Oil-in-water emulsion composition

Abstract

To provide an oil-in-water emulsion composition that excels in terms of smooth spread during use, water resistance, and ease of wash-off.SOLUTION: The present invention is an oil-in-water emulsion composition containing (a) a cationized polysaccharide and (b) a nonionic surfactant, (a) the cationized polysaccharide being present in a continuous phase, and the total HLB of the surfactants blended being 12 or less.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an oil-in-water emulsion composition.

Background Art

[0002] Oil-in-water emulsified cosmetics are mainly used in lotions, creams, etc. because they provide a fresh and refreshing feeling. On the other hand, oil-in-water emulsified cosmetics have a problem of poor water resistance and are easily washed away by sweat, resulting in poor makeup retention. Therefore, in order to impart water resistance to oil-in-water emulsified cosmetics, for example, film-forming agents such as trimethylsiloxysilicic acid may be added. In addition, formulations using cationic polymer emulsifiers in which fatty acid groups such as acyl groups are partially introduced into cationic polymers have been reported (see Patent Document 1). Furthermore, it has also been proposed to impart water resistance by an ion complex formed by an anionic polymer and a cationic compound (see Patent Documents 2 and 3). Additionally, a technique for forming a film with a cationized polysaccharide and a cross-linking agent having at least three or more acid groups to impart water resistance has also been proposed (see Patent Document 4).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, when adjusting water resistance to a sufficient level using a film-forming agent, there are problems such as not being able to obtain a good elongation and fresh feel of use, or not being easily washable with soap. Also, when using a cationic polymer emulsifier, there is a problem that it is not a general-purpose raw material and is difficult to obtain, and the formulation is limited. Furthermore, when using an ion complex, there is a problem that the formulation is limited and it is difficult to stably blend powder components. As an oil-in-water type emulsified cosmetic, a formulation that sufficiently satisfies all of good elongation feel of use, water resistance, and ease of washing has not yet been proposed. Therefore, the present invention has been made in view of the above problems, and an object thereof is to provide an oil-in-water type emulsified composition excellent in good elongation feel of use, water resistance, and ease of washing.

Means for Solving the Problems

[0005] As a result of intensive studies, the present inventor has found that the above problems can be solved by dispersing a cationized polysaccharide in an aqueous phase and further containing a nonionic surfactant, and thus has reached the present invention.

[0006] That is, the present invention is an oil-in-water type emulsified composition having (a) a cationized polysaccharide in a continuous phase, (b) containing a nonionic surfactant, and the total HLB of the blended surfactants being 12 or less.

[0007] (a) The cationized polysaccharide is preferably at least one selected from cationized cellulose, cationized fenugreek gum, cationized guar gum, cationized tara gum, cationized locust bean gum, and cationized xanthan gum.

[0008] The total HLB of the blended surfactants is preferably 6 or more.

[0009] (a) The blending amount of the cationized polysaccharide is preferably 0.1% by mass or more and 2.0% by mass or less based on the total amount of the oil-in-water type emulsified composition.

[0010] (c) It contains an oily component, and the blending amount of the (c) oily component is preferably 10% by mass or more based on the total amount of the oil-in-water type emulsion composition.

[0011] (b) The blending amount of the nonionic surfactant is preferably 0.05% by mass or more and 10.0% by mass or less based on the total amount of the oil-in-water type emulsion composition.

[0012] The oil-in-water type emulsion composition of the present invention may contain a hydrophobic powder.

[0013] The hydrophobic powder is preferably at least one selected from hydrophobic treated titanium oxide, hydrophobic treated zinc oxide, hydrophobic treated cerium oxide, and hydrophobic treated pigments.

Effect of the Invention

[0014] According to the present invention, it is possible to provide an oil-in-water type emulsified cosmetic excellent in a good feeling of use with good elongation, water resistance, and ease of washing.

Modes for Carrying Out the Invention

[0015] Hereinafter, embodiments of the present invention will be described in detail.

[0016] [Oil-in-Water Type Emulsion Composition] The present invention is an oil-in-water type emulsion composition having (a) a cationized polysaccharide in the continuous phase, containing (b) a nonionic surfactant, and the total HLB (Hydrophilic-Lypophilic Balance) of the blended surfactants is 12 or less.

[0017] (a) Cationized Polysaccharide (a) The cationized polysaccharide is preferably at least one selected from cationized cellulose, cationized fenugreek gum, cationized guar gum, cationized tara gum, cationized locust bean gum, and cationized xanthan gum. Examples of cationized cellulose include polyquaternium-10 and polyquaternium-67. Examples of cationized fenugreek gum include cholohydroxypropyltrimonium chloride. Examples of cationized guar gum include guar hydroxypropyltrimonium chloride. Examples of cationized tara gum include Caesalpinia spinosa hydroxypropyltrimonium chloride. Examples of cationized locust bean gum include locust bean hydroxypropyltrimonium chloride. Examples of cationized xanthan gum include xanthan hydroxypropyltrimonium chloride. (a) By blending the cationized polysaccharide, the formulation state can be maintained in a good state without separation and aggregation, and water resistance can be exhibited. However, when the blending amount of the cationized polysaccharide increases, the product becomes sticky and the good feeling of elongation is impaired. Therefore, the blending amount of (a) the cationized polysaccharide is preferably 0.10% by mass or more and 2.00% by mass or less, more preferably 0.15% by mass or more and 1.50% by mass or less, and still more preferably 0.20% by mass or more and 1.0% by mass or less based on the total amount of the oil-in-water type emulsion composition.

[0018] The oil-in-water type emulsion composition of the present invention has (a) a cationized polysaccharide in the continuous phase (aqueous phase), so that it can adhere to the skin surface, retain the components in the formulation on the skin, and be difficult to flow away with sweat or water. And during washing, it can be easily washed away with an anionic surfactant generally contained in the detergent. Therefore, the oil-in-water type emulsion composition of the present invention can achieve easy washability while having strong water resistance to water and sweat.

