KR102678098B1 - Sunscreen composition comprising surface modified cerium oxide particles and organic sunscreen and method of preparing the same - Google Patents

Abstract

A sunscreen composition comprising cerium oxide (CeO ₂ ) particles surface-modified with saturated or unsaturated fatty acid having a secondary particle size of 100 to 200 nm and an organic sunscreen, and a method for manufacturing the sunscreen composition are disclosed. The sunscreen composition may exhibit high sun protection factor (SPF) and PA index.

Description

Sunscreen composition comprising surface-modified cerium oxide particles and organic sunscreen and method for manufacturing same {SUNSCREEN COMPOSITION COMPRISING SURFACE MODIFIED CERIUM OXIDE PARTICLES AND ORGANIC SUNSCREEN AND METHOD OF PREPARING THE SAME}

The present invention relates to a sunscreen composition comprising cerium oxide (CeO ₂ ) particles surface-modified with saturated or unsaturated fatty acid having a secondary particle size of 100 to 200 nm and an organic sunscreen, and a method for producing the sunscreen composition. .

Since the first cosmetics containing sunscreen were developed in the United States in 1928, the demand for sunscreen has been steadily increasing. Sunscreen is used to prevent skin cancer, sunburn, and sun aging caused by ultraviolet rays. Recently, interest in preventing sun aging by blocking ultraviolet rays corresponding to UVA1 and UVA2 wavelengths for cosmetic purposes is increasing. In addition to sunscreen, UV blocking functions are added to most formulations such as BB cream, CC cream, cushion, sun spray, and sun stick.

To block ultraviolet rays, sunscreen is used, and it can be divided into organic sunscreen and inorganic sunscreen. Organic sunscreens typically include chemical blockers that convert light into heat, while inorganic sunscreens typically include physical blockers that reflect, scatter, and absorb light. Unlike basic cosmetics, sunscreen is used for the main purpose of attenuating ultraviolet rays in the upper epidermis, that is, in the outermost layer of the skin. However, organic sunscreens such as avobenzone have a small molecular size and are likely to penetrate the skin. Organic sunscreens have the advantage of less white cast and various absorption wavelengths, but they may cause skin problems or cause side effects such as stinging eyes when applied around the eyes in sensitive cases. On the other hand, inorganic sunscreens are relatively safe and have good blocking power, but since they are white pigments with a high refractive index, problems such as white clouding may occur. Due to the recent nature-friendly trend in cosmetic materials, there is a growing preference for sunscreen products in the 'inorganic sunscreen' formulation, which contains functional ingredients only from inorganic sunscreens, in Korea.

Titanium dioxide (TiO2) and zinc oxide (ZnO) are used as inorganic sunscreens, but they have various disadvantages. First, the energy band gaps of titanium dioxide and zinc oxide are 3.0 eV and 3.2 eV, respectively, which are advantageous for UVB and UVA2 absorption, so titanium dioxide and zinc oxide alone cannot absorb mid-wavelength UVA1. Second, titanium dioxide and zinc oxide have high refractive indices of 2.7 and 2.2, respectively, so a white clouding phenomenon may appear prominently when applied to the skin. Third, titanium dioxide and zinc oxide have a large photocatalytic power to decompose or denature organic substances, especially pigments, under light energy, which can cause denaturation of formulation ingredients and pigmentation. In particular, when the photocatalytic power is large, the surface must be covered with a second material for safety reasons. In the case of titanium dioxide, it is covered with aluminum oxide (Al2O3) or silicon dioxide (SiO2) at a maximum of 20 weight fraction or more. However, covering the surface with aluminum oxide and silicon dioxide has the disadvantage that the powder texture is heavy and does not apply smoothly, resulting in a stiff feeling when used. Therefore, there is a need to develop a sunscreen composition that can compensate for the above shortcomings.

Accordingly, while researching to solve the above problem, the present inventors found that when cerium oxide was surface modified with fatty acid and used as a sunscreen composition, UVA1 was absorbed, the white clouding phenomenon was suppressed due to the low refractive index, and the photocatalytic power was low. We discovered that a stable sunscreen composition can be formed and applied for it (Korean Patent Application No. 10-2017-0142617).

However, in the case of a sunscreen composition containing cerium oxide surface-modified with fatty acid as described above, the sun protection factor (SPF) and PA index may vary depending on the secondary size of the cerium oxide particles surface-modified with fatty acid. It was discovered that there was. In addition, it was found that when the sunscreen composition further contains an organic sunscreen, it can exhibit high sun protection factor (SPF) and PA index. Accordingly, while studying the effects of the SPF index and PA index according to the secondary size of the cerium oxide particles and the organic sunscreen, when the size of the secondary particles is 100 to 200 nm and the organic sunscreen is further included, the SPF index and PA index were found to be particularly high, thereby completing the present invention.

In this regard, Republic of Korea Patent No. 10-1600058 discloses metal oxide complex highly flat cellulose powder and cosmetics containing it.

The present invention was devised to solve the above-described problem, and one embodiment of the present invention is cerium oxide (CeO ₂ ) particles surface-modified with saturated or unsaturated fatty acids with a secondary particle size of 100 to 200 nm and an organic sunscreen. It provides a sunscreen composition containing a.

Additionally, another embodiment of the present invention provides a method for manufacturing the sunscreen composition.

The technical problem to be achieved by the present invention is not limited to the technical problem mentioned above, and other technical problems not mentioned can be clearly understood by those skilled in the art from the description below. There will be.

