JP2017197434A - Oil-in-water sunscreen cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an oil-in-water type sunscreen cosmetic which has good blending stability in an oil-in-water system of an ultraviolet scattering agent, no squeaky feeling during application and good spreadability to the skin, leaves no white residue after application and is easily washed away.SOLUTION: There is provide an oil-in-water type sunscreen cosmetic which comprises the following components (A), (B), (C) and (D): (A) more than 3 mass% and 20 mass% or less of titanium oxide particles surface-treated with a surface treatment agent having a carboxyl group, (B) a water-soluble polymer having a structural unit derived from a (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.SELECTED DRAWING: None

Description

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

Sunscreen cosmetics are blended with UV absorbers and UV scattering agents in order to obtain high SPF values by blocking UV irradiation on the skin. And 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 has stickiness and sliminess at the time of application, and when it contains a high amount of UV absorber, it may become oily and sticky, and may also become contaminated due to secondary adhesion to clothes. was there. Moreover, when the ultraviolet absorber is highly blended, there is a possibility that rough skin may occur for users of sensitive skin.

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

JP 2014-185137 A JP 2014-105207 A JP 2008-162930 A International Publication No. 2013/018827

However, in these oil-in-water sunscreen cosmetics, the blending stability of the ultraviolet light scattering agent into the oil-in-water system is not sufficient, the point that squeaky sensation, etc. occurs, the elongation to the skin is not sufficient, It became clear that there were problems such as white residue being easily generated and not being easily removed.
Therefore, the problem of the present invention is that the blending stability of the UV scattering agent into the oil-in-water system is good, there is no squeaky feeling at the time of application, the elongation to the skin is good, and no white residue after application occurs. Another object is to provide an oil-in-water sunscreen cosmetic that is 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 whose surface is treated with a component having a carboxyl group, and a nonionic property having a specific water-soluble polymer and a specific HLB. In addition to a surfactant, if an oil agent that is liquid at 25 ° C. is blended to form an oil-in-water composition, the blending stability of the titanium oxide particles, which are UV scattering agents, is good, and the squeaky feeling during coating In addition, the present inventors have found that an oil-in-water sunscreen cosmetic that has good elongation to the skin, no white residue after application, and that is easy to remove can be obtained.

That is, the present invention provides 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 less than 20% by mass,
(B) a water-soluble polymer having a structural unit derived from (meth) acrylic acid or sulfonic acid,
(C) Provided is an oil-in-water sunscreen cosmetic containing a nonionic surfactant having an HLB of 6 to 10 and (D) an oil that is liquid at 25 ° C.

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

The oil-in-water sunscreen cosmetic of the present invention (hereinafter sometimes 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 less than 20% by mass,
(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 that is liquid at 25 ° C.

  Component (A) is titanium oxide particles that are surface-treated with a surface treatment agent having a carboxyl group. Here, as a specific example of the surface treatment agent having a carboxyl group, the viewpoint of improving the dispersibility of the titanium oxide particles in the cosmetic and improving the ultraviolet protection effect of the cosmetic, the viewpoint of suppressing the whiteness of the appearance, and From the viewpoint of improving smoothness, fatty acids are preferable, higher fatty acids having 14 to 22 carbon atoms are more preferable, and higher fatty acids having 16 to 20 carbon atoms are more preferable. From the same viewpoint, the carbon number of the fatty acid in the surface treatment agent is preferably 14 or more, more preferably 16 or more, and preferably 22 or less, more preferably 20 or less. Moreover, as a specific example of the titanium oxide particle surface-treated with the surface treatment agent having a carboxyl group, fatty acid-treated titanium oxide particles having 14 to 22 carbon atoms, and alumina carbon numbers 14 to 22 fatty acid-treated titanium oxide particles can be mentioned, More preferable examples include alumina stearic acid-treated titanium oxide particles and alumina isostearic acid-treated titanium oxide particles. Above all, from the viewpoints of improving the dispersibility of titanium oxide particles in cosmetics and improving the UV protection effect of cosmetics, reducing the whiteness of appearance, and improving the smoothness, alumina stearic acid treatment oxidation Titanium particles are preferred.

