CN115607464A

CN115607464A - Antibacterial stain-removing toothpaste and preparation method thereof

Info

Publication number: CN115607464A
Application number: CN202211413785.6A
Authority: CN
Inventors: 童怀洲; 童星; 杜永卫
Original assignee: Jiangsu Xuebao Daily Chemical Co ltd
Current assignee: Jiangsu Xuebao Daily Chemical Co ltd
Priority date: 2022-11-11
Filing date: 2022-11-11
Publication date: 2023-01-17
Anticipated expiration: 2042-11-11
Also published as: CN115607464B

Abstract

The invention provides antibacterial stain-removing toothpaste and a preparation method thereof, and belongs to the technical field of toothpaste. After the nano-montmorillonite is pretreated, the surface of the nano-montmorillonite is modified by polydopamine, dipotassium glycyrrhizinate, sodium azulene sulfonate and paeonol are fixed, porous silicon dioxide is coated on the surface of the nano-montmorillonite, lysozyme and glucanase are fixed to obtain a modified abrasive, and then the modified abrasive is uniformly mixed with sodium alginate microspheres embedded with probiotics and prebiotics, a humectant, a sweetening agent, a foaming agent, a thickening agent, essence and water, and subjected to vacuum degassing to form paste, so that the antibacterial and stain-removing toothpaste is prepared. The toothpaste can effectively inhibit the adhesion and aggregation of oral bacteria, simultaneously remove stain and dirt on the surface of teeth, synergistically remove the stain and inhibit the formation of dental plaque, has the effects of astringing, relieving allergy and repairing canker sore, achieves the effects of nursing oral cavity and removing the stain in the oral cavity, can prevent oral diseases such as periodontitis, gingivitis, dental calculus, dental caries, halitosis and the like, and has wide application prospect.

Description

Antibacterial stain-removing toothpaste and preparation method thereof

Technical Field

The invention relates to the technical field of toothpaste, in particular to antibacterial stain-removing toothpaste and a preparation method thereof.

Background

Along with the enhancement of consciousness of people on health and the improvement of life quality, the attention degree on oral care is greatly enhanced. Most diseases of human are caused by oral cavity, and the maintenance of oral hygiene is an important link for preventing diseases, and the key for maintaining oral hygiene is to maintain the hygiene of teeth. If teeth are unsanitary, a large amount of microorganisms are propagated therein, and corrode teeth, causing halitosis, gingival swelling, etc., and more serious dental diseases may also cause other serious systemic diseases. Dental plaque is an ecological environment of bacteria present on the tooth surface or in the periodontal pocket, where bacteria grow, develop and die, and undergo complex metabolic activities, under certain conditions, the bacteria and their products will destroy the teeth and periodontal tissues. Plaque is a soft, unmineralized bacterial plaque that adheres to the tooth surface and is not easily detectable in small quantities. However, as time goes on, the plaque is not removed in time, which can cause stubborn spots and stains which can not be removed by daily oral care, and the tooth surface loses luster and becomes yellow and dark.

The tooth whitening toothpaste disclosed in the Chinese patent CN101889960B is prepared from an adhesive, a foaming agent, a humectant, a sweetening agent, an abrasive, a spice, deionized water, a covering agent, a preservative and a stain removing agent by a conventional method, wherein the abrasive adopted by the tooth whitening and stain removing toothpaste is precipitated silica, and the stain removing agent is sodium phytate. Although the precipitated silica is the first choice as the abrasive of the toothpaste at present and has better friction stain removal effect, the addition of the precipitated silica can cause the obtained toothpaste to be unstable and has higher requirements on other components in the formula of the toothpaste, and experiments prove that not all the precipitated silica is suitable for preparing the stain removal toothpaste, and different silicas as the abrasive can cause great difference of the stain removal effect and the toothpaste performance. In the toothpaste, the adopted stain remover is sodium phytate which is a natural extract, has extremely strong chelating action with metal ions, is a safe and efficient ion complexing agent, is safe and reliable as the stain remover in the toothpaste, and can inhibit the formation of dental calculus. However, in practical use, it has been found that the type of precipitated silica also has a large influence on the performance of sodium phytate in stain removing performance.

Meanwhile, consumers have a strong demand for whitening teeth at present, and are interested in whitening teeth, and some people whiten teeth by means of tooth washing and the like, but the cost is high and certain risks exist. Most people want to whiten teeth on various toothpastes with whitening effects, the existing whitening toothpastes mostly adopt special granular abrasive agents or peroxides to be added into the toothpastes to achieve the whitening effect, but the granular abrasive agents can damage tooth enamel and damage the tooth surface, so that tooth stains are more easily deposited on the tooth surface. The peroxide bleaching has quick effect on teeth, has definite irritation to oral cavity and definite risk.

Therefore, the toothpaste is developed, can effectively remove dental plaque to prevent the dental plaque from being enlarged, treats related oral diseases, has definite whitening and stain removing effects, and has wide application prospect.

Disclosure of Invention

The invention aims to provide the antibacterial stain-removing toothpaste and the preparation method thereof, the antibacterial stain-removing toothpaste is mild and non-irritant, can effectively inhibit the adhesion and aggregation of oral bacteria, and simultaneously removes color stains and dirt on the surfaces of teeth, and each functional component can synergistically and fundamentally remove the dental stains to inhibit the formation of dental plaque, has the effects of astringing, soothing and repairing dental ulcer, achieves the effects of nursing the oral cavity and removing the dental stains in the oral cavity, can prevent oral diseases such as periodontitis, gingivitis, dental calculus, dental caries, halitosis and the like, and has wide application prospects.

The technical scheme of the invention is realized as follows:

the invention provides a preparation method of antibacterial stain-removing toothpaste, which comprises the steps of pretreating nano montmorillonite, modifying the surface with polydopamine, fixing dipotassium glycyrrhizinate, sodium azulene sulfonate and paeonol, coating porous silicon dioxide on the surface, fixing lysozyme and glucanase to obtain a modified abrasive, uniformly mixing the modified abrasive with sodium alginate microspheres embedded with probiotics and prebiotics, a humectant, a sweetening agent, a foaming agent, a thickening agent, essence and water, and degassing in vacuum to obtain the antibacterial stain-removing toothpaste.

As a further improvement of the invention, the method comprises the following steps:

s1, surface treatment of nano montmorillonite: soaking the nano montmorillonite in alkali liquor, centrifuging, washing and drying to obtain pretreated nano montmorillonite;

s2, modifying polydopamine: uniformly dispersing the pretreated nano montmorillonite prepared in the step S1 in water, adding dopamine hydrochloride and a catalyst, heating for reaction, centrifuging, washing and drying to obtain polydopamine modified montmorillonite;

s3, fixing the composite preparation: uniformly mixing dipotassium glycyrrhizinate, sodium azulene sulfonate and paeonol, dissolving in an ethanol water solution, adding the polydopamine modified montmorillonite prepared in the step S2, uniformly dispersing by ultrasonic waves, carrying out heating reaction, centrifuging, washing and drying to obtain modified montmorillonite;

s4, coating of silicon dioxide: dissolving alkyl orthosilicate in an ethanol water solution, adding the modified montmorillonite prepared in the step S3, uniformly dispersing by ultrasonic, adjusting the pH value of the solution to be alkaline, adding a pore-foaming agent and an emulsifying agent, emulsifying, stirring for reaction, centrifuging, washing and drying to obtain modified montmorillonite coated with porous silicon dioxide;

s5, complex enzyme immobilization: dissolving lysozyme and dextranase in water to obtain an antibacterial enzyme mixed solution, adding the porous silicon dioxide coated modified montmorillonite prepared in the step S4, stirring and fixing, and volatilizing at normal temperature to obtain a modified friction agent;

s6, preparation of the probiotic and prebiotics embedded microspheres: mixing the composite probiotics and the composite prebiotics in water, adding sodium alginate for dissolving, adding silicon oil, quickly emulsifying by a membrane, dripping a calcium chloride solution, and solidifying at normal temperature to obtain the microspheres embedded with the probiotics and the prebiotics;

s7, preparing the antibacterial stain-removing toothpaste: and (4) uniformly mixing the modified abrasive prepared in the step (S5), the probiotic and prebiotics embedded microspheres prepared in the step (S6), a humectant, a sweetening agent, a foaming agent, a thickening agent, essence and water, stirring and mixing at a high speed, and degassing in vacuum to form paste, thus obtaining the antibacterial stain-removing toothpaste.

