JP6087576B2 - Topical skin preparation - Google Patents

Description

  The present invention relates to a sunscreen cosmetic.

  A large number of sunscreen cosmetics containing UV absorbers and UV scattering agents have been developed so far. In general, sunscreen cosmetics often take the form of water-in-oil emulsions or oil-in-water emulsions, and are used for applications suitable for the respective characteristics.

Water-in-oil emulsions can be highly blended with oil-soluble UV absorbers and UV scattering agents, so high SPF (index to prevent UV B wave; sun protection factor) and PA (index to prevent UV A wave; Sun protection grade of UVA) can be expected and it is excellent in water resistance, but the feeling of use such as oily stickiness is a problem.
Oil-in-water emulsions provide a fresh feeling of use, but when using a water-soluble UV absorber, it is difficult to achieve a high SPF, and when trying to add a high amount of oil-soluble UV absorbers However, the oil component in the preparation is increased, and as a result, there is a problem that a feeling of use such as oily stickiness is obtained. In addition, when the ultraviolet scattering agent is blended in a high amount, stability is impaired or a squeaky feeling is caused.

  For the purpose of improving these issues, sunscreen cosmetics (Patent Documents 1 and 2 etc.) combining water-soluble and oil-soluble UV absorbers, specified as volatile silicone oil and specific polyether-modified silicone Sunscreen cosmetics (Patent Document 3) and the like, which are combined with other ultraviolet absorbers, have been reported.

JP 2011-111444 A JP 2002-284683 A JP 2009-79019 A

However, although the feeling of use such as stickiness and squeakiness can be improved to some extent, it has not been fully satisfactory.
Therefore, the subject of this invention is providing the sunscreen cosmetics which do not produce a sticky feeling and a squeaky feeling, and are excellent also in the ultraviolet-ray protective effect.

  As a result of intensive studies in view of such circumstances, the present inventors have found that (A) one or more selected from pentaerythritol and an alkyl acetal derivative of pentaerythritol represented by a specific formula; and (B) an ultraviolet absorber. And / or (C) The sunscreen cosmetics combined with the ultraviolet light scattering agent have been found to have an excellent ultraviolet protection effect, no stickiness or squeaky feeling, and excellent stability, thereby completing the present invention.

That is, this invention provides the sunscreen cosmetics containing the following component (A), a component (B), and / or a component (C).
(A) Pentaerythritol, one or more selected from alkylacetal derivatives of pentaerythritol represented by the following general formulas (1) and (2)

(In formula, R < ¹ > and R < ² > show a C1-C4 alkyl group which may mutually differ.)

(In formula, R < ³ > -R < ⁶ > shows a C1-C4 alkyl group which may mutually differ.)
(B) UV absorber (C) UV scattering agent

  The sunscreen cosmetic of the present invention has an excellent ultraviolet protection effect, does not produce a sticky feeling or a squeaky feeling, and has excellent stability.

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

Component (A) used in the present invention is selected from pentaerythritol and alkyl acetal derivatives of pentaerythritol.
Pentaerythritol is one type of sugar alcohol represented by the formula C (CH ₂ OH) ₄ .
Moreover, the alkyl acetal derivative of pentaerythritol is represented by the following general formula (1) or (2).

(In formula, R < ¹ > and R < ² > show a C1-C4 alkyl group which may mutually differ.)

(In formula, R < ³ > -R < ⁶ > shows a C1-C4 alkyl group which may mutually differ.)

In the general formula (1) or (2), the alkyl group represented by R ^{1 to} R ⁶ is preferably an alkyl group having 1 to 3 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. A methyl group, an ethyl group, and an n-propyl group are preferable, and a methyl group and an ethyl group are particularly preferable.

  As the alkyl acetal derivative of pentaerythritol represented by the formula (1), monoisopropylidene pentaerythritol, mono (1-methylpropylidene) pentaerythritol, mono (1-methylbutylidene) pentaerythritol, mono (1-ethyl) Propylidene) pentaerythritol, mono (1-ethylbutylidene) pentaerythritol, mono (1-propylbutylidene) pentaerythritol and the like.