  The average particle diameter of the titanium oxide particles surface-treated with the surface treatment agent having a carboxyl group as 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. Moreover, 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 applying a cosmetic and improving smoothness, 1 nm or more is preferable, 7 nm or more is more preferable, 8 nm or more is more 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 short diameter of the particle diameter of 300 particles in the image under a condition of 100000 magnification with a transmission electron microscope (TEM). It is obtained by measuring and calculating the average value. Here, the maximum minor axis means the minor axis having the largest diameter among the minor axes 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 not more than 20% by mass from the viewpoint of obtaining an excellent UV protection effect, the lack of white residue after application, and the feeling of use. Further, the content of the component (A) in the cosmetic of the present invention is preferably 5% by mass or more and 6% by mass or more from the viewpoint of obtaining an excellent UV protection effect and improving the stability of the cosmetic. More preferably, 7% by mass or more is more preferable, and from the viewpoints of no white residue after coating, no squeaky feeling, and ease of removal, it is preferably 14% by mass or less, more preferably 11% by mass or less, and 9% by mass. % 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 is applied to the skin and then washed off from the skin with a cleaning agent or the like.

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 structural unit derived from (meth) acrylic acid, a homopolymer having a monomer selected from methacrylic acid, acrylic acid, methacrylate, acrylate, methacrylamide, and acrylamide as a structural unit, or two or more of these monomers Including copolymers. More specifically, carboxyvinyl polymer (for example, syntarene K, L; manufactured by Wako Pure Chemical Industries, Ltd.), acrylic acid / alkyl methacrylate copolymer (for example, PEMULEN TR-1, TR-2; manufactured by Lubrizol) ), Polyacrylamide (SEPIGEL 305), (Na / acryloyldimethyltaurine Na) copolymer (SIMULG EL EG), (hydroxyethyl acrylate / acryloyldimethyltaurine Na) copolymer (SIMULGEL FL, SIMULGEL) sold by SEPPIC NS, SEPIPLUS S, SEPINOV EMT 10), (acrylamide / ammonium acrylate) copolymer (SEPIPLUS 265), polyacrylate-13 (SEPIPLUS 400). Etc. The. One or more of (meth) acrylic acid polymers selected from these can be used.
Moreover, stearoxy PG hydroxyethyl cellulose sulfonic acid Na (poise 310; Kao company make) is mentioned as a water-soluble polymer which has a structural unit derived from a sulfonic acid.
Among these, when one or two or more selected from acrylic acid / methacrylic acid copolymer and (Na acrylate / acryloyldimethyltaurine Na) copolymer are used, the composition is stable even in a small amount, and at the time of coating. This is preferable from the viewpoint of the anti-shrinking effect and the improvement in the feeling of use.

In the cosmetic of the present invention, from the viewpoint of improving the stability of the cosmetic and the convenience of use of the container, the component (B) in the cosmetic is preferably 0.02% by mass or more, more preferably 0.15. It is preferably contained in an amount of 1.0% by mass or less, more preferably 0.8% by mass or less, from the viewpoint of improving the lightness of elongation and freshness. Specifically, the content of the component (B) in the cosmetic is preferably 0.02 to 1.0% by mass, and more preferably 0.15 to 0.8% by mass. Here, content of a component (B) is content of the active ingredient contained in a product, and is not the quantity of a commercial item.
In addition, in the range which does not impair the effect of this invention, water-soluble polymers other than a component (B) can be contained in cosmetics. From the viewpoint of improving the stability of the cosmetic, lightness of elongation, and freshness, the water-soluble polymer other than the component (B) is preferably 1% by mass or less, and 0.5% by mass or less in the cosmetic. More preferably, it is more preferably 0.1% by mass or less, and still more preferably 0% by mass.