As a further improvement of the invention, the particle size of the nano montmorillonite in the step S1 is less than 100nm, the alkali liquor is NaOH or KOH solution with the concentration of 1-3mol/L, and the soaking time is 30-50min; the mass ratio of the pretreated nano montmorillonite, dopamine hydrochloride and the catalyst in the step S2 is 15-22 ₂ The temperature of the heating reaction is 50-70 ℃, and the time is 2-3h.

As a further improvement of the invention, in step S3, the mass ratio of the dipotassium glycyrrhizinate, the sodium azulene sulfonate, the paeonol and the polydopamine modified montmorillonite is 3-5 to 1-3, the concentration of ethanol in the ethanol aqueous solution is 40-60wt%, and the balance is water, wherein the heating reaction temperature is 40-50 ℃, and the heating reaction time is 1-2h; the mass ratio of the alkyl orthosilicate in the step S4 is 5-10, namely, 12-17.

As a further improvement of the invention, the mass ratio of the lysozyme, the dextranase and the porous silica coated modified montmorillonite in the step S5 is 2-4; in the step S6, the composite probiotics are selected from at least two of lactobacillus acidophilus, lactobacillus paracasei and lactobacillus salivarius, the composite prebiotics are selected from fructo-oligosaccharide, galacto-oligosaccharide, xylo-oligosaccharide, isomalto-oligosaccharide, soybean oligosaccharide and inulin, the mass ratio of the composite probiotics to the composite prebiotics to sodium alginate is (5-10) and (17-25), the concentration of the calcium chloride solution is 3-5wt%, the pore diameter of the membrane in the rapid membrane emulsification is 1000-3000nm, and the normal-temperature curing time is 30-50min.

As a further improvement of the invention, the composite probiotics is a mixture of lactobacillus paracasei and lactobacillus salivarius, and the mass ratio is 3-5; the composite prebiotics are a mixture of fructo-oligosaccharide and xylo-oligosaccharide, and the mass ratio is 3-5.

As a further improvement of the invention, the mass ratio of the modified friction agent, the probiotics and prebiotics embedded microspheres, the humectant, the sweetener, the foaming agent, the thickener, the essence and the water in the step S7 is 20-40:4-7, 20-35, 0.1-0.2, 1-3, 0.5-1.5, 1-1.5, 30-50; the rotating speed of the high-speed stirring and mixing is 1000-1200r/min, and the mixing time is 15-30min.

As a further improvement of the present invention, the humectant is selected from at least one of glycerin, sorbitol and polyethylene glycol 400; the sweetening agent is at least one of sucralose, aspartame, acesulfame potassium, sodium cyclamate, saccharin and xylitol; the foaming agent is betaine; the thickening agent is at least one of xanthan gum, carrageenan and sodium carboxymethylcellulose.

As a further improvement of the invention, the method specifically comprises the following steps:

s1, surface treatment of nano montmorillonite: soaking nanometer montmorillonite with particle size less than 100nm in 1-3mol/L NaOH or KOH solution for 30-50min, centrifuging, washing, and drying to obtain pretreated nanometer montmorillonite;

s2, polydopamine modification treatment: uniformly dispersing 15 parts by weight of the pretreated nano montmorillonite prepared in the step S1 in water, adding 17-22 parts by weight of dopamine hydrochloride and 1-3 parts by weight of catalyst, heating to 50-70 ℃ for reaction for 2-3h, centrifuging, washing and drying to obtain polydopamine modified montmorillonite;

the catalyst is CoCl containing 3-5wt% ₂ The pH value of the Tris-HCl solution is 5-6;

s3, fixing a composite preparation: uniformly mixing 3-5 parts by weight of dipotassium glycyrrhizinate, 2-4 parts by weight of sodium azulene sulfonate and 1-3 parts by weight of paeonol, dissolving the mixture in 100 parts by weight of 40-60wt% ethanol water solution, adding 30 parts by weight of the polydopamine modified montmorillonite prepared in the step S2, uniformly dispersing by ultrasonic waves, heating to 40-50 ℃ for reaction for 1-2 hours, centrifuging, washing and drying to obtain modified montmorillonite;

s4, coating of silicon dioxide: dissolving 5-10 parts by weight of tetraethoxysilane or methyl orthosilicate in 100 parts by weight of 50-70wt% ethanol water solution, adding 12-17 parts by weight of the modified montmorillonite prepared in the step S3, uniformly dispersing by ultrasonic, adjusting the pH value of the solution to 8-9, adding 1-3 parts by weight of pore-foaming agent and 0.5-1 part by weight of emulsifier, emulsifying for 3-5min at 12000-15000r/min, stirring for reaction, centrifuging, washing and drying to obtain the modified montmorillonite coated with porous silicon dioxide;

s5, complex enzyme immobilization: dissolving 2-4 parts by weight of lysozyme and 1-3 parts by weight of dextranase in 20 parts by weight of water to obtain an antibacterial enzyme mixed solution, adding 15-20 parts by weight of the modified montmorillonite coated with the porous silicon dioxide prepared in the step S4, stirring and fixing, and volatilizing at normal temperature to obtain a modified friction agent;

s6, preparation of the probiotic and prebiotics embedded microspheres: mixing 5-10 parts by weight of composite probiotics and 2-4 parts by weight of composite prebiotics in 50 parts by weight of water, adding 17-25 parts by weight of sodium alginate for dissolution and 2-3 parts by weight of emulsifier for dissolution, adding the mixture into 100 parts by weight of silicone oil, emulsifying by using a rapid film with the aperture of 1000-3000nm, dropwise adding 10-15 parts by weight of 3-5wt% calcium chloride solution, and curing at normal temperature for 30-50min to obtain microspheres embedding the probiotics and the prebiotics;

the composite probiotics are a mixture of lactobacillus paracasei and lactobacillus salivarius, and the mass ratio is (3-5);

the composite prebiotics are a mixture of fructo-oligosaccharide and xylo-oligosaccharide, and the mass ratio is 3-5;

s7, preparing the antibacterial stain-removing toothpaste: and (2) uniformly mixing 20-40 parts by weight of the modified abrasive prepared in the step (S5), 4-7 parts by weight of the microspheres embedding probiotics and prebiotics prepared in the step (S6), 20-35 parts by weight of humectant, 0.1-0.2 part by weight of sweetening agent, 1-3 parts by weight of foaming agent, 0.5-1.5 parts by weight of thickening agent, 1-1.5 parts by weight of essence and 30-50 parts by weight of water, stirring and mixing at 1000-1200r/min for 15-30min, and degassing in vacuum to form paste to prepare the antibacterial stain-removing toothpaste.

The invention further protects the antibacterial stain-removing toothpaste prepared by the preparation method.

The invention has the following beneficial effects:

actinobacillus actinomycetemcomitans is a gram-negative oral pathogenic bacterium with high pathogenic potential, and is easy to colonize in the oral cavity to form dental plaque biomembranes with complex structures, so as to cause periodontal disease. Meanwhile, actinobacillus actinomycetemcomitans can secrete and synthesize various high-toxicity factors to cause the occurrence and development of periodontitis, and further causes symptoms such as gingival bleeding, tooth loosening and halitosis. Porphyromonas gingivalis is a typical pathogenic bacterium of gingivitis, is a gram-negative obligate anaerobe, and is a dominant pathogenic bacterium of subgingival bacterial plaque of periodontal disease. The streptococcus mutans is pathogenic bacteria of dental caries, can form water-insoluble polysaccharides on dental surfaces, and is firmly adhered to the dental surfaces; under the same pH condition, the streptococcus mutans can dissolve more calcium than streptococcus sanguis, lactobacillus and the like; mutans streptococci can convert sucrose to glucan and convert glucose almost entirely to lactic acid.

