WO2019151004A1 - Cosmetic material for sunscreen - Google Patents

Cosmetic material for sunscreen Download PDF

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Publication number
WO2019151004A1
WO2019151004A1 PCT/JP2019/001594 JP2019001594W WO2019151004A1 WO 2019151004 A1 WO2019151004 A1 WO 2019151004A1 JP 2019001594 W JP2019001594 W JP 2019001594W WO 2019151004 A1 WO2019151004 A1 WO 2019151004A1
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WO
WIPO (PCT)
Prior art keywords
powder
sunscreen
skin
hours
spotting
Prior art date
Application number
PCT/JP2019/001594
Other languages
French (fr)
Japanese (ja)
Inventor
近藤 淳
百合香 渡辺
も絵 東條
朋子 松本
香織 桜田
佐和子 大竹
圭太 西田
Original Assignee
株式会社 資生堂
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2018167805A external-priority patent/JP7188945B2/en
Application filed by 株式会社 資生堂 filed Critical 株式会社 資生堂
Publication of WO2019151004A1 publication Critical patent/WO2019151004A1/en

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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/06Emulsions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/25Silicon; Compounds thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/27Zinc; Compounds thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/37Esters of carboxylic acids
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/96Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
    • A61K8/97Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution from algae, fungi, lichens or plants; from derivatives thereof
    • A61K8/9783Angiosperms [Magnoliophyta]
    • A61K8/9789Magnoliopsida [dicotyledons]
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations

Definitions

  • the present invention relates to a sunscreen cosmetic. More specifically, the present invention relates to a sunscreen cosmetic that hardly spreads on the skin after application and has little irritation to eyes.
  • Sunscreen cosmetics a type of UV care cosmetics, absorb or scatter UVA and UVB on the skin by covering the skin with a coating film containing a UV absorber or UV scattering agent. It suppresses the amount of ultraviolet rays that reach it, and protects the skin from the harm of ultraviolet rays (Non-Patent Document 1).
  • Ethylhexyl methoxycinnamate and octocrylene are liquid UV absorbers having an absorption wavelength mainly in the UVB region, and are used in a large number of sunscreen cosmetics because of their excellent UV absorbing ability and availability. These liquid UV absorbers also serve as an oil solvent at the same time as UV absorbers. Therefore, it is possible to suppress the occurrence of stickiness by reducing the blending ratio of other oils, and the UV absorbers for the entire cosmetics. It is possible to achieve a high UV protection effect (high SPF) while maintaining a high blending ratio.
  • high SPF high UV protection effect
  • UV absorbers are known to irritate the skin of sensitive skin users.
  • the UV absorber may move on the skin due to sebum, sweat, etc., and may invade the eyes from the corners of the eyes and cause pain in the eyes. It is a problem.
  • Patent Document 1 proposes blending polypropylene glycol dimethyl ether to suppress percutaneous absorption of ethylhexyl methoxycinnamate for the purpose of alleviating irritation caused by such an ultraviolet absorber.
  • the skin irritation can be suppressed, it does not suppress the spread of the UV absorber over time, and thus the irritation to the eyes cannot be alleviated.
  • Patent Document 2 proposes that a combination of a plurality of powder components having an ultraviolet scattering action is combined instead of mixing ethylhexyl methoxycinnamate and octocrylene.
  • a combination of a plurality of powder components having an ultraviolet scattering action is combined instead of mixing ethylhexyl methoxycinnamate and octocrylene.
  • JP 2003-206214 A Japanese Patent Laying-Open No. 2015-124172
  • the present invention has been made in view of the drawbacks of the prior art described above, and is a tan that is less irritating to the eye despite containing ethylhexyl methoxycinnamate and / or octocrylene, which are widely used as ultraviolet absorbers.
  • the purpose is to provide stop cosmetics.
  • the present inventors have formulated a specific powder component together with ethylhexyl methoxycinnamate and / or octocrylene, so that it is difficult to spread on the skin after application and irritate the eyes.
  • the present inventors have found that a sunscreen cosmetic that is difficult to carry out can be obtained, and have completed the present invention.
  • the present invention (A) at least one ultraviolet absorber selected from ethylhexyl methoxycinnamate and octocrylene; (B) Spot area obtained 3 hours after spotting a suspension obtained by mixing 10 times amount (mass ratio) with (A) UV absorber on skin substitute membrane, (A) UV absorber Powder that is less than 60% of the area of the spot obtained 3 hours after spotting only, Sunscreen cosmetics including Spots obtained 3 hours after spotting the final product on the skin substitute membrane, the spot area obtained 3 hours after spotting a composition different from the final product on the skin substitute membrane only in that (B) it does not contain powder Sunscreen cosmetics that are 70% or less of the area of
  • the sunscreen cosmetic of the present invention can suppress the spread of the sunscreen cosmetic containing ethylhexyl methoxycinnamate and octocrylene on the skin by blending the powder component having the above specific properties. Therefore, especially when applied to the face, it is possible to suppress the ultraviolet absorber from entering the eye, there is little irritation to the eye, and the use feeling and safety are excellent.
  • the sunscreen cosmetic of the present invention essentially contains (A) an ultraviolet absorber and (B) a specific powder. This will be described in detail below.
  • the (A) ultraviolet absorber in the present invention is selected from ethylhexyl methoxycinnamate and octocrylene, which are ultraviolet absorbers that are liquid at room temperature.
  • Ethyl hexyl methoxycinnamate that is, octyl methoxycinnamate
  • octyl methoxycinnamate is a light yellow liquid UV absorber having a maximum absorption wavelength at 308 nm and excellent UVB cutting ability.
  • "Pulsol MCX" DSM Nutrition Japan Co., Ltd.) etc. can be used, for example.
  • Octocrylene that is, 2-ethylhexyl 2-cyano-3,3-diphenyl acrylate
  • “Ubinal N539T” BASF Japan Ltd.
  • “Pulsol 340” DSM Nutrition Japan Ltd.
  • the blending amount of the (A) ultraviolet absorber in the sunscreen cosmetic of the present invention is 3 to 30% by mass, preferably 5 to 20% by mass, more preferably 5 to 12% by mass with respect to the total sunscreen cosmetic. is there.
  • the (B) powder in the present invention is a spot obtained after 3 hours after spotting the suspension on the skin substitute membrane when the suspension is mixed with the (A) ultraviolet absorber at a predetermined ratio to form a suspension.
  • Suspension spreading ratio (%) ([suspension spot area] / [(A) spot area of ultraviolet absorber only]) ⁇ 100
  • the candidate powder is mixed with 10 times the mass ratio of the (A) ultraviolet absorber, that is, ethylhexyl methoxycinnamate, octocrylene, or a mixture thereof to obtain a suspension. Since these ultraviolet absorbers are liquid at room temperature, a uniform suspension can be obtained simply by adding powder and stirring.
  • the (A) ultraviolet absorber that is, ethylhexyl methoxycinnamate, octocrylene, or a mixture thereof. Since these ultraviolet absorbers are liquid at room temperature, a uniform suspension can be obtained simply by adding powder and stirring.
  • the skin substitute membrane is a pseudo artificial skin substrate for measurement, which is made of a hydrophobic material close to human skin, and has a lattice-like unevenness (or groove) formed on the surface imitating the texture of human skin. is there.
  • the hydrophobic material close to human skin include resins such as polymethyl methacrylate (PMMA), polyethylene, and nylon. Among these, polymethyl methacrylate having excellent ultraviolet transmission characteristics is preferable because it is advantageous for measuring the area of a spot described later.
  • the arithmetic mean roughness Sa of the surface of the skin substitute membrane is 10 to 50 ⁇ m, more preferably 13 to 30 ⁇ m.
  • the width of the recess is preferably 50 to 500 ⁇ m, more preferably 200 to 400 ⁇ m.
  • the depth of the recess is preferably 30 to 150 ⁇ m, more preferably 50 to 100 ⁇ m.
  • the unevenness can be formed by a conventionally known method such as sandblasting or molding.
  • Such a skin substitute membrane is disclosed in, for example, Japanese Patent No. 4871385.
  • SPF MASTER registered trademark
  • PA-01 Shiseido Medical Rika Technology Co., Ltd.
  • arithmetic average roughness Sa 17 ⁇ m
  • the method of spotting (applying) the suspension to the skin substitute membrane is not particularly limited as long as the application conditions between the samples can be made uniform. For example, using a micropipette or the like that can accurately measure the liquid volume.
  • 4-6 ⁇ l of the suspension droplet is gently placed on a horizontally placed skin substitute membrane.
  • the spot diameter during spotting is preferably 5 to 6 mm.
  • the skin substitute membrane After spotting the suspension, the skin substitute membrane is allowed to stand at room temperature and normal pressure (25 ° C., 1 atm) for 3 hours. During this time, the suspension spreads along the recesses on the surface of the skin substitute membrane, and the area of the spot increases.
  • the area of the spot spread on the skin substitute membrane ([area of the suspension spot]) is measured.
  • an ultraviolet irradiator and an ultraviolet camera taking advantage of the fact that the suspension contains an ultraviolet absorber.
  • the skin substitute membrane is irradiated with ultraviolet rays of black light and photographed with an ultraviolet camera. Since the suspension contains (A) an ultraviolet absorber, the spot portion absorbs ultraviolet rays and appears black on the ultraviolet camera.
  • the area of the spot spread on the skin substitute film can be accurately measured by binarizing the image data with a computer.
  • the powder having a suspension spreading ratio of 60% or less, more preferably 40% or less, is determined as (B) powder that can be used in the present invention.
  • the powder (B) satisfying the spreading ratio of the suspension include (i) fumed hydrophobic silica, (ii) spherical porous silica, and (iii) spherical porous polymethyl methacrylate (PMMA).
  • PMMA polymethyl methacrylate
  • These powders have nothing in common in oil absorption capacity, specific surface area, etc., and cannot be properly specified at present unless they are based on the above-mentioned “suspension rate of suspension”.
  • the “resin spreading ratio” of the silicone resin fine particles far exceeds 60% even when the average particle diameter and specific surface area are close to those of these powders.
  • the fumed hydrophobized silica has an average particle size of 5 to 20 nm, a specific surface area of 50 to 200 m 2 / g according to the BET method, and an oil absorption measured according to JIS K5101-13-2 of 30 to 35 ml / It is preferable to use 100 g of fine silica whose surface is hydrophobized with a treating agent such as dimethyldichlorosilane or dimethylpolysiloxane. Specifically, Aerosil R972 (Nippon Aerosil Co., Ltd.) etc. can be illustrated.
  • the spherical porous silica preferably has an average particle size of 3 to 10 ⁇ m, a specific surface area of 250 to 350 m 2 / g, and an oil absorption of 100 to 200 ml / 100 g.