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 cosmetics, 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. .6 is more preferred, and 8.5 to 9.4 is even more preferred.
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 determined by the Griffin equation. The HLB in the case of using two or more kinds of nonionic surfactants is an arithmetic average of the HLB values of the respective nonionic surfactants 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, Polyoxyethylene alkyl ether, polyoxyethylene phytosterol, polyoxyethylene phytostanol, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene lanolin , Polyoxyethylene lanolin alcohol, polyoxyethylene honey C derivatives, polyoxyethylene alkyl amines, polyoxyethylene fatty acid amides, polyoxyethylene alkylphenyl formaldehyde condensates, single chain length polyoxyethylene alkyl ethers, polyether-modified silicone, and the like. In these, 1 type, or 2 or more types chosen from polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester, polyoxyethylene alkyl ether, and polyoxyethylene hydrogenated castor oil are preferable, sorbitan fatty acid ester and polyoxyethylene sorbitan fatty acid One or more selected from esters are more preferred. The number of polyoxyethylenes, fatty acids, and alkyl groups of these nonionic surfactants is preferably selected so that the HLB is 6-10.

  In the cosmetic of the present invention, from the viewpoint of improving the stability of the cosmetic, the component (C) in the cosmetic is preferably 0.01% by mass or more, more preferably 0.5% by mass or more, and still more preferably. 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, and further preferably 2% by mass or less from the viewpoint of improving the lightness at the time of coating and the 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 still more preferably 1.0 to 2% by mass.

  Component (D) used in the present invention is an oil agent that is liquid at 25 ° C. Here, the liquid state at 25 ° C. means having fluidity at 25 ° C. Component (D) includes (D1) an oil agent that is liquid at 25 ° C. other than silicone oil, and (D2) a silicone oil that is liquid at 25 ° C. Here, (D1) Liquid oils other than silicone oils include hydrocarbon oils, ester oils, higher fatty acids, higher alcohols, or oil-soluble UV absorbers often used in sunscreen cosmetics. These may be naturally derived. The ester oil includes naturally derived fats and oils and synthetic ester oils.

  Naturally derived oils (natural 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, sasanqua oil, castor oil, flaxseed oil, safflower oil, cottonseed oil, eno oil, soybean oil, peanut oil, teaseed oil, kaya oil, rice bran oil, cinnabari oil, Japanese kiri oil, jojoba oil, germ Oil etc. are mentioned.

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

  Synthetic ester oils include isononyl isononanoate, isotridecyl isononanoate, neopentyl glycol dicaprate, neopentyl glycol diethylhexanoate, ethylhexyl palmitate, glyceryl tri-2-ethylhexylate, alkyl benzoate, di (caprylic acid / capric acid) ) Provandiol, propanediol diisostearate, glyceryl tri (capryl / caprate), isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate , Hexyldecyl dimethyloctanoate, cetyl lactate, myristyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearate Di-2-ethylhexyl acid ethylene glycol, dipentaerythritol fatty acid ester, N-alkyl glycol monoisostearate, diisostearyl malate, glycerin di-2-heptylundecanoate, tri-2-ethylhexyl trimethylolpropane, triisostearin Trimethylolpropane acid, pentaerythritol tetra-2-ethylhexylate, trimethylolpropane triisostearate, cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, glyceryl trimyristate, glyceride tri-2-heptylundecanoate, castor Oil fatty acid methyl ester, oleyl oleate, acetoglyceride, 2-heptylundecyl palmitate, diisobutyl adipate, N-lauroyl-L- Glutamic acid-2-octyldodecyl ester, di-2-heptylundecyl adipate, ethyl laurate, di-2-ethylhexyl sebacate, 2-hexyldecyl myristate, 2-hexyldecyl palmitate, 2-hexyldecyl adipate , Diisopropyl sebacate, 2-ethylhexyl succinate and the like.

