JP6815093B2 - Underwater oil type sunscreen cosmetics - Google Patents

Description

The present invention relates to an oil-in-water sunscreen cosmetic.

Sunscreen cosmetics contain an ultraviolet absorber and an ultraviolet scattering agent in order to block ultraviolet irradiation of the skin and obtain a high SPF value. The form of sunscreen cosmetics having a high SPF value is often a water-in-oil composition in order to obtain excellent water resistance.
However, the water-in-oil composition is sticky or sticky at the time of application, and when a high amount of an ultraviolet absorber is added, it causes oiliness and stickiness, and further stains due to secondary adhesion to clothes. was there. In addition, if a high amount of UV absorber is added, it may cause rough skin for users with sensitive skin.

Therefore, oil-in-water sunscreen cosmetics that suppress stickiness and sliminess have been reported (Patent Documents 1 to 4).

Japanese Unexamined Patent Publication No. 2014-185137 Japanese Unexamined Patent Publication No. 2014-105207 Japanese Unexamined Patent Publication No. 2008-162930 International Publication No. 2013/018827

However, in these oil-in-water sunscreen cosmetics, the stability of blending the ultraviolet scattering agent into the oil-in-water type system is not sufficient, causing a squeaky feeling, etc., and the spread on the skin is not sufficient, after application. It was found that there are problems such as white residue being easily generated and not being easy to remove.
Therefore, the subject of the present invention is that the stability of blending the ultraviolet scattering agent into an oil-in-water type system is good, there is no squeaky feeling at the time of application, the spread to the skin is good, and no white residue occurs after application. The purpose is to provide underwater oil-type sunscreen cosmetics that are easy to remove.

Therefore, as a result of various studies to solve the above problems, the present inventor has blended a large amount of titanium oxide particles in which a component having a carboxyl group has been surface-treated, and has a nonionic property having a specific water-soluble polymer and a specific HLB. If an oil agent that is liquid at 25 ° C. is blended in addition to the surfactant to form an oil-in-water composition, the compounding stability of the titanium oxide particles that are ultraviolet scattering agents is good, and a squeaky feeling at the time of application is obtained. The present invention has been completed by finding that an oil-in-water sunscreen cosmetic that spreads well on the skin, does not leave white residue after application, and is easy to remove can be obtained.

That is, in the present invention, the components (A), (B), (C) and (D):
(A) Titanium oxide particles surface-treated with a surface treatment agent having a carboxyl group, more than 3% by mass and 20% by mass or less,
(B) A water-soluble polymer having a structural unit derived from (meth) acrylic acid or sulfonic acid,
The present invention provides an oil-in-water sunscreen cosmetic containing (C) a nonionic surfactant having an HLB of 6 or more and 10 or less, and (D) an oil agent that is liquid at 25 ° C.

The oil-in-water sunscreen cosmetic of the present invention has a high SPF value, excellent stability, no squeaky feeling, no stickiness or sliminess, a fresh coating feeling, and little white residue after application. It also has the effect of being easy to drop.

The oil-in-water sunscreen cosmetic of the present invention (hereinafter, may be simply referred to as cosmetic) contains the following components (A), (B), (C) and (D).
(A) Titanium oxide particles surface-treated with a surface treatment agent having a carboxyl group, more than 3% by mass and 20% by mass or less,
(B) A water-soluble polymer having a structural unit derived from (meth) acrylic acid or sulfonic acid,
(C) A nonionic surfactant having an HLB of 6 or more and 10 or less, and (D) an oil agent which is liquid at 25 ° C.

The component (A) is titanium oxide particles surface-treated with a surface treatment agent having a carboxyl group. Here, as specific examples of the surface treatment agent having a carboxyl group, from the viewpoint of increasing the dispersibility of the titanium oxide particles in the cosmetics to improve the ultraviolet protection effect of the cosmetics, from the viewpoint of suppressing the whiteness of the appearance, and From the viewpoint of improving the smoothness, a fatty acid is preferable, a higher fatty acid having 14 to 22 carbon atoms is more preferable, and a higher fatty acid having 16 to 20 carbon atoms is more preferable. From the same viewpoint, the fatty acid of the surface treatment agent preferably has 14 or more carbon atoms, more preferably 16 or more carbon atoms, and preferably 22 or less, more preferably 20 or less carbon atoms. Specific examples of the titanium oxide particles surface-treated with a surface treatment agent having a carboxyl group include fatty acid-treated titanium oxide particles having 14 to 22 carbon atoms and alumina carbon-treated titanium oxide particles having 14 to 22 carbon atoms. More preferable examples include alumina stearic acid-treated titanium oxide particles and alumina isostearic acid-treated titanium oxide particles. Among them, alumina stearic acid treatment oxidation from the viewpoint of enhancing the dispersibility of titanium oxide particles in cosmetics, improving the UV protection effect of cosmetics, suppressing the whiteness of appearance, and improving the smoothness. Titanium particles are preferred.

