CN115721580A - Sunscreen product with metal oxide micro-nanosheets and preparation method thereof - Google Patents

Sunscreen product with metal oxide micro-nanosheets and preparation method thereof Download PDF

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CN115721580A
CN115721580A CN202211430995.6A CN202211430995A CN115721580A CN 115721580 A CN115721580 A CN 115721580A CN 202211430995 A CN202211430995 A CN 202211430995A CN 115721580 A CN115721580 A CN 115721580A
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sunscreen product
metal oxide
titanium
emulsifier
containing oxide
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丘陵
成会明
杨若凝
周煜
丁宝福
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Shenzhen International Graduate School of Tsinghua University
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Shenzhen International Graduate School of Tsinghua University
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Priority to CN202211430995.6A priority Critical patent/CN115721580A/en
Publication of CN115721580A publication Critical patent/CN115721580A/en
Priority to PCT/CN2023/080882 priority patent/WO2024103578A1/en
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/27—Zinc; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/29—Titanium; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/31—Hydrocarbons
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/37—Esters of carboxylic acids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/60—Sugars; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/92—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations

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  • Chemical & Material Sciences (AREA)
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Abstract

The application provides a sunscreen product with metal oxide micro-nano sheets and a preparation method thereof, wherein the sunscreen product comprises an aqueous phase matrix, a first emulsifier and an oil matrix, the aqueous phase matrix comprises the metal oxide micro-nano sheets and water, and the metal oxide micro-nano sheets comprise at least one of titanium-containing oxide micro-nano sheets or zinc-containing oxide micro-nano sheets. The sunscreen product provided by the application can improve the optical transparency of the sunscreen product in a visible light region, and improve the phenomenon of whitening of the skin surface after being smeared; and the penetration rate of the sunscreen product into the skin can be reduced, so that the biological safety of the sunscreen product is improved.

Description

Sunscreen product with metal oxide micro-nanosheets and preparation method thereof
Technical Field
The application relates to the technical field of sunscreen creams, in particular to a sunscreen product with metal oxide micro-nanosheets and a preparation method thereof.
Background
At present, titanium dioxide is one of accepted common physical sunscreen materials, and the titanium dioxide in the sunscreen agent achieves the sunscreen effect through reflection, scattering and absorption. The traditional titanium dioxide as a sun-screening agent and the traditional titanium dioxide as a coloring agent have the problems that the skin surface is whitened, unnatural and the like in the using process, which do not meet the aesthetic requirements of the public. Meanwhile, the titanium dioxide nanoparticles with the hundred nanometer size level are easy to penetrate through the horny layer of the skin to reach the inside of the body, and the biological safety of the human body is damaged to a certain extent.
Disclosure of Invention
In view of the above, the present application provides a sunscreen product having metal oxide nanosheets and a method for preparing the same.
To achieve the above object, the present application provides a sunscreen product having metal oxide nanoplatelets, the sunscreen product comprising an aqueous phase matrix comprising metal oxide nanoplatelets and water, a first emulsifier and an oil-based matrix.
In some embodiments, the metal oxide nanoplatelets comprise at least one of titanium-containing oxide nanoplatelets or zinc-containing oxide nanoplatelets.
In some embodiments, the titanium-containing oxide nanosheets have the chemical formula Ti (1-x) O (2-2x) ，0≤x＜1。
In some embodiments, the titanium-containing oxide nanosheets have the formula M a Ti (1-x-a) O (2-2x) X is more than or equal to 0 and less than 1, wherein M is a metal element with the same period as Ti.
In some embodiments, the zinc-containing oxide nanosheets are of the chemical formula ZnO.
In some embodiments, the zinc-containing oxide nanosheets have the chemical formula N b Zn (1-b) And O, wherein N is a metal element in the same period as Zn.
In some embodiments, the metal oxide nanoplatelets are present in an amount of 0.1 to 40wt% in the sunscreen product.
In some embodiments, the first emulsifier comprises at least one of cetearyl glucoside, methyl glucose sesquistearate, or an alkyl glucoside in which the number of carbon atoms is between 14 and 22.
In some embodiments, the first emulsifier is added in an amount of 0.5 to 15% by weight of the oil base in the sunscreen product.
In some embodiments, the sunscreen product further comprises a secondary emulsifier comprising at least one of sodium stearoyl glutamate, sodium lauroyl glutamate or sodium cocoyl glutamate, said secondary emulsifier added in an amount of 0.1 to 10wt% of the aqueous phase base.
In some embodiments, the oil base comprises at least one of liquid paraffin, caprylic/capric glycerides, jojoba oil, shea butter.
The application also provides a preparation method of the sunscreen product, which comprises the following steps: mixing an oil substrate and a first emulsifier, and heating to obtain a mixed solution; and adding a metal oxide dispersion liquid into the mixed solution, and heating to obtain a sunscreen product, wherein the metal oxide dispersion liquid comprises titanium-containing oxide micro-nano sheets and water, and the metal oxide micro-nano sheets comprise at least one of titanium-containing oxide micro-nano sheets or zinc-containing oxide micro-nano sheets.
