JP2020105109A - Water-in-oil type sunscreen cosmetic - Google Patents

Abstract

To provide a water-in-oil type sunscreen cosmetic having high stability while using a solid ultraviolet absorber and having an excellent ultraviolet protection effect and excellent sense of use.SOLUTION: There is provided a water-in-oil type sunscreen cosmetic which comprises the following components (A) to (D): (A) the following (a1) and (a2), (a1) ethylhexyl triazone, (a2) a solid ultraviolet absorber containing hexyl diethylaminohydroxybenzoate and/or bis-ethylhexyloxyphenol methoxyphenyl triazine, (B) one or two or more polar oils selected from diisopropyl sebacate, diethyl hexyl succinate and diisopropyl adipate, (C) a volatile hydrocarbon oil and (D) a poly (12-hydroxystearic acid) ester of a polyhydric alcohol.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a water-in-oil type sunscreen cosmetic which has a high stability, an excellent ultraviolet protection effect and a feeling of use while dissolving and using a solid ultraviolet absorber at room temperature.

2. Description of the Related Art Conventionally, UV absorbents that are liquid at room temperature, such as ethylhexyl methoxycinnamate and octocrylene, which have absorption wavelengths in the UVB region, have been widely used for sunscreen cosmetics having an ultraviolet protection effect. However, it has been pointed out that these liquid ultraviolet absorbers have skin irritation and adverse effects on the environment. On the other hand, it is possible to replace the liquid ultraviolet absorber with a powder ultraviolet scattering agent, but with the increase in the amount used, there is a problem that it becomes unnaturally white when applied and has a powdery feel. Can occur separately.

Therefore, alternatives to solid UV absorbers are being investigated, but liquid UV absorbers not only have UV absorbing ability by themselves, but are solid solvent or poorly soluble UV absorber solvents that are co-blended. Also works. Therefore, if these liquid ultraviolet absorbers are not blended, in order to prevent precipitation or destabilization of the solid UV absorbers that are co-blended, there is no choice but to blend a large amount of polar oil as a solvent, As a result, there have been concerns about problems such as an oily feeling in use and stickiness.

Various studies have been made to solve such problems. For example, a specific solid ultraviolet absorber is combined, an ester oil having high solubility is used for these, and a certain amount or more of an ultraviolet scatterer is blended. A sunscreen cosmetic is disclosed (Patent Document 1). However, this cosmetic material lacks stability and, when solubility is poor, the UV protection effect of the solid UV absorber is not sufficient, and a UV scatterer of a certain amount or more is added to enhance the UV protection ability. Since it is necessary, the problem of powderiness and whitening still remains. In addition, a cosmetic (Patent Document 2) in which a solid polar UV absorber is combined with a liquid polar oil having a specific IOB value and a polyoxyethylene alkyl/alkenyl ether, and three types of solid UV absorbers and water-soluble Cosmetics (Patent Document 3) in which a polar oil, a higher alcohol, and a nonionic surfactant are further used in combination with an ultraviolet absorber have been proposed, but these also have stability and ultraviolet protection effects. It is difficult to evaluate as sufficient.

JP, 2017-78054, A JP, 2014-114273, A JP, 2018-145117, A

An object of the present invention is to provide a water-in-oil type sunscreen cosmetic having high stability while using a solid ultraviolet absorber, and having excellent ultraviolet protection effect and feeling of use.

As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have combined a specific solid-state ultraviolet absorber, and further added a specific polar oil, volatile hydrocarbon oil, and poly(12- It was found that the incorporation of (hydroxystearic acid) ester improves the emulsion stability of the solid ultraviolet absorber, exerts a high ultraviolet protection effect, and provides a refreshing and good usability without stickiness. The present invention has been completed.

