CN113274309A

CN113274309A - Oral care active particles, preparation method thereof and oral care product

Info

Publication number: CN113274309A
Application number: CN202110512666.5A
Authority: CN
Inventors: 胡璠; 李立芬; 潘志
Original assignee: Guangzhou Stars Pulse Co Ltd
Current assignee: Guangzhou Stars Pulse Co Ltd
Priority date: 2021-05-11
Filing date: 2021-05-11
Publication date: 2021-08-20

Abstract

The application belongs to the technical field of materials, and particularly relates to an oral care active particle, a preparation method thereof and an oral care product. The oral care active particles are of a core-shell structure and comprise an active inner core, an intermediate shell layer and an outer shell layer; the raw material components of the intermediate shell layer comprise chitosan, and the outer shell layer comprises a high polymer material. The oral care active particles have the effects of oral care, tooth demineralization prevention and biofilm formation inhibition, and the active ingredients can be protected from being influenced by moisture, anionic surfactant, alkaline environment and the like in the oral care product through the protection effect of the intermediate shell layer and the outer shell layer on the active ingredients, so that the stability of the active particles in the oral care product is good.

Description

Oral care active particles, preparation method thereof and oral care product

Technical Field

The application belongs to the technical field of materials, and particularly relates to an oral care active particle, a preparation method thereof and an oral care product.

Background

The oral cavity is a colonizer of endogenous microorganisms that grow in the salivary matrix and form specialized biofilms, i.e., dental plaque, on hard and soft surfaces. The dynamic balance between the host's saliva, healthy diet, oral hygiene and biofilm limits the growth of microorganisms and creates a commensal protection against opportunistic pathogens. Any factor that can unbalance the oral ecosystem can lead to uncontrolled growth of microorganisms. Thus, the oral cavity is at risk of infection, causing caries, periodontitis, candidiasis, and resultant bad breath. Among them, periodontitis is a bacterial infection of the supporting structures of the teeth, such as gingiva, cementum, periodontal ligament and alveolar bone. The first stage of periodontitis is generally gingivitis, which is associated with the accumulation of plaque. Streptococcus mutans (Streptococcus mutans) is considered one of the major cariogenic bacteria, which are both acid-philic and acid-producing, and produce proteins on the cell surface, which adhere to teeth, ultimately form biofilms, and produce intracellular and extracellular polysaccharides. These intracellular and extracellular polysaccharides produced can serve as anchor points for other bacteria, allowing them to adhere to biofilms. Thus, the cellular polysaccharide matrix in the biofilm reduces its sensitivity to host defense systems, as well as to antibiotics and other drugs, thereby perpetuating bacterial infections and tending to be chronic.

At present, enzyme preparations, polyphenols, saponins and the like can play roles in inhibiting dental plaque growth, periodontal microorganism proliferation, adhesion and the like. Toothpastes and tooth powders are widely used oral care products for controlling dental biofilm and obtaining oral cosmetic agents that meet social standards. However, many of the ingredients in current toothpastes and toothpowders, such as anionic surfactants, have a profound effect on the stability of enzyme preparations, polyphenols and saponins. In addition, the alkaline pH of the toothpaste (pH of about 8.5) is also very detrimental to the stability of the enzyme preparation, polyphenols and saponins. These factors have all greatly limited the use of functional ingredients such as enzyme preparations, polyphenols and saponins in oral care products.

Disclosure of Invention

The application aims to provide an oral care active particle, a preparation method thereof and an oral care product, and aims to solve the problem of poor stability of the oral care active substance in the existing oral care product to a certain extent.

In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:

in a first aspect, the present application provides an oral care active particle that is a core-shell structure comprising an active core, an intermediate shell, and an outer shell; the raw material components of the intermediate shell layer comprise chitosan, and the outer shell layer comprises a high polymer material.

Further, the active inner core comprises the following raw material components: 5-40 parts of efficacy active substance and 5-40 parts of auxiliary material;

the raw material components of the intermediate shell layer comprise: 1-30 parts of chitosan, 1-40 parts of organic acid, 0.5-3 parts of emulsifier and neutralizer;

the outer shell layer includes: 10-30 parts of high molecular material and 0-2 parts of essence.

Further, the efficacy actives include: at least one of dextranase, glucose oxidase, lysozyme, solidago virgaurea extract, centella asiatica extract, polygonum cuspidatum root extract, scutellaria baicalensis root extract, green tea extract, licorice root extract, sage extract, chamomile extract, rosemary leaf extract, perilla seed extract, strawberry fruit extract, strawberry extract, blueberry berry extract, seabuckthorn fruit extract, downy raspberry fruit extract, wolfberry fruit extract, currant juice, and ribes nigrum fruit extract.

Further, the chitosan is selected from chitosan which is at least 60% deacetylated.

Further, the viscosity average molecular weight of the chitosan is 3000-310000 daltons.

Further, the organic acid has a pKa value of not higher than 6.

Further, the emulsifier is an oil-in-water nonionic emulsifier having an HLB value of greater than 10.

Further, the polymer material includes: at least one of alginic acid, propylene glycol alginate, acacia, gelatin, xanthan gum, guar gum, locust bean gum, tara gum, cassia gum, carrageenan, polylactic acid, and polycaprolactone.

Further, the neutralizing agent comprises: at least one of arginine, sodium hydroxide and potassium hydroxide.

Further, the auxiliary materials include: at least one of starches, modified starches, trehalose, and mannitol.

Further, the emulsifier comprises: at least one of polysorbate, fatty alcohol polyether, PEG-40 hydrogenated castor oil, and PEG-60 hydrogenated castor oil.

Further, the organic acid includes: at least one of glycolic acid, pyruvic acid, citric acid, lactic acid, lactobionic acid, gluconic acid, aspartic acid and glutamic acid.