The average particle size of the titanium oxide particles surface-treated with the surface treatment agent having a carboxyl group of the component (A) is preferably 1 nm or more, more preferably 5 nm or more, from the viewpoint of improving the ultraviolet protection effect of the cosmetic. Further, 100 nm or less is preferable, and 80 nm or less is more preferable. Further, from the viewpoint of suppressing stickiness at the time of application of cosmetics and improving smoothness, 1 nm or more is preferable, 7 nm or more is more preferable, 8 nm or more is further preferable, 100 nm or less is preferable, and 50 nm or less is more preferable. , 30 nm or less is more preferable. Here, the average particle diameter of the component (A) is the maximum minor diameter of the particle diameters of 300 particles in the image under the condition of 100,000 magnification with a transmission electron microscope (TEM). It is obtained by measuring and calculating the average value. Here, the maximum minor diameter means the minor diameter having the maximum diameter among the minor diameters orthogonal to the major axis.

In the cosmetic of the present invention, the component (A) is contained in the cosmetic in an amount of more than 3% by mass and 20% by mass or less from the viewpoint of obtaining an excellent ultraviolet protection effect, no white residue after application, and a feeling of use. The content of the component (A) in the cosmetic of the present invention is preferably 5% by mass or more, preferably 6% by mass or more, from the viewpoint of obtaining an excellent ultraviolet protection effect and improving the stability of the cosmetic. More preferably, 7% by mass or more is further preferable, and 14% by mass or less is preferable, 11% by mass or less is more preferable, and 9% by mass is preferable from the viewpoint of no white residue after application, no squeaky feeling, and ease of removal. % Or less is more preferable. Specifically, the content of the component (A) in the cosmetic is preferably 5 to 14% by mass, more preferably 6 to 11% by mass, and even more preferably 7 to 11% by mass. In the present invention, "easy to remove" means the ease with which the cosmetic of the present invention can be applied to the skin and then washed off the skin with a cleaning agent or the like.

The component (B) used in the present invention is a water-soluble polymer having a structural unit derived from (meth) acrylic acid or sulfonic acid. Here, (meth) acrylic acid is a concept including methacrylic acid and acrylic acid.
As a water-soluble polymer having a constituent unit derived from (meth) acrylic acid, a homopolymer having a monomer selected from methacrylic acid, acrylic acid, methacrylate, acrylate, methacrylamide, and acrylamide as a constituent unit, or two or more kinds of these monomers. Examples include copolymers containing. More specifically, carboxyvinyl polymers (for example, Syntaren K, L; manufactured by Wako Pure Chemical Industries, Ltd.) and acrylic acid / alkyl methacrylate copolymers (for example, PEMULEN TR-1, TR-2; manufactured by Lubrizol). ), Polyacrylamide (SEPIGEL 305), (Na acrylate / Na acryloyldimethyltaurine) copolymer (SIMULG EL EG), (Hydroxyethyl acrylate / Na acryloyldimethyltaurine) copolymer (SIMULGEL FL, SIMULGEL) sold by SEPPIC. NS, SEPIPLUS S, SEPINOV EMT 10), (acrylamide / ammonium acrylate) copolymer (SEPIPLUS 265), polyacrylate-13 (SEPIPLUS 400) and the like can be mentioned. One or more of the (meth) acrylic acid-based polymers selected from these can be used.
In addition, examples of the water-soluble polymer having a structural unit derived from sulfonic acid include stearoxy PG hydroxyethyl cellulose sulfonic acid Na (Poise 310; manufactured by Kao Corporation).
Of these, when one or more selected from the acrylic acid / methacrylic acid copolymer and the (Na acrylate / acryloyldimethyltaurine Na) copolymer is used, the composition is stable even in a small amount, and at the time of application. It is preferable from the viewpoint of preventing kinks and improving usability.

In the cosmetic of the present invention, the component (B) in the cosmetic is preferably 0.02% by mass or more, more preferably 0.15, from the viewpoint of improving the stability of the cosmetic and the usability of the container. It is contained in an amount of 1.0% by mass or less, more preferably 0.8% by mass or less, from the viewpoint of improving lightness of elongation and freshness. Specifically, the content of the component (B) in the cosmetic is preferably 0.02 to 1.0% by mass, more preferably 0.15 to 0.8% by mass. Here, the content of the component (B) is the content of the active ingredient contained in the product, not the amount of the commercially available product.
In addition, a water-soluble polymer other than the component (B) can be contained in the cosmetic as long as the effect of the present invention is not impaired. From the viewpoint of improving the stability, lightness of elongation and freshness of the cosmetic, the water-soluble polymer other than the component (B) is preferably 1% by mass or less, preferably 0.5% by mass or less in the cosmetic. It is more preferably 0.1% by mass or less, further preferably substantially 0% by mass.

The component (C) used in the present invention is a nonionic surfactant having an HLB of 6 or more and 10 or less. In the present invention, from the viewpoint of improving the stability of the cosmetic, a nonionic surfactant having an HLB of 6.4 or more and 9.8 or less is preferable, an HLB of 6.8 to 9.7 is more preferable, and an HLB of 7.4 to 9 is preferable. The one of 6.6 is more preferable, and the one of 8.5 to 9.4 is even more preferable.
Here, HLB (hydrophilic-lipophilic balance) indicates the molecular weight of the hydrophilic group portion in the total molecular weight of the nonionic surfactant, and is obtained by the formula of Griffin. The HLB when two or more kinds of nonionic surfactants are used is an arithmetic mean of the HLB values of each nonionic surfactant based on the blending ratio. Therefore, even if the HLB value of each nonionic surfactant is less than 6 or more than 10, if the mixed HLB is in the above range, the nonionic surfactant in the present invention has an HLB of 6 or more and 10 or less. ..

