achieve an antibacterial network of "local targeting (bamboo charcoal-nanosilver) and global coverage (hydrated silica-PVP-I)" of the antibacterial agent. Friction during brushing destroys the pores of bamboo charcoal, gradually releasing nanosilver ions (Ag + ), prolonging the inhibitory effect on oral bacteria (such as Streptococcus mutans and Porphyromonas gingivalis) and avoiding instantaneous high concentration irritation to the mucosa;

[0021] 2. The compound abrasive of the present invention also has a synergistic cleaning effect. Hydrated silica, as the mainstream abrasive, has a moderate hardness (Mohs hardness of about 5 to 6), which can effectively remove dental plaque and food residues without excessively wearing the tooth enamel. Its natural porous structure can absorb the liquid components in toothpaste (such as povidone iodine) to form a stable carrier. Medium-sized bamboo charcoal provides physical friction support, enhancing the cleaning power of stubborn stains (such as smoke stains and tea stains); small-sized bamboo charcoal has a large specific surface area and strong adsorption capacity, which can assist in removing tooth surface pigments and odors, fill the gaps between hydrated silica particles, and form a "delicate-rough" compound friction system, while providing a porous carrier with a high loading rate for nanosilver. The specific mass ratio of the present invention balances friction (mainly hydrated silica) and adsorption capacity (supplemented by bamboo charcoal), avoiding excessive friction or insufficient cleaning power caused by single bamboo charcoal.

[0022] 3. The raw materials used in this invention are safe, the nanosilver content is low, and it is less irritating to human tissue, making it suitable for long-term use in oral care products. Furthermore, the nanosilver concentration in the mouth is low and is gradually diluted and excreted by saliva over time, preventing accumulation in the body and avoiding the potential risks associated with long-term use. Silver ions and iodide ions target different species, covering a wider bacterial spectrum, reducing the risk of single-component drug resistance and enhancing the long-term antibacterial effect. Furthermore, the naturally porous structure of bamboo charcoal can absorb oral odor molecules, further assisting in improving breath. DETAILED DESCRIPTION

[0023] 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.

[0024] It should be noted that references to "embodiments" herein mean that a particular feature, structure, or characteristic described in connection with the embodiments may be included in at least one embodiment of the present invention. The appearance of such phrases in various locations in the specification does not necessarily refer to the same embodiment, nor do they constitute 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.

[0025] 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.

[0026] The toothpastes of each embodiment and comparative example were tested as follows:

[0027] 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 12 hours, and randomly put it into a constant temperature incubator at 70℃±1℃. Take it out after 30 hours, return to room temperature, open the lid, and check the state of the paste.

[0028] 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 0.5g 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.

[0029] 3. Abrasive Effect Testing: The Radioactivity of Dentin Abrasion (RDA) test is an internationally standardized method for evaluating the effects of toothpaste on tooth wear. The dentin under test is irradiated with gamma rays, generating the radioactive nuclide phosphorus 32P. The test toothpaste homogenate is then fixed to a vertical toothbrush and brushed 1500 times. The activity of the radioactive phosphorus 32P in the toothpaste homogenate is then measured.

[0030] Example 1

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

[0032] (1) Prepare nano silver-bamboo charcoal composite material, prepare 10mM / L AgNO3 aqueous solution and 5mM / L polyvinyl pyrrolidone solution, take 10mL of the prepared AgNO3 solution and 5mL of polyvinyl pyrrolidone solution in a beaker and stir at room temperature for half an hour to allow the silver ions to be fully dispersed, weigh bamboo charcoal according to the mass ratio of silver to bamboo charcoal of 0.02:4 and add it to the mixed solution, wherein the bamboo charcoal consists of medium-sized bamboo charcoal with a particle size of 10μm-50μm and small-sized bamboo charcoal with a particle size of 0.2μm-5μm in a mass ratio of 1:3, stir at room temperature for 4h under ultraviolet light, and then filter to obtain solid. The mixture was repeatedly washed with deionized water and filtered, and then washed and dehydrated with 85% ethanol and anhydrous ethanol in sequence, and filtered. Finally, the solid was vacuum-dried at 50°C for 8 hours to obtain the obtained product. (2) The raw materials were weighed according to the following mass fractions: 16% hydrated silica, 4.02% nanosilver-bamboo charcoal composite material, 15% polyethylene glycol, 1% hydroxyethyl cellulose, 0.5% sodium lauryl sulfate, 0.05% sodium saccharin, 1% povidone iodine, and the balance was water. The hydrated silica and povidone iodine were mixed and ball-milled to make the povidone iodine completely dispersed in the pores inside the hydrated silica. The mixture was rinsed with deionized water and dried to obtain the povidone iodine-hydrated silica composite material.

