JP5122999B2 - Oil-in-water sunscreen cosmetics - Google Patents

Description

  The present invention relates to a water-in-oil type sunscreen cosmetic, and more specifically, a partially crosslinked polyether-modified organopolysiloxane polymer, organic titanate-treated fine particle zinc oxide and / or organic titanate-treated fine particle titanium oxide and silicone oil. Water-in-oil type sunscreen cosmetics, one or more oils selected from glyceryl trioctanoate, glyceryl trioctacaprate / capric acid, neopentyl glycol dioctanoate, inulin fatty acid ester and / or hydrolyzed inulin By adding a fatty acid ester, the present invention relates to a water-in-oil type sunscreen cosmetic that has good dispersion and emulsion stability, is excellent in feeling of use and makeup, and can exhibit a high UV protection effect.

Sunscreen cosmetics are required not only to have sunscreen effects but also to be resistant to sweat and sebum because of their usage environment. For this reason, many water-in-oil formulations are used. Since the outer phase is oil-based, the stickiness peculiar to oil may be felt strongly. From such a background, in recent water-in-oil type sunscreen cosmetics, silicone oil is often used as an oil agent in order to give a refreshing and non-sticky feeling and to improve the long-lasting makeup. .
However, silicone oils are not compatible with other cosmetic oils such as other hydrocarbons and ester oils, and if mixed in a large amount, the stability over time is impaired. Therefore, in cosmetics formulated with silicone oil, various studies have been made on the types of silicone oils to be blended and additives to be blended, and various cosmetics have been proposed. For example, cosmetics with a refreshing feel when blended with partially cross-linked polyether-modified organopolysiloxane polymer and silicone oil have been proposed, and silicic anhydride, hydrophobic silica, saccharides and sugar alcohols are added to this. Cosmetics that have been blended to improve stability have been proposed (see Patent Documents 1 and 2).

  In recent years, sunscreen cosmetics are often used in combination with UV absorbers and UV screening agents such as titanium oxide and zinc oxide in order to achieve a higher sunscreen effect. In order to obtain good adhesion to the surface, a powder obtained by atomizing titanium oxide, zinc oxide or the like may be used, and various studies have been made on techniques for this purpose. For example, the technology of blending powder treated with organic titanate, the powder with adjusted oil absorption by organic titanate treatment, etc. and surfactant such as partially cross-linked polyether modified silicone can be blended stably and burdened. Techniques for reducing the feeling are disclosed (see Patent Documents 3 and 4).

JP-A-6-40847 Japanese Patent Laid-Open No. 6-40848 Japanese Patent Laid-Open No. 11-322542 JP-A-2005-002078

However, cosmetics containing the partially crosslinked polyether-modified organopolysiloxane polymer described above tend to lack moist feeling, although they have no oily feeling and are excellent in usability such as a refreshing feeling and long-lasting makeup. In terms of compatibility with other general oils and stability over time, it was not sufficient.
Also, those containing a powder treated with an organic titanate, a powder whose oil absorption is adjusted by an organic titanate treatment, etc., and a surfactant such as a partially crosslinked polyether-modified silicone are used in combination. Although the adhesion to the skin is somewhat improved, thickening and aggregation may be seen over time, and it is not always satisfactory in terms of stability, feeling of use, and longevity, and has sufficient UV protection effect In some cases, it could not be demonstrated, and further improvement was desired.
The present invention responds to such demands, is excellent in dispersion and emulsification stability, spreads well, has no oiliness, and feels moist, has a long-lasting makeup, and has an ultraviolet protection effect. It is an object of the present invention to provide a water-in-oil type sunscreen cosmetic that fully develops.

  In this situation, the present inventors have conducted extensive studies to solve the above problems, and as a result, partially crosslinked polyether-modified organopolysiloxane polymer, organic titanate-treated fine particle zinc oxide and / or organic titanate-treated fine particle titanium oxide and silicone. A water-in-oil sunscreen cosmetic compounded with an oil, a specific oil agent, that is, one or more oils selected from glyceryl trioctanoate, glyceryl tri (capryl / caprate), neopentyl glycol dioctanoate, and inulin By blending with a fatty acid ester and / or a hydrolyzed inulin fatty acid ester, it has been found that the dispersion / emulsion stability is good, the feeling of use and cosmetics are excellent, and the UV protection effect is sufficiently expressed. It came to complete.