In some embodiments, the method of making further comprises: before the titanium-containing oxide dispersion liquid is added into the mixed liquid, a second emulsifier is also added into the titanium-containing oxide dispersion liquid, the first emulsifier comprises an oil-phase emulsifier, and the second emulsifier is a water-phase emulsifier.
In some embodiments, the method of making further comprises a method of making the titanium-containing oxide nanosheets, the method comprising: one of a sintering-stripping method, a hydrothermal method, a tube-sealing sintering method or a chemical vapor deposition method is adopted.
According to the application, the metal oxide nanosheets are doped into the sunscreen product, and the metal oxide nanosheets have corresponding sizes ranging from several micrometers to dozens of micrometers due to the fact that the metal oxide nanosheets have the nanometer or micrometer layer thicknesses, so that the metal oxide nanosheets have high specific surface areas, the optical transparency of the metal oxide nanosheets in a visible light area is far higher than that of titanium dioxide (or zinc oxide) nanoparticles under the condition of the same volume percentage concentration, the optical transparency of the visible light area of the sunscreen product is improved, the phenomenon that the skin surface is whitened after being smeared is improved, and the natural skin color index is improved. Meanwhile, in the process of coating the sunscreen product, the sunscreen product can be uniformly coated on the surface of the skin due to the characteristics of large transverse size and high specific surface area of the metal oxide micro-nano sheet, and the sunscreen product is difficult to penetrate through the horny layer of the skin with gaps of hundreds of nanometers, so that the permeability of the sunscreen product penetrating into the skin is reduced, the biological safety of the sunscreen product is improved, and the metal oxide micro-nano sheet has wide application prospects in the fields of cosmetics and sunscreen.
Drawings
Fig. 1 is an atomic force microscope image of titanium-containing oxide nanosheets in a titanium-containing oxide dispersion according to one embodiment of the present application.
Fig. 2 is an atomic force microscope image of titanium-containing oxide nanosheets in the titanium-containing oxide dispersion of example three of the present application.
FIG. 3 is a schematic view showing the Tyndall effect of the titanium oxide-containing dispersion of example two in the present application and the spherical titania dispersion of comparative example one.
FIG. 4 is a scanning electron micrograph of titanium-containing oxide nanosheets in the titanium-containing oxide dispersion according to example III of the present application; FIG. B is a graph showing a distribution energy spectrum of Ti element in (A); FIG. C is a distribution energy spectrum of Fe element in (A); FIG. D is a spectrum of the distribution energy of the O element in FIG. A.
FIG. 5 is a graph showing a transmittance spectrum in the ultraviolet visible light (280 to 700 nm) band of each of the titanium-containing oxide dispersions of examples two, three and first comparative examples.
FIG. 6 is a graph showing the comparison of the permeability of the titanium-containing oxide dispersions of examples two and comparative examples one to three of the present application in the Franz diffusion cell test at the same concentration.
FIG. 7 is a graph showing the comparison of permeability of the titanium-containing oxide dispersions of the third example and the second example of the present application in the Franz diffusion cell test at the same concentration.
Fig. 8A and 8B are scanning electron micrographs of titanium-containing oxide micro-nanosheets prepared in example four at different magnifications, respectively.
Fig. 9A and 9B are scanning electron micrographs of titanium-containing oxide micro-nanosheets prepared in example five and at different magnifications, respectively.
Fig. 10A and fig. 10B are scanning electron microscope images of titanium-containing oxide micro-nanosheets prepared in example six at different magnifications, respectively.
FIG. 11 is a graph showing the transmittance in the ultraviolet-visible (280-700 nm) band of each of the titanium-containing oxide dispersions of examples four to six of the present application and comparative example one.
Detailed Description
The following describes embodiments of the present invention in detail. The embodiments described below with reference to the accompanying drawings are illustrative only for the purpose of explaining the present invention, and are not to be construed as limiting the present invention.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
In this application, it should be noted that the micro-nano sheet means that the thickness of the sheet layer is in the range of nanometer or micrometer.
The application provides a preparation method of a sunscreen product with metal oxide micro-nano sheets, which comprises the following steps:
s100, providing a metal oxide dispersion liquid, a first emulsifier and an oil matrix, wherein the metal oxide dispersion liquid comprises metal oxide micro-nano sheets and water, and the metal oxide micro-nano sheets comprise at least one of titanium-containing oxide micro-nano sheets or zinc-containing oxide micro-nano sheets.
In some embodiments, the method of preparing metal oxide nanosheets further comprises one of a sinter-lift-off process, a hydrothermal process, a tube-sealing sintering process, or a chemical vapor deposition process.
In some embodiments, the metal oxide nanoplatelets are titanium oxide-containing nanoplatelets and the metal oxide dispersion is a titanium oxide-containing dispersion. The chemical formula of the titanium-containing oxide micro-nano sheet is Ti (1-x) O (2-2x) X is more than or equal to 0 and less than 1. The titanium-containing oxide micro-nanosheet is illustrated by taking a sintering-stripping method as an example, and the preparation method of the titanium-containing oxide dispersion liquid comprises the following steps:
s111, providing titanium dioxide, lithium carbonate and potassium carbonate.
