JP5649051B2 - Fine particle metal oxide dispersion composition - Google Patents

Description

  The present invention relates to a fine particle metal oxide dispersion composition in which a fine metal oxide is dispersed in a non-silicone-based oil. More specifically, the present invention is excellent in dispersibility and stability over time, has no stickiness and spreads well. The present invention relates to a fine particle metal oxide dispersion composition having usability.

  Organic UV absorbers and inorganic UV scattering agents are blended in cosmetics having UV protection effects. As the inorganic ultraviolet scattering agent, metal oxides such as titanium oxide and zinc oxide are used, but the refractive index is high, and the skin becomes white after application, which is not preferable as a cosmetic. In order to improve the whiteness after coating, a technique for improving the visible light transmittance by making metal oxide fine particles has been reported (for example, see Patent Document 1). Furthermore, in order to improve the ultraviolet protective effect and visible light transmittance of the fine particle metal oxide, it is necessary to uniformly disperse the fine particle metal oxide. Therefore, a specific organopolysiloxane copolymer is used as a dispersant. (For example, refer to Patent Document 2) and polyglycerin-modified silicone (for example, refer to Patent Document 3). Also, decamethylcyclopentasiloxane is used as a dispersion medium for improving dispersibility and improving usability. Volatile silicone oils such as are used. Studies using oils other than volatile silicone oils such as decamethylcyclopentasiloxane as dispersion media include ricinoleic acid and hydroxystearic acid as dispersants, and paraffin oil and triglyceride esters as dispersion media (for example, patents) There are studies using polyhydroxystearic acid as a dispersant and ester oil or triglyceride ester as a dispersion medium (see, for example, Patent Document 5).

JP-A-9-175721 JP-A-11-263708 JP 2004-169015 A JP-A-6-39272 Special table 2009-508920

  However, as disclosed in Patent Document 1, if the metal oxide is made into fine particles in order to improve the transparency, the surface area of the powder increases, the cohesive force becomes strong, and it becomes difficult to disperse. The silicone-based dispersant used in Patent Documents 2 and 3 is a low HLB surfactant in which a hydrophilic portion is introduced into a silicone chain, and is an oil-in-water emulsion cosmetic or water-in-oil emulsion that contains water. In cosmetics, the silicone dispersant may be oriented at the interface between oil and water, and the dispersibility of the particulate metal oxide may be reduced. Further, the silicone-based dispersants used in Patent Documents 2 and 3 are designed to have a large molecular weight for stabilizing the dispersion, and have problems in usability such as stickiness and poor spread. When ricinoleic acid or hydroxystearic acid is used as a non-silicone dispersant as in Patent Document 4, or when polyhydroxystearic acid is used as a dispersant as in Patent Document 5, a large amount of the dispersant is used. It was necessary to blend, and it became sticky usability, spread poorly, and stability over time was not sufficient. As described above, it has not been sufficient to study a fine particle metal oxide dispersion composition that is excellent in dispersibility and stability over time, has no stickiness, and has good usability of spreading.

  In such a situation, the present inventor has conducted extensive research to solve the above problems, and as a result, by dispersing the fine particle metal oxide surface-treated with alkyl titanate in a non-silicone oil agent with polyhydroxystearic acid, The inventors have found that a fine particle metal oxide dispersion composition having excellent dispersibility and stability over time, no stickiness, and good spreading can be obtained, and the present invention has been completed.

That is, the present invention includes the following components (a) to (c):
Component (a) Fine particle metal oxide component surface-treated with alkyl titanate (b) Polyhydroxystearic acid component (c) Non-silicone oil agent It is.

  Provided is a fine particle metal oxide dispersion composition wherein the surface treatment amount of the component (a) with an alkyl titanate is surface treatment agent / fine particle metal oxide = 0.02 to 0.25 in terms of mass ratio. Is.

  The particulate metal oxide dispersion composition is characterized in that the particulate metal oxide of the component (a) is further treated with a (dimethicone / methicone) copolymer.

  The content of the component (a) is 30 to 70% by mass, and a fine particle metal oxide dispersion composition is provided.

  Provided is a fine particle metal oxide dispersion composition in which the mass ratio (b) / (a) of the component (a) to the component (b) is 0.01 to 0.5.

  The component (c) non-silicone oil agent is a hydrocarbon oil or an ester oil, and provides a fine particle metal oxide dispersion composition.

