HK1196550B - Water-in-oil emulsion sunscreen cosmetic - Google Patents

Description

Water-in-oil type emulsified sunscreen cosmetic

Technical Field

The present invention relates to a water-in-oil type emulsified sunscreen cosmetic. More specifically, the present invention relates to a water-in-oil type emulsion sunscreen cosmetic composition in which a large amount of hydrophobized zinc oxide and hydrophobized titanium oxide are mixed as an ultraviolet scattering agent powder in an amount to exhibit sufficient ultraviolet protection ability, and the water-in-oil type emulsion sunscreen cosmetic composition has an improved feeling of use due to the large amount of the ultraviolet scattering agent powder and an improved washing property due to the mixing of the ultraviolet scattering agent powder.

Background

As shown in patent document 1, a water-in-oil type emulsion sunscreen cosmetic composition containing an ultraviolet scattering agent is known.

However, patent document 1 discloses a sunscreen cosmetic which is a water-in-oil emulsion composition like most water-in-oil emulsion sunscreen cosmetics and therefore has the advantages of good spreadability and excellent water resistance, while a high SPF value can be achieved without mixing a large amount of an ultraviolet scattering agent which causes a rough feeling (きしみ) or powdery mildew residue (whiter bloom き), and patent document 1 does not provide a water-in-oil emulsion sunscreen cosmetic in which a large amount of an ultraviolet scattering agent can be mixed. That is, the technical problem of mixing a large amount of the ultraviolet scattering agent is avoided, and the amount of the ultraviolet scattering agent is limited to 5 mass% or less from the viewpoint of the feeling of use. When the amount of the ultraviolet scattering agent to be mixed is limited, it is necessary to mix a sufficient amount of the ultraviolet absorber in order to improve the ultraviolet protection effect.

Patent document 2 discloses an oil-in-water or water-in-oil emulsion sunscreen cosmetic composition containing (a) isodecyl neopentanoate, (b) an ultraviolet absorber, (c) an ultraviolet scattering agent, and (d) silicone oil, and describes: (c) the component is zinc oxide and/or titanium dioxide. The object of the invention of patent document 2 is to provide a sunscreen cosmetic which sufficiently exhibits excellent ultraviolet shielding effects of an ultraviolet absorber and an ultraviolet scattering agent, has good compatibility with the skin, has excellent feeling of use without stickiness, and is easy to remove from the skin after use (good washability).

Patent document 3 discloses a water-in-oil type emulsion sunscreen cosmetic in which a hydrophobized powder having a remarkable effect of low oil absorption and low apparent specific volume is stably mixed as an ultraviolet scattering agent in a sunscreen cosmetic, stickiness due to mixing of the hydrophobized powder is reduced, and a feeling in use is excellent, wherein: comprises (a) a specific hydrophobized zinc oxide powder, (b) a volatile silicone, (c) a polyoxyalkylene-modified organopolysiloxane having a specific structure, and (d) water. Further, this document records: although titanium oxide or zinc oxide is used as the hydrophobic powder of the ultraviolet scattering agent, zinc oxide having a low refractive index is often mixed in recent years in terms of transparency at the time of coating.

On the other hand, patent document 4 discloses a water-in-oil or oil-in-water sunscreen cosmetic composition which is not mixed with an ultraviolet scattering agent composed of zinc oxide and/or titanium oxide, in order to provide a sunscreen cosmetic composition which can easily remove dirt secondarily adhered to clothes by washing.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2011-126832;

patent document 2: japanese patent laid-open publication No. 2010-222349;

patent document 3: japanese patent laid-open No. 2005-232068;

patent document 4: japanese patent application laid-open No. 2010-059136.

Disclosure of Invention

Problems to be solved by the invention

The subject of the invention is to provide: a water-in-oil type emulsion sunscreen cosmetic composition which comprises a large amount of hydrophobized zinc oxide and hydrophobized titanium oxide as an ultraviolet scattering agent powder in an amount sufficient to exert ultraviolet protection ability, wherein the use feeling is deteriorated due to the large amount of the ultraviolet scattering agent powder and the cleaning performance is deteriorated due to the ultraviolet scattering agent powder.

