JP6935202B2 - Water-in-oil sunscreen - Google Patents

Description

The present invention relates to a water-in-oil sunscreen containing a (vinyl dimethicone / lauryl dimethicone) crosspolymer, and more specifically, to form a water-resistant cosmetic film that does not twist against movement and is stable over time. Regarding water-in-oil sunscreens with excellent properties.

Conventionally, a water-in-oil emulsified composition has been widely used as a sunscreen because it has good spreadability and high water resistance. In recent years, in sunscreens, as the effects of UVA (long-wavelength ultraviolet rays with a wavelength of 320 to 400 nm) on the skin have been understood, not only UVB (medium-wavelength ultraviolet rays with a wavelength of 290 to 320 nm) but also UVA is prevented. Is required. However, many UVA absorbers are solid at room temperature and poorly soluble (poorly soluble in both water and non-polar oil), and the stability over time is impaired, especially in the low temperature range, and the ultraviolet rays expected due to the aggregation of active ingredients. Problems such as lack of defensive ability may occur. Therefore, various studies have been made on the stable formulation of the sparingly soluble UV absorber (see, for example, Patent Documents 1 to 3), but stickiness is likely to occur due to the increase in the content of the oil agent and the surfactant. , In terms of usability, there were cases where I was not satisfied.

Also, especially in outdoor and sports scenes where sunscreens are often used, it has a waterproof function (water resistance) that is resistant to water and sweat, and it does not get twisted or uneven even with vigorous movements, and it protects against UV rays. Noh is also required to last. However, when an oil-soluble resin or the like is blended to improve water resistance (see, for example, Patent Documents 4 and 5), the surface of the cosmetic film tends to be strong, and the makeup follows the movement of the skin without twisting or unevenness. It was difficult to sustain the membrane.

Japanese Unexamined Patent Publication No. 2009-23546 Japanese Unexamined Patent Publication No. 2014-118383 JP-A-2009-091307 Japanese Unexamined Patent Publication No. 2013-147482 Japanese Unexamined Patent Publication No. 2011-105681

The present invention contains a sparingly soluble UV absorber, yet has an excellent feeling of use without stickiness, good stability over time, and the cosmetic film after application does not get twisted against the movement of the skin. The subject is to provide water-in-oil sunscreen cosmetics.

In view of these circumstances, the present inventors have conducted diligent research focusing on the flexibility of the cosmetic film, and as a result, in the water-in-oil sunscreen, as a resin component (vinyl dimethicone / lauryl dimethicone) crosspolymer. By selecting, in combination with a silicone resin powder that has a unique feel, and by using a solid water-insoluble UV absorber and dimethicodiethylbenzalmalonate at 25 ° C, it is water resistant and has a twist against movement. We have found that a water-in-oil sunscreen that does not form a flexible cosmetic film and has excellent usability and stability over time can be obtained, and has completed the present invention.

That is, the present invention describes the following components (a) to (e):
(A) Solid water-insoluble UV absorber at 25 ° C. (b) Dimethicodiethylbenzalmalonate (c) (Vinyl dimethicone / Lauryl dimethicone) Crosspolymer (d) Polyether-modified silicone (e) Silicone resin powder The component (a) contained is 2- [4- (diethylamino) -2-hydroxybenzoyl] benzoic acid hexyl ester and / or 2,4-bis {[4- (2-ethyl-hexyloxy) -2- It is hydroxy] -phenyl} -6- (4-methoxyphenyl)-(1,3,5) -triazine, and the content of the component (b) is 0.5 to 7% by mass, and the above (c). ) Provides a water-in-oil sunscreen having a component content of 1 to 20% by mass.

The water-in-oil sunscreen of the present invention forms a highly durable cosmetic film against sweat, water and movement, so even in the midsummer sports scene, it has a high UV protection effect and a beautiful finish without unevenness or whitening. Is something that lasts. Therefore, it is useful not only in sunscreens having a high SPF, but also in cosmetics such as make-up cosmetics and daytime beauty essences for the purpose of protecting against ultraviolet rays.