Mixed HLB = Σ (HLBx × Wx) / ΣWx
HLBx indicates the HLB value of the nonionic surfactant X.
Wx indicates the weight (g) of the nonionic surfactant X having a value of HLBx.

Preferred nonionic surfactants include polyglycerin fatty acid ester, propylene glycol fatty acid ester, pentaerythritol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbit fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyethylene glycol fatty acid ester, and the like. Polyoxyethylene alkyl ether, polyoxyethylene phytosterol, polyoxyethylene phytostanol, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene lanolin , Polyoxyethylene lanolin alcohol, polyoxyethylene honey wax derivative, polyoxyethylene alkylamine, polyoxyethylene fatty acid amide, polyoxyethylene alkylphenyl formaldehyde condensate, single chain length polyoxyethylene alkyl ether, polyether-modified silicone, etc. Can be mentioned. Among these, one or more selected from polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester, polyoxyethylene alkyl ether, and polyoxyethylene cured castor oil are preferable, and sorbitan fatty acid ester and polyoxyethylene sorbitan fatty acid. More preferably, one or more selected from the esters. The polyoxyethylene number, fatty acid, and alkyl group chain length of these nonionic surfactants are preferably selected so that the HLB is 6 to 10.

In the cosmetic of the present invention, the component (C) in the cosmetic is preferably 0.01% by mass or more, more preferably 0.5% by mass or more, still more preferably, from the viewpoint of improving the stability of the cosmetic. Is contained in an amount of 1.0% by mass or more, and is preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 2% by mass or less from the viewpoint of improving lightness at the time of coating and stickiness after coating. contains. Specifically, the content of the component (C) in the cosmetic is preferably 0.01 to 5% by mass, more preferably 0.5 to 3% by mass, and even more preferably 1.0 to 2% by mass.

The component (D) used in the present invention is an oil agent in a liquid state at 25 ° C. Here, the term "liquid at 25 ° C." means having fluidity at 25 ° C. The component (D) includes an oil agent liquid at 25 ° C. other than (D1) silicone oil and a silicone oil liquid at 25 ° C. (D2). Here, examples of the liquid oil agent other than (D1) silicone oil include hydrocarbon oils, ester oils, higher fatty acids, higher alcohols, and oil-soluble ultraviolet absorbers often used in sunscreen cosmetics. These may be of natural origin. In addition, ester oils include naturally occurring fats and oils and synthetic ester oils.

Naturally derived fats and oils (natural fats and oils) include lavender oil, evening primrose oil, olive oil, avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, and persic oil. , Wheat germ oil, Southern ka oil, Himasi oil, Amani oil, Saflower oil, Cotton seed oil, Eno oil, Soybean oil, Peanut oil, Tea seed oil, Kaya oil, Rice bran oil, Shinagiri oil, Japanese millet oil, Johoba oil, Germ Examples include oil.

Examples of the hydrocarbon oil include liquid paraffin, liquid isoparaffin, liquid zokerite, squalane, pristane, squalene and the like.

Synthetic ester oils include isononyl isononanoate, isotridecyl isononanoate, neopentyl glycol dicaprate, neopentyl glycol diethylhexanate, ethylhexyl palminate, glycerin tri-2-ethylhexylate, alkyl benzoate, di (caprylic acid / capric acid). ) Provandiol, propanediol diisostearate, glyceryl tri (caprylic / capric acid), isopropyl myristate, cetyl octanate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate , Hexyldecyl dimethyloctanoate, cetyl lactate, myristyl lactate, lanolin acetate, isosetyl stearate, isosetyl isostearate, ethylene glycol di-2-ethylhexylate, dipentaerythritol fatty acid ester, N-alkylglycol monoisostearate, diapple acid Isostearyl, glycerin di-2-heptylundecanoate, trimethylolpropane tri-2-ethylhexylate, trimethylolpropane triisostearate, pentaerythritol tetra-2-ethylhexylate, trimethylolpropane triisostearate, cetyl2-ethylhexa Noate, 2-ethylhexyl palmitate, glycerin trimyristate, glyceride tri-2-heptyl undecanoic acid, methyl ester of castor oil fatty acid, oleyl oleate, acetoglyceride, 2-heptyl undecyl palmitate, diisobutyl adipate, N- Lauroyl-L-glutamate-2-octyldodecyl ester, di-2-heptylundecyl adipate, ethyllaurate, di-2-ethylhexyl sebatate, 2-hexyldecyl myristate, 2-hexyldecyl palmitate, adipate Examples thereof include 2-hexyldecyl, diisopropyl sebatate and 2-ethylhexyl succinate.

Examples of higher fatty acids include branched or unsaturated higher fatty acids having 12 to 20 carbon atoms such as oleic acid, isostearic acid, linoleic acid, and linoleic acid.

Examples of the higher alcohol include branched or unsaturated higher alcohols having 12 to 20 carbon atoms such as oleyl alcohol, 2-decyltetradecinol, lanolin alcohol, dodecanol, isostearyl alcohol and octyldodecanol.