S112, mixing titanium dioxide, lithium carbonate and potassium carbonate to obtain a first mixture, wherein the ratio of lithium carbonate: potassium carbonate: the molar ratio of titanium dioxide is 1:3: (12-13).
S113, sintering the first mixture in an air atmosphere at the temperature of 600-1800 ℃ for 15-28h to obtain a first sintered product.
In this step, lithium carbonate and potassium carbonate act on titanium dioxide at high temperature to give a first sintered product of a layered structure, which is an oxide formed from lithium titanium potassium.
In some embodiments, the sintering temperature may be 600 ℃, 800 ℃,1000 ℃, 1100 ℃, or 1800 ℃, and the sintering time may be 15h, 20h, 22h, 24h, or 28h.
S114, adding an acid solution into the first sintering product, and washing to obtain a first parent material.
In this step, an acidic solution was added to remove lithium and potassium from the first sintered product, and excess acidic solution was removed by deionized water.
In some embodiments, the acidic solution is at least one of hydrochloric acid, dilute nitric acid, acetic acid, or dilute sulfuric acid. The concentration of the acid solution is 0.5-1 mol/L, and the treatment time of the acid solution is 24-30 h.
S115, mixing the first matrix material with water and carrying out ultrasonic treatment to obtain the titanium-containing oxide dispersion liquid, wherein the chemical formula of the obtained titanium-containing oxide micro-nano sheet is Ti (1-x) O (2-2x) ，0≤x＜1。
The parent material and water are mixed and subjected to ultrasonic oscillation treatment, so that the lamella of the parent material is stripped, and the titanium-containing oxide micro-nano sheet is obtained. In some embodiments, the sonication time is 1-6 hours.
In some embodiments, the first precursor material is mixed with water and may also be exfoliated using ball milling, sanding, mechanical exfoliation, mechanical agitation, high speed shearing, high pressure homogenization, or microfluidization.
In some embodiments, prior to mixing the parent material with water, the parent material is further subjected to a pre-intercalation process comprising: adding organic alkali solution into the parent material, stirring and washing. The organic base solution includes an organic base and water. The organic base comprises at least one of tetrabutylammonium hydroxide, tetrapropylammonium hydroxide or trimethylethylammonium hydroxide.
Because the organic alkali solution contains large-group organic cations, the organic cations can be inserted between the lamellar layers of the lamellar parent material, so that the distance between the layers in the parent material is enlarged, and the nanosheet can be obtained conveniently by subsequent stripping. After the parent material is treated with the organic alkali solution, the parent material is washed with deionized water for a plurality of times to remove the organic alkali.
In some embodiments, the concentration of the organic base solution is 0.5 to 1mol/L, and the treatment time of the organic base solution is 1.5 to 2 hours.
In some embodiments, the concentration of the metal oxide dispersion is 0.1 to 5g/L, such as 0.1g/L, 0.5g/L, 1g/L, or 5g/L. The concentration herein means the mass ratio of the metal oxide nanosheets in 1L of solvent water.
In some embodiments, the metal oxide microsheet has a platelet diameter of 0.2 to 1 μm, such as 0.2 μm, 0.5 μm, 0.8 μm, or 1 μm.
In some embodiments, the titanium-containing oxide nanoplatelets have the chemical formula M a Ti (1-x-a) O (2-2x) X is more than or equal to 0 and less than 1, M is a metal element having the same period as Ti, for example, M is at least one of metal elements such as K, ca, sc, V, gr, ga, ge, cr, fe, ni, mn, cu, zn or Co, and the preparation method of the titanium-containing oxide dispersion liquid comprises the following steps:
s121, providing titanium dioxide, lithium carbonate, potassium carbonate and M 2 O 3 ；
S122, mixing titanium dioxide, lithium carbonate, potassium carbonate and M 2 O 3 Obtaining a second mixture;
s123, sintering the second mixture in an air atmosphere at the temperature of 600-1800 ℃ for 15-28h to obtain a second sintered product;
s124, adding an acidic solution into the second sintering product, and washing to obtain a second parent material;
and S125, mixing the second parent material with water and carrying out ultrasonic treatment to obtain the titanium-containing oxide dispersion liquid.
The above steps S121 to S125 are different from the steps S111 to S115 in that M is further added to the mixture of step S122 2 O 3 . Wherein, the ratio of titanium dioxide: m 2 O 3 The molar ratio of (0.1-0.4): 1. in step S123, at high temperature, lithium carbonate, potassium carbonate, titanium dioxide and M 2 O 3 The metal M replaces part of Ti to obtain a sintering product with a laminated structure, for example, when M is iron, the sintering product is an oxide formed by lithium titanium potassium iron. The rest is the same as the steps S113 to S115, and the titanium-containing oxide dispersion liquid is obtained, wherein the chemical formula of the titanium-containing oxide micro-nano sheet is M a Ti (1-x-a) O (2-2x) ，0≤x＜1。
In some embodiments, the metal oxide nanosheets are zinc-containing oxide nanosheets and the metal oxide dispersion is a zinc-containing oxide dispersion. The chemical formula of the zinc-containing oxide micro-nano sheet is ZnO. The preparation method of the zinc-containing oxide dispersion liquid comprises the following steps:
s131, providing zinc acetate and sodium hydroxide.