As a technical means for achieving the above-described technical problem, one aspect of the present invention is,

It includes cerium oxide (CeO ₂ ) particles surface-modified with a saturated fatty acid having 10 to 30 carbon atoms or an unsaturated fatty acid having 10 to 30 carbon atoms, and an organic sunscreen, wherein the cerium oxide (CeO ₂ ) has a primary particle size of 10 to 30. nm, the secondary particle size is 100 to 200 nm, and the ratio of the secondary particle size to the primary particle size is 3 to 20.

The saturated fatty acids having 10 to 30 carbon atoms include capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, and palmitate. Palmitic acid, Margaric acid, Stearic acid, Nonadecylic acid, Arachidic acid, Heneicosanoic acid, Behenic acid , Tricosanoic acid, Lignoceric acid, Pentacosanoic acid, Cerotic acid, Heptacosanoic acid, Montanic acid, Nonacosanoic acid It may contain a fatty acid selected from the group consisting of (nonacosanoic acid), melissic acid, and combinations thereof.

The unsaturated fatty acid having 10 to 30 carbon atoms may have a double bond number of 18:1 to 18:3 relative to the number of carbon atoms.

The unsaturated fatty acids having 10 to 30 carbon atoms include α-linolenic acid, linoleic acid, γ-linolenic acid, Dihomo-γ-linolenic acid, and palmylic acid. It may contain a fatty acid selected from the group consisting of palmitoleic acid, vaccenic acid, oleic acid, trans-Elaidic acid, and combinations thereof.

The content of the saturated fatty acid or unsaturated fatty acid may be 1 to 10 parts by weight based on 100 parts by weight of surface-modified cerium oxide (CeO ₂ ) particles.

The content of the surface-modified cerium oxide particles may be 1 to 50 parts by weight based on 100 parts by weight of the total sunscreen composition.

The organic sunscreen may include a substance selected from the group consisting of octyl methoxycinnamate, ethylhexylsalicylate, homosalate, and combinations thereof.

The content of the organic sunscreen may be 1 to 20 parts by weight based on 100 parts by weight of the total sunscreen composition.

The sunscreen composition may further include one or more particles selected from the group consisting of titanium oxide particles and zinc oxide particles.

The content of the titanium oxide particles may be 1 part by weight to 25 parts by weight based on 100 parts by weight of the total sunscreen composition, and the content of the zinc oxide particles may be 1 part by weight to 25 parts by weight based on 100 parts by weight of the total sunscreen composition.

In addition, another aspect of the present invention is,

Cerium hydroxide, cerium oxide, cerium carbonate, cerium nitrate, cerium chloride, ammonium cerium nitrate and their Obtaining cerium oxide (CeO ₂ ) particles by heat treating a material selected from the group consisting of combinations; Stirring the obtained cerium oxide particles with a saturated fatty acid or an unsaturated fatty acid to obtain cerium oxide (CeO ₂ ) particles surface-modified with a saturated fatty acid having 10 to 30 carbon atoms or an unsaturated fatty acid having 10 to 30 carbon atoms; Dispersing the cerium oxide (CeO ₂ ) particles surface-modified with the fatty acid in an organic solvent; and mixing the organic solvent and an organic sunscreen, wherein the cerium oxide (CeO ₂ ) surface-modified with the fatty acid has a primary particle size of 10 to 30 nm and a secondary particle size of 100 to 200 nm. and provides a method for producing a sunscreen composition in which the ratio of secondary particle size to primary particle size is 3 to 20.

The method of manufacturing the sunscreen composition includes mixing the organic solvent and the organic sunscreen agent with silicone oil, fiber, emulsifier, moisturizer, plasticizer, purified water, and combinations thereof. It may further include mixing with a material selected from the group consisting of.

According to one embodiment of the present invention, a sunscreen composition containing cerium oxide particles surface-modified with fatty acid with a secondary particle size of 100 to 200 nm and an organic sunscreen agent has a high sun protection factor (SPF). and PA index, and can exhibit excellent dispersion stability because layer separation does not occur even after a long period of time.

In addition, the sunscreen composition exhibits high dynamic viscosity in the low frequency range and residential frequency range, so the formulation has excellent emulsification/dispersion phase-stability and excellent spreadability, so it can be usefully used as a cosmetic composition for sunscreen.

Furthermore, the sunscreen composition according to an embodiment of the present invention is capable of absorbing UVA1 in the mid-ultraviolet wavelength range, so it can absorb ultraviolet rays in the entire UVA1 to UVA2 range, and has a high UV protection index, so it has an excellent UV blocking effect. .

Furthermore, since the sunscreen composition according to an embodiment of the present invention has a low light refractive index of particles, it does not cause a white clouding phenomenon when applied to the skin, and can be used as a sunscreen cosmetic composition that exhibits a natural color.

In addition, the sunscreen composition according to an embodiment of the present invention has high emulsibility in oil-in-water, water-in-oil, and non-aqueous formulations by surface-modifying the cerium oxide particles with saturated fatty acids or unsaturated fatty acids, so it can be used for sunscreen in various formulations. It can be used to prepare cosmetic compositions.

The effects of the present invention are not limited to the effects described above, and should be understood to include all effects that can be inferred from the configuration of the invention described in the detailed description or claims of the present invention.

Figure 1 is a graph showing the secondary particle size distribution of cerium oxide particles surface-modified with fatty acid according to an embodiment of the present invention.
Figure 2 is an FT-IR analysis graph showing whether the surface of cerium oxide particles has been modified according to an embodiment of the present invention.
Figure 3a is a graph showing the monochromatic protection factor (MPF) of a sunscreen composition containing an organic sunscreen according to an embodiment of the present invention.
Figure 3b is a graph showing the monochromatic protection factor (MPF) of a sunscreen composition that does not contain an organic sunscreen according to a comparative example of the present invention.