  A cosmetic comprising the fine particle metal oxide dispersion composition is provided.

  The fine particle metal oxide dispersion composition of the present invention has excellent dispersibility and stability over time, has no stickiness, and has good usability of spreading.

  Hereinafter, the present invention will be described in detail.

  Examples of the particulate metal oxide constituting the component (a) used in the present invention include zinc oxide, titanium oxide, cerium oxide, zirconium oxide, iron oxide and the like, and these may be used alone or in combination of two or more. it can. The particle size, shape, etc. of these metal oxides are not particularly limited, but it is preferable to use a metal oxide having an average particle size of 1 to 100 nm, which has a high UV protection effect, so that fine particle metal oxide having excellent stability over time A product dispersion composition can be obtained. Here, the average particle diameter can be determined, for example, by measurement using an image analyzer (Luzex IIIU, manufactured by Nicoles).

  Examples of the alkyl titanate constituting the component (a) used in the present invention include long-chain carboxylic acid type, pyrophosphoric acid type, phosphorous acid type, amino acid type alkyl titanate and the like. More preferred are alkyl titanates having an alkyl group having 8 to 24 carbon atoms, and examples thereof include compounds represented by the following general formula (1).

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

  Specifically, the alkyl titanate is, as a long chain carboxylic acid type alkyl titanate, isopropyl triisostearoyl titanate, isopropyl trioctanoyl titanate, isopropyl dimethacrylisostearoyl titanate, isopropyl isostearoyl diacryl titanate, diisostearoyl ethylene. Titanates and the like, and as pyrophosphate type alkyl titanates, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis ( Ditridecyl phosphite) titanate and the like, and phosphite-type alkyl titanates include isopropyl tri (dioctyl pyrophosphate) titanate. And bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate and the like, and amino acid type alkyl titanate includes isopropyl tri (N-amidoethyl / aminoethyl) titanate and the like. Or it can use 2 or more types.

  Among these alkyl titanates, it is preferable to select isopropyl triisostearoyl titanate represented by p = 17 in the general formula (1) because the spread is good.

  In the present invention, the method of coating the surface of the fine particle metal oxide with an alkyl titanate surface treatment agent is not particularly limited, and a generally known treatment method is used. Specifically, a method of directly mixing an alkyl titanate and a particulate metal oxide, a dry coating method of directly mixing with a particulate metal oxide and heating to coat, ethanol, isopropyl alcohol, n-hexane, methylene chloride, benzene, Dissolve or disperse alkyl titanate in a solvent such as toluene, add fine particle metal oxide to this solution or dispersion, and after mixing, remove the solvent by drying, heat, pulverize, etc. Examples thereof include a vapor phase coating method and a mechanochemical method in which a dispersed alkyl titanate is spray-coated on a powder in a fluidized bed.

  The component (b) polyhydroxystearic acid used in the present invention is used to disperse the component (a). The hydroxyl group of hydroxystearic acid is preferably at position 12, and the degree of polymerization of hydroxystearic acid is 3-12. The degree of polymerization is more preferably 4-8. As a commercially available product, ARLACEL P-100 (manufactured by Unikema) can be mentioned.

