CN109771306B - Inorganic-organic sunscreen agent composite microsphere and preparation method thereof - Google Patents
Inorganic-organic sunscreen agent composite microsphere and preparation method thereof Download PDFInfo
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- CN109771306B CN109771306B CN201910001997.5A CN201910001997A CN109771306B CN 109771306 B CN109771306 B CN 109771306B CN 201910001997 A CN201910001997 A CN 201910001997A CN 109771306 B CN109771306 B CN 109771306B
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Abstract
The invention discloses an inorganic-organic sun-screening agent composite microsphere, which comprises a polymer microsphere, inorganic sun-screening agent nanoparticles and an organic sun-screening agent, wherein the inorganic sun-screening agent nanoparticles are loaded on the surface of the polymer microsphere; organic sunscreen agents are encapsulated within the polymeric microspheres. The sun-proof effect of full wave band has, and this application excitement is low, the security is good.
Description
Technical Field
The invention relates to the field of daily chemical industry, in particular to an inorganic-organic sunscreen composite microsphere and a preparation method thereof.
Background
With the continuous improvement of the pursuit of people for skin beauty and health, the sunscreen becomes the fastest branch of the development of daily chemicals. China belongs to the new market of sunscreen products, and the development potential of sunscreen cosmetics is still huge. Ultraviolet bands having skin-damaging effects in sunlight include short-wave UVB (290-320nm) which causes immediate damage to the skin (e.g., erythema, sunburn) and long-wave UVA (320-400nm) which penetrates deep into the dermis and generates Reactive Oxygen Species (ROS), which are important factors in causing photoaging and even lesions of the skin. The core functional component of the sunscreen product is a sunscreen agent, and the existing commercial sunscreen agents comprise organic sunscreen agents (such as octyl methoxycinnamate, p-aminobenzoic acid, benzophenone-3 and the like) and inorganic sunscreen agents (TiO2 and ZnO). Currently, consumers increasingly pay more attention to the broad-spectrum protection function (simultaneously protecting UVA and UVB) of sunscreen products, so that most products adopt a formula design of compounding an inorganic sunscreen agent and an organic sunscreen agent, and high sun protection index and broad-spectrum protection performance can be simultaneously realized by utilizing the complementary absorption wave bands of different sunscreen agents. However, the existing various inorganic and organic sunscreen raw materials generally have the problems of human body safety risk, poor use feeling and the like. On one hand, most of organic sunscreen agents are aromatic compounds, are easy to degrade and generate ROS under the induction of ultraviolet rays, increase skin allergy, aging and lesion risks, can penetrate into dermis through cuticle or hair follicles and are absorbed by the whole body to cause potential safety hazards, and meanwhile, the organic sunscreen agents are greasy in skin feel. On the other hand, inorganic sunscreen nanoparticles also have the risks of hair follicle accumulation and percutaneous absorption, and generate ROS to cause adverse skin reactions; in order to obtain an ideal protection effect, high-concentration inorganic nano-particles (10-30%) are often added in the formula, the particles are easy to agglomerate to generate obvious whitening feeling, and the skin feeling is thick and poor in usability. Currently, the increasing consumer demand places higher demands on low irritation, safety and good use feel of sunscreens. The above problems are problems that the art needs to solve.
Disclosure of Invention
The invention aims to provide an inorganic-organic sunscreen composite microsphere which has a full-wave band sunscreen effect, low irritation and good safety and a preparation method thereof.
In order to solve the technical problem, the invention provides the following scheme: an inorganic-organic sunscreen composite microsphere comprising a polymeric microsphere;
inorganic sunscreen nanoparticles supported on the surface of the polymeric microspheres;
an organic sunscreen agent encapsulated within the polymeric microspheres.
Further, the method comprises the following steps: the polymeric microspheres have a size of 0.1 to 200 μm.
Further, the method comprises the following steps: the inorganic sunscreen nanoparticles are zinc oxide or titanium dioxide nanoparticles.
Further, the method comprises the following steps: the organic sunscreen agent is one or two of avobenzone, octocrylene, ethylhexyl methoxycinnamate, ethylhexyl dimethyl PABA, ethylhexyl salicylate, triethanolamine salicylic acid, phenyl benzimidazole sulfonic acid and its potassium, sodium and triethanolamine salt, benzophenone-3, p-xylylene dicamphor sulfonic acid, and diethyl amino hydroxybenzoyl hexyl benzoate.
Further, the method comprises the following steps: the polymer microsphere is one of methyl methacrylate cross-linked polymer, vinyl dimethyl siloxane/methyl siloxane silsesquioxane cross-linked polymer and polystyrene microsphere.