Hereinafter, the present invention will be described in more detail. However, the present invention can be implemented in various different forms, and the present invention is not limited to the embodiments described herein, and the present invention is only defined by the claims to be described later.

In addition, the terms used in the present invention are only used to describe specific embodiments and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly dictates otherwise. In the entire specification of the present invention, 'including' a certain element means that other elements may be further included rather than excluding other elements, unless specifically stated to the contrary.

The first aspect of the present application is,

It includes cerium oxide (CeO ₂ ) particles surface-modified with a saturated fatty acid having 10 to 30 carbon atoms or an unsaturated fatty acid having 10 to 30 carbon atoms, and an organic sunscreen, wherein the cerium oxide (CeO ₂ ) has a primary particle size of 10 to 30. nm, the secondary particle size is 100 to 200 nm, and the ratio of the secondary particle size to the primary particle size is 3 to 20.

Hereinafter, the sunscreen composition according to the first aspect of the present application will be described in detail.

In one embodiment of the present application, the cerium oxide particles are cerium hydroxide, cerium oxide, cerium carbonate, cerium nitrate, and cerium chloride. It can be manufactured from cerium precursors such as materials selected from the group consisting of ammonium cerium nitrate and combinations thereof, and any cerium oxide particles manufactured by a conventional cerium oxide manufacturing method can be used without particular limitation. You can.

In one embodiment of the present application, the cerium oxide particles may be plate-shaped, flake-shaped, or spherical, and there is no particular limitation on the shape of the cerium oxide particles.

In one embodiment of the present application, the cerium oxide (CeO ₂ ) particles may have a primary particle size of 3 to 35 nm, 5 to 32 nm, preferably 10 to 30 nm, and 2 The primary particle size may be 100 to 200 nm, preferably 100 to 150 nm, and the ratio of the secondary particle size to the primary particle size may be 1 to 55, or 3 to 50. , preferably 3 to 20.

In one embodiment of the present application, since the secondary particle size of the cerium oxide particles is 100 to 200 nm, the sunscreen composition containing it has a high sun protection factor (SPF) of 20 or more and a high sun protection factor (SPF) of 10 or more. It can have a PA index. In addition, the sunscreen composition can have a high sun protection factor (SPF) of 40 or more and a high PA index of 20 or more by further including an organic sunscreen in addition to the secondary size of the cerium oxide particles as described above, making it effective. This could be something very outstanding.

In one embodiment of the present application, the cerium oxide particles are included in the sunscreen composition according to the present invention and can absorb the wavelength of the UVA1 region, which is the mid-wavelength region of ultraviolet rays, thereby serving to expand the UV-blocking absorption region of the sunscreen composition. You can.

In one embodiment of the present application, the saturated fatty acid having 10 to 30 carbon atoms is capric acid, undecylic acid, lauric acid, tridecylic acid, and myrist. Myristic acid, Palmitic acid, Margaric acid, Stearic acid, Nonadecylic acid, Arachidic acid, Heneicosanoic acid ), Behenic acid, Tricosanoic acid, Lignoceric acid, Pentacosanoic acid, Cerotic acid, Heptacosanoic acid, Montanic acid It may contain a fatty acid selected from the group consisting of Montanic acid, Nonacosanoic acid, Melissic acid, and combinations thereof.

In one embodiment of the present application, the unsaturated fatty acid having 10 to 30 carbon atoms may have a double bond number of 18:1 to 18:3 relative to the number of carbon atoms.

In one embodiment of the present application, the unsaturated fatty acid having 10 to 30 carbon atoms is α-linolenic acid, linoleic acid, γ-linolenic acid, Dihomo-γ-linolenic acid (Dihomo -γ-linolenic acid, palmitoleic acid, vaccenic acid, oleic acid, trans-Elaidic acid, and combinations thereof. It may contain fatty acids.

In one embodiment of the present application, the saturated fatty acid having 10 to 30 carbon atoms or the unsaturated fatty acid having 10 to 30 carbon atoms is not limited to the types presented above, and may include all saturated or unsaturated fatty acids having a hydrocarbon ring having 10 to 30 carbon atoms. You can.

In one embodiment of the present application, the sunscreen composition can have excellent emulsification/dispersion phase-stability and excellent spreadability by surface-modifying cerium oxide particles with a fatty acid of a specific length of 10 to 30 carbon atoms. When surface modification is performed with fatty acids having 10 to 30 carbon atoms, emulsification is smooth and the dispersion stability of the formulation can be excellent. If the carbon number is less than 10, it may not properly associate with the oil phase due to the lack of lipophilicity, and if the carbon number is more than 30, when the cosmetic is manufactured and applied to the skin, the oily feeling may be excessive, which may impede the feeling of use.

