JP7408890B2 - sunscreen cosmetics - Google Patents

Description

The present invention relates to a water-in-oil emulsion sunscreen cosmetic.

Sunscreen cosmetics contain fine powder of metal oxide in order to obtain a high SPF (Sun Protection Factor) effect. It is known that this metal oxide has a strong ultraviolet shielding effect. In recent years, there has been a trend to incorporate large amounts of ultraviolet scattering agents and ultraviolet absorbers made of metal oxides into sunscreen cosmetics. An organic ultraviolet absorber is also added to absorb ultraviolet rays. Examples of organic UV absorbers include salicylic acids such as homomenthyl salicylate, octyl salicylate, and triethanolamine salicylate; para-aminobenzoic acid, ethyl dihydroxypropyl para-aminobenzoic acid, glyceryl para-aminobenzoic acid, octyldimethyl para-aminobenzoic acid, and para-dimethylaminobenzoic acid. PABA series such as amyl, 2-ethylhexyl paradimethylaminobenzoate; 4-(2-β-glucopyranosiloxy)propoxy-2-hydroxybenzophenone, dihydroxydimethoxybenzophenone, dihydroxydimethoxybenzophenone sodium disulfonate, 2-hydroxy -4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfuric acid, 2,2'-dihydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2,2'4,4'-tetrahydroxybenzophenone , 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-N-octoxybenzophenone, and other benzophenones; 2-ethylhexyl para-methoxycinnamate (also known as octyl para-methoxycinnamate) , glyceryl mono-2-ethylhexanoate diparamethoxycinnamate, methyl 2,5-diisopropylcinnamate, 2,4,6-tris[4-(2-ethylhexyloxycarbonyl)anilino]-1, Cinnamic acids such as 3,5-triazine, methylbis(trimethylsiloxy)silylisopentyl trimethoxycinnamate, isopropyl/diisopropyl paramethoxycinnamate/diisopropylcinnamate mixture, p-methoxyhydrocinnamate diethanolamine salt; Benzoylmethanes such as 2-phenyl-benzimidazole-5-sulfuric acid, 4-isopropyldibenzoylmethane, 4-tert-butyl-4'-methoxydibenzoylmethane; 2-cyano-3,3-diphenylpropane-2- Enoic acid 2-ethylhexyl ester (also known as octocrylene), dimethoxybenzylidene dioxoimidazolidine propionate 2-ethylhexyl, 1-(3,4-dimethoxyphenyl)-4,4-dimethyl-1,3-pentanedione, Cinoxate, methyl-O-aminobenzoate, 2-ethylhexyl-2-cyano-3,3-diphenylacrylate, 3-(4-methylbenzylidene)camphor, octyltriazone, 4-(3,4-dimethoxyphenylmethylene)- Examples include 2-ethylhexyl 2,5-dioxo-1-imidazolidine propionate, polymer derivatives thereof, and silane derivatives. However, there have been many reports of skin disorders caused by these organic UV absorbers, so in recent years water-in-oil emulsion sunscreen cosmetics that do not contain organic UV absorbers have been developed in consideration of the effects they may have on the skin. It has increased.
When trying to obtain a sunscreen cosmetic with high UV protection ability by blending only metal oxides (e.g., titanium oxide, zinc oxide, cerium oxide) as UV shielding agents without blending organic UV absorbers. Inevitably, the amount of metal oxide added will further increase. In addition, in order to obtain high UV protection ability with only one type of metal oxide, it is necessary to mix a larger amount, so two or more types, such as titanium oxide and zinc oxide, are used together to effectively protect against UV rays. often obtains abilities.
However, when a large amount of particulate metal oxide is blended, the more the blended amount increases, the more a defect called white floating after coating appears.

Furthermore, when a metal oxide is blended into a water-in-oil emulsion sunscreen cosmetic, a hydrophobically treated fine particle metal oxide is often blended to improve dispersibility in the oil phase. In that case, if you try to wash it after application, the drawback is that because of its high water repellency, particulate metal oxides remain on the skin and are difficult to wash off.

To address these drawbacks, Patent Document 1 describes a water-in-oil emulsion sunscreen cosmetic that does not contain an organic ultraviolet absorber: (a) hydrophobized zinc oxide and hydrophobized titanium oxide: 10 to 30; Consisting of mass%, (b) lipophilic nonionic surfactant: 0.5 to 5 mass%, (c) N-lauroyl L-glutamine di(phytosteryl, 2-octyldodecyl), macadamia nut fatty acid phytosteryl, macadamia nut fatty acid cholesteryl One or more oils selected from the group: 1 to 5% by mass, (d) volatile silicone oil and/or hydrocarbon oil: 10 to 40% by mass, (e) water: 5 to 30% by mass A water-in-oil emulsion cosmetic containing the following is disclosed.