[0033] (3) The weighed polyethylene glycol, hydroxyethyl cellulose, sodium lauryl sulfate, sodium saccharin and water were mixed and stirred evenly, and then the nanosilver-bamboo charcoal composite material was added and continued to be stirred until uniformly dispersed. The pH was adjusted to 6 using sodium hydrogen phosphate and sodium dihydrogen phosphate, and then the povidone iodine-hydrated silica composite material was added and continued to be stirred until uniformly dispersed. The pH was further adjusted to 7 and stirred for 1 hour to obtain a uniform paste. The paste was vacuum degassed and canned.

[0034] Testing of the toothpaste product revealed that it was stable in shape. After stability testing, the toothpaste showed no delamination, sedimentation, or water precipitation. The paste was smooth and had an appropriate consistency, with no yellow solids present. Its RDA was 110. The 3-minute sterilization rates against Escherichia coli ATCC 8739, Staphylococcus aureus ATCC 25923, and Candida albicans were 100%, 100%, and 100%, respectively, and the 24-hour sterilization rates were also 100%, 100%, and 100%, respectively. This demonstrates that the toothpaste containing this composite antibacterial agent exhibits strong bactericidal activity against these pathogens, resulting in a superior finished toothpaste with stability that meets the requirements of GB / T8372-2017.

[0035] Example 2

[0036] (1) Prepare nano silver-bamboo charcoal composite material, prepare 10mM / L AgNO3 aqueous solution and 5mM / L polyvinyl pyrrolidone solution, take 10mL of the prepared AgNO3 solution and 5mL of polyvinyl pyrrolidone solution in a beaker and stir at room temperature for half an hour to allow the silver ions to be fully dispersed, weigh bamboo charcoal according to the mass ratio of silver to bamboo charcoal of 1:8 and add it to the mixed solution, wherein the bamboo charcoal consists of medium-sized bamboo charcoal with a particle size of 10μm-50μm and small-sized bamboo charcoal with a particle size of 0.2μm-5μm in a mass ratio of 1:3, stir at room temperature for 4h under ultraviolet light, and then filter to obtain The solid was repeatedly washed with deionized water and filtered, and then washed and dehydrated with 85% ethanol and anhydrous ethanol in sequence, and filtered. Finally, the obtained solid was vacuum dried at 50°C for 8h to obtain the obtained solid. (2) The raw materials were weighed according to the following mass fractions: 32% of hydrated silica, 9% of nanosilver-bamboo charcoal composite material, 25% of glycerol, 5% of xanthan gum, 1% of sodium lauryl sulfate, 0.5% of stevia, 5% of povidone iodine, and the balance of water. The hydrated silica and povidone iodine were mixed and ball-milled to make the povidone iodine completely dispersed in the pores inside the hydrated silica. The mixture was rinsed with deionized water and dried to obtain the povidone iodine-hydrated silica composite material.

[0037] (3) The weighed glycerol, xanthan gum, sodium lauryl sulfate, stevia and water were mixed and stirred evenly, and then the nanosilver-bamboo charcoal composite material was added and continued to be stirred until uniformly dispersed. The pH was adjusted to 7 using sodium hydrogen phosphate and sodium dihydrogen phosphate, and then the povidone iodine-hydrated silica composite material was added and continued to be stirred until uniformly dispersed. The pH was further adjusted to 6 and stirred for 5 hours to obtain a uniform paste. The paste was vacuum degassed and canned.