Hereinafter, the present invention will be described in detail.
The component (a) water-insoluble ultraviolet absorber solid at 25 ° C. used in the present invention is for protecting the skin from ultraviolet rays, and is not particularly limited as long as it is solid at 25 ° C. and water-insoluble. , For example, 2- [4- (diethylamino) -2-hydroxybenzoyl] benzoic acid hexyl ester, ethyl paraaminobenzoate, benzophenone-1, benzophenone-3, benzophenone-6, benzophenone-9, 2,4,6-tris. [4- (2-Ethylhexyloxycarbonyl) anilino] -1,3,5-triazine, dioctylbutamidotriazone, 4-tert-butyl-4'-methoxy-dibenzoylmethane, 2,4-bis {[4 -(2-Ethyl-hexyloxy) -2-hydroxy] -phenyl} -6- (4-methoxyphenyl)-(1,3,5) -triazine, 2,2'-methylenebis [6- (2H-benzotriazole) -2yl) -4- (1,1,3,3-tetramethylbutyl) phenol] and the like, and one or more of these can be used. Among these, 2- [4- (diethylamino) -2-hydroxybenzoyl] benzoic acid hexyl ester, 2,4-bis {[4- (2-ethyl-hexyloxy) -2-hydroxy] -phenyl} -6- (4-Methoxyphenyl)-(1,3,5) -triazine is preferable because it has a high protective effect on UVA.

The content of the component (a) in the present invention is not particularly limited, but is preferably 0.5 to 7.0% by mass (hereinafter, simply abbreviated as "%"), and particularly preferably 2 to 5%. Within this range, a high UVA prevention effect can be obtained, the back skin is less sticky, and the feeling of use is improved.

The component (b) dimethicodiethylbenzalmalonate used in the present invention is named INCI (INTERNATIONAL NOMENCLATTURE of COSMETIC INGREDINITS) as Polysilicone-15, and about 7.5% of the dimethicone having a chain length of about 60 is about 7.5%. It is a silicone derivative substituted with two types of substituents, and while it has high UV protection ability itself, it is known that it improves the values of SPA and PA by synergistic effect with other UV protection agents (booster effect). Has been done. In the present invention, it also functions as a solvent for improving the compatibility between the component (a) and the component (c), and contributes to the stability of the cosmetic. As a commercially available product, "PARSOL SLX" (manufactured by DSM NUTRITION PRODUCTS) can be exemplified.

The content of the component (b) in the present invention is not particularly limited, but is preferably 0.5 to 7%, particularly preferably 1 to 5%. Within this range, not only a high UV protection effect can be obtained, but also the dispersibility and solubility of the component (a) and the component (c) can be improved, and the stability over time is also good, which is preferable.

The component (c) (vinyl dimethicone / lauryl dimethicone) crosspolymer used in the present invention is a compound listed in INCI and is obtained by cross-linking organopolysiloxane and has a partially three-dimensional cross-linked structure. It is a kind of partially crosslinked organopolysiloxane polymer (silicone elastomer) which is a polymer. Since the component (c) has good adhesion to the skin among the silicone elastomers due to alkyl modification, it contributes to the formation of a flexible cosmetic film, and at the same time, the component (a) and the component (b) are mediated by a solvent. Since the compatibility is high, the stability over time and the UV protection effect can be improved.

The component (c) may be blended alone as a (vinyldimethicone / lauryldimethicone) crosspolymer, but a silicone gel composition swollen with an oil agent may also be used. "KSG-41" (mixture with liquid paraffin with solid content of about 30%), "KSG-42" (mixture with light isoparaffin with solid content of about 25%), "KSG-43" (tri2-ethyl) Examples thereof include "KSG-44" (a mixture with glyceryl hexanate having a solid content of about 30%) and "KSG-44" (a mixture with squalane having a solid content of about 30%) (all manufactured by Shin-Etsu Chemical Co., Ltd.). Among them, "KSG-43" is particularly preferable because it is excellent in stability over time and usability.

The content of the component (c) in the present invention is not particularly limited, but is preferably 1 to 20%, more preferably 5 to 20%, and even more preferably 10 to 18%. Within this range, it is more excellent from the viewpoint of forming a flexible cosmetic film that does not twist with respect to movement, and the usability is also better.