Patent Document 2 describes an oil-in-water emulsion sunscreen cosmetic that does not contain an organic ultraviolet absorber, containing (A) zinc oxide hydrophobized with octyltriethoxysilane and/or dimethylpolysiloxane and/or hydrophobized. Cosmetics containing titanium oxide, (B) liquid higher fatty acid, (C) silicone or sugar ester having a carboxyl group in its structure, (D) nonionic surfactant, (E) sodium carboxymethyl cellulose, and (F) water. Fees are disclosed. All of these cosmetics have favorable ultraviolet shielding effects and are easy to wash and remove due to their oil-in-water emulsification characteristics.
However, it has been pointed out that when hydrophobized zinc oxide or titanium oxide is added, it may give a dry feeling to the skin.

Japanese Patent Application Publication No. 2013-43875 Japanese Patent Application Publication No. 2013-091625

The present inventors have solved the difficulty of washing and removing due to the water repellency of water-in-oil emulsion sunscreen cosmetics that do not contain organic ultraviolet absorbers when hydrophobized metal oxide powder is blended. However, the present invention was achieved by discovering a preferable formulation that has a different effect of imparting moisturizing properties to the skin despite containing metal oxides that tend to give a dry feeling.
That is, the present invention is a sunscreen cosmetic that does not contain an organic ultraviolet absorber, contains hydrophobized metal oxide powder, has high ultraviolet protection ability and skin moisturizing ability, and is washable after use. An object of the present invention is to provide a water-in-oil emulsion sunscreen cosmetic with high detergency.

The main configuration of the present invention is as follows.
(1) A water-in-oil emulsion sunscreen cosmetic that does not contain an organic ultraviolet absorber and contains the following (A) to (C).
(A) Hydrophobized fine particles of zinc oxide and hydrophobized fine particles of titanium oxide (B) Water-soluble polymer compound (C) Spherical powder with a volume average particle diameter of 1 μm or more (2) (B) is (acrylates/acrylic The sunscreen cosmetic according to (1), which is one or more substances selected from acid alkyl (C10-30) crosspolymer, xanthan gum, agar, hydroxypropylmethylcellulose, white fungus polysaccharide, and sodium hyaluronate.
(1) or (2) where (C) is a spherical powder made of one or more substances selected from (vinyl dimethicone/methicone silsesquioxane) crosspolymer, silica, and polymethyl methacrylate. Sunscreen cosmetics described in .
(4) The sunscreen cosmetic according to any one of (1) to (3), wherein the spherical powder (C) has a volume average particle diameter of 2 to 30 μm.

The sunscreen cosmetic of the present invention has high ultraviolet protection ability and moisturizing properties, and has high detergency when washed. Furthermore, since the sunscreen cosmetic of the present invention does not contain organic ultraviolet absorbers, it can be used safely even by people who are prone to skin allergies and atopic dermatitis caused by such chemical substances. .