The application further provides a preparation method of the inorganic-organic sunscreen composite microsphere, which comprises the following steps: the method comprises the following steps:
mixing a polymer monomer and the organic sunscreen agent according to a mass ratio of 1: 0.05-1: 0.5 to form an oil phase;
dispersing the inorganic sunscreen nanoparticles in water to form an aqueous dispersion, wherein the inorganic sunscreen nanoparticles account for 0.01-10% of the aqueous dispersion by mass;
mixing and homogenizing the oil phase, the water dispersant and the polymerization reaction catalyst/initiator to form emulsion, and reacting for 1-24 hours at the temperature of 20-60 ℃;
and drying the emulsion to obtain the inorganic-organic sunscreen agent composite microspheres.
Further, the method comprises the following steps: the inorganic sunscreen agent nano particles in the water dispersion agent are 0.5-3% by mass.
Further, the method comprises the following steps: when the polymeric microspheres are methyl methacrylate crosspolymers, the polymeric monomer is methyl methacrylate,
when the polymeric microspheres are vinyl dimethicone/methyl silsesquioxane crosspolymers, the polymeric monomer is a mixture of vinyl terminated silicone oil and hydrogen containing silicone oil,
when the polymeric microspheres are polystyrene microspheres, the polymeric monomer is styrene.
Further, the method comprises the following steps: the aqueous dispersion also comprises 0.1-1.0 wt% of nano silicon dioxide and/or 10-5～10-3mol/L hexadecyltrimethylammonium bromide.
Further, the method comprises the following steps: the polymerization catalyst or initiator accounts for 0.001-0.1 wt% of the oil phase.
The invention has the beneficial effects that: (1) the organic sunscreen agent is embedded in the polymer microspheres, so that greasiness and degradation loss can be avoided, and the inorganic sunscreen agent is uniformly and dispersedly coated on the surfaces of the microspheres, so that agglomeration and whitening can be avoided;
(2) the inorganic and organic sunscreens are compounded synergistically, and the optimal ultraviolet full-wave band (UVA + UVB) protection effect is obtained by optimizing the type and the proportion;
(3) the polymer spheres have the functions of embedding the organic sun-screening agent and loading the inorganic nano sun-screening agent, prevent the sun-screening agent from permeating into skin or hair follicles, inhibit the generation of ROS, realize the space isolation of the inorganic sun-screening agent and the organic sun-screening agent, obviously reduce the photodegradation and skin irritation of the organic sun-screening agent and have excellent human body safety.
Drawings
FIG. 1(a) is a photomicrograph of the emulsion of example 1; (b) is an SEM image of the inorganic-organic sunscreen composite microspheres of example 1.
FIG. 2 is a photograph showing (a) the oxygen radical fluorescence staining of the inorganic-organic sunscreen composite microsphere in example 1, (b) the oxygen radical fluorescence staining of the organic sunscreen, and (c) the oxygen radical fluorescence intensity vs. histogram.
Detailed Description
The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.
An inorganic-organic sunscreen composite microsphere includes a polymeric microsphere, an inorganic sunscreen nanoparticle, and an organic sunscreen.
Wherein, the inorganic sunscreen nanoparticles are loaded on the surface of the polymer microsphere, in particular, the inorganic sunscreen nanoparticles are zinc oxide or titanium dioxide nanoparticles.
The organic sunscreen agent is one or two of butyl methoxy dibenzoyl methane (avobenzone), octocrylene, ethylhexyl methoxycinnamate, dimethyl PABA ethylhexyl salicylate, triethanolamine salicylic acid, phenyl benzimidazole sulfonic acid and potassium, sodium and triethanolamine salts thereof, benzophenone-3, p-xylylene dicamphor sulfonic acid, and diethyl hydroxyamphor benzoyl benzoic acid hexyl ester.
The size of the polymeric microsphere is 0.1-200 mu m, and specifically, the polymeric microsphere is one of methyl methacrylate cross-linked polymer, vinyl polydimethylsiloxane/methyl siloxane silsesquioxane cross-linked polymer and polystyrene microsphere.
According to the application, the organic sunscreen agent is embedded in the polymer microsphere, and the inorganic sunscreen agent nano particles are loaded on the surface of the polymer microsphere, so that the optimal protective performance of the composite sunscreen agent is realized, and the problems of safety and usability of the inorganic and organic sunscreen agents are solved.
In order to facilitate the understanding of the present application, the present application further provides the following specific examples:
example 1
Adjusting pH of 0.9g nanometer titanium dioxide (particle diameter of 10-25nm, anatase type) to 3, and performing ultrasonic treatment for 5min to obtain water dispersant, wherein the water dispersant is used as water phase;
weighing 4.3g of hydrogen-containing silicone oil (PMHS, the hydrogen content is 3%), 7.5g of avobenzone and 10.7g of vinyl-terminated silicone oil (Vi-PDMS), and uniformly mixing to obtain an oil phase;
mixing the above water phase and oil phase, and adding 2 × 10－5Homogenizing the chloroplatinic acid catalyst (calculated by the mass fraction of Pt in a mixture of PMHS and Vi-PDMS) at 20000r/min for 2min to obtain white emulsion, reacting at 25 ℃ in the dark for 24h, and drying and grinding the product at 60 ℃ to obtain the inorganic-organic sunscreen agent composite microspheres.
