A camellia seed oil microcapsule emulsion, its preparation method, and its application.

Abstract

This invention, entitled "A Camellia Seed Oil Microcapsule Emulsion and Its Preparation Method and Application," belongs to the field of cosmetic technology. The technical problem it aims to solve is the deficiency in existing technologies where camellia seed oil is prone to rancidity, leading to reduced stability and bioavailability of formulations. This invention provides a camellia seed oil microcapsule emulsion system that can slow down the rancidity process, thus achieving a transition from oil-soluble to water-soluble camellia seed oil. The key technical solution is a camellia seed oil microcapsule emulsion, the raw materials of which consist of camellia seed oil, sodium caseinate, chitosan hydrochloride, PE9010, and a solvent.

Description

Technical Field

[0001] This invention relates to the field of cosmetic technology, specifically to a camellia seed oil microcapsule emulsion, its preparation method, and its application. Background Technology

[0002] Camellia seed oil, primarily obtained from the seeds of the Camellia oleifera tree (family Theaceae), contains over 80% oleic acid, a monounsaturated fatty acid, and possesses repairing, anti-aging, and antioxidant properties. However, camellia seed oil is prone to rancidity, which reduces the stability and bioavailability of its formulations, significantly limiting its application in cosmetics. Therefore, developing a microencapsulation system that can slow down rancidity and achieve a leap from oil-soluble to water-soluble camellia seed oil is imperative.

[0003] Microcapsules are miniature containers formed by encapsulating a core material within a polymer or inorganic wall. They offer advantages such as effectively reducing the material's responsiveness to external environmental factors, altering the physical and chemical properties of the core material, and masking odors. Among the microcapsule preparation processes, the composite coagulation method boasts advantages such as simple operation, high encapsulation efficiency, and wide applicability, and holds promise for enabling camellia seed oil to transition from oil-soluble to water-soluble.

[0004] Relevant patent documents retrieved: The document, published in China (CN104982558A) on October 21, 2015, discloses a novel camellia seed oil microcapsule powder and its preparation method. The core material of the microcapsule powder is camellia seed oil, the emulsifiers are monoglycerides and sucrose esters, the wall material is sodium caseinate, pure gum, maltodextrin, and cyclodextrin, and the filler is corn starch. The preparation method is as follows: wall material, filler, and antioxidant are added to water in sequence, the temperature is maintained at 80℃ and stirred for 15-30 minutes until dissolved to obtain an aqueous phase; camellia seed oil and emulsifier are mixed at a temperature of 40℃-90℃ to obtain an oil phase; the oil phase is slowly added to the aqueous phase to obtain a mixture, and the mixture is emulsified by high-speed shearing using a shear mill to form an O / W type emulsion; the emulsion is homogenized using a two-stage pressure homogenizer, the first homogenization time is 30 minutes and the homogenization pressure is 30 MPa, the second homogenization time is 25 minutes and the homogenization pressure is 40 MPa; the emulsion is spray-dried to obtain camellia seed oil microcapsule powder.

[0005] This document, published in China (CN105010574A) on November 4, 2015, discloses a novel linseed oil / grape seed oil / camellia oil microcapsule powder and its preparation method. The preparation method involves sequentially adding a wall material and a stabilizer to water, maintaining a temperature of 40℃-90℃ and stirring for 15-30 minutes until dissolved, to obtain an aqueous phase. Linseed oil, grape seed oil, and camellia oil are mixed and then mixed with an emulsifier at 40℃-90℃ to obtain an oil phase. The oil phase is slowly added to the aqueous phase to obtain a mixture, which is then emulsified at high speed using a shear mill to form an O / W type emulsion. The emulsion is homogenized using a two-stage pressure homogenizer: the first homogenization time is 15-50 minutes and the homogenization pressure is 20-40 MPa; the second homogenization time is 15-50 minutes and the homogenization pressure is 20-50 MPa. The emulsion is spray-dried at a temperature of 50-80℃ to obtain granules.

[0006] This document, published in China (CN102048159A) on November 15, 2010, discloses a camellia oil microcapsule powder and its preparation method. The preparation method involves adding camellia oil to an aqueous solution of sodium octenyl succinate starch, stirring the solution until a homogeneous emulsion system is formed, then homogenizing the emulsion under high pressure using a high-pressure homogenizer to obtain a camellia oil emulsion. Finally, spray drying or freeze drying yields a white camellia oil microcapsule powder with high stability, good flowability, and a particle size of less than 1000 nm.

[0007] Relevant non-patent literature retrieved: Journal name: 《ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY》, literature name: 《Fabrication, characterization, and antimicrobial activities of thymol-loaded zein nanoparticles stabilized by sodium caseinate-chitosanhydrochloride double layers》, volume number: Volume 246, publication date: December 7, 2020. This literature discloses that "Thymol-loaded zein nanoparticles stabilized with sodium caseinate (SC) andchitosan hydrochloride (CHC) were prepared and characterized. The SCstabilized nanoparticles had well-defined size range and negatively chargedsurface. Due to the presence of SC, the stabilized zein nanoparticles showeda shift of isoelectric point from 6.18 to 5.05, and had a desirableredispersibility in water at neutral pH after lyophilization. Coating withCHC onto the SC stabilized zein nanoparticles resulted in increased particlesize, reversal of zeta potential value from negative to positive, andimproved encapsulation efficiency."Both thymol-loaded zein nanoparticles andSC stabilized zein nanoparticles had a spherical shape and smooth surface,while the surfaces of CHC-SC stabilized zein nanoparticles seemed rough andhad some clumps. Encapsulated thymol was more effective in suppressing gram-positive bacterium than un-encapsulated thymol for a longer time (Translation: Thymol-loaded zein nanoparticles stabilized with sodium casein (SC) and chitosan hydrochloride (CHC) were prepared and characterized. SC-stabilized nanoparticles exhibited a well-defined particle size distribution and a negatively charged surface. Due to the presence of SC, the isoelectric point of the stabilized zein nanoparticles shifted from 6.18 to 5.05, and they exhibited ideal water redispersibility under neutral pH conditions after lyophilization. When CHC was coated onto the surface of SC-stabilized zein nanoparticles, the particle size increased, the zeta potential changed from negative to positive, and the encapsulation efficiency was improved. Both anethole-loaded and SC-stabilized zein nanoparticles were spherical and had smooth surfaces, while CHC-SC-stabilized zein nanoparticles showed a rough surface and clumping. Encapsulated anethole was more effective and had a longer duration of action in inhibiting Gram-positive bacteria than unencapsulated anethole.)