Furthermore, the particle size of the active inner core is 0.3-300 mu m.

Further, the thickness of the intermediate shell layer is 0.3-300 mu m.

Further, the thickness of the outer shell layer is 0.4-400 mu m.

In a second aspect, the present application provides a method of making an oral care active particle comprising:

preparing the active substance into an active inner core;

encapsulating chitosan on the outer surface of the active inner core, and forming an intermediate shell layer on the surface of the active inner core;

and encapsulating a high polymer material on the outer surface of the intermediate shell layer, and forming an outer shell layer on the outer surface of the intermediate shell layer.

Further, forming the efficacy active into an active core comprises: mixing 5-40 parts of the efficacy active substance and 5-40 parts of auxiliary materials, and carrying out fluidized bed boiling granulation at the temperature of 50-80 ℃ for 60-120 min to obtain the active core.

Further, encapsulating the chitosan on the outer surface of the active core comprises: preparing chitosan mixed slurry from 1-30 parts of chitosan, 1-40 parts of organic acid, 0.5-3 parts of emulsifier, neutralizer and water, mixing the chitosan mixed slurry with the active core, and carrying out fluidized bed boiling granulation under the conditions that the temperature is 50-80 ℃ and the boiling time is 60-120 min to obtain particles with the active core wrapped by the intermediate shell layer.

Further, the preparing of the chitosan mixed slurry comprises: dissolving 1-40 parts of the organic acid in water, and adding 1-30 parts of chitosan for mixing treatment to obtain a chitosan solution;

dissolving 0.5-3 parts of the emulsifier in water, mixing with the chitosan solution, adding the neutralizer to adjust the pH value to 6-8, and obtaining the chitosan mixed slurry.

Further, encapsulating the polymer material on the outer surface of the intermediate shell layer comprises: preparing 10-30 parts of the high polymer material, 0-2 parts of essence and water into the high polymer mixed slurry, mixing the high polymer mixed slurry with the particles of the active core wrapped by the intermediate shell layer, and performing fluidized bed boiling granulation under the conditions that the temperature is 50-80 ℃ and the boiling time is 60-120 min to form an outer shell layer to obtain the oral care active particles.

In a third aspect, the present application provides an oral care product comprising the oral care active particles described above, or comprising the oral care active particles prepared by the method described above.

The oral care active particles provided by the first aspect of the present application have a core-shell structure, wherein the raw material components of the active core may comprise active ingredients such as an enzyme preparation, plant-extracted polyphenols, plant-extracted saponins, and the like, which have oral care effects, prevent tooth demineralization, and inhibit biofilm formation. The intermediate shell layer and the outer shell layer can protect the stability and compatibility of active functional ingredients in the active inner core in aqueous solution, atmosphere, oral cavity, toothpaste or dentifrice and other oral care products. The raw material component of the middle shell layer contains chitosan, so that the chitosan is not mutually soluble with water, the active ingredients of the inner core can be protected, and the chitosan and the active ingredients of the inner core can achieve a synergistic oral care effect in an acidic disease oral environment through the broad-spectrum antibacterial activity of the chitosan. The shell layer contains the polymer raw materials, and the formed polymer layer has better stability, so that the stability of the active core and the middle shell layer in the acidic environment and the like can be further protected, wherein the essence can improve the use feeling of the oral care active particles, and the user experience is improved.

In a second aspect of the present application, a method of preparing an oral care active particle is provided, by first preparing an active core with an efficacy active; then, encapsulating chitosan on the outer surface of the active core to form an intermediate shell layer; and then, encapsulating the high polymer material on the outer surface of the intermediate shell layer, and forming an outer shell layer on the outer surface of the intermediate shell layer to obtain the oral care active particles with the active core-intermediate shell layer-outer shell layer structure. The preparation method of the oral care active particles is simple in process and suitable for industrial large-scale production and application, and the prepared oral care active particles are good in stability, compatibility and application flexibility in oral care products such as water, atmosphere, oral cavity and toothpaste.

The oral care product provided by the third aspect of the application has the oral care efficacy, the tooth demineralization prevention and the biofilm formation inhibition effect due to the oral care active particles, and the active ingredients in the active core can be protected from being influenced by moisture, anionic surfactant, alkaline environment and the like in the oral care product through the protection effect of the intermediate shell layer and the outer shell layer, so that the oral care active particles have good stability in the oral care product, and the oral care active particles cannot be damaged by other components in the oral care product to release the active ingredients in advance, thereby reducing or even destroying the oral care effect of the product.

Detailed Description

In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.

In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.

In the present application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (one) of a, b, or c," or "at least one (one) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.

It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.

The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.

The weight of the related components mentioned in the description of the embodiments of the present application may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present application as long as it is scaled up or down according to the description of the embodiments of the present application. Specifically, the mass in the description of the embodiments of the present application may be in units of mass known in the chemical industry, such as μ g, mg, g, and kg.

The terms "first" and "second" are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another, and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.

In a first aspect, the embodiments of the present application provide an oral care active particle, which is a core-shell structure and includes an active core, an intermediate shell, and an outer shell; the raw material components of the intermediate shell layer comprise chitosan, and the outer shell layer comprises a high polymer material.