[0038] Testing of the toothpaste product revealed that it was viscous but generally stable. After stability testing, the toothpaste showed no signs of stratification, sedimentation, or water precipitation. The paste was smooth, with a slightly thick consistency and no yellow solids. Its RDA was 108. The 3-minute sterilization rates against Escherichia coli ATCC 8739, Staphylococcus aureus ATCC 25923, and Candida albicans were 100%, 100%, and 100%, respectively, and the 24-hour sterilization rates were also 100%, 100%, and 100%, respectively. This indicates that the toothpaste containing this composite antibacterial agent exhibits strong antibacterial activity against these pathogens. The finished toothpaste is of good quality, and its stability meets the requirements of GB / T8372-2017.

[0039] Example 3

[0040] (1) Prepare nano silver-bamboo charcoal composite material, prepare 10mM / L AgNO3 aqueous solution and 5mM / L polyvinyl pyrrolidone solution, take 10mL of the prepared AgNO3 solution and 5mL of polyvinyl pyrrolidone solution in a beaker and stir at room temperature for half an hour to allow the silver ions to be fully dispersed, weigh bamboo charcoal according to the mass ratio of silver to bamboo charcoal of 0.5:8 and add it to the mixed solution, wherein the bamboo charcoal consists of medium-sized bamboo charcoal with a particle size of 10μm-50μm and small-sized bamboo charcoal with a particle size of 0.2μm-5μm in a mass ratio of 1:3, stir at room temperature for 4h under ultraviolet light, and then filter to obtain solid The mixture was washed and filtered repeatedly with deionized water, and then washed and dehydrated with 85% ethanol and anhydrous ethanol in sequence, and filtered. Finally, the solid was vacuum-dried at 50°C for 8h to obtain the obtained product. (2) The raw materials were weighed according to the following mass fractions: 30% hydrated silica, 6.2% nanosilver-bamboo charcoal composite material, 18% sorbitol, 4% hydroxyethyl cellulose, 0.5% sodium lauryl sulfate, 0.5% sodium saccharin, 2% povidone iodine, and the balance was water. The hydrated silica and povidone iodine were mixed and ball-milled to make the povidone iodine completely dispersed in the pores inside the hydrated silica. The mixture was rinsed with deionized water and dried to obtain the povidone iodine-hydrated silica composite material.

[0041] (3) The weighed sorbitol, hydroxyethyl cellulose, sodium lauryl sulfate, sodium saccharin and water were mixed and stirred evenly, and then the nanosilver-bamboo charcoal composite material was added and continued to be stirred until uniformly dispersed. The pH was adjusted to 6 using sodium hydrogen phosphate and sodium dihydrogen phosphate, and then the povidone iodine-hydrated silica composite material was added and continued to be stirred until uniformly dispersed. The pH was further adjusted to 6 and then stirred for 4 hours to obtain a uniform paste. The paste was vacuum degassed and canned.

[0042] Testing of the toothpaste product revealed that it was viscous but generally stable. After stability testing, the toothpaste showed no signs of stratification, sedimentation, or water precipitation. The paste was smooth, with a slightly thick consistency and no yellow solids. Its RDA was 107. The 3-minute sterilization rates against Escherichia coli ATCC 8739, Staphylococcus aureus ATCC 25923, and Candida albicans were 100%, 100%, and 100%, respectively, and the 24-hour sterilization rates were also 100%, 100%, and 100%, respectively. This indicates that the toothpaste containing this composite antibacterial agent exhibits strong bactericidal and inhibitory activity against the aforementioned pathogens. The finished toothpaste is of good quality, and its stability meets the requirements of GB / T8372-2017.