In one embodiment of the present application, the content of the saturated fatty acid or unsaturated fatty acid may be 0.3 parts by weight to 15 parts by weight, and 0.5 parts by weight to 11 parts by weight, based on 100 parts by weight of the surface-modified cerium oxide (CeO ₂ ) particles. , preferably 1 to 10 parts by weight. When the content of the saturated fatty acid or unsaturated fatty acid is surface modified to less than 0.3 parts by weight, the entire cerium oxide particle is not surface modified, which may cause problems with emulsification/dispersion when manufactured with a solvent. In addition, when the surface modification is performed so that the content of the saturated fatty acid or unsaturated fatty acid exceeds 15 parts by weight, the excess fatty acid molecules remaining surrounding the surface of the particle are scattered and may act as impurities in the manufacture of cosmetics. Furthermore, if the fatty acid content is too small, the particle surface cannot be sufficiently coated, and if the fatty acid content is too high, it is scattered as excess molecules, which may act as an impurity during cosmetic production, causing rancidity of the cosmetic, and may impair the feeling of use due to excessive oiliness. there is.

In one embodiment of the present application, the cerium oxide particles, which are hydrophobic particles, can be made to have excellent emulsification/dispersion phase-stability by surface modifying the cerium oxide particles with fatty acid.

In one embodiment of the present application, the content of the surface-modified cerium oxide particles may be 1 part by weight to 50 parts by weight, 2 parts by weight to 40 parts by weight, and preferably 5 parts by weight, based on 100 parts by weight of the total sunscreen composition. It may be from 20 parts by weight to 20 parts by weight. If the content of the surface-modified cerium oxide particles is less than 1 part by weight, the content of the cerium oxide particles is too small to absorb the wavelength in the UVA1 region, and the effect of the sunscreen composition according to the present invention may not be exhibited, and the surface If the content of the modified cerium oxide particles exceeds 50 parts by weight, the solid content may be too high and the viscosity of the cosmetic may become too high, impairing spreadability. Additionally, if the content of the surface-modified cerium oxide particles is less than 1 part by weight, it may be difficult to expect a UV blocking effect.

In one embodiment of the present application, the organic sunscreen is a material selected from the group consisting of octyl methoxycinnamate, ethylhexylsalicylate, homosalate, and combinations thereof. It may contain, and preferably may contain octyl methoxycinnamate or homosalate. When the organic sunscreen contains octyl methoxycinnamate or homosalate, the sunscreen composition has a high sun protection factor (SPF) of 40 or more and a high PA index of 20 or more. It can be very effective.

In one embodiment of the present application, the content of the organic sunscreen may be 1 part by weight to 20 parts by weight, preferably 5 parts by weight to 10 parts by weight, more preferably 6 parts by weight, based on 100 parts by weight of the total sunscreen composition. It may be from 8 parts by weight to 8 parts by weight. If the content of the organic sunscreen is less than 1 part by weight compared to 100 parts by weight of the total sunscreen composition, the efficacy of the organic sunscreen may not be shown, and the UV protection index and PA index of the sunscreen composition may be low. If the content is more than 20 parts by weight, the organic sunscreen may not be effective. If the content of sunscreen is too high, dispersion stability may decrease.

In one embodiment of the present application, the sunscreen composition may further include one or more particles selected from the group consisting of titanium oxide particles and zinc oxide particles.

In one embodiment of the present application, the content of the titanium oxide particles may be 1 part by weight to 25 parts by weight, 2 parts by weight to 23 parts by weight, and preferably 5 parts by weight to 100 parts by weight of the total sunscreen composition. It may be 20 parts by weight. Additionally, the content of the zinc oxide particles may be 1 part by weight to 25 parts by weight, 2 parts by weight to 23 parts by weight, and preferably 5 parts by weight to 20 parts by weight, based on 100 parts by weight of the total sunscreen composition. At this time, the content ratio of the titanium oxide particles and zinc oxide particles can be used without particular limitation depending on the intended purpose and use as long as it does not impair the effect of the present invention.

In one embodiment of the present application, the sunscreen composition may further include an organic solvent, silicone oil, fiber agent, emulsifier, humectant, plasticizer, or purified water.

In one embodiment of the present application, the organic solvent may be alcohol, glycol, silicone oil, natural oil, vegetable oil, nut oil, or mineral oil. The organic solvent serves as a solvent for dispersing cerium oxide particles surface-modified with fatty acid. In addition, the organic solvent is capable of dispersing cerium oxide particles surface-modified with fatty acid, and any organic solvent suitable for preparing a cosmetic composition with a good spreadability can be used without particular limitation.

In one embodiment of the present application, the silicone oil may be dimethicone, cetyl dimethicone, cyclopentasiloxane, cyclohexasiloxane, or stearyl dimethicone. The silicone oil can form an oil phase when emulsifying cosmetics and plays a role in improving the feeling of use.

In one embodiment of the present application, the fiber agent such as VGL silk may be used. The fiber agent serves to improve the feeling of use of the sunscreen composition.

In one embodiment of the present application, the emulsifier may be a PEG silicone emulsifier, a nonionic W/O emulsifier, a cationic emulsifier, or an anionic emulsifier. The emulsifier allows each component of the sunscreen composition according to the present invention to be emulsified. In addition, it serves to improve the stability of the formulation by trapping the particles in the oily emulsion particles.

In one embodiment of the present application, the moisturizing agent is a natural moisturizing agent such as 1,2-hexanediol, glycerin, propylene glycol, butylene glycol, polyethylene glycol, polyol such as sorbitol or trehalose, amino acid, urea, lactate, or PCA-Na. Polymeric moisturizers such as factor (NMF), hyaluronic acid, chondroitin sulfate, or hydrolyzed collagen may be used. The moisturizing agent increases the moisturizing power of the sunscreen composition according to the present invention and can simultaneously act as a preservative.

In one embodiment of the present application, DPG (Dipropylene glycol) or the like may be used as the plasticizer.