The component (d) polyether-modified silicone used in the present invention is blended for the purpose of stably emulsifying a water-in-oil sunscreen, and any of the following may be used as long as the purpose is not deviated. The component (d) is a copolymer having at least an organopolysiloxane group and a hydrophilic group having a plurality of ether structures, and has a graft copolymer having the organopolysiloxane group as a main chain and the hydrophilic group in a side chain. It may be a coalescence or a linear block copolymer in which the organopolysiloxane group and the hydrophilic group are alternately bonded. The organopolysiloxane group may be linear or have a branched structure, and the hydrophilic group is not particularly limited, but a polyoxyalkylene group, a polyglyceryl group, or the like can be used. Further, the component (d) may be a co-modified base oil group such as a long-chain alkyl group, a long-chain alkenyl group, a long-chain alkoxy group, or a fluorine-substituted alkyl group.

The component (d) is not particularly limited as long as it is used in ordinary cosmetics, but specific examples thereof include a polyoxyalkylene-modified organopolysiloxane copolymer, for example, PEG-9 dimethicone (as a commercially available product). For example, "KF-6019" manufactured by Shin-Etsu Chemical Industry Co., Ltd.), as a silicone-branched polyoxyalkylene-modified silicone, for example, PEG-9 polydimethylsiloxyethyl dimethicone (as a commercial product, for example, "KF-6028" manufactured by Shin-Etsu Chemical Industry Co., Ltd. ), Lauryl PEG-9 polydimethylsiloxyethyl dimethicone (commercially available, for example, "KF-6038" manufactured by Shinetsu Chemical Industry Co., Ltd.), silicone branched polyglycerin-modified silicone, for example, lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone (manufactured). Examples of commercially available products include "KF-6105" manufactured by Shin-Etsu Chemical Industry Co., Ltd.). In the present invention, one or more of these can be used. Among these, the component (d) is more preferably a silicone-branched polyoxyalkylene-modified silicone or a silicone-branched polyglycerin-modified silicone from the viewpoint of stability over time and usability, and the HLB of the component (d) is 10 or less. It is preferable to have.

The content of the component (d) in the present invention is not particularly limited, but is preferably 0.1 to 5.0%, more preferably 0.5 to 2.0%. Within this range, a stable water-in-oil emulsified composition can be easily obtained, and the usability becomes better.

Since the component (e) silicone resin powder used in the present invention has a silky feel, the stickiness of the component (a) is reduced, and further, the interaction with the component (c) makes it possible to obtain a uniform cosmetic film. Contributes to formation. The component (e) is not particularly limited as long as it is used in ordinary cosmetics, but for example, both reticulated silicone and crosslinked silicone, and crosslinked silicone and reticulated silicone blocks which are composite powders thereof Examples thereof include crosslinked silicones, and crosslinked silicones are preferable in terms of usability. Specific examples of the component (e) include polymethylsilsesquioxane, (dimethicone / vinyldimethicone) crosspolymer, (vinyldimethicone / methicone silsesquioxane) crosspolymer, (diphenyldimethicone / vinyldiphenyldimethicone / silsesquioki). Sun) Cross polymer and the like. The shape of the component (e) is preferably substantially spherical to true spherical, and the particle size is preferably 1 to 50 μm, and one or a combination of two or more of these can be used.

Commercially available products of component (e) include Tospearl series (Tospearl 145A, etc.) manufactured by Momentive Performance Materials, KSP series (KSP-100, KSP-300, etc.) manufactured by Shin-Etsu Chemical Co., Ltd., Toray Industries, Inc. Examples thereof include the Dow Corning Trefil series (Trefil E506W, Trefil E505C, Trefil E506C, Trefil E505W, etc.). Further, the component (e) may be blended alone as a powder, but it may be used without any problem even if a silicone powder dispersed in various solvents or a mixture previously mixed with other components is used. Examples of these include Trefil E507, E508, BY29-119, and BY29-122 (all manufactured by Toray Dow Corning).