[0043] Example 4

[0044] (1) Prepare nano silver-bamboo charcoal composite material, prepare 10mM / L AgNO3 aqueous solution and 5mM / L polyvinyl pyrrolidone solution, take 10mL of the prepared AgNO3 solution and 5mL of polyvinyl pyrrolidone solution in a beaker and stir at room temperature for half an hour to allow the silver ions to be fully dispersed, weigh bamboo charcoal according to the mass ratio of silver to bamboo charcoal of 0.05:6.4 and add it to the mixed solution, wherein the bamboo charcoal consists of medium-sized bamboo charcoal with a particle size of 10μm-50μm and small-sized bamboo charcoal with a particle size of 0.2μm-5μm in a mass ratio of 1:3, stir at room temperature for 4h under ultraviolet light, and then filter to obtain solid The solid was repeatedly washed with deionized water and filtered, and then washed and dehydrated with 85% ethanol and anhydrous ethanol in sequence, and filtered. Finally, the obtained solid was vacuum dried at 50°C for 8h to obtain; (2) the raw materials were weighed according to the following mass fractions: 25.6% of hydrated silica, 6.45% of nanosilver-bamboo charcoal composite material, 20% of sorbitol, 2% of carrageenan, 1% of sodium lauryl sulfate, 0.5% of sodium saccharin, 3% of povidone iodine, and the balance was water. The hydrated silica and povidone iodine were mixed and ball-milled to make the povidone iodine completely dispersed in the pores inside the hydrated silica. The mixture was rinsed with deionized water and dried to obtain the povidone iodine-hydrated silica composite material;

[0045] (3) The weighed sorbitol, carrageenan, sodium lauryl sulfate, sodium saccharin and water were mixed and stirred evenly, and then the nanosilver-bamboo charcoal composite material was added and continued to be stirred until uniformly dispersed. The pH was adjusted to 7 using sodium hydrogen phosphate and sodium dihydrogen phosphate, and then the povidone iodine-hydrated silica composite material was added and continued to be stirred until uniformly dispersed. The pH was further adjusted to 7 and stirred for 3 hours to obtain a uniform paste. The paste was vacuum degassed and canned.

[0046] Testing of the toothpaste product revealed that it was viscous but generally stable. After stability testing, the toothpaste showed no signs of stratification, sedimentation, or water precipitation. The paste was smooth, with a slightly thick consistency and no yellow solids. Its RDA was 110. The 3-minute sterilization rates against Escherichia coli ATCC 8739, Staphylococcus aureus ATCC 25923, and Candida albicans were 100%, 100%, and 100%, respectively, and the 24-hour sterilization rates were also 100%, 100%, and 100%, respectively. This indicates that the toothpaste containing this composite antibacterial agent exhibits strong bactericidal activity against these pathogens. The finished toothpaste is of good quality, and its stability meets the requirements of GB / T8372-2017.

[0047] Comparative Example 1

[0048] (1) Weighing the following raw materials according to mass fractions: 32% hydrated silica, 20% sorbitol, 2% carrageenan, 1% sodium lauryl sulfate, 0.5% sodium saccharin, 3% povidone iodine, and the balance water, mixing the hydrated silica and povidone iodine and ball milling them until the povidone iodine is completely dispersed in the pores of the hydrated silica, rinsing with deionized water, and drying to obtain a povidone iodine-hydrated silica composite material;

[0049] (2) The weighed sorbitol, carrageenan, sodium lauryl sulfate, sodium saccharin and water were mixed and stirred evenly, and then the pH was adjusted to 7 using sodium hydrogen phosphate and sodium dihydrogen phosphate. Then, the povidone iodine-hydrated silica composite material was added and stirred until uniformly dispersed. The pH was further adjusted to 7 and stirred for 3 hours to obtain a uniform paste. The paste was vacuum degassed and canned.

[0050] Testing of the toothpaste product revealed that it was viscous but generally stable. After stability testing, the toothpaste showed no signs of stratification, sedimentation, or water precipitation. The paste was smooth, with a slightly thick consistency and no yellow solids. Its RDA was 112. The 3-minute sterilization rates for Escherichia coli ATCC 8739, Staphylococcus aureus ATCC 25923, and Candida albicans were 100%, 100%, and 100%, respectively, and 95%, 96%, and 92%, respectively, after 24 hours. The basic stability of the toothpaste met the requirements of GB / T8372-2017. However, when toothpaste containing only povidone-iodine as an antibacterial agent was left for an extended period, the povidone-iodine decomposed, reducing the active iodine content and leading to a reduction in antibacterial effectiveness.