S132, adding water into the zinc acetate, dissolving to obtain a zinc acetate solution, adding sodium hydroxide into the zinc acetate solution, and adjusting the pH value of the solution to 13.
S133, placing the mixed solution obtained in the step S132 into a high-pressure reaction kettle with a polytetrafluoroethylene lining, wherein the reaction temperature is 130-250 ℃, and the reaction time is 24-28 h, so as to obtain a reaction product.
S134, separating the reaction product obtained in the step S133 to obtain a precipitate, washing the precipitate by using deionized water, treating by using sodium citrate, washing and drying to obtain the zinc oxide nanosheet.
S135, mixing the zinc oxide nano-sheets with water to obtain the zinc-containing oxide dispersion liquid.
In some embodiments, the zinc-containing oxide nanosheets have the chemical formula N b Zn (1-b) And O, wherein N is a metal element having the same period as Zn, for example, N is at least one of metal elements such as K, ca, sc, V, gr, ga, ge, cr, fe, ni, mn, cu, ti or Co. The preparation method of the zinc-containing oxide dispersion liquid comprises the following steps:
s141, providing zinc acetate, a salt solution and sodium hydroxide.
In some embodiments, the salt solution may be copper acetate, iron acetate, cobalt acetate, or the like.
S142, adding water into zinc acetate, dissolving to obtain a zinc acetate solution, adding the solution and sodium hydroxide into the zinc acetate solution, and adjusting the pH of the solution to 13, wherein the weight ratio of zinc acetate: the molar ratio of the salt is (0.1-0.4): 1.
s143, placing the mixed solution obtained in the step S142 into a high-pressure reaction kettle with a polytetrafluoroethylene lining, wherein the reaction temperature is 130-250 ℃, and the reaction time is 24-28 hours, so as to obtain a reaction product.
S144, separating the reaction product obtained in the step S143 to obtain a precipitate, washing the precipitate with deionized water, treating with sodium citrate, washing, and drying to obtain the zinc-containing oxide micro-nanosheet.
S145, mixing the zinc oxide nano-sheet with water to obtain the zinc-containing oxide dispersion liquid.
S200, mixing the first emulsifier with the oil matrix, and heating to obtain a mixed solution.
In the step, the first emulsifier and the oil matrix are uniformly mixed, and the first emulsifier is dissolved by heating treatment, so that the oil emulsifying efficiency of the first emulsifier is improved. In some embodiments, the oil base comprises at least one of liquid paraffin, glyceryl caprylate/caprate, jojoba oil, shea butter. The first emulsifier comprises at least one of cetearyl glucoside, methylgluco sesquistearate (PEG-20) or an alkyl glucoside, the number of carbon atoms in the alkyl glucoside being between 14 and 22.
In some embodiments, the heating temperature is 60-80 ℃ and the heating time is 15-40min.
S300, adding the metal oxide dispersion liquid into the mixed liquid, and heating to obtain the sunscreen product with the metal oxide nanosheets.
After the metal oxide dispersion liquid is added into the mixed liquid, the metal oxide dispersion liquid and the oil matrix become emulsion under the action of the first emulsifier. The sunscreen product is a water-in-oil emulsion, the metal oxide nanosheets are dispersed in water, the first emulsifier is formed at the interface of the metal oxide dispersion and the oil matrix, and the metal oxide nanosheets also play a role in stabilizing the emulsion in water.
In some embodiments, the first emulsifier is an oil phase emulsifier, which provides better emulsification of the metal oxide dispersion and the oil matrix than the water phase emulsifier.
According to the application, the metal oxide micro-nanosheets are introduced into an application system of the sunscreen product, and the optical transparency of the nanosheets in the visible light region is far higher than that of titanium dioxide nanoparticles under the condition of the same volume percentage concentration by utilizing the high specific surface area of the metal oxide micro-nanosheets, so that the optical transparency of the nanosheets in the visible light region is improved, and the phenomenon of whitening of the skin surface after being smeared is improved. And experiments prove that the ultraviolet light shielding material also has good ultraviolet light shielding property. Meanwhile, in the process of smearing the sunscreen product, the large transverse size and the high specific surface area of the metal oxide micro-nano sheets enable the sunscreen product to be evenly smeared on the surface of the skin and hardly penetrate through the horny layer of the skin in gaps of hundreds of nanometers, so that the penetration rate of the sunscreen product into the skin is reduced, and the biological safety and the skin color natural index of the sunscreen product are improved.
In some embodiments, a second emulsifier is added to the metal oxide dispersion before the metal oxide dispersion is added to the mixed liquor. And the second emulsifier is added to reduce the tension between the metal oxide micro-nano sheet and water, so that the stability of the metal oxide micro-nano sheet dispersion liquid is improved.