The content of the component (e) used in the present invention is preferably 0.5 to 10%, more preferably 3 to 8%. Within this range, the stickiness of the component (a) can be suppressed, and a smoother and better usability can be obtained.

Since the water-in-oil sunscreen of the present invention forms a flexible and uniform cosmetic film, it has excellent durability of the cosmetic film and has an ultraviolet protection ability without adding an ultraviolet scattering agent such as titanium oxide or zinc oxide. Therefore, it is very useful as a sunscreen with a beautiful finish because the agglomeration (whitening) of the ultraviolet scattering agent that is seen over time or when sweating does not occur.

In the water-in-oil sunscreen of the present invention, ingredients used in ordinary cosmetics can be blended as necessary within a quantitative and qualitative range that does not impair the effects of the present invention. For example, an aqueous component for forming a water-in-oil emulsified composition, an oily component, a surfactant other than the component (d), an ultraviolet absorber other than the components (a) and (b), and a component other than the component (e). Powder, water-soluble polymer, moisturizer, antioxidant, beauty ingredient, preservative, fragrance, refreshing agent and the like can be blended.

The aqueous component may be any component that is soluble in water, for example, glycols such as propylene glycol, 1,3-butylene glycol, dipropylene glycol, polyethylene glycol, glycerin, diglycerin, polyglycerin and the like. Examples thereof include glycerols, sugar alcohols such as sorbitol, martitol and glucose, and lower alcohols such as ethanol. The water is not particularly limited, and examples thereof include plant extracts such as normal water, purified water, hot spring water, deep water, aloe vera, witch hazel, hamamelis, cucumber, lemon, lavender, and rose. Can be used.

Oily components include hydrocarbons, fats and oils, waxes, regardless of the origin of animal oils, vegetable oils, synthetic oils, etc. commonly used in cosmetics, and the properties of solid oils, semi-solid oils, liquid oils, volatile oils, etc. , Hydrogenated oils, ester oils, fatty acids, higher alcohols, silicone oils, fluorine-based oils, lanolin derivatives, oil-based gelling agents and the like. Specifically, hydrocarbons such as liquid paraffin, squalane, vaseline, polyisobutylene, and polybutene, fats and oils such as mokurou, olive oil, castor oil, minced oil, macadamian nut oil, waxes such as honey wax and gay wax, and jojoba. Oil, glyceryl trioctanoate, polyglyceryl diisostearate, diglyceryl triisostearate, glyceryl tribehenate, glyceryl tri2-ethylhexaneate, cetyl 2-ethylhexaneate, isopropyl myristate, isopropyl palmitate, octyldodecyl myristate, loginate Esters such as pentaerythrit ester, neopentyl glycol dioctanoate, cholesterol fatty acid ester, phytosterol fatty acid ester, triglyceride, di (capryl / capric acid) propylene glycol, propylene glycol dicaprate, diisostearyl malate, stearic acid, laurin Fatty acids such as acids, myristic acid, behenic acid, isostearic acid, and oleic acid, higher alcohols such as stearyl alcohol, cetyl alcohol, lauryl alcohol, oleyl alcohol, isostearyl alcohol, and behenyl alcohol, dimethylpolysiloxane, methylphenylpolysiloxane, Decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, trimethylsiloxysilicate, high degree of polymerization methylphenylpolysiloxane, methacryl-modified organopolysiloxane, stearyl-modified organopolysiloxane, oleyl-modified organopolysiloxane, behenyl-modified organopolysiloxane, high Degree of Polymerization Silicones such as dimethylpolysiloxane, alkoxy-modified organopolysiloxane, fluorine-modified organopolysiloxane, fluorine-based oils such as perfluorodecane, perfluorooctane, and perfluoropolyether, lanolin, lanolin acetate, lanolin fatty acid isopropyl, Examples thereof include lanolin derivatives such as lanolin alcohol, oil-based gelling agents such as sucrose fatty acid ester, starch fatty acid ester, aluminum isostearate, and 12-hydroxystearic acid, and one or more of these can be used. Among these, glyceryl tri2-ethylhexanoate and propylene glycol dicaprate are preferable because they have good compatibility with the component (a) and the component (c).