  Examples of the alkyl acetal derivative of pentaerythritol represented by the formula (2) include diisopropylidene pentaerythritol, di (1-methylpropylidene) pentaerythritol, di (1-methylbutylidene) pentaerythritol, di (1-ethyl). Propylidene) pentaerythritol, di (1-ethylbutylidene) pentaerythritol, di (1-propylbutylidene) pentaerythritol and the like.

  The alkyl acetal derivative of pentaerythritol represented by the general formulas (1) and (2) according to the present invention can be synthesized from pentaerythritol and an alkyl ketone compound by a known method.

  The preferable content of the component (A) in the present invention is 0.01% by mass (hereinafter abbreviated as%) or more, more preferably 0.1% or more, based on the total amount of the sunscreen cosmetic. More preferably, it is 0.5% or more, 10% or less is preferable, 8% or less is more preferable, and 5% or less is more preferable. The preferable range of the content of the specific component (A) is 0.01 to 10%, more preferably 0.1 to 8%, and further preferably 0.5 to 5%. Within this range, an excellent feeling of use that does not cause a sticky feeling can be obtained.

Although the ultraviolet absorber which is the component (B) used in the present invention is not particularly limited, for example, 2-methoxyhexyl dimethoxybenzylideneoxoimidazolidinepropionate, bisethylhexyloxyphenol methoxyphenyltriazine, methylenebisbenzotriazolyltetramethyl Butylphenol, diethylaminohydroxybenzoyl hexyl benzoate, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfate, 2,2'-dihydroxy-4-methoxybenzophenone, 2-ethylhexyl methoxycinnamate , P-methoxyhydrocinnamic acid diethanolamine salt, paraaminobenzoic acid (hereinafter abbreviated as PABA), ethyldihydroxypropyl PABA, glyceryl PABA, salicy Homomenthyl phosphate, methyl-O-aminobenzoate, 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, 2-ethylhexyl paradimethylaminobenzoate, 2-phenyl-benzimidazole-5-sulfate, triethanolamine salicylate Ethylhexyl salicylate, 3- (4-methylbenzylidene) camphor, 2,4-dihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2, -Hydroxy-4-N-octoxybenzophenone, 4-isopropyl dibenzoylmethane, 4-tert-butyl-4'-methoxydibenzoylmethane, octyl triazone, dimethoxycinnamic acid isooctanoic acid glyceride, dimethicone ethyl Polymer derivatives such Nzarumaroneto, silane derivatives, and the like.
Among these, in particular, 2-methoxyhexyl dimethoxybenzylideneoxoimidazolidinepropionate, bisethylhexyloxyphenol methoxyphenyltriazine, methylenebisbenzotriazolyltetramethylbutylphenol, hexyl diethylaminohydroxybenzoylbenzoate, 4-tert-butyl-4 ′ -Methoxydibenzoylmethane, 2-ethylhexyl methoxycinnamate, 2-ethylhexyl 2-cyano-3,3-diphenyl acrylate, 2-ethylhexyl paradimethylaminobenzoate, ethylhexyl salicylate, octyltriazone, dimethicone ethylbenzalmalonate 2-phenyl-benzimidazole-5-sulfuric acid is preferred from the viewpoint of ultraviolet protection effect.
These components (B) may be used independently and may be used in combination of 2 or more type.

  The content of the component (B) in the present invention is preferably 1% or more, more preferably 2% or more, further preferably 3% or more, and 20% based on the total amount of the sunscreen cosmetic. Or less, more preferably 15% or less, and even more preferably 10% or less. The content range of the specific component (B) is preferably 1 to 20%, more preferably 2 to 15%, and further preferably 3 to 10%. Within this range, a sufficient UV protection effect is obtained, and a feeling of use such as stickiness is also good.