The non-silicone oil agent of component (c) used in the present invention is a medium in which component (a) is dispersed, and is not particularly limited as long as it is an oil agent having no polysiloxane skeleton, such as animal oil, vegetable oil, and synthetic oil. Regardless of the origin and properties of solid oil, semi-solid oil, liquid oil, volatile oil, etc., liquid oil that is liquid at normal temperature (15 ° C. to 25 ° C.) is preferred from the viewpoint of dispersibility of component (a). . For example, hydrocarbons, fats and oils, hardened oils, ester oils, fluorine-based oil agents, lanolin derivatives and the like can be blended, and more specifically, liquid paraffin, light liquid isoparaffin, squalane, vegetable squalane, Hydrocarbons such as petroleum jelly, polyisobutylene and polybutene, oils and fats such as owl, olive oil, castor oil, mink oil, macadamian nut oil, camelia oil, rose pip oil and avocado oil, jojoba oil, cetyl 2-ethylhexanoate , Isononyl isononanoate, isopropyl myristate, isopropyl palmitate, octyldodecyl myristate, isotridecyl isononanoate, glyceryl tri-2-ethylhexanoate, propylene glycol dicaprate, neopentyl glycol dicaprate, polyglyceryl diisostearate Diglyceryl triisostearate, glyceryl tribethenate, hexa (hydroxystearic acid / stearic acid / rosin acid) dipentaerythrityl, diisostearyl malate, neopentyl glycol dioctanoate, cholesteryl isostearate, cholesteryl hydroxystearate, cholesteryl stearate, lanolin Esters such as fatty acid cholesteryl, oleic fatty acid phytosteryl, N-lauroyl-L-glutamate di (cholesteryl / behenyl / octyldodecyl), N-lauroyl-L-glutamate di (phytosteryl / 2-octyldodecyl), p-aminobenzoic acid Ethylhexyldimethyl, ethylhexyl salicylate, ethylhexyl methoxycinnamate, octocrylene, dineopentyl-4'-methoxybe Examples include oil-soluble ultraviolet absorbers such as zarmalonate, fluorine oils such as perfluorodecane, perfluorooctane, and perfluoropolyether, lanolin derivatives such as lanolin, lanolin acetate, lanolin fatty acid isopropyl, and lanolin alcohol. Of these, one or more of them can be used in combination. Of these, hydrocarbon oils and ester oils are preferred, and among them, hydrocarbon oils having a viscosity at 40 ° C. of 16 mm ² / s or less or ester oils having 27 or less carbon atoms are particularly preferred. It is possible to obtain a particulate metal oxide dispersion composition that has excellent stability over time, has no stickiness, and has good usability of spreading.

The surface treatment amount of the fine particle metal oxide of component (a) with alkyl titanate is preferably surface treatment agent / fine particle metal oxide = 0.02 to 0.25, more preferably 0.03 to 0.00. 18. Within this range, better usability can be given, and dispersibility and stability over time are also improved. When the surface treatment agent / particulate metal oxide is less than 0.02, it may be difficult to obtain the above effect sufficiently. When the component (a) is prepared in excess of 0.25, it does not become a uniform powder. It may not be preferable.
The surface treatment of the fine particle metal oxide may be only alkyl titanate, and may further be combined with a (dimethicone / methicone) copolymer or other surface treatment agent.

  When the component (a) used in the present invention is further surface-treated with a (dimethicone / methicone) copolymer, the oil absorption amount of the component (a) is decreased, and a larger amount of the component (a) can be added to the dispersion composition. . The (dimethicone / methicone) copolymer is a compound listed as (dimethicone / methicone) copolymer in INTERNATIONAL NOMENCLATURE of COSMETIC INGREDIENTS, and is a copolymer composed of dimethylsiloxane and methylhydrogensiloxane. Usually, it is used as a surface treatment agent for powders, and is widely used as a surface treatment agent that imparts water repellency to powders and hardly generates hydrogen over time. Specifically, the compound shown by following General formula (2) can be illustrated as a preferable compound.

(A and b are each a positive integer, a + b = 7 to 50, a: b = 1: 0.2 to 1: 4)

  The amount of surface treatment with the component (a) (dimethicone / methicone) copolymer is preferably (surface treatment agent) / (particulate metal oxide surface-treated with alkyl titanate) = 0.01 to 0.15 by mass ratio, More preferably, it is 0.03-0.08. Within this range, better usability can be given, and dispersibility and stability over time are also improved. If it is less than 0.01, it may be difficult to obtain the above effect sufficiently, and even if it exceeds 0.15, further improvement in the effect is difficult to obtain, and dispersibility and spread spread worsen. It may be difficult to obtain good usability.

  In this invention, it is preferable that content of a component (a) is 30-70 mass% (henceforth "%"), More preferably, it is 40-60%. Within this range, even better usability can be provided. If it is less than 30%, there is a case where a sufficient amount capable of exhibiting an ultraviolet ray preventing effect cannot be blended when blended into a cosmetic as a masterbatch (intermediate raw material). A large amount of component (b) may be required, and it may be difficult to obtain good usability.

  In the present invention, the mass ratio (b) / (a) of the component (a) and the component (b) is preferably 0.01 to 0.5, and more preferably 0.02 to 0.3. Within this range, better usability can be given, and dispersibility and stability over time are also improved. If it is less than 0.01, it may be impossible to disperse even to the primary particles, and even if it exceeds 0.5, it is difficult to obtain further improvement of the effect, and it may be difficult to obtain good usability. .