Means for solving the problems

That is, the present invention provides a water-in-oil type emulsion sunscreen cosmetic characterized by: comprises the following (a) to (e):

(a) hydrophobized zinc oxide and hydrophobized titanium oxide: 10 to 30 mass%;

(b) lipophilic nonionic surfactant: 0.5 to 5 mass%;

(c) one or more oil components selected from N-lauroyl-L-glutamine di (phytosterol 2-octyldodecanol) ester, macadamia fatty acid phytosterol ester and macadamia fatty acid cholesteryl ester: 1-5 mass%;

(d) volatile silicone oils and/or hydrocarbon oils: 10 to 40 mass%;

(e) water: 5 to 30 mass%.

In addition, the present invention provides the water-in-oil type emulsion sunscreen cosmetic composition described above, characterized in that: the lipophilic nonionic surfactant is polyoxyethylene-methyl polysiloxane copolymer.

Effects of the invention

(1) A water-in-oil type emulsion sunscreen cosmetic composition which exhibits a sufficient ultraviolet ray protection ability can be provided by mixing a large amount of hydrophobized zinc oxide and hydrophobized titanium oxide as an ultraviolet ray scattering agent. Therefore, it is not necessary to mix an ultraviolet absorber, which is a large feature and advantage of the present invention. If the ultraviolet absorber is mixed, a small amount of mixing is sufficient, and it is suitable for mixing a small amount of a hardly soluble ultraviolet absorber.

(2) Can improve the poor use feeling caused by mixing a large amount of ultraviolet scattering agent powder.

(3) The poor cleaning property caused by mixing the ultraviolet scattering agent powder can be improved.

Drawings

FIG. 1 is an absorbance spectrum of example 1 and example 4.

Detailed Description

The present invention will be described in detail below.

(a) Hydrophobized zinc oxide and hydrophobized titanium oxide

In the water-in-oil type emulsion sunscreen cosmetic of the present invention, zinc oxide and titanium oxide powders are mixed as an ultraviolet scattering agent having a sufficient ultraviolet protection ability. In the present invention, particulate titanium oxide and particulate zinc oxide having an average primary particle diameter of 10nm to 100nm, preferably 10nm to 50nm, are particularly preferable. The average particle diameter is measured by a conventional method such as the number average diameter by image analysis of an electron micrograph.

The hydrophobized zinc oxide and the hydrophobized titanium oxide are obtained by hydrophobizing powders of zinc oxide and titanium oxide. The hydrophobized powder is dispersed in oil of water-in-oil emulsion sunscreen cosmetic. The kind of the hydrophobizing agent is not limited, and examples thereof include: fatty acids, higher alcohols, hydrocarbons, triglycerols, esters, silicone oils, silicone resins, fluorine compounds.

Examples of the hydrophobizing agent preferably used in the present invention include: alkyltriethoxysilane, alkyltrimethoxysilane, perfluoroalkyl phosphoric acid, an alkyl acrylate/dimethyl silicone copolymer, dextrin palmitate, triethoxysilylethyl polydimethylsiloxyethylhexyl dimethicone, a polysiloxane, a dimethicone, a high molecular silicone, sodium acryloyldimethyl taurate/methacrylamidoic acid copolymer, and the like.

In particular, as zinc oxide, octyltrimethoxysilane treatment and silicone (dimethylpolysiloxane-hydrodimethylpolysiloxane) treatment are preferable.

In addition, as for titanium oxide, sodium acryloyldimethyltaurate/methacrylamide lauric acid copolymer treatment and stearic acid/alumina treatment are particularly preferable.

The method of the hydrophobization treatment is not particularly limited, and the surface treatment is carried out according to a conventional method. For example, zinc oxide hydrophobized with octyltriethoxysilane and/or dimethylpolysiloxane can be prepared by mixing and stirring zinc oxide in octyltriethoxysilane and/or dimethylpolysiloxane for a certain period of time, and then filtering the mixture. The dimethylpolysiloxane used herein is a liquid dimethylpolysiloxane that can be subjected to a hydrophobic treatment.