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

  Oil-soluble UV absorbers include salicylic acid series such as homomenthyl salicylate, octyl salicylate, triethanolamine salicylate; paraaminobenzoic acid, ethyldihydroxypropylparaaminobenzoic acid, glycerylparaaminobenzoic acid, octyldimethylparaaminobenzoic acid, paradimethylaminobenzoic acid Amyl, paraaminobenzoic acid series such as 2-ethylhexyl paradimethylaminobenzoate; 4- (2-β-glucopyranosyloxy) propoxy-2-hydroxybenzophenone, dihydroxydimethoxybenzophenone, dihydroxydimethoxybenzophenone sodium disulfonate, 2 -Hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfate, 2,2'-dihydroxy-4-methoxy Nzophenone, 2,4-dihydroxybenzophenone, 2,2′4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2-hydroxy-4-N-octoxybenzophenone, etc. Benzophenone series: 2-ethylhexyl paramethoxycinnamate (Ubinal MC80; manufactured by BASF), glyceryl di-2-methoxycinnamate mono-2-ethylhexanoate, methyl 2,5-diisopropylcinnamate, 2,4,6 -Tris [4- (2-ethylhexyloxycarbonyl) anilino] -1,3,5-triazine (Ubinal T150; manufactured by BASF), methyl bis (trimethylsiloxy) silylisopentyl trimethoxycinnamate, paramethoxysilicate Isopropyl cinnamate / Diisopropyl cinnamate Cinnamic acid system such as ester mixture, p-methoxyhydrocinnamic acid diethanolamine salt; 2-phenyl-benzimidazole-5-sulfuric acid, 4-isopropyldibenzoylmethane, 4-tert-butyl-4′-methoxydibenzoylmethane (Parasol 1789; manufactured by DSM Nutrition Japan Co., Ltd.), etc .; Octocrylene (Parasol 340; manufactured by DSM Nutrition Japan Co., Ltd.), dimethoxybenzylidene dioxoimidazolidinepropionate 2-ethylhexyl (Soft Shade DH; manufactured by Ajinomoto Co.), 1 -(3,4-Dimethoxyphenyl) -4,4-dimethyl-1,3-pentanedione, sinoxate, methyl-O-aminobenzoate, 3- (4-methylbenzylidene) camphor, octyl triazone, di Ethylaminohydroxybenzoyl benzoic acid hexyl ester (Ubinal Plus; manufactured by BASF), bisethylhexyloxyphenol methoxyphenyl triazine (Tinosorb S; manufactured by BASF), methylenebisbenzotriazolyltetramethylbutylphenol (Tinosorb M; manufactured by BASF) 1 type, or 2 or more types selected from these can be used.

  Among these, 2-methoxyhexyl paramethoxycinnamate (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), octocrylene (parasol 340; manufactured by DSM Nutrition Japan), dimethoxybenzylidene dioxoimidazo 2-ethylhexyl lysine propionate (soft shade DH; manufactured by Ajinomoto Co., Inc.), diethylaminohydroxybenzoyl benzoic acid hexyl ester (ubibinal plus; manufactured by BASF), bisethylhexyloxyphenol methoxyphene One or more selected from lutriazine (Tinosorb S; manufactured by BASF) and methylenebisbenzotriazolyltetramethylbutylphenol (Tinosorb M; manufactured by BASF) are preferable from the viewpoint of ultraviolet absorption effect, and two or more are selected. It is more preferable to combine them.

  Further, the oil agent other than the silicone oil that is liquid at 25 ° C. used in the present invention is (A) organic based on an organic conceptual diagram (written by Jun Fujita: organic qualitative analysis) from the viewpoint of improving the dispersibility of the powder and SPF. The IOB value determined from the property value and the inorganic value is preferably 0.02 to 0.6, more preferably 0.1 to 0.4.