In some embodiments, the raw material components of the active core include: 5-40 parts of efficacy active substance and 5-40 parts of auxiliary material;

In the oral care active particles of the embodiment of the application, the oral care effect of the oral care active particles can be influenced by the content of the efficacy active substance, the oral care effect is poor if the content is too low, the protective force of the middle shell layer and the outer shell layer to the active inner core can be reduced if the content is too high, the particles are easy to break, and the stability of the oral care active particles is reduced. The auxiliary materials not only have a filling effect and are convenient for nucleation of the functional active substances, but also have the function of additionally protecting the functional active substances, and if the content of the auxiliary materials is too low, the forming of the inner core of the core is not facilitated; if the content of the auxiliary material is too high, the oral care effect and stability of the granule are reduced. The dosage of the chitosan is related to the protection effect of the intermediate shell layer, if the dosage of the chitosan is too small, the encapsulation protection capability of the intermediate shell layer on the active inner core is weak, and the synergistic oral care effect of the chitosan and the active substance with the inner core effect is not good; if the dosage of the chitosan is too high, the oral care effect of the efficacy active ingredients in the oral care active particles on the oral cavity is reduced. Wherein, the organic acid plays a role in reducing the pH value of the solution and dissolving the chitosan, and if the content of the organic acid is too low, the chitosan cannot be dissolved, so that a chitosan intermediate shell layer with uniform protective thickness is difficult to form; an excessive organic acid content results in the need for more neutralizing agent, on the one hand resulting in waste, and in addition an excessive salt content has a negative effect on the stability of the oral care active particles, as well as on the compatibility of the efficacy active in the particles. Wherein, the emulsifier plays a role in uniformly dispersing the chitosan, and if the content of the emulsifier is too low, the chitosan cannot be uniformly dispersed; if the content is too large, non-uniform particle size is likely to occur, which is also disadvantageous to dispersion of chitosan and causes waste. The shell layer prepared from the high polymer material plays a role of protecting the oral care active particles at the outermost layer, if the content is too low, the shell layer has weak encapsulation protection capability on the inner core and the middle shell layer, and the oral care active particles are easy to swell in oral care products such as toothpaste, tooth powder and the like, so that the stability of functional components is reduced; if the content is too high, the oral care effect of the efficacy active ingredients in the oral care active particles is reduced, and the particle size of the particles is too large, so that the compatibility in the formula is weakened.

In the practical application process of the oral care active particles, the middle shell layer and the outer shell layer can be damaged by external force to release active ingredients in the active core, so that the oral care effect is achieved. Examples of the present application the manner in which the raw material components of the oral care active particles are combined/used is described with reference to the preparation steps in the following process examples.

In some embodiments, in the active core, the efficacy actives include: at least one of dextranase, glucose oxidase, lysozyme, solidago virgaurea extract, centella asiatica extract, polygonum cuspidatum root extract, scutellaria baicalensis root extract, green tea extract, licorice root extract, sage extract, chamomile extract, rosemary leaf extract, perilla seed extract, strawberry fruit extract, strawberry extract, blueberry berry extract, seabuckthorn fruit extract, downy raspberry fruit extract, wolfberry fruit extract, currant juice, and ribes nigrum fruit extract. In the oral care active particles of the embodiments herein, the efficacy active can be an enzyme, wherein the glucanase can enzymatically hydrolyze the polysaccharide biofilm produced by streptococcus mutans; the glucose oxidase can catalyze and oxidize mycoderm and lysozyme produced by streptococcus mutans, and inhibit oral pathogenic bacteria. The effective active substance can also be plant saponins, wherein the herba Solidaginis extract can inhibit Candida albicans; extracts of centella asiatica, polygonum cuspidatum, scutellaria baicalensis, green tea, glycyrrhiza, sage, chamomile and rosemary can synergistically inhibit gingival inflammation. The effective active substance can also be plant polyphenols, wherein the extract of perilla seed can inhibit Streptococcus mutans and periodontal disease-causing bacteria. The efficacy active substance may also be other plant extract types containing polyphenols, saponins, vitamins, etc., such as: the oral care product can be used as a natural pigment, generates color and enriches the appearance diversity of the oral care product. In addition, the efficacy active ingredients such as the raspberry fruit extract and the raspberry fruit extract in the embodiment of the application have the efficacies of diminishing inflammation and inhibiting oral pathogenic bacteria, and have bright color and fragrant smell, so that the oral care active particles have additional visual and olfactory enjoyment besides the efficacies in the use process, and are pleasant for users.

In some embodiments, in the active core, the excipient comprises: at least one of starches, modified starches, trehalose, and mannitol. The auxiliary materials in the embodiment of the application can play a role in filling and forming and help the forming and nucleation of the efficacy active substances. In addition, the starch and the modified starch in the auxiliary materials can form a supermolecular structure with the functional active ingredients; trehalose and mannitol can be combined with the effective active ingredients through hydrogen bond action, and the effective active ingredients are protected and stabilized by the active inner core. In addition, after the oral care active particles are applied to an oral care product, the auxiliary material absorbs water and swells to reach osmotic pressure balance with the outside, so that the active substances with the efficacy are protected from being released stably. In some embodiments, the starch includes one or more of corn starch, wheat starch, tapioca starch, pea starch, oat starch, and rice starch; the modified starch includes one or more of cyclodextrin, maltodextrin, starch dextrin, amylopectin, hydroxypropyl starch phosphate, and starch acetate.

In some embodiments, the chitosan is selected from chitosan with at least 60% of acetyl groups removed, chitosan can be called chitosan only with more than 55% of acetyl groups removed, the higher the deacetylation degree of the chitosan is, the better the adsorptivity, film-forming permeability, moisture absorption and retention property, biological activity and the like are, and the chitosan with at least 60% of acetyl groups removed is adopted, so that the chitosan has better adsorptivity, film-forming permeability, moisture absorption and retention property, biological activity and the like, and the active inner core can be better protected.

In some embodiments, the viscosity average molecular weight of the chitosan is 3000 to 310000 daltons, the chitosan with the viscosity average molecular weight has a better protection effect on the active core, if the molecular weight is too low, the protection effect on the active core by the formed intermediate shell layer is low, and if the molecular weight is too high, the active core is too much bound, so that the intermediate shell layer is not broken to release the core active substance.