[0008] The prior art represented by the aforementioned documents has at least the following unresolved technical problems or defects: The wall material system is too simple, resulting in poor encapsulation stability and failing to address the issue of core material oxidation and loss. Relevant evidence is provided by publication number CN104982558A, which uses a single polymer material as the wall material. The film density of a single wall material is insufficient, and it cannot effectively isolate the contact between external oxygen and moisture and camellia seed oil (or similar oil core materials). This leads to easy oxidation and decomposition of the core material, loss of effective components, and problems such as rancidity and off-odors during long-term storage. It does not solve the industry pain point of poor stability after encapsulation of oil-based core materials.

[0009] The process is cumbersome and energy-intensive. The relevant evidence is CN102048159A, which describes a complicated preparation process that requires high-temperature baking and complex cross-linking. This process not only consumes a lot of energy but also leads to degradation of the wall material and oxidation of the core material. It also increases production costs and process difficulty, and does not solve the technical problems of high energy consumption, complex process and high cost in the industrial production of microcapsule emulsions.

[0010] Camellia seed oil is widely used in the cosmetics industry due to its repairing, anti-aging, and antioxidant properties. However, there are currently no patents utilizing microencapsulation emulsion technology to address the water solubility issue and slow down rancidity of camellia seed oil. Existing patents mainly focus on the food processing field and study microcapsule powders. For the widespread application of camellia seed oil microencapsulation emulsions in cosmetics, existing technologies do not provide effective support. Therefore, developing a camellia seed oil microencapsulation emulsion system that can slow down rancidity and achieving a leap from oil-soluble to water-soluble camellia seed oil is imperative.

[0011] In solving the above problems or overcoming the above defects, the present invention encountered the following difficulties and obstacles: Microencapsulated emulsions are highly susceptible to water-oil separation during storage due to inadequate encapsulation. During the invention process, multiple comparisons and adjustments were made to conditions such as the type and ratio of microcapsule wall materials, coagulation pH, and mixing and homogenization processes, ultimately resulting in a microencapsulated emulsion that can exist stably and uniformly under normal storage conditions. Summary of the Invention

[0012] The purpose of this invention is to provide: A camellia seed oil microcapsule emulsion, and related technologies thereof, to solve technical problems such as improving system stability and delaying rancidity, or combinations thereof.

[0013] Terminology Explanation: Unless otherwise defined, all technical terms used herein have the same meanings as commonly understood by one of ordinary skill in the art to which this subject matter pertains. Unless otherwise stated, all patents, patent inventions, and disclosures cited throughout this document are incorporated herein by reference in their entirety. Where multiple definitions exist for terms herein, the definitions provided in this chapter shall prevail.

[0014] It should be understood that the above brief description and the following detailed description are exemplary and for illustrative purposes only, and do not limit the subject matter of the invention in any way. In this invention, the singular is used in conjunction with the plural unless otherwise specifically stated. It should also be noted that, unless otherwise stated, the use of “or” or “or” means “and / or”. Furthermore, the use of the term “comprising” and other forms such as “including,” “containing,” and “contains” are not limiting.

[0015] Definitions of standard chemical terms can be found in the references "Dictionary of Cosmetic Raw Materials", "Cosmetic Professional English" (Appendix: Raw Material Dictionary) and GB / T27578-2011 "Cosmetic Terminology".

[0016] Unless otherwise stated, conventional methods within the scope of the art, such as emulsification index (EAI) testing, emulsification stability (ESI) testing, particle size analysis, polydispersity index testing, and zeta potential testing, shall be used.

[0017] Unless specifically defined herein, the use of all commercially available products herein employs standard techniques. For example, it may be carried out using the manufacturer's instructions for use with the kit, or in accordance with methods known in the art or the description of this invention. The techniques and methods described herein can generally be implemented according to conventional methods well known in the art, based on the descriptions in the various summary and more specific documents cited and discussed in this specification.

[0018] The term "microencapsulated emulsion" as used in this article refers to an O / W type emulsion in which the oil phase is dispersed in the aqueous phase through emulsification and homogenization, with camellia seed oil as the core material and composite wall material and emulsifier as the main raw materials. This emulsion is an intermediate system for the preparation of microcapsules and can be dried and encapsulated to form solid camellia seed oil microcapsules, combining the dispersibility of emulsions with the encapsulation characteristics of microcapsule precursors.

[0019] The term "homogenization" as used in this article refers to the process of breaking down and refining large oil phase droplets in a crude emulsion of camellia seed oil into nano- / micron-sized droplets under high pressure or high-speed shearing, so that the oil phase is uniformly dispersed in the aqueous phase, thereby reducing the emulsion particle size and improving the stability of the system.