That is, the present invention provides the following components (A) to (D);
(A) The following (a1) and (a2);
(A1) Ethylhexyltriazone (a2) Solid UV absorber containing hexyl diethylaminohydroxybenzoylbenzoate and/or bisethylhexyloxyphenol methoxyphenyltriazine (B) Diisopropyl sebacate, diethylhexyl succinate and diisopropylpropionate adipate A water-in-oil type characterized by containing a poly(12-hydroxystearic acid) ester of a polar oil (C) a volatile hydrocarbon oil (D) a polyhydric alcohol selected from the group consisting of It is a sunscreen cosmetic.

The water-in-oil type sunscreen cosmetic of the present invention has a high emulsion stability and water resistance while using a solid ultraviolet absorber dissolved in a polar oil and exhibits an excellent ultraviolet protection effect. It has no stickiness and a refreshing good feeling. In addition, even if you do not use liquid UV absorbers or UV scatterers together, you can achieve a very good UV protection effect.By suppressing the use of these components, you can increase safety and create an unnatural appearance during application. It is possible to reduce whiteness and powderiness.

The water-in-oil type sunscreen cosmetic of the present invention comprises (A) a specific solid ultraviolet absorber, (B) a specific polar oil, (C) a volatile hydrocarbon oil, and (D) a polyhydric alcohol poly( 12-hydroxystearic acid) ester as an essential component.

In the water-in-oil type sunscreen cosmetic of the present invention, (a1) ethylhexyltriazone is used as the component (A) solid ultraviolet absorber. Ethylhexyltriazone is commercially available as Uvinul T-150 (manufactured by BASF). In addition, in this specification, a solid state means a solid state at normal temperature (25° C.).

As the component (A), hexyl diethylaminohydroxybenzoylbenzoate and/or bisethylhexyloxyphenol methoxyphenyltriazine (a2) is used together with the above (a1). Hexyl ethylaminohydroxybenzoylbenzoate is commercially available as UVINUL A Plus Granular (manufactured by BASF), and bisethylhexyloxyphenol methoxyphenyltriazine is marketed as Tinosorb S (manufactured by BASF).

The content of the component (A) in the cosmetic of the present invention is preferably 1 to 20% by mass (hereinafter simply referred to as “%”), and 5 to 18%, from the viewpoint of the ultraviolet protection effect, stability and the like. More preferable. From the same viewpoint, the content of the component (a1) in the cosmetic is, for example, 0.1 to 8%, preferably 0.5 to 5%, more preferably 3 to 5%. .. The content of the component (a2) is preferably 1 to 20%, more preferably 2 to 8%, and particularly preferably 3 to 6%. Further, the content mass ratio ((a1):(a2)) of the components (a1) and (a2) is preferably in the range of 1:0.2 to 1:40, and 1:0.4 to 1:15. Is more preferable, and 1:0.6 to 1:12 is particularly preferable. On the other hand, from the viewpoint of skin irritation and the like, it is preferable not to use a liquid ultraviolet absorber such as ethylhexyl methoxycinnamate and octocrylene in the cosmetic of the present invention at room temperature.

Component (B) is one or more polar oils selected from diisopropyl sebacate, diethylhexyl succinate and diisopropyl adipate. Of these, diisopropyl sebacate is preferably used in terms of the ultraviolet protection effect and stability. Among commercially available products, FineNeo-iPSE, FineNeo-EHSU, FineNeo-DIA and the like manufactured by Nippon Seika can be preferably used.

The content of the component (B) is preferably 5 to 25%, more preferably 10 to 20%, particularly preferably 15 to 20%, from the viewpoints of the ultraviolet protection effect, stability, feeling of use and the like.

The component (C) is one or more volatile hydrocarbon oils selected from isododecane, isohexadecane and hydrogenated polyisobutene. Among these, isododecane is preferable from the viewpoints of stability and feeling of use.

The content of the component (C) is preferably 0.1 to 40%, more preferably 5 to 25%, from the viewpoint of stability, feeling of use and the like. Since the cosmetics of the present invention may impair stability and the like, it is preferable that the cosmetics do not substantially contain other volatile non-polar oils such as volatile silicone oils. In the present specification, “not substantially containing” means that the content in the cosmetic is 0.1% or less, preferably 0.01% or less. Further, in the present specification, volatile means that it is volatile at 1 atm and 25°C.