As shown in fig. 1(a) and (b), as can be seen from the SEM images of the microspheres and the micrographs of the emulsion, the microspheres had a particle size of 3 to 20 μm; ultraviolet light tests show that the inorganic-organic sunscreen composite microspheres have a full-wave band sunscreen effect; oxygen free radical test is carried out on the inorganic-organic sunscreen agent composite microsphere, as shown in figure 2, which shows that the inorganic-organic sunscreen agent composite microsphere can effectively reduce oxygen free radicals generated by the degradation of avobenzone.
Example 2
0.15g of zinc oxide (particle size 30nm) was dispersed to 30g of 10 by sonication-4Adding 0.15g of nano silicon dioxide (about 16 nm) into mol/L Cetyl Trimethyl Ammonium Bromide (CTAB) aqueous solution, adjusting the pH value to 4, and performing ultrasonic treatment for 5min to obtain water dispersant, wherein the water dispersant is used as a water phase for later use;
weighing 9g of Methyl Methacrylate (MMA), adding 0.45g of p-xylylene dicamphor sulfonic acid (Mexican filter ring), and mixing uniformly to obtain an oil phase;
mixing the water phase and the oil phase, adding 0.3g of potassium persulfate (KPS) as a catalyst, homogenizing at 20000r/min for 2min to obtain a white emulsion, introducing nitrogen, stirring at 20 ℃ in the dark for 12h, simply filtering the product, and vacuum drying at 40 ℃ in the dark for 36h to obtain the PMMA microsphere with the Maifanin filter ring encapsulated inside and titanium dioxide loaded on the surface.
The particle size of the microsphere is 0.1-10 μm; ultraviolet light tests show that the inorganic-organic sunscreen composite microspheres have a full-wave band sunscreen effect; oxygen free radical tests show that the compound can reduce oxygen free radicals generated by degrading Mexicanin filtering rings and can prolong the degradation time of the Mexicanin filtering rings to a certain extent.
Example 3
Dispersing 0.6g of nano titanium dioxide (the particle size is 100nm) into 30g of 10-4mol/LCTAB solution by using ultrasonic waves, and performing ultrasonic treatment for 10min to obtain a water dispersing agent which is used as a water phase for later use;
weighing 20g of styrene, 3g of Octocrylene (OCR) and 3g of ethylhexyl methoxycinnamate (EHMC) and uniformly mixing to obtain an oil phase;
mixing the water phase and the oil phase, adding 0.2g of azobisisobutyronitrile as a catalyst, homogenizing at 20000r/min for 5min to obtain a white emulsion, reacting at 60 ℃ in the dark for 1h, vacuum drying the product at 40 ℃ for 36h, and grinding to obtain the PS microspheres with ORC and EHMC being contained inside and zinc oxide being loaded on the surfaces.
The particle size of the microspheres is 100-200 mu m; ultraviolet light tests show that the inorganic-organic sunscreen composite microspheres have a full-wave-band sunscreen effect which is 2 times higher than that of zinc oxide alone and ORC and EHMC; the oxygen free radical test shows that the oxygen free radical generated by degrading ORC and EHMC can be reduced, and the degradation time of ORC and EHMC can be prolonged to a certain extent.
Example 4
Dispersing 0.6g of nano zinc oxide (with the particle size of 40nm) into 30g of 10-4mol/L CTAB solution by using ultrasonic, adjusting the pH value to 4, and performing ultrasonic treatment for 10min to obtain a water dispersing agent which is used as a water phase for later use;
weighing 20g of styrene, 4g of benzophenone-3 and 2g of bis-ethylhexyloxyphenol methoxyphenyl triazine, and uniformly mixing to obtain an oil phase;
mixing the water phase and the oil phase, adding 0.2g of azobisisobutyronitrile as a catalyst, homogenizing at 20000r/min for 5min to obtain a white emulsion, reacting at 60 ℃ in the dark for 1h, vacuum drying the product at 40 ℃ for 36h, and grinding to obtain the PS microspheres which are internally coated with the organic sunscreen agent and have zinc oxide loaded on the surfaces.
The average particle size of the microspheres is 60-100 mu m; ultraviolet light tests show that the inorganic-organic sunscreen agent composite microspheres have a full-wave-band sunscreen effect which is 2-3 times higher than that of zinc oxide alone and benzophenone-3 and bis-ethylhexyloxyphenol methoxyphenyl triazine; oxygen free radical tests show that the composition can reduce oxygen free radicals generated by degradation of an organic sunscreen agent, and transdermal absorption experiments show that the composition can effectively reduce the absorption of the skin on benzophenone-3.