In some embodiments, the organic acid has a pKa value (acidity coefficient) no greater than 6. The organic acid in the embodiment of the application has the main function that the chitosan is made water-soluble by adjusting the pH value, and the pKa of a-NH 2 group in the chitosan is about 6.3, so that the-NH 2 can be protonated by adopting the organic acid with the pKa value not higher than 6, so that the chitosan is made water-soluble. In some embodiments, the organic acid comprises: at least one of glycolic acid, pyruvic acid, citric acid, lactic acid, lactobionic acid, gluconic acid, aspartic acid and glutamic acid, wherein the pKa value of the acid is less than or equal to 6, the chitosan can be protonated, the solubility is improved, and the organic acids are suitable for oral cavity and food and have good safety.

In some embodiments, the emulsifier has an HLB (hydrophilic-lipophilic balance of surfactant) above 10 and is an oil-in-water nonionic emulsifier that solubilizes or uniformly disperses chitosan in aqueous solution to uniformly encapsulate chitosan on the outer surface of the active core, particularly after readjustment of the pH, thus requiring an emulsifier that can form an oil-in-water emulsion, i.e., an emulsifier having an HLB > 10. In some embodiments, the emulsifier comprises: at least one of polysorbate, fatty alcohol polyether, PEG-40 hydrogenated castor oil, and PEG-60 hydrogenated castor oil.

In some embodiments, the neutralizing agent comprises: the neutralizing agent can adjust the pH value of a system after chitosan is dissolved in water, the pH value in the system is increased through the alkaline neutralizing agents to harden the chitosan to form a chitosan intermediate shell layer, and meanwhile, the user adaptability of the oral care active particles is improved through adjusting the pH value, so that the situation that the pH value of the oral care active particles is too low to influence the application is avoided.

In some embodiments, the polymeric material comprises: at least one of alginic acid, propylene glycol alginate, acacia, gelatin, xanthan gum, guar gum, locust bean gum, tara gum, cassia gum, carrageenan, polylactic acid, and polycaprolactone; the high molecular materials belong to natural sugar gum, and have the following advantages except that the high molecular materials can isolate the damage of moisture to active substances with the active core effect: on one hand, the outer shell layer formed by the high polymer materials is not influenced by pH value and salt, and the compatibility is higher in the preparation process and the formula; on the other hand, the natural carbohydrate gum polymer materials have high safety and can be used in oral cavities and even foods; on the other hand, the natural carbohydrate gum polymer material has shear thinning property in rheology, so when the oral care active particles are applied to oral care products such as toothpaste, tooth powder and the like, the oral care active particles can be broken in the tooth brushing process to release functional components.

In some embodiments, the flavoring is water-soluble, food grade flavoring, which enhances the flavor properties of the oral care active particles, allowing the oral care active particles to enjoy additional visual and olfactory enjoyment, in addition to efficacy, during use, and to be pleasant to the user.

In some embodiments, the particle size of the active core is 0.3 to 300 μm; if the particle size is too small, the packaging efficiency is too low; if the particle size is too large, the protective power provided by the intermediate shell and the outer shell is reduced, and the particles are easily broken, especially in the formulation of oral products such as toothpaste. In some embodiments, the particle size of the active core can be 0.3-1 μm, 1-10 μm, 10-100 μm, 100-300 μm, and the like.

In some embodiments, the thickness of the intermediate shell layer is 0.3-300 μm; if the thickness is too low, the protective capability of the intermediate shell layer on the active inner core is weak, and the intermediate shell layer and the active ingredients may not have synergistic interaction; if the thickness is too high, the content of the effective active substance in the oral care active particles is low, the oral care effect is not good, and the cost performance is low. In some embodiments, the thickness of the intermediate shell layer may be 0.3-1 μm, 1-10 μm, 10-100 μm, 100-300 μm, etc.

In some embodiments, the thickness of the outer shell is 0.4 to 400 μm, and if the thickness is too low, the outer shell has weak protection capability on the active core and the intermediate shell, and the oral care active particles are easy to swell in the formulation of oral products such as toothpaste, so that the stability of the oral care active particles is weakened; if the thickness is too high, the content of the active functional substances in the oral care active particles is low, the oral care effect is poor, the cost performance is low, and the particle size of the particles is too large, so that the compatibility in the formula of oral products such as toothpaste and the like is weakened. In some embodiments, the shell layer may have a thickness of 0.4-1 μm, 1-10 μm, 10-100 μm, 100-200 μm, 200-400 μm, and the like.

The oral care active particles of the examples herein can be made by the following example methods.

In a second aspect, embodiments of the present application provide a method for preparing oral care active particles, comprising the steps of:

s10, preparing an active core from the functional active substance;

s20, encapsulating chitosan on the outer surface of the active core, and forming an intermediate shell layer on the surface of the active core;

and S30, encapsulating a high polymer material on the outer surface of the intermediate shell layer, and forming an outer shell layer on the outer surface of the intermediate shell layer.

According to the preparation method of the oral care active particles provided by the second aspect of the application, firstly, an active inner core is prepared from an efficacy active substance and auxiliary materials; then, encapsulating chitosan on the outer surface of the active core to form an intermediate shell layer; and then, encapsulating the high polymer material on the outer surface of the intermediate shell layer, and forming an outer shell layer on the outer surface of the intermediate shell layer to obtain the oral care active particles with the active core-intermediate shell layer-outer shell layer structure. The preparation method of the oral care active particles is simple in process and suitable for industrial large-scale production and application, and the prepared oral care active particles are good in stability, compatibility and application flexibility in oral care products such as water, atmosphere, oral cavity and toothpaste.

In some embodiments, in step S10, the step of forming the efficacy active into an active core comprises: mixing 5-40 parts of the efficacy active substance and 5-40 parts of auxiliary materials, and carrying out fluidized bed boiling granulation at the temperature of 50-80 ℃ for 60-120 min to obtain the active core. In some embodiments, fluidized bed ebullient granulation may employ a fluidized bed ebullient granulation dryer to produce the active core by atomizing water spray.