  Although the manufacturing method of the particulate metal oxide dispersion composition of the present invention is not particularly limited, for example, the component (b) and the component (c) are mixed, and the component (a) is added to this, and the uniform It can be obtained by dispersing. In this case, examples of the equipment for uniform dispersion include a disper mixer, a homomixer, a ball mill, a bead mill, and the like, and a wet grinding apparatus such as a ball mill and a bead mill using a medium is more preferable.

  In addition to the components described above, the fine particle metal oxide dispersion composition of the present invention includes powders and surfactants other than those described above, gelation in a quantitative and qualitative range depending on the purpose. Agents, antioxidants, preservatives, colorants, fragrances, cosmetic ingredients and the like can be blended.

  The fine particle metal oxide dispersion composition of the present invention can be used for pharmaceuticals, paints, inks, optical filters, papermaking papers, etc., in addition to cosmetic applications.

  The fine-particle metal oxide dispersion composition of the present invention is usually in addition to the fine-particle metal dispersion composition containing the components (a) to (c), as long as the effects of the present invention are not impaired. As components to be blended in the material, oily components other than components (a) to (c), powders such as inorganic pigments, organic pigments and extender pigments, surfactants and polyhydric alcohols, lower alcohols, water-soluble polymers, Aqueous components such as humectants, saccharides, ultraviolet absorbers, antioxidants, anti-fading agents, preservatives, medicinal components, stabilizers, pigments, fragrances, and the like can be appropriately blended for imparting various effects. . In addition to the fine particle metal dispersion composition containing the components (a) to (c), the components (a) to (c) may be changed to fine particle metal oxides as necessary, as long as the effects of the present invention are not impaired. You may mix | blend each component separately, without preparing in a dispersion composition.

  In addition to the fine particle metal dispersion composition containing components (a) to (c), the oily component blended in the cosmetic of the present invention includes low-polymerization degree dimethylpolysiloxane, high-polymerization degree dimethylpolysiloxane, methyl Examples include silicones such as phenyl polysiloxane, alkyl-modified polysiloxane, amino-modified polysiloxane, cross-linked organopolysiloxane, and fluorine-modified polysiloxane.

  In the cosmetic of the present invention, a powder component can be blended in addition to the fine particle metal dispersion composition containing the components (a) to (c). It is not particularly limited by the shape of plate, needle, etc., particle size such as fumes, fine particles, pigment grade, etc., particle structure such as porous, non-porous, etc., inorganic powders, glittering powders, organic Examples thereof include powders, pigment powders, metal powders, and composite powders. Specifically, white inorganic pigments such as titanium oxide, zinc oxide, cerium oxide, barium sulfate, iron oxide, carbon black, titanium / titanium oxide sintered product, chromium oxide, chromium hydroxide, bitumen, ultramarine blue, etc. Colored inorganic pigments, talc, muscovite, phlogopite, saucite, biotite, synthetic mica, sericite (sericite), synthetic sericite, silicon carbide, silicon dioxide, aluminum oxide, magnesium oxide, zirconium oxide, antimony oxide, Silica, aluminum silicate, magnesium aluminum silicate, calcium silicate, barium silicate, magnesium silicate, calcium carbonate, magnesium carbonate, hydroxyapatite, boron nitride, etc., white powder, kaolin, bentonite, smectite, hect Clay minerals such as light and montmorillonite, and it Organically modified products, titanium oxide coated mica, titanium oxide coated bismuth oxychloride, iron mica titanium, bituminized mica titanium, carmine treated mica titanium, bismuth oxychloride, fish scale foil, polyethylene terephthalate / aluminum / epoxy laminated powder, polyethylene terephthalate・ Polyolefin laminated film powder, polyethylene terephthalate / polymethyl methacrylate laminated film powder, glitter powder such as titanium oxide coated glass flakes, polyamide resin, polyethylene resin, polyacrylic resin, polyester resin, fluorine resin, cellulose Resin, polystyrene resin, copolymer resin such as styrene-acrylic copolymer resin, polypropylene polymer, organic polymer resin powder such as silicone resin, urethane resin, zinc stearate, N-acid Organic low molecular weight powder such as lysine, natural organic powder such as silk powder, cellulose powder, red 201, red 202, red 205, red 226, red 228, orange 203, orange 204, Organic pigment powders such as blue No. 404 and yellow No. 401, red No. 3, red No. 104, red No. 106, orange No. 205, yellow No. 4, yellow No. 5, green No. 3, blue No. 1, etc. zirconium, barium Or organic pigment powder such as aluminum lake or metal powder such as aluminum powder, gold powder, silver powder, fine titanium oxide coated mica titanium, fine zinc oxide coated mica titanium, barium sulfate coated mica titanium, titanium oxide containing silicon dioxide, oxidation Examples thereof include composite powders such as zinc-containing silicon dioxide. These powders may be used singly or in combination of two or more, and may be used in combination. These powders are one or two of fluorine compounds, silicone compounds, metal soaps, lecithins, hydrogenated lecithins, collagens, hydrocarbons, higher fatty acids, higher alcohols, esters, waxes, waxes, surfactants, etc. Surface treatment may be performed using the above.

