WO2012090297A1

WO2012090297A1 - Sunscreen cosmetic

Info

Publication number: WO2012090297A1
Application number: PCT/JP2010/073701
Authority: WO
Inventors: 吉田　晋; 公司阿部; 由紀杉山; 秀人上田; 登美子高倉
Original assignee: 株式会社資生堂
Priority date: 2010-12-28
Filing date: 2010-12-28
Publication date: 2012-07-05

Abstract

The purpose of the invention is to provide, from a different perspective from the prior art, a sunscreen cosmetic containing a water-soluble ultraviolet absorber, wherein increasing SPF, while maintaining the excellent property of having a moist feel during use, has been made possible. The invention provides a sunscreen cosmetic characterized in containing (a) 0.1-5 mass% of phenylbenzimidazole sulfonic acid, and (b) N,N, N',N'-tetrax (2-hydroxypropyl) ethylene diamine in an amount appropriate for neutralizing the phenylbenzimidazole sulfonic acid (a).

Description

Sunscreen cosmetics

The present invention relates to a sunscreen cosmetic. More specifically, the present invention relates to a sunscreen cosmetic that exhibits a high SPF value and is excellent in usability such as a fresh feeling of use.

In sunscreen cosmetics, it is necessary to add inorganic powder, organic UV absorbers, etc. to the formulation in order to provide Sun Protection Factor (SPF), an index that prevents UV rays. . In general, sunscreen cosmetics often take the form of water-in-oil emulsions or oil-in-water emulsions, and are used for suitable applications based on the characteristics of each.

The water-in-oil emulsion has the characteristics that it can easily achieve high SPF and has excellent water resistance because it can be highly blended with oil-soluble UV absorbers and inorganic powders, but it is problematic in terms of oily and sticky feeling. May occur. On the other hand, oil-in-water emulsions provide a fresh feeling of use, but oil-soluble UV absorbers and inorganic powders cannot be blended in high amounts, and water-soluble UV absorbers do not function well in formulations and have high SPF. There was a problem that it was difficult to achieve. In addition, when trying to increase the blending amount of an oil-soluble ultraviolet absorber or the like in order to increase SPF, there is a problem that the amount of oily components in the preparation increases and the fresh feeling of use is lost.

In connection with these problems, for example, Patent Document 1 discloses that an oil-soluble ultraviolet absorber is not highly blended, achieves both UV protection effect and stability without impairing a fresh feeling of use. As an oil-in-water emulsified sunscreen cosmetic with excellent film uniformity and usability (skin familiarity), in addition to oil-soluble and water-soluble UV absorbers, specified as water-soluble thickener (acrylic water-soluble polymer) Containing a hydrophilic nonionic surfactant.

Patent Document 2 discloses that an oil-in-water emulsified cosmetic containing a specific amount of alkylmethyl tauric acid, a water-soluble ultraviolet absorber, an oil agent, and water has an excellent UV protection effect, and has a feeling of use (no freshness or stickiness). ) And stability over time are also described.
Patent Document 3 is mainly an oil-based composition, but by itself blending an organopolysiloxane elastomer spherical powder that does not have an ultraviolet absorption effect or a scattering effect, the ultraviolet protection effect is improved and extended. It is described that the feeling of refreshment is also improved.

JP 2008-162930 A JP 2002-284638 A JP-A-8-259419

The problem in the present invention is that the sunscreen cosmetic containing a water-soluble UV absorber retains excellent usability such as a fresh touch from a viewpoint different from the prior art including Patent Documents 1 to 3 described above. An object of the present invention is to provide a cosmetic that can increase SPF.

In order to solve the above-mentioned problems, the present inventors have intensively studied. As a result, a high SPF can be obtained by selecting and combining a combination of phenylbenzimidazolesulfonic acid, which is a water-soluble ultraviolet absorber, and a specific neutralizing agent. The inventors have found that a value can be achieved and have come to make the present invention.

That is, the present invention
(A) 0.1 to 5% by mass of phenylbenzimidazolesulfonic acid, and (b) N, N, N ′, N′— in an amount suitable for neutralizing the phenylbenzimidazolesulfonic acid (a). A sunscreen cosmetic comprising tetrakis (2-hydroxypropyl) ethylenediamine is provided.