In some embodiments, in the step S20, the step of encapsulating the chitosan on the outer surface of the active core comprises: preparing chitosan mixed slurry from 1-30 parts of chitosan, 1-40 parts of organic acid, 0.5-3 parts of emulsifier, neutralizer and water, mixing the chitosan mixed slurry with the active core, and carrying out fluidized bed boiling granulation under the conditions that the temperature is 50-80 ℃ and the boiling time is 60-120 min to obtain particles with the active core wrapped by the intermediate shell layer. In some embodiments, the chitosan mixed slurry is mixed with the active core, and then added into a fluidized bed boiling granulation dryer, and the intermediate shell layer on the outer surface of the active core is prepared by atomizing and spraying water.

In some embodiments, the preparation of the chitosan mixed slurry comprises the steps of: dissolving 1-40 parts of organic acid in water, and adding 1-30 parts of chitosan for mixing treatment to obtain a chitosan solution; first, -NH2 in chitosan is protonated by an aqueous solution prepared with an organic acid, dissolving the chitosan to form a chitosan solution. Then, 0.5-3 parts of emulsifier is dissolved in water and then mixed with the chitosan solution for treatment, and the uniform dispersion effect of the chitosan in the water solution is enhanced by the emulsifier. And adding a neutralizing agent to adjust the pH value to 6-8 so as to harden the chitosan, and simultaneously, uniformly dispersing the hardened chitosan in an aqueous solution under the action of an emulsifying agent to obtain the chitosan mixed slurry with stable dispersion.

In some embodiments, in step S30, the step of encapsulating the polymer blend slurry on the outer surface of the intermediate shell includes: preparing 10-30 parts of the high polymer material, 0-2 parts of essence and water into high polymer mixed slurry, mixing the high polymer mixed slurry with particles of an intermediate shell layer wrapping an active core, and carrying out fluidized bed boiling granulation under the conditions that the temperature is 50-80 ℃ and the boiling time is 60-120 min to obtain the oral care active particles with outer shells wrapping the outer surfaces of the intermediate shell layers. In some embodiments, the method for preparing the oral care active particles with the core-shell structure comprises the steps of mixing the polymer mixed slurry with particles with active cores wrapped by intermediate shell layers, adding the mixture into a fluidized bed boiling granulation dryer, and preparing an outer shell layer on the outer surface of the active intermediate shell layers by atomizing and spraying water.

The temperature conditions for fluidized bed boiling granulation in the above example stage of the present application are mainly in view of the balance between the stability of the core efficacy active ingredient and the water evaporation rate. The active ingredients with the effects of enzymes, polyphenols, saponins and the like in the active core are unstable at high temperature, so that the fluidized bed boiling granulation temperature cannot be too high, for example, the granulation temperature is higher than 80 ℃. However, temperatures too low, e.g., below 50 ℃, do not dry out effectively to remove water, resulting in a final oral care active particle with too high a water content, which is also detrimental to the storage and application stability of the oral care active particle and unacceptable quality. Additionally, the level of boiling time also affects the stability of the efficacy active and the moisture content of the oral care active particles, if the time is too low, the moisture cannot be completely dried, and if the time is too high, the efficacy active may be destroyed.

In some embodiments, the efficacy actives include: at least one of dextranase, glucose oxidase, lysozyme, solidago virgaurea extract, centella asiatica extract, polygonum cuspidatum root extract, scutellaria baicalensis root extract, green tea extract, licorice root extract, sage extract, chamomile extract, rosemary leaf extract, perilla seed extract, strawberry fruit extract, strawberry extract, blueberry berry extract, seabuckthorn fruit extract, downy raspberry fruit extract, lycium barbarum fruit extract, currant juice, ribes nigrum fruit extract;

in some embodiments, the chitosan is selected from chitosan that has been at least 60% deacetylated.

In some embodiments, the chitosan has a viscosity average molecular weight of 3000 to 310000 daltons.

In some embodiments, the organic acid has a pKa value no greater than 6.

In some embodiments, the emulsifier is an oil-in-water nonionic emulsifier having an HLB value greater than 10.

In some embodiments, the polymeric material comprises: at least one of alginic acid, propylene glycol alginate, acacia, gelatin, xanthan gum, guar gum, locust bean gum, tara gum, cassia gum, carrageenan, polylactic acid, and polycaprolactone.

In some embodiments, the neutralizing agent comprises: at least one of arginine, sodium hydroxide and potassium hydroxide.

In some embodiments, the adjunct comprises: at least one of starches, modified starches, trehalose, and mannitol.

In some embodiments, the emulsifier comprises: at least one of polysorbate, fatty alcohol polyether, PEG-40 hydrogenated castor oil, and PEG-60 hydrogenated castor oil.

In some embodiments, the organic acid comprises: at least one of glycolic acid, pyruvic acid, citric acid, lactic acid, lactobionic acid, gluconic acid, aspartic acid and glutamic acid.

In some embodiments, the active core has a particle size of 0.3 to 300 μm.

In some embodiments, the thickness of the intermediate shell layer is 0.3-300 μm.

In some embodiments, the shell layer has a thickness of 0.4 to 400 μm.

The weight fraction ratios of the raw material components used for preparing the oral care active particles in the examples of the present application and the effects of the oral care active particles in the above examples are discussed in detail in the foregoing, and are not repeated herein.

In a third aspect, embodiments of the present invention provide an oral care product comprising the oral care active particles described above, or comprising the oral care active particles prepared by the method described above.

The oral care product of the embodiment of the application can be toothpaste, tooth powder, mouthwash and other products.