The total amount of the hydrophobized zinc oxide and the hydrophobized titanium oxide (a) is 10 to 30% by mass, preferably 12 to 25% by mass, based on the total amount of the water-in-oil emulsion sunscreen cosmetic.

(b) Lipophilic nonionic surfactant

Examples of the lipophilic nonionic surfactant used in the present invention include: sorbitan fatty acid esters (e.g., sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan trioleate, diglycerin sorbitan penta-2-ethylhexanoate, diglycerin sorbitan tetra-2-ethylhexanoate, and the like); glycerol or polyglycerol fatty acid esters (e.g., cottonseed oil fatty acid glyceride, erucic acid glyceride, sesquioleic acid glyceride, glyceryl monostearate, glyceryl stearate,α,α' -glyceryl pyroglutamate oleate, glyceryl malate monostearate, etc.); propylene glycol fatty acid esters (e.g., propylene glycol monostearate); POE-castor oil-POE hardened castor oil derivatives; glycerin alkyl ether, polyoxyethylene-methylpolysiloxane copolymer, and the like.

In the present invention, a polyoxyethylene-methylpolysiloxane copolymer is particularly preferably used for providing a stable emulsion. As the polyoxyethylene/methylpolysiloxane copolymer, a commercially available product of shin-Etsu chemical Co., Ltd. "KF-6028" can be preferably used.

The amount of the lipophilic nonionic surfactant (b) is 0.5 to 5% by mass, preferably 0.5 to 3% by mass, based on the total amount of the water-in-oil emulsion sunscreen cosmetic.

(c) One or more oil components selected from N-lauroyl-L-glutamine di (phytosterol 2-octyldodecanol) ester, macadamia nut fatty acid phytosterol ester, and macadamia nut fatty acid cholesteryl ester

The oil component used in the present invention contains one or more kinds selected from the group consisting of N-lauroyl-L-glutamine di (phytosterol 2-octyldodecanol) ester, macadamia fatty acid phytosterol ester, and macadamia fatty acid cholesteryl ester, and is an oil component constituting an oil phase of an outer phase of the water-in-oil type emulsified sunscreen cosmetic. Commercially available products can be used as these oils.

N-lauroyl-L-glutamine di (phytosterol 2-octyldodecanol) ester is particularly preferred.

In the present invention, although the detailed principle is not clear, the following is presumed: the oil component of the component (c), the volatile silicone oil (d) and the hydrocarbon oil are mixed in the water-in-oil type emulsion sunscreen cosmetic to form an oil phase, and the ultraviolet scattering agent of the hydrophobized zinc oxide and the hydrophobized titanium oxide (a) is dispersed in the oil phase, so that the poor feeling in use due to the mixing of a large amount of the ultraviolet scattering agent powder and the poor cleaning performance due to the mixing of the ultraviolet scattering agent powder can be improved.

The amount of the oil component (c) selected from one or more of N-lauroyl-L-glutamine di (phytosterol 2-octyldodecanol) ester, macadamia fatty acid phytosterol ester, and macadamia fatty acid cholesteryl ester is 1 to 5% by mass, preferably 1 to 3% by mass, based on the total amount of the water-in-oil emulsified sunscreen cosmetic.

(d) Volatile silicone oils and/or hydrocarbon oils

As the volatile silicone oil used in the present invention, for example, low-polymerized dimethylpolysiloxane or cyclic polysiloxane (for example, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, etc.) can be used.

Examples of the hydrocarbon oil used in the present invention include: liquid paraffin, ceresin, squalane, pristane, paraffin, squalene, vaseline, etc.

In the present invention, either volatile silicone oil or hydrocarbon oil may be used, or both of them may be used. Two or more kinds of volatile silicone oils and two or more kinds of hydrocarbon oils may also be used.

The oil component is an oil component constituting an oil phase of the water-in-oil type emulsion sunscreen cosmetic.

The amount of the volatile silicone oil and/or hydrocarbon oil (d) is 10 to 40% by mass, preferably 20 to 40% by mass, based on the total amount of the water-in-oil emulsion sunscreen cosmetic.

The oil component constituting the oil phase of the water-in-oil emulsion sunscreen cosmetic may be only the above-mentioned component (c) and component (d), but any other oil component may be mixed.