The dipotassium glycyrrhizinate can completely inhibit the formation of dental plaque by inhibiting and killing actinobacillus actinomycetemcomitans and streptococcus mutans. Paeonol is colorless or white or yellowish needle-shaped crystal with luster, has strong antibacterial effect on Staphylococcus aureus, streptococcus faecalis, escherichia coli, etc., and has tranquilizing, antiinflammatory, antipyretic, and antiallergic effects. The sodium azulene sulfonate is an effective component of chamomile, has strong effects of resisting pepsin, diminishing inflammation, resisting bacteria and allergy and promoting mucosal metabolism, and inhibits inflammatory cells from releasing histamine by local direct action; increase synthesis of prostaglandin E2 in mucous membrane, promote granulation and epithelial cell regeneration, and has good effect of repairing epithelial cell and high safety. The three components are compounded and enter the oral cavity, so that the surfaces of harmful thalli become uneven, part of the thalli are broken, substances in cells flow out, and the integrity of bacterial cells is damaged, and the prepared toothpaste has good effects of inhibiting bacteria, resisting bacteria, diminishing inflammation, relieving heat, repairing epithelial cells and promoting mucosal metabolism, can effectively inhibit the formation of dental plaque, inhibit gingival bleeding, tooth loosening and halitosis, and repair oral ulcer.

According to the invention, through carrying out polydopamine modification on the surface of nano montmorillonite, rich hydroxyl, amino, carboxyl and other groups of polydopamine can form hydrogen bond fixation with dipotassium glycyrrhizinate, paeonol and sodium azulene sulfonate, so that a composite preparation can be stably fixed on the polydopamine modified montmorillonite, and further through sol-gel reaction, a layer of porous silicon dioxide (under the action of a pore-forming agent) is coated on the surface, the coating of the porous silicon dioxide can further enhance the strength of particles, and meanwhile, a larger specific surface area is provided, so that rich site fixation is provided for lysozyme and glucanase, and a modified abrasive is prepared.

Streptococcus mutans among oral bacteria has been widely recognized as the major causative agent of dental caries. The mechanism responsible for caries formation is that Glucosyltransferases (GTFs) in streptococcus mutans break down sucrose and synthesize extracellular polysaccharides that can attach to tooth surfaces, and, in addition, the acids produced by streptococcus mutans promote tooth demineralization, which is exacerbated in the presence of oral sugars, and it is important to prevent glucan synthesis and acid production in order to protect teeth. Streptococcus mutans can synthesize glucan rich in alpha-1, 6 glycoside chains, glucan rich in alpha-1, 3 glycoside chains, and water-soluble glucan by the produced glucosyltransferase.

The glucanase can effectively decompose glucan produced by streptococcus mutans, thereby preventing dental caries and dental plaque formation.

The lysozyme is a non-specific substance component, can inhibit the growth of microorganisms, and does not have drug resistance after long-term use. The lysozyme can effectively hydrolyze peptidoglycan of bacterial cell walls, and has different peptidoglycan contents in the cell walls of gram-positive bacteria (G +), such as staphylococcus aureus, bacillus subtilis or micrococcus lyticus, and gram-negative bacteria (G-), such as escherichia coli, fusobacterium nucleatum, porphyromonas gingivalis, bacillus pneumoniae, and the like, the G + bacterial cell walls almost completely consist of the peptidoglycan, and only the inner wall layer of the G-bacteria is the peptidoglycan, so the lysozyme has good inhibition and killing effects on the G + bacteria and certain inhibition effects on the G-bacteria. The lysozyme can selectively dissolve the cell wall of a target microorganism to inactivate the cell wall, and mammals have no cell wall, so the lysozyme has no damage to oral tissues but plays a role in protection.

The probiotics hinder colonization of pathogenic bacteria by competing with oral pathogenic bacteria for binding sites, thereby allowing the pathogenic bacteria to be excreted from the oral cavity, thereby improving oral health. Metabolites such as organic acids, bacteriocins and the like generated by probiotics can effectively inhibit the growth of pathogenic bacteria and the formation of a biological membrane.

The lactobacillus paracasei is the most common lactobacillus in oral microbiota, and the inactivated bacteria powder can generate coagulation precipitation with oral pathogenic bacteria. The lactobacillus salivarius can inhibit the growth of pathogenic bacteria of caries, so as to prevent and treat caries, has a certain adsorption effect, and can well colonize and grow on the surface of intestinal tract to further exert the immune effect. The probiotic bacteria and the pathogenic bacteria have-CH simultaneously on the surface ₂ -and-CH ₃ The probiotic bacteria and the pathogenic bacteria with the similar low surface energy groups can be co-agglomerated, the surface roughness of the probiotic bacteria is Ra =19.5nm, and the surface of the probiotic bacteria is rougher than that of the pathogenic bacteria, so that the adhesion effect of the probiotic bacteria is stronger, and the adhesion sites can be competed with the pathogenic bacteria in the oral cavity, so that the quantity of the pathogenic bacteria is reduced. Through compounding with the prebiotics, the sodium alginate shell embeds the probiotics and the prebiotics, the survival rate of the probiotics can be obviously improved, the microsphere shell is broken in the repeated friction process of the abrasive in the toothpaste, and the probiotics and the prebiotics are dissolved out, so that the functions of bacteriostasis, antibiosis and oral health protection are achieved.

Xylo-oligosaccharide and fructo-oligosaccharide are prebiotics, and the fructo-oligosaccharide can selectively proliferate bifidobacterium, thereby regulating the micro-ecological balance of the intestinal tract and maintaining the health of the intestinal tract. Xylo-oligosaccharide is also called xylo-oligosaccharide, is a functional polysaccharide formed by combining 2-7 xylose molecules by beta-1, 4 glycosidic bonds, is difficult to decompose by human digestive enzyme, has good acid and heat stability, and has extremely strong function of proliferating bifidobacterium, inhibiting the growth of harmful bacteria and leading probiotics to be massively proliferated in intestinal tracts. The fructo-oligosaccharide as water-soluble dietary fiber can stimulate intestinal tract peristalsis, change osmotic pressure of intestinal contents, increase feces water content, relax bowel, relieve constipation, effectively reduce content of free fatty acid, triglyceride and serum cholesterol in vivo, and improve cardiovascular diseases such as arteriosclerosis and hypertension. The xylo-oligosaccharide and fructo-oligosaccharide can be fermented by intestinal bacteria to produce short chain fatty acids such as acetic acid, propionic acid and butyric acid, lactic acid and the like, reduce the pH value of the intestinal environment, inhibit the growth and propagation of harmful bacteria and pathogenic bacteria, and reduce the generation and accumulation of toxins and putrefactive substances in the field.

The modified frictionizer and the compound probiotics have antibacterial effects, the compound prebiotics comprise fructo-oligosaccharide which can promote the proliferation of beneficial bacteria, on one hand, lysozyme and dextranase in the modified frictionizer have the antibacterial effect, and on the other hand, xylo-oligosaccharide and fructo-oligosaccharide form a competitive relationship with pathogenic bacteria through the proliferation of the beneficial bacteria to indirectly inhibit the pathogenic bacteria in the oral cavity. Under the multiple actions, the prepared toothpaste has good effects of inhibiting bacteria, removing dental plaque and removing stains.

The antibacterial stain-removing toothpaste provided by the invention is mild and non-irritant, can effectively inhibit the adhesion and aggregation of oral bacteria, and simultaneously removes stain dirt on the surface of teeth, and each functional component can synergistically and fundamentally remove the stains to inhibit the formation of dental plaque, and also has the effects of astringing, relieving allergy and repairing oral ulcer, so that the effects of nursing the oral cavity and removing the stains in the oral cavity are achieved, oral diseases such as periodontitis, gingivitis, dental calculus, dental caries, halitosis and the like can be prevented, and the antibacterial stain-removing toothpaste has a wide application prospect.