  • Specific examples include Sunsphere L-51 (AGC S-Tech Co., Ltd.).
  • Spherical polymethylmethacrylate is a spherical polymer formed so as to have an average particle size of 5 to 10 ⁇ m, a specific surface area of 80 to 100 m 2 / g, and an oil absorption of 100 to 200 ml / 100 g.
  • (Meth) acrylate particles are preferred.
  • Techpolymer MBP-8 (Sekisui Plastics Co., Ltd.) can be preferably used.
  • the blending amount of the (B) powder in the sunscreen cosmetic of the present invention is 0.5 to 15% by mass, preferably 2 to 10% by mass, and most preferably about 5% by mass with respect to the total sunscreen cosmetic. .
  • the sunscreen cosmetic of the present invention has other optional components that can be usually blended in the sunscreen cosmetic with the effects of the present invention. You may include in the range which does not inhibit.
  • the sunscreen cosmetic of the present invention may contain an ultraviolet absorber other than (A).
  • an ultraviolet absorber other than ethylhexyl methoxycinnamate and octocrylene By blending an ultraviolet absorber other than ethylhexyl methoxycinnamate and octocrylene, the UV protection ability in the UVA and / or UVB region can be further improved. Even in this case, it is preferable that the total blending amount of the ultraviolet absorbers other than (A) and (A) is within the blending amount range described above for (A). Such an ultraviolet absorber is not particularly limited.
  • t-butylmethoxydibenzoylmethane ethylhexyltriazone, bisethylhexyloxyphenol methoxyphenyltriazine, diethylaminohydroxybenzoyl hexyl benzoate, oxybenzone-3 And methylenebisbenzotriazolyltetramethylbutylphenol, polysilicone-15, phenylbenzimidazolesulfonic acid, homosalate, ethylhexyl salicylate, and the like.
  • the sunscreen cosmetic of the present invention may contain a powder (ultraviolet scattering agent) that physically shields ultraviolet rays by reflection / scattering.
  • the ultraviolet scattering agent that can be blended in the present invention is not particularly limited as long as it is a powder used as an ultraviolet scattering agent in the cosmetics field. Specific examples include one selected from titanium oxide, zinc oxide, barium sulfate, iron oxide, talc, mica, sericite, kaolin, titanium mica, bitumen, chromium oxide, chromium hydroxide, silica, cerium oxide, and the like. Two or more types can be mentioned. In particular, it is preferable from the viewpoint of optical properties to use a powder having a refractive index of 1.5 or more, such as zinc oxide or titanium oxide.
  • the particle surface of the UV scattering agent may be hydrophobized. Dispersibility in oil and water resistance are improved by subjecting the surface to hydrophobic treatment.
  • Surface treatment methods include silicone treatment such as methylhydrogenpolysiloxane and methylpolysiloxane; alkylsilane treatment; fluorine treatment with perfluoroalkyl phosphate ester, perfluoroalcohol, etc .; amino acid treatment with N-acyl glutamic acid, etc. And lecithin treatment; metal soap treatment; fatty acid treatment; alkyl phosphate ester treatment and the like.
  • an ultraviolet scattering agent is added too much, whiteness at the time of application may be noticeable or a powdery feeling may be produced.
  • the spread of sunscreen cosmetics on the skin can be reduced by blending the powder (B). Therefore, even in the situation where the blending amount of the UV scattering agent is small or not blended at all, The spread of the absorbent can be reduced.
  • a particularly excellent eye irritation reduction effect is achieved in a formulation in which the total amount of UV scattering agent is 3% by mass or less based on the total amount of sunscreen cosmetics. it can.
  • a particularly excellent ocular irritation reduction effect can be achieved in a formulation in which the total amount of ultraviolet scattering agent is 10% by mass or less.
  • TRPV1 activity inhibitor The present inventors have found that the irritation to the eye can be further suppressed by adding a TRPV1 activity inhibitor to the sunscreen cosmetic of the present invention.
  • TRPV1 belongs to the TRP (transient receptor potential) ion channel superfamily and is known as a capsaicin receptor.
  • the present inventors have revealed that the cause of irritation when ethylhexyl methoxycinnamate and octocrylene entered the eye is due to the activation of TRPV1, and that the eye irritation is further suppressed by suppressing the activation of TRPV1. Newly found. When TRPV1 is activated, calcium ions are taken into the cells.
  • TRPV1 activity inhibitors use, for example, HEK293 cells in which TRPV1 is forcibly expressed, and have an inhibitory effect on the reaction caused by a positive control substance (capsaicin, etc.). Screening can be done by imaging. As a result of the above screening, it was confirmed that Yuzu seed oil, resveratrol, orange oil, PEG-9 polydimethylsiloxyethyl dimethicone, ethylene glycol distearate, stearic acid, and zinc myristate had a TRPV1 activity inhibitory effect.
  • yuzu seed oil and resveratrol are particularly preferable from the viewpoint of the effect of suppressing eye irritation. Most preferred is yuzu seed oil.
  • a TRPV1 activity inhibitor When a TRPV1 activity inhibitor is added to the sunscreen cosmetic of the present invention, it is 0.5 to 5% by mass, more preferably 0.5 to 3% by mass, and most preferably about 1% by mass with respect to the total sunscreen cosmetic. %.
  • the blending amount of the TRPV1 activity inhibitor is less than 0.5% by mass, the effect of the TRPV1 activity inhibitor can hardly be realized, and when the blending amount is more than 5% by mass, the feeling of use tends to be impaired.
  • Examples of other optional components include alcohols, water-soluble polymers, oil-soluble polymers, surfactants, powder components other than the above (B) powder and ultraviolet scattering agent, various oils, and the like. It is not limited.
  • alcohols examples include lower alcohols such as ethanol and isopropanol, and polyhydric alcohols such as glycerin, ethylene glycol, propylene glycol, 1,3-butylene glycol, dipropylene glycol, and polybutylene glycol.
  • water-soluble polymer examples include homopolymers or copolymers of 2-acrylamido-2-methylpropanesulfonic acid (hereinafter abbreviated as “AMPS”).
  • the copolymer is a copolymer composed of a comonomer such as vinyl pyrrolidone, acrylic acid amide, sodium acrylate, hydroxyethyl acrylate and the like. That is, an AMPS homopolymer, a vinylpyrrolidone / AMPS copolymer, a dimethylacrylamide / AMPS copolymer, an acrylic amide / AMPS copolymer, a sodium acrylate / AMPS copolymer, and the like are exemplified.
  • carboxyvinyl polymer ammonium polyacrylate, sodium polyacrylate, sodium acrylate / alkyl acrylate / sodium methacrylate / alkyl methacrylate copolymer, carrageenan, pectin, mannan, curdlan, chondroitin sulfate, starch, Glycogen, gum arabic, sodium hyaluronate, tragacanth gum, xanthan gum, mucoitin sulfate, hydroxyethyl guar gum, carboxymethyl guar gum, guar gum, dextran, kerato sulfate, locust bean gum, succinoglucan, chitin, chitosan, carboxymethyl chitin, agar etc. Illustrated.
  • oil-soluble polymer examples include trimethylsiloxysilicic acid, alkyl-modified silicone, polyamide-modified silicone, dimethicone crosspolymer, (dimethicone / vinyl dimethicone) crosspolymer, polymethylsilsesquioxane, and the like.
  • surfactant examples include anionic, cationic, nonionic, and amphoteric surfactants, and include silicone-based or hydrocarbon-based surfactants.
  • powder components other than the above (B) powder and ultraviolet scattering agent include nylon and acrylic polymer spherical powder, silica powder, silicone powder, metal oxide powder surface-treated with a metal-free surface treatment agent, and the like. Is done.
  • the sunscreen cosmetic of the present invention spotts a composition that differs from the final product only in that the spot area after 3 hours after spotting the final product on the skin substitute film does not contain powder. Thus, it is 70% or less of the area of the spot after 3 hours.
  • the sunscreen cosmetic of the present invention is required to have a “extended product spreading ratio” represented by the following formula of 70% or less.
  • Spread ratio of final product (%) ([area of spot of final product] / [area of spot of composition excluding (B) powder from final product]) ⁇ 100
  • the spread ratio of the final product is spotted on the skin substitute membrane in the same manner as the evaluation of the “suspension spread ratio”. After leaving the skin substitute membrane as it is at room temperature and normal pressure (25 ° C., 1 atm) for 3 hours, the area of the spot ([spot area of the final product]) spreading on the skin substitute membrane is measured. Since the final product contains an ultraviolet absorber, an ultraviolet irradiator and an ultraviolet camera can also be used here for measuring the area.
  • composition different from the final product was prepared only in that it did not contain (B) powder, and the spot area after 3 hours ([B) Spot area]). From these areas, the “extension rate of the final product” is calculated by the above formula.
  • a product having a final product spreading rate of 70% or less, more preferably 50% or less, is determined as the sunscreen cosmetic of the present invention. If the spread rate of the final product is 70% or less, the cosmetic is less likely to spread on the skin and less likely to enter the eye.
  • the sunscreen cosmetic of the present invention can be provided in the form of an oil-in-water emulsified cosmetic, a water-in-oil emulsified cosmetic, or an oily cosmetic.
  • an oil-in-water emulsified cosmetic emulsified cosmetic
  • a water-in-oil emulsified cosmetic emulsified cosmetic
  • an oily cosmetic emulsified cosmetic
  • dosage forms such as sunscreen milky lotion and sunscreen cream, which can be produced using a conventional method suitable for each dosage form.
  • the (A) ultraviolet absorber and the (B) powder coexist in the same phase, they tend to exhibit a particularly high eye irritation reducing effect.
  • “coexistence in the same phase” means that (A) the ultraviolet absorber and (B) powder are not required to be completely present in the same phase, but substantially coexist. Refers to the state of Specifically, 90% or more, more preferably 95% or more, and still more preferably 98% or more of each of the (A) ultraviolet absorber and (B) powder may coexist in the same phase.
  • both (A) the ultraviolet absorber and (B) the powder coexist in the same oil phase, that is, the sunscreen cosmetic is an oil-in-water emulsified cosmetic.
  • (A) UV absorber and (B) powder are both present in the internal phase (oil phase), while in the form of a water-in-oil emulsified cosmetic, It is preferable that both A) the ultraviolet absorber and (B) powder are present in the outer phase (oil phase).
  • the sunscreen cosmetic of the present invention that can suppress the spread on the skin without relying on an ultraviolet scattering agent is a form of an oil-in-water emulsified cosmetic that can realize both good spreading and a refreshing feeling of use. Highly effective in.
  • the sunscreen cosmetic of the present invention is in the form of an oil-in-water emulsified cosmetic and has a formulation in which both (A) the ultraviolet absorber and (B) powder are present in the internal phase (oil phase).
  • the sunscreen cosmetic of the present invention can exhibit a particularly high effect and can significantly reduce irritation to the eyes.