For example, liquid oils and fats, solid oils and fats, waxes, higher fatty acids, higher alcohols, ester oils, silicone oils, and the like can be appropriately mixed.

(e) Water (W)

Water used in the present invention is a component of the aqueous phase constituting the inner phase of the water-in-oil type emulsion sunscreen cosmetic. The amount of the water-in-oil emulsion sunscreen cosmetic is about 5 to 30% by mass based on the total amount of the water-in-oil emulsion sunscreen cosmetic.

In the water-in-oil type emulsified sunscreen cosmetic composition of the present invention, the mass ratio of the aqueous phase (including also water-soluble components dissolved in water) to the oil phase (including also components dissolved or dispersed in oil) is: oil phase 2: 8-1: and 9, in the above range.

(f) Ultraviolet absorber

The water-in-oil type emulsified sunscreen cosmetic of the present invention is characterized in that: it is also advantageous that the uv scattering agent is mixed in a large amount to exhibit sufficient uv protection ability without mixing the uv absorber. On the other hand, it is needless to say that an arbitrary ultraviolet absorber may be mixed. The present invention has sufficient ultraviolet protection ability, and therefore, has the following advantages: even when a small amount of the ultraviolet absorber is mixed, a hardly soluble ultraviolet absorber can be stably mixed.

As the ultraviolet absorber, specifically, there can be mixed: (1) benzoic acid ultraviolet absorbers, (2) anthranilic acid ultraviolet absorbers, (3) salicylic acid ultraviolet absorbers, (4) cinnamic acid ultraviolet absorbers, (5) triazine ultraviolet absorbers, and (6) other ultraviolet absorbers.

The water-in-oil type emulsified sunscreen cosmetic composition of the present invention may contain, in addition to the above essential components, components to be mixed in usual cosmetic compositions such as a humectant, a thickener, a powder, an alcohol, a natural polymer, a synthetic polymer, a saccharide, an antioxidant, a buffer, various extracts, a stabilizer, a preservative, a pigment, a perfume, etc., as appropriate, within the range not impairing the effects of the present invention.

The water-in-oil type emulsion sunscreen cosmetic of the present invention can be produced by a conventional method. Generally, a dispersion portion (パーツ) is prepared by mixing and stirring (a) hydrophobized zinc oxide, hydrophobized titanium oxide, and (d) volatile silicone oil and/or hydrocarbon oil having good dispersibility of the powder, (c) one or more selected from the group consisting of N-lauroyl-L-glutamine di (phytosterol 2-octyldodecanol) ester, macadamia nut fatty acid phytosterol ester, and macadamia nut fatty acid cholesteryl ester, and (b) a lipophilic nonionic surfactant, using an HM mixer or the like. Then, when another oil component or oily component is mixed (when a lipophilic ultraviolet absorber is mixed, etc.), another part is prepared, and this other part is mixed with the dispersion part to form an oil phase.

On the other hand, water (e) is mixed with an aqueous component such as ethanol, a thickener, a humectant, or the like to form an aqueous phase. Finally, the water phase and the oil phase are emulsified by a conventional method to obtain the water-in-oil type emulsified sunscreen cosmetic of the present invention.

Examples

The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples. Unless otherwise specified, the amount to be mixed represents mass% based on the total amount.

Emulsions as water-in-oil emulsion sunscreen cosmetics were prepared according to the formulations shown in "table 1" and "table 2" by a conventional method, and the following evaluations were performed.

[ Table 1]

"UV defense ability"

0.75mg of the preparation prepared according to each formulation per square centimeter was applied to a commercially available PMMA plate (5 cm. times.5 cm). The absorbance spectra of the examples and comparative examples were compared by measuring the absorbance in the range of 290 to 500nm using a spectrophotometer ("U-4100": Hitachi ハイテクノロージーズ, Ltd.).

< evaluation criteria >

O: the composition containing the ultraviolet scattering agent in an amount equivalent to that in example 1 (14% by mass in total) showed the same absorbance spectrum as in example 1. Therefore, the UV protection ability was as excellent as example 1.