  That is, the present invention comprises components (A) to (E); (A) a partially crosslinked polyether-modified organopolysiloxane polymer, (B) finely divided zinc oxide treated with organic titanate and / or finely divided titanium titanate treated fine particulate titanium oxide. (C) Silicone oil (D) One or more oils selected from glyceryl trioctanoate, glyceryl tri (capryl / caprate), neopentyl glycol dioctanoate, (E) inulin fatty acid ester and / or hydrolyzed inulin The present invention provides a water-in-oil type sunscreen cosmetic characterized by containing a fatty acid ester.

  Moreover, in this invention, the compounding mass ratio of said component (C), (D), (E) is (C) :( D) :( E) = 5: 1: 1: 0.01-0. The water-in-oil type sunscreen cosmetic is characterized in that it is 05 and the total amount of (C) and (D) is 30 to 60% by mass.

  The water-in-oil type sunscreen cosmetic of the present invention has excellent dispersion and emulsification stability, spreads well, has no oiliness and feels moist, has a long-lasting makeup, and has an ultraviolet protection effect. It is a fully water-in-oil sunscreen cosmetic.

The configuration of the present invention will be described below.
The partially crosslinked polyether-modified organopolysiloxane polymer of component (A) used in the present invention contains (i) a Si-H group-containing siloxane compound and (b) at least two alkenyl groups in the molecule. It is a polymer obtained by addition reaction with a compound to be produced, and contains at least one polyoxyalkylene group in the molecule. Examples of this polymer include those described in JP-A-4-272932 and JP-A-5-140320.

That is, the partially crosslinked polyether-modified organopolysiloxane polymer can be produced using, for example, the following (A) and (B) as raw materials. Examples of the Si-H group-containing siloxane compound (a) include the following general formula (1):
R ¹ _a R ² _b H _c SiO _{(4-abc) / 2} (1)
[Wherein R ¹ is the same or different, unsubstituted or substituted alkyl group, aryl group, aralkyl group or halogenated hydrocarbon group having 1 to 18 carbon atoms, R ² is a general formula C _n H _2n O (C ₂ H ₄ O) _d (C ₃ H ₆ O) _e R ³ [wherein R ³ is a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, or — (CO) —R ⁴ (R ⁴ is carbon A group represented by a saturated aliphatic hydrocarbon group of 1 to 5, d is an integer of 2 to 200, e is an integer of 0 to 200, d + e is an integer of 3 to 200, and n is 2 to 6, respectively. A represents 1.0 ≦ a ≦ 2.5, b represents 0.001 ≦ b ≦ 1.0, and c represents 0.001 ≦ c ≦ 1.0. And / or the following general formula (2)
R ¹ _f H _g SiO _{(4-fg) / 2} (2)
(Wherein R ¹ is the same as above, f is 1.0 ≦ f ≦ 3.0, and g is 0.001 ≦ g ≦ 1.5, respectively). .

Examples of the compound containing at least two alkenyl groups in the molecule (b) include the following general formula (3):
C _m H _2m-1 O (C ₂ H ₄ O) _h (C ₃ H ₆ O) _i C _m H _2m-1 (3)
(Wherein h represents an integer of 2 to 200, i represents an integer of 0 to 200, h + i represents an integer of 3 to 200, and m represents 2 to 6, respectively) and / or the following general formula (4)
R ¹ _j R ⁵ _k SiO _{(4-jk) / 2} (4)
(Wherein R ¹ is the same as above, R ⁵ is a monovalent hydrocarbon group having 2 to 10 carbon atoms having an aliphatic unsaturated group at the end, j is 1.0 ≦ j ≦ 3.0, and k is 0) .001 ≦ k ≦ 1.5, respectively.) And / or α, ω-unsaturated alkenes.

The partially crosslinked polyether-modified organopolysiloxane polymer used in the present invention is a component represented by the general formula (1) and / or a component represented by the general formula (2) of (a), and (B) The component represented by the general formula (3) and / or the component represented by the general formula (4) and / or the α, ω-unsaturated alkene are combined and produced by addition polymerization. The component represented by the general formula (1) and / or the component represented by the general formula (3) are polymerized as essential components. Although it does not specifically limit in this other point, The polymer which has as essential components the component represented by General formula (2) and the component represented by General formula (3) is preferable on sensory characteristics, such as freshness and a refreshing feeling. . In addition, the partially crosslinked polyether-modified organopolysiloxane polymer used in the present invention can be used in the molecule to improve the affinity and compatibility with hydrocarbon oils other than silicone oils, ester oils, and triglyceride oils. It is preferable to use a polymer containing at least one alkyl group having 8 to 18 carbon atoms.