[0019] (b) Nonionic surfactant (b) As the nonionic surfactant, it is appropriately selected and blended from lipophilic or hydrophilic ones so that the total HLB of the surfactants blended in the oil-in-water type emulsion composition of the present invention is 12 or less. (b) Examples of nonionic surfactants include polyglycerol fatty acid esters, propylene glycol fatty acid esters, pentaerythritol fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbit fatty acid esters, polyoxyethylene glycerol fatty acid esters, polyethylene glycol fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene phytosterol, polyoxyethylene phytostanol, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene lanolin, polyoxyethylene lanolin alcohol, polyoxyethylene beeswax derivatives, polyoxyethylene alkyl amines, polyoxyethylene fatty acid amides, polyoxyethylene alkyl phenyl formaldehyde condensates, single-chain-length polyoxyethylene alkyl ethers, polyether-modified silicones, and the like. (b) One or more nonionic surfactants can be combined and blended from the above.

[0020] (b) The blending amount of the nonionic surfactant depends on the blending amount of the components to be emulsified and dispersed. However, the nonionic surfactant functions substantially, and in the range where it does not impair the fresh and good stretch feeling of the preparation, it is preferably 0.1% by mass or more and 10.0% by mass or less, more preferably 0.3% by mass or more and 8.0% by mass or less, and still more preferably 0.5% by mass or more and 6.0% by mass or less, based on the total amount of the oil-in-water type emulsion composition.

[0021] (c) Oil component The oil-in-water type emulsion composition of the present invention contains a (c) oil component. The (c) oil component constitutes the internal phase (oil phase) of the oil-in-water type emulsion cosmetic. Examples of the (c) oil component include ester oils, hydrocarbon oils, silicone oils, higher fatty acids, higher alcohols, alkyl glyceryl ethers, liquid oils, solid oils, semi-solid oils, fluorine-based oils, ultraviolet absorbers, hydrophobic powders, and the like.

[0022] Examples of ester oils include octyl octanoate, nonyl nonanoate, cetyl octanoate, isopropyl myristate, octyldodecyl myristate, isopropyl palmitate, ethylhexyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyldecyl dimethyloctanoate, cetyl lactate, myristyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearate, ethylene glycol di-2-ethylhexanoate, dipentaerythritol fatty acid ester, N-alkyl glycol monoisostearate, neopentyl glycol dicaprate, tripropylene glycol pivalate, diisostearyl malate, glycerin di-2-heptylundecanoate, glycerin diisostearate, trimethylolpropane tri-2-ethylhexanoate, trimethylolpropane triisostearate, pentaerythrityl tetraethylhexanoate, glyceryl tri-2-ethylhexanoate (triethylhexanoin), glyceryl trioctanoate, glyceryl triisopalmitate, cetyl 2-ethylhexanoate-2-ethylhexyl palmitate, glyceryl trimyristate, glyceride di-2-heptylundecanoate, methyl ester of castor oil fatty acid, oleyl oleate, acetoglyceride, 2-heptylundecyl palmitate, diisobutyl adipate, 2-octyldodecyl N-lauroyl-L-glutamate, di-2-heptylundecyl adipate, ethyl laurate, di-2-ethylhexyl sebacate, 2-hexyldecyl myristate, 2-hexyldecyl palmitate, 2-hexyldecyl adipate, diisopropyl sebacate, 2-ethylhexyl succinate, triethyl citrate, cetyl ethylhexanoate, phytosteryl macadamia nut fatty acid, etc. Preferably, it is pentaerythrityl tetraethylhexanoate.

[0023] Examples of hydrocarbon oils include isododecane, isohexadecane, isoparaffin, mineral oil (liquid paraffin), ozokerite, squalane, pristane, paraffin, ceresin, squalene, petrolatum, microcrystalline wax, hydrogenated polydecene, and the like.

[0024] Examples of silicone oils include linear polysiloxanes (e.g., dimethicone, diphenylsiloxyphenyltrimethicone, diphenylpolysiloxane, etc.), cyclic polysiloxanes (e.g., octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, etc.), silicone resins forming a three-dimensional network structure, silicone rubbers, various modified polysiloxanes (amino-modified polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, fluorine-modified polysiloxane, etc.), acrylic silicones, and the like. Preferred is a linear polysiloxane.

[0025] Examples of higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, undecylenic acid, toluic acid, isostearic acid, linoleic acid, linolenic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), and the like.

[0026] Examples of higher alcohols include linear alcohols (e.g., lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetostearyl alcohol, etc.), branched-chain alcohols (e.g., lanolin alcohol, cholesterol, phytosterol, hexyl dodecanol, isostearyl alcohol, octyl dodecanol, etc.), and the like.

[0027] Examples of alkyl glyceryl ethers include batyl alcohol, chimyl alcohol, and the like.

[0028] Examples of liquid oils include avocado oil, camellia oil, macadamia nut oil, corn oil, olive oil, rapeseed oil, sesame oil, persic oil, wheat germ oil, southern magnolia oil, castor oil, linseed oil, safflower oil, cottonseed oil, eno oil, soybean oil, peanut oil, tea seed oil, kaya oil, rice bran oil, sinagiri oil, Japanese cedar oil, jojoba oil, germ oil, triglycerin, and the like. Examples of solid oils include cocoa butter, coconut oil, hydrogenated coconut oil, palm oil, palm kernel oil, hydrogenated palm oil, candelilla wax kernel oil, hydrogenated oil, candelilla wax, and the like. Examples of semi-solid oils include shea butter, partially hydrogenated coconut oil, partially hydrogenated jojoba oil, and the like. (c) One or more oily components can be blended.

[0029] Examples of fluorine-based oils include fluorine-modified dimethylpolysiloxane, fluorine-modified methylphenylpolysiloxane, perfluoropolyether, perfluorocarbon, and the like.