  • the viscosity of the sunscreen cosmetic of the present invention is not particularly limited. However, when the viscosity is 10,000 mPa ⁇ s or more, the problem due to extension is hardly caused in the first place. Therefore, the present invention is particularly effective in a system having a viscosity of 10,000 mPa ⁇ s or less.
  • the blending amount is expressed in mass% with respect to the system in which the component is blended.
  • each suspension was spotted at 10 locations, and the average of the spot areas was used to calculate the spreading ratio of the suspension.
  • only octocrylene was spotted on the skin substitute membrane under the same conditions, and the area of the spot after 3 hours was measured. Again, spotting was performed 10 times, and the average of the areas of those spots was used to calculate the spreading rate. From the area of each suspension and the spot of octocrylene, the spreading ratio of each suspension was calculated. The results are shown in Table 1.
  • Oil-in-water emulsified sunscreen cosmetics In the formulation shown in Table 3, oil-in-water emulsified sunscreen cosmetics were produced by conventional methods. Specifically, (1) to (9) and (23) were added to (24) and mixed uniformly, and then the powder of (21) was uniformly dispersed to obtain an aqueous phase. On the other hand, after (10) to (20) were uniformly mixed, (22) was added and uniformly dispersed to obtain an oil phase. Thereafter, the oil phase was gradually added to the aqueous phase, and after uniform dispersion with a homomixer, the emulsified particles were prepared to obtain the sunscreen cosmetic of Example 1. In Comparative Example 1, a sunscreen cosmetic was obtained without adding (20) and (22).
  • Example 1 5 ⁇ l of the sunscreen cosmetic of Example 1 was gently spotted using a micropipette on a skin substitute membrane (trade name “SPF MASTER (registered trademark) PA-01”; Shiseido Medical Rika Technology Co., Ltd.). After leaving the skin substitute membrane at room temperature and normal pressure (25 ° C, 1 atm) for 3 hours, it is photographed using an ultraviolet irradiator and an ultraviolet camera, and the image data is binarized by a computer to replace the skin. The area of the spot spread on the film was measured. Spotting was performed at three locations, and the average of them was used to calculate the spreading ratio of the final product.
  • SPF MASTER registered trademark
  • PA-01 Shiseido Medical Rika Technology Co., Ltd.
  • Example 1 in which fumed hydrophobic silica was blended, the spread of the cosmetic material on the skin substitute film was compared with that in Comparative Example 1 in which this powder was not blended (final product). It was confirmed that the spread ratio of the film could be reduced to 41.9%.
  • water-in-oil emulsified sunscreen cosmetics were prepared according to the formulation shown in Table 4 by a conventional method. Specifically, after the components constituting the oil phase were uniformly mixed, methyl methacrylate crosspolymer was added and uniformly dispersed to obtain an oil phase. On the other hand, the components constituting the aqueous phase were uniformly mixed and dissolved to obtain an aqueous phase. The oil phase was gradually added to the aqueous phase, and after uniform dispersion with a homomixer, the emulsified particles were prepared to obtain sunscreen cosmetics of Examples 2-4. In Comparative Examples 2 and 3, sunscreen cosmetics were obtained without adding methyl methacrylate crosspolymer. The spread ratio of the final product was calculated in the same manner as in Example 1. The results are shown in Table 4.

Abstract

Provided is a cosmetic material for sunscreen that is less irritating to the eyes despite containing ethylhexyl methoxycinnamate and/or octocrylene, which are widely used as UV absorbers. The present invention relates to a cosmetic material for sunscreen that contains (A) at least one UV absorber selected from ethylhexyl methoxycinnamate and octocrylene and (B) a powder of which the area of a spot obtained three hours after spotting a suspension obtained by mixing with a 10-fold quantity (mass ratio) of the (A) UV absorber on a skin substitution membrane is 60% or less the area of a spot obtained three hours after spotting the (A) UV absorber alone, wherein the area of a spot obtained three hours after spotting the final product on a skin substitution membrane is 70% or less the area of a spot obtained three hours after spotting a composition different from the final product only by not containing the (B) powder on a skin substitution membrane.

Description

日焼け止め化粧料Sunscreen cosmetics
 本発明は、日焼け止め化粧料に関する。より詳しくは、適用後に皮膚上を広がりにくく、眼に対して刺激の少ない日焼け止め化粧料に関する。 The present invention relates to a sunscreen cosmetic. More specifically, the present invention relates to a sunscreen cosmetic that hardly spreads on the skin after application and has little irritation to eyes.
 紫外線の害から皮膚を守ることはスキンケア、ボディケアにおける重要な課題の一つであり、紫外線が皮膚に与える悪影響を最小限に抑えるために種々のUVケア化粧料が開発されている。UVケア化粧料の1種である日焼け止め化粧料(サンスクリーン化粧料)は、紫外線吸収剤や紫外線散乱剤を配合した塗膜で皮膚を覆うことによりUVA及びUVBを吸収又は散乱させて皮膚に到達する紫外線量を抑制し、紫外線の害から皮膚を守る(非特許文献1)。 Protecting the skin from the damage of ultraviolet rays is one of the important issues in skin care and body care, and various UV care cosmetics have been developed to minimize the adverse effects of ultraviolet rays on the skin. Sunscreen cosmetics (sunscreen cosmetics), a type of UV care cosmetics, absorb or scatter UVA and UVB on the skin by covering the skin with a coating film containing a UV absorber or UV scattering agent. It suppresses the amount of ultraviolet rays that reach it, and protects the skin from the harm of ultraviolet rays (Non-Patent Document 1).
 メトキシケイヒ酸エチルヘキシル及びオクトクリレンは、主にUVB領域に吸収波長を持つ液状の紫外線吸収剤であり、優れた紫外線吸収能や入手容易性から非常に多くの日焼け止め化粧料に使用されている。これらの液状紫外線吸収剤は、紫外線吸収剤であると同時に油性溶媒としての役割も果たすため、他の油分の配合比率を低減してべたつきの発生を抑えることや、化粧料全体に対する紫外線吸収剤の配合比率を高く維持して高い紫外線防御効果(高SPF)を実現することが可能である。 Ethylhexyl methoxycinnamate and octocrylene are liquid UV absorbers having an absorption wavelength mainly in the UVB region, and are used in a large number of sunscreen cosmetics because of their excellent UV absorbing ability and availability. These liquid UV absorbers also serve as an oil solvent at the same time as UV absorbers. Therefore, it is possible to suppress the occurrence of stickiness by reducing the blending ratio of other oils, and the UV absorbers for the entire cosmetics. It is possible to achieve a high UV protection effect (high SPF) while maintaining a high blending ratio.
 しかしながら、これらの紫外線吸収剤は、敏感肌の使用者には皮膚に刺激を与えることが知られている。また、敏感肌によらず、顔に適用した場合には、皮脂や汗などにより皮膚上を紫外線吸収剤が移動し、目尻等から眼に侵入して、眼にしみるような痛みを与えることが問題となっている。 However, these UV absorbers are known to irritate the skin of sensitive skin users. In addition, when applied to the face regardless of sensitive skin, the UV absorber may move on the skin due to sebum, sweat, etc., and may invade the eyes from the corners of the eyes and cause pain in the eyes. It is a problem.
 こうした紫外線吸収剤による刺激を緩和することを目的として、例えば、特許文献1にはポリプロピレングリコールジメチルエーテルを配合して、メトキシケイヒ酸エチルヘキシルの経皮吸収を抑制することが提案されている。しかし、皮膚刺激は抑制できても、紫外線吸収剤の経時的な広がりを抑制するものではないため、眼に対する刺激は緩和することができない。 For example, Patent Document 1 proposes blending polypropylene glycol dimethyl ether to suppress percutaneous absorption of ethylhexyl methoxycinnamate for the purpose of alleviating irritation caused by such an ultraviolet absorber. However, even if the skin irritation can be suppressed, it does not suppress the spread of the UV absorber over time, and thus the irritation to the eyes cannot be alleviated.
 また、特許文献2には、メトキシケイヒ酸エチルヘキシル及びオクトクリレンを配合しない代わりに、紫外線散乱作用のある複数の粉末成分を組み合わせて配合することが提案されている。しかしながら、高SPFを得るためには粉末成分を大量に配合する必要があり、皮膚に塗布した際に白浮きしたり、使用感触が著しく損なわれる場合がある。 In addition, Patent Document 2 proposes that a combination of a plurality of powder components having an ultraviolet scattering action is combined instead of mixing ethylhexyl methoxycinnamate and octocrylene. However, in order to obtain a high SPF, it is necessary to add a large amount of the powder component, and when applied to the skin, whitening may occur and the feeling of use may be significantly impaired.
特開2003-206214号公報JP 2003-206214 A 特開2015-124172号公報Japanese Patent Laying-Open No. 2015-124172
 本発明は、前記従来技術の欠点に鑑みてなされたものであり、紫外線吸収剤として汎用されているメトキシケイヒ酸エチルヘキシル及び/又はオクトクリレンを含有するにも拘わらず、眼に対して刺激の少ない日焼け止め化粧料を提供することを目的とする。 The present invention has been made in view of the drawbacks of the prior art described above, and is a tan that is less irritating to the eye despite containing ethylhexyl methoxycinnamate and / or octocrylene, which are widely used as ultraviolet absorbers. The purpose is to provide stop cosmetics.
 本発明者等は上記の課題を解決すべく鋭意研究を行った結果、メトキシケイヒ酸エチルヘキシル及び/又はオクトクリレンとともに、特定の粉末成分を配合することにより、適用後に皮膚上で広がりにくく、眼を刺激しにくい日焼け止め化粧料が得られることを見出し、本発明を完成するに至った。 As a result of diligent research to solve the above problems, the present inventors have formulated a specific powder component together with ethylhexyl methoxycinnamate and / or octocrylene, so that it is difficult to spread on the skin after application and irritate the eyes. The present inventors have found that a sunscreen cosmetic that is difficult to carry out can be obtained, and have completed the present invention.