The sunscreen cosmetic of the present invention can achieve a high SPF value and is excellent in feeling of use such as freshness and non-stickiness. Paying attention to the neutralized salt to be blended in combination with the water-soluble ultraviolet absorber, the ultraviolet absorbing ability improving effect obtained by using a specific neutralized salt is an effect first found in the present invention.

When sodium hydroxide (NaOH) was used as a neutralized salt of phenylbenzimidazolesulfonic acid (solid line) and N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine (N-TE) was used It is a figure which shows the ultraviolet absorption spectrum of a case (broken line).

As described above, the sunscreen cosmetic of the present invention uses phenylbenzimidazolesulfonic acid as a water-soluble ultraviolet absorber, and N, N, N ′, N′-tetrakis (2-hydroxypropyl) as a neutralized salt thereof. Using ethylenediamine, the specific combination is selected and blended.

The phenylbenzimidazolesulfonic acid (component a) used in the cosmetics of the present invention has been conventionally used in cosmetics and the like as a water-soluble ultraviolet absorber, and is mainly used in the UV-B region (290- It is an organic compound that effectively absorbs ultraviolet rays of 320 nm). In the present invention, for example, commercially available Ortholex 232 (manufactured by Merck) or Neo Heliopan Hydro (manufactured by Simrise) can be suitably used.

The blending amount of phenylbenzimidazolesulfonic acid in the present invention is 0.1 to 5% by mass, preferably 0.5 to 4% by mass, more preferably 1 to 3% by mass. When the blending amount is less than 0.1% by mass, it is difficult to obtain a sufficient ultraviolet ray preventing effect. When the blending amount exceeds 5% by mass, precipitation of crystals and irritation to the skin tend to be strong.

In the cosmetic of the present invention, N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine (component b) is used as a neutralized salt of phenylbenzimidazolesulfonic acid. N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine used in the present invention may be a commercially available product, for example, trade name Neutrole TE (BASF).

In the present invention, the amount of N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine is an amount suitable for neutralizing the phenylbenzimidazolesulfonic acid. Specifically, the concentration may be about 10% above and below the concentration (mass%) serving as the neutralization point of the blended phenylbenzimidazolesulfonic acid. For example, when the concentration serving as the neutralization point is 3% by mass, it is within the range of 2.7% by mass to 3.3% by mass.

The cosmetic of the present invention is required to contain N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine as a neutralized salt, but in addition to that, conventionally, such as NaOH and KOH. It is not excluded to add the neutralized salt used. When other neutralized salts are contained, the total amount of these other neutralized salts and N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine neutralizes phenylbenzimidazolesulfonic acid. It is sufficient that the amount is suitable for.
In addition, in the case where the cosmetic of the present invention contains a component to be neutralized with a neutralization salt (alkali source) in addition to phenylbenzimidazolesulfonic acid, and further contains another neutralization salt, Needless to say, the total amount of N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine and other neutralized salts is an amount necessary to neutralize the entire system. In that case, part of the other neutralized salt may contribute to the neutralization of phenylbenzimidazolesulfonic acid, and the other part of the neutralized salt and N, N, N ′, N′-tetrakis The total blending amount with (2-hydroxypropyl) ethylenediamine is an amount suitable for neutralizing phenylbenzimidazolesulfonic acid.

The cosmetic of the present invention is preferably provided as an aqueous composition or an oil-in-water emulsion composition in order to ensure a fresh and refreshing feeling of use. In the cosmetic of the present invention, SPF based on a water-soluble ultraviolet absorber is remarkably improved by blending a specific neutralizing agent, so that it is not necessary to blend an oil-soluble ultraviolet absorber as in the prior art. . However, the addition of oil-soluble UV absorbers is not excluded, and additional effects such as further improvement of SPF and enhancement of UV-absorbing ability in the UV-A region by further adding oil-soluble UV absorbers. Can be obtained.