[0051] Comparative Example 2

[0052] (1) Prepare nano silver-bamboo charcoal composite material, prepare 10mM / L AgNO3 aqueous solution and 5mM / L polyvinyl pyrrolidone solution, take 10mL of the prepared AgNO3 solution and 5mL of polyvinyl pyrrolidone solution in a beaker and stir at room temperature for half an hour to allow the silver ions to be fully dispersed, weigh bamboo charcoal according to the mass ratio of silver to bamboo charcoal of 0.05:6.4 and add it to the mixed solution, wherein the bamboo charcoal particle size is 20μm-60μm, stir at room temperature for 4h under ultraviolet light, then filter and wash the obtained solid with deionized water repeatedly, then wash and dehydrate with 85% ethanol and anhydrous ethanol in turn, filter and finally vacuum freeze the obtained solid at 50℃. Air drying for 8 hours to obtain the product; (2) weighing the raw materials according to the following mass fractions: 34% of hydrated silica, 6.45% of nano silver-bamboo charcoal composite material, 20% of sorbitol, 2% of carrageenan, 1% of sodium lauryl sulfate, 0.5% of sodium saccharin, 3% of povidone iodine, and the balance of water; mixing the weighed hydrated silica, sorbitol, carrageenan, sodium lauryl sulfate, sodium saccharin and water, and then adding the nano silver-bamboo charcoal composite material and continuing to stir until it is evenly dispersed; using sodium hydrogen phosphate and sodium dihydrogen phosphate to adjust the pH to 7, adding povidone iodine and continuing to stir until it is evenly dispersed; continuing to adjust the pH to 7 and continuing to stir for 3 hours to obtain a uniform paste; vacuum degassing the paste and canning it to obtain the product.

[0053] Testing of the toothpaste product revealed that it was viscous but generally stable. After stability testing, the toothpaste showed no signs of delamination, sedimentation, or water precipitation. The paste was smooth and had a slightly high consistency. A small amount of yellow solids appeared after prolonged storage. Its RDA was 106. The 3-minute sterilization rates against Escherichia coli ATCC 8739, Staphylococcus aureus ATCC 25923, and Candida albicans were 96%, 100%, and 93%, respectively, and 72%, 84%, and 71%, respectively, after 24 hours. This indicates that the toothpaste using this composite antibacterial agent exhibits poor stability. The nanosilver particles readily react with the iodine in povidone-iodine to produce a yellow precipitate, which compromises the antibacterial efficacy of the toothpaste.

[0054] Comparative Example 3

[0055] (1) Prepare nano silver-bamboo charcoal composite material, prepare 10mM / L AgNO3 aqueous solution and 5mM / L polyvinyl pyrrolidone solution, take 10mL of the prepared AgNO3 solution and 5mL of polyvinyl pyrrolidone solution in a beaker and stir at room temperature for half an hour to allow the silver ions to be fully dispersed, weigh bamboo charcoal according to the mass ratio of silver to bamboo charcoal of 0.05:6.4 and add it to the mixed solution, wherein the bamboo charcoal consists of medium-sized bamboo charcoal with a particle size of 10μm-50μm and small-sized bamboo charcoal with a particle size of 0.2μm-5μm in a mass ratio of 1:3, stir at room temperature for 4h under ultraviolet light, then filter and wash the obtained solid with deionized water repeatedly, filter and wash with 85% ethanol and anhydrous ethanol in turn. The obtained solid was washed, dehydrated, and filtered, and finally vacuum-dried at 50°C for 8h to obtain the obtained solid; (2) the raw materials were weighed according to the following mass fractions: 25.6% of hydrated silica, 6.45% of nano silver-bamboo charcoal composite material, 20% of sorbitol, 2% of carrageenan, 1% of sodium lauryl sulfate, 0.5% of sodium saccharin, and the balance was water. The weighed sorbitol, carrageenan, sodium lauryl sulfate, sodium saccharin and water were mixed and stirred evenly, and then the nano silver-bamboo charcoal composite material was added and stirred until uniformly dispersed. Sodium hydrogen phosphate and sodium dihydrogen phosphate were used to adjust the pH to 7, and then the hydrated silica composite material was added and stirred until uniformly dispersed. The pH was continued to be adjusted to 7 and stirred for 3h to obtain a uniform paste. The paste was vacuum degassed and canned.