 すなわち、本発明は、
(A)メトキシケイヒ酸エチルヘキシル及びオクトクリレンから選択される少なくとも1種以上の紫外線吸収剤と、
(B)10倍量(質量比)の(A)紫外線吸収剤と混合して得た懸濁液を皮膚代替膜にスポッティングして3時間後に得られるスポットの面積が、(A)紫外線吸収剤のみをスポッティングして3時間後に得られるスポットの面積の60%以下である粉末と、
を含む日焼け止め化粧料であって、
最終製品を皮膚代替膜にスポッティングして3時間後に得られるスポットの面積が、(B)粉末を含まない点においてのみ最終製品と異なる組成物を皮膚代替膜にスポッティングして3時間後に得られるスポットの面積の70%以下である日焼け止め化粧料を提供する。
That is, the present invention
(A) at least one ultraviolet absorber selected from ethylhexyl methoxycinnamate and octocrylene;
(B) Spot area obtained 3 hours after spotting a suspension obtained by mixing 10 times amount (mass ratio) with (A) UV absorber on skin substitute membrane, (A) UV absorber Powder that is less than 60% of the area of the spot obtained 3 hours after spotting only,
Sunscreen cosmetics including
Spots obtained 3 hours after spotting the final product on the skin substitute membrane, the spot area obtained 3 hours after spotting a composition different from the final product on the skin substitute membrane only in that (B) it does not contain powder Sunscreen cosmetics that are 70% or less of the area of
 本発明の日焼け止め化粧料は、上記特定の性質を有する粉末成分を配合することにより、メトキシケイヒ酸エチルヘキシル及びオクトクリレンを含有する日焼け止め化粧料の皮膚上での広がりを抑制することができる。そのため、特に顔に塗布した場合に、紫外線吸収剤が眼に侵入するのを抑えることができ、眼に対して刺激が少なく、使用感及び安全性に優れている。 The sunscreen cosmetic of the present invention can suppress the spread of the sunscreen cosmetic containing ethylhexyl methoxycinnamate and octocrylene on the skin by blending the powder component having the above specific properties. Therefore, especially when applied to the face, it is possible to suppress the ultraviolet absorber from entering the eye, there is little irritation to the eye, and the use feeling and safety are excellent.
 本発明の日焼け止め化粧料は、(A)紫外線吸収剤と、(B)特定の粉末とを必須に含有する。以下に詳しく説明する。 The sunscreen cosmetic of the present invention essentially contains (A) an ultraviolet absorber and (B) a specific powder. This will be described in detail below.
<(A)紫外線吸収剤>
 本発明における(A)紫外線吸収剤は、常温で液状の紫外線吸収剤であるメトキシケイヒ酸エチルヘキシル及びオクトクリレンから選択される。
 メトキシケイヒ酸エチルヘキシル(すなわちオクチルメトキシシンナメート)は、308nmに極大吸収波長を有するUVBカット能に優れた淡黄色の液状紫外線吸収剤である。市販品としては、例えば「パルソールMCX」(DSM ニュートリション ジャパン株式会社)等を使用することができる。
<(A) UV absorber>
The (A) ultraviolet absorber in the present invention is selected from ethylhexyl methoxycinnamate and octocrylene, which are ultraviolet absorbers that are liquid at room temperature.
Ethyl hexyl methoxycinnamate (that is, octyl methoxycinnamate) is a light yellow liquid UV absorber having a maximum absorption wavelength at 308 nm and excellent UVB cutting ability. As a commercial item, "Pulsol MCX" (DSM Nutrition Japan Co., Ltd.) etc. can be used, for example.
 オクトクリレン(すなわち2-エチルヘキシル 2-シアノ-3,3-ジフェニルアクリレート)は、310nmを極大吸収波長としつつ、290~350nmの幅広い波長域をカットできる黄色の液状紫外線吸収剤である。市販品としては、例えば「ユビナールN539T」(BASFジャパン株式会社)、「パルソール340」(DSM ニュートリション ジャパン株式会社)等を使用することができる。 Octocrylene (that is, 2-ethylhexyl 2-cyano-3,3-diphenyl acrylate) is a yellow liquid ultraviolet absorber capable of cutting a wide wavelength range of 290 to 350 nm while setting 310 nm as a maximum absorption wavelength. As a commercially available product, for example, “Ubinal N539T” (BASF Japan Ltd.), “Pulsol 340” (DSM Nutrition Japan Ltd.) or the like can be used.
 本発明の日焼け止め化粧料における(A)紫外線吸収剤の配合量は、日焼け止め化粧料全体に対して3~30質量%、好ましくは5~20質量%、さらに好ましくは5~12質量%である。(A)紫外線吸収剤の配合量が3質量%未満の場合には紫外線防御効果が十分に発揮されず、30質量%よりも多いとべたつきを生じて使用感を損なったり、皮膚や眼に対する刺激が強くなり過ぎる傾向があるため好ましくない。 The blending amount of the (A) ultraviolet absorber in the sunscreen cosmetic of the present invention is 3 to 30% by mass, preferably 5 to 20% by mass, more preferably 5 to 12% by mass with respect to the total sunscreen cosmetic. is there. (A) When the blending amount of the UV absorber is less than 3% by mass, the UV protection effect is not sufficiently exhibited, and when it exceeds 30% by mass, stickiness is caused and the feeling of use is impaired, or irritation to the skin and eyes Is not preferred because it tends to be too strong.
<(B)粉末>
 本発明における(B)粉末は、前記(A)紫外線吸収剤と所定の比率で混合して懸濁液とした場合に、懸濁液を皮膚代替膜上にスポッティングして3時間後に得られるスポットの面積が、(A)紫外線吸収剤のみをスポッティングして3時間後に得られるスポットの面積の60%以下となる粉末である。
 すなわち、(B)粉末は、以下の式によって表される「懸濁液の延展率」が60%以下となることを要件とする。
懸濁液の延展率(%)=([懸濁液のスポットの面積]/[(A)紫外線吸収剤のみのスポットの面積])×100
<(B) Powder>
The (B) powder in the present invention is a spot obtained after 3 hours after spotting the suspension on the skin substitute membrane when the suspension is mixed with the (A) ultraviolet absorber at a predetermined ratio to form a suspension. Is a powder that is 60% or less of the area of the spot obtained 3 hours after spotting only the ultraviolet absorber (A).
That is, the (B) powder is required to have a “suspension ratio of suspension” represented by the following formula of 60% or less.
Suspension spreading ratio (%) = ([suspension spot area] / [(A) spot area of ultraviolet absorber only]) × 100
 以下、「懸濁液の延展率」の評価方法について説明する。
 まず、候補となる粉末を、質量比で10倍量の(A)紫外線吸収剤、すなわちメトキシケイヒ酸エチルヘキシル、オクトクリレン又はこれらの混合物と混合して懸濁液を得る。これらの紫外線吸収剤は室温で液状であるため、粉末を加えて攪拌するだけで均一な懸濁液が得られる。
Hereinafter, an evaluation method of “suspension rate of suspension” will be described.
First, the candidate powder is mixed with 10 times the mass ratio of the (A) ultraviolet absorber, that is, ethylhexyl methoxycinnamate, octocrylene, or a mixture thereof to obtain a suspension. Since these ultraviolet absorbers are liquid at room temperature, a uniform suspension can be obtained simply by adding powder and stirring.
 皮膚代替膜は、ヒトの肌に近い疎水性の材料から構成され、なおかつ、ヒトの肌の肌理を模して表面に格子状の凹凸(又は溝)が形成された測定用擬似人工皮膚基板である。
 ヒトの肌に近い疎水性を有する材質としては、ポリメタクリル酸メチル(PMMA)、ポリエチレン、ナイロン等の樹脂を挙げることができる。なかでも、後述するスポットの面積の測定に有利であることから、紫外線透過特性に優れるポリメタクリル酸メチルが好ましい。
The skin substitute membrane is a pseudo artificial skin substrate for measurement, which is made of a hydrophobic material close to human skin, and has a lattice-like unevenness (or groove) formed on the surface imitating the texture of human skin. is there.
Examples of the hydrophobic material close to human skin include resins such as polymethyl methacrylate (PMMA), polyethylene, and nylon. Among these, polymethyl methacrylate having excellent ultraviolet transmission characteristics is preferable because it is advantageous for measuring the area of a spot described later.
 ヒトの肌の肌理を再現するために、皮膚代替膜表面の算術平均粗さSaが10~50μm、より好ましくは13~30μmとなるように凹凸が形成されているのが好ましい。また、凹部の幅は、50~500μmが好ましく、より好ましくは200~400μmである。凹部の深さは、30~150μmが好ましく、より好ましくは50~100μmである。凹凸は、サンドブラスト加工、モールド加工等の従来より公知の方法により形成することができる。 In order to reproduce the texture of human skin, it is preferable that irregularities are formed so that the arithmetic mean roughness Sa of the surface of the skin substitute membrane is 10 to 50 μm, more preferably 13 to 30 μm. The width of the recess is preferably 50 to 500 μm, more preferably 200 to 400 μm. The depth of the recess is preferably 30 to 150 μm, more preferably 50 to 100 μm. The unevenness can be formed by a conventionally known method such as sandblasting or molding.
 このような皮膚代替膜は、例えば特許第4871385号に開示されている。皮膚代替膜の市販品としては、「SPF MASTER(登録商標) PA-01」(資生堂医理化テクノロジー株式会社)(PMMA樹脂製;表面の算術平均粗さSa=17μm)等を使用することができる。 Such a skin substitute membrane is disclosed in, for example, Japanese Patent No. 4871385. As a commercially available skin substitute membrane, “SPF MASTER (registered trademark) PA-01” (Shiseido Medical Rika Technology Co., Ltd.) (made of PMMA resin; arithmetic average roughness Sa = 17 μm) can be used. .
 懸濁液を皮膚代替膜にスポッティング(適用)する方法は、サンプル間の適用条件を一定に揃えることができれば特に限定されないが、例えば、液量を正確に測ることができるマイクロピペット等を用いて、水平に配置した皮膚代替膜上に4~6μlの懸濁液の液滴を静かに載せるのが好ましい。スポッティング時のスポットの直径は5~6mmが好ましい。 The method of spotting (applying) the suspension to the skin substitute membrane is not particularly limited as long as the application conditions between the samples can be made uniform. For example, using a micropipette or the like that can accurately measure the liquid volume. Preferably, 4-6 μl of the suspension droplet is gently placed on a horizontally placed skin substitute membrane. The spot diameter during spotting is preferably 5 to 6 mm.
 懸濁液をスポッティングした後、皮膚代替膜をそのまま常温常圧(25℃、1気圧)下にて3時間静置する。この間に、懸濁液が皮膚代替膜表面の凹部を伝って拡散し、スポットの面積が広がる。 After spotting the suspension, the skin substitute membrane is allowed to stand at room temperature and normal pressure (25 ° C., 1 atm) for 3 hours. During this time, the suspension spreads along the recesses on the surface of the skin substitute membrane, and the area of the spot increases.