The oil-soluble ultraviolet absorber that can be blended in the cosmetic of the present invention is not particularly limited, and examples thereof include paraaminobenzoic acid (PABA), PABA monoglycerin ester, N, N-dipropoxy PABA ethyl ester, N, N -Benzoic acid UV absorbers such as diethoxy PABA ethyl ester, N, N-dimethyl PABA ethyl ester, N, N-dimethyl PABA butyl ester, diethylaminohydroxybenzoyl hexyl benzoate; anthranyl such as homomenthyl-N-acetylanthranylate Acid ultraviolet absorbers; salicylic acid such as amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropanol phenyl salicylate UV absorber: octyl cinnamate, ethyl-4-isopropyl cinnamate, methyl-2,5-diisopropyl cinnamate, ethyl-2,4-diisopropyl cinnamate, methyl-2,4-diisopropyl cinnamate, propyl-p- Methoxycinnamate, isopropyl-p-methoxycinnamate, isoamyl-p-methoxycinnamate, octyl-p-methoxycinnamate [= 2-ethylhexyl-p-methoxycinnamate], 2-ethoxyethyl-p-methoxycinnamate Cyclohexyl-p-methoxycinnamate, ethyl-α-cyano-β-phenylcinnamate, 2-ethylhexyl-α-cyano-β-phenylcinnamate, glyceryl mono-2-ethylhexanoyl-diparamethoxycinnamate, 3 , 4,5-trimethoxycinnamic acid 3-methyl-4- [methylbis (trimethylsiloxy) silyl] butyl and other cinnamic acid-based UV absorbers; 2-phenyl-5-methylbenzoxazole, 2,2 '-Hydroxy-5-methylphenylbenzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenylbenzotriazole), dibenzalazine, dianisoyl Methane, 4-tert-butyl-4′-methoxydibenzoylmethane, 4- (1,1-dimethylethyl) -4′-methoxydibenzoylmethane, 5- (3,3-dimethyl-2-norbornylidene) -3 -Pentan-2-one, octocrylene [= 2-cyano-3,3-diphenyl-2-propenoate-2-ethyl Hexyl ester], polysilicon -15 = dimethicone co diethyl benzalmalonate], and the like.

When the oil-soluble ultraviolet absorber is blended, the blending amount is at most 1% by mass, preferably 0.5% by mass or less. If the blending amount exceeds 1% by mass, the blending amount of the oil agent for dissolving it also increases, so that the freshness tends to deteriorate not only for the whole preparation.

The cosmetics of the present invention can be blended with other ingredients usually used in sunscreen cosmetics and the like within a range that does not impair the effects of the present invention. For example, vitamins, fats and oils, waxes, hydrocarbon oils, higher alcohols, synthetic ester oils, silicones, humectants, anionic surfactants, cationic surfactants, amphoteric surfactants, antiseptics, anti-inflammatory agents, whitening agents, Examples include plant extracts, activators, blood circulation promoters, water-soluble polymers, thickeners, powder components, and sequestering agents.

The dosage form of the sunscreen cosmetic of the present invention is not particularly limited, but it is preferably provided in the form of lotion, milky lotion, cream or the like.

Hereinafter, the present invention will be described in more detail with specific examples, but the present invention is not limited to these examples. Moreover, in the following examples etc., unless otherwise indicated, the blending amount represents mass%.

(Test example)
The aqueous solution containing phenylbenzimidazolesulfonic acid (5% by mass) was neutralized by adding sodium hydroxide or N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine.
Each neutralized aqueous solution was coated with 1 mg / cm ² on a substrate made of PMMA, and the absorption spectrum in the ultraviolet region was measured (measuring device: UV-4100 (manufactured by Hitachi)).
The measurement results are shown in FIG. As is apparent from the figure, when N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine is used as the neutralization salt, ultraviolet rays are used compared with the case where NaOH is used as the neutralization salt. Absorption capacity improved significantly.