In some embodiments, the oral care active particles are present in the oral care product in an amount of from 0.001 to 10% by weight, wherein the oral care active particles are present in the oral care product in an amount of from 0.001% by weight to 10% by weight, which ensures oral care benefits and avoids the stability and efficacy of other ingredients of the product from being affected by an excessive amount of the oral care active particles in the product. In some embodiments, the mass percentage of the oral care active particles in the oral care product can be 0.001-0.1%, 0.1-0.3%, 0.3-1%, 1-3%, 3-6%, 6-8%, 8-10%, etc.

In order that the details of the foregoing implementations and operation of the present application will be clearly understood by those skilled in the art, and in order that the performance of the improvements made in the oral care active particles and methods of making the same of the examples of the present application may be more fully apparent, the following examples are provided to illustrate the above aspects.

Example 1

An oral care active particle prepared comprising the steps of:

(1) weighing 25g of dextranase and 10g of mannitol, uniformly mixing, adding into a fluidized bed boiling granulation dryer, and preparing dextranase core by spraying 30g of atomized water; boiling the granulation dryer at 55 deg.C for 90min to obtain active core with particle size of 100 μm;

(2) dispersing 20g of chitosan in 20g of deionized water and 20g of citric acid, and uniformly stirring for later use;

(3) weighing 40g of deionized water and 2g of polysorbate-20, adding the polysorbate-20 into the deionized water under stirring, and continuously stirring until the mixture is uniformly dispersed;

(4) adding chitosan organic acid mixture, and continuously stirring until the mixture is uniformly dispersed; adding sodium hydroxide, and adjusting the pH value to 6.5 for later use;

(5) encapsulating the chitosan mixture on a dextranase core by a fluidized bed boiling granulation dryer to prepare a middle layer of particles; the temperature of the fluidized bed boiling granulation dryer is 55 ℃, the boiling time is 90min, and an intermediate shell layer with the thickness of 100 mu m is formed on the outer surface of the active core;

(6) continuously stirring 30g of xanthan gum in 70g of deionized water until the xanthan gum is uniformly dispersed;

(7) encapsulating the high molecular mixture on the outer surface of the intermediate shell by using a fluidized bed boiling granulation dryer to prepare an outermost shell of the oral care active particles, wherein the thickness of the outermost shell is 300 microns, so as to obtain the oral care active particles with an active core-intermediate shell-outer shell structure; the temperature of the boiling granulation dryer is 55 deg.C, and the boiling time is 120 min.

Example 2

An oral care active particle prepared comprising the steps of:

(1) weighing 5g of glucose oxidase and 10g of mannitol, uniformly mixing, adding into a fluidized bed boiling granulation dryer, and atomizing and spraying 5g of water to prepare a glucose oxidase core; boiling in a fluidized bed at 55 deg.C for 90min to obtain active core with particle size of 200 μm;

(2) dispersing 1g of chitosan in 10g of deionized water and 5g of citric acid, and uniformly stirring for later use;

(3) weighing 20g of deionized water and 1g of PEG-60 hydrogenated castor oil, adding the emulsifier into the deionized water under stirring, and continuously stirring until the mixture is uniformly dispersed;

(4) adding chitosan organic acid mixture, and continuously stirring until the mixture is uniformly dispersed; adding potassium hydroxide, and adjusting the pH value to 7 for later use;

(5) encapsulating the chitosan mixture on a glucose oxidase core by using a fluidized bed boiling granulation dryer to prepare a middle layer of particles; boiling the granulation dryer at 55 deg.C for 90min to form an intermediate shell layer with a thickness of 200 μm on the outer surface of the active core;

(6) continuously stirring 8g of guar gum in 25g of deionized water until the guar gum is uniformly dispersed;

(7) encapsulating the high molecular mixture on the outer surface of the intermediate shell by using a fluidized bed boiling granulation dryer to prepare an outermost shell of the oral care active particles, wherein the thickness of the outermost shell is 300 microns, so as to obtain the oral care active particles with an active core-intermediate shell-outer shell structure; the temperature of the fluidized bed boiling granulation dryer is 55 ℃, and the boiling time is 100 min.

Example 3

An oral care active particle prepared comprising the steps of:

(1) weighing 10g of solidago virgaurea extract, 2g of centella asiatica extract, 3g of polygonum cuspidatum root extract, 3g of scutellaria baicalensis root extract, 2g of green tea extract, 2g of liquorice root extract, 3g of chamomile extract, 5g of rosemary leaf extract, 10g of perilla seed extract and 40g of corn starch, uniformly mixing, adding into a fluidized bed boiling granulation dryer, and spraying 30g of atomized water to prepare a plant extract core; boiling at 60 deg.C for 80min to obtain active core with particle size of 300 μm;

(2) dispersing 30g of chitosan in 20g of lactic acid and 20g of citric acid, and uniformly stirring for later use;

(3) weighing 40g of deionized water and 2g of polysorbate-80, adding the emulsifier into the deionized water under stirring, and continuously stirring until the mixture is uniformly dispersed;

(4) adding chitosan organic acid mixture, and continuously stirring until the mixture is uniformly dispersed; adding arginine, adjusting pH to 7, and keeping;

(5) encapsulating the chitosan mixture on the plant extract core with fluidized bed boiling granulation dryer to prepare intermediate layer of microparticles; boiling the granulation dryer at 70 deg.C for 65min to form an intermediate shell layer with a thickness of 100 μm on the outer surface of the active core;

(6) continuously stirring 13.5g of xanthan gum and 16.5g of Arabic gum in 70g of deionized water until the components are uniformly dispersed;

(7) encapsulating the high molecular mixture on the outer surface of the intermediate shell by using a fluidized bed boiling granulation dryer to prepare an outermost shell of the oral care active particles, wherein the thickness of the outermost shell is 400 microns, so as to obtain the oral care active particles with an active core-intermediate shell-outer shell structure; the temperature of the boiling granulation dryer is 70 ℃, and the boiling time is 90 min.