In the present invention, poly(12-hydroxystearic acid) ester of polyhydric alcohol is used as the component (D). The poly(12-hydroxystearic acid) preferably has an average molecular weight of 1000 to 3000. As the di(12-hydroxystearic acid) ester of polyethylene glycol, PEG-30 of dipolyhydroxystearic acid is suitable, and as a commercial product thereof, CITHOL DPHS (manufactured by Croda Japan Co., Ltd.) and the like can be mentioned.

The content of the component (D) is preferably 0.5 to 6%, more preferably 1 to 5%, and particularly preferably 1 to 4%, from the viewpoint of the ultraviolet protection effect and stability.

The cosmetic of the present invention may further contain an ultraviolet scattering agent as the component (E). Examples of the ultraviolet scattering agent include zinc oxide, titanium oxide, iron oxide and the like. Of these, zinc oxide and titanium oxide are preferably used. These may be subjected to various known surface treatments such as silicone treatment, fluorine-containing compound treatment, fatty acid treatment, amino acid treatment, and metal soap treatment. The average particle size of the ultraviolet scattering agent is preferably 100 nm or less, more preferably 80 nm or less.

The content of the component (E) is 3% or less, preferably 1% or less, and further preferably substantially not contained. If it is more than 3%, it may have a powdery feel or may be unnaturally white when applied.

As the aqueous component to be blended in the cosmetic of the present invention, in addition to water, glycols such as propylene glycol, 1,3-butylene glycol, dipropylene glycol and polyethylene glycol, and glycerin having three or more hydroxyl groups in the molecule. , Diglycerin, triglycerin, polyglycerin such as tetraglycerin, maltose, maltitol, sucrose, fructose, mannitol, xylitol, sorbitol, maltotriose, slateol, erythritol, polyethylene glycol, polyoxyalkylene alkyl glycosides and other glucose Examples thereof include derivatives. The water content is not particularly limited, but is preferably 30 to 80%, more preferably 45 to 70% from the viewpoint of stability, feeling of use and the like. The content of the aqueous component other than water is preferably 3 to 20% by mass, and more preferably 5 to 15% by mass from the viewpoint of stability, usability and the like.

In addition to the water-in-oil type cosmetic composition of the present invention, other components that are usually used in cosmetics can be appropriately blended within a range not impairing the effects of the present invention. Examples of such components include surfactants other than the component (D), waxes, fatty acids, silicone compounds, higher alcohols, polar oils such as esters other than the component (B), powders other than the ultraviolet scattering agent, and additives. Examples include sticky agents, antibacterial preservatives, fragrances, alcohols, salts, antioxidants, chelating agents, pH adjusters, physiologically active ingredients and the like.

The water-in-oil type sunscreen makeup of the present invention is prepared by mixing the above-mentioned components (A) to (D) and the optional component (E) and other optional components, using an emulsifying disperser or the like, according to a conventional method. The ingredients can be prepared.

The viscosity of the cosmetic of the present invention is preferably 20,000 mPa·s or less (viscosity measured using a B-type viscometer at a measurement temperature of 25° C.) from the viewpoint of feeling of use and the like, 10,000 mPa·s It is more preferably s or less. In this specification, the viscosity of cosmetics is a value measured by the method shown in the examples.

The SPF of the cosmetic of the present invention is preferably 15 or more, more preferably 20 or more. In the present specification, SPF is a value measured by the method shown in the examples.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.

Examples 1-7 and Comparative Examples 1-4
Water-in-oil type cosmetics having the compositions shown in Tables 1 and 2 below were prepared according to the following production method. For each, SPF, UVAPF, and viscosity were measured by the following methods. The emulsion stability and the feeling of use were evaluated according to the following evaluation methods. The results are also shown in Tables 1 and 2.

(SPF measurement method)
Each sample was applied to a PMMA plate, dried, and then measured at predetermined 5 points on the PMMA plate using an SPF analyzer (Labsphere UV-2000S, manufactured by Labsphere).