Detailed Description

The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Nanometer montmorillonite with a content of less than 100nm and a content of more than 99% is purchased from processing plants of Bochuan mineral products in Ling shou county; dipotassium glycyrrhizinate with content more than 98%, gansu Pan plant Biotech Co., ltd; sodium azulene sulfonate, the content of which is more than 95 percent, is purchased from Huzhou Purui biomedicine technology Co., ltd; paeonol, with a content of more than 98%, was purchased from Shanghai Yuan leaf Biotech Co., ltd. Lysozyme, light yellow or white solid powder, and dextranase which is beta-dextranase are all purchased from Nanning Dong Henghuadao Biotech, inc. Lactobacillus paracasei, 200 hundred million cfu/g, purchased from Qianye grass Biotech limited; lactobacillus salivarius JYLS-372 (100 hundred million cfu/g) purchased from Jiayi bioengineering Co., ltd, katayi, shandong, zhongke; fructo-oligosaccharide and xylo-oligosaccharide are both purchased from Nanjing Songguan biological science and technology Co.

Example 1

The embodiment provides a preparation method of antibacterial stain-removing toothpaste, which specifically comprises the following steps:

s1, surface treatment of nano montmorillonite: soaking nano montmorillonite with particle size less than 100nm in 1mol/L NaOH solution for 30min, centrifuging at 5000r/min for 15min, washing with clear water, and drying at 70 deg.C for 2h to obtain pretreated nano montmorillonite;

s2, modifying polydopamine: adding 15 parts by weight of the pretreated nano montmorillonite prepared in the step S1 into water, performing ultrasonic dispersion for 20min at 1000W, adding 17 parts by weight of dopamine hydrochloride and 1 part by weight of catalyst, heating to 50 ℃ for reaction for 2h, centrifuging for 15min at 5000r/min, washing with clear water, and drying for 2h at 70 ℃ to obtain poly-dopamine modified montmorillonite;

the catalyst is CoCl containing 3wt% ₂ Tris-HCl solution of pH 5;

s3, fixing the composite preparation: uniformly mixing 3 parts by weight of dipotassium glycyrrhizinate, 2 parts by weight of sodium azulene sulfonate and 1 part by weight of paeonol, dissolving the mixture in 100 parts by weight of 40wt% ethanol aqueous solution, adding 30 parts by weight of the polydopamine modified montmorillonite prepared in the step S2, carrying out 1500W ultrasonic dispersion for 20min, heating to 40 ℃ for reaction for 1h, centrifuging at 5000r/min for 15min, washing with clear water, and drying at 70 ℃ for 2h to obtain modified montmorillonite;

s4, coating of silicon dioxide: dissolving 5 parts by weight of tetraethoxysilane in 100 parts by weight of 50wt% ethanol water solution, adding 12 parts by weight of the modified montmorillonite prepared in the step S3, performing 1500W ultrasonic dispersion for 20min, adjusting the pH value of the solution to be 8, adding 1 part by weight of hexadecyl trimethyl ammonium bromide and 0.5 part by weight of Tween-40, emulsifying at 12000r/min for 3min, stirring for reaction for 3h, centrifuging at 5000r/min for 15min, washing with clear water, and drying at 70 ℃ for 2h to obtain porous silica coated modified montmorillonite;

s5, complex enzyme immobilization: dissolving 2 parts by weight of lysozyme and 1 part by weight of dextranase in 20 parts by weight of water to obtain an antibacterial enzyme mixed solution, adding 15 parts by weight of the porous silicon dioxide coated modified montmorillonite prepared in the step S4, stirring and fixing for 30min at the rotating speed of 500/min, and volatilizing at normal temperature to obtain a modified friction agent;

s6, preparation of the microspheres embedding the probiotics and the prebiotics: mixing 5 parts by weight of composite probiotics and 2 parts by weight of composite prebiotics in 50 parts by weight of water, adding 17 parts by weight of sodium alginate for dissolution and 2 parts by weight of tween-80 for dissolution, adding the mixture into 100 parts by weight of silicone oil, emulsifying by using a rapid membrane with the pore diameter of 1000nm, dropwise adding 10 parts by weight of 3wt% calcium chloride solution, and curing at normal temperature for 30min to obtain microspheres embedded with the probiotics and the prebiotics;

the composite probiotics is a mixture of lactobacillus paracasei and lactobacillus salivarius, and the mass ratio is 3;

the composite prebiotics are a mixture of fructo-oligosaccharide and xylo-oligosaccharide, and the mass ratio is 3;

s7, preparing the antibacterial stain-removing toothpaste: and (2) uniformly mixing 20 parts by weight of the modified friction agent prepared in the step (S5), 4 parts by weight of the microspheres embedding probiotics and prebiotics prepared in the step (S6), 20 parts by weight of polyethylene glycol 400, 0.1 part by weight of saccharin, 1 part by weight of betaine, 0.5 part by weight of xanthan gum, 1 part by weight of lemon essence and 30 parts by weight of water, stirring and mixing for 15min at the speed of 1000r/min, and performing vacuum degassing to obtain the antibacterial stain-removing toothpaste.

Example 2

s1, surface treatment of nano montmorillonite: soaking nanometer montmorillonite with particle size less than 100nm in 3mol/L KOH solution for 50min, centrifuging at 5000r/min for 15min, washing with clear water, and drying at 70 deg.C for 2 hr to obtain pretreated nanometer montmorillonite;

s2, modifying polydopamine: adding 15 parts by weight of the pretreated nano montmorillonite prepared in the step S1 into water, performing ultrasonic dispersion at 1000W for 20min, adding 22 parts by weight of dopamine hydrochloride and 3 parts by weight of catalyst, heating to 70 ℃ for reaction for 3h, centrifuging at 5000r/min for 15min, washing with clear water, and drying at 70 ℃ for 2h to obtain poly-dopamine modified montmorillonite;

the catalyst is CoCl containing 5wt% ₂ Tris-HCl solution with pH value of 6;

s3, fixing the composite preparation: uniformly mixing 5 parts by weight of dipotassium glycyrrhizinate, 4 parts by weight of sodium azulene sulfonate and 3 parts by weight of paeonol, dissolving the mixture in 100 parts by weight of 60wt% ethanol aqueous solution, adding 30 parts by weight of the polydopamine modified montmorillonite prepared in the step S2, carrying out 1500W ultrasonic dispersion for 20min, heating to 50 ℃ for reaction for 2h, centrifuging at 5000r/min for 15min, washing with clear water, and drying at 70 ℃ for 2h to obtain modified montmorillonite;

s4, coating of silicon dioxide: dissolving 10 parts by weight of methyl orthosilicate in 100 parts by weight of 70wt% ethanol aqueous solution, adding 17 parts by weight of modified montmorillonite prepared in the step S3, performing 1500W ultrasonic dispersion for 20min, adjusting the pH value of the solution to 9, adding 3 parts by weight of ethylene oxide-propylene oxide triblock copolymer PEO20-PPO70-PEO20 and 1 part by weight of Tween-60, emulsifying for 5min at 15000r/min, stirring for reaction for 5h, centrifuging for 15min at 5000r/min, washing with clear water, and drying at 70 ℃ for 2h to obtain modified montmorillonite coated with porous silica;

s5, complex enzyme immobilization: dissolving 4 parts by weight of lysozyme and 3 parts by weight of dextranase in 20 parts by weight of water to obtain an antibacterial enzyme mixed solution, adding 20 parts by weight of the porous silica-coated modified montmorillonite prepared in the step S4, stirring and fixing for 50min at the rotating speed of 500/min, and volatilizing at normal temperature to obtain a modified friction agent;

s6, preparation of the probiotic and prebiotics embedded microspheres: mixing 10 parts by weight of composite probiotics and 4 parts by weight of composite prebiotics in 50 parts by weight of water, adding 25 parts by weight of sodium alginate and 3 parts by weight of tween-80 for dissolution, adding the mixture into 100 parts by weight of silicone oil, emulsifying by using a rapid membrane with the pore diameter of 3000nm, dropwise adding 15 parts by weight of 5wt% calcium chloride solution, and curing at normal temperature for 50min to obtain microspheres embedded with the probiotics and the prebiotics;

the composite probiotics are a mixture of lactobacillus paracasei and lactobacillus salivarius, and the mass ratio is 5;

the composite prebiotics are a mixture of fructo-oligosaccharide and xylo-oligosaccharide, and the mass ratio is 5;

s7, preparing the antibacterial stain-removing toothpaste: and (3) uniformly mixing 40 parts by weight of the modified friction agent prepared in the step (S5), 7 parts by weight of the microspheres embedding probiotics and prebiotics prepared in the step (S6), 35 parts by weight of glycerol, 0.2 part by weight of xylitol, 3 parts by weight of betaine, 1.5 parts by weight of sodium carboxymethyl cellulose, 1.5 parts by weight of lemon essence and 50 parts by weight of water, stirring and mixing at 1200r/min for 30min, and performing vacuum degassing to obtain the antibacterial stain-removing toothpaste.