 次いで、皮膚代替膜上に広がったスポットの面積([懸濁液のスポットの面積])を測定する。面積の測定には、懸濁液が紫外線吸収剤を含有することを利用して、紫外線照射器と紫外線カメラを用いるのが好ましい。具体的には、皮膚代替膜にブラックライトの紫外線を照射し、紫外線カメラで撮影する。懸濁液は(A)紫外線吸収剤を含むため、スポットの部分は紫外線を吸収し、紫外線カメラに黒く写る。この画像データをコンピュータで2値化するなどして、皮膚代替膜上に広がったスポットの面積を正確に測定することができる。 Next, the area of the spot spread on the skin substitute membrane ([area of the suspension spot]) is measured. For the measurement of the area, it is preferable to use an ultraviolet irradiator and an ultraviolet camera taking advantage of the fact that the suspension contains an ultraviolet absorber. Specifically, the skin substitute membrane is irradiated with ultraviolet rays of black light and photographed with an ultraviolet camera. Since the suspension contains (A) an ultraviolet absorber, the spot portion absorbs ultraviolet rays and appears black on the ultraviolet camera. The area of the spot spread on the skin substitute film can be accurately measured by binarizing the image data with a computer.
 一方、懸濁液に用いたものと同一の(A)紫外線吸収剤を、懸濁液と同一の条件で皮膚代替膜上にスポッティングし、3時間経過後のスポットの面積([(A)紫外線吸収剤のみのスポットの面積])を測定する。
 最後に、これらの面積から、上記の式により「懸濁液の延展率」を算出する。
 懸濁液の延展率が60%以下、より好ましくは40%以下となる粉末を、本発明に使用可能な(B)粉末と判定する。
On the other hand, the same (A) UV absorber as that used for the suspension was spotted on the skin substitute membrane under the same conditions as the suspension, and the spot area after 3 hours ([(A) UV Measure spot area of absorbent only]).
Finally, from these areas, the “suspension rate of the suspension” is calculated by the above formula.
The powder having a suspension spreading ratio of 60% or less, more preferably 40% or less, is determined as (B) powder that can be used in the present invention.
 このような懸濁液の延展率を満たす具体的な(B)粉末としては、(i)煙霧状疎水化シリカ、(ii)球状多孔性シリカ、(iii)球状多孔性ポリメチルメタクリレート(PMMA)を挙げることができる。これらの粉末は吸油能、比表面積等に共通するところがなく、現在のところ、上記の「懸濁液の延展率」によらなければ適切に特定することができない。一方、シリコーン樹脂微粒子は、これらの粉末と平均粒子径や比表面積が近いものであっても「懸濁液の延展率」が60%をはるかに超えてしまうことが確認されている。 Specific examples of the powder (B) satisfying the spreading ratio of the suspension include (i) fumed hydrophobic silica, (ii) spherical porous silica, and (iii) spherical porous polymethyl methacrylate (PMMA). Can be mentioned. These powders have nothing in common in oil absorption capacity, specific surface area, etc., and cannot be properly specified at present unless they are based on the above-mentioned “suspension rate of suspension”. On the other hand, it has been confirmed that the “resin spreading ratio” of the silicone resin fine particles far exceeds 60% even when the average particle diameter and specific surface area are close to those of these powders.
 (i)煙霧状疎水化シリカとしては、平均粒子径が5~20nm、BET法による比表面積が50~200m/g、JIS K5101-13-2に準じて測定した吸油量が30~35ml/100gの微細なシリカで、その表面をジメチルジクロロシラン、ジメチルポリシロキサン等の処理剤にて疎水化処理したものが好ましい。具体的には、アエロジル R972(日本アエロジル株式会社)等が例示できる。 (I) The fumed hydrophobized silica has an average particle size of 5 to 20 nm, a specific surface area of 50 to 200 m 2 / g according to the BET method, and an oil absorption measured according to JIS K5101-13-2 of 30 to 35 ml / It is preferable to use 100 g of fine silica whose surface is hydrophobized with a treating agent such as dimethyldichlorosilane or dimethylpolysiloxane. Specifically, Aerosil R972 (Nippon Aerosil Co., Ltd.) etc. can be illustrated.
 (ii)球状多孔性シリカとしては、平均粒子径が3~10μm、比表面積が250~350m/g、吸油量が100~200ml/100gのものが好ましい。具体的には、サンスフェアL-51(AGCエスアイテック株式会社)等が例示できる。 (Ii) The spherical porous silica preferably has an average particle size of 3 to 10 μm, a specific surface area of 250 to 350 m 2 / g, and an oil absorption of 100 to 200 ml / 100 g. Specific examples include Sunsphere L-51 (AGC S-Tech Co., Ltd.).
 (iii)球状多孔性ポリメチルメタクリレート(PMMA)としては、平均粒子径が5~10μm、比表面積が80~100m/g、吸油量が100~200ml/100gとなるように形成された球状ポリ(メタ)アクリレート粒子が好ましい。具体的には、テクポリマーMBP-8(積水化成品工業株式会社)を好適に用いることができる。 (Iii) Spherical polymethylmethacrylate (PMMA) is a spherical polymer formed so as to have an average particle size of 5 to 10 μm, a specific surface area of 80 to 100 m 2 / g, and an oil absorption of 100 to 200 ml / 100 g. (Meth) acrylate particles are preferred. Specifically, Techpolymer MBP-8 (Sekisui Plastics Co., Ltd.) can be preferably used.
 本発明の日焼け止め化粧料における(B)粉末の配合量は、日焼け止め化粧料全体に対して0.5~15質量%、好ましくは2~10質量%、最も好ましくは約5質量%である。(B)粉末の配合量が0.5質量%未満の場合には皮膚や眼に対する刺激を十分に抑えるのが難しく、15質量%よりも多いと使用感が損なわれる傾向があるため好ましくない。 The blending amount of the (B) powder in the sunscreen cosmetic of the present invention is 0.5 to 15% by mass, preferably 2 to 10% by mass, and most preferably about 5% by mass with respect to the total sunscreen cosmetic. . (B) When the blending amount of the powder is less than 0.5% by mass, it is difficult to sufficiently suppress irritation to the skin and eyes, and when it is more than 15% by mass, the feeling of use tends to be impaired.
 本発明の日焼け止め化粧料は、前記特定の(A)紫外線吸収剤と(B)粉末という必須成分に加えて、日焼け止め化粧料に通常配合し得る他の任意成分を、本発明の効果を阻害しない範囲で含んでいてもよい。 In addition to the essential components (A) UV absorber and (B) powder described above, the sunscreen cosmetic of the present invention has other optional components that can be usually blended in the sunscreen cosmetic with the effects of the present invention. You may include in the range which does not inhibit.
<上記(A)以外の紫外線吸収剤>
 本発明の日焼け止め化粧料は、(A)以外の紫外線吸収剤を含んでもよい。メトキシケイヒ酸エチルヘキシル及びオクトクリレン以外の紫外線吸収剤を配合することにより、UVA及び/又はUVB領域の紫外線防御能をさらに向上させることができる。なお、この場合であっても、(A)と(A)以外の紫外線吸収剤との合計配合量が、(A)について上述した配合量の範囲内にあることが好ましい。
 このような紫外線吸収剤としては、特に限定されるものではないが、例えば、t-ブチルメトキシジベンゾイルメタン、エチルヘキシルトリアゾン、ビスエチルヘキシルオキシフェノールメトキシフェニルトリアジン、ジエチルアミノヒドロキシベンゾイル安息香酸ヘキシル、オキシベンゾン-3、メチレンビスベンゾトリアゾリルテトラメチルブチルフェノール、ポリシリコーン-15、フェニルベンズイミダゾールスルホン酸、ホモサレート、サリチル酸エチルへキシル等を挙げることができる。
<Ultraviolet absorber other than (A) above>
The sunscreen cosmetic of the present invention may contain an ultraviolet absorber other than (A). By blending an ultraviolet absorber other than ethylhexyl methoxycinnamate and octocrylene, the UV protection ability in the UVA and / or UVB region can be further improved. Even in this case, it is preferable that the total blending amount of the ultraviolet absorbers other than (A) and (A) is within the blending amount range described above for (A).
Such an ultraviolet absorber is not particularly limited. For example, t-butylmethoxydibenzoylmethane, ethylhexyltriazone, bisethylhexyloxyphenol methoxyphenyltriazine, diethylaminohydroxybenzoyl hexyl benzoate, oxybenzone-3 And methylenebisbenzotriazolyltetramethylbutylphenol, polysilicone-15, phenylbenzimidazolesulfonic acid, homosalate, ethylhexyl salicylate, and the like.
<紫外線散乱剤>
 本発明の日焼け止め化粧料は、反射・散乱により紫外線を物理的に遮蔽する粉体(紫外線散乱剤)を含有してもよい。
 本発明に配合することができる紫外線散乱剤は、化粧料の分野で紫外線散乱剤として用いられている粉体であれば特に限定されない。具体例としては、酸化チタン、酸化亜鉛、硫酸バリウム、酸化鉄、タルク、マイカ、セリサイト、カオリン、雲母チタン、紺青、酸化クロム、水酸化クロム、シリカ、酸化セリウム等から選択される1種又は2種以上が挙げられる。特に、1.5以上の屈折率を有する粉体、例えば酸化亜鉛、酸化チタンを用いるのが光学的特性から好ましい。
<Ultraviolet scattering agent>
The sunscreen cosmetic of the present invention may contain a powder (ultraviolet scattering agent) that physically shields ultraviolet rays by reflection / scattering.
The ultraviolet scattering agent that can be blended in the present invention is not particularly limited as long as it is a powder used as an ultraviolet scattering agent in the cosmetics field. Specific examples include one selected from titanium oxide, zinc oxide, barium sulfate, iron oxide, talc, mica, sericite, kaolin, titanium mica, bitumen, chromium oxide, chromium hydroxide, silica, cerium oxide, and the like. Two or more types can be mentioned. In particular, it is preferable from the viewpoint of optical properties to use a powder having a refractive index of 1.5 or more, such as zinc oxide or titanium oxide.
 また、紫外線散乱剤は、粒子表面が疎水化処理されていてもよい。表面疎水化処理することにより、油中への分散性や耐水性が向上する。表面処理の方法としては、メチルハイドロジェンポリシロキサン、メチルポリシロキサン等のシリコーン処理;アルキルシラン処理;パーフルオロアルキルリン酸エステル、パーフルオロアルコール等によるフッ素処理;N-アシルグルタミン酸等によるアミノ酸処理;その他、レシチン処理;金属石鹸処理;脂肪酸処理;アルキルリン酸エステル処理等が挙げられる。 Further, the particle surface of the UV scattering agent may be hydrophobized. Dispersibility in oil and water resistance are improved by subjecting the surface to hydrophobic treatment. Surface treatment methods include silicone treatment such as methylhydrogenpolysiloxane and methylpolysiloxane; alkylsilane treatment; fluorine treatment with perfluoroalkyl phosphate ester, perfluoroalcohol, etc .; amino acid treatment with N-acyl glutamic acid, etc. And lecithin treatment; metal soap treatment; fatty acid treatment; alkyl phosphate ester treatment and the like.