As a commercial item of the polymer of the component (A) used in the present invention, for example, a silicone KSG-21, a hydrocarbon oil or an ester as a mixture of a partially crosslinked polyether-modified organopolysiloxane polymer with a silicone oil Examples of oil blends include silicon KSG-31, silicon KSG-32, silicon KSG-33, and silicon KSG-34 (all manufactured by Shin-Etsu Chemical Co., Ltd.). The blending amount of the partially crosslinked polyether-modified organopolysiloxane polymer of the component (A) used in the present invention is not particularly limited, but 0.01 to 5% by mass (hereinafter, It is preferably “%”), more preferably 0.1 to 3%. The partially crosslinked polyether-modified organopolysiloxane polymer can be used alone or in combination of two or more as required.

Component (B) organic titanate-treated fine particle zinc oxide and / or organic titanate-treated fine particle titanium oxide (hereinafter sometimes referred to as “surface-treated fine particle zinc oxide” or “surface-treated fine particle titanium oxide”) used in the present invention, Fine zinc oxide or fine titanium oxide usually used in sunscreen cosmetics is treated with organic titanate. By performing this treatment, the inulin fatty acid ester and / or hydrolyzed inulin fatty acid ester as component (E), glyceryl trioctanoate, tri (caprylic / capric acid) glyceryl, and neopentyl glycol dioctanoate as component (D) Increases the affinity and improves dispersion stability. Examples of the organic titanate in the component (B) include long-chain carboxylic acid type, pyrophosphoric acid type, phosphorous acid type, amino acid type alkyl titanate, etc., and alkyl titanates having an alkyl group having 8 to 24 carbon atoms. Preferably, these can be exemplified by compounds represented by the following general formula (5).

(P is a positive integer, p = 8-24)

Specifically, the organic titanate is, as a long chain carboxylic acid type alkyl titanate, isopropyl triisostearoyl titanate, isopropyl trioctanoyl titanate, isopropyl dimethacrylisostearoyl titanate, isopropyl isostearoyl diacryl titanate, diisostearoyl ethylene. Titanates and the like, and as pyrophosphate type alkyl titanates, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis ( Ditridecyl phosphite) titanate, etc., and phosphite-type alkyl titanate, isopropyl tri (dioctyl pyrophosphate) titanate Bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate and the like, and amino acid type alkyl titanate include isopropyltri (N-amidoethyl / aminoethyl) titanate and the like. More than one species can be used.
Among these organic titanates, when the isopropyl triisostearoyl titanate represented by p = 17 in the above general formula (5) is selected, the dispersion stability, adhesion and usability of the powder in the oil are better. Become.

As a method of preparing the organic titanate-treated zinc oxide and / or organic titanate-treated fine particle titanium oxide in the component (B), generally known treatment methods are used, and are not particularly limited. Examples thereof include a mixing method, a wet method using a solvent such as water, ethanol, isopropyl alcohol, n-hexane, benzene, and toluene, a gas phase method, and a mechanochemical method. Moreover, the treatment ratio of the organic titanate and the powder in the component (B) is preferably 0.5: 99.5 to 10:90, more preferably 1.5: 98.5 to 8:92, as a mass ratio. . When fine particle zinc oxide and / or organic titanate-treated fine particle titanium oxide treated in this range is blended, a water-in-oil sunscreen cosmetic with no aggregation and better dispersion stability and adhesion can be obtained.

Component (B), organic titanate-treated zinc oxide and / or organic titanate-treated fine particle titanium oxide, is a silicone such as trialkoxyalkylsilane for the purpose of improving dispersibility with other components in cosmetics and improving touch. A compound, a fluorine compound, an oil agent, an oil or fat, a higher alcohol, a wax, a polymer, a resin, a metal soap, silica or the like may be used.

Although the compounding quantity of the component (B) in the water-in-oil type sunscreen cosmetics of this invention does not have limitation in particular, 0.5-25% is preferable and 1-20% is more preferable. When the component (B) is blended in this range, the dispersion stability and the ultraviolet protection effect are the best, and a water-in-oil sunscreen cosmetic with better usability and stability over time can be obtained.