[0020] The term "PE9010" used in this article refers to a preservative compounded with phenoxyethanol and ethylhexylglycerin, whose main components include 90% phenoxyethanol and 10% ethylhexylglycerin. The ethylhexylglycerin affects the surface tension on the cell membrane of microorganisms, thereby improving the preservative ability of phenoxyethanol.

[0021] The term "sodium caseinate" used in this article refers to a water-soluble milk protein food additive prepared by reacting casein with sodium hydroxide. It has both wall material and emulsifying auxiliary functions. As a wall material, it can form a film layer on the surface of oil droplets to achieve encapsulation. As an emulsifier, it can reduce the oil-water interfacial tension and help emulsion formation and stability. It is a dual-functional component of composite wall material / emulsifier prepared by microcapsule preparation.

[0022] The term "chitosan hydrochloride" used in this article refers to a water-soluble natural polymer derivative of chitosan obtained by acidification with hydrochloric acid. It has no emulsifying activity and can be used as an auxiliary wall material / wall material crosslinking component in the preparation of camellia seed oil microcapsules. It can form a dense crosslinked film with the basic wall material through electrostatic compounding and molecular entanglement, thereby strengthening the encapsulation structure of the microcapsules and improving the retention rate and storage stability of the core material.

[0023] The term “Emulsification Index (EAI)” used in this article refers to the core indicator for evaluating the emulsifying ability of an emulsifier. It characterizes the ability of a unit mass of emulsifier to form a stable film at the oil-water interface. The value is the percentage of the volume of the emulsion layer to the total volume of the emulsion after emulsification. The higher the value, the better the emulsification effect of the emulsifier and the stronger the initial dispersion stability of the emulsion.

[0024] The term “emulsion stability (ESI)” used in this article refers to an index that evaluates the ability of an emulsion to maintain an oil-water dispersion state after standing, heating, or centrifugation. It is usually expressed as the percentage of the remaining emulsion volume to the initial emulsion volume after the emulsion has been treated under certain conditions. The higher the value, the stronger the emulsion’s ability to resist stratification and aggregation, and the better its storage stability.

[0025] The term "polydispersity index" used in this article refers to an index characterizing the uniformity of droplet size distribution in the oil phase of microcapsule emulsions. The value ranges from 0 to 1. The closer the value is to 0, the more uniform the droplet size distribution. The closer the value is to 1, the greater the difference in droplet size and the wider the distribution. Emulsions with poor particle size uniformity are prone to aggregation and stratification. This index is an important parameter for evaluating the stability of emulsions.

[0026] The term "Zeta potential" used in this article refers to an electrochemical index characterizing the surface charge and amount of charge of oil phase droplets in microcapsule emulsions. The unit is mV. Its absolute value reflects the magnitude of the electrostatic repulsion between droplets. The larger the absolute value (usually ≥30mV), the less likely the droplets are to aggregate, and the stronger the colloidal stability of the emulsion. The smaller the absolute value, the more likely the emulsion is to separate due to particle aggregation.

[0027] The term "SDS solution" used in this article refers to sodium dodecyl sulfate solution, which is an anionic surfactant that is readily soluble in water and has good emulsifying, dispersing, and solubilizing effects.

[0028] In a first aspect, the present invention provides: a camellia seed oil microcapsule emulsion, the raw materials of which are composed of camellia seed oil, sodium caseinate, chitosan hydrochloride, PE9010 and solvent.

[0029] Preferably, the solvent is selected from at least one of water and glycerin; More preferably, the solvent is water or a mixture of water and glycerin; In some specific cases, the mass percentage of glycerin ranges from 0% to 5.0%. More preferably, the solvent is deionized water; Preferably, the sodium caseinate and chitosan hydrochloric acid in the camellia seed oil microcapsule emulsion are of equal mass; Preferably, the raw materials of the camellia seed oil microcapsule emulsion are composed of the following components by mass percentage: 5.0%-20.0% camellia seed oil, 1.0%-2.5% sodium caseinate, 1.0%-2.5% chitosan hydrochloride, 0.5%-0.8% PE9010, and the balance being solvent.

[0030] For example: The mass percentage of the camellia seed oil may be 5.0%, 6.0%, 7.0%, 8.0%, 9.0%, 10.0%, 11.0%, 12.0%, 13.0%, 14.0%, 15.0%, 16.0%, 17.0%, 18.0%, 19.0%, or 20.0%, and may include a range consisting of any two points. The mass percentage of sodium caseinate may be 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, or 2.5%, and may include a range consisting of any two values; The mass percentage of the chitosan hydrochloride can be 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, or 2.5%, and can include a range consisting of any two values; The mass percentage of PE9010 can be 0.5%, 0.6%, 0.7%, or 0.8%, or a range including any two values. More preferably, the raw materials of the camellia seed oil microcapsule emulsion are composed of the following components by mass percentage: 5.0%-15.0% camellia seed oil, 1.0%-2.0% sodium caseinate, 1.0%-2.0% chitosan hydrochloride, 0.5%-0.7% PE9010, and the balance being solvent; More preferably, the raw materials of the camellia seed oil microcapsule emulsion are composed of the following components by mass percentage: 10.0% camellia seed oil, 1.5% sodium caseinate, 1.5% chitosan hydrochloride, 0.6% PE9010, and the balance being solvent.

[0031] Based on further solutions to the technical problems of the present invention, or simultaneous solutions to multiple technical problems, the preferred solution in the technical solution provided in the first aspect of the present invention includes: The first preferred embodiment: the solvent is selected from at least one of water and glycerol; preferably water or a mixture of water and glycerol; more preferably deionized water. This technical solution, having solved the technical problem of "reducing particle size, improving dispersion uniformity and system stability," further solves the technical problem of "further reducing particle size, improving dispersion uniformity and system stability."