  In the cosmetic of the present invention, a surfactant can be blended in addition to the fine particle metal dispersion composition containing the components (a) to (c). Examples include ionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. For example, nonionic surfactants include reoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene hydrogenated castor oil, hydrogenated castor oil, polyoxyethylene sorbitol tetra fatty acid ester, glycerin fatty acid ester, sorbitan fatty acid ester. , Polyglycerin fatty acid ester, sucrose fatty acid ester, alkyl polyglucoside, N-alkyldimethylamine oxide polyoxyethylene glyceryl fatty acid ester, polyoxyethylene cholesteryl ether, polyoxyethylene phytosteryl ether, polyoxyethylene alkyl ether, polyoxyethylene Polyoxypropylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyether-modified silicone, polyester Ether alkyl co-modified silicone, polyether-alkyl-Shirokishiechiru co-modified silicone, polyglycerin modified silicone, polyglycerin-alkyl co-modified silicone, and the like polyglycerol, alkyl Shirokishiechiru co-modified silicone. For example, anionic surfactants include sodium salts or triethanolamine salts of fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, sodium cocoyl methyl taurate, sodium lauroylmethyl taurate, sodium myristoyl methyl taurate, N-acylmethyl taurine salts such as sodium palmitoylmethyl taurate and sodium stearoylmethyl taurine, polyoxyethylene lauryl ether phosphate, polyoxyethylene cetyl ether phosphate, polyoxyethylene oleyl ether phosphate, polyoxyethylene nonylphenyl ether phosphate, etc. And polyoxyethylene alkyl ether phosphate esters. Examples of cationic surfactants include stearyl trimethyl ammonium chloride, stearyl trimethyl ammonium bromide, behenyl trimethyl ammonium chloride, behenyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide, distearyl dimethyl ammonium chloride, odor Distearyldimethylammonium chloride, dibehenyldimethylammonium chloride, dibehenyldimethylammonium bromide, dicetyldimethylammonium chloride, dicetyldimethylammonium bromide, stearyldimethylbenzylammonium chloride, dilauryldimethylammonium chloride, dipolyoxyethylene chloride ( 15E.O.) Coconut oil alkylmethylammonium chloride, dipolyoxyethylene chloride (4E.O.) lauryl ester -Tetradimethylammonium chloride, amidopropyltrimethylammonium chloride, dicocoylethylhydroxyethylmethylammonium methylsulfate and the like. For example, amphoteric surfactants include phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidylglycerol, phosphatidylinositol, sphingophospholipid, soy lecithin, egg yolk lecithin, or hydrogenated products such as phospholipids and phospholipid / cholesterol composites. And phospholipid complexes such as phospholipid / phytosterol complex.

  In addition to the fine particle metal dispersion composition containing components (a) to (c), the cosmetic of the present invention can contain an aqueous component, and the aqueous component blended in the cosmetic can be water. Any soluble component may be used, for example, alcohols such as ethyl alcohol, glycols such as propylene glycol, 1,3-butylene glycol, dipropylene glycol, and polyethylene glycol, glycerol such as glycerin, diglycerin, and polyglycerin. , Plant extracts such as aloe vera, witch hazel, hamamelis, cucumber, lemon, lavender and rose.