 本発明における(A)紫外線吸収剤であるメトキシケイヒ酸エチルヘキシル及びオクトクリレンは、紫外線散乱剤の配合量が少ない場合に皮膚上で広がりやすい傾向がある。その一方で、紫外線散乱剤を配合し過ぎると塗布時の白さが目立つようになったり、粉っぽい使用感を生じる場合がある。
 本発明は、(B)粉末を配合することで日焼け止め化粧料の皮膚上での広がりを低減できることから、紫外線散乱剤の配合量が少ない状況、又は、全く配合しない状況でも、(A)紫外線吸収剤の広がりを緩和することができる。具体的には、水中油型乳化形態をとる場合には、紫外線散乱剤の合計配合量が日焼け止め化粧料全体に対して3質量%以下である処方において、特に優れた眼刺激低減効果を達成できる。一方、油中水型乳化形態をとる場合には、紫外線散乱剤の合計配合量が10質量%以下である処方において、特に優れた眼刺激低減効果を達成できる。
In the present invention, (A) ethylhexyl methoxycinnamate and octocrylene, which are ultraviolet absorbers, tend to spread on the skin when the amount of the ultraviolet scattering agent is small. On the other hand, if an ultraviolet scattering agent is added too much, whiteness at the time of application may be noticeable or a powdery feeling may be produced.
In the present invention, the spread of sunscreen cosmetics on the skin can be reduced by blending the powder (B). Therefore, even in the situation where the blending amount of the UV scattering agent is small or not blended at all, The spread of the absorbent can be reduced. Specifically, when taking the oil-in-water emulsified form, a particularly excellent eye irritation reduction effect is achieved in a formulation in which the total amount of UV scattering agent is 3% by mass or less based on the total amount of sunscreen cosmetics. it can. On the other hand, when taking the water-in-oil type emulsified form, a particularly excellent ocular irritation reduction effect can be achieved in a formulation in which the total amount of ultraviolet scattering agent is 10% by mass or less.
<TRPV1活性阻害剤>
 本発明者らは、本発明の日焼け止め化粧料に、TRPV1活性阻害剤を配合することにより、眼に対する刺激をさらに抑制できることを見出した。TRPV1とは、TRP(transient receptor potential)イオンチャネルスーパーファミリーに属し、カプサイシン受容体として知られている。本発明者らは、メトキシケイヒ酸エチルヘキシル及びオクトクリレンが眼に入った際の刺激の原因がTRPV1の活性化によることを明らかにし、TRPV1の活性化を抑制することで眼刺激がさらに抑制されることを新たに見出した。
 TRPV1は活性化されると細胞内にカルシウムイオンを取り込むため、TRPV1活性阻害剤は、例えば、TRPV1を強制発現させたHEK293細胞を用いて、陽性対照物質(カプサイシン等)による反応に対する抑制効果をカルシウムイメージングで評価することによってスクリーニングできる。
 上記スクリーニングの結果、ユズ種子油、レスベラトロール、オレンジ油、PEG-9 ポリジメチルシロキシエチルジメチコン、ジステアリン酸エチレングリコール、ステリアン酸、ミリスチン酸亜鉛にTRPV1活性阻害効果が確認できた。これらの中でも、ユズ種子油、レスベラトロールが眼刺激抑制効果の観点で特に好ましい。最も好ましいのはユズ種子油である。
<TRPV1 activity inhibitor>
The present inventors have found that the irritation to the eye can be further suppressed by adding a TRPV1 activity inhibitor to the sunscreen cosmetic of the present invention. TRPV1 belongs to the TRP (transient receptor potential) ion channel superfamily and is known as a capsaicin receptor. The present inventors have revealed that the cause of irritation when ethylhexyl methoxycinnamate and octocrylene entered the eye is due to the activation of TRPV1, and that the eye irritation is further suppressed by suppressing the activation of TRPV1. Newly found.
When TRPV1 is activated, calcium ions are taken into the cells. Therefore, TRPV1 activity inhibitors use, for example, HEK293 cells in which TRPV1 is forcibly expressed, and have an inhibitory effect on the reaction caused by a positive control substance (capsaicin, etc.). Screening can be done by imaging.
As a result of the above screening, it was confirmed that Yuzu seed oil, resveratrol, orange oil, PEG-9 polydimethylsiloxyethyl dimethicone, ethylene glycol distearate, stearic acid, and zinc myristate had a TRPV1 activity inhibitory effect. Among these, yuzu seed oil and resveratrol are particularly preferable from the viewpoint of the effect of suppressing eye irritation. Most preferred is yuzu seed oil.
 本発明の日焼け止め化粧料にTRPV1活性阻害剤を配合する場合、日焼け止め化粧料全体に対して0.5~5質量%、より好ましくは0.5~3質量%、最も好ましくは約1質量%である。TRPV1活性阻害剤の配合量が0.5質量%未満の場合にはTRPV1活性阻害剤の効果をほとんど実感できず、5質量%よりも多く配合すると使用感が損なわれる傾向があるため好ましくない。 When a TRPV1 activity inhibitor is added to the sunscreen cosmetic of the present invention, it is 0.5 to 5% by mass, more preferably 0.5 to 3% by mass, and most preferably about 1% by mass with respect to the total sunscreen cosmetic. %. When the blending amount of the TRPV1 activity inhibitor is less than 0.5% by mass, the effect of the TRPV1 activity inhibitor can hardly be realized, and when the blending amount is more than 5% by mass, the feeling of use tends to be impaired.
 その他の任意成分としては、アルコール類、水溶性高分子、油溶性高分子、界面活性剤、上記(B)粉末及び紫外線散乱剤以外の粉末成分、各種油分等が挙げられるが、これらの例示に限定されるものではない。 Examples of other optional components include alcohols, water-soluble polymers, oil-soluble polymers, surfactants, powder components other than the above (B) powder and ultraviolet scattering agent, various oils, and the like. It is not limited.
 アルコール類としては、エタノール、イソプロパノールなどの低級アルコール、グリセリン、エチレングリコール、プロピレングリコール、1,3-ブチレングリコール、ジプロピレングリコール、ポリブチレングリコールなどの多価アルコール等が例示される。 Examples of alcohols include lower alcohols such as ethanol and isopropanol, and polyhydric alcohols such as glycerin, ethylene glycol, propylene glycol, 1,3-butylene glycol, dipropylene glycol, and polybutylene glycol.
 水溶性高分子としては、2-アクリルアミド-2-メチルプロパンスルホン酸(以下、「AMPS」と略記する)のホモポリマー、あるいはコポリマーが挙げられる。コポリマーは、ビニルピロリドン、アクリル酸アミド、アクリル酸ナトリウム、アクリル酸ヒドロキシエチル等のコモノマーからなるコポリマーである。すなわち、AMPSホモポリマー、ビニルピロリドン/AMPS共重合体、ジメチルアクリルアミド/AMPS共重合体、アクリル酸アミド/AMPS共重合体、アクリル酸ナトリウム/AMPS共重合体等が例示される。さらには、カルボキシビニルポリマー、ポリアクリル酸アンモニウム、ポリアクリル酸ナトリウム、アクリル酸ナトリウム/アクリル酸アルキル/メタクリル酸ナトリウム/メタクリル酸アルキル共重合体、カラギーナン、ペクチン、マンナン、カードラン、コンドロイチン硫酸、デンプン、グリコーゲン、アラビアガム、ヒアルロン酸ナトリウム、トラガントガム、キサンタンガム、ムコイチン硫酸、ヒドロキシエチルグアガム、カルボキシメチルグアガム、グアガム、デキストラン、ケラト硫酸、ローカストビーンガム、サクシノグルカン、キチン、キトサン、カルボキシメチルキチン、寒天等が例示される。 Examples of the water-soluble polymer include homopolymers or copolymers of 2-acrylamido-2-methylpropanesulfonic acid (hereinafter abbreviated as “AMPS”). The copolymer is a copolymer composed of a comonomer such as vinyl pyrrolidone, acrylic acid amide, sodium acrylate, hydroxyethyl acrylate and the like. That is, an AMPS homopolymer, a vinylpyrrolidone / AMPS copolymer, a dimethylacrylamide / AMPS copolymer, an acrylic amide / AMPS copolymer, a sodium acrylate / AMPS copolymer, and the like are exemplified. Furthermore, carboxyvinyl polymer, ammonium polyacrylate, sodium polyacrylate, sodium acrylate / alkyl acrylate / sodium methacrylate / alkyl methacrylate copolymer, carrageenan, pectin, mannan, curdlan, chondroitin sulfate, starch, Glycogen, gum arabic, sodium hyaluronate, tragacanth gum, xanthan gum, mucoitin sulfate, hydroxyethyl guar gum, carboxymethyl guar gum, guar gum, dextran, kerato sulfate, locust bean gum, succinoglucan, chitin, chitosan, carboxymethyl chitin, agar etc. Illustrated.
 油溶性高分子としては、トリメチルシロキシケイ酸、アルキル変性シリコーン、ポリアミド変性シリコーン、ジメチコンクロスポリマー、(ジメチコン/ビニルジメチコン)クロスポリマー、ポリメチルシルセスキオキサン等が例示される。 Examples of the oil-soluble polymer include trimethylsiloxysilicic acid, alkyl-modified silicone, polyamide-modified silicone, dimethicone crosspolymer, (dimethicone / vinyl dimethicone) crosspolymer, polymethylsilsesquioxane, and the like.
 界面活性剤は、アニオン性、カチオン性、ノニオン性、又は両性の界面活性剤が挙げられ、シリコーン系又は炭化水素系の界面活性剤が含まれる。 Examples of the surfactant include anionic, cationic, nonionic, and amphoteric surfactants, and include silicone-based or hydrocarbon-based surfactants.
 上記(B)粉末及び紫外線散乱剤以外の粉末成分としては、ナイロンやアクリル系のポリマー球状粉末、シリカ粉末、シリコーン粉末、金属を含まない表面処理剤で表面処理された金属酸化物粉末等が例示される。 Examples of powder components other than the above (B) powder and ultraviolet scattering agent include nylon and acrylic polymer spherical powder, silica powder, silicone powder, metal oxide powder surface-treated with a metal-free surface treatment agent, and the like. Is done.
<日焼け止め化粧料>
 本発明の日焼け止め化粧料は、最終製品を皮膚代替膜にスポッティングして3時間後のスポットの面積が、(B)粉末を含まない点においてのみ最終製品と異なる組成物を皮膚代替膜にスポッティングして3時間後のスポットの面積の70%以下である。
 すなわち、本発明の日焼け止め化粧料は、以下の式によって表される「最終製品の延展率」が70%以下となることを要件とする。
最終製品の延展率(%)=([最終製品のスポットの面積]/[最終製品から(B)粉末を除いた組成物のスポットの面積])×100
<Sunscreen cosmetics>
The sunscreen cosmetic of the present invention spotts a composition that differs from the final product only in that the spot area after 3 hours after spotting the final product on the skin substitute film does not contain powder. Thus, it is 70% or less of the area of the spot after 3 hours.