The inorganic sunscreen nanoparticles are directly used as an emulsifier, an oil-water system containing a polymer monomer, an organic sunscreen agent and a solvent is emulsified and stabilized, and then emulsion polymerization is carried out to obtain the composite microsphere. The inorganic nano-particles can play the role of an emulsifier and can be coated on the surface of the microsphere without using a surfactant, and the preparation method is simple, convenient and green; the obtained composite microsphere has strong anti-caking property, easy dispersion and smooth and dry skin.
According to the application, the organic sunscreen agent is embedded in the polymer microspheres, so that greasiness and degradation loss can be avoided, and the inorganic sunscreen agent is uniformly and dispersedly coated on the surfaces of the microspheres, so that agglomeration and whitening can be avoided.
According to the ultraviolet protection film, the inorganic sunscreen agent and the organic sunscreen agent are compounded in a synergistic manner, and the best ultraviolet full-wave band (UVA + UVB) protection effect is obtained by optimizing the type and the proportion.
The polymer microspheres prepared by the method can provide smooth and dry skin feeling, adjust the oil absorption according to the requirements of different skin types, and are suitable for various dry and oily skins.
In the application, the polymer spheres have the functions of embedding the organic sun-screening agent and loading the inorganic nano sun-screening agent, prevent the sun-screening agent from permeating into skin or hair follicle and inhibiting the generation of ROS, realize the space isolation of the inorganic sun-screening agent and the organic sun-screening agent, can obviously reduce the photodegradation and skin irritation of the organic sun-screening agent, and have excellent human body safety.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.
Claims (6)
1. An inorganic-organic sunscreen composite microsphere comprising a polymeric microsphere;
inorganic sunscreen nanoparticles supported on the surface of the polymeric microspheres;
an organic sunscreen agent encapsulated within the polymeric microspheres;
the polymeric microspheres have a size of 0.1 to 200 μm;
the inorganic sunscreen nanoparticles are zinc oxide or titanium dioxide nanoparticles;
the polymer microsphere is one of methyl methacrylate cross-linked polymer, vinyl polydimethylsiloxane, methyl silsesquioxane cross-linked polymer and polystyrene microsphere.
2. The inorganic-organic sunscreen composite microspheres according to claim 1, wherein the organic sunscreen agent is one or two of avobenzone, octocrylene, ethylhexyl methoxycinnamate, ethylhexyl dimethyl PABA, ethylhexyl salicylate, triethanolamine salicylic acid, phenylbenzimidazole sulfonic acid and potassium, sodium and triethanolamine salts thereof, benzophenone-3, p-xylylene dicamphor sulfonic acid, and diethyl oxybenzoyl hexyl benzoate.
3. A method for preparing the inorganic-organic sunscreen composite microspheres according to any one of claims 1 to 2, comprising the steps of:
mixing a polymer monomer and the organic sunscreen agent according to a mass ratio of 1: 0.05-1: 0.5 to form an oil phase;
dispersing the inorganic sunscreen nanoparticles in water to form an aqueous dispersion, wherein the inorganic sunscreen nanoparticles account for 0.01-10% of the aqueous dispersion by mass;
mixing and homogenizing the oil phase, the water dispersion and a polymerization reaction catalyst or an initiator to form an emulsion, and reacting for 1-24 hours at the temperature of 20-60 ℃;
and drying the emulsion to obtain the inorganic-organic sunscreen agent composite microspheres.
4. The method according to claim 3, wherein the inorganic sunscreen nanoparticles are present in the aqueous dispersion in an amount of 0.5 to 3% by mass.
5. The method according to claim 3, wherein the aqueous dispersion further comprises nano silica and/or cetyltrimethylammonium bromide, the nano silica is contained in the aqueous dispersion in an amount of 0.1 to 1.0wt%, and the concentration of the cetyltrimethylammonium bromide in the aqueous dispersion is 10-5～10-3mol/L。
6. The method of claim 3, wherein the polymerization catalyst or initiator is 0.001 to 0.1wt% of the oil phase.
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| CN114569478A (en) * | 2020-11-30 | 2022-06-03 | 中国科学院理化技术研究所 | Amphiphilic sunscreen microsphere and preparation method and application thereof |
| CN112545907B (en) * | 2020-12-16 | 2022-02-22 | 江南大学 | Preparation method of wax beads with embedded chemical sun-screening agent and surface loaded with nano titanium dioxide and application of wax beads in sunscreen cream |
| CN117398322A (en) * | 2023-12-13 | 2024-01-16 | 广州悦瑞化妆品有限公司 | Microbead essence and preparation method thereof |
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