  As polar oil agents having an IOB value of 0.1 to 0.4, octyl palmitate (IOB = 0.13), cetyl 2-ethylhexanoate (IOB = 0.13), cetyl octanoate (IOB = 0.13) , Trimethylolpropane triisostearate (IOB = 0.14), isotridecyl isononanoate (IOB = 0.15), propylene glycol diisostearate (IOB = 0.15), glycol distearate (IOB = 0.16), myristic Isopropyl acid (IOB = 0.18), glyceryl triisostearate (IOB = 0.18), trimethylolpropane triisostearate (IOB = 0.20), isononyl isononanoate (IOB = 0.20), isodecylbenzoate (IOB = 0.23), neopentylglycol dicaprylate (IOB = 0.25), neopentyl glycol dicaprate (IOB = 0.25), diisostearyl malate (IOB = 0.27), octyl methoxycinnamate (IOB = 0.28), diisostearic acid Glyceryl (IOB = 0.29), trimethylolpropane triethylhexanoate (IOB = 0.31), trimethylolpropane trioctanoate (IOB = 0.31), glyceryl tri (caprylate / caprate) (IOB = 0.32) ), Propylene glycol dicaprylate (IOB = 0.32), di-2-ethylhexyl succinate (IOB = 0.32), tetra (behenic acid / benzoic acid / ethylhexanoic acid) pentaerythritol (IOB = 0.35) , Trioctanoin (IOB = 0.35), tetraethyl hexanoate pentae Srityl (IOB = 0.35), pentaoctyl slit tetraoctanoate (IOB = 0.35), pentaerythritol tetratetraethylhexanoate (IOB = 0.35), triethylhexanoin (IOB = 0.35) , Ester oils such as glyceryl tri-2-ethylhexanoate (IOB = 0.36), diisopropyl sebacate (IOB = 0.40); olive oil (IOB = 0.16), macadamia nut oil (IOB = 0.17) Natural oils and fats such as: higher alcohols such as decyltetradecanol (IOB = 0.21), octyldodecanol (IOB = 0.26), oleyl alcohol (IOB = 0.28), and the like.

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

  Moreover, the non-stickiness can be further improved by using a liquid silicone oil at 25 ° C. as the component (D2). As specific examples of the silicone oil that is liquid at 25 ° C., from the same viewpoint, those having a viscosity at 25 ° C. of 200 mPa · s or less are preferable, those having 1 to 100 mPa · s are more preferable, and those having 1 to 50 mPa · s are preferable. Is 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. More preferred are dimethylpolysiloxanes of s or less. Viscosity can be measured at 25 ° C. using a B-type viscometer (TOKI SANGYO VISCOMETER TVB-10M, manufactured by Toki Sangyo Co., Ltd.) and 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 the ultraviolet protection effect and stability. 42 or more is more preferable, 0.5 or more is further more preferable, and 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 even more 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 more preferably 0.5 to 0.94.

  In the cosmetic of the present invention, from the viewpoints of white residue after application, squeakiness, dispersibility of component (A) and improvement of SPF, the mass ratio (D / A) of component (D) to component (A) is 1. The above is preferable, 1.5 or more is more preferable, 1.6 or more is further preferable, 1.7 or more is further more preferable, and 10 or less is preferable from the viewpoint of cosmetic stability, 5 or less is more preferable, 2 0.5 or less is more preferable, 2.0 or less is more preferable, and 1.9 or less is further preferable. Specifically, 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 preferred.

Moreover, it is preferable that the cosmetics of this invention contain (E) dextrin fatty acid ester in addition to the said component from a viewpoint of a ultraviolet-ray protective effect, a freshness, and cosmetics 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. 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 palmitate / 2-ethylhexanoate, dextrin stearate, dextrin palmitate / dextrin stearate, dextrin oleate, dextrin isopalmitate, dextrin isostearate, etc. 1 type (s) or 2 or more types can be used.
Commercially available products include dextrin palmitate (Leopard KL2, Leopard KS2, Leopard TL2), palmitic acid / 2-ethylhexanoic acid dextrin (Leopard TT2), myristate dextrin (Leopard MKL2) (all Chiba). Etc.).