Example 4

An oral care active particle prepared comprising the steps of:

(1) weighing 5g of strawberry fruit extract, 5g of vaccinium uliginosum berry extract, 5g of sea buckthorn fruit extract and 20g of cyclodextrin, uniformly mixing, adding into a fluidized bed boiling granulation dryer, and atomizing and spraying 30g of water to prepare a berry fruit extract core; boiling at 60 deg.C for 80min to obtain active core with particle size of 50 μm;

(2) dispersing 10g of chitosan in 20g of gluconic acid, and uniformly stirring for later use;

(3) weighing 60g of deionized water and 2g of steareth-21, adding the emulsifier into the deionized water under the stirring state, and continuously stirring until the mixture is uniformly dispersed;

(5) encapsulating the chitosan mixture on the berry extract core with a fluidized bed boiling granulation dryer to prepare a middle layer of microparticles; boiling the granulation dryer at 60 deg.C for 90min to form an intermediate shell layer with a thickness of 100 μm on the outer surface of the active core;

(6) uniformly dispersing 15g of carrageenan in 40g of deionized water, adding 1g of strawberry essence and 0.5g of blueberry essence, and continuously stirring until the carrageenan is uniformly dispersed;

(7) encapsulating the high molecular mixture on the outer surface of the intermediate shell by using a fluidized bed boiling granulation dryer to prepare an outermost shell of the oral care active particles, wherein the thickness of the outermost shell is 100 microns, so as to obtain the oral care active particles with an active core-intermediate shell-outer shell structure; the temperature of the boiling granulation dryer is 60 deg.C, and the boiling time is 70 min.

Example 5

An oral care active particle prepared comprising the steps of:

(1) weighing 10g of downy raspberry fruit extract, 10g of raspberry fruit extract, 2g of red currant juice, 10g of maltodextrin and 8g of amylodextrin, uniformly mixing, adding into a fluidized bed boiling granulation dryer, and spraying 25g of atomized water to prepare a raspberry fruit extract core; boiling at 60 deg.C for 80min to obtain active core with particle size of 250 μm;

(2) dispersing 11g of chitosan in 25g of lactic acid, and uniformly stirring for later use;

(3) weighing 65g of deionized water and 2.5g of PEG-40 hydrogenated castor oil, adding the emulsifier into the deionized water under stirring, and continuously stirring until the mixture is uniformly dispersed;

(4) adding chitosan organic acid mixture, and continuously stirring until the mixture is uniformly dispersed; adding sodium hydroxide, adjusting pH to 7, and keeping;

(5) encapsulating the chitosan mixture on the core of the raspberry fruit extract with a fluidized bed boiling granulation dryer to prepare a middle layer of microparticles; boiling at 60 deg.C for 100min to form an intermediate shell layer with a thickness of 100 μm on the outer surface of the active core;

(6) uniformly dispersing 16g of gelatin in 45g of deionized water, and continuously stirring until the gelatin is uniformly dispersed;

(7) encapsulating the high molecular mixture on the outer surface of the intermediate shell by using a fluidized bed boiling granulation dryer to prepare an outermost shell of the oral care active particles, wherein the thickness of the outermost shell is 300 microns, so as to obtain the oral care active particles with an active core-intermediate shell-outer shell structure; the temperature of the boiling granulation dryer is 60 ℃, and the boiling time is 100 min.

Comparative example 1

An oral care active particle prepared comprising the steps of:

(5) encapsulating the chitosan mixture on a dextranase core by a fluidized bed boiling granulation dryer to prepare a chitosan layer of particles with a thickness of 100 μm; obtaining layered packaging particles containing glucanase/chitosan; the temperature of the fluidized bed boiling granulation dryer is 55 ℃, and the boiling time is 90 min.

Comparative example 2

An oral care active particle prepared comprising the steps of:

(5) encapsulating the chitosan mixture on a glucose oxidase core by using a fluidized bed boiling granulation dryer to prepare a chitosan layer of particles with the thickness of 200 mu m; obtaining layered packaging particles containing glucose oxidase/chitosan; the temperature of the boiling granulation dryer is 55 deg.C, and the boiling time is 90 min.

Comparative example 3

An oral care active particle prepared comprising the steps of:

(5) encapsulating the chitosan mixture on the plant extract core with fluidized bed fluidized granulating drier to obtain chitosan layer with thickness of 100 μm; obtaining layered packaging particles containing plant extracts/chitosan; the temperature of the boiling granulation dryer is 70 ℃, and the boiling time is 65 min.

Comparative example 4

An oral care active particle prepared comprising the steps of:

(4) adding chitosan organic acid mixture, and continuously stirring until the mixture is uniformly dispersed; adding sodium hydroxide, adjusting pH to 6.5, adding 1g of strawberry essence and 0.5g of blueberry essence, and continuously stirring until the mixture is uniformly dispersed for later use;

(5) encapsulating the chitosan mixture on the core of the berry extract with fluidized bed fluidized granulation dryer to obtain chitosan layer with thickness of 100 μm; obtaining layer-by-layer encapsulated particles containing berry extract/chitosan; the temperature of the boiling granulation dryer is 60 ℃, and the boiling time is 90 min.

Comparative example 5

An oral care active particle prepared comprising the steps of:

(5) encapsulating the chitosan mixture on core of Rubi fructus extract with fluidized bed fluidized granulating drier to obtain chitosan layer with thickness of 100 μ; obtaining raspberry fruit extract/chitosan layered packaging particles; the temperature of the boiling granulation dryer is 60 ℃, and the boiling time is 100 min.

Further, to verify the advancement of the examples of the present application, the stability of the oral care active particles prepared in examples 1 to 5 and comparative examples 1 to 5 was tested. The oral care active particles prepared in examples 1-5 and comparative examples 1-5 were applied to a microcapsule ointment having the following formulation as shown in table 1 below:

TABLE 1

Placing the toothpaste samples containing the oral care active particles of examples 1-5 and comparative examples 1-5 into a thermostat at a temperature of 48 ℃, and observing the appearance, color and smell of the toothpaste samples after 1 month; no particle damage phenomenon is found inside and outside the toothpaste body.