The component (C) silicone oil used in the present invention is an oily component usually used in cosmetics. Examples thereof include chain silicones such as dimethylpolysiloxane and methylphenylpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclohexane. Examples include cyclic silicones such as pentasiloxane, modified silicones such as fluorine-modified polysiloxane, amino-modified polysiloxane, fatty acid-modified polysiloxane, and higher alcohol-modified polysiloxane, and these can be used alone or in combination. Among these, when a low molecular weight chain silicone having a molecular weight of 20000 or less or a volatile silicone oil such as octamethylcyclotetrasiloxane or decamethylcyclopentasiloxane is selected as the component (C), the coating is smooth. A water-in-oil type sunscreen cosmetic that is excellent in spreading and refreshing and has no stickiness or oiliness can be obtained.

The compounding amount of the component (C) in the water-in-oil sunscreen cosmetic of the present invention is not particularly limited, but is preferably 15 to 50%, and more preferably 20 to 35% in terms of expression and usability. preferable. When component (C) is used within this range, a water-in-oil sunscreen cosmetic that is more excellent in smooth spreading during application can be obtained.

The component (D) glyceryl trioctanoate, tri (capryl / capric acid) glyceryl, and neopentyl glycol dioctanoate used in the present invention are oils that are liquid at room temperature and are generally used in cosmetics. Not only increases the compatibility of the component (C) silicone oil, but also increases the dispersibility of the component (B) organic titanate-treated fine particle zinc oxide and / or organic titanate-treated fine particle titanium oxide. Furthermore, when used in combination with the inulin fatty acid ester and / or hydrolyzed inulin fatty acid ester of component (E), the dispersion / emulsion stability is very good as compared with other hydrocarbon oils and vegetable oils, which is useful. Ingredients (D blended with conventional water-in-oil type sunscreen cosmetics, which did not provide sufficient oil, provided a refreshing feel and smoothness with no oiliness, with a smooth spread Combined with effects, it has excellent makeup, and as a result, it can exhibit a high UV protection effect.

The blending amount of the component (D) in the water-in-oil type sunscreen cosmetic of the present invention is preferably 5 to 30%, more preferably 10 to 25% in terms of expression and usability. preferable. If it is this range, it is excellent in compatibility with the partially crosslinked polyether-modified organopolysiloxane polymer of component (A) and silicone oil of component (C), and the organic titanate-treated fine particle zinc oxide of component (B) and / or Alternatively, the dispersion stability of the organic titanate-treated fine particle titanium oxide is good, and the emulsification / dispersion stabilization effect of the preparation by combining with the inulin fatty acid ester and / or the hydrolyzed inulin fatty acid ester of the component (E) is sufficient. It is preferable because it expresses, has a good feeling of use and a long-lasting makeup, and exhibits a sufficient UV protection effect.

The inulin fatty acid ester and / or hydrolyzed inulin fatty acid ester of the component (E) used in the present invention has not only the effect of gelling an oil agent and imparting viscosity in a wide range, but also with the component (B) and the component (D). Affinity is high and dispersion stability can be improved. Since the dispersion stability is good, it is possible to obtain a water-in-oil type sunscreen cosmetic with a good feeling of use and a long-lasting makeup and a high UV protection effect. Component (E) Fatty acid ester of inulin fatty acid ester and / or hydrolyzed inulin is an ester of inulin which is a kind of polysaccharide and / or hydrolyzed inulin which is a hydrolyzate of the inulin and fatty acid or fatty acid derivative. Specifically, those described in JP-A-2002-284620 can be mentioned. Examples of commercially available products include Leo Pearl ISK (manufactured by Chiba Flour Mills).
The inulin fatty acid ester of component (E) and / or the fatty acid ester of hydrolyzed inulin preferably have a gelling ability of the oil with a fatty acid substitution degree per monosaccharide unit of 2.2 or more. The fatty acid substitution degree shown here indicates the average number of moles obtained by esterifying three hydroxyl groups in a monosaccharide unit with a fatty acid. In the acyl group of the ester, 60 mol% or more of the total acyl group is preferably an acyl group having a straight chain hydrocarbon skeleton having 16 to 22 carbon atoms, specifically, a hexadecanoyl group or an octadecanoyl group. , Eicosanoyl group and docosanoyl group. With regard to the carbon chain length of the acyl group, an acyl group having a carbon number smaller than that of the hexadecanoyl group does not provide sufficient solubility or gel structure with the oil component, and conversely, an acyl group having a larger number of carbon atoms than the docosanoyl group. Then, it may be accompanied by a heavy feel during use or may precipitate over time.
Moreover, less than 40 mol% of the total acyl groups may be substituted with other acyl groups. Examples of other acyl groups include acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, hexanoyl group, octanoyl group, decanoyl group, dodecanoyl group, tetradecanoyl group, tetracosanoyl group Hexacosanoyl group, octacosanoyl group, triacontanoyl group, oleoyl group, benzoyl group, naphthoyl group, isostearoyl group, isohexadecanoyl group, isodecanoyl group, isooctanoyl group and the like.