(UVAPF measurement method)
Each sample was applied to a PMMA plate, dried, and then measured at predetermined 5 points on the PMMA plate using an SPF analyzer (Labsphere UV-2000S, manufactured by Labsphere).

(Viscosity measuring method)
The sample was stored at 25° C., and the viscosity on the day after preparation was measured using a B-type viscometer (manufactured by Toki Sangyo). (No. 3 rotor, rotor rotation speed 30 rpm, 60 seconds after the start of measurement)

(Stability evaluation method)
The appearance of the sample stored at 40° C. for one month was visually observed and evaluated according to the following criteria.
[Stability evaluation criteria]
◯: No abnormality X: Crystal precipitation or phase separation was observed

(Usability evaluation method)
Each sample was evaluated by 10 panelists specializing in sensory evaluation of the feeling of use (no oiliness during application, no stickiness after application, no whiteness during application) according to the following criteria. A rating was given, and the average value was calculated from the total rating of all the panel members of each sample, and the judgment was made according to the following three-step judgment criteria.
〔Evaluation criteria〕
(Score): (Evaluation)
5 points: Good 4 points: Slightly good 3 points: Normal 2 points: Slightly bad 1 point: Poor 3 step judgment standard (judgment): (average score)
○: 4 points or more △: More than 2 points and less than 4 points ×: 2 points or less

(Production method)
The oily component (A) of the components 1 to 16 and the aqueous component (B) of the components 19 to 22 were weighed in separate beakers and dissolved by heating. (B) was gradually added to (A) and emulsified using a homomixer. The mixture was cooled to 40° C. or lower, and the powder components 17 and 18 were added if necessary and uniformly mixed with a homomixer to obtain a water-in-oil emulsion.

By blending PEG-30 dipolyhydroxystearate as a surfactant and using it alone or in combination with other surfactants, cosmetics exhibiting sufficient SPF and having good stability and usability were obtained ( Examples 1-7). On the other hand, when other surfactants were used without blending PEG-30 dipolyhydroxystearate, the emulsion stability was significantly reduced (Comparative Example 1). In Comparative Example 2 in which the volatile silicone oil was blended and Comparative Example 3 in which the polar oil was blended with an ester oil other than the specific ester oil, precipitation of crystals was observed and a stable cosmetic material could not be obtained. In Comparative Example 4 in which the ultraviolet scattering agent was blended beyond the predetermined range (3% or less) of the present invention, the whiteness during coating was particularly conspicuous and the usability was not satisfactory.

Treatment example 1
A BB cream was prepared according to the following formulation and manufacturing method.
(Prescription)
Ingredient name Mixing amount (%)
1. Iron oxide mica titanium/dimethicone ^*6 0.5
2. Titanium oxide/silica/Al hydroxide/hydrogen dimethicone ^*7 1.0
3. Zinc oxide/silica/hydrogen dimethicone ^*8 1.0
4. Talc/Dimethicone ^*9 1.0
5. Iron oxide/dimethicone ^*10 0.1
6. Diisopropyl sebacate 10.0
7. Diisopropyl adipate 4.0
8. Diethylhexyl succinate 4.0
9. Bisethylhexyloxyphenol methoxyphenyl triazine 3.0
10. Hexyl diethylaminohydroxybenzoylbenzoate 3.0
11. Ethylhexyltriazone 5.0
12. Alkyl (C30-45) dimethylsilyl polypropyl silsesquioxane 1.5
13. Isododecane/(Dimethicone/Bisisobutyl PPG-20)
Cross polymer ^*11 5.0
14. Isododecane 5.6
15. (Acrylates/Polytrimethylsiloxy Methacrylate) Copolymer/
Cyclopentasiloxane ^*1 0.1
16. Isododecane/Disteardimonium Hectorite/Propylene Carbonate ^*2 5.0
17. Dipolyhydroxystearic acid PEG-30 2.0
18.PEG-10 Dimethicone 2.0
19. Water 38.3
20.BG 5.0
21. Ethanol 2.0
22.Phenoxyethanol 0.4
23.Na chloride 0.5
Total 100.0
*6 SA Colorona Oriental Beige (manufactured by Miyoshi Kasei)
*7 STR-100A-LA (made by Sakai Chemical Industry)
*8 FINEX-33W-LP2 (made by Sakai Chemical Industry)
*9 SA-talc JA-46R (manufactured by Miyoshi Kasei)
*10 SA-Yellow LL-100P (manufactured by Miyoshi Kasei)
*11 EL-8050 ID Silicone Organic Elastomer Blend (Toray Dow Corning)
(Production method)
The oil component (A) of the components 6 to 18 and the aqueous component (B) of the components 19 to 23 were weighed in separate beakers and heated and dissolved. (B) was gradually added to (A) and emulsified using a homomixer. The mixture was cooled to 40° C. or lower, powder components 1 to 5 were added, and the components were uniformly mixed with a homomixer to obtain a water-in-oil emulsion.