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

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

Moreover, it is preferable that the cosmetics of this invention contain (F) solid oil agent at 25 degreeC in addition to the said component from a viewpoint of suppression of stickiness, moisture retention, and smoothness of skin.
As the component (F), straight chain saturated higher alcohols having 12 to 22 carbon atoms, mono fatty acid glycerin esters having 14 to 22 carbon atoms, monoalkyl glyceryl ethers having 14 to 22 carbon atoms, mono fatty acids having 14 to 22 carbon atoms Waxes 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; cholesterols; myristic acid Ester oils such as myristyl, cholesteryl isostearate, behenyl behenate, glyceryl trimyristate; hydrocarbon oils such as petrolatum, ceresin, ozokerite, microcrystalline wax, ceramides, etc. 2 Higher alcohols linear saturated, one or the like are preferable more selected from hydrocarbon oils and ceramides, and more preferably an alcohol having 12 to 22 carbon atoms. Examples of the linear saturated higher alcohol having 12 to 22 carbon atoms include myristyl alcohol, cetyl alcohol (cetanol), stearyl alcohol, and behenyl alcohol. Among these, Preferably it is 1 type, or 2 or more types chosen from a C16-C18 linear saturated higher alcohol.

  The content of the component (F) in the cosmetic of the present invention is preferable to the entire cosmetic from the viewpoint of improving the stability of the cosmetic, and from the viewpoints of suppression of stickiness, moisturization, and smoothness of 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, preferably 5% by mass or less, more preferably 3% by mass or less. More preferably, it is 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 still more preferably 0.5 to 2% by mass.

  In addition to the above components, 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 cosmetic ingredient, a medicinal ingredient, and a component (B). Excluding thickeners, oil gelling agents, bactericides, pH adjusters, antioxidants, preservatives, alcohols having 1 to 5 carbon atoms, and the like. In addition, it is preferable that it is 10 mass% or less in cosmetics, as for content of a ultraviolet absorber, it is more preferable to set it as 6 mass% or less, and it is more preferable to set it as 3 mass% or less.

  The water content may be an amount that can hold the oil-in-water emulsion.

  As the surfactant, known anionic surfactants, cationic surfactants, amphoteric surfactants and nonionic surfactants other than those described above 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, lightness at the time of application, and stickiness after application. 5 mass% or less is more preferable, 0.1 mass% or less is further more preferable, and substantially 0 mass% is further more preferable.

  Specific examples of the humectant include glycerin, 1,3-butylene glycol, hyaluronic acid and salts thereof. Specific examples of cosmetic ingredients or medicinal ingredients include sunflower oil, citrus extract, cranberry extract, lemon extract, chamomile extract, asunaro extract, rosemary extract, kyoukyo extract, orange extract, grapefruit extract, and ginger extract. Can be mentioned. Specific examples of the pH adjusting agent include bases such as sodium hydroxide, potassium hydroxide, ammonium chloride and triethanolamine; acids such as organic acids. A specific example of the preservative is phenoxyethanol.

  Moreover, powders other than the components described above may be included, and specific examples thereof include talc, starch, resin powder, and the like. Among these, specific examples of the resin powder include a silicone resin powder and a powder of lauryl methacrylate / ethylene glycol / methacrylic acid / sodium methacrylate copolymer, and more specifically, JP-A-2006-225311. The resin powder described in the publication No. is mentioned. A chelating agent such as disodium edetate may also be included.

  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., component (C), component (D) and, if necessary, component (E) and component (F) are added, and component (A) is mixed. An oil phase is prepared. Thereafter, the oily phase and other components are added to the aqueous phase, and the mixture is cooled to about room temperature while stirring to obtain the cosmetic of the present invention.

  The cosmetics obtained by the present invention include makeup cosmetics having a sunscreen action such as a makeup base, an emulsified foundation, and an eye shadow; sunscreen cosmetics such as a sunscreen cream. Moreover, as a dosage form, it can be set as emulsions, creams, etc., for example.

  In the present invention, by using the components (A) to (D) in combination, they have a high SPF value, excellent stability, no squeaky feeling, no stickiness or sliminess, and a fresh application feeling. In addition, an oil-in-water sunscreen cosmetic with little white residue after application and easy to remove is obtained. Examples of the application target of the sunscreen cosmetic of the present invention include skin, especially skin excluding hair, preferably face, body, limbs and the like.

  EXAMPLES Next, an Example is given and this invention is demonstrated in detail.