In other words, the sunscreen cosmetic of the present invention is required to have a “extended product spreading ratio” represented by the following formula of 70% or less.
Spread ratio of final product (%) = ([area of spot of final product] / [area of spot of composition excluding (B) powder from final product]) × 100
 以下、「最終製品の延展率」の評価方法について説明する。
 評価対象の最終製品を、上記「懸濁液の延展率」の評価と同様に皮膚代替膜にスポッティングする。皮膚代替膜をそのまま常温常圧(25℃、1気圧)下にて3時間静置した後、皮膚代替膜上に広がったスポットの面積([最終製品のスポットの面積])を測定する。最終製品は紫外線吸収剤を含有するため、ここでも面積の測定には紫外線照射器と紫外線カメラを用いることができる。
Hereinafter, an evaluation method of “the spread ratio of the final product” will be described.
The final product to be evaluated is spotted on the skin substitute membrane in the same manner as the evaluation of the “suspension spread ratio”. After leaving the skin substitute membrane as it is at room temperature and normal pressure (25 ° C., 1 atm) for 3 hours, the area of the spot ([spot area of the final product]) spreading on the skin substitute membrane is measured. Since the final product contains an ultraviolet absorber, an ultraviolet irradiator and an ultraviolet camera can also be used here for measuring the area.
 一方で、(B)粉末を含まない点においてのみ最終製品と異なる組成物を調製し、最終製品と同様に3時間後のスポットの面積([最終製品から(B)粉末を除いた組成物のスポットの面積])を測定する。
 これらの面積から、上記の式により「最終製品の延展率」を算出する。
 最終製品の延展率が70%以下、より好ましくは50%以下となるものを、本発明の日焼け止め化粧料と判定する。最終製品の延展率が70%以下であれば、化粧料が皮膚上で広がりにくく、眼に侵入しにくくなるため、眼に対して低刺激性で安全である。
On the other hand, a composition different from the final product was prepared only in that it did not contain (B) powder, and the spot area after 3 hours ([B) Spot area]).
From these areas, the “extension rate of the final product” is calculated by the above formula.
A product having a final product spreading rate of 70% or less, more preferably 50% or less, is determined as the sunscreen cosmetic of the present invention. If the spread rate of the final product is 70% or less, the cosmetic is less likely to spread on the skin and less likely to enter the eye.
 本発明の日焼け止め化粧料は、水中油型乳化化粧料、油中水型乳化化粧料、あるいは油性化粧料の形態で提供することが可能である。具体的な剤型としては、日焼け止め乳液、日焼け止めクリームといった剤型であり、各剤型に適した常法を用いて製造することができる。 The sunscreen cosmetic of the present invention can be provided in the form of an oil-in-water emulsified cosmetic, a water-in-oil emulsified cosmetic, or an oily cosmetic. As a specific dosage form, there are dosage forms such as sunscreen milky lotion and sunscreen cream, which can be produced using a conventional method suitable for each dosage form.
 (A)紫外線吸収剤及び(B)粉末は、同一相内に共存している場合に、特に高い眼刺激低減効果を示す傾向がある。ここで、「同一相内に共存」とは、(A)紫外線吸収剤及び(B)粉末の全てが完全に同一相内に存在していることを必要とするものではなく、実質的に共存している状態を指す。具体的には、(A)紫外線吸収剤及び(B)粉末それぞれの90%以上、より好ましくは95%以上、さらに好ましくは98%以上が同一相内に共存していればよい。メトキシケイヒ酸エチルヘキシル及びオクトクリレンは油溶性であるため、(A)紫外線吸収剤及び(B)粉末の両方を同一の油相内に共存させること、すなわち、日焼け止め化粧料が水中油型乳化化粧料の形態である場合には、(A)紫外線吸収剤及び(B)粉末をいずれも内相(油相)に存在させ、一方、油中水型乳化化粧料の形態である場合には、(A)紫外線吸収剤及び(B)粉末をいずれも外相(油相)に存在させることが好ましい。
 特に、水中油型乳化化粧料の場合、使用性の観点からは、微粒子酸化チタン、微粒子酸化亜鉛等の紫外線散乱剤を用いないものが好まれる傾向にあり、このような場合にメトキシケイヒ酸エチルヘキシル及びオクトクリレンは眼を刺激しやすくなる。紫外線散乱剤に頼らなくても皮膚上での広がりを抑制できる本発明の日焼け止め化粧料は、のびの良さとさっぱりとした使用感を併せて実現することができる水中油型乳化化粧料の形態において特に高い効果を発揮する。
 従って、本発明の日焼け止め化粧料は、水中油型乳化化粧料の形態であって、(A)紫外線吸収剤及び(B)粉末の両方をその内相(油相)に存在させる処方とした場合に、特に高い効果を発揮し、眼に対する刺激を大幅に低減することができる。
When the (A) ultraviolet absorber and the (B) powder coexist in the same phase, they tend to exhibit a particularly high eye irritation reducing effect. Here, “coexistence in the same phase” means that (A) the ultraviolet absorber and (B) powder are not required to be completely present in the same phase, but substantially coexist. Refers to the state of Specifically, 90% or more, more preferably 95% or more, and still more preferably 98% or more of each of the (A) ultraviolet absorber and (B) powder may coexist in the same phase. Since ethylhexyl methoxycinnamate and octocrylene are oil-soluble, both (A) the ultraviolet absorber and (B) the powder coexist in the same oil phase, that is, the sunscreen cosmetic is an oil-in-water emulsified cosmetic. (A) UV absorber and (B) powder are both present in the internal phase (oil phase), while in the form of a water-in-oil emulsified cosmetic, It is preferable that both A) the ultraviolet absorber and (B) powder are present in the outer phase (oil phase).
In particular, in the case of oil-in-water emulsified cosmetics, from the viewpoint of usability, those which do not use ultraviolet scattering agents such as fine particle titanium oxide and fine particle zinc oxide tend to be preferred. In such a case, ethylhexyl methoxycinnamate And octocrylene tends to irritate eyes. The sunscreen cosmetic of the present invention that can suppress the spread on the skin without relying on an ultraviolet scattering agent is a form of an oil-in-water emulsified cosmetic that can realize both good spreading and a refreshing feeling of use. Highly effective in.
Therefore, the sunscreen cosmetic of the present invention is in the form of an oil-in-water emulsified cosmetic and has a formulation in which both (A) the ultraviolet absorber and (B) powder are present in the internal phase (oil phase). In particular, it can exhibit a particularly high effect and can significantly reduce irritation to the eyes.
 また、本発明の日焼け止め化粧料の粘度は特に限定されるものではないが、粘度が10000mPa・s以上の場合にはそもそも延展による問題を生じにくい。従って、本発明は、粘度が10000mPa・s以下である系において特に有効である。 Further, the viscosity of the sunscreen cosmetic of the present invention is not particularly limited. However, when the viscosity is 10,000 mPa · s or more, the problem due to extension is hardly caused in the first place. Therefore, the present invention is particularly effective in a system having a viscosity of 10,000 mPa · s or less.
 以下に実施例を挙げて本発明をさらに詳述するが、本発明はこれらにより何ら限定されるものではない。配合量は特記しない限り、その成分が配合される系に対する質量%で示す。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. Unless otherwise specified, the blending amount is expressed in mass% with respect to the system in which the component is blended.
<懸濁液の延展率評価>
 オクトクリレン(商品名「ユビナールN539T」;BASFジャパン株式会社)10gに、表1記載の粉末を1g混合して懸濁液をそれぞれ得た。この懸濁液5μlを、皮膚代替膜(商品名「SPF MASTER(登録商標) PA-01」;資生堂医理化テクノロジー株式会社)上に、マイクロピペットを用いて静かにスポッティングした。皮膚代替膜を常温常圧(25℃、1気圧)下にて3時間静置した後に、紫外線照射器と紫外線カメラを用いて撮影し、画像データをコンピュータで2値化処理して、皮膚代替膜上に広がった懸濁液のスポットの面積を測定した。各懸濁液についてそれぞれ10箇所にスポッティングを行い、それらのスポットの面積の平均をその懸濁液の延展率の算出に用いた。
 一方で、オクトクリレンのみを同一の条件で皮膚代替膜上にスポッティングし、3時間経過後のスポットの面積を測定した。こちらも10回のスポッティングを行い、それらのスポットの面積の平均を延展率の算出に用いた。
 各懸濁液及びオクトクリレンのスポットの面積から、各懸濁液の延展率を算出した。結果を表1に示す。
<Evaluation of spreading ratio of suspension>
1 g of the powder described in Table 1 was mixed with 10 g of octocrylene (trade name “Ubinal N539T”; BASF Japan Ltd.) to obtain suspensions. 5 μl of this suspension was gently spotted using a micropipette on a skin substitute membrane (trade name “SPF MASTER (registered trademark) PA-01”; Shiseido Medical Rika Technology Co., Ltd.). After leaving the skin substitute membrane at room temperature and normal pressure (25 ° C, 1 atm) for 3 hours, it is photographed using an ultraviolet irradiator and an ultraviolet camera, and the image data is binarized by a computer to replace the skin. The area of the suspension spot spread on the membrane was measured. Each suspension was spotted at 10 locations, and the average of the spot areas was used to calculate the spreading ratio of the suspension.
On the other hand, only octocrylene was spotted on the skin substitute membrane under the same conditions, and the area of the spot after 3 hours was measured. Again, spotting was performed 10 times, and the average of the areas of those spots was used to calculate the spreading rate.
From the area of each suspension and the spot of octocrylene, the spreading ratio of each suspension was calculated. The results are shown in Table 1.
 また、オクトクリレンの代わりに、メトキシケイヒ酸エチルヘキシル(商品名「パルソールMCX」;DSMニュートリションジャパン株式会社)を用いて、同様に懸濁液の延展率を算出した。結果を表2に示す。 In addition, the spreading ratio of the suspension was calculated in the same manner using ethylhexyl methoxycinnamate (trade name “Pulsol MCX”; DSM Nutrition Japan Co., Ltd.) instead of octocrylene. The results are shown in Table 2.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
 表1及び表2に示した結果から明らかなように、煙霧状疎水化シリカ、球状多孔性シリカ、球状多孔性ポリメチルメタクリレートを配合した場合には、粉末を配合しない場合と比べて、オクトクリレン又はメトキシケイヒ酸エチルヘキシルの皮膚代替膜上での広がり(懸濁液の延展率)を60%以下に低減できることが確認された。なかでも、煙霧状疎水化シリカは、懸濁液の延展率を10%程度にまで低減でき、極めて高い効果を有することが確認された。これに対し、シリコーン樹脂微粒子を配合した場合には、オクトクリレン又はメトキシケイヒ酸エチルヘキシルのいずれについてもスポットの広がりをほとんど抑制することができなかった。 As is clear from the results shown in Tables 1 and 2, when blended with fumed hydrophobic silica, spherical porous silica, and spherical porous polymethyl methacrylate, octocrylene or It was confirmed that the spread of ethylhexyl methoxycinnamate on the skin substitute membrane (suspension rate of suspension) can be reduced to 60% or less. Especially, it was confirmed that the fumed hydrophobized silica can reduce the spreading ratio of the suspension to about 10% and has an extremely high effect. On the other hand, when the silicone resin fine particles were blended, the spread of the spot could hardly be suppressed for either octocrylene or ethylhexyl methoxycinnamate.