In some embodiments, the second emulsifier comprises at least one of the emulsifiers sodium stearoyl glutamate, sodium lauroyl glutamate or sodium cocoyl glutamate.
In the application, a first emulsifier and a second emulsifier are mixed and then jointly act on a metal oxide dispersion liquid and an oil substrate, the first emulsifier and the second emulsifier are distributed at the intersection of the metal oxide dispersion liquid and the oil substrate, a metal oxide nanosheet is dispersed in water to form a water-phase substrate, and a continuous-phase oil substrate is coated on the water-phase substrate to form a stable water-in-oil emulsion.
In some embodiments, the metal oxide dispersion and the second emulsifier are mixed and then heated at 60-80 ℃ for 15-40min. At this heating temperature and time, the emulsifying effect of the second emulsifier is improved, and the stability of the metal oxide dispersion is further improved. In this step, during the heating process, as water evaporates, deionized water needs to be added to ensure that the concentration of the metal oxide dispersion is constant.
In some embodiments, the heated metal oxide dispersion and the mixed solution are mixed and further placed in a homogenizer for homogenization before obtaining the sunscreen product, so as to improve the uniformity of the obtained sunscreen product, and the sunscreen product is obtained after natural cooling to the normal temperature. The sunscreen product forms a water-in-oil emulsion, so that the water phase of the metal oxide micro-nano sheet is coated by the oil matrix, and the metal oxide micro-nano sheet in the water phase in the sunscreen product is more uniform and stable.
In some embodiments, the homogenizer is operated at 10000-12000r/min for 1-2 min.
In some embodiments, the oil base is present in the sunscreen product in an amount of 20 to 50% by weight, e.g., 20%, 30%, 40% or 50% by weight. The addition amount of the first emulsifier is 0.5-15wt% of the oil base. For example, the first emulsifier can be 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 8wt%, 10wt%, or 15wt% of the oil-based substrate.
In some embodiments, the metal oxide dispersion is present in an amount of 50 to 80wt% of the sunscreen product, e.g., the metal oxide dispersion is present in an amount of 50wt%, 60wt%, 70wt%, or 80wt%. The second emulsifier is added in an amount of 0.1 to 10wt% based on the metal oxide dispersion, and the second emulsifier is in the above range so that the metal oxide dispersion is emulsified. Such as 0.1wt%, 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 8wt% or 10wt%.
In the sunscreen product, the metal oxide micro-nanosheet is present in an amount of 0.1 to 40wt%, such as 0.1wt%, 0.5wt%, 4wt%, 10wt%, 25wt% or 40wt%. The metal oxide micro-nano sheet accounts for less than 40wt% and has good dispersibility and stability. In some embodiments, the metal oxide nanoplatelets are present in an amount of 0.1 to 25wt%.
In some embodiments, the sunscreen product may be made into any of a sunscreen spray, a sunscreen cream, or a sunscreen cream.
The present application also provides a sunscreen product having metal oxide nanoplatelets, the sunscreen product comprising an aqueous phase matrix comprising metal oxide nanoplatelets and water, a first emulsifier, and an oil-based matrix. The sunscreen product may be a water-in-oil emulsion.
According to the application, the metal oxide micro-nano sheet is doped into the sunscreen product, and the metal oxide micro-nano sheet has the corresponding size of several micrometers to dozens of micrometers due to the fact that the metal oxide micro-nano sheet has the nanometer or micrometer thickness, so that the metal oxide micro-nano sheet has a high specific surface area, the optical transparency of the nano sheet in a visible light area is far higher than that of titanium dioxide nano particles under the condition of the same volume percentage concentration, the optical transparency of the visible light area of the sunscreen product is improved, the phenomenon that the skin surface is whitened after being smeared is improved, and the natural index of skin color is improved. Meanwhile, in the process of coating the sunscreen product, the large transverse size and high specific surface area of the metal oxide micro-nano sheet enable the sunscreen product to be uniformly coated on the surface of the skin and hardly penetrate through the horny layer of the skin with gaps of hundreds of nanometers, and the penetration rate of the sunscreen product into the skin is reduced, so that the biological safety of the sunscreen product is improved, and the metal oxide micro-nano sheet has wide application prospects in the fields of cosmetics and sun protection.
The scheme of the invention will be explained with reference to the following examples. It will be appreciated by those skilled in the art that the following examples are illustrative only and are not to be construed as limiting the invention. Reagents, software and equipment not specifically submitted to the following examples are conventional commercial products or open sources unless otherwise submitted.
Example one
1) Preparing a titanium-containing oxide dispersion:
providing raw materials of titanium dioxide, lithium carbonate and potassium carbonate, wherein the weight ratio of lithium carbonate: potassium carbonate: the molar ratio of titanium dioxide is 1:3:12. titanium dioxide, lithium carbonate and potassium carbonate were mixed to obtain a mixture. Sintering the mixture at 1000 ℃ for 15-24h in air atmosphere, and naturally cooling to obtain a sintered product K 0.8 Ti 1.7 Li 0.27 O 4 。
And adding 1mol/L dilute hydrochloric acid into the sintered product, stirring for 24 hours under the condition of magnetic stirring, and then washing for 3 times by using 500mL of deionized water to obtain a parent material.
