JP2013147482A - Sunscreen cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sunscreen cosmetic which is excellent in water resistance and makeup durability, and can easily be removed by a cleaning agent without placing a burden on a skin when being washed.SOLUTION: A sunscreen cosmetic containing the following components (A) to (C) is provided where (A) is a metal oxide surface-treated by alkyl alkoxysilane, (B) is (trifluoropropyl dimethyl siloxy/trimethylsiloxy) silsesquioxane and (C) is a silicone powder.

Description

  The present invention relates to a sunscreen cosmetic.

  Conventionally, in order to protect ultraviolet rays, organic ultraviolet absorbers that efficiently absorb ultraviolet rays and protective powders that scatter ultraviolet rays are used. Titanium oxide and zinc oxide are widely used as UV protection powder. In particular, UV protection powder whose surface is hydrophobized for the purpose of improving water resistance, makeup durability, and dispersibility. (Metal oxide) is used (for example, Patent Document 1). In these techniques, improvement in water resistance is excellent in long-lasting makeup, but there is a problem that it is difficult to remove with a normal cleaning agent or facial cleanser.

  In order to improve such a problem, for example, by making the surface of the UV protection powder a special modified powder coated with a hydrophobic treatment agent and a cationic surfactant, both water resistance and detergency can be achieved. Has been proposed (Patent Document 2).

  On the other hand, sunscreen cosmetics using a specific polyether-modified silicone and a specific ultraviolet absorber in combination with a metal oxide powder surface-treated with alkylalkoxysilane as a hydrophobized powder have excellent water resistance. Is disclosed (Patent Document 3).

Japanese Patent Laid-Open No. 8-119832 JP 2007-217361 A JP 2010-111625 A

  However, although the sunscreen cosmetic of Patent Document 3 is excellent in water resistance and can be removed with a normal cleaning agent or facial cleanser, further improvement is expected in consideration of the burden on the skin during cleaning. Yes.

  Therefore, the present invention also provides a tan which is excellent in water resistance even in a metal oxide surface-treated with an alkylalkoxysilane as a hydrophobizing agent and can be easily removed with a cleaning agent without imposing a burden on the skin during cleaning. It is an object to provide stop cosmetics.

  The present inventor has made various studies to solve the above problems, and uses the specific fluorine-modified silicone resin found by the present applicants, a metal oxide surface-treated with an alkylalkoxysilane, and a silicone powder in combination. Thus, the inventors have found that a sunscreen cosmetic that can achieve both water resistance and cleanability and that also reduces the burden on the skin during cleaning has been obtained, and the present invention has been completed.

That is, this invention provides the sunscreen cosmetics characterized by containing the following component (A)-(C).
(A) Metal oxide surface-treated with alkylalkoxysilane (B) (trifluoropropyldimethylsiloxy / trimethylsiloxy) silsesquioxane (C) silicone powder

  The sunscreen cosmetic of the present invention is excellent in UV protection effect and water resistance, and can be easily removed with a detergent without imposing a burden on the skin during washing.

  Hereinafter, embodiments of the present invention will be described in detail.

  Examples of the component (A) used in the present invention include those obtained by subjecting metal oxide powders such as titanium oxide, zinc oxide, iron oxide, cerium oxide and the like to surface treatment with an alkylalkoxysilane by a known method. Among these, titanium oxide, zinc oxide, and cerium oxide are preferable as the metal oxide, and zinc oxide fine particle powder (average particle diameter of 10 nm to 200 μm) is preferable because of its excellent ultraviolet protection effect. The average particle diameter of the metal oxide is preferably 10 nm to 200 μm, more preferably 10 nm to 100 μm, and further preferably 15 nm to 50 μm. The average particle diameter is measured by transmission electron microscopy.

The alkylalkoxysilane used for the surface treatment of the component (A) is represented by the general formula: R ¹ _X Si (OR ² ) _4-x [wherein R ¹ is a linear or branched chain having 1 to 20 carbon atoms. It is an alkyl chain, R < ² > is a C1-C6 linear or branched alkyl chain, and X is 1-3. Among these, R ¹ is preferably an alkyl chain having 8 to 10 carbon atoms, and R ² is preferably methyl or ethyl.
Specific examples of the compound include hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, octadecyltrimethoxysilane, and octyltriethoxysilane. Of these, surface treatment with octyltriethoxysilane or octyltrimethoxysilane is more preferable because of excellent water resistance.