[0056] Testing of the toothpaste product revealed that it was viscous but generally stable. After stability testing, the toothpaste showed no signs of delamination, sedimentation, or water precipitation. The paste was smooth, with a slightly thick consistency and no yellow solids. Its RDA was 110. The 3-minute bactericidal rates against Escherichia coli ATCC 8739, Staphylococcus aureus ATCC 25923, and Candida albicans were 58%, 82%, and 72%, respectively, and the 24-hour bactericidal rates were 46%, 71%, and 56%, respectively. This indicates that the single nanosilver antibacterial agent is less effective than povidone-iodine in killing bacteria, resulting in a low overall antibacterial effect. Observation of the toothpaste particles revealed no significant color darkening, indicating that while the antibacterial effect of the toothpaste is less than ideal, the nanosilver-modified graphene oxide structure is relatively stable, allowing the silver nanoparticles to persist stably for extended periods without significant oxidation.

[0057] Comparative Example 4

[0058] (1) preparation of nano-silver particles, configuration of concentration 10 mM / L AgNO3 aqueous solution, 5 mM / L polyvinyl pyrrolidone solution, 10 mL of prepared AgNO3 solution, 5 mL of polyvinyl pyrrolidone solution in a beaker, stirring at room temperature for half an hour, so that silver ions can be fully dispersed, under ultraviolet light irradiation, stirring at room temperature for 4 h, then suction filtration, obtaining solid repeatedly washing with deionized water, suction filtration, then sequentially washing with 85% ethanol, anhydrous ethanol, dehydration, suction filtration, finally vacuum drying the obtained solid at 50℃ for 8 h, obtaining; (2) according to the following mass fraction, the raw materials are weighed, hydrated silica 32%, medium particle size bamboo charcoal 2%, small particle size bamboo charcoal 3%, polyethylene glycol 15%, carrageenan 5%, sodium dodecyl sulfate 1%, saccharin sodium 0.5%, nano-silver particles prepared in step (1) 2%, povidone-iodine 4%, and the rest is water, the above raw materials are mixed and stirred until uniformly dispersed, the pH is adjusted to 8 with sodium hydrogen phosphate and sodium dihydrogen phosphate, and then continuously stirred for 3 h to obtain a uniform paste, and the paste is vacuum degassed and then filled into a tank to obtain.

[0059] The toothpaste product is detected, and the detection shows that a small amount of yellow precipitate appears in the toothpaste preparation process, the stability test shows that the yellow particles increase after heating, and the paste appears a little delamination, the 3min sterilization rate of the test strains of escherichia coli ATCC 8739, staphylococcus aureus ATCC 25923 and candida albicans is 78%, 62% and 69% respectively, and the 24h sterilization rate is 54%, 43% and 61% respectively, it can be seen that simply adding the bacteriostatic agent as a raw material into the toothpaste cannot effectively obtain the synergistic bacteriostatic effect, the bacteriostatic effect of the toothpaste obtained after adding the nano-silver particles and povidone-iodine respectively is poor, silver iodide yellow precipitate appears in the toothpaste, which reduces the stability of the toothpaste.

[0060] The above describes a composite antibacterial toothpaste in detail, and the above content is a further detailed description of the present application combined with specific preferred embodiments, and cannot be considered as limiting the specific implementation of the present application to these descriptions. For ordinary skilled persons in the technical field to which the present application belongs, the architecture form can be flexible and variable without departing from the concept of the present application, and a series of products can be derived. Any simple deduction or replacement should be considered as belonging to the patent protection scope determined by the submitted claims.

Claims

1. A composite antibacterial toothpaste comprising an abrasive, a moisturizing agent, a thickener, a foaming agent, a sweetener, water, and an antibacterial agent, wherein the antibacterial agent is nanosilver particles and povidone iodine, characterized in that: The friction agent consists of hydrated silica, medium-sized bamboo charcoal and small-sized bamboo charcoal in a mass ratio of 8:0.5:1.5, and the nano silver particles are loaded in the medium-sized bamboo charcoal and small-sized bamboo charcoal.

2. The composite antibacterial toothpaste according to claim 1, characterized in that The particle size of the medium-sized bamboo charcoal is 10 μm-50 μm, the particle size of the small-sized bamboo charcoal is 0.2 μm-5 μm, the particle size of the hydrated silica is 10-80 μm, and the mass ratio of the nanosilver particles to povidone iodine in the antibacterial agent is 0.02-1:1-5.