Example 3

s1, surface treatment of nano montmorillonite: soaking nano montmorillonite with particle size less than 100nm in 2mol/L NaOH solution for 40min, centrifuging at 5000r/min for 15min, washing with clear water, and drying at 70 deg.C for 2 hr to obtain pretreated nano montmorillonite;

s2, modifying polydopamine: adding 15 parts by weight of the pretreated nano montmorillonite prepared in the step S1 into water, performing ultrasonic dispersion at 1000W for 20min, adding 20 parts by weight of dopamine hydrochloride and 2 parts by weight of catalyst, heating to 60 ℃, reacting for 2.5h, centrifuging at 5000r/min for 15min, washing with clear water, and drying at 70 ℃ for 2h to obtain poly-dopamine modified montmorillonite;

the catalyst is 4wt%CoCl of ₂ Tris-HCl solution of pH 5.5;

s3, fixing a composite preparation: uniformly mixing 4 parts by weight of dipotassium glycyrrhizinate, 3 parts by weight of sodium azulene sulfonate and 2 parts by weight of paeonol, dissolving the mixture in 100 parts by weight of 50wt% ethanol aqueous solution, adding 30 parts by weight of the polydopamine modified montmorillonite prepared in the step S2, carrying out 1500W ultrasonic dispersion for 20min, heating to 45 ℃ for reaction for 1.5h, centrifuging at 5000r/min for 15min, washing with clear water, and drying at 70 ℃ for 2h to obtain modified montmorillonite;

s4, coating of silicon dioxide: dissolving 7 parts by weight of tetraethoxysilane in 100 parts by weight of 60wt% ethanol water solution, adding 15 parts by weight of the modified montmorillonite prepared in the step S3, performing 1500W ultrasonic dispersion for 20min, adjusting the pH value of the solution to 8.5, adding 2 parts by weight of polyoxyethylene sorbitan fatty acid ester and 0.7 part by weight of Tween-80, 13500r/min, emulsifying for 4min, performing stirring reaction for 4h, centrifuging for 15min at 5000r/min, washing with clear water, and drying at 70 ℃ for 2h to obtain porous silica coated modified montmorillonite;

s5, complex enzyme immobilization: dissolving 3 parts by weight of lysozyme and 2 parts by weight of dextranase in 20 parts by weight of water to obtain an antibacterial enzyme mixed solution, adding 17 parts by weight of the porous silicon dioxide coated modified montmorillonite prepared in the step S4, stirring and fixing for 40min at the rotating speed of 500/min, and volatilizing at normal temperature to obtain a modified friction agent;

s6, preparation of the probiotic and prebiotics embedded microspheres: mixing 7 parts by weight of composite probiotics and 3 parts by weight of composite prebiotics in 50 parts by weight of water, adding 22 parts by weight of sodium alginate and 2.5 parts by weight of tween-80 to dissolve, adding the mixture into 100 parts by weight of silicone oil, emulsifying by using a rapid membrane with the aperture of 2000nm, dropwise adding 12 parts by weight of 4wt% calcium chloride solution, and curing at normal temperature for 40min to obtain microspheres embedded with the probiotics and the prebiotics;

the composite probiotics is a mixture of lactobacillus paracasei and lactobacillus salivarius, and the mass ratio is 4;

the composite prebiotics are a mixture of fructo-oligosaccharide and xylo-oligosaccharide, and the mass ratio is 4;

s7, preparing the antibacterial stain-removing toothpaste: and (3) uniformly mixing 30 parts by weight of the modified friction agent prepared in the step (S5), 5 parts by weight of the probiotics and prebiotics-embedded microspheres prepared in the step (S6), 27 parts by weight of polyethylene glycol 400, 0.15 part by weight of sucralose, 2 parts by weight of betaine, 1 part by weight of carrageenan, 1.2 parts by weight of lemon essence and 40 parts by weight of water, stirring and mixing at 1100r/min for 20min, and degassing in vacuum to obtain the antibacterial and stain-removing toothpaste.

Example 4

Compared with example 3, the difference is that the composite probiotic is single lactobacillus paracasei.

Example 5

Compared with example 3, the difference is that the composite probiotic is a single lactobacillus salivarius.

Example 6

Compared with example 3, the difference is that the composite prebiotics are single fructo-oligosaccharide.

Example 7

Compared with example 3, the difference is that the composite prebiotics are single xylo-oligosaccharide.

Comparative example 1

The difference from example 3 is that step S2 is not performed.

Comparative example 2

Compared with the embodiment 3, the difference is that the dipotassium glycyrrhizinate is not added in the step S3.

Comparative example 3

Compared with the example 3, the difference is that sodium azulene sulfonate is not added in the step S3.

Comparative example 4

The difference compared to example 3 is that no paeonol was added in step S3.

Comparative example 5

The difference from example 3 is that step S3 is not performed.

Comparative example 6

The difference from example 3 is that step S4 is not performed.

Comparative example 7

Compared with example 3, the difference is that no lysozyme is added in step S5.

Comparative example 8

Compared to example 3, the difference is that no dextranase is added in step S5.

Comparative example 9

The difference from example 3 is that step S5 is not performed.

Comparative example 10

Compared with example 3, the difference is that no complex probiotics are added in step S6.

Comparative example 11

Compared with example 3, the difference is that no complex prebiotics are added in step S6.

Comparative example 12

Compared with the example 3, the difference is that the composite probiotics and the composite prebiotics in the step S6 are only simply mixed and are not embedded by the sodium alginate.

Comparative example 13

The difference compared to example 3 is that the friction modifier is replaced by an equal amount of silica in step S7.

Comparative example 14

Compared with example 3, the difference is that no microspheres embedding probiotics and prebiotics are added in step S7.

Comparative example 15

Compared with example 3, the difference is that no microspheres embedding probiotics and prebiotics are added in step S7, and the modified abrasive is replaced by silicon dioxide with the same quantity.

Test example 1 inhibition of Actinobacillus actinomycetemcomitans ATCC 29523

The strain source is as follows: actinobacillus actinomycetemcomitans ATCC 29523 was provided by the institute of microbiology, academy of sciences, guangdong province. Streptococcus mutans CGMCC 12499 and Fusobacterium nucleatum ATCC25586 are provided by food institute of Jiangsu university.