  The compounding amount of the inulin fatty acid ester of component (E) and / or the fatty acid ester of hydrolyzed inulin in the water-in-oil sunscreen cosmetic of the present invention is not particularly limited, but is preferably 0.05 to 1.5%. More preferably, it is 0.1 to 0.5%. If it is this range, the thing excellent in dispersion stability, an ultraviolet-ray protective effect, temporal stability, and a usability | use_condition will be obtained. These inulin fatty acid esters and / or hydrolyzed inulin fatty acid esters can be used singly or in combination as required.

  In the present invention, among the above components, the blending mass ratio of the components (C), (D), and (E) is (C) :( D) :( E) = 5 to 1: 1: 0.01. When 0.05 to 0.05 and the total blending amount of (C) and (D) is 30 to 60%, the dispersion and emulsification stability is particularly excellent, and it spreads smoothly and is not sticky. Good feeling of use and moist feeling, good makeup, and high UV protection effect.

  In the water-in-oil type sunscreen cosmetics of the present invention, in addition to the essential components (A) to (E), water (hot spring water, deep sea water, purified water) is used in order to obtain a water-in-oil type sunscreen cosmetic. Etc.) (generally 5 to 60%), and other ingredients that can be added to the usual water-in-oil sunscreen cosmetics can be added as appropriate within a qualitative and quantitative range that does not impair the effects of the present invention. . For example, emulsifier, oil component, polyhydric alcohol, lower alcohol, water-soluble polymer, viscosity modifier, moisturizer, antioxidant, pH adjuster, chelating agent, salt, preservative, bactericidal agent, fragrance, pigment Pigments, powders, ultraviolet absorbers, vitamins, amino acids, cosmetic ingredients, and the like.

  The emulsifier is not particularly limited as long as it forms a water-in-oil emulsification. If specifically exemplified, diglyceryl monostearate, diglyceryl monooleate, diglyceryl dioleate Diglyceryl monoisostearate, tetraglyceryl monostearate, tetraglyceryl monooleate, hexaglyceryl tristearate, decaglyceryl trioleate, decaglyceryl pentastearate, decaglyceryl pentaoleate, decaglyceryl pentaisostearate, mono Sorbitan palmitate, sorbitan monostearate, sorbitan sesquistearate, sorbitan tristearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan trioleate, monoisoste Sorbitan phosphate, sorbitan sesquiisostearate, polyoxyethylene (3) castor oil, polyoxyethylene (10) castor oil, polyoxyethylene (5) hydrogenated castor oil, polyoxyethylene (10) hydrogenated castor oil, monostearic acid Polyethylene glycol (1E.O.), polyethylene glycol monostearate (2E.O.), polyethylene glycol monostearate (4E.O.), polyethylene glycol monooleate (2E.O.), ethylene glycol monostearate , Diethylene glycol stearate, polyoxyethylene / methylpolysiloxane copolymer, methylpolysiloxane / cetylmethylpolysiloxane / poly (oxyethylene / oxypropylene) methylpolysiloxane copolymer, poly (oxy) Ethylene / oxypropylene) methylpolysiloxane copolymer, PEG-9 polydimethylsiloxyethyl dimethicone, polyoxyethylenemethylsiloxane / polyoxypropyleneoleylmethylsiloxane / dimethylsiloxane copolymer, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, etc. Is mentioned. Among these, from the viewpoint of the stability over time and the usability improvement effect of the present invention, a silicone-based surfactant is preferable. Specific examples of the polyoxyethylene / methylpolysiloxane copolymer include KF-6015 and KF. -6016, KF-6017 (manufactured by Shin-Etsu Chemical Co., Ltd.), methylpolysiloxane / cetylmethylpolysiloxane / poly (oxyethylene / oxypropylene) methylpolysiloxane copolymer, ABIL-EM90 (manufactured by Goldschmidt), ABIL-EM97 (manufactured by Goldschmidt) is used as the poly (oxyethylene / oxypropylene) methylpolysiloxane copolymer, and KF-6028 (manufactured by Shin-Etsu Chemical Co., Ltd.) is used as the PEG-9 polydimethylsiloxyethyl dimethicone. Oxyethylene methylsiloxane poly KF-6026 (manufactured by Shin-Etsu Chemical Co., Ltd.) as the propylene oleylmethylsiloxane / dimethylsiloxane copolymer, KF6104, KF6105 (manufactured by Shin-Etsu Chemical Co., Ltd.), and lauryl PEG-9 polydimethyl as the polyglycerin-modified organopolysiloxane. Commercially available products such as KF-6038 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be used as siloxyethyl dimethicone. Among these, PEG-9 polydimethylsiloxyethyl dimethicone, polyoxyethylene methylsiloxane / polyoxypropylene oleylmethylsiloxane / dimethylsiloxane copolymer), polyglycerin-modified organopoly, from the viewpoints of stability over time and improvement in usability. Siloxane and lauryl PEG-9 polydimethylsiloxyethyl dimethicone are more preferred. These components can be used by appropriately selecting one or two or more kinds as necessary, and the blending amount thereof is not limited by the type and combination of the oil agent, but is generally 0.05 to 5% is preferred.