  Although the ultraviolet-ray scattering agent which is the component (C) used for this invention is not specifically limited, It is preferable to mix | blend the powder which has an ultraviolet-ray protective effect. Examples thereof include metal oxides such as titanium oxide, zinc oxide, cerium oxide, and iron oxide, metal hydroxides such as iron hydroxide, metal flakes such as aluminum flakes, and ceramics such as silicon carbide. These are conventionally known hydrophobic surface treatments such as fluorine compound treatment (perfluoroalkyl phosphate treatment or perfluoroalkylsilane treatment, perfluoropolyether treatment, fluorosilicone treatment, fluorinated silicone resin treatment), Silicone treatment (methylhydrogenpolysiloxane treatment, dimethylpolysiloxane treatment, vapor phase tetramethyltetrahydrogencyclotetrasiloxane treatment is preferred), silicone resin treatment (trimethylsiloxysilicate treatment is preferred), pendant treatment (vapor phase method) Method of adding alkyl chain after silicone treatment), silane coupling agent treatment, titanium coupling agent treatment, silane treatment (alkyl silane or alkylsilazane treatment is preferred), oil agent treatment, N-acylated lysine treatment , Polyacrylic acid treatment, metal soap treatment (stearic acid or myristic acid salts are preferred), acrylic resin treatment, it is preferable that the surface treatment with a metal oxide treatment or the like.

Among these, metal oxides such as titanium oxide, zinc oxide, and cerium oxide, and hydrophobized products thereof are particularly preferable from the viewpoint of ultraviolet protection effect.
The metal oxide preferably has an average particle diameter measured by a transmission electron microscope of 10 nm or more, more preferably 15 nm or more, further preferably 20 nm or more, and 200 μm or less. Are preferable, those having a size of 100 μm or less are more preferable, and those having a size of 50 μm or less are more preferable. The specific average particle diameter of these metal oxides is preferably 10 nm to 200 μm, more preferably 10 nm to 100 μm, further preferably 15 nm to 50 μm, and 20 nm to 50 μm. Further preferred.
Of the above hydrophobized surface treatments, those treated with a silicone treatment, a silicone resin treatment, a silane treatment, or an oil agent treatment are particularly preferred.
These components (C) may be used independently and may be used in combination of 2 or more type.

  The preferable content of the component (C) in the present invention is 1% or more, more preferably 2% or more, further preferably 3% or more, and 30% based on the total amount of the sunscreen cosmetic. The following is preferable, 20% or less is more preferable, and 15% or less is more preferable. The content of the specific component (C) is preferably 1 to 30%, more preferably 2 to 20%, and further preferably 3 to 15%. If it is in this range, a sufficient UV protection effect is obtained, and a feeling of use such as a squeaky feeling is also good.

  The sunscreen cosmetic of the present invention can use any components that are usually used within the range not impairing the effects of the present invention, if necessary, in addition to the essential components described above. Examples of these components include various surfactants such as anionic surfactants, cationic surfactants, and nonionic surfactants, oils, preservatives, moisturizers, polymers, amino acid derivatives, sugar derivatives, A fragrance | flavor, water, alcohol, a thickener, a coloring agent, a sequestering agent, an antioxidant, a chemical | medical agent, the extract derived from animals and plants, a pH adjuster, etc. are mentioned.

  The dosage form of the sunscreen cosmetic of the present invention is not particularly limited, but it is preferably provided in the form of, for example, cream, milky lotion, cosmetic liquid, lotion, foundation, sunscreen agent, makeup base and the like.

  Next, the present invention and preferred embodiments of the present invention will be shown.

<1> A sunscreen cosmetic containing the following component (A), component (B) and / or component (C).
(A) Pentaerythritol, one or more selected from alkylacetal derivatives of pentaerythritol represented by the following general formulas (1) and (2)

(In formula, R < ¹ > and R < ² > show a C1-C4 alkyl group which may mutually differ.)