Preparing a bacterial liquid:

1. actinobacillus actinomycetemcomitans bacterial liquid: culturing Actinobacillus actinomycetemcomitans ATCC 29523 in a blood plating medium (TSA +5% defibrinated sheep blood) at 37 ℃ with a 5% CO content ₂ Culturing for 48h under environment, adjusting the bacterial concentration to 1 × 10 with PBS phosphate buffer (pH = 7.2) ⁹ CFU/mL。

2. Streptococcus mutans CGMCC 12499 bacterial liquid: inoculating Streptococcus mutans CGMCC 12499 strain on blood plate, and placing into a container containing 80% N ₂ 、10％ H ₂ 、10％ CO ₂ Culturing at 37 deg.C for 48h in anaerobic bag, and adjusting thallus concentration to 1 × 10 ⁹ CFU/mL。

3. Fusobacterium nucleatum ATCC25586: inoculating Fusobacterium nucleatum ATCC25586 bacteria to a blood plate, adding a solution containing 80% of ₂ 、10％ H ₂ 、10％ CO ₂ Culturing at 37 deg.C for 48h in anaerobic bag, and adjusting thallus concentration to 1 × 10 ⁹ CFU/mL。

Repeatedly rubbing 1mL of the antibacterial stain-removing toothpaste prepared in examples 1-7 and comparative examples 1-15 with a toothbrush for 5min, adding 50mL of water, and uniformly mixing to obtain toothpaste liquid;

(1) The results are shown in table 1, by using an Oxford cup double-layer plate method, respectively using actinobacillus actinomycetemcomitans, streptococcus mutans and Fusobacterium nucleatum suspensions, sucking 100. Mu.L of the prepared toothpaste liquid, adding the toothpaste liquid into an Oxford cup hole, and measuring the diameter of the inhibition zone after culturing in a culture dish at 37 ℃ for 48 h.

TABLE 1

(2) Mixing with prepared Actinobacillus actinomycetemcomitans, streptococcus mutans and Fusobacterium nucleatum suspension at a volume of 1: 1, standing for 1h, slightly sucking 100 μ L of supernatant, diluting with ten-fold dilution method, sucking 100 μ L of diluent at different proportions, coating, culturing at 37 deg.C for 48h, counting, and comparing the decrease of Actinobacillus actinomycetemcomitans, the result is shown in Table 2.

TABLE 2

As can be seen from the above table, the antibacterial stain-removing toothpaste prepared in the embodiments 1-3 of the invention has better effects of inhibiting actinobacillus actinomycetemcomitans, streptococcus mutans and fusobacterium nucleatum after being used.

Test example 2 stability test

The antibacterial stain-removing toothpaste prepared in the examples 1-7 and the comparative examples 1-15 is subjected to an accelerated test, placed in an electrothermal constant-temperature drying oven at 45 ℃ for 3 months, taken out and compared with a sample stored at normal temperature, and the appearance, the fragrance and the change of pH value of the high-temperature sample are observed, so that the stability of the toothpaste within the shelf life of 3 years is deduced.

The results are shown in Table 3

TABLE 3

As can be seen from the above table, in the accelerated test of the antibacterial stain-removing toothpaste prepared in the embodiments 1 to 3 of the present invention, the changes of the appearance, the flavor and the pH value are not large after being placed at 45 ℃ for 3 months.

Test example 3 Effect of Paralyne on auricle swelling in mice

240 male NIH mice (SPF grade) were divided into 24 groups, distilled water was used as a negative control group, fluocinolone acetonide ointment was used as a positive control group, and the antibacterial stain-removing toothpastes prepared in examples 1-7 and comparative examples 1-15 were used as test groups 1-7 and comparative groups 1-15.

Uniformly coating the inner and outer surfaces of the right auricle of each mouse with xylene to cause inflammation, wherein the dosage is 100 μ L/mouse, the left auricle is not treated as a blank control group, after xylene causes inflammation for 30min, except for the negative control group, each group of animals is respectively administered with the corresponding test substance at the right ear with the dosage of 0.1 g/animal, and the test substance is uniformly smeared on the inner and outer surfaces of the right auricle during administration. The negative control group animals were given distilled water at a dose of 0.1 mL/mouse to the right auricle. After the test object is given for 1h, the cervical vertebra of the animal is dislocated and killed, auricles on two sides are cut off, the test object on the right auricle is cleaned by normal saline, and water cost is wiped off. Overlapping the auricles on both sides, punching the left auricle and the right auricle by using a puncher with the diameter of 8mm, respectively weighing the auricles, and calculating swelling values, wherein the smaller the swelling value is, the better the anti-inflammatory effect is.

Swelling value = m _{Right ear tab} -m _{Left ear piece}

The results are shown in Table 4.

TABLE 4

Note: p < 0.01, P < 0.05 compared to negative controls.

As can be seen from the above table, the antibacterial stain-removing toothpaste prepared in the embodiments 1-3 of the invention has a good anti-inflammatory effect.

Test example 4

The friction values Ra of the bacteriostatic and stain-removing toothpaste prepared in examples 1-7 and comparative examples 1-15 and the similar commercially available toothpaste were tested by the toothpaste friction value test method (GB/T35832-2018), and the results are shown in Table 5.

TABLE 5

As can be seen from the above table, the bacteriostatic stain-removing toothpastes prepared in examples 1-3 of the present invention have relatively low friction values. Although toothpaste with a large abrasion value can clean teeth well after being used for a long time, the toothpaste can abrade the teeth, and enamel is lost. The larger the abrasion value is, the higher the degree of abrasion to teeth is, the whitening toothpaste can achieve the effect of removing stains on the tooth surfaces, and the cleaning and stain removal effects of the abrasive are higher than those of other types of toothpaste, so that the friction value is also improved to a certain extent. The toothpaste is selected from products having a high cleaning rate and a relatively low abrasion value. The toothpaste has the advantages that the toothpaste can well remove dental plaque by inhibiting the growth of harmful bacteria in the oral cavity, and can better clean teeth and whiten teeth by the interaction between different abrasives and the moderate friction with the teeth.

Examples 4 and 5 differ from example 3 in that the probiotic complex is a single lactobacillus paracasei or lactobacillus salivarius with reduced inhibition of actinobacillus actinomycetemcomitans, streptococcus mutans, fusobacterium nucleatum. The comparative example 10 is different from example 3 in that the inhibition effect on actinobacillus actinomycetemcomitans, streptococcus mutans, and fusobacterium nucleatum is remarkably reduced without adding the composite probiotic in the step S6. The lactobacillus paracasei is the most common lactobacillus in oral microbiota, and the inactivated bacteria powder of the lactobacillus paracasei can generate coagulation precipitation with oral pathogenic bacteria. The lactobacillus salivarius can inhibit the growth of pathogenic bacteria of caries, so as to prevent and treat caries, has a certain adsorption effect, and can well colonize and grow on the surface of intestinal tract to further exert the immune effect. The probiotics and the pathogenic bacteria have-CH simultaneously on the surface ₂ -and-CH ₃ The probiotic bacteria and the pathogenic bacteria with the similar low surface energy groups can be co-agglomerated, the surface roughness of the probiotic bacteria is Ra =19.5nm, and the surface of the probiotic bacteria is rougher than that of the pathogenic bacteria, so that the adhesion effect of the probiotic bacteria is stronger, and the adhesion sites can be competed with the pathogenic bacteria in the oral cavity, so that the quantity of the pathogenic bacteria is reduced. The probiotics hinder colonization of pathogenic bacteria by competing with oral pathogenic bacteria for binding sites, thereby allowing the pathogenic bacteria to be excreted from the oral cavity, thereby improving oral health. Metabolites generated by the probiotics, such as organic acid, bacteriocin and the like, can effectively inhibit the growth of pathogenic bacteria and the formation of a biological film.