3. The composite antibacterial toothpaste according to claim 1, characterized in that The nano silver particles are evenly distributed on the surface and in the internal pores of the medium-sized bamboo charcoal and the small-sized bamboo charcoal, and the povidone iodine is distributed in the internal pores of the hydrated silica.

4. The composite antibacterial toothpaste according to claim 1, characterized in that The moisturizing agent is at least one of polyethylene glycol, glycerin, and sorbitol; the thickener is at least one of hydroxyethyl cellulose, xanthan gum, and carrageenan; the foaming agent is at least one of sodium lauryl sulfate and sodium lauryl sulfate; and the sweetener is at least one of saccharin sodium and stevia.

5. The composite antibacterial toothpaste according to claim 1, characterized in that The toothpaste further comprises a pH regulator, which is sodium hydrogen phosphate and sodium dihydrogen phosphate. The pH of the toothpaste is 6-7.

6. The composite antibacterial toothpaste according to claim 1, characterized in that: The toothpaste comprises the following components in percentage by weight: 16-32% hydrated silica, 1-2% medium-sized bamboo charcoal, 3-6% small-sized bamboo charcoal, 15-25% moisturizer, 1-5% thickener, 0.5-1% foaming agent, 0.05-0.5% sweetener, 0.02-1% nano-silver particles, 1-5% povidone-iodine, and the balance is water.

7. The composite antibacterial toothpaste according to claim 5, characterized in that: The toothpaste comprises the following components by weight: 25.6% hydrated silica, 1.6% medium-sized bamboo charcoal, 4.8% small-sized bamboo charcoal, 20% moisturizer, 2% thickener, 1% foaming agent, 0.5% sweetener, 0.05% nano-silver particles, 3% povidone-iodine, and the balance is water.

8. A method for preparing the composite antibacterial toothpaste according to any one of claims 1 to 7, characterized in that: The steps include: (1) Prepare nanosilver-bamboo charcoal composite material, prepare 10mM / L AgNO3 aqueous solution and 5mM / L polyvinyl pyrrolidone solution, take 10mL of the prepared AgNO3 solution and 5mL of polyvinyl pyrrolidone solution in a beaker and stir at room temperature for half an hour to allow the silver ions to be fully dispersed, weigh bamboo charcoal according to the mass ratio of silver to bamboo charcoal of 0.02-1:4-8 and add it to the mixed solution, wherein the bamboo charcoal consists of medium-sized bamboo charcoal and small-sized bamboo charcoal in a mass ratio of 1:3, stir at room temperature for 4h under ultraviolet light, then filter, wash and filter the obtained solid repeatedly with deionized water, then wash and dehydrate with 85% ethanol and anhydrous ethanol in turn, filter, and finally dry the obtained solid at 50℃ under vacuum for 8h. (2) weighing raw materials hydrated silica, a moisturizing agent, a thickener, a foaming agent, a sweetener, water, povidone iodine, and a nanosilver-bamboo charcoal composite material according to a mass ratio, mixing the hydrated silica and povidone iodine and ball milling them so that the povidone iodine is completely dispersed in the pores inside the hydrated silica, rinsing with deionized water, and drying to obtain the povidone iodine-hydrated silica composite material; (3) Preparation of toothpaste: The weighed moisturizer, thickener, foaming agent, sweetener and water are mixed and stirred evenly, and then the nanosilver-bamboo charcoal composite material is added and stirred until uniformly dispersed. After adjusting the pH, the povidone iodine-hydrated silica composite material is added and stirred until uniformly dispersed. After further adjusting the pH, stirring is continued for 1 to 5 hours to obtain a uniform paste. The paste is vacuum degassed and canned.

9. The method for preparing the composite antibacterial toothpaste according to claim 8, characterized in that: The particle size of the medium-sized bamboo charcoal is 10 μm-50 μm, the particle size of the small-sized bamboo charcoal is 0.2 μm-5 μm, the particle size of the hydrated silica is 10-80 μm, and the mass ratio of the nanosilver particles to povidone iodine in the antibacterial agent is 0.02-1:1-5.

10. The method for preparing the composite antibacterial toothpaste according to claim 8, characterized in that: The pH is 6-7.