The present invention is a sunscreen cosmetic that does not contain an organic ultraviolet absorber, comprising (A) hydrophobized fine particle zinc oxide and hydrophobized fine particle titanium oxide, (B) a water-soluble polymer compound, and (C) a volume average This invention relates to a water-in-oil emulsion sunscreen cosmetic containing spherical powder with a particle size of 1 μm or more.
The constituent components (blended components) of the present invention will be explained.
(A) Component: Hydrophobized fine particle titanium oxide and hydrophobized fine particle zinc oxide The hydrophobized metal oxide is powder of oxides of metal atoms such as zinc, titanium, aluminum, iron, and cerium, silicone oil, and fatty acids. Although there are products whose surface is treated with alkylsilane or the like to reduce elution into water, in the present invention, hydrophobized fine particles of titanium oxide and hydrophobized fine particles of zinc oxide are used.
The hydrophobized powder will exist dispersed in the oil of the water-in-oil emulsion sunscreen cosmetic. The type of hydrophobizing agent is not limited, but examples include fatty acids, higher fatty acids, higher alcohols, hydrocarbons, triglycerides, esters, silicone oils, silicone resins, fluorine compounds, and acylamino acids.
The hydrophobizing agent for particulate zinc oxide used in the present invention is alkyltriethoxysilane, alkyltrimethoxysilane, perfluoroalkyl phosphoric acid, (alkyl acrylate/dimethyl silicone) copolymer, dextrin palmitate, triethoxysilylethyl poly Examples include dimethylsiloxyethylhexyl dimethicone, methicone, dimethicone, polymer silicone, sodium acryloyl dimethyl taurate/methacrylamidolauric acid copolymer, hydrogen dimethicone, and acyl glutamic acid.
In the case of fine particle titanium oxide, alkyltriethoxysilane, alkyltrimethoxysilane, perfluoroalkylphosphoric acid, (alkyl acrylate/dimethylsilicone) copolymer, palmitic acid dextrin, triethoxysilylethyl polydimethylsiloxyethylhexyl dimethicone, Examples include methicone, dimethicone, polymeric silicone, sodium acryloyldimethyltaurate/methacrylamide lauric acid copolymer, hydrogen dimethicone, and acylglutamic acid.
The method of hydrophobization treatment is not particularly limited, and the surface treatment is carried out according to a conventional method. For example, hydrophobized zinc oxide can be produced by mixing and stirring zinc oxide in octyltriethoxysilane, dimethylpolysiloxane, or hydrogen dimethicone for a certain period of time, and filtering the mixture. Hydrophobically treated titanium oxide can also be produced by a similar method.

The total amount of hydrophobized zinc oxide and hydrophobized titanium oxide is 5 to 45% by mass, preferably 10 to 35% by mass, based on the total amount of the water-in-oil emulsion sunscreen cosmetic. %, particularly preferably 20 to 26% by weight. Note that the blending amount can be increased or decreased as appropriate depending on the target SPF value.
The particle size of the hydrophobized zinc oxide and hydrophobized titanium oxide is preferably fine particles, and it is particularly preferable that the average particle size of the primary particles is 0.001 to 0.3 μm.

For the purpose of preparing the cosmetics of the present invention, the hydrophobized metal oxide powder can be mixed in advance with an oil agent such as silicone to be incorporated into the cosmetics to facilitate dispersion when preparing the cosmetics. It can be carried out. In carrying out the present invention, it is preferable to use a mixture for preparing cosmetics which is dispersed in such an oil agent.
A commercially available raw material containing hydrophobized fine particles of zinc oxide is "LZ-021" (Tayka Co., Ltd.), which is hydrogen dimethicone hydrophobized fine particles of zinc oxide dispersed in tocopherol, cyclopentasiloxane, and PEG-9 polydimethylsiloxyethyl dimethicone. ) can be exemplified.
Commercially available raw materials containing hydrophobized fine particles of titanium oxide include "FLT-", which is made by dispersing fine particles of titanium oxide hydrophobized with hydrogen dimethicone, dimethicone, aluminum hydroxide, and hydrated silica in cyclopentasiloxane and trimethylsiloxysilicic acid. 01 (Tayka Corporation), or "Cosmeserve WP-40TSF" (Tayka Co., Ltd.), which is made by dispersing titanium oxide hydrophobized with hydrogen dimethicone, Al hydroxide, and silica in cyclopentasiloxane and PEG-9 polydimethylsiloxyethyl dimethicone. Nippon Kasei Co., Ltd.) is an example. Any of these raw materials can be used as an oily raw material in preparing the sunscreen cosmetic composition of the present invention.

(B) Component: Water-soluble polymeric compound Water-soluble polymeric substances used in the present invention include organic polymeric substances such as polymerized sugars, amino acids, acrylic acid, etc., or derivatives thereof, and colloidal hydrated silicone. Refers to inorganic polymeric substances such as acid aluminum. Any of these substances can be used in the present invention as long as they are hydrated with water and exhibit viscosity. As such substances, typical substances used in the present invention can be used alone or in an appropriate combination of two or more. Because of their ease of application to various dosage forms, carboxyvinyl polymers, acrylic acid/alkyl methacrylate copolymers, xanthan gum, hydroxypropyl methylcellulose, polyacrylamide, (sodium acrylate/sodium acryloyldimethyltaurine) copolymers, and (acrylic One or more selected from the group consisting of hydroxyethyl acid/Na acryloyldimethyltaurine copolymer, (acrylamide/ammonium acrylate) copolymer, polyacrylate-13, white fungus polysaccharide, and hyaluronic acid or an alkali metal salt thereof is used. (Acrylates/Alkyl acrylate (C10-30)) One or more selected from cross polymers, xanthan gum, agar, hydroxypropyl methylcellulose, sodium hyaluronate, and white fungus polysaccharide are preferred; (Acrylates/Alkyl acrylate (C10-30)) Particularly preferred is one or more selected from C10-30)) crosspolymer, xanthan gum, agar, hydroxypropylmethylcellulose, and white fungus polysaccharide.
When a water-soluble polymer compound is incorporated into the cosmetic of the present invention, the total amount is 0.01 to 2% by mass, preferably 0.02% by mass, based on the total amount of the water-in-oil emulsion sunscreen cosmetic. ~1% by weight, particularly preferably from 0.05 to 0.2% by weight.