Examples 6 and 7 are different from example 3 in that the composite prebiotics is single fructo-oligosaccharide or xylo-oligosaccharide, and the inhibition effect on actinobacillus actinomycetemcomitans, streptococcus mutans and fusobacterium nucleatum is slightly reduced. Comparative example 11 is different from example 3 in that the inhibition effect against actinobacillus actinomycetemcomitans, streptococcus mutans, and fusobacterium nucleatum is reduced without adding the composite prebiotic in step S6. The xylo-oligosaccharide and fructo-oligosaccharide are prebiotics, and the fructo-oligosaccharide can selectively proliferate bifidobacteria, thereby regulating intestinal microecological balance and maintaining intestinal health. Xylo-oligosaccharide is also called xylo-oligosaccharide, is a functional polysaccharide formed by combining 2-7 xylose molecules by beta-1, 4 glycosidic bonds, is difficult to decompose by human digestive enzyme, has good acid and heat stability, and has extremely strong function of proliferating bifidobacterium, inhibiting the growth of harmful bacteria and leading probiotics to be massively proliferated in intestinal tracts. The fructo-oligosaccharide as water-soluble dietary fiber can stimulate intestinal tract peristalsis, change osmotic pressure of intestinal contents, increase feces water content, relax bowel, relieve constipation, effectively reduce content of free fatty acid, triglyceride and serum cholesterol in vivo, and improve cardiovascular diseases such as arteriosclerosis and hypertension. The xylo-oligosaccharide and fructo-oligosaccharide can be fermented by intestinal bacteria to produce short chain fatty acids such as acetic acid, propionic acid and butyric acid, lactic acid and the like, reduce the pH value of the intestinal environment, inhibit the growth and propagation of harmful bacteria and pathogenic bacteria, and reduce the generation and accumulation of toxins and putrefactive substances in the field.

Comparative example 1 is different from example 3 in that the inhibition of actinobacillus actinomycetemcomitans, streptococcus mutans, and fusobacterium nucleatum is decreased without performing step S2, the swelling value is increased, and the appearance of the paste is slightly changed after 3 months at 45 ℃. Comparative example 6 is different from example 3 in that step S4 is not performed, the inhibitory effect on Actinobacillus actinomycetemcomitans, streptococcus mutans, and Fusobacterium nucleatum is reduced, and the abrasion value Ra is reduced. According to the invention, through carrying out polydopamine modification on the surface of nano montmorillonite, abundant hydroxyl, amino, carboxyl and other groups of polydopamine can form hydrogen bond fixation with dipotassium glycyrrhizinate, paeonol and sodium azulene sulfonate, so that a composite preparation can be stably fixed on the polydopamine modified montmorillonite, and further through a sol-gel reaction, a layer of porous silicon dioxide (under the action of a pore-forming agent) is coated on the surface of the polydopamine modified montmorillonite, and the coating of the porous silicon dioxide can further enhance the strength of particles, and meanwhile, a larger specific surface area is provided, so that abundant site fixation is provided for lysozyme and glucanase, and the modified abrasive is prepared.

Comparative examples 2, 3 and 4 are different from example 3 in that dipotassium glycyrrhizinate, sodium azulene sulfonate or paeonol are not added in step S3, and the inhibition effect on actinobacillus actinomycetemcomitans, streptococcus mutans and fusobacterium nucleatum is reduced and the swelling value is increased. Comparative example 5 is different from example 3 in that step S3 was not performed, and the inhibitory effects on Actinobacillus actinomycetemcomitans, streptococcus mutans, and Fusobacterium nucleatum were significantly reduced and the swelling value was significantly increased. The dipotassium glycyrrhizinate can completely inhibit the formation of dental plaque by inhibiting and killing actinobacillus actinomycetemcomitans and streptococcus mutans. Paeonol is colorless or white or yellowish needle crystal with luster, has strong antibacterial effect on Staphylococcus aureus, streptococcus faecalis, escherichia coli, etc., and has tranquilizing, antiinflammatory, antipyretic, and antiallergic effects. The sodium azulene sulfonate is an active ingredient of chamomile, has strong pepsin resistance, anti-inflammation, antibacterial, anti-allergy and mucosa metabolism promotion effects, and inhibits inflammatory cells from releasing histamine through local direct action; increase synthesis of prostaglandin E2 in the mucous membrane, promote granulation and neogenesis of epithelial cells, have good effect of repairing the epithelial cells and have high safety. The three components are compounded to enter the oral cavity, so that the surface of harmful thalli becomes uneven, partial thalli are broken, substances in cells flow out, the integrity of bacterial cells is damaged, and the prepared toothpaste has good effects of inhibiting bacteria, resisting bacteria, diminishing inflammation, relieving fever, repairing epithelial cells and promoting mucosal metabolism, can effectively inhibit the formation of dental plaque, inhibit gingival bleeding, tooth looseness and halitosis and repair oral ulcer.

Comparative examples 7 and 8 are different from example 3 in that lysozyme or dextranase was not added in step S5, and the inhibition effect on Actinobacillus actinomycetemcomitans, streptococcus mutans, and Fusobacterium nucleatum was significantly reduced and the swelling value was increased. Comparative example 9 is different from example 3 in that the inhibition effect against actinobacillus actinomycetemcomitans, streptococcus mutans, and fusobacterium nucleatum is remarkably reduced and the swelling value is remarkably increased without performing step S5. Streptococcus mutans among oral bacteria has been widely recognized as the major causative agent of dental caries. The mechanism responsible for caries formation is that glucosyltransferases (GTFs for short) in streptococcus mutans break down sucrose and synthesize extracellular polysaccharides that can attach to tooth surfaces, and-on the other hand, the acids produced by streptococcus mutans promote tooth demineralization, which is exacerbated in the presence of oral sugars, and it is important to prevent glucan synthesis and acid production in order to protect teeth. Streptococcus mutans can synthesize glucan rich in alpha-1, 6 glycoside chains, glucan rich in alpha-1, 3 glycoside chains, and water-soluble glucan by the produced glucosyltransferase. The glucanase can effectively decompose glucan produced by streptococcus mutans, thereby preventing dental caries and dental plaque formation. The lysozyme is a non-specific substance component, can inhibit the growth of microorganisms, and does not have drug resistance after long-term use. The lysozyme can effectively hydrolyze peptidoglycan of bacterial cell walls, and has different peptidoglycan contents in the cell walls of gram-positive bacteria (G +), such as staphylococcus aureus, bacillus subtilis or micrococcus lyticus, and gram-negative bacteria (G-), such as escherichia coli, fusobacterium nucleatum, porphyromonas gingivalis, bacillus pneumoniae, and the like, the G + bacterial cell walls almost completely consist of the peptidoglycan, and only the inner wall layer of the G-bacteria is the peptidoglycan, so the lysozyme has good inhibition and killing effects on the G + bacteria and certain inhibition effects on the G-bacteria. The lysozyme can selectively dissolve the cell wall of a target microorganism to inactivate the cell wall, and mammals have no cell wall, so the lysozyme has no damage to oral tissues but plays a role in protection.

Compared with the example 3, the difference of the comparative example 12 is that the composite probiotics and the composite prebiotics in the step S6 are only simply mixed and are not embedded by sodium alginate, the inhibition effect on actinobacillus actinomycetemcomitans, streptococcus mutans and fusobacterium nucleatum is obviously reduced, and the swelling value is improved. By compounding with the prebiotics, the sodium alginate shell embeds the probiotics and the prebiotics, the survival rate of the probiotics can be obviously improved, and the microsphere shell is broken and the probiotics and the prebiotics are dissolved out in the repeated friction process of the friction agent in the toothpaste, so that the functions of bacteriostasis, antibiosis and oral health protection are achieved.

Comparative example 13 is different from example 3 in that the modified abrasive is replaced with the same amount of silica in step S7, and the inhibition effect on actinobacillus actinomycetemcomitans, streptococcus mutans, and fusobacterium nucleatum is remarkably reduced, the swelling value is remarkably increased, and the friction value Ra is increased. Comparative example 14 is different from example 3 in that the microspheres embedding probiotics and prebiotics are not added in step S7, and the inhibitory effect on Actinobacillus actinomycetemcomitans, streptococcus mutans, and Fusobacterium nucleatum is significantly reduced. Compared with the embodiment 3, the difference of the comparative example 15 is that the microspheres for embedding the probiotics and the prebiotics are not added in the step S7, the modified abrasive is replaced by the same amount of silicon dioxide, the inhibition effect on actinobacillus actinomycetemcomitans, streptococcus mutans and fusobacterium nucleatum is obviously reduced, the swelling value is obviously improved, and the friction value Ra is improved. The modified frictionizer and the compound probiotics have antibacterial effects, the compound prebiotics comprise fructo-oligosaccharide which can promote the proliferation of beneficial bacteria, on one hand, lysozyme and dextranase in the modified frictionizer have the antibacterial effect, and on the other hand, xylo-oligosaccharide and fructo-oligosaccharide form a competitive relationship with pathogenic bacteria through the proliferation of the beneficial bacteria to indirectly inhibit the pathogenic bacteria in the oral cavity. Under multiple effects, the prepared toothpaste has good effects of inhibiting bacteria, removing dental plaque and removing stains.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the scope of the present invention, which is intended to cover any modifications, equivalents, improvements, etc. within the spirit and scope of the present invention.