  The surface treatment method using the alkylalkoxysilane is not particularly limited. For example, a dry treatment method such as mixing an alkylalkoxysilane and a metal oxide powder using a high-speed stirrer such as a Henschel mixer or a supermixer. Alternatively, a wet processing method such as adding alkylalkoxysilane to a slurry of metal oxide powder and stirring and mixing can be used.

  When the component (A) used in the present invention coats a metal oxide with an alkylalkoxysilane, the mass ratio (a1: a2) between the alkylalkoxysilane (a1) and the metal oxide (a2) is 1: 100-1: 3 are preferable and 1: 20-1: 5 are especially preferable. If it is this range, sufficient ultraviolet-ray protective effect and water resistance will be acquired.

  The content of the component (A) used in the present invention is not particularly limited and can be appropriately blended according to the target product, but the content in the sunscreen cosmetic of the present invention is 1 to 4 based on the total amount of the cosmetic. 50% by mass (hereinafter simply referred to as%), preferably 5 to 30%, more preferably 5 to 25%. Within this range, the UV protection effect and water resistance are excellent.

  The component (B) (trifluoropropyldimethylsiloxy / trimethylsiloxy) silsesquioxane used in the present invention is generally commercially available. For example, SilForm FR-10 Fluid (Momentive Performance Materials).

  The content of the component (B) used in the present invention is preferably 0.05 to 10%, more preferably 0.1 to 5%, still more preferably 0.2 to 3% based on the total amount of the cosmetic. If it is in this range, in the sunscreen cosmetics containing the component (A), both water resistance and ease of washing can be obtained.

Specific examples of the (C) silicone powder used in the present invention include a methylpolysiloxane network polymer and a crosslinked methylpolysiloxane, which can be used alone or in combination of two or more.
The methylpolysiloxane network polymer is a solid obtained by emulsion polymerization of methyltrimethoxysiloxane in an alkaline aqueous solution, and examples thereof include Tospearl series (Tospearl 145A, etc.) manufactured by Momentive Performance Materials. . The crosslinked methylpolysiloxane is obtained by polymerizing dimethoxydimethylsiloxane with a small amount of methyltrimethoxysiloxane, and has a crosslinked structure of methyltrimethoxysiloxane inside. This can be produced by emulsion polymerization in the same manner as the above-mentioned methylpolysiloxane network polymer. For example, the Trefill series (Torefill E506W, Trefil E505C, Trefil E506C, Trefil E505W, etc.) manufactured by Toray Dow Corning, etc. Is mentioned. These silicone powders may be used alone or in combination of two or more. Moreover, even if it uses what disperse | distributed these silicone powders in various solvents etc., and what was previously mixed with the other component, it can be used without any problem. Examples of these include Trefill E507 solution, E508, BY29-119, and BY29-122 (above, manufactured by Toray Dow Corning).

  As content of (C) component used for this invention, 0.5-10% is preferable on the basis of cosmetics total amount, 3-10% is more preferable, 4-10% is more preferable, 3-8 % Is more preferable, 4 to 8% is more preferable, and 4 to 7% is more preferable. If it is in this range, the sunscreen cosmetic containing the components (A) and (B) is preferable because it does not impose a burden on the skin during washing.

  Further, in the present invention, as component (D), dihydroxypolydimethylsiloxane (hereinafter referred to as dimethiconol) and / or fluorinated dihydroxypolydimethylsiloxane (hereinafter referred to as fluorinated dimethiconol) in which the terminal methyl group of dimethylpolysiloxane is a hydroxyl group. Is preferable because the burden on the skin during washing is reduced. Fluorinated dimethiconols include fluorinated alkyl dimethiconols such as trifluoropropyl dimethiconol.

  As content of (D) component used for this invention, 0.05 to 5% is preferable on the basis of cosmetics total amount, and 0.1 to 3% is more preferable.