[0030] Examples of the ultraviolet absorber include benzoic acid-based ultraviolet absorbers (e.g., para-aminobenzoic acid (hereinafter abbreviated as PABA), PABA monoglycerin ester, N,N-dipropoxy PABA ethyl ester, N,N-diethoxy PABA ethyl ester, N,N-dimethyl PABA ethyl ester, N,N-dimethyl PABA butyl ester, etc.); anthranilic acid-based ultraviolet absorbers (e.g., homomenthyl-N-acetylanthranilate, etc.); salicylic acid-based ultraviolet absorbers (e.g., amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropanolphenyl salicylate, etc.); cinnamic acid-based ultraviolet absorbers (e.g., octyl cinnamate, ethyl-4-isopropyl cinnamate, methyl-2,5-diisopropyl cinnamate, ethyl-2,4-diisopropyl cinnamate, methyl-2,4-diisopropyl cinnamate, propyl-p-methoxy cinnamate, isopropyl-p-methoxy cinnamate, isoamyl-p-methoxy cinnamate, octyl-p-methoxy cinnamate (2-ethylhexyl-p-methoxy cinnamate), 2-ethoxyethyl-p-methoxy cinnamate, cyclohexyl-p-methoxy cinnamate, ethyl-α-cyano-β-phenyl cinnamate, 2-ethylhexyl-α-cyano-β-phenyl cinnamate, glyceryl mono-2-ethylhexanoyl-diparamethoxy cinnamate, etc.); pyridazine derivatives (dimorpholinopyridazine); 3-(4'-methylbenzylidene)-d,l-camphor, 3-benzylidene-d,l-camphor; 2-phenyl-5-methylbenzoxazole; 2,2'-hydroxy-5-methylphenylbenzotriazole; 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole; 2-(2'-hydroxy-5'-methylphenylbenzotriazole; dibenzalazine; dianisoylmethane; 4-methoxy-4'-t-butyldibenzoylmethane; 5-(3,3-dimethyl-2-norbornylidene)-3-pentan-2-one, etc.

[0031] The hydrophobic powder is not particularly limited as long as the surface of the powder is hydrophobic, and it may be a powder that is inherently hydrophobic or a hydrophobic-treated inorganic powder.

[0032] Examples of the hydrophobic powder include organic powders such as polyethylene powder, polymethyl methacrylate powder, polystyrene powder, copolymer resin powder of styrene and acrylic acid, benzoguanamine resin powder, polytetrafluoroethylene powder, and cellulose powder, silicone powders such as trimethylsilyl sesquioxane powder, and polyamide resin powder (nylon powder).

[0033] Examples of the inorganic powder to be hydrophobically treated include inorganic powders such as talc, kaolin, mica, sericite, muscovite, phlogopite, synthetic mica, biotite, lepidolite, permiculite, magnesium carbonate, calcium carbonate, aluminum silicate, barium silicate, calcium silicate, magnesium silicate, strontium silicate, metal tungstate salts, magnesium, silica, zeolite, barium sulfate, calcined calcium sulfate (calcined gypsum), calcium phosphate, fluorapatite, hydroxyapatite, ceramic powder, metal soaps (such as zinc myristate, calcium palmitate, aluminum stearate, etc.), boron nitride, etc.; inorganic white pigments such as titanium dioxide and zinc oxide; inorganic red pigments such as iron oxide (red iron oxide) and iron titanate; inorganic brown pigments such as γ-iron oxide; inorganic yellow pigments such as yellow iron oxide and loess; inorganic black pigments such as black iron oxide, carbon black, and sub-titanium dioxide; inorganic purple pigments such as manganese violet and balt violet; inorganic green pigments such as chromium oxide, chromium hydroxide, and cobalt titanate; inorganic blue pigments such as ultramarine and navy blue; pearl pigments such as titanium dioxide-coated mica, titanium dioxide-coated bismuth oxychloride, titanium dioxide-coated talc, colored titanium dioxide-coated mica, bismuth oxychloride, and fish scale foil; metal powder pigments such as aluminum powder and copper powder; and fine particle metal oxides such as fine particle titanium dioxide, fine particle zinc oxide, fine particle iron oxide, and fine particle cerium oxide. Here, pigment-grade particles mean particles having an average particle diameter of generally about 200 nm or more, and fine particles mean particles having an average particle diameter of generally less than 200 nm, typically 100 nm or less.

[0034] As a method for hydrophobizing an inorganic powder, any method can be used as long as it can impart water repellency, regardless of the method. For example, ordinary surface treatment methods such as vapor phase method, liquid phase method, autoclave method, mechanochemical method, etc. can be used. The hydrophobizing agent is not particularly limited, but fatty acid dextrin-treated powder, trimethylsiloxy silicic acid-treated powder, fluorine-modified trimethylsiloxy silicic acid-treated powder, methylphenylsiloxy silicic acid-treated powder, fluorine-modified methylphenylsiloxy silicic acid-treated powder, dimethylpolysiloxane, diphenylpolysiloxane, methylphenylpolysiloxane and other low-viscosity to high-viscosity oily polysiloxane-treated powders, gum-like polysiloxane-treated powders, methylhydrogen polysiloxane-treated powders, fluorine-modified methylhydrogen polysiloxane-treated powders, methyltrichlorosilane, methyltrialkoxysilane, hexamethyldisilane, dimethyldichlorosilane, dimethyldialkoxysilane, trimethylchlorosilane trimethylalkoxysilane and other organic silyl compounds or their fluorine-substituted products-treated powders, ethyltrichlorosilane, ethyltrialkoxysilane, propyltrichlorosilane, propyltrialkoxysilane, hexyltrichlorosilane, hexyltrialkoxysilane, long-chain alkyltrichlorosilane, long-chain alkyltriethoxysilane and other organically modified silanes or their fluorine-substituted products-treated powders, amino-modified polysiloxane-treated powders, fluorine-modified polysiloxane-treated powders, alkyl phosphate fluoride-treated powders, etc. can be mentioned.