(C) Component: Spherical powder The spherical powder used in the present invention refers to powder in which the particles constituting the powder have a spherical shape.
Spherical shape includes true sphere, substantially spherical shape, and spheroid, and even if the surface is uneven, if the overall shape of the particle can be determined to be spherical, it corresponds to "spherical shape" as used in the present invention. Furthermore, the spherical particles of the present invention are not limited to true spheres, but preferably have a ratio of short axis/long axis of the particles constituting the spherical powder, that is, an ellipticity of 1.5 or less, and 1.2 The following are more preferred, and those of 1.1 or less are even more preferred.
Particle materials constituting the spherical powder include inorganic powders such as silica, calcium silicate, and magnesium silicate; organic powders such as crystalline cellulose, nylon powder, and poly(meth)acrylic acid ester (methyl ester, ethyl ester); Examples include polymethylsilsesquioxane powder, which has a network structure in which siloxane bonds extend three-dimensionally, and has an intermediate structure between inorganic and organic structures in which a methyl group is bonded to one silicon atom.
In the present invention, the components constituting the particles of the spherical powder are preferably (vinyl dimethicone/methicone silsesquioxane) crosspolymer, silica, and polymethyl methacrylate, particularly preferably (vinyl dimethicone/methicone silsesquioxane). oxane) crosspolymer. Further, the volume average particle diameter of the particles constituting the spherical powder needs to be 1 μm or more. Preferably it is 2 to 30 μm.
The amount of spherical powder blended is 0.01 to 15% by weight, preferably 0.1 to 10% by weight, particularly preferably 0.5 to 7% by weight.

(D) Other ingredients The sunscreen cosmetic of the present invention may contain other ingredients as long as they do not affect the effects of the present invention. Such ingredients include water, higher alcohols, fatty acids, esters, sterols, sterol fatty acid esters, hydrocarbons, oils and fats, silicone oil, humectants, surfactants, water-soluble polymers, and plants. Extracts, vitamins, antioxidants, antibacterial preservatives, anti-inflammatory agents, insect repellents, physiologically active ingredients, salts, chelating agents, neutralizing agents, pH adjusters, fragrances, etc. can be added.

The sunscreen cosmetic of the present invention can be easily manufactured by mixing and dissolving the oil phase component and the aqueous phase component, respectively, and then emulsifying and mixing them while stirring using a stirring mixing device such as a homomixer. I can do it.

EXAMPLES Hereinafter, the present invention will be explained in detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
<Examples 1 to 16>
Table 1 below shows the compositions of Examples 1 to 16. As component (A), a hydrophobized fine particle metal oxide dispersion sold for cosmetics was used, so the hydrophobized metal oxide and the dispersion solvent are shown separately in the table. The ingredients of the sunscreen cosmetics are adjusted so that the SPF is 50 or higher. The particle size of component (C) listed in the table is the volume average particle size.

<Evaluation test method>
Evaluation of the cleanability of the obtained sunscreen cosmetic. Drop 0.03 g of the sunscreen cosmetic on the skin on the inner side of the upper arm, spread it over a 3 cm x 3 cm area, lather the body shampoo, and rub it several times with the palm of your hand. Wash with water at 25°C to 25°C. Then, gently wipe off the moisture and let dry for 10 minutes. After drying, the condition of the paint film is checked by visually observing the difference in whiteness from bare skin and by the squeaky feeling when touched with a finger.The less white parts remain or the less squeaky feeling, the higher the cleaning performance. did.
○: High cleaning performance.
Δ: There is a change in the state of the coating film before and after cleaning, but the cleaning performance is slightly low.
×: There is little change in the state of the coating film before and after washing, and the washability is low.