(In formula, R < ³ > -R < ⁶ > shows a C1-C4 alkyl group which may mutually differ.)
(B) UV absorber (C) UV scattering agent

<2> The content of the component (A) is 0.01% or more, preferably 0.1% or more, more preferably 0.5% or more, and 10% based on the total amount of the sunscreen cosmetic. The sunscreen cosmetic according to <1>, preferably 8% or less, more preferably 5% or less.
<3> Sunscreen makeup according to <1> or <2>, wherein the content of component (A) is 0.01 to 10%, preferably 0.1 to 8%, more preferably 0.5 to 5%. Fee.
<4> The component (B) is 2-methoxyhexyl dimethoxybenzylideneoxoimidazolidinepropionate, bisethylhexyloxyphenol methoxyphenyltriazine, methylenebisbenzotriazolyltetramethylbutylphenol, hexyl diethylaminohydroxybenzoylbenzoate, 2-hydroxy-4 -Methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfuric acid, 2,2'-dihydroxy-4-methoxybenzophenone, 2-ethylhexyl methoxycinnamate, p-methoxyhydrocinnamic acid diethanolamine salt, paraaminobenzoic acid (Hereinafter abbreviated as PABA), ethyldihydroxypropyl PABA, glyceryl PABA, homomenthyl salicylate, methyl-O-aminobenzoate, 2-ethyl Ruhexyl-2-cyano-3,3-diphenyl acrylate, 2-ethylhexyl paradimethylaminobenzoate, 2-phenyl-benzimidazole-5-sulfate, ethyl hexyl salicylate triethanolamine, 3- (4-methylbenzylidene) camphor, 2,4-dihydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2-hydroxy-4-N-octoxybenzophenone, 4- One or two kinds selected from isopropyl dibenzoylmethane, 4-tert-butyl-4′-methoxydibenzoylmethane, octyl triazone, dimethoxycinnamic acid isooctanoic acid glyceride, dimethicone ethylbenzalmalonate, and silane derivatives Is above <1> to sunscreen cosmetics of the <3>.
<5> Component (B) is 2-ethylhexyl dimethoxybenzylideneoxoimidazolidinepropionate, bisethylhexyloxyphenol methoxyphenyltriazine, methylenebisbenzotriazolyltetramethylbutylphenol, hexyl diethylaminohydroxybenzoylbenzoate, 4-tert-butyl -4'-methoxydibenzoylmethane, 2-ethylhexyl methoxycinnamate, 2-ethylhexyl 2-cyano-3,3-diphenyl acrylate, 2-ethylhexyl paradimethylaminobenzoate, ethylhexyl salicylate, octyltriazone, dimethicone ethylben <1> to <4> sunscreen cosmetics, which are one or more selected from zarmalonate and 2-phenyl-benzimidazole-5-sulfuric acid.
<6> The content of component (B) is 1% or more, preferably 2% or more, more preferably 3% or more, and 20% or less, preferably 15%, based on the total amount of sunscreen cosmetics. Hereinafter, sunscreen cosmetics according to <1> to <5>, more preferably 10% or less.
<7> Sunscreen cosmetics according to <1> to <6>, wherein the content of the component (B) is 1 to 20%, preferably 2 to 15%, more preferably 3 to 10%.
<8> Tanning of <1> to <7>, wherein component (C) is one or more selected from metal oxides, metal hydroxides, metal flakes, ceramics, and hydrophobized surface treated products thereof Stop cosmetics.
<1> Sunscreen cosmetics of <1> to <8>, wherein <9> component (C) is one or more selected from titanium oxide, zinc oxide, cerium oxide and their hydrophobized surface treated products.
<10> The average particle size of the component (C) is 10 nm or more, preferably 15 nm or more, more preferably 20 nm or more, and 200 μm or less, preferably 100 μm or less, more preferably 50 μm or less <1> to <9> sunscreen cosmetics.
<11> Sunscreen cosmetics according to <1> to <10>, wherein the average particle size of component (C) is 10 nm to 200 μm, preferably 10 nm to 100 μm, more preferably 15 nm to 50 μm, and further preferably 20 nm to 50 μm. .
<12> Hydrophobized surface treatment is fluorine compound treatment, silicone treatment, silicone resin treatment, pendant treatment, silane coupling treatment, titanium coupling treatment, silane treatment, oil agent treatment, N-acyl lysine treatment, polyacrylic acid treatment and metal <8> to <11> sunscreen cosmetics, which is a treatment selected from soap treatment.
<13> The content of component (C) is 1% or more, preferably 2% or more, more preferably 3% or more, and 30% or less, preferably 20%, based on the total amount of sunscreen cosmetics. The sunscreen cosmetics according to <1> to <12>, more preferably 15% or less.
<14> The sunscreen cosmetic according to <1> to <13>, wherein the content of the component (C) is 1 to 30%, preferably 2 to 20%, more preferably 3 to 15%.
<15> A sunscreen cosmetic according to <1> to <14>, which contains the component (B) and the component (C).