  In the sunscreen cosmetics of the present invention, in addition to the above components, various surfactants and oily components that are usually blended in pharmaceuticals, quasi drugs, cosmetics, etc., as long as the effects of the present invention are not impaired. , Silicone compounds, higher alcohols, lower alcohols, fluorine compounds, resins, humectants, thickeners, preservatives, pH adjusters, chelating agents, neutralizing agents, water, chemicals, UV absorbers, dyes, fragrances, etc. Can be appropriately blended as necessary. Examples of ultraviolet absorbers include 2-methoxyhexyl paramethoxycinnamate, 2- (4-diethylamino-2-hydroxybenzoyl) benzoic acid hexyl ester, benzyl paramethoxycinnamate, 2-ethylhexyl paramethoxycinnamate, paramethoxycinnamate Cinnamic acid UV absorbers such as 2-ethoxyethyl acid, diparamethoxycinnamate mono-2-ethylhexanoate glyceryl, paramethoxycinnamate isopropyl diisopropylcinnamate ester mixture, hydroxymethoxybenzophenone, hydroxymethoxy Benzophenone sulfonic acid, sodium hydroxymethoxybenzophenone sulfonate, dihydroxymethoxybenzophenone, dihydroxymethoxybenzophenone sodium disulfonate, dihydroxybenzophenone, tetra Benzophenone ultraviolet absorbers such as droxybenzidiphenone, paraaminobenzoic acid, ethyl paraaminobenzoate, glyceryl paraaminobenzoate, amyl paradimethylaminobenzoate, octyl paradimethylaminobenzoate, 4- [N, N-di (2 -Hydroxypropyl) amino] ethyl benzoate, 2- (4-diethylamino-2-hydroxybenzoyl) -benzoic acid ester UV absorbers such as hexyl benzoate, ethylene glycol salicylate, phenyl salicylate, octyl salicylate, benzyl salicylate, Salicylic acid ultraviolet absorbers such as p-tert-butylphenyl salicylate and homomenthyl salicylate, 2,4,6-trianilino-p- (carbo-2′-ethylhexyl-1′-oxy) -1,3,5-triazine Triazine-based UV absorbers, 4-tert-butyl-4′-methoxydibenzoylmethane, oxybenzone, octocrylene, menthyl anthranilate, 2- (2-hydroxy-5-methylphenyl) benzotriazole, dimethoxybenzylidene dioxoimidazolidine 2-Ethylhexyl propionate, 2-phenylbenzimidazole-5-sulfonic acid, 2-cyano-3,3-diphenyl acrylate, and the like can be used.

  The sunscreen cosmetic of the present invention is not particularly limited, but is preferably a water-in-oil emulsion composition because it is easy to prepare into a water-in-oil emulsion and is excellent in stability over time.

  The dosage form of the sunscreen cosmetic of the present invention is arbitrary, and can be applied to liquids, emulsions, creams, pastes, solids, multilayers, etc., and further as sheet agents, spray agents, mousse agents, etc. Is also applicable.

In relation to the above-described embodiment, the present invention further discloses the following sunscreen cosmetics.
This invention is cosmetics as described in following <1>.
<1> A sunscreen cosmetic comprising the following components (A) to (C):
(A) Metal oxide surface-treated with alkylalkoxysilane (B) (trifluoropropyldimethylsiloxy / trimethylsiloxy) silsesquioxane (C) silicone powder

The present invention preferably further comprises the following cosmetics.
<2> The sunscreen cosmetic according to <1>, wherein the component (A) is a metal oxide surface-treated with octyltriethoxysilane or octyltrimethoxysilane.
<3> The sunscreen cosmetic according to <1> or <2>, wherein the metal oxide of component (A) is a fine powder of zinc oxide having an average particle size of 10 nm to 200 μm.
<4> The mass ratio (a1: a2) between the alkylalkoxysilane (a1) and the metal oxide (a2) as the component (A) is preferably 1: 100 to 1: 3, and 1:20 to 1: 5. More preferable sunscreen cosmetics according to the above <1> to <3>.
<5> Said <1> whose content of (A) component is 1-50 mass% on the basis of the total amount of sunscreen cosmetics, preferably 5-30 mass%, more preferably 5-25 mass% > To <4> sunscreen cosmetics.
<6> The content of the component (B) is preferably 0.05 to 10% by mass, more preferably 0.1 to 5% by mass, and 0.2 to 3% by mass based on the total amount of the sunscreen cosmetic. More preferable sunscreen cosmetics according to the above <1> to <5>.
<7> The content of the component (C) is preferably 0.5 to 10% by mass, more preferably 3 to 10% by mass, further preferably 4 to 10% by mass, based on the total amount of the sunscreen cosmetic. The sunscreen cosmetic according to <1> to <6>, more preferably ˜8% by mass, further preferably 4 to 8% by mass, and further preferably 4 to 7% by mass.
<8> Further, the tanning according to the above <1> to <7>, which further contains dihydroxypolydimethylsiloxane and / or fluorinated dihydroxypolydimethylsiloxane as component (D), and is preferably dimethiconol and / or trifluoropropyldimethiconol. Stop cosmetics.
<9> The sunscreen of <1> to <8>, wherein the content of the component (D) is preferably 0.05 to 5%, more preferably 0.1 to 3%, based on the total amount of the sunscreen cosmetic. Cosmetics.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these. In addition, the compounding quantity shown below is the mass%.