Oil-soluble UV absorbers include salicylic acids such as homomentyl salicylate, octyl salicylate, and triethanolamine salicylate; paraaminobenzoic acid, ethyldihydroxypropyl paraaminobenzoic acid, glyceryl paraaminobenzoic acid, octyldimethylparaaminobenzoic acid, paradimethylaminobenzoic acid. Paraaminobenzoic acid series such as amyl, 2-ethylhexyl paradimethylaminobenzoate; 4- (2-β-glucopyranosiloxy) propoxy-2-hydroxybenzophenone, dihydroxydimethoxybenzophenone, sodium dihydroxydimethoxybenzophenone disulfonate, 2 -Hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfate, 2,2'-dihydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2,2'4,4'-tetra Benzophenones such as hydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-N-octoxybenzophenone; 2-ethylhexyl paramethoxysilicate (Ubinal MC80; manufactured by BASF) , Mono-2-ethylhexanate glyceryl diparamethoxysilicate, methyl 2,5-diisopropylsilicate, 2,4,6-tris [4- (2-ethylhexyloxycarbonyl) anilino] -1, 3,5-Triazine (Ubinal T150; manufactured by BASF), Methylbis trimethoxycinerate (trimethylsiloxy) silylisopentyl, isopropyl-diisopropylsilicate ester mixture of paramethoxycinerate, diethanolamine p-methoxyhydrosilicate Silica such as salts; 2-phenyl-benzimidazole-5-sulfate, 4-isopropyldibenzoylmethane, 4-tert-butyl-4'-methoxydibenzoylmethane (parasol 1789; manufactured by DSM Nutrition Japan), etc. Benzophenone methane-based; Octocrylene (Parasol 340; manufactured by DSM Nutrition Japan), 2-ethylhexyl dimethoxybenzidenedioxoimidazolidinepropionate (soft shade DH; manufactured by Ajinomoto), 1- (3,4-dimethoxyphenyl) -4 , 4-Dimethyl-1,3-Pentandione, Synoxate, Methyl-O-Aminobenzoate, 3- (4-Methylbenzylene) camphor, Octiltriazo Diethylaminohydroxybenzoyl benzoic acid hexyl ester (Ubinal Aplus; manufactured by BASF), bisethylhexyloxyphenol methoxyphenyltriazine (Tinosorb S; manufactured by BASF), methylenebisbenzotriazolyl tetramethylbutylphenol (Tinosorb M; manufactured by BASF) ), And one or more selected from these can be used.

Of these, 2-ethylhexyl paramethoxysilicate (Ubinal MC80; manufactured by BASF), 2,4,6-tris [4- (2-ethylhexyloxycarbonyl) anilino] -1,3,5-triazine (Ubinal T150; manufactured by BASF), 4-tert-butyl-4'-methoxydibenzoylmethane (parasol 1789; manufactured by DSM Nutrition Japan), octoclilen (parasol 340; manufactured by DSM Nutrition Japan), dimethoxybenzylidendioxoimidazo 2-Ethylhexyl lysine propionate (soft shade DH; manufactured by Ajinomoto Co., Ltd.), diethylaminohydroxybenzoyl benzoic acid hexyl ester (Ubinal Aplus; manufactured by BASF), bisethylhexyloxyphenol methoxyphenyltriazine (Tinosorb S; manufactured by BASF), methylenebis One or more selected from benzotriazolyltetramethylbutylphenol (Tinosorb M; manufactured by BASF) is preferable from the viewpoint of ultraviolet absorption effect, and it is more preferable to combine two or more.

In addition, the oils other than the silicone oil liquid at 25 ° C. used in the present invention are organic based on the organic conceptual diagram (written by Akira Fujita: organic qualitative analysis) from the viewpoint of (A) powder dispersibility and improvement of SPF. The IOB value obtained from the sex value and the inorganic value is preferably 0.02 to 0.6, more preferably 0.1 to 0.4.

Examples of polar oils having an IOB value of 0.1 to 0.4 include octyl palmitate (IOB = 0.13), cetyl 2-ethylhexanoate (IOB = 0.13), and cetyl octanoate (IOB = 0.13). , Trimethylolpropane triisostearate (IOB = 0.14), Isotridecyl isononanoate (IOB = 0.15), Propropylene glycol diisostearate (IOB = 0.15), Glycol distearate (IOB = 0.16), Myristin Isopropyl acid (IOB = 0.18), glyceryl triisostearate (IOB = 0.18), trimethylolpropane triisostearate (IOB = 0.20), isononyl isononanoate (IOB = 0.20), isodecylbenzoate (IOB = 0.23), neopentyl glycol dicaprylate (IOB = 0.25), neopentyl glycol dicaprate (IOB = 0.25), diisostearyl malate (IOB = 0.25), methoxycinnamic acid Octyl (IOB = 0.28), Glyceryl diisostearate (IOB = 0.29), Trimethylol propane triethylhexanoate (IOB = 0.31), Trimethylol propane trioctanoate (IOB = 0.31), Tri (caprylic) -Caprylic acid) glyceryl (IOB = 0.32), propylene glycol dicaprylate (IOB = 0.32), di2-ethylhexyl succinate (IOB = 0.32), tetra (bechenic acid / benzoic acid / ethylhexanoic acid) ) Pentaerislit (IOB = 0.35), trioctanoin (IOB = 0.35), pentaerythricyl tetraethylhexanoate (IOB = 0.35), pentaerythlit tetraoctanoate (IOB = 0.35) , Tetra2-ethylhexanoate pentaerythlit (IOB = 0.35), triethylhexanoine (IOB = 0.35), glyceryl tri2-ethylhexanoate (IOB = 0.36), diisopropyl sebacate (IOB =) Ester oils such as 0.40); natural fats and oils such as olive oil (IOB = 0.16), macadamia nut oil (IOB = 0.17); decyltetradecanol (IOB = 0.21), octyldodecanol (IOB) = 0.26), higher alcohols such as oleyl alcohol (IOB = 0.28) and the like.