[0035] (c) The blending amount of the oily component is preferably 3% by mass or more, more preferably 5% by mass or more, and even more preferably 10% or more based on the total amount of the oil-in-water type emulsion composition in order to sufficiently exhibit the functions of the preparation. Also, in order to obtain a good elongation and a fresh feeling of use, it is preferably 80% by mass or less, more preferably 70% or less, and even more preferably 60% or less.

[0036] The oil-in-water emulsion composition of the present invention has a cationized polysaccharide in the aqueous phase and further contains (b) a nonionic surfactant, enabling stable high incorporation of hydrophobic powder. To make the formulation more highly functional, the hydrophobic powder can be stably incorporated in an amount of 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, and even more preferably 10% by mass or more, based on the total amount of the oil-in-water emulsion composition. From the perspective of emulsion stability as a formulation, the upper limit of the incorporation amount is preferably 60% by mass or less, more preferably 55% by mass or less, and still more preferably 50% by mass or less.

[0037] (d) Water-soluble solvent The oil-in-water emulsion composition of the present invention contains (d) a water-soluble solvent. The (d) water-soluble solvent dissolves the (d) cationized polysaccharide to form a continuous phase. Examples of the water-soluble solvent include water and water-soluble alcohols. The water that can be used in the oil-in-water emulsion composition of the present invention is not particularly limited, and water used in cosmetics, quasi-drugs, etc. can be used. For example, purified water, ion-exchanged water, tap water, etc. can be used.

[0038] Examples of the water-soluble alcohol include lower alcohols, higher alcohols, polyhydric alcohols, polyhydric alcohol polymers, dihydric alcohol alkyl ethers, dihydric alcohol alkyl ethers, dihydric alcohol ether esters, glycerin monoalkyl ethers, sugar alcohols, monosaccharides, oligosaccharides, polysaccharides, and their derivatives. These can be used alone or in combination of two or more.

[0039] Examples of the lower alcohol include ethanol, propanol, isopropanol, isobutyl alcohol, t-butyl alcohol, etc.

[0040] The higher alcohol is preferably a higher alcohol having 6 or more carbon atoms, and examples include saturated straight-chain monohydric alcohols and unsaturated monohydric alcohols.

[0041] Examples of saturated straight-chain monohydric alcohols include dodecanol (lauryl alcohol), tridodecanol, tetradodecanol (myristyl alcohol), pentadecanol, hexadecanol (cetyl alcohol), heptadecanol, octadecanol (stearyl alcohol), nonadecanol, icosanol (arachidyl alcohol), heneicosanol, docosanol (behenyl alcohol), tricosanol, tetracosanol (ceryl alcohol), pentacosanol, hexacosanol (ceryl alcohol), and the like.

[0042] Examples of unsaturated monohydric alcohols include erucyl alcohol and the like. In the present invention, saturated straight-chain monohydric alcohols are preferred from the viewpoint of stability over time. Higher alcohols can be used alone or in combination of two or more of the above. In the present invention, it is preferable to use monohydric aliphatic alcohols having 16 to 22 carbon atoms.

[0043] Examples of polyhydric alcohols include dihydric alcohols (e.g., ethylene glycol, propylene glycol, trimethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, tetramethylene glycol, 2,3-butylene glycol, pentamethylene glycol, 2-butene-1,4-diol, hexylene glycol, octylene glycol, etc.); trihydric alcohols (e.g., glycerin, trimethylolpropane, etc.); tetrahydric alcohols (e.g., pentaerythritol such as 1,2,6-hexanetriol, etc.); pentahydric alcohols (e.g., xylitol, etc.); hexahydric alcohols (e.g., sorbitol, mannitol, etc.).

[0044] Examples of polyhydric alcohol polymers include diethylene glycol, dipropylene glycol, triethylene glycol, polypropylene glycol, tetraethylene glycol, diglycerin, polyethylene glycol, triglycerin, tetraglycerin, polyglycerin, and the like.

[0045] Examples of the divalent alcohol alkyl ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-methylhexyl ether, ethylene glycol isoamyl ether, ethylene glycol benzyl ether, ethylene glycol isopropyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, and the like.

[0046] Examples of the divalent alcohol alkyl ethers include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol butyl ether, diethylene glycol methyl ethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol isopropyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol butyl ether, and the like.

[0047] Examples of the divalent alcohol ether esters include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, ethylene glycol diadipate, ethylene glycol disuccinate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monophenyl ether acetate, and the like.

[0048] Examples of the glycerin monoalkyl ether include xylyl alcohol, ceralkyl alcohol, batyl alcohol, and the like.

[0049] Examples of the sugar alcohol include sorbitol, maltitol, maltotriose, mannitol, erythritol, glucose, fructose, starch decomposition sugar, maltose, xylitol, starch decomposition sugar-reduced alcohol, and the like.

[0050] Examples of monosaccharides include trioses (e.g., D-glyceraldehyde, dihydroxyacetone, etc.), tetroses (e.g., D-erythrose, D-erythrulose, D-threose, erythritol, etc.), pentoses (e.g., L-arabinose, D-xylose, L-lyxose, D-arabinose, D-ribose, D-ribulose, D-xylulose, L-xylulose, etc.), hexoses (e.g., D-glucose, D-talose, D-bucicose, D-galactose, D-fructose, L-galactose, L-mannose, D-tagatose, etc.), heptoses (e.g., aldoheptose, heptulose, etc.), octoses (e.g., octulose, etc.), deoxy sugars (e.g., 2-deoxy-D-ribose, 6-deoxy-L-galactose, 6-deoxy-L-mannose, etc.), amino sugars (e.g., D-glucosamine, D-galactosamine, sialic acid, amino uronic acid, muramic acid, etc.), uronic acids (e.g., D-glucuronic acid, D-mannuronic acid, L-guluronic acid, D-galacturonic acid, L-iduronic acid, etc.), and the like.

[0051] Examples of oligosaccharides include sucrose, gentiobiose, umbelliferose, lactose, planteose, isolichenins, α,α-trehalose, raffinose, lichenins, umbellisin, stachyose, verbascose, and the like.