Production Example 1 (Production of alkylalkoxysilane-treated zinc oxide)
A slurry composed of 93 parts by mass of finely divided zinc oxide powder (substantially spherical, average particle size 20 nm), 7 parts by mass of octyltriethoxysilane, and toluene was prepared, and pulverized and disassembled using a bead mill (Dynomill manufactured by Shinmaru Enterprises) Crushed. Subsequently, toluene was distilled off by heating under reduced pressure, followed by heat treatment at 150 ° C. for 4 hours using an air blast dryer to obtain octyltriethoxysilane-treated fine particle zinc oxide.

Production Example 2 (Production of alkylalkoxysilane-treated titanium oxide)
Instead of the fine particle zinc oxide powder of Production Example 1, titanium oxide (needle shape, average particle diameter 35 nm) was used and treated by the same production method as Production Example 1 to obtain octyltriethoxysilane-treated titanium oxide.

Production Example 3 (Production of cerium oxide treated with alkylalkoxysilane)
Instead of the fine particle zinc oxide powder of Production Example 1, cerium oxide (spherical, average particle size 30 nm) was used and treated by the same production method as Production Example 1 to obtain octyltriethoxysilane-treated cerium oxide.

(1) UV protection effect A sample was applied at a rate of ² mg / cm ² onto a resin tape affixed on quartz glass, and the transmittance at a wavelength of 300 nm was measured using SPF analyzer UV-1000S (manufactured by Labsphere). The following criteria are shown.
[UVB protection effect evaluation criteria]
◎: UVB transmittance is less than 10% ○: UVB transmittance is 10 or more and less than 20% Δ: UVB transmittance is 20 or more and less than 30% ×: UVB transmittance is 30% or more

(2) Water resistance test After 0.1 mg of a sample was applied to a quartz plate and uniformly stretched with a bar coder and dried for 10 minutes, an SPF analyzer UV-1000S (manufactured by Labsphere) was used to measure the SPF value. Subsequently, the SPF value was measured again after immersion in water for 80 minutes.
Next, the sustainability of SPF was calculated from each SPF value.
SPF persistence (%) = SPF value after water treatment / SPF value before water treatment × 100
SPF persistence was determined according to the following criteria and used as an index of water resistance.
(Criteria)
○: SPF persistence is 90% or more; water resistance is very high Δ: SPF persistence is 70% or more and less than 90%; water resistance is high x: SPF persistence is less than 70%; water resistance is low

(3) Ease of cleaning test A sample is uniformly applied to black artificial leather so as to be ² mg / cm ² and dried at room temperature for 15 minutes. After that, cleansing agent (trade name: Biore Make Melt Liquid, manufactured by Kao Co., Ltd.) is applied at about 1.0 mg / cm ² , washed while rubbing with a finger, rinsed with 35 ° C. hot water, and visually left on artificial leather. The thing was confirmed and judged using the following four-step criteria.
(Criteria)
◎: No residue when rubbing with fingers 5 times, very easy to wash ○: No residue when rubbing with fingers 10 times, easy to wash Δ: No residue after rubbing with fingers 15 times , Cleaning is somewhat difficult ×: There is a residue even after rubbing with a finger 15 times, poor cleaning properties

(4) Sensory evaluation at the time of cleaning 10 expert panelists evaluated the sense of burden on the skin when the sample was actually used and then washed with normal cleaning materials according to the following evaluation criteria. did. Five points were given when responding that they did not feel any burden on the skin, and one point was given when responding that they felt the burden on the skin. Then, the average score of 10 professional panelists was determined, 4 or more points were marked as ◎, 3 points or more and less than 4 points as ◯, 2 points or more and less than 3 points as Δ, and less than 2 points as x.

Examples 1-7, Comparative Examples 1-5
A sunscreen cosmetic was prepared according to the formulation described in Table 1. Using these, the above test was carried out. The test results are also shown in Table 1.