In one embodiment of the present application, the sunscreen composition contains, in addition to the above components, fats and oils, waxes, surfactants, thickeners, pigments, cosmetic additives, powders, sugars, antioxidants, buffers, Ingredients commonly mixed in cosmetic compositions, such as various extracts, stabilizers, preservatives, and fragrances, can be appropriately mixed.

In one embodiment of the present application, the oil includes vegetable oil such as colostrum, rosehip oil, castor oil or olive oil, animal oil such as mink oil or squalene, mineral oil such as liquid paraffin or vaseline, silicone oil or myristin. Synthetic oils such as isopropyl acid may be used.

In one embodiment of the present application, the waxes may be vegetable waxes such as carnauba wax, candelilla wax, or jojoba oil, or animal waxes such as beeswax or lanolin.

In one embodiment of the present application, the surfactant may be an anionic surfactant, a cationic surfactant, an amphoteric surfactant, or a nonionic surfactant.

In one embodiment of the present application, the thickener may be, for example, a water-soluble polymer.

In one embodiment of the present application, the water-soluble polymer is a plant-based (polysaccharide-based) natural polymer such as guar gum, locast bean gum, queen's seed, carrageenan, galactan, gum arabic, tragacanth gum, pectin, mannan, or starch. , microbial (polysaccharide-based) natural polymers such as xanthan gum, textran, succinol glucan, cadran or hyaluronic acid, animal-based (protein-based) natural polymers such as gelatin, casein, albumin or collagen, methylcellulose, and ethylcellulose. , cellulose-based semi-synthetic polymers such as hydroxy, ethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose or methylhydroxypropyl cellulose, starch-based semi-synthetic polymers such as soluble starch, carboxymethyl starch or methyl starch, alginic acid propylene glycol ester or alginic acid. Alginic acid-based semi-synthetic polymers such as salts, other polysaccharide-based derivative semi-synthetic polymers, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl methyl ether, carboxyvinyl polymer or sodium polyacrylate, vinyl-based synthetic polymers, polyethylene oxide, and ethylene oxide. Alternatively, other synthetic polymers such as propylene oxide block copolymer, and inorganic materials such as betnite, laponite, microdispersed silicon oxide, and colloidal alumina may be used.

In one embodiment of the present application, the pigment may be, for example, a synthetic pigment or a natural pigment, and the synthetic pigment may be a water-soluble/oil-soluble dye such as FD&C Yellow No 6 or FD&C Red No 4, iron oxide, or ultramarine. Inorganic pigments, organic pigments such as D&C Red No 30 or D&C Red No 36, and lakes such as FD&C Yellow No 6 Al lake can be used, and the natural pigments include β-carotene, β-apo-8-carotene, and lyro. Carotenoid pigments such as pin, capxanthin, bixanthin, crocin or candaxanthin, flavonoid pigments such as cissonin, ramanin, ninocyanin, karsamine, safrol yellow, rutin, guellcetin or cacao pigment, Flavin-based pigments such as riboflavin, lacaic acid, carminic acid (cochinyl), kermesic acid, quinone-based pigments such as arizarin, cicholine, arcanine or nikinochrome, porphyrin-based pigments such as chlorophyll or hemoglobin, Diketone-based pigments such as quermine (dameric), betacyanidin-based pigments such as betanin, etc. may be used.

In one embodiment of the present application, the cosmetic additive may be, for example, a vitamin, a plant extract, or an animal extract, and the vitamin may include retinol (vitamin A), tocopherol (vitamin E), or ascorbic acid (vitamin X). The plant extract may be menthol (peppermint), azulene (chamomile), allantoin (wheat), caffeine (coffee), licorice extract, cinnamon extract, green tea extract, lavender extract, or lemon extract. Animal extracts include placenta (cow placenta), royal jelly (bee secretion), and snail extract (mucus secretion).

The second aspect of the present application is,

Cerium hydroxide, cerium oxide, cerium carbonate, cerium nitrate, cerium chloride, ammonium cerium nitrate and their Obtaining cerium oxide (CeO ₂ ) particles by heat treating a material selected from the group consisting of combinations; Stirring the obtained cerium oxide particles with a saturated fatty acid or an unsaturated fatty acid to obtain cerium oxide (CeO ₂ ) particles surface-modified with a saturated fatty acid having 10 to 30 carbon atoms or an unsaturated fatty acid having 10 to 30 carbon atoms; Dispersing the cerium oxide (CeO ₂ ) particles surface-modified with the fatty acid in an organic solvent; and mixing the organic solvent and an organic sunscreen, wherein the cerium oxide (CeO ₂ ) surface-modified with the fatty acid has a primary particle size of 10 to 30 nm and a secondary particle size of 100 to 200 nm. and provides a method for producing a sunscreen composition in which the ratio of secondary particle size to primary particle size is 3 to 20.

Detailed description of parts overlapping with the first aspect of the present application has been omitted, but the content described in the first aspect of the present application can be applied equally even if the description is omitted in the second aspect.

Hereinafter, the method for producing the sunscreen composition according to the second aspect of the present application will be described in detail.

First, in one embodiment of the present application, the method for producing the sunscreen composition includes cerium hydroxide, cerium oxide, cerium carbonate, cerium nitrate, and cerium. It includes obtaining cerium oxide (CeO ₂ ) particles by heat-treating a material selected from the group consisting of cerium chloride, ammonium cerium nitrate, and combinations thereof. The obtained cerium oxide particles are then added to purified water and stirred to prepare a supernatant. This is a process for dispersing the cerium oxide particles in purified water. Cerium oxide is used as a solvent phase so that the fatty acid can be evenly modified on the surface of the cerium oxide. It is a manufacturing process.