As the oil component, as long as it is other than the above components (C) and (D), the origin of animal oil, vegetable oil, synthetic oil, etc. and the properties of solid oil, semi-solid oil, liquid oil, volatile oil, etc. Oils such as hydrocarbons, fats and oils, waxes, hardened oils, ester oils other than component (D), triglycerides, fatty acids, higher alcohols, fluorine-based oils, lanolin derivatives, etc. The composition may be appropriately blended depending on the purpose such as imparting emollient feeling or adjusting feeling.
Specifically, hydrocarbons such as liquid paraffin, squalane, petrolatum, polybutene, oils and fats such as olive oil, castor oil, mink oil, macadamian nut oil, jojoba oil, diisostearyl malate, cetyl isooctanoate, Esters such as isopropyl myristate, isopropyl palmitate, octyldodecyl myristate, polyglyceryl diisostearate, diglyceryl triisostearate, glyceryl tribehenate, cholesterol fatty acid esters, N-lauroyl-L-glutamate di (cholesteryl, behenyl, octyldodecyl) Fatty acids such as stearic acid, lauric acid, myristic acid, behenic acid, isostearic acid, oleic acid, stearyl alcohol, cetyl alcohol, lauryl alcohol, oleyl alcohol , Fluorinated oils such as perfluorodecane, perfluorooctane and perfluoropolyether, lanolin, lanolin acetate, lanolin fatty acid isopropyl, lanolin derivatives such as lanolin alcohol, dextrin fatty acid Examples thereof include oily gelling agents such as esters, sucrose fatty acid esters, starch fatty acid esters, 12-hydroxystearic acid, aluminum isostearate and calcium stearate.

The powder is not particularly limited as long as it is usually used for cosmetics and is other than the component (B). Specifically, mica, synthetic mica, sericite, mica titanium, Bengala-coated mica titanium, Boron nitride, bismuth oxychloride, plate-like alumina, talc, kaolin, magnesium carbonate, calcium carbonate, aluminum silicate, magnesium silicate, aluminum magnesium silicate, calcium silicate, anhydrous silicic acid and other inorganic pigments, titanium oxide, Inorganic white pigments such as cerium oxide, bengara, yellow iron oxide, black iron oxide, gunjou, conger, carbon black and other inorganic color pigments, tar colorants, organic color pigments such as natural pigments, nylon powder, silicone resin powder, silk Powder, polystyrene, polyethylene powder, crystalline cellulose, -Fluorine compounds, silicone compounds, metal soaps, waxes, fats and oils, etc. other than those used as treatment agents in the present invention are used, as long as organic powders such as acyl lysine are not particularly impaired. A combination of a surface-treated product and an untreated product may be used.

In addition, as an aqueous component, lower alcohols such as ethyl alcohol and isopropyl alcohol, glycols such as propylene glycol, 1,3-butylene glycol, dipropylene glycol and polyethylene glycol, glycerols such as glycerin, diglycerin and polyglycerin, Sugars such as sorbitol, maltitol, sucrose, starch sugar, lactitol, guar gum, sodium chondroitin sulfate, sodium hyaluronate, gum arabic, sodium alginate, xanthan gum, carrageenan, methylcellulose, hydroxyethylcellulose, carboxymethylcellulose, carboxyvinyl polymer, polyvinyl alcohol , Polyvinylpyrrolidone, alkylated carboxyvinyl polymer, sodium polyacrylate Water-soluble polymers, acids such as citric acid, lactic acid, malic acid, tartaric acid or salts thereof, salts such as sodium chloride, magnesium chloride, aloe vera, witch hazel, hamamelis, cucumber, lemon, lavender, rose Cosmetic ingredients such as liquid, water-soluble vitamin C and derivatives thereof, proteins such as collagen, and salts thereof can be blended.