Example 1
Sunscreen latex:
Compounding component amount (% by mass)
1. Ion exchange water 50
2. Acrylic acid / alkyl methacrylate copolymer (Pemulene TR-1 manufactured by Goodrich) 0.1
3. Agar 0.5
4). Potassium hydroxide 0.05
5. Dimethylpolysiloxane 3
6). Decamethylcyclopentasiloxane 4
7. Squalane 2
8). Sunflower oil 1
9. Ethanol 5
10. Glycerin 6
11.1,3-butylene glycol 5
12 Polyoxyethylene methyl glucoside 3
13. Sodium hexametaphosphate 0.05
14 Hydroxypropyl-β-cyclodextrin 0.1
15. Dipotassium glycyrrhizinate 0.05
16. Loquat leaf extract 0.1
17. Sodium L-glutamate 0.05
18. Fennel extract 0.1
19. Yeast extract 0.1
20. Lavender oil 0.1
21. Giant extract 0.1
22. Xanthan gum 0.1
23. Bengala appropriate amount 24. Yellow iron oxide Paraben appropriate amount 26. Purified water residue 27. Phenylbenzimidazolesulfonic acid 3
28. N, N, N ′, N′-tetrakis- (2-hydroxypropyl)
Ethylenediamine (Neutrol TE: manufactured by Merck & Co., Inc.) 3.2

<Manufacturing method>
(1) 1 and 2 are heated and dissolved, cooled to room temperature, and then pulverized with a homomixer to form mixture 1.
(2) Add 3 and 4 to mixture 1 to form mixture 2.
(3) Add 8 to 28 to the mixture 2 at room temperature and mix to obtain the mixture 3.
(4) Add 5 to 7 to the mixture 3 at room temperature and emulsify with a homomixer to obtain the desired product.

(Example 2)
Sunscreen lotion:
Compounding component amount (% by mass)
1. Ion exchange water 50
2. Glycerin 1
3. Agar 0.5
4. 1,3-Butylene glycol 5
5. Sodium hexametaphosphate 0.03
6). Trimethylglycine 1
7. Sodium polyaspartate 0.1
8). α-tocopherol 2-L-ascorbic acid potassium phosphate diester 0.1
9. Thiotaurine 0.1
10. Green tea extract 0.1
11. Western mint extract 0.1
12 Iris root extract 0.1
13. EDTA3 sodium 0.1
14 Purified water residue 15. Ethyl alcohol 5
16. POE, POP decyl tetradecyl ether 0.2
17. Phenoxyethanol appropriate amount 18. Perfume proper amount19. Phenylbenzimidazolesulfonic acid 3
20. N, N, N ′, N′-tetrakis- (2-hydroxypropyl)
Ethylenediamine (Neutrol TE: manufactured by Merck & Co., Inc.) 3.2

<Manufacturing method>
(1) 1 and 2 are heated and dissolved, cooled to room temperature, and then pulverized with a homomixer to form mixture 1.
(2) 3 to 15 are mixed with the mixture 1 at room temperature to obtain a mixture 2.
(3) 16 to 18 are mixed at room temperature and then added to mixture 2 to form mixture 3.
(4) 19 and 20 are added to the mixture 3 at room temperature to obtain the desired product.

(Example 3)
Lotion:
Compounding component amount (% by mass)
1. Ion exchange water 50
2. Ethanol 10
3. Agar 0.5
4). Dipolopylene glycol 1
5. Polyethylene glycol 1000 1
6). Polyoxyethylene methyl glucoside 1
7. Jojoba oil 0.01
8). Glyceryl tri-2-ethylhexanoate 0.1
9. Polyoxyethylene hydrogenated castor oil 0.2
10. Polyglyceryl diisostearate 0.15
11. N-stearoyl-L-glutamate sodium 0.1
12 Citric acid 0.05
13. Sodium citrate 0.2
14 Sodium hydroxide 0.4
15. Dipotassium glycyrrhizinate 0.1
16. Arginine hydrochloride 0.1
17. L-ascorbic acid 2-glucoside 2
18. Ogon Extract 0.1
19. Yukinoshita extract 0.1
20. Nettle extract 0.1
21. Tranexamic acid 1
22. Edetate trisodium 0.05
23. 2-Ethylhexyl paramethoxycinnamate 0.01
24. Dibutylhydroxytoluene Suitable amount 25. Paraben appropriate amount 26. Deep sea water 3
27. Purified water Residual 28. Perfume appropriate amount29. Phenylbenzimidazolesulfonic acid 3
30. N, N, N ′, N′-tetrakis- (2-hydroxypropyl)
Ethylenediamine (Neutrol TE: manufactured by Merck & Co., Inc.) 3.2

<Manufacturing method>
(1) 1 and 2 are heated and dissolved, cooled to room temperature, and then pulverized with a homomixer to form mixture 1.
(2) 3 to 11, 23 to 25 and 28 are dissolved by heating at 70 ° C. and added to mixture 1 to form mixture 2.
(3) 12-22, 26, 27, 29 and 30 are mixed and dissolved at room temperature and added to the mixture 2 to obtain the desired product.