(Examples 1-20 and Comparative Examples 1-3)
Manufactures oil-in-water sunscreen cosmetics with the compositions shown in Tables 1 and 2 and evaluates UV protection effect, no white residue after application, no squeaky feeling, freshness, ease of removal, and good stability did. A result is combined with Table 1-2 and shown.

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

(Evaluation method)
(1) UV protection effect (SPF value)
On the PMMA plate, the cosmetic was uniformly applied for 1 minute so as to be ² mg / cm ^2, and dried for 15 minutes in a cool dark place. After drying the sample, the SPF analyzer (SPF 290S plus, manufactured by Optometricus USA, Inc.) has a total of nine absorption spectra (wavelengths) of the middle point on the square PMMA plate, each vertex, and the middle point connecting each vertex. 350 nm) transmittance (%) was measured, and the average of 9 locations was determined. The result showed the SPF value (-) calculated | required from the transmittance | permeability (%).
The SPF values are shown in the table based on the following criteria.
SPF
> 22 ◎
18 to 22 ○
14 to less than 18
Less than 14 ×

(2) No white residue after application Two professional panelists applied 0.02 mL of cosmetics to a 3 cm diameter diameter on the inner side of the forearm. After applying the cosmetic, after 20 minutes at 30 ° C. and 45 RH, sensory evaluation was performed on the whiteness of the coated part. The standard of no white balance was divided into four stages.
◎ I do not feel any white residue.
○ I do not feel any white residue.
Δ Somewhat white residue is felt, but it is within the allowable range.
× Feeling the white residue tightly is out of the allowable range.

(3) No squeaky feeling Two panelists applied 0.02 mL of cosmetic to a 3 cm diameter inside the forearm. Sensory evaluation was performed on the squeaky feeling during application. The evaluation criteria were divided into four stages.
◎ No squeaky feeling.
○ I do not feel a squeak.
ΔSlightly squeaky, but acceptable.
× Feels squeaky and is outside the allowable range.

(4) Freshness Two panelists applied 0.02 mL of cosmetic material to a 3 cm diameter on the inner side of the forearm. Sensory evaluation was performed for freshness only at the time of application. The evaluation criteria were divided into four stages.
◎ I feel a strong sense of freshness.
○ I feel freshness.
△ Slightly feel freshness.
× I do not feel freshness.

(5) Ease of dropping 0.02 mL of cosmetic material having a diameter of 3 cm was applied to the inner side of the forearm by two specialized panelists. After applying the cosmetic, it was removed with soap after 2 hours at room temperature. After dropping, sensory evaluation was performed on the remaining white skin. The standard of no white balance was divided into four stages.
◎ I do not feel any white residue.
○ I do not feel any white residue.
Δ Somewhat white residue is felt, but it is within the allowable range.
× Feeling the white residue tightly is out of the allowable range.

(6) Good stability 50 g of an oil-in-water emulsified cosmetic is placed in a 50 mL glass bottle, sealed, stored at 50 ° C. for 1 month, and the presence or absence of separation of the oil phase in the cosmetic and an optical microscope The particle size of the oil droplets was evaluated by one expert panelist and indicated by the following criteria.
The standard was divided into 4 stages.
◎ No oil separation, the particle size of oil droplets is almost the same as before storage.
○ No oil separation, the particle size of oil droplets is slightly larger than before storage.
Δ Although there is no oil separation, the particle size of the oil droplets is larger than before storage.
X Oil separated.