  EXAMPLES Hereinafter, although an Example demonstrates in detail regarding this invention, this invention is not limited by this.

Examples 1-9 and Comparative Examples 1-10
The sunscreen cosmetics shown in Table 1 were prepared according to a conventional method, and (1) UV protection effect, (2) Use feeling (stickiness), (3) Use feeling (squeak feeling) were evaluated by the following methods, The results are also shown in Table 1.

<UV protection effect>
Samples of sunscreen cosmetics of Examples and Comparative Examples were applied at a rate of 2 mg / cm2 on a resin tape affixed on quartz glass, and UV protection was achieved using an SPF analyzer (Labsphere, UV-1000S). It was measured.

Using the performance of Comparative Example 1 as a comparative control, the performance of the evaluation sample was evaluated according to the following criteria.
○: UV protection effect is superior to Comparative Example 1.
(Triangle | delta): The comparative example 1 and a ultraviolet-ray protective effect are comparable.
X: The ultraviolet-ray protective effect is inferior to the comparative example 1.

<Sensory property evaluation test>
The sunscreen cosmetics of Examples and Comparative Examples were prepared by a conventional method and subjected to a sensory property evaluation test. In the sensory property evaluation test, 10 expert panelists use each sample, and evaluate each sensory property of stickiness and squeakiness in five stages according to the following criteria, obtain an average score thereof, and determine 4.0 or more. , 3.0 or more and less than 4.0 were evaluated as ◯, 2.0 or more and less than 3.0 as Δ, and less than 2.0 as x.

(Evaluation criteria)
5: Very preferable.
4: Preferred.
3: Neither can be said.
2: Not preferred.
1: Very unfavorable.

  From Table 1 above, Comparative Examples 1 to 10, which do not contain the component (A), had an ultraviolet protection effect, but were unable to improve both stickiness and squeaky feeling. On the other hand, Examples 1-9 containing a component (A) had an ultraviolet-ray protective effect, and both the sticky feeling and the squeaky feeling were improved. In particular, in Example 5, a volatile silicone oil as described in Patent Document 3 and a specific polyether-modified silicone are used in combination with Comparative Example 5 in which the stickiness is slightly improved. A sunscreen cosmetic which was contained and significantly improved in both stickiness and squeakiness was obtained.

Examples 10-19
Sunscreen cosmetics having the compositions shown in Table 2 below were produced by a conventional method.

  The sunscreen cosmetics obtained in Examples 10 to 19 are excellent in UV protection effect, do not give a sticky feeling or squeaky feeling, have excellent sensory characteristics, do not cause separation after long-term storage, and also have storage stability. It was excellent.

Examples 20-22
A sunscreen cosmetic having the following composition was produced by a conventional method.

Example 20 (Foundation)
(Ingredient) (Mixed amount%)
Pentaerythritol 3.0
4-tert-Butyl-4′-methoxybenzoylmethane 1.0
(Product name: Parasol 1789, manufactured by Roche)
Diethylaminohydroxybenzoyl hexyl benzoate 0.5
(Product name: Yubinar Plus, manufactured by BASF)
2-ethylhexyl methoxycinnamate 6.0
(Product name: Yubinar MC-80, manufactured by BASF)
Silicone-treated fine particle zinc oxide 15.0
Silicone-treated titanium oxide 10.0
Silicone-treated talc 3.0
Silicone-treated yellow iron oxide 0.8
Silicone-treated black iron oxide 0.16
Isohexadecane 5.0
Tristrimethylsiloxymethylsilane (trade name: TMF-1.5, manufactured by Shin-Etsu Chemical Co., Ltd.) 5.0
Polyoxyethylene hydrogenated castor oil (60 EO) 2.0
1,3-butylene glycol 6.0
SEPIGEL 501 3.0
(Contains 20% by mass of polyacrylamide: manufactured by SEPPIC)
Succinoglycan 0.2
Carboxymethylcellulose 0.3
Ethanol 5.0
Purified water residue