As the component (D), it is preferable that (D1) contains at least one oil agent other than the liquid silicone oil at 25 ° C. (D1) As the oil agent other than the silicone oil liquid at 25 ° C., an ester oil liquid at 25 ° C. and a hydrocarbon oil liquid at 25 ° C. are preferable. By using an oil agent other than the silicone oil which is liquid at 25 ° C. (D1), good dispersibility of the component (A) can be obtained.

Further, by using a silicone oil liquid at 25 ° C. as the component (D2), the non-stickiness can be further improved. As a specific example of the silicone oil liquid at 25 ° C., from the same viewpoint, the one having a viscosity at 25 ° C. of 200 mPa · s or less is preferable, the one having a viscosity of 1 to 100 mPa · s is more preferable, and the one having a viscosity of 1 to 50 mPa · s. Is even more preferable. From the same viewpoint, the silicone oil is preferably dimethylpolysiloxane or dimethylcyclopolysiloxane, more preferably dimethylpolysiloxane or dimethylcyclopolysiloxane having a viscosity at 25 ° C. of 200 mPa · s or less, and a viscosity at 25 ° C. of 200 mPa · s. Dimethylpolysiloxane of s or less is more preferable. The viscosity can be measured at 25 ° C. with a B-type viscometer (TOKI SANGYO VISCOMETER TVB-10M, manufactured by Toki Sangyo Co., Ltd.) and a rotor 1 at 60 rpm for 1 minute.

In the present invention, the mass ratio (D1 / D) of the component (D1) to the component (D) is preferably 0.3 or more, more preferably 0.38 or more, from the viewpoint of ultraviolet protection effect and stability. 42 or more is further preferable, 0.5 or more is further preferable, 1 or less is preferable from the viewpoint of non-stickiness, 0.98 or less is more preferable, 0.95 or less is further preferable, and 0.94 or less is further more preferable. preferable. Specifically, D1 / D is preferably 0.3 to 1, more preferably 0.38 to 0.98, further preferably 0.42 to 0.95, and even more preferably 0.5 to 0.94.

In the cosmetic of the present invention, the mass ratio (D / A) of the component (D) to the component (A) is 1 from the viewpoints of white residue after application, squeaky feeling, dispersibility of the component (A) and improvement of SPF. The above is preferable, 1.5 or more is more preferable, 1.6 or more is further preferable, 1.7 or more is further preferable, and 10 or less is preferable, 5 or less is more preferable, and 2 or less is more preferable from the viewpoint of the stability of the cosmetic. It is more preferably 5.5 or less, further preferably 2.0 or less, and further preferably 1.9 or less. Specifically, the D / A is preferably 1 to 10, more preferably 1 to 5, further preferably 1.5 to 2.5, more preferably 1.6 to 2.0, and 1.7 to 1. 9 is even more preferable.

Further, the cosmetic of the present invention preferably contains (E) dextrin fatty acid ester in addition to the above components from the viewpoint of ultraviolet protection effect, freshness and cosmetic stability.
The (E) dextrin fatty acid ester used in the present invention is an ester of fatty acid and dextrin, and the fatty acid preferably has 8 to 24 carbon atoms, more preferably 14 to 18 carbon atoms, and the fatty acid. Is a linear or branched saturated or unsaturated fatty acid, and the average degree of polymerization of the component (E) is preferably 10 to 50, more preferably 20 to 30.
Specific examples include dextrin palmitate, dextrin palmitic acid / 2-ethylhexanoic acid, dextrin stearate, dextrin palmitic acid / dextrin stearate, dextrin oleate, dextrin isopalmitate, dextrin isostearate, and the like. One type or two or more types can be used.
Commercially available products include dextrin palmitate (Leopard KL2, Leopard KS2, Leopard TL2), dextrin palmitic acid / 2-ethylhexanoate (Leopard TT2), and dextrin myristate (Leopard MKL2) manufactured by Chiba Flour Milling Co., Ltd. (Made by Flour Milling Co., Ltd.) and the like.

The content of the component (E) in the cosmetic is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and 5 by mass, from the viewpoint of improving the ultraviolet protection effect, freshness and cosmetic stability. It is preferably mass% or less, preferably 2 mass% or less. Specifically, the content of the component (E) is preferably 0.1 to 5% by mass, more preferably 0.3 to 2% by mass.

The mass ratio (E / D) of the component (E) to the component (D) is preferably 0.01 or more, preferably 0.02 or more, from the viewpoint of improving the ultraviolet protection effect, freshness and cosmetic stability. More preferably, 0.15 or less is preferable, and 0.05 or less is more preferable, from the viewpoint of improving stability. Specifically, the E / D is preferably 0.01 to 0.15, more preferably 0.02 to 0.5.