X: the content of the ultraviolet scattering agent is less than 10% by mass, and the UV protection ability is poor.

< results >

The absorbance spectrum of example 1 is shown in FIG. 1.

The method is characterized in that: the absorbance spectra of examples 2 to 3 and comparative examples 1 to 6 were the same as the absorbance spectrum of example 1, and all the evaluations of examples 1 to 3 and comparative examples 1 to 6 were "o", and the UV protective ability was also excellent.

That is, all of the examples and comparative examples of "Table 1" were sufficiently mixed with (a) powder of an ultraviolet scattering agent (octyltrimethoxysilane treated zinc oxide and sodium acryloyldimethyl taurate/methacrylamide lauric acid copolymer treated titanium oxide) in a total of 14 mass%, and showed a spectrum showing high absorbance.

Therefore, it is known that the water-in-oil type emulsion sunscreen cosmetic of the present invention shows an extremely high UV protection ability. In the present invention, the following excellent advantages are obtained: the UV protection film exerts excellent UV protection ability even without mixing an ultraviolet absorber.

Feeling of use "

Practical use tests (applying the sunscreen cosmetics of examples and comparative examples on the wrist) were conducted by 10 professional panelists to evaluate whether or not there was a rough sensation without powder (plucked from the scratch らつき), smoothness (さらっと), and excellent feeling of use in combination.

< evaluation criteria >

Very good: the responses of 7 or more out of 10 were excellent in feeling of use;

o: among 10, 5 or more and less than 7 answers are excellent in sense of use;

and (delta): the answers of more than 3 and less than 5 out of 10 were excellent in feeling of use;

x: among 10, 2 or less answers were excellent in feeling of use.

< results >

The method is characterized in that: although examples 1 to 3 and comparative example 1 each contain a large amount of the ultraviolet scattering agent powder amounting to 14 mass%, they all showed an excellent feeling in use as compared with comparative examples 2 to 6.

Further, the method is characterized in that: (c) example 1, which used N-lauroyl-L-glutamine di (phytosterol 2-octyldodecanol) ester as a component, had a particularly excellent feeling of use.

Cleaning property "

The actual use test was conducted by 10 professional reviewers. 18mg of the sunscreen cosmetics of examples and comparative examples were applied to the upper arm of each panelist in a 3cm X3 cm frame, and then sufficiently blended and dried for 30 minutes. Thereafter, the coated part was washed with a commercially available hand-washing detergent (soap). After washing, the skin was touched for 15 minutes to confirm a feeling of residue.

< evaluation criteria >

O: no residual feeling was felt in 6 out of 10;

and (delta): 3 or more of the 10 patients did not feel any residual sensation;

x: no residual sensation was felt in 2 or less of 10.

< results >

The method is characterized in that: the cleaning performance of examples 1 to 3 was superior to that of comparative examples 1 to 6. The method is characterized in that: in comparative example 1, the cleansing performance was inferior to examples 1 to 3 because the amount of N-lauroyl-L-glutaminedi (phytosterol 2-octyldodecanol) ester contained in component (c) was 0.5% by mass.

[ Table 2]

"stability"

The emulsion just prepared was filled in a sample tube, left at 50 ℃ for 1 month, and visually observed.

< evaluation criteria >

O: the oil phase is compatible, colorless and transparent, and is in a stable state.

X: the oil phases were not mixed with each other, and were cloudy and not in a stable state.

< results >

The method is characterized in that: examples 4 to 6 and comparative examples 8 to 11 are excellent in stability. It is also known that: comparative example 7, in which the amount of N-lauroyl-L-glutamine di (phytosterol 2-octyldodecanol) ester contained only in component (c) was 7 mass%, was poor in stability.

In comparative example 7, the stability was poor and the state was not stable, and therefore the following tests of UV protective ability, feeling of use, and cleaning property were not carried out.

"UV defense ability"

0.75mg of the preparation prepared according to each formulation per square centimeter was applied to a commercially available PMMA plate (5 cm. times.5 cm). The absorbance spectra of the examples and comparative examples were compared by measuring the absorbance in the range of 290 to 500nm using a spectrophotometer ("U-4100": Hitachi ハイテクノロージーズ, Ltd.).