In one embodiment of the present application, the size of the cerium oxide particles used may be 0.01 to 1 μm, 0.05 to 0.5 μm, and preferably 0.08 to 0.2 μm. The amount of purified water is preferably 2 to 10 times the weight of cerium oxide.

Next, in one embodiment of the present application, the method for producing the sunscreen composition is to mix the obtained cerium oxide particles with saturated fatty acid or unsaturated fatty acid to form saturated fatty acid with 10 to 30 carbon atoms or unsaturated fatty acid with 10 to 30 carbon atoms. It includes obtaining surface-modified cerium oxide (CeO ₂ ) particles.

In one embodiment of the present application, the saturated fatty acid or unsaturated fatty acid may be dissolved in a solvent. In this case, the solvent is not particularly limited as long as it is an organic solvent, for example, alkyl benzoate, methylene chloride. It may be a solvent selected from the group consisting of (methylene chloride), xylene, dimethylformamide (DMF), nitrobenzene, methylethylketone, and combinations thereof. Additionally, the content of the saturated fatty acid or unsaturated fatty acid relative to 100 parts by weight of the solvent may be 1 part by weight to 5 parts by weight, and preferably 2 parts by weight.

In one embodiment of the present application, the mixing ratio of the cerium oxide particles and saturated fatty acid or unsaturated fatty acid may be 1:0.5 to 1.5, preferably 1:1.

In one embodiment of the present application, the stirring is not particularly limited as long as it uses a general stirring method. For example, it may be stirred through milling in a bead mill equipment.

In one embodiment of the present application, the saturated fatty acid having 10 to 30 carbon atoms is capric acid, undecylic acid, lauric acid, tridecylic acid, and myrist. Myristic acid, Palmitic acid, Margaric acid, Stearic acid, Nonadecylic acid, Arachidic acid, Heneicosanoic acid ), Behenic acid, Tricosanoic acid, Lignoceric acid, Pentacosanoic acid, Cerotic acid, Heptacosanoic acid, Montanic acid It may contain a fatty acid selected from the group consisting of Montanic acid, Nonacosanoic acid, Melissic acid, and combinations thereof.

In one embodiment of the present application, the unsaturated fatty acid having 10 to 30 carbon atoms may have a double bond number of 18:1 to 18:3 relative to the number of carbon atoms.

In one embodiment of the present application, the unsaturated fatty acid having 10 to 30 carbon atoms is α-linolenic acid, linoleic acid, γ-linolenic acid, Dihomo-γ-linolenic acid (Dihomo -γ-linolenic acid, palmitoleic acid, vaccenic acid, oleic acid, trans-Elaidic acid, and combinations thereof. It may contain fatty acids.

In one embodiment of the present application, the saturated fatty acid having 10 to 30 carbon atoms or the unsaturated fatty acid having 10 to 30 carbon atoms is not limited to the types presented above, and may include all saturated or unsaturated fatty acids having a hydrocarbon ring having 10 to 30 carbon atoms. You can.

In one embodiment of the present application, the stirring temperature may be 20 to 50°C, preferably 25 to 35°C, and the stirring time may be 10 to 180 minutes, preferably It may be 30 to 60 minutes, and the stirring speed may be 100 to 2,000 rpm, preferably 500 rpm to 1,000 rpm.

In one embodiment of the present application, the step of drying may be further included to remove the solvent used to dissolve the saturated fatty acid or unsaturated fatty acid after the stirring, wherein the drying is performed at a temperature of 30 to 80° C. It may be performed for 1 hour to 30 hours.

Next, in one embodiment of the present application, the method for producing the sunscreen composition includes dispersing the cerium oxide (CeO ₂ ) particles surface-modified with the fatty acid in an organic solvent.

In one embodiment of the present application, the step of dispersing the cerium oxide particles surface-modified with fatty acid in an organic solvent is a process of evenly dispersing the cerium oxide particles whose emulsification/dispersion power is increased by surface modification in the organic solvent. At this time, the organic solvent may be alkyl benzoate, ethyl alcohol, behenyl alcohol, phenethyl alcohol, glycol, or derivatives thereof. there is.

In one embodiment of the present application, the mixing ratio of the cerium oxide particles surface-modified with the fatty acid and the organic solvent may be 1:0.5 to 1.5, and preferably 1:1.

In one embodiment of the present application, the dispersion is not particularly limited as long as it uses a general dispersion method, and for example, it may be dispersed through milling in a bead mill equipment.

In one embodiment of the present application, the cerium oxide particles surface-modified with fatty acids recovered through the above process may have a secondary particle size of 100 to 200 nm.

Next, in one embodiment of the present application, the method for producing the sunscreen composition includes mixing the organic solvent and the organic sunscreen agent.

In one embodiment of the present application, the organic sunscreen is a material selected from the group consisting of octyl methoxycinnamate, ethylhexylsalicylate, homosalate, and combinations thereof. It may contain, and preferably may contain octyl methoxycinnamate or homosalate. When the organic sunscreen contains octyl methoxycinnamate or homosalate, the manufactured sunscreen composition has a high sun protection factor (SPF) of 40 or more and a high PA of 20 or more. Because it can have an index, it can be very effective.