Further, from the viewpoint of suppressing stickiness, moisturizing and smoothing the skin, the cosmetic of the present invention preferably contains (F) a solid oil at 25 ° C. in addition to the above-mentioned components.
The component (F) includes a linearly saturated higher alcohol having 12 to 22 carbon atoms, a monofatty acid glycerin ester having 14 to 22 carbon atoms, a monoalkyl glyceryl ether having 14 to 22 carbon atoms, and a monofatty acid having 14 to 22 carbon atoms. Rows such as sorbitan ester, candelilla wax, carnauba wax, bayberry wax; higher fatty acids having 12 to 22 carbon atoms such as lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, 12-hydroxystearic acid; cholesterol; myristic acid Ester oils such as myristyl, cholesteryl isostearate, behenyl behenylate, glycerin trimyristate; hydrocarbon oils such as vaseline, selecin, ozokelite, microcrystallin wax, ceramides, etc., among which 12 to 12 carbon atoms One or more selected from 22 linearly saturated higher alcohols, hydrocarbon oils and ceramides are preferable, and alcohols having 12 to 22 carbon atoms are more preferable. Examples of the linearly saturated higher alcohol having 12 to 22 carbon atoms include myristyl alcohol, cetyl alcohol (cetyl alcohol), stearyl alcohol, and behenyl alcohol. Of these, one or more are preferably selected from linearly saturated higher alcohols having 16 to 18 carbon atoms.

The content of the component (F) in the cosmetic of the present invention is preferable with respect to the whole cosmetic from the viewpoint of improving the stability of the cosmetic, suppressing stickiness, moisturizing and smoothing the skin. Is 0.1% by mass or more, more preferably 0.3% by mass or more, further preferably 0.5% by mass or more, and preferably 5% by mass or less, more preferably 3% by mass or less. , More preferably 2% by mass or less. The content of the specific component (F) is preferably 0.1 to 5% by mass, more preferably 0.3 to 3% by mass, and even more preferably 0.5 to 2% by mass.

In addition to the above-mentioned ingredients, the cosmetic of the present invention contains water, an ultraviolet scattering agent other than titanium oxide, an ultraviolet absorber, a surfactant other than the above, a fragrance, a moisturizer, a beauty ingredient, a medicinal ingredient, and an ingredient (B). Excluded thickeners, oil gelling agents, bactericidal agents, pH adjusters, antioxidants, preservatives, alcohols having 1 to 5 carbon atoms and the like can be contained. The content of the ultraviolet absorber is preferably 10% by mass or less, more preferably 6% by mass or less, and more preferably 3% by mass or less in the cosmetic.

The water content may be an amount capable of retaining the oil-in-water emulsion.

As the surfactant, known anionic surfactants, cationic surfactants and amphoteric surfactants can be used. The content of the surfactant other than the component (C) in the cosmetic is preferably 1% by mass or less from the viewpoint of improving the stability of the cosmetic, the lightness at the time of application, and the non-stickiness after application. 5% by mass or less is more preferable, 0.1% by mass or less is further preferable, and substantially 0% by mass is even more preferable.

Specific examples of the moisturizer include glycerin, 1,3-butylene glycol, hyaluronic acid and salts thereof. Specific examples of beauty or medicinal ingredients include sunflower oil, yuzu extract, hamamelis extract, lemon extract, chamomile extract, asunaro extract, rosemary extract, kikyo extract, orange extract, grapefruit extract, and ginger extract. Can be mentioned. Specific examples of the pH adjuster include bases such as sodium hydroxide, potassium hydroxide, ammonium chloride and triethanolamine; and acids such as organic acids. Further, a specific example of the preservative is phenoxyethanol.

Further, powders other than the above-mentioned components may be contained, and specific examples thereof include talc, starch, resin powder and the like. Among these, specific examples of the resin powder include silicone resin powder, powder of lauryl methacrylate, ethylene glycol dimethacrylate, and sodium methacrylate copolymer, and more specifically, Japanese Patent Application Laid-Open No. 2006-225311. Examples thereof include the resin powder described in Japanese Patent Publication No. It may also contain a chelating agent such as disodium edetate.

The oil-in-water sunscreen cosmetic of the present invention can be produced according to a usual method. That is, at a predetermined temperature of about 25 ° C., the component (B) and water are mixed to prepare an aqueous phase. On the other hand, at a predetermined temperature of about 80 ° C. to 90 ° C., the component (C), the component (D) and, if necessary, the component (E) and the component (F) are added, and the component (A) is mixed. Prepare the oil phase. After that, the oil phase and other components are added to the aqueous phase, and the mixture is cooled to about room temperature with stirring to obtain the cosmetic of the present invention.

In addition, the cosmetics obtained by the present invention include makeup bases, emulsifying foundations, eye shadows and other makeup cosmetics having a sunscreen effect; sunscreen creams and the like. The dosage form may be, for example, emulsions, creams or the like.

In the present invention, by using the above components (A) to (D) in combination, it has a high SPF value, excellent stability, no squeaky feeling, no stickiness or sliminess, and a fresh coating feeling. However, an oil-in-water sunscreen cosmetic that has little white residue after application and is easy to remove can be obtained. The application target of the sunscreen cosmetic of the present invention includes skin, especially skin excluding hair, preferably face, body, limbs and the like.

Next, the present invention will be described in more detail with reference to examples. In addition, Examples 2, 3, 5, 6, 8 , 13 , 15, 18 and 20 are reference examples.

(Examples 1 to 20 and Comparative Examples 1 to 3)
We manufacture oil-in-water sunscreen cosmetics with the compositions shown in Tables 1 and 2, and evaluate their UV protection effect, no white residue after application, no squeaky feeling, freshness, ease of removal, and good stability. did. The results are also shown in Tables 1 and 2.