And toothpaste samples containing the oral care active particles of examples 1 to 5 and comparative examples 1 to 5 were dissolved in 20g of deionized water for 5g of toothpaste, respectively, and the pH of the toothpaste diluted solution was measured, and the pH and viscosity of the toothpaste samples were measured with a pH meter and a viscometer, respectively. Wherein, the viscosity test adopts a Brookfield VISCOMETER DV2T VISCOMETER, and the experiment selects a rotor TD-96, a rotating speed of 5R/MIN and an ending condition set as time 00:01: 00. And predicting the long-term stability of the toothpaste at room temperature through the stability result.

The results of the above tests are shown in table 2 below:

TABLE 2

From the test results, compared with the oral care active particles only comprising a single chitosan shell layer in comparative examples 1 to 5, the oral care active particles of the active core-intermediate shell layer-outer shell layer structure prepared in examples 1 to 5 of the present application have better stability in toothpaste, after 1 month acceleration test, the oral care active particles in the oral care product are basically not damaged, and the product appearance, color and smell are normal; whereas the oral care active particles in the comparative documents 1 to 5 were slightly broken. In addition, the oral care products corresponding to the oral care active particles of examples 1-5 also exhibited more stable and moderate pH and viscosity.

The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.

Claims

1. An oral care active particle, wherein the oral care active particle is of a core-shell structure and comprises an active inner core, an intermediate shell layer and an outer shell layer; the raw material components of the intermediate shell layer comprise chitosan, and the outer shell layer comprises a high polymer material.

2. The oral care active particle of claim 1, wherein the raw material components of the active core comprise: 5-40 parts of efficacy active substance and 5-40 parts of auxiliary material;

3. The oral care active particle of claim 2, wherein the efficacy active comprises: at least one of dextranase, glucose oxidase, lysozyme, solidago virgaurea extract, centella asiatica extract, polygonum cuspidatum root extract, scutellaria baicalensis root extract, green tea extract, licorice root extract, sage extract, chamomile extract, rosemary leaf extract, perilla seed extract, strawberry fruit extract, strawberry extract, blueberry berry extract, seabuckthorn fruit extract, downy raspberry fruit extract, wolfberry fruit extract, currant juice, and ribes nigrum fruit extract.

4. The oral care active particle of claim 3, wherein the chitosan is selected from the group consisting of chitosan depleted in at least 60% of acetyl groups;

and/or the viscosity average molecular weight of the chitosan is 3000-310000 daltons.

5. The oral care active particle of claim 2 or 4, wherein the organic acid has a pKa value of no more than 6;

and/or, the emulsifier has an HLB value greater than 10;

and/or, the neutralizing agent comprises: at least one of arginine, sodium hydroxide and potassium hydroxide.

6. The oral care active particle of claim 5, wherein the polymeric material comprises: at least one of alginic acid, propylene glycol alginate, acacia, gelatin, xanthan gum, guar gum, locust bean gum, tara gum, cassia gum, carrageenan, polylactic acid, and polycaprolactone;

and/or, the auxiliary materials comprise: at least one of starches, modified starches, trehalose, and mannitol;

and/or, the emulsifier comprises: at least one of polysorbate, fatty alcohol polyether, PEG-40 hydrogenated castor oil, and PEG-60 hydrogenated castor oil;

and/or, the organic acid comprises: at least one of glycolic acid, pyruvic acid, citric acid, lactic acid, lactobionic acid, gluconic acid, aspartic acid and glutamic acid.

7. The oral care active particle of any one of claims 1 to 4 or 6, wherein the particle size of the active core is from 0.3 to 300 μm;

and/or the thickness of the intermediate shell layer is 0.3-300 mu m;

and/or the thickness of the outer shell layer is 0.4-400 mu m.

8. A method of preparing an oral care active particle, comprising:

preparing the active substance into an active inner core;

9. The method of making an oral care active particle of claim 8, wherein forming the efficacy active into an active core comprises: mixing 5-40 parts of the efficacy active substance and 5-40 parts of auxiliary materials, and carrying out fluidized bed boiling granulation at the temperature of 50-80 ℃ for 60-120 min to obtain the active core.

10. The method of making an oral care active particle of claim 8 or 9, wherein encapsulating the chitosan on the outer surface of the active core comprises: preparing chitosan mixed slurry from 1-30 parts of chitosan, 1-40 parts of organic acid, 0.5-3 parts of emulsifier, neutralizer and water, mixing the chitosan mixed slurry with the active core, and carrying out fluidized bed boiling granulation under the conditions that the temperature is 50-80 ℃ and the boiling time is 60-120 min to obtain particles with the active core wrapped by the intermediate shell layer.

11. The method of making an oral care active particle according to claim 10, wherein forming the chitosan blend slurry comprises: dissolving 1-40 parts of the organic acid in water, and adding 1-30 parts of chitosan for mixing treatment to obtain a chitosan solution;

12. The method of preparing an oral care active particle according to claim 11, wherein encapsulating the polymeric material on the outer surface of the intermediate shell layer comprises: preparing 10-30 parts of the high polymer material, 0-2 parts of essence and water into the high polymer mixed slurry, mixing the high polymer mixed slurry with the particles of the active core wrapped by the intermediate shell layer, and performing fluidized bed boiling granulation under the conditions that the temperature is 50-80 ℃ and the boiling time is 60-120 min to form an outer shell layer to obtain the oral care active particles.

13. An oral care product comprising the oral care active particles of any one of claims 1 to 7 or the oral care active particles prepared by the process of any one of claims 8 to 12.