* 1: MT-100TV manufactured by Teika
* 2: STR-100A-LP manufactured by Sakai Chemical
* 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 / acryloyldimethyltaurate copolymer in claim 1 is 37.5%.
* 5: Daicel Finechem HEC Daicel SE400
* 6: Leodoll TW-S120V (HLB 14.9) manufactured by Kao
* 7: Leodoll SP-S10V (HLB 4.7) manufactured by Kao
* 8: SALACOS 913 manufactured by Nisshin Oillio Group
* 9: Saracos 99 manufactured by Nisshin Oillio Group
* 10: Esthetic Mall N-01, manufactured by Nisshin Oillio Group
* 11: EXCEPARL TGO made by Nisshin Oillio Group
* 12: Yubinal MC80 manufactured by BASF Japan
* 13: NOF Pearl Ream EX
* 14: Silicone KF-96A-6CS (-G) manufactured by Shin-Etsu Chemical Co., Ltd.
* 15: Leopard KL2 from Chiba Flour Mills
* 16: Stearyl alcohol NX manufactured by Higher Alcohol Industry
* 17: TRIS AMINO Ultra PC (J) Tromethamine manufactured by ANGUS CHEMICAL COMPANY
* 18: Liquid caustic potash manufactured by Asahi Glass Co., Ltd. (48%)
* 19: Clewat N manufactured by Nagase ChemteX
* 20: Toho Chemical Industries High Solve EPH
* 21: 1,3-butylene glycol-P manufactured by KH Neochem

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

* 1: MT-100TV manufactured by Teika
* 2-1: PEMULEN TR-1 made by Lubrizol Advanced Materials, Inc.
* 2-2: Lubrizol Advanced Materials, Inc. PEMULEN TR-2
* 3: Leodoll TW-S120V (HLB 14.9) manufactured by Kao
* 4: Leodoll SP-S10V (HLB 4.7) manufactured by Kao
* 5: SALACOS 913 manufactured by Nisshin Oillio Group
* 6: Nissin Oilio Group Saracos 99
* 7: Nisshin Oillio Group Co., Ltd. Beauty Mall N-01
* 8: Excepal TGO made by Nisshin Oillio Group
* 9: FINSOLV TN manufactured by Innospec Active Chemicals LLC
* 10: Pearl Dream EX manufactured by NOF Corporation
* 11: Silicone KF-96A-6CS (-G) manufactured by Shin-Etsu Chemical Co., Ltd.
* 12: Leopard KL2 from Chiba Flour Mills
* 13: Stearyl alcohol NX manufactured by Higher Alcohol Industry
* 14: Super white protopet made by Sonneborn, LLC
* 15: Kao Sphingolipid E
* 16: ANGUS CHEMICAL COMPANY TRIS AMINO Ultra PC (J) Tromethamine
* 17: Liquid caustic potash manufactured by Asahi Glass Co., Ltd. (48%)
* 18: Nagase ChemteX Clewat N
* 19: Toho Chemical Industries Highsolv EPH
* 20: 1,3-butylene glycol-P manufactured by KH Neochem
* 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: Ichimaru Falcos Asnarolo Liquid KB
* 26: Nikkor SMT manufactured by Nippon Surfactant

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

Claims (8)

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 less than 20% by mass,
(B) a water-soluble polymer having a structural unit derived from (meth) acrylic acid or sulfonic acid,
(C) An oil-in-water sunscreen cosmetic containing a nonionic surfactant having an HLB of 6 to 10 and (D) an oil that is liquid at 25 ° C.   The oil-in-water sunscreen cosmetic according to claim 1, wherein component (D) is an oil containing (D1) an oil other than a silicone oil that is liquid at 25 ° C.   The oil-in-water sunscreen cosmetic according to claim 1 or 2, wherein a mass ratio (D1 / D) of the component (D1) to the component (D) is 0.3 or more and 1 or less.   The oil-in-water sunscreen cosmetic according to any one of claims 1 to 3, wherein the mass ratio (D / A) of the component (D) to the component (A) is 1 or more and 10 or less.   The oil-in-water sunscreen cosmetic according to any one of claims 1 to 4, further comprising (E) a dextrin fatty acid ester.   The oil-in-water sunscreen cosmetic according to claim 5, wherein the mass ratio (E / D) of component (E) to component (D) is 0.01 or more and 0.15 or less.   Furthermore, (F) Oil-in-water type sunscreen cosmetics of any one of Claims 1-6 containing a solid oil agent at 25 degreeC.   8. The oil-in-water type sunscreen cosmetic according to any one of claims 1 to 7, having a pH of 7 or more and 9 or less.