Example 4
Sunscreen latex:
Compounding component amount (% by mass)
1. Ion exchange water 50
2. Carboxyvinyl polymer 0.1
3. Agar 0.5
4). Potassium hydroxide appropriate amount 5. Dimethylpolysiloxane 2
6). Behenyl alcohol 1
7. Batyl alcohol 0.5
8). Squalane 6
9. Tetra-2-ethylhexanoic acid pentaerythrit slit 2
10. Polyoxyethylene glyceryl isostearate 1
11. Polyoxyethylene glyceryl monostearate 1
12 Hardened oil 3
13. Glycerin 5
14.1,3-Butylene glycol 7
15. Erythritol 2
16. Sodium hexametaphosphate 0.05
17. Phenoxyethanol appropriate amount 18. Phenylbenzimidazolesulfonic acid 3
19. N, N, N ′, N′-tetrakis- (2-hydroxypropyl)
Ethylenediamine (Neutrol TE: manufactured by Merck & Co., Inc.) 3.2
20. Purified water residue

<Manufacturing method>
(1) 1 and 2 are heated and dissolved, cooled to room temperature, and then pulverized with a homomixer to form mixture 1.
(2) Add 3 and 4 to mixture 1 to form mixture 2.
(3) After 5 to 12 are dissolved by heating, they are added to the mixture 2 and emulsified with a homomixer to obtain an emulsion 1.
(4) Add 13 to 20 to Emulsion 1 to obtain the desired product.

(Example 5)
Sunscreen cream:
Compounding component amount (% by mass)
1. Ion exchange water 50
2. Bentonite 1
3. Agar 0.5
4). Stearic acid 1
5. Palmitic acid 1
6). Glyceryl tri-2-ethylhexanoate 3
7. Cetyl 2-ethylhexanoate 2
8). Polyoxyethylene glyceryl isostearate 1
9. Glycerol monostearate 1
10. Polyoxyethylene glyceryl monostearate 1
11.4-t-butyl-4'-methoxy-
Dibenzoylmethane 1
12 2-Ethylhexyl paramethoxycinnamate 7
13. Eicosene / vinylpyrrolidone copolymer 2
14 Fine particle tyrene oxide (30 nm) 2
15. Sodium hexametaphosphate 0.1
16. Phenoxyethanol appropriate amount17. Edetate trisodium appropriate amount 18. Dipropylene glycol 5
19. Purified water Residual 20. Perfume appropriate amount 21. Phenylbenzimidazolesulfonic acid 3
22. N, N, N ′, N′-tetrakis- (2-hydroxypropyl)
Ethylenediamine (Neutrol TE: manufactured by Merck & Co., Inc.) 3.2

<Manufacturing method>
(1) 1 and 2 are heated and dissolved, cooled to room temperature, and then pulverized with a homomixer to form mixture 1.
(2) Add 3 to the mixture 1 and disperse with a homomixer to make dispersion 1.
(3) After 4 to 13 are dissolved by heating, they are added to the heated dispersion 1 and emulsified with a homomixer to obtain emulsion 1.
(4) Add 14 and 15 to Emulsion 1 and disperse with a homomixer to make Dispersion 2.
(5) Add 16 to 22 to Dispersion 2, and after dispersing with a homomixer, cool to room temperature to obtain the desired product.

Claims

(A) 0.1 to 5% by mass of phenylbenzimidazolesulfonic acid, and (b) N, N, N ′, N′— in an amount suitable for neutralizing the phenylbenzimidazolesulfonic acid (a). A sunscreen cosmetic comprising tetrakis (2-hydroxypropyl) ethylenediamine.
The cosmetic according to claim 1, wherein the cosmetic is in the form of an aqueous composition or an oil-in-water emulsion composition.