  In the cosmetic of the present invention, a water-soluble polymer can be blended in addition to the fine particle metal dispersion composition containing the components (a) to (c). Natural products such as guar gum, sodium chondroitin sulfate, sodium hyaluronate, gum arabic, sodium alginate, carrageenan, semi-synthetic products such as methylcellulose, hydroxyethylcellulose, carboxymethylcellulose, carboxyvinyl polymer, alkyl-added carboxyvinyl polymer, Synthetic materials such as polyvinyl alcohol, polyvinyl pyrrolidone, and sodium polyacrylate, as well as proteins, mucopolysaccharides, collagen, elastin, keratin and the like.

  In addition to the fine particle metal dispersion composition containing components (a) to (c), an additive can be added to the cosmetic of the present invention. Examples of the additive added to the cosmetic include α- Antioxidants such as tocopherol and ascorbic acid, vitamins, anti-inflammatory agents, cosmetic ingredients such as herbal medicines, and preservatives such as paraoxybenzoic acid esters and phenoxyethanol.

  Although the manufacturing method of the cosmetics of this invention is not specifically limited, For example, what mixed the fine metal oxide containing component (a), component (b), and component (c), and arbitrary oil-based components Can be added to a uniformly mixed surfactant or aqueous component and emulsified, and then filled into a container or mold.

  The cosmetic of the present invention is not particularly limited, but examples of the shape include liquid, semi-solid, and solid. In addition, the dosage form and product form are not particularly limited, and can be a dosage form such as a water-in-oil type, an oil-in-water type, a water-dispersed type, a powder type, etc. Foam cream, cleansing, massage cream, pack, lotion, milky lotion, cream, serum, makeup base, sunscreen and other skin cosmetics, foundation, white powder, eye shadow, eyeliner, mascara, eyebrow, concealer, lipstick Examples of cosmetics for finishing hair such as lip balm, hair mist, shampoo, rinse, treatment, hair tonic, hair cream, pomade, tic, liquid hair styling, set lotion, hair spray, hair dye, etc. be able to. Among these, sunscreens, foundations, makeup bases and the like are cosmetics in which the effects of the present invention are easily exhibited.

  Next, the present invention will be described in more detail with reference to production examples and examples. The present invention is not limited at all by these.

Production Examples 1-13
Surface-treated fine particle metal oxides having the compositions shown in Tables 1 and 2 were prepared by the following production method.

(Note 1) MT-100SA (manufactured by Teica)
(Note 2) MZ-500 (manufactured by Teika)
(Note 3) KF-9901 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 4) KF-96 (100cs) (manufactured by Shin-Etsu Chemical)

(Production method)
100 parts of isopropyl alcohol and components 3 to 6 are mixed and mixed with components 1 and 2 in a Henschel mixer (Mitsui Mining Co., Ltd.). Thereafter, isopropyl alcohol was collected at 60 ° C. under reduced pressure and pulverized to obtain a surface-treated fine particle metal oxide.

Example 1 and Comparative Examples 1-6; Fine Particle Metal Oxide Dispersion Composition A fine particle metal oxide dispersion composition having the composition shown in Table 3 was prepared by the following production method. The stability of the product and the goodness of the spread were evaluated, and the results are also shown in Table 3.

(Production method)
All components 1 to 8 are mixed uniformly and dispersed for 5 hours at a beads filling rate of 60% and agitator rotation speed of 2000 rpm using a 3 mm zirconia bead in a bead mill (LMZ-0.6) manufactured by Ashizawa Corporation. To obtain a fine-particle metal oxide dispersion composition.

(Evaluation Method 1) Dispersibility If the dispersion of the powder is good, the viscosity of the fine particle metal oxide dispersion composition becomes low. Therefore, after the fine particle metal oxide dispersion composition is produced, it is stored in a 30 ° C. constant temperature bath for 1 day. After that, the viscosity of the dispersion composition was measured with a B-type viscometer, and the dispersibility was judged according to the following criteria.