[0032] The second preferred embodiment: the raw materials of the camellia seed oil microcapsule emulsion, by mass percentage, consist of the following components: 5.0%-20.0% camellia seed oil, 1.0%-2.5% sodium caseinate, 1.0%-2.5% chitosan hydrochloride, 0.5%-0.8% PE9010, with the balance being solvent; preferably, the raw materials of the camellia seed oil microcapsule emulsion, by mass percentage, consist of the following components: 5.0%-15.0% camellia seed oil, 1.0%-2.0% sodium caseinate, 1.0%-2.0% chitosan hydrochloride, 0.5%-0.7% PE9010, with the balance being solvent; more preferably, the raw materials of the camellia seed oil microcapsule emulsion, by mass percentage, consist of the following components: 10.0% camellia seed oil, 1.5% sodium caseinate, 1.5% chitosan hydrochloride, 0.6% PE9010, with the balance being solvent. This technical solution, having already addressed the technical issues of "reducing particle size, improving dispersion uniformity and system stability," further addresses the technical problem of "further reducing particle size, improving dispersion uniformity and system stability."

[0033] Secondly, the present invention provides a method for preparing the camellia seed oil microcapsule emulsion, comprising the following steps: (1) Dissolve sodium caseinate and chitosan hydrochloride in solvents respectively to obtain solution A and solution B, and then keep warm; (2) The solutions A and B obtained in step (1) and camellia seed oil are homogenized and mixed to obtain a primary emulsion; (3) Adjust the pH of the primary emulsion obtained in step (2) to 7-9.5, and after homogenization, add PE9010 to obtain camellia seed oil microcapsule emulsion.

[0034] The insulation temperature in step (1) is 50-65℃; The preferred temperature for heat preservation in step (1) is 60℃; Preferably, the heat preservation method in step (1) is water bath heat preservation; Preferably, the solvent masses of solutions A and B in step (1) are the same; Preferably, the homogenization method in step (2) is at least one of high-speed shear homogenization, ultrasonic homogenization, and stirring homogenization; More preferably, the homogenization method in step (2) is high-speed shear homogenization; More preferably, the homogenization method in step (2) is high-speed shear homogenization using a homogenizer; Preferably, the homogenization mixing order in step (2) is as follows: after adding camellia seed oil to solution A for one homogenization, solution B is added for a second homogenization; More preferably, the homogenization mixing order in step (2) is as follows: solution A is homogenized first, then camellia seed oil is added for a first homogenization, and then solution B is added for a second homogenization; More preferably, the homogenization speed of solution A is 6000-20000 rpm; the time is 3-15 min. Most preferably, the homogenization speed of solution A is 10,000 rpm; the time is 5 min. More preferably, the rotational speed of the first homogenization is 6000-20000 rpm; the duration is 3-15 min. Most preferably, the rotational speed of the first homogenization is 10,000 rpm; the duration is 5 minutes. More preferably, the rotation speed of the secondary homogenization is 6000-20000 rpm; the duration is 3-15 min. Most preferably, the rotation speed of the secondary homogenization is 10,000 rpm; the duration is 5 minutes. Preferably, the pH value range in step (3) is 7-9; More preferably, the pH value in step (3) is 9; Preferably, the homogenization pressure range in step (3) is selected from 500-900 bar, and the number of homogenization cycles is selected from 2-6. More preferably, the homogenization pressure range in step (3) is selected from 700-900 bar, and the number of homogenization cycles is selected from 3-5. More preferably, the homogenization pressure range in step (3) is selected from 800 bar, and the number of homogenization cycles is selected from 5.

[0035] Preferably, the preparation method of the camellia seed oil microcapsule emulsion includes the following steps: (1) Dissolve sodium caseinate in deionized water to obtain solution A, and dissolve chitosan hydrochloride in deionized water to obtain solution B. Incubate solutions A and B in a water bath at 60°C. (2) Homogenize solution A at 10,000 rpm for 5 min using a homogenizer, slowly add camellia seed oil, and homogenize at 10,000 rpm for 5 min; then add solution B and continue homogenizing at 10,000 rpm for 5 min to obtain a primary emulsion. (3) Adjust the pH of the primary emulsion obtained in step (2) to 9±0.1, homogenize it under high pressure at 800 bar 5 times, and add PE9010 after completion to obtain camellia seed oil microcapsule emulsion.

[0036] Based on further solutions to the technical problems of the present invention, or simultaneous solutions to multiple technical problems, the preferred solution in the technical solution provided in the second aspect of the present invention includes: The first preferred embodiment: Preferably, the homogenization mixing order in step (2) is as follows: after adding camellia seed oil to solution A for one homogenization, solution B is added for a second homogenization; more preferably, the homogenization mixing order in step (2) is as follows: solution A is homogenized first, then camellia seed oil is added for one homogenization, and then solution B is added for a second homogenization. This technical solution, based on solving the technical problem of "reducing particle size, improving dispersion uniformity and system stability", further solves the technical problem of "further reducing particle size, improving dispersion uniformity and system stability".

[0037] The second preferred embodiment: Preferably, the pH value range in step (3) is 7-9; more preferably, the pH value in step (3) is 9. This technical solution, based on solving the technical problem of "reducing particle size, improving dispersion uniformity and system stability", further solves the technical problem of "further reducing particle size, improving dispersion uniformity and system stability".