[0052] Examples of polysaccharides include cellulose, quince seed, chondroitin sulfate, starch, galactan, dermatan sulfate, glycogen, gum arabic, heparan sulfate, hyaluronic acid, tragacanth gum, keratan sulfate, chondroitin, xanthan gum, mucoitin sulfate, guar gum, dextran, kerato sulfate, locust bean gum, succinoglucan, caronin acid, and the like.

[0053] In addition, for example, glyceryl solid, tetrahydrofurfuryl alcohol, POE-tetrahydrofurfuryl alcohol, POP-butyl ether, POP·POE-butyl ether, tripolyoxypropylene glycerin ether, POP-glycerin ether, POP-glycerin ether phosphate, POP·POE-pentaerythritol ether, polyglycerin, etc. can also be used. Also, polyols such as polyoxyethylene methyl glucoside (glucam E-10) and polyoxypropylene methyl glucoside (glucam P-10) can also be used. Here, POP means a polyoxypropylene group.

[0054] From the viewpoint of emulsion stability and the like, the content of the (d) water-soluble solvent in the oil-in-water type emulsion composition is preferably 20% by mass or more, more preferably 25% by mass or more, based on the total amount of the oil-in-water type emulsion composition. In the present invention, it is possible to maintain the stability of the preparation without blending a higher alcohol. However, when blending a higher alcohol, from the viewpoint of obtaining a fresh feeling in use, it is preferably 2.0% by mass or less, more preferably 1.5% by mass or less, and still more preferably 1.0% by mass or less, based on the total amount of the oil-in-water type emulsion composition.

[0055] <Other components> The oil-in-water type emulsion composition of the present invention includes, as other components, inorganic powder, anionic surfactant, amphoteric surfactant, humectant, water-soluble polymer, sequestering agent, amino acid, organic amine, pH adjuster, antioxidant, and antioxidant aid.

[0056] (Anionic surfactant) In the present invention, it is possible to maintain the stability of the preparation without blending an anionic surfactant, but an anionic surfactant may be contained as long as the mechanism and effects of the present invention are not impaired. However, in order to maintain water resistance, the blending amount of the anionic surfactant is preferably 5% by mass or less, more preferably 4.0% by mass or less, still more preferably 4% by mass or less, even more preferably 3.0% by mass or less, particularly preferably 2.0% by mass or less, and most preferably 1.0% by mass or less with respect to the total amount of the oil-in-water type emulsified composition.

[0057] Examples of such anionic surfactants include: fatty acid soaps (e.g., sodium laurate, sodium palmitate, etc.); higher alkyl sulfate salts (e.g., sodium lauryl sulfate, potassium lauryl sulfate, etc.); alkyl ether sulfate salts (e.g., triethanolamine POE-lauryl ether sulfate, sodium POE-lauryl ether sulfate, sodium laureth sulfate, etc.); N-acyl sarcosinic acids (e.g., sodium lauroyl sarcosinate, etc.); higher fatty acid amide sulfonates (e.g., sodium N-stearoyl-N-methyl taurate, sodium N-myristoyl-N-methyl taurate, sodium cocoyl methyl taurate, sodium lauryl methyl tauride, etc.); phosphate ester salts (sodium POE-oleyl ether phosphate, POE-stearyl ether phosphate, etc.); sulfosuccinates (e.g., sodium di-2-ethylhexyl sulfosuccinate, sodium monolauroyl monoethanolamide polyoxyethylene sulfosuccinate, sodium lauryl polypropylene glycol sulfosuccinate, etc.); alkylbenzene sulfonates (e.g., sodium linear dodecylbenzene sulfonate, triethanolamine linear dodecylbenzene sulfonate, linear dodecylbenzene sulfonic acid, etc.); higher fatty acid ester sulfate salts (e.g., sodium hardened coconut oil fatty acid glycerol sulfate, etc.); N-acyl glutamates (e.g., monosodium N-lauroyl glutamate, disodium N-stearoyl glutamate, monosodium N-myristoyl-L-glutamate, etc.); sulfated oils (e.g., tall oil, etc.); POE-alkyl ether carboxylic acids; POE-alkyl allyl ether carboxylates; α-olefin sulfonates; higher fatty acid ester sulfonates; secondary alcohol sulfate salts; higher fatty acid alkanolamide sulfate salts; sodium lauroyl monoethanolamide succinate; N-palmitoyl aspartic acid ditriethanolamine; sodium caseinate, etc.

[0058] (Amphoteric surfactant) Examples of amphoteric surfactants include imidazoline-based amphoteric surfactants (e.g., 2-undecyl-N,N,N-(hydroxyethyl carboxymethyl)-2-imidazoline sodium, 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy 2 sodium salt, etc.); betaine-based surfactants (e.g., 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, lauryldimethylaminoacetic acid betaine, alkyl betaine, amide betaine, sulfobetaine, etc.).

[0059] (Humectant) Examples of humectants include xylitol, sorbitol, maltitol, trehalose, erythritol, chondroitin sulfate, hyaluronic acid, mucin sulfate, calonic acid, fish collagen, phytosteryl-12-hydroxystearate, sodium lactate, dl-pyrrolidone carboxylate, diglycerin (EO) PO adduct, Rosa multiflora Thunb. extract, Viola arvensis Murray extract, Prunus mume Sieb. et Zucc. extract, etc.

[0060] (Water-soluble polymer) Examples of natural water-soluble polymers include plant-based polymers (e.g., gum arabic, tragacanth gum, galactan, guar gum, carob gum, karaya gum, carrageenan, pectin, agar, quince seed, algal colloid (Laminaria japonica Aresch. extract), starch (rice, corn, potato, wheat)); microorganism-based polymers (e.g., xanthan gum, dextran, succinoglucan, pullulan, etc.).

[0061] Examples of semi-synthetic water-soluble polymers include starch-based polymers (e.g., carboxymethyl starch, methyl hydroxypropyl starch, etc.); cellulose-based polymers (methyl cellulose, ethyl cellulose, methyl hydroxypropyl cellulose, hydroxyethyl cellulose, sodium cellulose sulfate, hydroxypropyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, crystalline cellulose, cellulose powder, etc.); alginic acid-based polymers (e.g., sodium alginate, propylene glycol alginate, etc.).