Claims

1. A preparation method of antibacterial stain-removing toothpaste is characterized in that nano-montmorillonite is pretreated, the surface of the nano-montmorillonite is modified by polydopamine, dipotassium glycyrrhizinate, sodium azulene sulfonate and paeonol are fixed, porous silicon dioxide is coated on the surface of the nano-montmorillonite, lysozyme and dextranase are fixed to obtain a modified abrasive, and then the modified abrasive is uniformly mixed with sodium alginate microspheres embedded with probiotics and prebiotics, a humectant, a sweetening agent, a foaming agent, a thickening agent, essence and water, and the mixture is subjected to vacuum degassing to form the antibacterial stain-removing toothpaste.

2. The method of claim 1, comprising the steps of:

s2, polydopamine modification treatment: uniformly dispersing the pretreated nano montmorillonite prepared in the step S1 in water, adding dopamine hydrochloride and a catalyst, heating for reaction, centrifuging, washing and drying to obtain polydopamine modified montmorillonite;

s3, fixing a composite preparation: uniformly mixing dipotassium glycyrrhizinate, sodium azulene sulfonate and paeonol, dissolving in an ethanol water solution, adding the polydopamine modified montmorillonite prepared in the step S2, uniformly dispersing by ultrasonic waves, carrying out heating reaction, centrifuging, washing and drying to obtain modified montmorillonite;

s7, preparing the antibacterial stain-removing toothpaste: and (4) uniformly mixing the modified friction agent prepared in the step (S5), the probiotics and prebiotics embedded microspheres prepared in the step (S6), a humectant, a sweetening agent, a foaming agent, a thickening agent, essence and water, stirring and mixing at a high speed, and degassing in vacuum to form paste, thus obtaining the antibacterial and stain-removing toothpaste.

3. The preparation method according to claim 2, wherein the particle size of the nano montmorillonite in step S1 is less than 100nm, the alkali solution is 1-3mol/L NaOH or KOH solution, and the soaking time is 30-50min; the mass ratio of the pretreated nano montmorillonite to dopamine hydrochloride to the catalyst in the step S2 is 15-22 ₂ The temperature of the heating reaction is 50-70 ℃ and the time is 2-3h.

4. The preparation method according to claim 2, wherein the mass ratio of the dipotassium glycyrrhizinate, the sodium azulene sulfonate, the paeonol and the polydopamine modified montmorillonite in step S3 is 3-5; the mass ratio of the alkyl orthosilicate in the step S4 is 5-10, namely, 12-17.

5. The production method according to claim 2, wherein the mass ratio of the lysozyme, the dextranase and the porous silica-coated modified montmorillonite in step S5 is 2 to 4; in the step S6, the composite probiotics are selected from at least two of lactobacillus acidophilus, lactobacillus paracasei and lactobacillus salivarius, the composite prebiotics are selected from fructo-oligosaccharide, galacto-oligosaccharide, xylo-oligosaccharide, isomalto-oligosaccharide, soybean oligosaccharide and inulin, the mass ratio of the composite probiotics to the composite prebiotics to sodium alginate is (5-10).

6. The preparation method according to claim 5, wherein the composite probiotics is a mixture of lactobacillus paracasei and lactobacillus salivarius, and the mass ratio of the composite probiotics to the lactobacillus paracasei is 3-5; the composite prebiotics are a mixture of fructo-oligosaccharide and xylo-oligosaccharide, and the mass ratio is 3-5.

7. The preparation method according to claim 2, wherein the mass ratio of the modified abrasive agent, the microspheres embedding probiotics and prebiotics, the humectant, the sweetener, the foaming agent, the thickening agent, the essence and the water in step S7 is 20-40:4-7, 20-35, 0.1-0.2, 1-3, 0.5-1.5, 1-1.5, 30-50; the rotating speed of the high-speed stirring and mixing is 1000-1200r/min, and the mixing time is 15-30min.

8. The method for preparing a moisturizing agent according to claim 2, wherein the moisturizing agent is at least one selected from the group consisting of glycerin, sorbitol, and polyethylene glycol 400; the sweetening agent is at least one of sucralose, aspartame, acesulfame potassium, sodium cyclamate, saccharin and xylitol; the foaming agent is betaine; the thickening agent is at least one of xanthan gum, carrageenan and sodium carboxymethyl cellulose.

9. The preparation method according to claim 2, comprising the steps of:

s2, polydopamine modification treatment: uniformly dispersing 15 parts by weight of the pretreated nano montmorillonite prepared in the step S1 in water, adding 17-22 parts by weight of dopamine hydrochloride and 1-3 parts by weight of catalyst, heating to 50-70 ℃ for reacting for 2-3h, centrifuging, washing and drying to obtain polydopamine modified montmorillonite;

the catalyst is CoCl with the weight percent of 3-5% ₂ The pH value of the Tris-HCl solution is 5-6;

s3, fixing a composite preparation: uniformly mixing 3-5 parts by weight of dipotassium glycyrrhizinate, 2-4 parts by weight of sodium azulene sulfonate and 1-3 parts by weight of paeonol, dissolving the mixture in 100 parts by weight of 40-60wt% ethanol aqueous solution, adding 30 parts by weight of the polydopamine modified montmorillonite prepared in the step S2, uniformly dispersing by ultrasonic waves, heating to 40-50 ℃ for reaction for 1-2 hours, centrifuging, washing and drying to obtain modified montmorillonite;

s4, coating of silicon dioxide: dissolving 5-10 parts by weight of ethyl orthosilicate or methyl orthosilicate in 100 parts by weight of 50-70wt% ethanol water solution, adding 12-17 parts by weight of the modified montmorillonite prepared in the step S3, uniformly dispersing by ultrasonic, adjusting the pH value of the solution to 8-9, adding 1-3 parts by weight of pore-foaming agent and 0.5-1 part by weight of emulsifier, emulsifying for 3-5min at 12000-15000r/min, stirring for reaction, centrifuging, washing and drying to obtain the modified montmorillonite coated with porous silicon dioxide;

s6, preparation of the microspheres embedding the probiotics and the prebiotics: mixing 5-10 parts by weight of composite probiotics and 2-4 parts by weight of composite prebiotics in 50 parts by weight of water, adding 17-25 parts by weight of sodium alginate and 2-3 parts by weight of emulsifier for dissolving, adding into 100 parts by weight of silicone oil, emulsifying by a rapid membrane with the pore diameter of 1000-3000nm, dropwise adding 10-15 parts by weight of 3-5wt% calcium chloride solution, and curing at normal temperature for 30-50min to obtain microspheres embedded with probiotics and prebiotics;

s7, preparing the antibacterial stain-removing toothpaste: and (2) uniformly mixing 20-40 parts by weight of the modified friction agent prepared in the step (S5), 4-7 parts by weight of the microspheres embedding probiotics and prebiotics prepared in the step (S6), 20-35 parts by weight of a humectant, 0.1-0.2 part by weight of a sweetening agent, 1-3 parts by weight of a foaming agent, 0.5-1.5 parts by weight of a thickening agent, 1-1.5 parts by weight of essence and 30-50 parts by weight of water, stirring and mixing at 1000-1200r/min for 15-30min, and degassing in vacuum to form paste, thus obtaining the antibacterial and stain-removing toothpaste.

10. A bacteriostatic tooth-paste for removing stains produced by the method of any one of claims 1-9.