(Production method)
a: Components 1 to 17 are mixed, heated and dissolved at 70 ° C., and mixed uniformly.
b: Components 19 and 20 are heated to 70 ° C.
c: While a is being stirred, b is gradually added to perform preliminary emulsification.
d: c was cooled to 35 ° C., component 18 was gradually added, and the mixture was stirred and mixed uniformly with a homomixer. Then, deaeration and cooling were performed to obtain a water-in-oil sunscreen cosmetic.

  As is apparent from Table 1, the sunscreen cosmetics of the examples using the components of the present invention are sunscreens of comparative examples in all points of UV protection effect, water resistance, ease of washing, and no burden on the skin. Clearly better than stop cosmetics.

  Next, a prescription example of the sunscreen cosmetic of the present invention is shown. All are expected to be excellent in UV protection effect, water resistance, easy cleaning, and no burden on the skin.

Formulation Example 1 (W / O type sunscreen emulsion)
(Ingredient) (mass%)
Ethanol 10.0
Lauryl PEG-9 polydimethylsiloxyethyl dimethicone 3.0
[KF6038; manufactured by Shin-Etsu Chemical Co., Ltd.]
Methyltrimethicone 10.0
[TMF-1.5; manufactured by Shin-Etsu Chemical Co., Ltd.]
Cyclomethicone 15.0
[KF-995; manufactured by Shin-Etsu Chemical Co., Ltd.]
Olefin oligomer 3.0
(Trifluoropropyldimethylsiloxy / trimethylsiloxy) silsesquioxane 1.0
Octyltriethoxysilane-treated zinc oxide 12.0
Octyltriethoxysilane-treated titanium oxide 5.0
Octyl methoxycinnamate 5.0
Octocrylene 2.0
Diethylaminohydroxybenzoyl hexyl benzoate 2.0
Dimethyl distearyl ammonium hectorite 1.0
Polymethylsilsesquioxane 4.5
[Tospearl 145A; made by Momentive Performance Materials]
Dimethiconol 0.5
[YF3802A; manufactured by Momentive Performance Materials]
1,3-butylene glycol 3.0
Phenoxyethanol 0.5
Purified water balance

Formulation example 2 (sun cream)
(Ingredient) (mass%)
Dimethicone copolyol dispersion 10.0
[Silicon BY22-008; manufactured by Toray Dow Corning]
Cyclomethicone 8.0
[KF-995; manufactured by Shin-Etsu Chemical Co., Ltd.]
Dimethylpolysiloxane 2.0
[KF-96 (2cs); manufactured by Shin-Etsu Chemical Co., Ltd.]
Phenyltrimethicone 5.0
[FZ-209; made by Toray Dow Corning]
Isononyl isononanoate 3.0
Octyl methoxycinnamate 7.5
Octyltriethoxysilane-treated zinc oxide 5.0
(Trifluoropropyldimethylsiloxy / trimethylsiloxy) silsesquioxane 2.5
Trifluoropropyl dimethiconol 1.0
Octocrylene 1.0
(Dimethicone (PEG-10 / 15)) Crosspolymer 3.0
[Trefill E508; manufactured by Toray Dow Corning]
Sodium citrate 0.05
(Dimethicone / vinyl dimethicone) cross polymer dispersion 10.0
[PF-2001 Powder in Fluid Emulsion (manufactured by Toray Dow Corning) (however, the elastomer component in the dispersion is 12%)]
Sodium chloride 1.0
Dipotassium glycyrrhizinate 0.1
Dipropylene glycol 5.0
Olive leaf extract 0.3
Hypericum extract 0.3
Paraben Appropriate amount Fragrance Appropriate amount Purified water Residual amount

  In addition, the composition of the fragrance | flavor used in said formulation example is shown in Table 2.

Claims (3)

A sunscreen cosmetic comprising the following components (A) to (C):
(A) Metal oxide surface-treated with alkylalkoxysilane (B) (trifluoropropyldimethylsiloxy / trimethylsiloxy) silsesquioxane (C) silicone powder   The sunscreen cosmetic according to claim 1, wherein the content of the component (C) is 3 to 10% by mass.   The sunscreen cosmetic according to claim 1 or 2, further comprising (D) dihydroxypolydimethylsiloxane and / or fluorinated dihydroxypolydimethylsiloxane.