The obtained BB cream had a high ultraviolet protection effect, and had good stability and a feeling of use.

Treatment example 2
A base was prepared according to the following formulation and manufacturing method.
(Prescription)
Ingredient name Mixing amount (%)
1. PEG-30 2.0 dipolyhydroxystearate
2. Polyglyceryl oleate-2/polyhydroxystearic acid/
Polyglyceryl stearate-2 ^*12 2.0
3. Cetyl diglyceryl tris(trimethylsiloxy)silylethyl dimethicone 1.0
4. Isododecane 8.2
5. Dimer dilinoleic acid (phytosteryl/isostearyl/cetyl/
Stearyl/behenyl) 0.5
6. Isododecane/(dimethicone/bisisobutyl PPG-20)
Cross polymer ^*11 4.0
7. Alkyl (C30-45) dimethylsilyl polypropyl silsesquioxane 1.0
8. Isododecane/Disteardimonium Hectorite/Propylene Carbonate ^*2 8.0
9. Tocopherol acetate 0.1
10. Bisethylhexyloxyphenol methoxyphenyltriazine 3.0
11. Hexyl diethylaminohydroxybenzoylbenzoate 3.0
12. Ethylhexyltriazone 5.0
13. Diisopropyl sebacate 18.0
14. Pentaerythrityl tetraethylhexanoate 1.0
15. Water 31.3
16.BG 7.0
17. Phenoxyethanol 0.4
18. Maltitol 2.0
19. Mica titanium/silica/dimethicone ^*13 2.5
Total 100.0
*12 PolyAquol OS2 (manufactured by Innovacos)
*13 SA-Xirona Volcanic Fire (manufactured by Miyoshi Kasei)
(Production method)
The oily component (A) of components 1 to 14 and the aqueous component (B) of components 15 to 18 were weighed in separate beakers and dissolved by heating. (B) was gradually added to (A) and emulsified using a homomixer. The mixture was cooled to 40° C. or lower, the powder component 19 was added, and the mixture was uniformly mixed with a homomixer to obtain a water-in-oil emulsion.

The obtained base had a high ultraviolet protection effect, and was excellent in stability and usability.

Treatment example 3
A beauty essence was prepared according to the following formulation and manufacturing method.
(Prescription)
Ingredient name Mixing amount (%)
1. PEG-30 2.0 dipolyhydroxystearate
2. Cetyl diglyceryl tris(trimethylsiloxy)silylethyl dimethicone 2.0
3. Bisethylhexyloxyphenol methoxyphenyl triazine 1.5
4. Ethylhexyltriazone 4.0
5. Cyclohexane-1,4-dicarboxylic acid bisethoxydiglycol 2.0
6. Diisopropyl sebacate 12.0
7. Diisostearyl malate ^*14 4.0
8. Shea butter 0.5
9. Isododecane/(Dimethicone/Bisisobutyl PPG-20) ^*11
Cross polymer 3.0
10. Isododecane 10.0
11. Stearyl dimethicone 2.0
12. Glycerin 5.0
13. Phenoxyethanol 0.5
14. Water 49.5
15. Ectoine 0.8
16. Hyaluronic acid Na 0.05
17. Maltitol 1.0
18. (Eicosanedioic acid/tetradecanedioic acid) polyglyceryl-10 0.2
Total 100.0
*14 Neosolue-DiSM (Nippon Seika)
(Production method)
The oily component (A) of the components 1 to 11 and the aqueous component (B) of the components 12 to 18 were weighed in separate beakers and dissolved by heating. (B) was gradually added to (A) and emulsified using a homomixer. The mixture was cooled to 40° C. or lower and uniformly mixed with a homomixer to obtain a water-in-oil emulsion.