(Production method)
At a temperature of 25 ° C., the component (B) was dispersed while stirring the compounding tank containing purified water with a disper to prepare an aqueous phase. On the other hand, at a temperature of about 90 ° C., the component (C), the component (D1), the component (D2), the component (E) and the component (F) are heated and stirred, and (A) is further added and dispersed by a disper. The oil phase was prepared. Then, an oil phase was added to the aqueous phase, and the mixture was stirred, and the remaining components were further added to obtain an oil-in-water sunscreen cosmetic.

(Evaluation method)
(1) UV protection effect (SPF value)
The cosmetic was uniformly applied on the PMMA board at a rate of 2 mg / cm ² for 1 minute, and dried in a cool and dark place for 15 minutes. After drying the sample, use an SPF analyzer (SPF 290S plus, manufactured by Optometricus USA, Inc.) to absorb a total of 9 absorption spectra (wavelengths) at the midpoint on the square PMMA plate, each vertex, and the midpoint of the side connecting each vertex. The transmittance (%) at 350 nm) was measured, and the average of 9 points was calculated. The result showed the SPF value (-) obtained from the transmittance (%).
The SPF values are shown in the table according to the following criteria.
SPF
> 22 ◎
18 or more and 22 or less ○
14 or more and less than 18 △
Less than 14 ×

(2) No white residue after application 0.02 mL of cosmetic was applied to the inside of the forearm in a circle with a diameter of 3 cm by two specialized panelists. After 20 minutes passed at 30 ° C. and 45 RH after applying the cosmetic, the whiteness of the applied portion was subjected to a sensory evaluation. The criteria for no white residue were divided into four stages.
◎ I don't feel any white residue.
○ I don't feel any white residue.
△ I feel a little white residue, but it is within the permissible range.
× I feel the white residue strongly and it is out of the allowable range.

(3) No squeaky feeling 0.02 mL of cosmetic was applied to the inside of the forearm in a circle with a diameter of 3 cm by two panelas. A sensory evaluation was performed on the squeaky feeling at the time of application. The evaluation criteria were divided into four stages.
◎ I don't feel any squeaky feeling.
○ I do not feel a squeaky feeling.
△ I feel a little squeak, but it is within the permissible range.
× I feel a squeaky feeling and it is out of the allowable range.

(4) Freshness 0.02 mL of cosmetics was applied to the inside of the forearm in a circle with a diameter of 3 cm by two panelas. A sensory evaluation was performed on the freshness at the time of application. The evaluation criteria were divided into four stages.
◎ I strongly feel the freshness.
○ Feel the freshness.
△ I feel a little freshness.
× I don't feel the freshness.

(5) Ease of removal 0.02 mL of cosmetic was applied to the inside of the forearm in a circle with a diameter of 3 cm by two specialized panelists. After applying the cosmetics, the mixture was removed with soap after 2 hours at room temperature. After dropping, a sensory evaluation was performed on the white residue on the skin. The criteria for no white residue were divided into four stages.
◎ I don't feel any white residue.
○ I don't feel any white residue.
△ I feel a little white residue, but it is within the permissible range.
× I feel the white residue strongly and it is out of the allowable range.

(6) Good stability Put 50 g of oil-in-water emulsified cosmetic in a 50 mL glass bottle, seal it, store it at 50 ° C for 1 month, and then check whether the oil phase in the cosmetic is separated and use an optical microscope. The particle size of the oil droplets was evaluated by one expert panelist and shown according to the following criteria.
The criteria were divided into four stages.
◎ There is no oil separation, and the particle size of the oil droplets is almost the same as before storage.
○ There is no oil separation, and the particle size of the oil droplets is slightly larger than before storage.
△ There is no oil separation, but the particle size of the oil droplets is larger than before storage.
× Oil separated.

* 1: MT-100TV manufactured by TAYCA
* 2: Sakai Chemical STR-100A-LP
* 3-1: Lubrizol Advanced Materials, Inc., PEMULEN TR-1
* 3-2: Lubrizol Advanced Materials, Inc., PEMULEN TR-2
* 4: In SIMULGEL EG manufactured by SEPPIC, the amount of A) component sodium acrylate / sodium acryloyl dimethyl taurine copolymer is 37.5%.
* 5: Daicel Finechem HEC Daicel SE400
* 6: Leodore TW-S120V (HLB 14.9) manufactured by Kao Corporation
* 7: Kao Leodor SP-S10V (HLB 4.7)
* 8: Sarakos 913 manufactured by Nisshin Oillio Group
* 9: Sarakos 99 manufactured by Nisshin Oillio Group
* 10: Esthetic Mall N-01 manufactured by Nisshin Oillio Group
* 11: Exepearl TGO manufactured by Nisshin Oillio Group
* 12: Ubinar MC80 manufactured by BASF Japan Ltd.
* 13: NOF Pearl Dream EX
* 14: Silicone KF-96A-6CS (-G) manufactured by Shin-Etsu Chemical Co., Ltd.
* 15: Leopard KL2 manufactured by Chiba Flour Milling Co., Ltd.
* 16: Stearyl alcohol NX manufactured by Higher Alcohol Industry Co., Ltd.
* 17: TRIS AMINO Ultra PC (J) Trometamine made by ANGUS CHEMICAL COMPANY
* 18: Liquid caustic potash (48%) manufactured by Asahi Glass Co., Ltd.
* 19: Clewat N manufactured by Nagase Chemtex
* 20: High Solve EPH manufactured by Toho Chemical Industry Co., Ltd.
* 21: KH Neochem 1,3-butylene glycol-P

(Prescription Examples 21-23)
The oil-in-water sunscreen cosmetics shown in Table 3 were produced in the same manner as in Examples 1 to 20. The obtained cosmetic has a high SPF value, excellent stability, no squeaky feeling, no stickiness or sliminess, has a fresh coating feeling, has little white residue after application, and is easy to remove. It had an effect.