As a method for producing a water-in-oil sunscreen of the present invention, it can be produced by a generally known method, and the manufacturing equipment may be any dispersion / emulsification equipment such as a general dispersion.
The form of the water-in-oil sunscreen of the present invention is not particularly limited, and examples thereof include liquid, emulsion, cream, and solid. In particular, a sunscreen that is liquid and shakes during use is suitable because it is easy to apply evenly to the skin and stability over time can be ensured with less surfactant. Further, the water-in-oil sunscreen of the present invention can be applied to a foundation, a foundation, a daytime beauty essence, and the like.

Hereinafter, the present invention will be described in detail with reference to examples. It should be noted that these do not limit the present invention in any way.

Examples 1 to 3 and Comparative Examples 1 to 4: Water-in-oil sunscreen (shaking type)
A sunscreen was prepared according to the composition shown in Table 1 and the following production method. The obtained sunscreen was evaluated by the following methods for UV protection, no twist against movement, no stickiness, and stability over time, and the results are also shown in Table 1.

(Production method)
A: Ingredients (1) to (6) are uniformly heated (80 ° C.) and dissolved.
B: Ingredients (7) to (15) are mixed.
C: A and B are mixed and uniformly dispersed.
D: Ingredients (16) and (17) are mixed.
E: D was added to C to disperse and emulsify to obtain a sunscreen.

(Evaluation method 1: UV protection ability)
The SPF value in In-Vitro was measured using an SPF analyzer (manufactured by UV-2000S Labsphere). The measurement conditions were as follows: the sample shown in Table 1 was ^{uniformly applied to the PMMA plate at a ratio of 20 mg / inch 2} , and then the SPF value in the range of 290 to 450 nm was measured using the above-mentioned measuring instrument, and 9 times. The average value was calculated and judged according to the following criteria.
<Criteria>
(SPF value): (Judgment)
35 or more: ◎
From 25 or more to less than 35: ○
From 15 or more to less than 25: △
Less than 15: ×

(Evaluation method 2: No twist on movement)
After applying 0.2 g of each sample shown in Table 1 to the wrist, the wrist was bent and stretched 20 times, and the state of the cosmetic film with respect to movement was visually and microscopically observed, and the determination was made according to the following criteria.
<Criteria>
(Evaluation): (Judgment)
No change: ◎
Only the deepest wrinkles on the wrist were slightly twisted: ○
I could see the twist on the deepest wrinkle on my wrist: △
Wrinkles on all wrists could be confirmed: ×

(Evaluation method 3: Non-sticky)
Ten expert panels were asked to use each sample shown in Table 1, and scores were given based on the following evaluation criteria, and the average value was judged according to the following criteria.
<Evaluation criteria>
(Evaluation result): (Score)
Very feel: 5 points Slightly feel: 4 points Normal: 3 points I don't feel much: 2 points I don't feel at all: 1 point <Judgment criteria>
(Average score): (Judgment)
4.5 points or more: ◎
3.5 points or more and less than 4.5 points: ○
1.5 points or more and less than 3.5 points: △
Less than 1.5 points: ×

(Evaluation method 4: Stability over time)
Each sample shown in Table 1 was placed in a standard glass bottle, and the state and the state after storage in a constant temperature bath at 5 ° C. for 1 month were observed visually and with an optical microscope, and according to the following criteria. Judged.
<Criteria>
(Evaluation): (Judgment)
No change at all: ◎
No visual change in appearance (microscopic observation shows slight crystals): ○
There are some precipitates (not felt even after use): △
There is a precipitate: ×

Examples 1 to 3 were sunscreens having excellent UV protection ability, the cosmetic film having no twist against movement, good usability, and excellent stability over time. On the other hand, in Comparative Example 1 in which another ultraviolet absorber was blended instead of the component (b), the cosmetic film after application was not uniform, so that there was no twist against movement, ultraviolet protection ability, and stability over time. Was inferior. In Comparative Example 2 in which another silicone elastomer was blended instead of the component (c), the compatibility with the components (a) and (b) was poor, so that there was no twist to movement and stability over time. It was inferior. In Comparative Example 3 in which another surfactant was blended instead of the component (d), the emulsion stability was poor and the mixture became non-uniform, which was particularly inferior in terms of usability. In Comparative Example 4 in which another organic powder was blended instead of the component (e), the decorative film after application was not uniform, so that it was twisted with respect to movement and also felt sticky, which was not preferable.