< evaluation criteria >

O: the composition containing the ultraviolet scattering agent in an amount equivalent to that in example 4 (19% by mass in total) showed the same absorbance spectrum as in example 4. Therefore, the UV protection ability was as excellent as example 4.

X: the content of the ultraviolet scattering agent is less than 10% by mass, and the UV protection ability is poor.

< results >

The absorbance spectrum of example 4 is shown in FIG. 1.

The method is characterized in that: examples 5 to 6 and comparative examples 8 to 11 all had the same absorbance spectrum as example 4, and all the evaluations of examples 4 to 6 and comparative examples 8 to 11 were "o", and the UV protective ability was also excellent.

That is, all of the examples and comparative examples in "table 2" were sufficiently mixed with (a) a powder of an ultraviolet scattering agent (stearic acid-alumina-treated titanium oxide and dimethylpolysiloxane-hydrodimethylpolysiloxane-treated zinc oxide) in a total amount of 19 mass%, and showed a spectrum showing a high absorbance.

Therefore, it is known that the water-in-oil type emulsion sunscreen cosmetic of the present invention shows an extremely high UV protection ability. In the present invention, the following excellent advantages are obtained: the UV protection film exerts excellent UV protection ability even without mixing an ultraviolet absorber.

Feeling in use, cleaning property "

The same tests as in the case of "table 1" above were carried out, and evaluations were carried out in the same manner.

The feeling of use was found to be: although examples 4 to 6 contained a large amount of ultraviolet scattering agent powder amounting to 19 mass%, they all showed superior feeling in use as compared with comparative examples 8 to 11. Further, the method is characterized in that: (c) example 4, in which N-lauroyl-L-glutamine di (phytosterol 2-octyldodecanol) ester was used as a component, had a particularly excellent feeling of use.

Concerning the cleaning property, it was found that: the cleaning performance of examples 4 to 6 was superior to that of comparative examples 8 to 11.

Other embodiments of the present invention are given below. All of which are water-in-oil type emulsion sunscreen cosmetics excellent in stability, UV protection ability, feeling in use, and cleansing property.

Example 7: W/O sunscreen cosmetic (emulsion)

< preparation method >

The oil phase was obtained by mixing (4) to (11). Next, wet (16) with (2) and mix (aqueous phase) with (1) with (18) dissolved in (17). The oil phase was charged with (3) and dispersed with a disperser (ディスパー), and then the oil phase was dispersed with dispersers (12) to (15) in the same manner. Finally, the oil phase and the aqueous phase were mixed and emulsified by an emulsifier.

Example 8: W/O sunscreen cosmetic (emulsion)

< preparation method >

Mixing (7) - (14), adding (4), (5) to the mixture to obtain oil phase. Next, the (21) is dissolved in the (22). To this was added (6), followed by dissolution (15) and addition of (1) - (3) (aqueous phase).

The oil phase was added with (16) to (20), dispersed with a disperser, mixed with the aqueous phase, and emulsified with an emulsifier.

Industrial applicability

The water-in-oil emulsion sunscreen cosmetic of the present invention is a novel and useful invention having excellent ultraviolet protection ability and excellent feeling of use and cleansing properties.

The water-in-oil type emulsified sunscreen cosmetic of the present invention is suitably used as a sunscreen lotion or a sunscreen cream.

Claims (2)

1. A water-in-oil emulsion sunscreen cosmetic characterized by containing the following (a) to (e):

(a) hydrophobized particulate zinc oxide and hydrophobized particulate titanium oxide having an average primary particle diameter of 10 to 100 nm: 10 to 30 mass%;

(b) lipophilic nonionic surfactant: 0.5 to 5 mass%;

(c) N-lauroyl-L-glutamine di (phytosterol 2-octyldodecanol) ester: 1 to 3 mass%;

(d) volatile silicone oils and/or hydrocarbon oils: 10 to 40 mass%;

(e) water: 5 to 30 mass%.

2. The water-in-oil emulsion sunscreen cosmetic composition according to claim 1, characterized in that: the lipophilic nonionic surfactant is polyoxyethylene-methyl polysiloxane copolymer.