[0062] Examples of synthetic water-soluble polymers include vinyl-based polymers (e.g., polyvinyl alcohol, polyvinyl pyrrolidone, carboxyvinyl polymer, etc.); polyoxyethylene-based polymers (e.g., polyethylene glycol 20000, 40000, 60000, 1000000 polyoxyethylene polyoxypropylene copolymer, etc.); acrylic-based polymers (e.g., sodium polyacrylate, polyethyl acrylate, polyacrylamide, etc.); cationic polymers, etc.

[0063] (Metal ion sequestering agent) Examples of metal ion sequestering agents include 1-hydroxyethane-1,1-diphosphonic acid, tetrasodium 1-hydroxyethane-1,1-diphosphonate, disodium edetate, trisodium edetate, tetrasodium edetate, sodium citrate, sodium polyphosphate, sodium metaphosphate, gluconic acid, phosphoric acid, citric acid, ascorbic acid, succinic acid, edetic acid, trisodium ethylenediamine hydroxyethyl triacetate, etc.

[0064] (Amino acid) Examples of amino acids include neutral amino acids (e.g., threonine, cysteine, etc.); basic amino acids (e.g., hydroxylysine, arginine, etc.). Examples of amino acid derivatives include sodium acyl sarcosinate (sodium lauroyl sarcosinate), acyl glutamate salts, acyl taurine salts, sodium acyl β-alanine, glutathione, pyrrolidone carboxylic acid, trimethylglycine, etc.

[0065] (Organic amine) Examples of organic amines include monoethanolamine, diethanolamine, triethanolamine, morpholine, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-methyl-1-propanol, etc.

[0066] (pH adjuster) Examples of pH adjusters include buffers such as lactic acid - sodium lactate, citric acid - sodium citrate, succinic acid - sodium succinate, etc.

[0067] (Antioxidant) Examples of antioxidants include δ-tocopherol, dibutylhydroxytoluene, butylhydroxyanisole, gallic acid esters, etc.

[0068] (Antioxidant aid) Examples of antioxidant aids include phosphoric acid, citric acid, ascorbic acid, maleic acid, malonic acid, succinic acid, fumaric acid, cephalin, hexametaphosphate, phytic acid, ethylenediaminetetraacetic acid, etc.

[0069] Examples of other components other than those described above include preservatives (ethyl paraben, butyl paraben, phenoxyethanol, etc.); water-soluble whitening agents (e.g., arbutin, tranexamic acid, potassium 4-methoxysalicylate, ellagic acid, ascorbic acid, ascorbic acid glucoside, ascorbic acid phosphate magnesium and other ascorbic acid derivatives, etc.); activators (e.g., royal jelly, photosensitizer, cholesterol derivatives, etc.); blood circulation promoters (e.g., valeryl amide nonylate, benzyl nicotinate, β-butoxyethyl nicotinate, capsaicin, gingerol, cantharis tincture, ichthyol, tannic acid, inositol hexanicotinate, cyclandelate, cinnarizine, tolazoline, acetylcholine, verapamil, cephalanthin, etc.); anti-seborrheic agents (e.g., sulfur, thiolanthrene, etc.); anti-inflammatory agents (e.g., glycyrrhizinate, salicylic acid derivatives, hinokitiol, zinc oxide, allantoin, thiotaurine, hypotaurine, etc.), vitamin B6 tripalmitate, vitamin B6 dioctanoate, vitamin B2, vitamin B2 derivatives, vitamin B12, vitamin B15, vitamin B15 derivatives, etc.

[0070] (Total HLB of surfactants to be formulated) In the oil-in-water emulsion composition of the present invention, the total HLB of the surfactants to be formulated is 12 or less. Here, the "surfactants to be formulated" means all surfactants including anionic surfactants and amphoteric surfactants, etc. formulated in the oil-in-water emulsion composition of the present invention, in addition to (a) cationized polysaccharides and (b) nonionic surfactants. Also, "HLB (Hydrophilic-Lypophilic Balance)" is a value generally indicating the affinity of a surfactant for water and oil, and is a parameter known as the hydrophilic-lipophilic balance, and can be easily obtained by a known calculation method such as the Griffin method. Furthermore, the "total HLB" is the weighted average of the HLB values of each surfactant based on its blending ratio, and can be obtained by the following formula (1). Total HLB = Σ(HLBx × Wx) / ΣWx ···(1) HLBx represents the HLB value of each surfactant, and Wx represents the blending amount (g) of surfactant X having the value of HLBx.

[0071] By adjusting the total HLB of the blended surfactants to 12 or less, it is possible to suppress the phenomenon that the formulation is re-emulsified and flows away by sweat or water after the formulation is applied. The total HLB of the surfactants is preferably 11 or less, more preferably 10 or less. Further, in order to maintain the stability of the formulation, the total HLB of the surfactants is preferably 6 or more, more preferably 6.5 or more, and even more preferably 7.0 or more.

[0072] The oil-in-water type emulsion composition of the present invention can be prepared according to a method commonly used for oil-in-water type emulsion compositions. That is, it can be prepared by separately mixing the aqueous phase component and the oil phase component, and adding the oil phase component while stirring the aqueous phase component for emulsification.

[0073] Since the oil-in-water type emulsion composition of the present invention has a good feeling of use in terms of elongation, water resistance, and ease of washing, it can be used, for example, in lotions, emulsions, creams, beauty essences, foundations, makeup bases, concealers, sunscreen cosmetics, etc.

Examples

[0074] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In addition, the blending amounts in the following examples and the like indicate mass% unless otherwise specified.

[0075] [Examples 1 to 9, Comparative Examples 1 to 5] Among the components listed in Table 1, the aqueous components were thoroughly mixed with a disperser. To this, the separately mixed oily components were added and stirred to prepare an oil-in-water type emulsion composition. The units of the numerical values in the table are mass%.