* 1: MT-100TV manufactured by TAYCA
* 2-1: PEMULEN TR-1 manufactured by Lubrizol Advanced Materials, Inc.
* 2-2: PEMULEN TR-2 manufactured by Lubrizol Advanced Materials, Inc.
* 3: Leodore TW-S120V (HLB 14.9) manufactured by Kao Corporation
* 4: Leodore SP-S10V (HLB 4.7) manufactured by Kao Corporation
* 5: Sarakos 913 manufactured by Nisshin Oillio Group
* 6: Sarakos 99 manufactured by Nisshin Oillio Group
* 7: Esthetic Mall N-01 manufactured by Nisshin Oillio Group
* 8: Exepearl TGO manufactured by Nisshin Oillio Group
* 9: FINSOLV TN manufactured by Innospec Active Chemicals LLC
* 10: NOF Pearl Dream EX
* 11: Silicone KF-96A-6CS (-G) manufactured by Shin-Etsu Chemical Co., Ltd.
* 12: Leopard KL2 manufactured by Chiba Flour Milling Co., Ltd.
* 13: Stearyl alcohol NX manufactured by Higher Alcohol Industry Co., Ltd.
* 14: Super White Protopet made by Sonneborn, LLC
* 15: Kao Sphingolipid E
* 16: ANGUS CHEMICAL COMPANY TRIS AMINO Ultra PC (J) Trometamine
* 17: Liquid caustic potash (48%) manufactured by Asahi Glass Co., Ltd.
* 18: Clewat N manufactured by Nagase Chemtex
* 19: High Solve EPH manufactured by Toho Chemical Industry Co., Ltd.
* 20: KH Neochem 1,3-butylene glycol-P
* 21: ADEKA DPG-RF
* 22: NOF PEG # 20000
* 23: Ina Agar CS-16A manufactured by Ina Food Industry Co., Ltd.
* 24: Eucalyptus extract manufactured by Shinwa Bussan Co., Ltd.
* 25: Asunaro Liquid KB manufactured by Ichimaru Falcos
* 26: Nikkor SMT manufactured by Nippon Surfant Industry Co., Ltd.

From Tables 1 to 3, the oil-in-water sunscreen cosmetic of the present invention contains a large amount of the component (A) and also contains the components (B), (C) and (D). It can be seen that it has a high SPF value, excellent stability, no squeaky feeling, no stickiness or sliminess, a fresh coating feeling, little white residue after coating, and easy to remove.

Claims (8)

Ingredients (A), (B), (C) , (D) and (E) :
(A) Titanium oxide particles 6 % by mass or more and 14 % by mass or less, which are surface-treated with a surface treatment agent having a carboxyl group.
(B) Water-soluble polymer having a structural unit derived from (meth) acrylic acid or sulfonic acid 0.02% by mass or more and 1.0% by mass or less ,
(C) Nonionic surfactant having an HLB of 6 or more and 10 or less determined by the formula of Griffin (However, when two or more kinds of nonionic surfactant are contained, the mixed HLB of the nonionic surfactant is 6 or more and 10 or more. Below) 1.0% by mass or more and 5% by mass or less, and (D) an oil that is liquid at 25 ° C.
(E) A liquid oil agent containing (E) dextrin fatty acid ester and having a component (D) of (D1) a liquid state at 25 ° C. having an IOB value of 0.02 to 0.6 other than the liquid silicone oil at 25 ° C. only containing component weight ratio of component (E) with respect to (D) (E / D) is 0.01 to 0.05, the weight ratio of component (D1) to component (D) (D1 / D) Is 0.3 or more and 0.98 or less, the mass ratio (D / A) of the component (D) to the component (A) is 1.6 or more and 5 or less, and the surfactant other than the component (C) An oil-in-water sunscreen cosmetic having a content of 0.125% by mass or less . The oil-in-water sunscreen cosmetic according to claim 1, wherein the content of the component (A) is 6 % by mass or more and 9% by mass or less. The oil-in-water sunscreen cosmetic according to claim 1 or 2, wherein the component (D1) is an ester oil in a liquid state at 25 ° C. having an IOB value of 0.02 to 0.6. The oil-in-water sunscreen cosmetic according to any one of claims 1 to 3, wherein the component (D) further contains (D2) a liquid silicone oil at 25 ° C. (F) The oil-in-water sunscreen cosmetic according to any one of claims 1 to 4 , which contains a solid oil agent at 25 ° C. The oil-in-water sunscreen cosmetic according to any one of claims 1 to 5 , wherein the content of the ultraviolet absorber is 10% by mass or less. The oil-in-water sunscreen cosmetic according to any one of claims 1 to 6 , wherein the content of the water-soluble polymer other than the component (B) is 1% by mass or less. The oil-in-water sunscreen cosmetic according to any one of claims 1 to 7 , wherein the pH is 7 or more and 9 or less.