[0038] The third preferred embodiment: Preferably, the homogenization pressure range in step (3) is selected from 50-90 MPa, and the number of homogenization cycles is selected from 2-6; more preferably, the homogenization pressure range in step (3) is selected from 700-900 bar, and the number of homogenization cycles is selected from 3-5; even more preferably, the homogenization pressure range in step (3) is selected from 800 bar, and the number of homogenization cycles is selected from 5. This technical solution, based on solving the technical problem of "reducing particle size, improving dispersion uniformity and system stability", further solves the technical problem of "further reducing particle size, improving dispersion uniformity and system stability".

[0039] Thirdly, the present invention provides the application of the preparation method in camellia seed oil cosmetics.

[0040] Among them, the camellia seed oil cosmetics are cosmetics containing camellia seed oil; The cosmetics include, but are not limited to, at least one of lotion, face cream, essence water, conditioner, hair mask, hair oil and makeup primer; Preferably, the application is as follows: the preparation method involves coating camellia seed oil with a sodium caseinate-chitosan hydrochloride composite wall material, combined with the preservative effect of PE9010, and optionally with glycerin to optimize the skin feel. The mixture is then processed into a microcapsule emulsion through high-speed shearing and high-pressure homogenization, which transforms camellia seed oil into an emulsion system with good water solubility, uniform particle size, and strong stability. Its microcapsule structure can delay the oxidative degradation of camellia seed oil, reduce the loss of active ingredients, reduce the greasiness of camellia seed oil, and improve the skin's absorption efficiency of its unsaturated fatty acids, vitamins, and other active ingredients, thus meeting the skin feel and efficacy requirements of cosmetics.

[0041] Examples 1-13 of this invention at least support the protection scope of "microencapsulated emulsion" and "homogenization".

[0042] The term "microcapsule emulsion" is derived from the aforementioned explanation and / or the corresponding technical feature in Examples 1-13, "a camellia seed oil microcapsule emulsion, the raw materials of which are composed of camellia seed oil, sodium caseinate, chitosan hydrochloride, PE9010 and solvent," and is summarized by the common feature "an O / W type emulsion in which the oil phase is dispersed in the aqueous phase through emulsification and homogenization, with core material, composite wall material and emulsifier as the main raw materials." Therefore, those skilled in the art can reasonably presume that "microcapsule emulsion," its subordinate concepts, its substantially equivalent technical means, and technical means that can replace it within the scope of conventional technical means and common knowledge based on the existing technical level should all fall within the protection scope of "microcapsule emulsion." For example, replacing "microcapsule emulsion" with "microencapsulation emulsion," "embedding emulsion," etc., while keeping other technical features unchanged, still falls within the protection scope of this invention.

[0043] "Homogeneous mixing" is summarized from the aforementioned explanation and / or the corresponding techniques in Examples 1-13, such as "the order of homogeneous mixing in step (2) is: after adding camellia seed oil to solution A for homogeneous mixing once, solution B is added for homogeneous mixing a second time", "using a homogenizer to homogenize solution A at 10,000 rpm for 5 min, slowly adding 20 g of camellia seed oil, homogenizing for 5 min; then adding solution B to it, and continuing to homogenize at 10,000 rpm for 5 min to obtain a primary emulsion", etc., through the common feature "under high pressure or high speed shearing, the large droplets of the oil phase in the crude emulsion are broken and refined into nano- / micron-sized droplets, so that the oil phase is uniformly dispersed in the aqueous phase, reducing the emulsion particle size and improving the stability of the system". Therefore, those skilled in the art can reasonably presume that "homogeneity," its subordinate concepts, its essentially equivalent technical means, and technical means that can replace it within the scope of conventional technical means and common knowledge based on the existing level of technology should all fall within the protection scope of "homogeneity." For example, if "homogeneity" is replaced with "dispersion homogenization," "high-speed shear homogenization," "shear homogenization," etc., while other technical features remain unchanged, it still falls within the protection scope of this invention.

[0044] Examples 1-13 of this invention at least support the scope of protection of "application of camellia seed oil in cosmetics".

[0045] The term "application of camellia seed oil in cosmetics" is summarized from the foregoing explanation and / or the corresponding technical features in Examples 1-13: "Camellia seed oil is coated with a sodium caseinate-chitosan hydrochloride composite wall material, combined with the emulsifying and stabilizing effect of PE9010, and glycerin can also be selected to assist in optimizing the skin feel. Through high-speed shearing, high-pressure homogenization, and other processes, a microcapsule emulsion is prepared, which can transform camellia seed oil into an emulsion system with good water solubility, uniform particle size, and strong stability. Its microcapsule structure can delay the oxidative degradation of camellia seed oil, reduce the loss of effective ingredients, reduce the greasiness of camellia seed oil, and improve the skin's absorption efficiency of its unsaturated fatty acids, vitamins, and other active ingredients, thus meeting the skin feel and efficacy requirements of cosmetics." Therefore, those skilled in the art can reasonably presume that "application of camellia seed oil in cosmetics," its subordinate concepts, its essentially equivalent technical means, and technical means that can replace it within the scope of conventional and common knowledge based on the existing technical level should all fall within the protection scope of this invention.

[0046] The beneficial effects of this invention are as follows: The present invention has at least the following beneficial effects: (1) Achieving the leap from "oil-soluble to water-soluble": Through the encapsulation effect of sodium caseinate-chitosan hydrochloride composite wall material, the originally oil-soluble camellia seed oil is transformed into water-soluble microcapsule emulsion, which solves the industry problem of uneven dispersion and easy stratification of traditional camellia seed oil in water-based cosmetics (such as emulsions and essences), and greatly expands its application scenarios in the cosmetics field.