In one embodiment of the present application, the content of the organic sunscreen may be 1 part by weight to 20 parts by weight, preferably 1 part by weight to 10 parts by weight, more preferably 5 parts by weight, based on 100 parts by weight of the total sunscreen composition. It may be from 10 parts by weight to 10 parts by weight. If the content of the organic sunscreen is less than 1 part by weight compared to 100 parts by weight of the total sunscreen composition, the efficacy of the organic sunscreen may not be shown, and the UV protection index and PA index of the sunscreen composition may be low. If the content is more than 20 parts by weight, the organic sunscreen may not be effective. If the content of sunscreen is too high, dispersion stability may decrease.

Next, in one embodiment of the present application, the method for producing the sunscreen composition includes mixing the organic solvent and the organic sunscreen agent, and then mixing the mixed organic solvent and the organic sunscreen agent with silicone oil, fiber, emulsifier, It may further include mixing with a material selected from the group consisting of a humectant, plasticizer, purified water, and combinations thereof.

In one embodiment of the present application, the step of mixing the organic solvent and the organic sunscreen with a material selected from the group consisting of silicone oil, fiber, emulsifier, humectant, plasticizer, purified water, and combinations thereof is dispersed in the organic solvent. This is the step of preparing a formulation that can be used as a cosmetic composition by mixing the cerium oxide particles with various mixtures for producing a cosmetic composition. At this time, the types of organic solvents, silicone oils, fibers, emulsifiers, moisturizers and plasticizers that can be used are as described in detail in the first aspect of the present application.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement it. However, the present invention may be implemented in many different forms and is not limited to the embodiments described herein.

Manufacturing example. Preparation of cerium oxide particles

Cerium oxide particles were prepared to prepare the sunscreen composition according to the present invention.

Cerium oxide particles were obtained by placing one of cerium hydroxide, cerium oxide, cerium carbonate, cerium nitrate, cerium chloride, and ammonium cerium nitrate in a crucible and heat treatment at 400 to 1200°C in a heating furnace.

Example 1. Preparation of a sunscreen composition containing cerium oxide particles surface-modified with stearic acid and having a secondary particle size of 152 nm and octyl methoxycinnamate.

Step 1: Preparation of cerium oxide particles surface-modified with stearic acid

50 g of stearic acid was added to 2,500 g of ethyl alcohol and stirred. After adding 2,500 g of cerium oxide particles prepared in the preparation example above to the prepared solution, a cerium oxide dispersion surface-modified with stearic acid was obtained through milling in a bead mill equipment. Thereafter, in order to remove the ethyl alcohol, the obtained cerium oxide dispersion was subjected to negative pressure in a vacuum oven, and then vacuum hot air dried at 60° C. for 24 hours to obtain surface-modified cerium oxide solid content.

Step 2: Preparation of sunscreen composition

After adding 1,000 g of the surface-modified cerium oxide solid obtained in step 1 to 1,000 g of alkyl benzoate, milling was performed in a bead mill equipment until dispersed to the desired particle size, thereby obtaining the secondary particle size. A cerium oxide solution containing 152.1 nm cerium oxide particles was prepared. Octyl methoxycinnamate as an organic sunscreen was mixed with the cerium oxide solution in an amount of 7 wt% based on the total weight of the sunscreen composition to be prepared thereafter. Afterwards, the prepared solution (54.55 wt%), silicone oil (DC 245, 10 wt%), fiber agent (VGL silk, 10 wt%), PEG silicone emulsifier (KF 6017, 3 wt%), nonionic W/ O A sunscreen composition was prepared by mixing an emulsifier (Abil em 90, 2.5 wt%), a moisturizer (1,2-Hexanediol, 2 wt%), a plasticizer (DPG, 10 wt%), and purified water (7.95 wt%). The secondary particle size distribution of the cerium oxide surface-modified with stearic acid was measured using a Nano zetasizer from Malvern, and is shown in Figure 1. As shown in Figure 1, it was confirmed that the secondary size of the cerium oxide particles surface-modified with stearic acid was mainly 150 nm. In addition, Figure 2 shows a graph in which FT-IR analysis was performed to confirm whether the surface of the cerium oxide particles was modified, through which it was confirmed that the cerium oxide particles were surface modified with stearic acid.

Example 2. Preparation of a sunscreen composition containing cerium oxide particles surface-modified with stearic acid and having a secondary particle size of 152 nm and ethylhexyl salicylate.

A sunscreen composition was prepared in the same manner as in Example 1, except that ethylhexyl salicylate was mixed instead of octyl methoxycinnamate as the organic sunscreen in step 2 of Example 1.

Example 3. Preparation of a sunscreen composition containing cerium oxide particles surface-modified with stearic acid and having a secondary particle size of 152 nm and homosalate.

A sunscreen composition was prepared in the same manner as Example 1, except that homosalate was mixed instead of octyl methoxycinnamate as the organic sunscreen in step 2 of Example 1.

Comparative example. Preparation of a sunscreen composition containing cerium oxide particles surface-modified with stearic acid and having a secondary particle size of 152 nm

A sunscreen composition was prepared in the same manner as Example 1, except that octyl methoxycinnamate was not mixed as an organic sunscreen in Step 2 of Example 1.

Experiment example. Ultraviolet protection factor (SPF) and PA index measurement experiment

In order to measure the sun protection factor (SPF) and PA index of the sunscreen compositions of the comparative examples and examples, SPF and PA were measured using SPF analyzer 290S from Laser components, UK. The results are shown in Table 1 below.

[Table 1]

As shown in Table 1, the sunscreen composition of the example containing cerium oxide particles with a secondary particle size of 152.1 nm and an organic sunscreen has higher SPF and PA than the sunscreen composition of the comparative example that does not contain an organic sunscreen. It was confirmed that it had an index. In particular, it was confirmed that the sunscreen composition containing octyl methoxycinnamate and homosalate of Examples 1 and 3 had an SPF index of 40 or more and a PA index of 20 or more, showing excellent efficacy.