[0076] [Evaluation] The following evaluations were performed on the above examples and comparative examples. The evaluation results are shown in Table 1.

[0077] <Formulation state> Separation and aggregation in each cosmetic were visually and tactilely confirmed and evaluated based on the following evaluation criteria. A was set as the practical level. (Evaluation criteria) A: Uniform and no aggregation C: Separation or aggregation occurred

[0078] <Evaluation of the feeling of use after application: Good elongation> Each cosmetic was applied to the skin of 10 panelists at 2 mg / cm 2 and the elongation of the cosmetic was scored according to the following evaluation criteria. (Score criteria) 3: Feels good elongation 2: Neither can be said 1: Feels poor elongation Also, the average value of 10 panelists was calculated and the feeling of use was evaluated based on the following comprehensive evaluation criteria. The evaluations of "AA" and "A" were judged as the practical level. (Comprehensive evaluation criteria) AA: The average value is 2.8 or more A: The average value is 2.5 or more and less than 2.8 B: The average value is 2.0 or more and less than 2.5 C: The average value is less than 2.0 -: Evaluation not implemented

[0079] <Water resistance> Each cosmetic was applied to the skin of 10 panelists at 2 mg / cm 2 and dried for 10 minutes. Then, the applied part was exposed to running water for 1 minute, and the remaining state of the cosmetic was visually and tactilely confirmed compared with before running water (after drying), and scored according to the following evaluation criteria. (Score criteria) 3: Compared with the state after application, it remains almost the same after running water 2: Compared with the state after application, it has slightly fallen but remains after running water 1: Compared with the state after application, it almost does not remain after running water Also, the average value of 10 panelists was calculated, and the usability was evaluated based on the following comprehensive evaluation criteria. The evaluations of "AA" and "A" were judged to be at the practical level. (Comprehensive Evaluation Criteria) AA: The average value is 2.8 or more. A: The average value is 2.5 or more and less than 2.8. B: The average value is 2.0 or more and less than 2.5. C: The average value is less than 2.0. -: Evaluation not implemented.

[0080] <Ease of Cleaning> Each cosmetic was applied to the skin of 10 panelists at 2 mg / cm 2 and dried for 10 minutes. Then, body soap (product name "Kuyura", manufactured by Fine Day Co., Ltd.) was applied and rubbed by hand in a circular motion 50 times, and then rinsed off with tap water. Compared with the state before applying the body soap (after drying), the remaining condition of the cosmetic was confirmed visually and by touch, and scored according to the following criteria. (Scoring Criteria) 3: Comparing the state after washing with that after application, almost none remains. 2: Comparing the state after with that after application, a little remains. 1: Comparing the state after washing with that after application, it remains almost unchanged. Also, the average value of 10 panelists was calculated, and the usability was evaluated based on the following comprehensive evaluation criteria. The evaluations of "AA" and "A" were judged to be at the practical level. (Comprehensive Evaluation Criteria) AA: The average value is 2.8 or more. A: The average value is 2.5 or more and less than 2.8. B: The average value is 2.0 or more and less than 2.5. C: The average value is less than 2.0. -: Evaluation not implemented.

[0081]

Table 1

[0082] As shown in Table 1, Examples in which (a) the cationized polysaccharide is in the continuous phase (aqueous phase), (b) a nonionic surfactant is contained, and the total HLB of the surfactants to be formulated is 12 or less are found to be excellent in terms of good elongation in use, water resistance, and ease of washing. Further, as shown in Example 8 of the present invention, it is possible to stably incorporate a large amount of hydrophobic powder into the oil-in-water type emulsion composition of the present invention.

[0083] Examples of the formulation of the oil-in-water type emulsion composition of the present invention are given below, but the present invention is not limited thereto. The oil-in-water type emulsion compositions obtained by the following formulation examples were all excellent in terms of good elongation in use, water resistance, and ease of washing.

[0084] [Formulation Example 1] Foundation (1) Purified water 43.46 (mass%) (2) Dipropylene glycol 7.00 (3) BG 3.00 (4) Guar hydroxypropyltrimonium chloride (cationized guar gum) 0.40 (5) Pentylene glycol 0.50 (6) Phenoxyethanol 0.30 (7) Polyglyceryl-10 laurate 0.50 (8) Polyglyceryl-10 trioleate 0.60 (9) Sorbitan sesquisisostearate 0.30 (10) Diisostearyl malate 3.00 (11) Isododecane 10.00 (12) Isopropyl myristate 5.00 (13) Isononyl isononanoate 5.00 (14) (C15-19) alkane 5.00 (15) Hydrophobically treated pigment grade titanium oxide 6.00 (16) Hydrophobically treated iron oxide (red) 1.48 (17) Hydrophobically treated iron oxide (yellow) 4.40 (18) Hydrophobically treated iron oxide (black) 0.06 (19) Silica 3.00 (20) Octenyl succinic acid starch Al 1.00

[0085] [Formulation Example 2] Foundation (1) Purified water 46.06 (mass%) (2) Dipropylene glycol 10.00 (3) Guar hydroxypropyltrimonium chloride (cationized guar gum) 0.40 (4) Pentylene glycol 0.50 (5) Phenoxyethanol 0.30 (6) Polyglyceryl-10 trioleate 1.50 (7) Sorbitan sesquioleate 0.30 (8) Dimethicone 3.00 (9) Cyclopentasiloxane 10.00 (10) Caprylyl methicone 3.00 (11) Diphenylsiloxy phenyl trimethicone 2.00 (12) Hydrophobically treated pigment grade titanium dioxide 6.00 (13) Hydrophobically treated iron oxide (red) 1.48 (14) Hydrophobically treated iron oxide (yellow) 4.40 (15) Hydrophobically treated iron oxide (black) 0.06 (16) Trimethylsiloxysilicic acid 5.00 (17) Polymethylsilsesquioxane 3.00 (18) (Vinyl dimethicone / methicone silsesquioxane) copolymer 1.00 (19) (HDI / trimethylolhexyl lactone) copolymer 2.00