1mol/L tetrabutylammonium hydroxide is added into the parent material and stirred for 2h. Mixing the parent material treated by tetrabutylammonium hydroxide with water, carrying out ultrasonic treatment and oscillation for 1h, and adjusting the concentration of the titanium-containing oxide dispersion liquid to 1.5g/L.
2) Preparing a sun-screening product:
1.5g/L titanium oxide-containing dispersion, shea butter, sodium stearyl glutamate, cetearyl glucoside are provided.
Under the condition of magnetic stirring, 50mL of titanium-containing oxide dispersion liquid and 0.5g of emulsifier sodium stearyl glutamate are heated and mixed at 80 ℃ to obtain water-phase mixed dispersion liquid. 20g of glyceryl caprylate/caprate and 0.8g of cetearyl glucoside as an emulsifier were mixed by heating at 80 ℃ under magnetic stirring to obtain an oil phase mixed dispersion. The aqueous phase mixed dispersion was added to the oil phase mixed dispersion under heating at 80 ℃ and water was supplemented to 100g. And then transferring the mixed water phase mixed dispersion liquid and oil phase mixed dispersion liquid to a homogenizer for homogenization, wherein the operation speed is 10000r/min, and the homogenization time is 1min. And cooling to normal temperature to obtain a sun-proof product, wherein the content of the titanium-containing oxide micro/nano tablets in the sun-proof product is 7.5wt%.
Example two
Example two differs from example one in that during the preparation of the sunscreen product, 27mL of the titanium-containing oxide dispersion and 0.5g of the emulsifier sodium stearyl glutamate were mixed under magnetic stirring with heating at 80 ℃ to give an aqueous phase mixture dispersion. In the sunscreen product, the content of the titanium-containing oxide micro-nano sheet is 4.0wt%. The remaining steps are the same as those of embodiment one.
EXAMPLE III
Example three differs from example two in the step of preparing a titanium-containing oxide dispersion:
providing raw materials of titanium dioxide, lithium carbonate, potassium carbonate and iron oxide, wherein the lithium carbonate: potassium carbonate: the molar ratio of titanium dioxide is 1:3:12, titanium dioxide: the molar ratio of iron oxide was 0.3. Titanium dioxide, lithium carbonate, potassium carbonate and iron oxide were mixed to obtain a mixture. Sintering the mixture at 1000 ℃ for 20h in the air atmosphere, naturally cooling,obtaining a sintered product K 0.8 Ti 1.2 Fe 0.4 Li 0.27 O 4 。
Example four
Example four differs from example one in that the precursor material and water were not mixed and then subjected to ultrasonic vibration in the preparation of the titanium-containing oxide dispersion, and the remaining steps were the same as those of example one.
EXAMPLE five
Example five differs from example one in that the precursor material and water were mixed and subjected to ultrasonic vibration for 2 hours in the preparation of the titanium-containing oxide dispersion, and the remaining steps were the same as those of example one.
EXAMPLE six
Example six differs from example one in that the precursor material and water were mixed and subjected to ultrasonic vibration for 4 hours in the preparation of the titanium-containing oxide dispersion, and the remaining steps were the same as those of example one.
Comparative example 1
Comparative example one differs from example two in that the "titanium-containing oxide dispersion" in example two was replaced with spherical titanium dioxide having a particle size of 30nm, and the remaining steps were the same as those of example two.
Comparative example No. two
Comparative example No. II is different from comparative example No. I in that the spherical titanium dioxide has a particle diameter of 50nm, and the remaining steps are the same as those of comparative example No.
Comparative example No. three
Comparative example three is different from comparative example one in that the spherical titanium dioxide has a particle size of 80nm, and the remaining steps are the same as those of comparative example one.
Table 1 preparation conditions of sunscreen products in examples one to six and comparative examples one to three
Figure BDA0003945121720000131
The titanium-containing oxide in the titanium-containing oxide dispersions prepared in examples one and three was subjected to a morphology test using an atomic force microscope. Referring to fig. 1 and 2, nanoplatelets are present in both fig. 1 and 2, indicating that nanoplatelets were produced in the titanium-containing oxide dispersions of examples one and three.
Referring to fig. 3, in fig. 3, (a) a bottle is the titanium oxide-containing nanosheet dispersion prepared in example two, and (B) a bottle is the spherical titanium dioxide in comparative example one at the same concentration. As can be seen from the above figures, the light transmittance of the (a) bottle is good, which indicates that the light transmittance of the titanium oxide-containing nanosheet is excellent as compared to that of spherical titanium dioxide. The dispersion liquid is also shown to be a relatively stable colloid in the application.