The obtained base had a high ultraviolet protection effect, and was excellent in stability and usability.

The cosmetic of the present invention has a high ultraviolet protection effect, and is excellent in stability and feeling in use, and thus can be suitably used as a sunscreen cosmetic. Further, it can be suitably used for makeup bases having SPF/PA as a sunscreen effect, cosmetics such as BB cream, CC cream, and beauty essence.

Claims (16)

The following components (A)-(D);
(A) The following (a1) and (a2);
(A1) Ethylhexyltriazone (a2) Solid UV absorber containing hexyl diethylaminohydroxybenzoylbenzoate and/or bisethylhexyloxyphenol methoxyphenyltriazine (B) Diisopropyl sebacate, diethylhexyl succinate and diisopropylpropionate adipate A water-in-oil type characterized by containing a poly(12-hydroxystearic acid) ester of a polar oil (C) a volatile hydrocarbon oil (D) a polyhydric alcohol selected from the group consisting of Sunscreen cosmetics. The water-in-oil type sunscreen cosmetic according to claim 1, wherein the content of the component (a1) is 0.1 to 8% by mass. The water-in-oil type sunscreen cosmetic according to claim 1 or 2, wherein the content of the component (a2) is 1 to 20% by mass. The water-in-oil type sunburn according to any one of claims 1 to 3, wherein the content mass ratio ((a1):(a2)) of the components (a1) and (a2) is 1:0.2 to 1:40. Stop cosmetics. The water-in-oil type sunscreen cosmetic according to any one of claims 1 to 4, wherein the component (B) contains diisopropyl sebacate. The water-in-oil type sunburn according to any one of claims 1 to 5, wherein the content mass ratio ((A):(B)) of the components (A) and (B) is 1:0.8 to 1:2. Stop cosmetics. The component (C) volatile hydrocarbon oil is one or more selected from the group consisting of isododecane, isohexadecane, and hydrogenated polyisobutene, and the water-in-oil type sunburn according to any one of claims 1 to 6. Stop cosmetics. Content of a component (C) is 0.1-40 mass %, The water-in-oil type sunscreen cosmetics in any one of Claims 1-7. The water-in-oil type sunscreen cosmetic according to any one of claims 1 to 8, wherein the poly(12-hydroxystearic acid) ester of the component (D) polyhydric alcohol is dipolyhydroxystearic acid PEG-30. The water-in-oil type sunscreen cosmetic according to any one of claims 1 to 9, wherein the content of the component (D) is 0.5 to 6 mass%. Furthermore, the water-in-oil type sunscreen cosmetic according to any one of claims 1 to 10, which further comprises the component (E) an ultraviolet scattering agent in a content of 3% by mass or less. The water-in-oil type sunscreen cosmetic according to any one of claims 1 to 11, wherein the component (E) ultraviolet scattering agent is one or two selected from the group consisting of zinc oxide and titanium oxide powder. The water-in-oil type sunscreen cosmetic according to any one of claims 1 to 12, which has an SPF of 15 or more. The water-in-oil type sunscreen cosmetic according to any one of claims 1 to 13, which has a viscosity of 20,000 mPa·s or less. The water-in-oil type sunscreen cosmetic according to any one of claims 1 to 14, which is substantially free of ethylhexyl methoxycinnamate and octocrylene. The water-in-oil type sunscreen cosmetic according to any one of claims 1 to 15, which does not substantially contain a volatile silicone oil.