[0047] (2) Significantly delays the rancidity of camellia seed oil: The composite wall material forms a dense coating structure, which isolates the camellia seed oil from external factors such as oxygen and light; at the same time, the anti-corrosion effect of PE9010 further enhances the antioxidant properties of the system, effectively reduces the rancidity rate of camellia seed oil, and extends the shelf life of the product.

[0048] (3) The process is simple and easy to operate, and the cost is controllable: The composite coagulation method is adopted, which only requires conventional steps such as water bath heat preservation, high-speed homogenization, and high-pressure homogenization. There is no need for high-temperature baking or complex cross-linking. The raw materials are conventional components of food / cosmetic grade, without expensive fillers or cross-linking agents, which reduces production costs and industrialization threshold.

[0049] (4) Compared with the prior art, the present invention has better technical effects in terms of particle size, PDI (polydispersity index) and Zeta potential (colloidal stability), and the overall performance is stable with no obvious batch differences.

[0050] According to experimental tests, the present invention reduces the particle size from above 2282nm in the prior art to the range of 532.9nm-1171nm, with the overall particle size controlled below 1200nm. Among them, the particle size of 7 processes is below 1000nm, which is significantly better than the prior art.

[0051] According to experimental tests, the present invention reduces the PDI (polydispersity index) from above 0.5913 in the prior art to the range of 0.2013-0.3751, with the overall PDI controlled below 0.4. Among them, the PDI of 8 processes is below 0.3, and the uniformity of particle size distribution is greatly improved.

[0052] According to experimental tests, this invention increases the zeta potential (colloidal stability) from 28.18mV in the prior art to the range of 37.13mV-47.79mV. The absolute value of the overall zeta potential is higher than 37mV, indicating excellent colloidal stability. All processes can effectively avoid emulsion separation and flocculation.

[0053] Furthermore, based on the present invention: 1. Based on the comparison of Examples 1-13 and Comparative Examples 1-6, the present invention employs a combination of technical means such as "sodium caseinate, chitosan hydrochloride", "PE9010", and "pH range 7-9.5" to achieve new technical effects such as "reducing particle size and significantly improving dispersion uniformity and system stability". The combined technical effect is superior to the sum of the effects of each individual technical means.

[0054] 2. Based on the comparison of Examples 1-13 and Comparative Examples 4-6, the present invention purposefully selects from the broad range of "sodium caseinate, pure gum, maltodextrin, cyclodextrin, gum arabic, gelatin, sodium alginate, calcium chloride" disclosed in the prior art a narrow range of "sodium caseinate, chitosan hydrochloride" not mentioned in the prior art, and achieves unexpected technical effects "reducing particle size and significantly improving dispersion uniformity and system stability". Detailed Implementation

[0055] The following non-limiting embodiments are intended to enable those skilled in the art to gain a more comprehensive understanding of the present invention, but do not limit the invention in any way. The following content is merely an exemplary description of the scope of protection claimed by the present invention, and those skilled in the art can make various changes and modifications to the present invention based on the disclosed content, and such changes should also fall within the scope of protection claimed by the present invention.

[0056] The present invention will be further described below by way of specific embodiments. Unless otherwise specified, all instruments, devices, equipment, reagents, products, etc., used in the embodiments of the present invention are obtained through conventional commercial means.

[0057] Specific raw material information is shown in Table 1: Table 1. Raw Material Information

[0058] Example 1 A camellia seed oil microcapsule emulsion is prepared by the following method: 1.5g of sodium caseinate was dissolved in 43.2g of deionized water to obtain solution A. 1.5g of chitosan hydrochloride was dissolved in 43.2g of deionized water to obtain solution B. The solutions were kept in a 60℃ water bath. Solution A was homogenized at 10000rpm for 5 minutes using a homogenizer. 10g of camellia seed oil was slowly added, and homogenization was continued for 5 minutes. Then, solution B was added, and homogenization was continued at 10000rpm for 5 minutes to obtain a primary emulsion. The pH of the emulsion was adjusted to 7±0.1. The emulsion was homogenized five times at 800bar. After completion, 0.6g of PE9010 was added to obtain a camellia seed oil microcapsule emulsion.

[0059] Example 2 A camellia seed oil microcapsule emulsion is prepared by the following method: Weigh out 1.5g of sodium caseinate and 2.5g of glycerol, and dissolve them in 40.7g of deionized water to obtain solution A. Weigh out 1.5g of chitosan hydrochloride and 2.5g of glycerol, and dissolve them in 40.7g of deionized water to obtain solution B. Keep the above solutions in a water bath at 60℃.

[0060] Solution A was homogenized at 10,000 rpm for 5 minutes using a homogenizer. 10 g of camellia seed oil was slowly added, and homogenization was continued for another 5 minutes. Solution B was then added, and homogenization was continued at 10,000 rpm for 5 minutes to obtain a primary emulsion. The pH of the emulsion was adjusted to 7 ± 0.1. The emulsion was homogenized five times at 800 bar. After completion, 0.6 g of PE9010 was added to obtain a camellia seed oil microcapsule emulsion.

[0061] Example 3 A camellia seed oil microcapsule emulsion is prepared by the following method: Weigh 2g of sodium caseinate and dissolve it in 43.2g of deionized water to obtain solution A. Weigh 1g of chitosan hydrochloride and dissolve it in 43.2g of deionized water to obtain solution B. Keep the above solutions in a water bath at 60℃.