Referring to fig. 4, an EDS spectrometer was used to test the titanium oxide-containing nanosheets in the titanium oxide-containing dispersion prepared in example three. And (A) is a scanning electron microscope image of titanium-containing oxide micro-nano sheets prepared in the third example. It can be seen from the graphs (B) and (D) that the titanium element and the oxygen element are uniformly distributed, respectively. The iron element in the graph (C) is uniformly distributed, and the iron element is doped in the titanium-containing oxide micro-nanosheets.
The titanium-containing oxide dispersions prepared in example two, example three and comparative example one were subjected to ultraviolet visible light (280-700 nm) band test using an ultraviolet spectrophotometer. The concentrations of the titanium-containing oxide dispersions were the same in the first and second examples.
Referring to fig. 5 in combination with table 1, it is apparent from fig. 5 that, compared to comparative example one, shielding by reflection scattering is mainly used in the uv-visible light (280-700 nm) band range, and both uv and visible light are blocked, however, the use of the titanium-containing oxide micro-nanosheet characteristic absorption peak in example two and example three not only can ensure a certain uv shielding performance, but also has good light transmittance in the uv-visible light (280-400 nm) band range, which indicates that reflection scattering is very weak in example two and example three compared to comparative example one. Meanwhile, in the visible light (400-700 nm) waveband range, the light transmittance of the titanium oxide-containing micro-nano sheet in the second embodiment and the third embodiment is larger than that of the first embodiment, which shows that the titanium oxide-containing micro-nano sheet has high visible light transmittance, so that the skin color natural index is high. The concentrations of the titanium-containing oxide dispersion in the first and second examples are the same, and the titanium-containing oxide nanosheet in the first example also has high visible light transmittance.
The permeability of the titanium-containing oxide dispersions prepared in example two, example three and comparative examples one to three at equal concentrations was also tested using Franz (Franz) diffusion cells. Franz diffusion cell test transdermal absorption adopts Franz diffusion cell, skin (such as skin-imitated membrane, model: SKBM02560 Start-MMembrane) is clamped between a diffusion cell cover (donor) and a diffusion cell (acceptor), the inner surface of the skin is immersed in isotonic solution, constant-temperature circulating water keeps the constant-temperature working state of the diffusion cell, and constant-speed magnetic stirring ensures the uniform distribution of the isotonic solution. Transdermal absorption experiments were performed using Franz diffusion cells. Testing at 32 ℃ and RH55% under the condition that the concentration of a sample to be tested (a sun-proof product) is 1.0g/L, carrying out permeation for 24h, taking a lower layer solution after the permeation is finished, calibrating the permeation concentration by using an ultraviolet-visible spectrophotometer, and taking a blank sample as deionized water.
Referring to fig. 6 and 7, it can be seen from fig. 6 and 7 that the permeation content in comparative examples one to three is higher than that in example two under the same conditions, which shows that the titanium oxide-containing micro-nanosheets are able to reduce permeation well and thus reduce permeation into the stratum corneum of skin compared to spherical titanium dioxide. Also, in fig. 7, the amount of permeation of titanium oxide-containing nanoplatelets is significantly less in example three compared to the amount of permeation of comparative example two, which further illustrates that titanium oxide-containing nanoplatelets can reduce the permeation into the stratum corneum of skin. This shows that the titanium oxide-containing micro-nano sheet provided by the application has the advantage of low skin permeability, and the biosafety of the sunscreen product is improved.
The application also performs scanning electron microscope tests on the titanium-containing oxide micro-nano sheets prepared in the fourth to sixth examples. Referring to fig. 8A and 8B, fig. 8A and 8B are electron microscope images of different magnifications of the titanium-containing oxide micro-nanosheet of the fourth embodiment, respectively. From fig. 8A, it can be seen that a sheet structure with a micron sheet size is obtained, and in combination with fig. 8B, it can be seen that the thickness of the titanium-containing oxide micro-nano sheet is in the micron range, which indicates that a titanium-containing oxide sheet structure with a micron thickness is obtained.
Referring to fig. 9A and 9B, fig. 9A and 9B are electron microscope images of titanium-containing oxide micro-nanosheets of example v, respectively, at different magnifications. From fig. 9B, it can be seen that the thickness of the titanium-containing oxide micro-nanosheet is in the nanometer range, which illustrates that a titanium-containing oxide sheet structure with nanometer thickness is obtained.
Referring to fig. 10A and 10B, fig. 10A and 10B are electron micrographs of titanium-containing oxide micro-nanosheets of example six, respectively, at different magnifications. From fig. 10B, it can be seen that the thickness of the titanium-containing oxide nanosheets is in the nanometer range, illustrating that a nanometer-thickness titanium-containing oxide sheet structure is obtained. As can also be seen from fig. 8 to fig. 10, under the same conditions, the thickness of the titanium-containing oxide nanosheet obtained by stripping becomes thinner and thinner as the ultrasonic oscillation time increases.