Furthermore, the sunscreen cosmetic of the present invention can be blended with an ultraviolet absorber in addition to the ultraviolet protective agent such as the component (B) for the purpose of further improving the sunscreen effect. As the ultraviolet absorber, any of those usually used in sunscreen cosmetics can be blended. Specifically, for example, 2-hydroxy-4-methoxybenzophenone, 2, 4, 6-trianilino-p- (carbo-2′-ethylhexyl-1′-oxy) -1,3,5-triazine, 2-ethylhexyl salicylate, ethyl paradihydroxypropylbenzoate, 2-ethylhexyl paramethoxycinnamate, 4 -Tert-4'-methoxydibenzoylmethane, 2- [4- (diethylamino) -2-hydroxybenzoyl] benzoic acid hexyl ester, dimethoxybenzylidenedioxoimidazolidinepropionate 2-ethylhexyl, 2,2'-methylenebis [6 -(2H-benzotriazol-2-yl) -4- (1,1, , 3-tetramethylbutyl) phenol], (1,3,5) -triazine-2,4-bis [{4- (2-ethylhexyloxy) -2-hydroxy} -phenyl] -6- (4- Methoxyphenyl) -1,3,5-triazine, dimethicodiethylbenzalmalonate, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its sodium salt, and the like, and one or more of these are used. be able to.

The present invention will be described in more detail below with reference to examples, but these do not limit the present invention.

Production Example 1: 500 g of organic titanate 5% treated fine particles of zinc oxide isopropyl alcohol and 50 g of isopropyl triisostearoyl titanate were mixed, and 950 g of zinc oxide [MZ-500 (manufactured by Teika)] in a Henschel mixer (Mitsui Mining Co., Ltd.) Mix. Thereafter, isopropyl alcohol was collected at 60 ° C. under reduced pressure and pulverized to obtain 5% organic titanate-treated fine particle zinc oxide.

Production Example 2: 3% organic titanate and 3% methylhydrogenpolysiloxane treated fine particle titanium oxide In the same manner as in Production Example 1, titanium oxide [MT-500B (manufactured by Teika)] was used instead of fine particle zinc oxide. 3% of organic titanate and 3% of methyl hydrogen polysiloxane were obtained.

Examples 1 to 6 and Comparative Examples 1 to 7 Water-in-oil type sunscreen cosmetics Water-in-oil type sunscreen cosmetics having the formulations shown in Table 1 were prepared by the following production method, and dispersion stability, emulsion stability, The feeling of use (spreading spread, non-stickiness, moist feeling) UV protection effect was evaluated by the following method.

Examples 1-6 and Comparative Examples 1-7 Water-in-oil sunscreen cosmetics

<Manufacturing method>
A. Components (1) to (19) are uniformly mixed and dispersed at room temperature.
B. Components (20) to (23) are mixed uniformly at room temperature.
C. B is added to A and emulsified to obtain a water-in-oil sunscreen cosmetic.

<Evaluation method>
(Dispersion stability)
After each sample was prepared and stored in a constant temperature bath at 40 ° C. for one month, a thin film (thickness 6 μm) of each sample was prepared on a quartz plate, a transmission spectrum was measured, and a transmittance at a wavelength of 400 nm was measured. .
Here, the transmittance of visible light 400 nm was compared immediately after and one month later, and determined using the following four-step criteria (c).
(C) Four-step criteria (evaluation) (Judgment)
The difference in transmittance was less than 5%: ◎
The difference in transmittance was less than 5 to 10%: ○
The difference in transmittance was less than 10-20%: Δ
The difference in transmittance was 20% or more: ×

[Emulsification stability]
Each sample was stored in a constant temperature bath at 40 ° C. for 3 months, and the change in appearance was determined using the following (d) four-stage criteria based on the state immediately after preparation.
(D) Four-step criteria (evaluation) (Judgment)
Good without change: ◎
There is a slight change in appearance such as oil oozing, but there is no problem as a cosmetic. : ○
There are changes in appearance and usability. : △
There is a clear change and it is difficult to maintain the shape. : ×