Moisturizing property evaluation/sensory evaluation Drop 0.03g of sunscreen cosmetics onto the skin on the inner side of the upper arm, spread it over a 3cm x 3cm area, and after 15 minutes touch the area where it has been applied with your finger to find out if it feels powdery. The moisturizing properties obtained from the absence of moisture and moist feeling were sensory evaluated.
○: Does not feel powdery, gives a moist feeling and has high moisturizing properties.
△: Slightly powdery feel, but moist feeling and moisturizing properties.
×: It feels powdery and it is hard to feel a moist feeling, so the moisturizing property is low.
The results of the detergency evaluation and moisture retention evaluation are shown in the bottom row of Table 1.

All of the compositions of Examples 1 to 16 were evaluated to have favorable cleansing properties and moisturizing properties.

<Comparative Examples 1 to 6>
Table 2 below shows the compositions of Comparative Examples 1 to 6. In addition, Comparative Examples 1 to 3 are compositions that do not contain the water-soluble polymer compound as component (B), Comparative Example 4 is a composition that does not contain spherical powder as component (C), and Comparative Example 5 is a composition that does not contain the spherical powder as component (C). Comparative Example 6, which is a composition in which no components are blended, is a composition in which spherical powder with an average particle diameter of 0.5 μm is blended. As component (A), a hydrophobized fine particle metal oxide dispersion sold for cosmetics was used, so the hydrophobized metal oxide and the dispersion solvent are shown separately in the table. Note that the ingredients were adjusted so that the SPF of the sunscreen cosmetic was 50 or more, similar to the examples.

<Evaluation test method>
The detergency and moisturizing properties were evaluated in the same manner as in the examples.
The evaluation results are shown at the bottom of Table 2.

As shown in Table 2, Comparative Examples 1 to 6 were all inferior in cleaning performance.
Furthermore, the test results of Comparative Example 6 revealed that component (C) needs to have a particle size exceeding 0.5 μm.

<Evaluation based on the moisture content of the skin stratum corneum>
The effects of the cosmetics of the present invention and comparative cosmetics on the moisture content of the skin's stratum corneum were evaluated.
As representative cosmetics of Examples and Comparative Examples, the compositions of Example 11 and Comparative Example 3 were arbitrarily selected and evaluated by the following measurement method.
The obtained sunscreen cosmetic was evaluated by measuring the change in water content of the stratum corneum by applying it to the skin. First, the inner side of the upper arm was washed and acclimatized for 10 minutes, and the water content was measured using a skin surface stratum corneum water content measuring device (manufactured by Yayoi Co., Ltd., device name: SKICON-200EX). 0.03g of the sample was dropped onto the measurement location, spread over a 3cm x 3cm area, and 15 minutes later, the moisture content of the sample application area was measured. Compare the moisture content of the stratum corneum without applying the sample with the moisture content of the stratum corneum in the sample-applied area, and if the moisture content of the stratum corneum in the sample-applied area has increased by 70 μS or more, the moisture retention is high. rated it as. When the increase in water content was less than 70 μS, the moisture retention property was evaluated as “x” indicating low moisture retention.
The evaluation results are shown in Table 3 below.

The cosmetic of Example 11 having the structure of the present invention resulted in a high increase in the moisture content of the stratum corneum, which was consistent with the sensory evaluation. That is, since it showed a high water content increasing effect on the stratum corneum of the skin, it was considered that the moisturizing effect of the cosmetic of the present invention was due to the specific effect of increasing the water content of the stratum corneum.
On the other hand, the cosmetic composition of Comparative Example 3 does not contain component B. Therefore, as in the sensory evaluation, it was found that the moisture content of the stratum corneum of the skin hardly increased.

Claims (2)

A water-in-oil emulsion sunscreen cosmetic that does not contain an organic ultraviolet absorber and contains the following (A) to (C).
(A) Hydrophobized fine particles of zinc oxide and hydrophobized fine particles of titanium oxide whose primary particles have an average particle diameter of 0.001 to 0.3 μm and a content of 20 to 26% by mass based on the total amount of the cosmetic (B) (Acrylates/alkyl acrylate (C10-30)) crosspolymer
(C) A spherical powder with a volume average particle diameter of 1 μm or more, which is made of one or more substances selected from (vinyl dimethicone/methicone silsesquioxane) crosspolymer and polymethyl methacrylate. The sunscreen cosmetic according to claim 1, wherein the spherical powder (C) has a volume average particle diameter of 2 to 30 μm.