[0086] [Formulation Example 3] Sunscreen (1) Purified water 46.40 (mass%) (2) Dipropylene glycol 10.00 (3) Guar hydroxypropyltrimonium chloride (cationized guar gum) 0.40 (4) Pentylene glycol 0.50 (5) Phenoxyethanol 0.30 (6) Polysorbate 80 0.65 (7) Sorbitan sesquioleate 0.75 (8) Diisostearyl malate 2.00 (9) PG dicaprate 5.00 (10) Alkyl (C12 - 15) benzoate 5.00 (11) Triethoxycaprylylsilane zinc oxide 5.00 (12) Triethoxycaprylylsilane titanium dioxide 1.50 (13) Ethylhexyl methoxycinnamate 7.50 (14) Bis - ethylhexyloxyphenol methoxyphenyltriazine 1.00 (15) Octocrylene 3.00 (16) Ethylhexyl salicylate 3.00 (17) Homosalate 5.00 (18) Polymethylsilsesquioxane 3.00

[0087] [Formulation Example 4] Non - chemical sunscreen (1) Purified water 43.90 (mass%) (2) Dipropylene glycol 10.00 (3) Guar hydroxypropyltrimonium chloride (cationized guar gum) 0.40 (4) Pentylene glycol 0.50 (5) Phenoxyethanol 0.30 (6) Polyglyceryl - 10 laurate 0.50 (7) Polyglyceryl - 10 trioleate 0.60 (8) Sorbitan sesquioleate 0.30 (9) Tricaprylyl / capryl glycerol 3.00 (10) Diisostearyl malate 1.50 (11) Dimethicone 3.00 (12) (C15-19) Alkane 15.00 (13) Sugar Squalane 3.00 (14) Triethoxycaprylylsilane Zinc Oxide 10.00 (15) Triethoxycaprylylsilane Titanium Oxide 3.00 (16) Silica 3.00 (17) Octenylsuccinic Starch Al 2.00

[0088] [Formulation Example 5] Makeup Base (1) Purified Water 58.40 (mass%) (2) Dipropylene Glycol 10.00 (3) Guar Hydroxypropyltrimonium Chloride (Cationized Guar Gum) 0.40 (4) Pentylene Glycol 0.50 (5) Phenoxyethanol 0.30 (6) Polysorbate 80 0.65 (7) Sesquiisostearic Acid Sorbitan 0.75 (8) Dimethicone 15.00 (9) Diphenylsiloxyphenyltrimethicone 2.00 (10) Isopropyl Myristate 1.00 (11) Trimethylsiloxysilicic Acid 3.00 (12) Octenylsuccinic Starch Al 3.00 (13) (Vinyldimethylsilicone / Methicone Silsesquioxane) Crosspolymer 5.00

[0089] [Formulation Example 6] Emulsion (1) Purified Water 67.30 (mass%) (2) BG 8.00 (3) Guar Hydroxypropyltrimonium Chloride (Cationized Guar Gum) 0.40 (4) Pentylene Glycol 1.00 (5) Phenoxyethanol 0.40 (6) Glycerin 3.00 (7) Diglycerin 1.00 (8) PEG - 1000 3.00 (9) Polyglyceryl - 10 Laurate 0.50 (10) Polysorbate 80 0.65 (11) Sorbitan Sesquioleate 0.75 (12) Ethylhexyl Palmitate 3.00 (13) Sugar Squalane 3.00 (14) Starch Octenylsuccinate Al 3.00 (15) (Vinyl Dimethicone / Methicone Silsesquioxane) Crosspolymer 5.00

[0090] [Formulation Example 7] Mist (1) Purified Water 71.00 (mass%) (2) BG 8.00 (3) Xanthan Hydroxypropyltrimonium Chloride (Cationized Xanthan Gum) 0.20 (4) Pentylene Glycol 1.00 (5) Phenoxyethanol 0.40 (6) PEG - 1000 3.00 (7) Polysorbate 80 0.65 (8) Sorbitan Sesquioleate 0.75 (9) Dimethicone 5.00 (10) Trimethylsiloxysilicate 5.00 (11) Polymethylsilsesquioxane 5.00

[0091] As described above, the preferred embodiments of the present invention have been described in detail. However, the present invention is not limited to the above-described embodiments, and various modifications and changes can be made within the scope of the gist of the present invention described in the claims.

Claims

1. An oil-in-water type emulsion composition having (a) a cationized polysaccharide in the continuous phase and containing (b) a nonionic surfactant, wherein the total HLB of the surfactants to be blended is 12 or less.

2. The oil-in-water type emulsion composition according to Claim 1, wherein the (a) cationized polysaccharide is at least one selected from cationized cellulose, cationized fenugreek gum, cationized guar gum, cationized tara gum, cationized locust bean gum, and cationized xanthan gum.

3. The oil-in-water type emulsion composition according to Claim 1, wherein the total HLB of the surfactants to be blended is 6 or more.

4. The oil-in-water type emulsion composition according to Claim 1, wherein the blending amount of the (a) cationized polysaccharide is 0.1% by mass or more and 2.0% by mass or less based on the total amount of the oil-in-water type emulsion composition.

5. The oil-in-water type emulsion composition according to Claim 1, containing (c) an oily component, wherein the blending amount of the (c) oily component is 10% by mass or more based on the total amount of the oil-in-water type emulsion composition.

6. The oil-in-water type emulsion composition according to Claim 1, wherein the blending amount of the (b) nonionic surfactant is 0.1% by mass or more and 10.0% by mass or less based on the total amount of the oil-in-water type emulsion composition.

7. The oil-in-water type emulsion composition according to Claim 1, containing a hydrophobic powder.

8. The oil-in-water type emulsion composition according to Claim 7, wherein the hydrophobic powder is at least one selected from hydrophobic treated titanium oxide, hydrophobic treated zinc oxide, hydrophobic treated cerium oxide, and hydrophobic treated pigments.

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