[Usage feeling (spreading, no stickiness, moist feeling)]
Each sample was applied to the face by 20 professional evaluation panels, and the feeling of use (growth, non-stickiness, moist feeling) was evaluated according to the following five-step evaluation criteria (e). The average value of the score was determined using the four-step criterion (f).
(E) Five-level evaluation criteria (score): (Evaluation)
4: Very good 3: Good 2: Normal 1: Slightly bad 0: Bad (f) Four-step criteria (average score): (Judgment)
3.5 or more: ◎
2.5 or more and less than 3.5: ○
1.5 or more and less than 2.5: △
Less than 1.5: ×

[UV protection effect]
40 mg of each sample was uniformly coated on a 5 cm × 8 cm square surgical tape (model number: 1526, manufactured by Sumitomo 3M), measured with SPF Analyzer System UV-1000S (manufactured by Labsphere), and measured for 15 points per sample (N = The transmittance at 300 nm, which is the UVB region, was calculated from the average value of 3), and judged using the following four-step criteria.
(G) 4-step criteria (evaluation): (judgment)
The UVB transmittance is less than 10%, and the blocking effect is very good: ◎
The UVB transmittance is 10 or more and less than 30%, and the blocking effect is good: ○
The UVB transmittance is 30 or more and less than 40%, and the blocking effect is slightly inferior: Δ
The UVB transmittance is 40% or more, and the blocking effect is inferior: ×

As is clear from the results in Table 1, the water-in-oil type sunscreen cosmetics of Examples 1 to 6 all have dispersion stability, emulsion stability, and feeling of use (providing spread, no stickiness, and moist feeling). It was a water-in-oil type sunscreen cosmetic that was excellent in all items of makeup retention and UV protection effects.
On the other hand, especially in the comparative example which confirmed the effect of mix | blending component (D) and (E), the oil agent of component (D) was replaced with isononyl isononanoate, liquid paraffin, neopentyl glycol dicaprate, macadamia nut oil. In Comparative Examples 1 to 4, the dispersion / emulsification stabilizing action was not sufficient, the feeling in use was poor, and the UV protection effect was inferior. Moreover, although the component (D) component is mix | blended, the comparative example 5 which has not mix | blended the component (E), or the comparative example 6 which replaced the component (E) with the dextrin palmitate which is another gelatinizer also. Both of them were inferior in dispersion / emulsification stabilizing action, poor in feeling of use, and inferior in ultraviolet protection effect. Furthermore, in Comparative Example 7 in which neither the oil agent of component (D) nor the inulin fatty acid ester of component (E) is blended, the surface-treated fine particle zinc oxide of component (B) thickens due to aggregation, resulting in poor dispersion stability. The emulsion stability was also impaired, and the feeling of use such as spreading and non-stickiness and the UV protection effect were inferior.
That is, the water-in-oil type sunscreen cosmetics of Examples 1 to 6 of the present invention have dispersion stability, especially by blending the components (D) and (E), as compared with Comparative Examples 1 to 7. Emulsification stability is very excellent. It has a good feeling of use such as spreading, non-stickiness, moisturizing, etc. during use and water-in-oil type sunscreen with high UV protection effect. It turned out to be cosmetics.

Claims (4)

The following components (A) to (E);
(A) Partially crosslinked polyether-modified organopolysiloxane (B) Organic titanate-treated fine particle zinc oxide and / or organic titanate-treated fine particle titanium oxide 0.5 to 25%
(C) Silicone oil (D) Oil agent : Tri (capryl / capric acid) glyceryl (E) inulin fatty acid ester and / or hydrolyzed inulin fatty acid ester 0.05 to 1.5%
A water-in-oil type sunscreen cosmetic characterized by comprising   The blending mass ratio of the components (C), (D) and (E) is (C) :( D) :( E) = 5: 1: 1: 0.01-0.05, and (C) The water-in-oil type sunscreen cosmetics according to claim 1, wherein the total amount of (D) and (D) is 30 to 60% by mass. The inulin fatty acid ester and / or hydrolyzed inulin fatty acid ester of the component (E) has a fatty acid esterification degree per monosaccharide unit of 2.2 or more, and in the acyl group of the ester, 60 mol of the total acyl group The water-in-oil type sunscreen cosmetic according to claim 1 or 2, wherein at least 1% is at least one selected from hexadecanoyl group, octadecanoyl group, eicosanoyl group and docosanoyl group. The component (B) is isopropyl titanate treated zinc oxide particles and / or isopropyl titanate process according to claim 1 or a water-in-oil according to any one of 3, characterized in that a particulate titanium oxide Sunscreen cosmetics.