The titanium oxide-containing dispersions of examples four to six and comparative example one were also tested for their transmittance in the ultraviolet visible (280-700 nm) band using an ultraviolet spectrophotometer. Referring to fig. 11, it can be seen that, as well, the examples four to six not only can ensure a certain uv shielding performance, but also have very good transmittance in the uv band range (280-400 nm), which indicates that the reflection scattering is very weak in the examples four to six compared to the comparative example one. Meanwhile, in the visible light (400-700 nm) waveband range, the light transmittance of the titanium oxide-containing micro-nano sheet in the fourth to sixth examples is greater than that of the first comparative example, which shows that the titanium oxide-containing micro-nano sheet has high visible light transmittance. And with the increase of the ultrasonic oscillation processing time of the titanium-containing oxide micro-nano sheet, the thinner the thickness of the titanium-containing oxide micro-nano sheet is, the higher the light transmittance of the titanium-containing oxide micro-nano sheet is, and the higher the skin color natural index is.
In the application, the steps of preparing the sunscreen product by the zinc-containing oxide micro-nano sheet are completely the same as the steps of preparing the sunscreen product by the titanium-containing oxide micro-nano sheet. Because zinc oxide and titanium oxide are both physical sunscreens, the characteristic absorption peak of visible light transmission/ultraviolet absorption of titanium oxide is about 350nm, the characteristic absorption peak of zinc oxide is about 370nm, both the zinc oxide and the titanium oxide have visible light transmission capability and do not have the characteristic absorption peak of visible light, the reflection scattering of the prepared zinc oxide-containing micro-nanosheets and titanium oxide-containing micro-nanosheets is reduced, and the zinc oxide-containing micro-nanosheets and titanium oxide-containing micro-nanosheets have high visible light transmittance. In addition, the zinc-containing oxide micro-nano sheet and the titanium-containing oxide micro-nano sheet are both ceramic materials, the properties of the micro-nano sheet structures are similar, the zinc-containing oxide micro-nano sheet has similar effects in sunscreen products, a water-in-oil emulsion can be formed, and the skin permeability is low.
Although the present invention has been described in detail with reference to the above embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the present invention.

Claims (14)

1. A sunscreen product having metal oxide nanoplatelets comprising an aqueous matrix comprising metal oxide nanoplatelets and water, a first emulsifier and an oil matrix.
2. The sunscreen product of claim 1, wherein said metal oxide nanoplatelets comprise at least one of titanium-containing oxide nanoplatelets or zinc-containing oxide nanoplatelets.
3. The sunscreen product of claim 2, wherein said titanium-containing oxide nanosheets have the formula Ti (1-x) O (2-2x) ，0≤x＜1。
4. The sunscreen product of claim 2, wherein said titanium-containing oxide nanosheets have the formula M a Ti (1-x-a) O (2-2x) X is more than or equal to 0 and less than 1, wherein M is a metal element with the same period as Ti.
5. The sunscreen product of claim 2, wherein said zinc-containing oxide nanoplatelets have a chemical formula of ZnO.
6. The sunscreen product of claim 2, wherein said zinc-containing oxide nanoplatelets have the chemical formula N b Zn (1-b) And O, wherein N is a metal element in the same period as Zn.
7. The sunscreen product of claim 1, wherein said metal oxide nanoplatelets are present in an amount of from 0.1 to 40wt% of the sunscreen product.
8. The sunscreen product of claim 1 wherein said first emulsifier comprises at least one of cetearyl glucoside, methyl glucosesquistearate, or an alkyl glucoside wherein the number of carbon atoms in said alkyl glucoside is between 14 and 22.
9. The sunscreen product of claim 1 wherein said first emulsifier is added in an amount of from 0.5 to 15% by weight of said oil base in said sunscreen product.
10. The sunscreen product of claim 1 further comprising a secondary emulsifier, said secondary emulsifier comprising at least one of sodium stearoyl glutamate, sodium lauroyl glutamate, or sodium cocoyl glutamate, said secondary emulsifier added in an amount of 0.1-10wt% of said aqueous phase base.
11. The sunscreen product of claim 1 wherein said oil base comprises at least one of liquid paraffin, glyceryl caprylate/caprate, jojoba oil, shea butter.
12. A method of making a sunscreen product comprising:
mixing an oil matrix and a first emulsifier, and heating to obtain a mixed solution;
adding a metal oxide dispersion liquid into the mixed solution, and heating to obtain a sunscreen product, wherein the metal oxide dispersion liquid comprises metal oxide micro-nano sheets and water, and the metal oxide micro-nano sheets comprise at least one of titanium-containing oxide micro-nano sheets or zinc-containing oxide micro-nano sheets.
13. The method of making a sunscreen product according to claim 12 further comprising:
before the metal oxide dispersion liquid is added into the mixed liquid, a second emulsifier is also added into the metal oxide dispersion liquid, the first emulsifier comprises an oil-phase emulsifier, and the second emulsifier is a water-phase emulsifier.
14. The method of preparing a sunscreen product according to claim 12 further comprising a method of preparing said metal oxide nanoplatelets, said method comprising:
one of a sintering-stripping method, a hydrothermal method, a tube-sealing sintering method or a chemical vapor deposition method is adopted.
CN202211430995.6A 2022-11-15 2022-11-15 Sunscreen product with metal oxide micro-nanosheets and preparation method thereof Pending CN115721580A (en)

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