<最終製品の延展率評価>
(1)水中油型乳化日焼け止め化粧料
 表3に示す処方にて、常法により、水中油型乳化日焼け止め化粧料を製造した。
 具体的には、(24)に(1)~(9)、(23)を添加し均一に混合した後に、(21)の粉末を均一に分散させて水相を得た。一方で、(10)~(20)を均一に混合した後に、(22)を添加して均一に分散させて油相を得た。その後、水相に油相を徐添し、ホモミキサーで均一分散後、乳化粒子を整え、実施例1の日焼け止め化粧料を得た。
 比較例1では、(20)及び(22)を添加せずに日焼け止め化粧料を得た。
<Evaluation of final product spread rate>
(1) Oil-in-water emulsified sunscreen cosmetics In the formulation shown in Table 3, oil-in-water emulsified sunscreen cosmetics were produced by conventional methods.
Specifically, (1) to (9) and (23) were added to (24) and mixed uniformly, and then the powder of (21) was uniformly dispersed to obtain an aqueous phase. On the other hand, after (10) to (20) were uniformly mixed, (22) was added and uniformly dispersed to obtain an oil phase. Thereafter, the oil phase was gradually added to the aqueous phase, and after uniform dispersion with a homomixer, the emulsified particles were prepared to obtain the sunscreen cosmetic of Example 1.
In Comparative Example 1, a sunscreen cosmetic was obtained without adding (20) and (22).
 実施例1の日焼け止め化粧料5μlを、皮膚代替膜(商品名「SPF MASTER(登録商標) PA-01」;資生堂医理化テクノロジー株式会社)上に、マイクロピペットを用いて静かにスポッティングした。皮膚代替膜を常温常圧(25℃、1気圧)下にて3時間静置した後に、紫外線照射器と紫外線カメラを用いて撮影し、画像データをコンピュータで2値化処理して、皮膚代替膜上に広がったスポットの面積を測定した。スポッティングは3箇所に行い、それらの平均を最終製品の延展率の算出に用いた。
 一方で、比較例1についても、同一の条件で皮膚代替膜上にスポッティングを行い、3時間経過後のスポットの面積を測定した。
 実施例1について得られたスポットの面積と、比較例1について得られたスポットの面積から、最終製品の延展率を算出した。結果を表3に示す。
5 μl of the sunscreen cosmetic of Example 1 was gently spotted using a micropipette on a skin substitute membrane (trade name “SPF MASTER (registered trademark) PA-01”; Shiseido Medical Rika Technology Co., Ltd.). After leaving the skin substitute membrane at room temperature and normal pressure (25 ° C, 1 atm) for 3 hours, it is photographed using an ultraviolet irradiator and an ultraviolet camera, and the image data is binarized by a computer to replace the skin. The area of the spot spread on the film was measured. Spotting was performed at three locations, and the average of them was used to calculate the spreading ratio of the final product.
On the other hand, for Comparative Example 1, spotting was performed on the skin substitute membrane under the same conditions, and the area of the spot after 3 hours was measured.
From the spot area obtained for Example 1 and the spot area obtained for Comparative Example 1, the spread ratio of the final product was calculated. The results are shown in Table 3.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
 表3に示した結果から明らかなように、煙霧状疎水化シリカを配合した実施例1では、この粉末を配合しない比較例1と比べて、化粧料の皮膚代替膜上での広がり(最終製品の延展率)を41.9%にまで低減できることが確認された。 As is apparent from the results shown in Table 3, in Example 1 in which fumed hydrophobic silica was blended, the spread of the cosmetic material on the skin substitute film was compared with that in Comparative Example 1 in which this powder was not blended (final product). It was confirmed that the spread ratio of the film could be reduced to 41.9%.
<日焼け止め化粧料の眼刺激性評価>
 専門パネル12名により、顔の左右(眼の周りを含む)にそれぞれ実施例1又は比較例1の日焼け止め化粧料を塗布して、3時間後の眼に対する刺激の有無を評価してもらった。
 比較例1を塗布した方の眼に刺激を感じた専門パネルは12名のうち11名であったのに対し、実施例1を塗布した方の眼に刺激を感じた専門パネルは5名のみであった。
<Evaluation of eye irritation of sunscreen cosmetics>
Twelve specialist panels applied the sunscreen cosmetics of Example 1 or Comparative Example 1 to the left and right sides of the face (including around the eyes), respectively, and evaluated the presence or absence of irritation to the eyes after 3 hours. .
There were 11 out of 12 specialized panels that felt irritation in the eye applied with Comparative Example 1, whereas only 5 specialized panels felt irritation in the eye applied with Example 1. Met.
(2)油中水型乳化日焼け止め化粧料
 さらに、表4に示す処方にて、常法により、油中水型乳化日焼け止め化粧料を製造した。
 具体的には、油相を構成する成分を均一に混合した後に、メタクリル酸メチルクロスポリマーを添加して均一に分散させて油相を得た。一方で、水相を構成する成分を均一に混合溶解して水相を得た。油相を水相に徐添し、ホモミキサーで均一分散後、乳化粒子を整え、実施例2~4の日焼け止め化粧料を得た。
 比較例2及び3では、メタクリル酸メチルクロスポリマーを添加せずに日焼け止め化粧料を得た。
 実施例1と同様に最終製品の延展率を算出した。結果を表4に示す。
(2) Water-in-oil emulsified sunscreen cosmetics In addition, water-in-oil emulsified sunscreen cosmetics were prepared according to the formulation shown in Table 4 by a conventional method.
Specifically, after the components constituting the oil phase were uniformly mixed, methyl methacrylate crosspolymer was added and uniformly dispersed to obtain an oil phase. On the other hand, the components constituting the aqueous phase were uniformly mixed and dissolved to obtain an aqueous phase. The oil phase was gradually added to the aqueous phase, and after uniform dispersion with a homomixer, the emulsified particles were prepared to obtain sunscreen cosmetics of Examples 2-4.
In Comparative Examples 2 and 3, sunscreen cosmetics were obtained without adding methyl methacrylate crosspolymer.
The spread ratio of the final product was calculated in the same manner as in Example 1. The results are shown in Table 4.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
 表4に示した結果から明らかなように、メタクリル酸メチルクロスポリマーを配合した実施例2~4では、この粉末を配合しない比較例2及び3と比べて、化粧料の皮膚代替膜上での広がり(最終製品の延展率)を60%以下にまで低減できることが確認された。 As is apparent from the results shown in Table 4, in Examples 2 to 4 in which methyl methacrylate crosspolymer was blended, compared with Comparative Examples 2 and 3 in which this powder was not blended, the cosmetics on the skin substitute film It was confirmed that the spread (the spread ratio of the final product) can be reduced to 60% or less.

Claims (7)

  1.  (A)メトキシケイヒ酸エチルヘキシル及びオクトクリレンから選択される少なくとも1種以上の紫外線吸収剤と、
     (B)10倍量(質量比)の(A)紫外線吸収剤と混合して得た懸濁液を皮膚代替膜にスポッティングして3時間後に得られるスポットの面積が、(A)紫外線吸収剤のみをスポッティングして3時間後に得られるスポットの面積の60%以下である粉末と、
    を含む日焼け止め化粧料であって、
     最終製品を皮膚代替膜にスポッティングして3時間後に得られるスポットの面積が、(B)粉末を含まない点においてのみ最終製品と異なる組成物を皮膚代替膜にスポッティングして3時間後に得られるスポットの面積の70%以下である日焼け止め化粧料。
    (A) at least one ultraviolet absorber selected from ethylhexyl methoxycinnamate and octocrylene;
    (B) Spot area obtained 3 hours after spotting a suspension obtained by mixing 10 times amount (mass ratio) with (A) UV absorber on skin substitute membrane, (A) UV absorber Powder that is less than 60% of the area of the spot obtained 3 hours after spotting only,
    Sunscreen cosmetics including
    Spots obtained 3 hours after spotting the final product on the skin substitute membrane, the spot area obtained 3 hours after spotting a composition different from the final product on the skin substitute membrane only in that (B) it does not contain powder Sunscreen cosmetics that are 70% or less of the area of the skin.
  2.  (A)紫外線吸収剤及び(B)粉末が同一相内に共存している、請求項1に記載の日焼け止め化粧料。 The sunscreen cosmetic according to claim 1, wherein (A) the ultraviolet absorber and (B) the powder coexist in the same phase.
  3.  水中油型乳化化粧料の形態であり、(A)紫外線吸収剤及び(B)粉末がいずれも内相(油相)に存在する、請求項2に記載の日焼け止め化粧料。 The sunscreen cosmetic according to claim 2, which is in the form of an oil-in-water emulsified cosmetic, wherein (A) the ultraviolet absorber and (B) powder are both present in the internal phase (oil phase).
  4.  紫外線散乱剤をさらに含有し、その合計配合量が日焼け止め化粧料全体に対して3質量%以下である、請求項3に記載の日焼け止め化粧料。 The sunscreen cosmetic according to claim 3, further comprising an ultraviolet scattering agent, the total amount of which is 3% by mass or less based on the total amount of the sunscreen cosmetic.
  5.  油中水型乳化化粧料の形態であり、(A)紫外線吸収剤及び(B)粉末がいずれも外相(油相)に存在する、請求項2に記載の日焼け止め化粧料。 The sunscreen cosmetic according to claim 2, which is in the form of a water-in-oil emulsified cosmetic, wherein (A) the ultraviolet absorber and (B) powder are both present in the outer phase (oil phase).
  6.  紫外線散乱剤をさらに含有し、その合計配合量が日焼け止め化粧料全体に対して10質量%以下である、請求項5に記載の日焼け止め化粧料。 The sunscreen cosmetic according to claim 5, further comprising an ultraviolet scattering agent, the total amount of which is 10% by mass or less based on the total amount of the sunscreen cosmetic.
  7.  TRPV1活性阻害剤をさらに含有する、請求項1~6のいずれか一項に記載の日焼け止め化粧料。 The sunscreen cosmetic according to any one of claims 1 to 6, further comprising a TRPV1 activity inhibitor.
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