Example 6: Sunscreen (creamy)
(Ingredient) (%)
1.2- [4- (diethylamino) -2-hydroxybenzoyl]
Benzoic acid hexyl ester 2.0
2.2,4-bis {[4- (2-ethyl-hexyloxy) -2-hydroxy] -phenyl}
-6- (4-Methoxyphenyl)-(1,3,5) -triazine 2.0
3. 3. Ethylhexyl methoxycinnamate 8.0
4. Dimethicodiethylbenzalmalonate 3.0
5. (Vinyl dimethicone / lauryl dimethicone) Cross-polymer mixture (Note 1) 10.0
6. Triethylhexanoin 2.0
7. Dimethicone (6cs) 1.5
8. Polymethylsilsesquioxane (particle size 4-8 μm) 3.0
9. Fragrance 0.1
10. PEG-9 Polydimethylsiloxyethyl Dimethicone 1.5
11. Lauryl PEG-9 Polydimethylsiloxyethyl Dimethicone 0.5
12. Residual amount of purified water 13. Ethanol 5.0
14. Sodium chloride 0.1

(Production method)
A: Ingredients (1) to (7) are uniformly heated and dissolved.
B: A and the components (8) and (9) are added and mixed and dispersed.
Ingredients (10) to (14) were added to C: B and emulsified to obtain a sunscreen cosmetic (creamy).
(result)
The sunscreen agent (creamy) of Example 6 was excellent in stability over time, while ensuring a high SPF, without twisting against movement, and having a good usability.

Example 7: Sunscreen (aerosol type)
(Ingredient) (%)
1.2,4-bis {[4- (2-ethyl-hexyloxy) -2-hydroxy] -phenyl}
-6- (4-Methoxyphenyl)-(1,3,5) -triazine 3.0
2. Dimethicodiethylbenzalmalonate 3.0
3. 3. (Vinyl dimethicone / lauryl dimethicone) Cross-polymer mixture (Note 1) 15.0
4. Ethylhexyl methoxycinnamate 8.0
5. Propylene Glycol Dicaprate 12.0
6. PEG-9 Polydimethylsiloxyethyl Dimethicone 1.5
7. (Vinyl dimethicone / methicone silsesquioxane) Cross polymer (particle size 9 to 15 μm) 5.0
8. Fragrance 0.1
9. Residual amount of purified water 10. Ethanol 40.0
11. Dipropylene glycol 2.0

(Production method)
A: Ingredients (1) to (5) are uniformly heated and dissolved.
B: A is mixed with components (6) to (8).
C: Ingredients (9) to (11) are added to B and emulsified.
After filling 15 g of the undiluted solution obtained in D: C into a pressure-resistant container made of aluminum, the valve was fixed, and 0.15 35 g of LPG was filled in the pressure-resistant container through the valve to obtain a sunscreen cosmetic (aerosol type).
(result)
The sunscreen cosmetic (aerosol type) of Example 7 had a uniform film having sufficient water resistance while having a fresh feel when applied.

Claims (2)

The following components (a) to (e):
(A) Solid water-insoluble UV absorber at 25 ° C. (b) Dimethicodiethylbenzalmalonate (c) (Vinyldimethicone / Lauryldimethicone) Crosspolymer (d) Polyether-modified silicone (e) Silicone resin powder Contains,
The component (a) is 2- [4- (diethylamino) -2-hydroxybenzoyl] benzoic acid hexyl ester and / or 2,4-bis {[4- (2-ethyl-hexyloxy) -2-hydroxy]-. Phenyl} -6- (4-methoxyphenyl)-(1,3,5) -triazine,
The content of the component (b) is 0.5 to 7% by mass.
The content of the component (c) is 1 to 20% by mass.
Water-in-oil sunscreen. The water-in-oil sunscreen according to claim 1 , wherein the content of the component (e) is 0.5 to 10% by mass.