[0062] Solution A was homogenized at 10,000 rpm for 5 minutes using a homogenizer. 10 g of camellia seed oil was slowly added, and homogenization was continued for another 5 minutes. Solution B was then added, and homogenization was continued at 10,000 rpm for 5 minutes to obtain a primary emulsion. The pH of the emulsion was adjusted to 7 ± 0.1. The emulsion was homogenized five times at 800 bar. After completion, 0.6 g of PE9010 was added to obtain a camellia seed oil microcapsule emulsion. Example 4 A camellia seed oil microcapsule emulsion is prepared by the following method: Weigh 1g of sodium caseinate and dissolve it in 43.2g of deionized water to obtain solution A. Weigh 2g of chitosan hydrochloride and dissolve it in 43.2g of deionized water to obtain solution B. Keep the above solutions in a water bath at 60℃.

[0063] Solution A was homogenized at 10,000 rpm for 5 minutes using a homogenizer. 10 g of camellia seed oil was slowly added, and homogenization was continued for another 5 minutes. Solution B was then added, and homogenization was continued at 10,000 rpm for 5 minutes to obtain a primary emulsion. The pH of the emulsion was adjusted to 7 ± 0.1. The emulsion was homogenized five times at 800 bar. After completion, 0.6 g of PE9010 was added to obtain a camellia seed oil microcapsule emulsion.

[0064] Example 5 A camellia seed oil microcapsule emulsion is prepared by the following method: Weigh 2.5g of sodium caseinate and dissolve it in 42.2g of deionized water to obtain solution A. Weigh 2.5g of chitosan hydrochloride and dissolve it in 42.2g of deionized water to obtain solution B. Keep the above solutions in a water bath at 60℃.

[0065] Solution A was homogenized at 10,000 rpm for 5 minutes using a homogenizer. 10 g of camellia seed oil was slowly added, and homogenization was continued for another 5 minutes. Solution B was then added, and homogenization was continued at 10,000 rpm for 5 minutes to obtain a primary emulsion. The pH of the emulsion was adjusted to 7 ± 0.1. The emulsion was homogenized five times at 800 bar. After completion, 0.6 g of PE9010 was added to obtain a camellia seed oil microcapsule emulsion.

[0066] Example 6 A camellia seed oil microcapsule emulsion is prepared by the following method: Weigh 1.5g of sodium caseinate and dissolve it in 43.2g of deionized water to obtain solution A. Weigh 1.5g of chitosan hydrochloride and dissolve it in 43.2g of deionized water to obtain solution B. Keep the above solutions in a water bath at 60℃.

[0067] Solution A was homogenized at 10,000 rpm for 5 minutes using a homogenizer. 10 g of camellia seed oil was slowly added, and homogenization was continued for another 5 minutes. Solution B was then added, and homogenization was continued at 10,000 rpm for 5 minutes to obtain a primary emulsion. The pH of the emulsion was adjusted to 9 ± 0.1. The emulsion was homogenized five times at 800 bar. After completion, 0.6 g of PE9010 was added to obtain a camellia seed oil microcapsule emulsion.

[0068] Example 7 Compared with Example 6, the only differences are: the weight of deionized water in both solution A and solution B is replaced with 45.7g; the pH of the emulsion is adjusted to 7±0.1; the amount of camellia seed oil added is replaced with 5g, and all other aspects are the same.

[0069] Example 8 Compared with Example 6, the only differences are: the weight of deionized water in both solution A and solution B is replaced with 40.7g; the pH of the emulsion is adjusted to 7±0.1; the amount of camellia seed oil added is replaced with 15g, and everything else is the same.

[0070] Example 9 Compared with Example 6, the only differences are: the weight of deionized water in both solution A and solution B is replaced with 38.2g; the pH of the emulsion is adjusted to 7±0.1; the amount of camellia seed oil added is replaced with 20g, and everything else is the same.

[0071] Example 10 Compared with Example 6, the only difference is that the number of high-pressure homogenization cycles is replaced with 3, and all other aspects are the same.

[0072] Example 11 Compared with Example 6, the only difference is that the solvents in both Solution A and Solution B are replaced with "5g glycerol and 38.2g deionized water"; the pH of the emulsion is adjusted to 7±0.1, and everything else is the same.

[0073] Example 12 Compared with Example 6, the only difference is that solution A is replaced with "2g of sodium caseinate dissolved in 43.2g of deionized water"; solution B is replaced with "1g of chitosan hydrochloride dissolved in 43.2g of deionized water", and all other aspects are the same.

[0074] Example 13 Compared with Example 6, the only difference is that solution A is replaced with "1g of sodium caseinate dissolved in 43.2g of deionized water"; solution B is replaced with "2g of chitosan hydrochloride dissolved in 43.2g of deionized water", and all other aspects are the same.

[0075] Comparative Example 1 Compared with Example 6, the only difference is that: solution A is replaced with "1g of sodium caseinate dissolved in 44.7g of deionized water"; solution B is replaced with "1g of chitosan hydrochloride dissolved in 44.7g of deionized water"; the pH of the emulsion is adjusted to 7±0.1, and everything else is the same.

[0076] Comparative Example 2 Compared with Example 6, the only difference is that: solution A is replaced with "5g of sodium caseinate dissolved in 39.7g of deionized water"; solution B is replaced with "5g of chitosan hydrochloride dissolved in 39.7g of deionized water"; the pH of the emulsion is adjusted to 7±0.1, and everything else is the same.

[0077] Comparative Example 3 Compared with Example 6, the only difference is that the pH of the emulsion was adjusted to 6.5±0.1, and everything else is the same.

[0078] Comparative Example 4 Compared with Example 6, the only difference is that "sodium caseinate" is replaced with "gelatin", and everything else is the same.

[0079] Comparative Example 5 Compared with Example 6, the only difference is that "chitosan hydrochloride" is replaced with "maltodextrin", and everything else is the same.