Example 21 (sunscreen cosmetics)
(Ingredient) (Mixed amount%)
Pentaerythritol 1.0
Monoisopropylidene pentaerythritol 0.5
Di (1-ethylpropylidene) pentaerythritol 3.0
2-Ethylhexyl paramethoxycinnamate 4.0
(Product name: Yubinar MC-80, manufactured by BASF)
4-tert-Butyl-4'-methoxydizenzoylmethane 1.0
(Product name: Parasol 1789, manufactured by Roche)
Diethylaminohydroxybenzoyl hexyl benzoate 0.5
(Product name: Yubinar Plus, manufactured by BASF)
Silicone-treated zinc titanium 10.0
Silicone-treated zinc oxide 10.0
Polymethylsilsesquioxane 3.0
Dimethylpolysiloxane 5.0
Octyldodecyl myristate 5.0
Polyoxyethylene hydrogenated castor oil (60 EO) 1.0
Monolauric acid polyoxyethylene sorbitan (20E.O.) 0.5
Glycerin 3.0
Trimethylsiloxysilicate 0.5
Ethanol 0.5
Phenoxyethanol 0.5
Edetate trisodium 0.01
Xanthan gum 0.1
Sodium hyaluronate 0.1
Purified water residue

Example 22 (sunscreen cosmetics)
(Ingredient) (Mixed amount%)
Pentaerythritol 2.0
2-Ethylhexyl 2-cyano-3,3-diphenyl acrylate (trade name: Ubinur N539, manufactured by BASF) 3.0
2-Phenyl-benzimidazole-5-sulfuric acid (trade name: Ortholex 232, manufactured by Merck & Co., Inc.) 2.0
Alumina / stearic acid-treated titanium oxide 8.0
Methylpolysiloxane / myristic acid-treated zinc oxide 4.0
Decamethylpentasiloxane 5.0
Tristrimethylsiloxymethylsilane (trade name: TMF-1.5, manufactured by Shin-Etsu Chemical Co., Ltd.) 20.0
Methylpolysiloxane 7.0
Polyglycerin-modified silicone 3.0
Organically modified bentonite 0.5
Glycerin 3.0
Triethanolamine 0.25
Ethanol 5.0
Pure water residue

  The sunscreen cosmetics obtained in Examples 20 to 22 were all excellent in UV protection effect, had no stickiness or squeaky feeling, had excellent sensory characteristics, and had excellent storage stability.

  According to the present invention, it is possible to provide a sunscreen cosmetic that has an excellent ultraviolet protection effect, does not produce a sticky feeling or a squeaky feeling, has excellent sensory characteristics, and has excellent stability.

Claims (1)

And the following components (A), sunscreen cosmetics containing component (B)及beauty component (C).
(A) Pentaerythritol, one or more selected from alkylacetal derivatives of pentaerythritol represented by the following general formulas (1) and (2) 0.5 to 4% by mass

(In formula, R < ¹ > and R < ² > show a C1-C4 alkyl group which may mutually differ.)

(In formula, R < ³ > -R < ⁶ > shows a C1-C4 alkyl group which may mutually differ.)
(B) 2-ethylhexyl dimethoxybenzylideneoxoimidazolidinepropionate, bisethylhexyloxyphenol methoxyphenyltriazine, hexyl diethylaminohydroxybenzoyl benzoate, 4-tert-butyl-4'-methoxydibenzoylmethane, ethylhexyl methoxycinnamate, 2 1 selected from ethylhexyl 2-cyano-3,3-diphenyl acrylate, 2-ethylhexyl paradimethylaminobenzoate, ethylhexyl salicylate, octyl triazone, methylenebisbenzotriazolyl tetramethylbutylphenol, and dimethicone ethylbenzalmalonate 3-10% by mass of seed or two or more kinds of ultraviolet absorbers
(C) One or two or more kinds of ultraviolet scattering agents selected from titanium oxide, zinc oxide, cerium oxide and their hydrophobized surface treated products 3 to 15% by mass