In addition, the monochromatic blocking index (single wavelength blocking efficiency, MPF) of the sunscreen compositions of Example 1 and Comparative Example was measured and shown in FIGS. 3A and 3B, respectively. As shown in Figures 2a and 2b, it was confirmed that the sunscreen composition of the example containing an organic sunscreen had a significantly higher MPF index than the sunscreen composition of the comparative example that did not contain an organic sunscreen.

Claims (12)

Contains cerium oxide (CeO ₂ ) particles surface-modified with a saturated fatty acid having 10 to 30 carbon atoms or an unsaturated fatty acid having 10 to 30 carbon atoms, and an organic sunscreen,
The cerium oxide (CeO ₂ ) has a primary particle size of 10 to 30 nm,
The secondary particle size is 100 to 200 nm,
The ratio of secondary particle size to primary particle size is 3.34 to 20,
The content of the saturated fatty acid or unsaturated fatty acid is 1 to 10 parts by weight based on 100 parts by weight of the surface-modified cerium oxide (CeO ₂ ) particles,
The content of the organic sunscreen is 1 to 10 parts by weight based on 100 parts by weight of the total sunscreen composition,
The content of the surface-modified cerium oxide particles is 1 part by weight to 50 parts by weight based on 100 parts by weight of the total sunscreen composition.
According to paragraph 1,
The saturated fatty acids having 10 to 30 carbon atoms include capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, and palmitate. Palmitic acid, Margaric acid, Stearic acid, Nonadecylic acid, Arachidic acid, Heneicosanoic acid, Behenic acid , Tricosanoic acid, Lignoceric acid, Pentacosanoic acid, Cerotic acid, Heptacosanoic acid, Montanic acid, Nonacosanoic acid A sunscreen composition comprising a fatty acid selected from the group consisting of (nonacosanoic acid), melissic acid, and combinations thereof.
According to paragraph 1,
A sunscreen composition wherein the unsaturated fatty acid having 10 to 30 carbon atoms has a double bond number of 18:1 to 18:3 relative to the number of carbon atoms.
According to paragraph 1,
The unsaturated fatty acids having 10 to 30 carbon atoms include α-linolenic acid, linoleic acid, γ-linolenic acid, Dihomo-γ-linolenic acid, and palmylic acid. A sunscreen containing a fatty acid selected from the group consisting of palmitoleic acid, vaccenic acid, oleic acid, trans-Elaidic acid, and combinations thereof. Composition.
delete delete According to paragraph 1,
The organic sunscreen is a sunscreen composition comprising a material selected from the group consisting of octyl methoxycinnamate, ethylhexylsalicylate, homosalate, and combinations thereof. .
delete According to paragraph 1,
The sunscreen composition further includes one or more particles selected from the group consisting of titanium oxide particles and zinc oxide particles.
According to clause 9,
The content of the titanium oxide particles is 1 to 25 parts by weight based on 100 parts by weight of the total sunscreen composition,
A sunscreen composition in which the content of the zinc oxide particles is 1 part by weight to 25 parts by weight based on 100 parts by weight of the total sunscreen composition.
Cerium hydroxide, cerium oxide, cerium carbonate, cerium nitrate, cerium chloride, ammonium cerium nitrate and their Obtaining cerium oxide (CeO ₂ ) particles by heat treating a material selected from the group consisting of combinations;
Stirring the obtained cerium oxide particles with a saturated fatty acid or an unsaturated fatty acid to obtain cerium oxide (CeO ₂ ) particles surface-modified with a saturated fatty acid having 10 to 30 carbon atoms or an unsaturated fatty acid having 10 to 30 carbon atoms;
Dispersing the cerium oxide (CeO ₂ ) particles surface-modified with the fatty acid in an organic solvent; and
Mixing the organic solvent and an organic sunscreen;
Including,
Cerium oxide (CeO ₂ ) surface-modified with the fatty acid has a primary particle size of 10 to 30 nm, a secondary particle size of 100 to 200 nm, and a ratio of secondary particle size to primary particle size of 3.34 to 3.34 nm. 20,
In the step of obtaining cerium oxide (CeO ₂ ) particles surface-modified with a saturated fatty acid having 10 to 30 carbon atoms or an unsaturated fatty acid having 10 to 30 carbon atoms by stirring the obtained cerium oxide particles with a saturated fatty acid or unsaturated fatty acid, saturated fatty acid or The content of unsaturated fatty acid is 1 to 10 parts by weight based on 100 parts by weight of surface-modified cerium oxide (CeO ₂ ) particles,
The content of the organic sunscreen is 1 to 10 parts by weight based on 100 parts by weight of the total sunscreen composition,
In the step of dispersing the cerium oxide (CeO ₂ ) particles surface-modified with fatty acid in an organic solvent, the content of the cerium oxide particles surface-modified with fatty acid is 1 part by weight to 50 parts by weight based on 100 parts by weight of the total sunscreen composition. Method for producing a barrier composition.
According to clause 11,
The method for producing the sunscreen composition includes mixing the organic solvent and the organic sunscreen agent,
A method for producing a sunscreen composition further comprising mixing the mixed organic solvent and organic sunscreen agent with a material selected from the group consisting of silicone oil, fiber, emulsifier, moisturizer, plasticizer, purified water, and combinations thereof. .