[0080] Comparative Example 6 Compared with Example 6, the only difference is that "sodium caseinate" is replaced with "hydrolyzed corn gluten powder", and everything else is the same.

[0081] The camellia seed oil microcapsule emulsion prepared in Comparative Example 6 exhibited stratification during storage, demonstrating instability.

[0082] Example 1: Determination of Emulsification Index (EAI) and Emulsification Stability (ESI) 1. Specific testing methods Take 6 mL of the camellia seed oil microcapsule emulsion prepared in Examples 1-13 and Comparative Examples 1-5, and mix it with 1 mL of 0.1% SDS solution until homogeneous. Measure the absorbance of the sample at 500 nm using an ELISA reader and record the absorbance as A0. After standing for 10 min, measure the absorbance again as A1. For the blank control, use 0.1% SDS solution. The calculation formula is as follows: How to calculate the Emulsification Index (EAI):

[0083] In the formula: A0 is the absorbance value at 0 min; A1 is the absorbance value at 10 min; N is the dilution factor; C is the sample concentration (g / mL); θ is the oil phase volume (mL).

[0084] How to calculate Emulsion Stability (ESI):

[0085] In the formula: A0 is the absorbance value at 0 min; A1 is the absorbance value at 10 min.

[0086] 2. Specific test data are shown in the table below: Table 2. EAI and ESI values ​​of different camellia seed oil microcapsule emulsions

[0087] Based on the above data, it can be seen that the camellia seed oil microcapsule emulsions prepared in Examples 1-13 and Comparative Examples 1-5 can all remain stable and have a high emulsion stability index, that is, sodium caseinate has a strong ability to maintain the stability of the dispersion system.

[0088] Example 2: Determination of particle size, polydispersity index, and zeta potential. 1. Specific steps: Take 0.5 mL of the prepared camellia seed oil microcapsule emulsion, add 1.5 mL of ultrapure water and mix thoroughly. Place the mixture in a Malvern sample cell and use a laser particle size analyzer to determine the particle size, polydispersity index and zeta potential of the camellia seed oil microcapsule emulsion.

[0089] The specific parameter settings for the laser particle size analyzer are as follows: The dispersion medium was water, the equilibration time was 2 minutes, the temperature was 25°C, the detection mode was set to general mode, the electrophoresis voltage was 100V, and the data model was set to "emulsion" model.

[0090] 2. Specific test data are shown in the table below: Table 3. Particle size, polydispersity index (PDI), and zeta potential of each test sample

[0091] Verification of technical effectiveness and / or analysis of technical problem solving Based on the comparative test results of the above examples and comparative examples, it can be seen that, considering the combined test results of the particle size, polydispersity index and Zeta potential of the camellia seed oil microcapsule emulsion, the overall effect of Examples 1-13 of this application is better than that of Comparative Examples 1-6. In particular, the camellia seed oil microcapsule emulsion product prepared in Example 6 still has a small particle size and good emulsification performance when the oil content reaches 10%, and the system is uniformly dispersed and has excellent stability.

[0092] Finally, it should be noted that the above content is only used to illustrate the technical solution of the present invention, and is not intended to limit the scope of protection of the present invention. Simple modifications or equivalent substitutions made by those skilled in the art to the technical solution of the present invention do not depart from the essence and scope of the technical solution of the present invention.

Claims

1. A camellia seed oil microcapsule emulsion, characterized in that, The raw materials consist of camellia seed oil, sodium caseinate, chitosan hydrochloride, PE9010, and solvent.

2. The microcapsule emulsion according to claim 1, characterized in that, The solvent is selected from at least one of water and glycerin; Preferably, it is water or a mixture of water and glycerin; Deionized water is preferred.

3. The microcapsule emulsion according to claim 1, characterized in that, The sodium caseinate and chitosan hydrochloric acid are of equal mass.

4. The microcapsule emulsion according to claim 1, characterized in that, The raw materials, by mass percentage, consist of the following components: 5.0%-20.0% camellia seed oil, 1.0%-2.5% sodium caseinate, 1.0%-2.5% chitosan hydrochloride, 0.5%-0.8% PE9010, with the remainder being solvent.

5. A method for preparing the microcapsule emulsion according to any one of claims 1-4, characterized in that, Including the following steps: (1) Dissolve sodium caseinate and chitosan hydrochloride in solvents respectively to obtain solution A and solution B, and then keep warm; (2) The solutions A and B obtained in step (1) and camellia seed oil are homogenized and mixed to obtain a primary emulsion; (3) Adjust the pH of the primary emulsion obtained in step (2) to 7-9.5, and after homogenization, add PE9010 to obtain camellia seed oil microcapsule emulsion.

6. The preparation method according to claim 5, characterized in that, The insulation temperature in step (1) is 50-65℃; In step (1), the solvents in solution A and solution B have the same mass.

7. The preparation method according to claim 5, characterized in that, The homogenization method described in step (2) is at least one of high-speed shear homogenization, ultrasonic homogenization, and stirring homogenization; The homogenization mixing sequence in step (2) is as follows: after adding camellia seed oil to solution A for one homogenization, solution B is added for a second homogenization. The rotation speed for both the first and second homogenization was 6000-20000 rpm, and the duration was 3-15 min.

8. The preparation method according to claim 5, characterized in that, The pH value range in step (3) is 7-9; preferably 9.

9. The preparation method according to claim 5, characterized in that, The homogenization pressure range in step (3) is selected from 500-900 bar, and the number of homogenization cycles is selected from 2-6.

10. The application of the preparation method according to any one of claims 5-9 in the cosmetics of camellia seed oil.

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