(Evaluation criteria for dispersibility of fine metal oxide dispersion composition)
(Evaluation): (Judgment)
Viscosity value is 0 mPa · s or more and less than 2000 mPa · s;
Viscosity value is 2000 mPa · s or more and less than 6000 mPa · s;
Viscosity value is 6000 mPa · s or more and less than 14000 mPa · s;
Viscosity value is 14000 mPa · s or more; ×

(Evaluation Method 2) Stability over time If the stability of the fine particle metal oxide dispersion composition is good, the viscosity change of the fine particle metal oxide dispersion composition before and after the acceleration test shown below is small and the stability is poor. Increases the viscosity change before and after the acceleration test. The accelerated test here is to store in a constant temperature bath at 50 ° C. for 4 weeks. After manufacturing the dispersion composition, after storing it in a 30 ° C. constant temperature bath for 1 day, and after storing it in a 50 ° C. constant temperature bath for 4 weeks and after storing it in a 30 ° C. constant temperature bath for 1 day The measured viscosity values were compared and judged according to the following criteria.

(Evaluation criteria for stability of fine particle metal oxide dispersion over time)
(Evaluation): (Judgment)
Viscosity change is 0 mPa · s or more and less than ± 1000 mPa · s;
Viscosity change is ± 1000 mPa · s or more and less than ± 2000 mPa · s;
Viscosity change is ± 2000 mPa · s or more and less than ± 4000 mPa · s;
Viscosity change is ± 4000 mPa · s or more; ×

(Evaluation Method 3) Good Spreadability The fine particle metal oxide dispersion composition was tested for use by 20 panelists specializing in cosmetics evaluation. Ask each panel to use each sample, evaluate it in 6 grades according to the following absolute evaluation criteria, give a score, calculate the average value from the total scores of all the panel members of each sample, and according to the following 4 criteria Judged.

Absolute Evaluation Criteria (Score): (Evaluation)
6 points: Very good 5 points: Good 4 points: Slightly good 3 points: Normal 2 points: Slightly bad 1 point: Bad 4 grade criteria (judgment): (Average score)
◎: Over 5 points ○: Over 5 points and under 5 points △: Over 2 points over 3.5 points ×: Up to 2 points

  As shown in Table 3, the fine particle metal oxide dispersion composition of Example 1 in which the fine particle metal oxide surface-treated with isopropyl triisostearoyl titanate, polyhydroxy stearic acid, and liquid paraffin was blended was “dispersibility”. It was a fine particle metal oxide dispersion composition excellent in all items of “stability over time” and “goodness of spread”. On the other hand, Comparative Example 1 containing no polyhydroxystearic acid, Comparative Example 2 containing inulin stearate instead of polyhydroxystearic acid, Comparative Example 3 containing dextrin palmitate, Comparative Example containing sorbitan sesquiisostearate 4, the fine particle metal oxide dispersion composition of Comparative Example 5 in which an (acrylates / dimethicone) copolymer was blended and Comparative Example 6 in which a polyoxyethylene / methylpolysiloxane copolymer was blended had a “dispersibility” ”,“ Stability over time ”, and“ Excellent spread ”.

Examples 2 to 18 and Comparative Examples 7 to 12; Fine Particle Metal Oxide Dispersion Composition Fine particle metal oxide dispersion compositions having the compositions shown in Tables 4 to 7 were prepared by the same production method as described above. Evaluation was made on “dispersibility”, “stability over time”, and “goodness of spreading”, and the results are also shown in Tables 4 to 7.

As shown in Tables 4 to 7, the fine particle metal oxide dispersion compositions of Examples 1 to 16 in which the fine particle metal oxide surface-treated with isopropyl triisostearoyl titanate, polyhydroxystearic acid, and liquid paraffin were blended. It was a fine particle metal oxide dispersion composition excellent in all items of “dispersibility”, “stability over time”, and “goodness of spread”. On the other hand, instead of the particulate metal oxide surface-treated with isopropyl triisostearoyl titanate, Comparative Example 7 in which the particulate metal oxide surface-treated with (dimethicone / methicone) copolymer was blended, particulate metal oxide surface-treated with dimethylpolysiloxane Comparative Example 8 in which a product was blended, Comparative Example 9 in which a particulate metal oxide surface-treated with trimethylsiloxysilicic acid was blended, and Comparative Example 10 in which a particulate metal oxide not subjected to any surface treatment was blended were all examples. Compared to 1, it was inferior to the items of “dispersibility”, “stability over time”, and “goodness of spread”.
Further, the fine particle metal oxide dispersion composition of Example 17 in which cetyl octanoate was blended instead of liquid paraffin and Example 18 in which glyceryl trioctanoate was blended was also “dispersibility”, “stability over time”, “ It was an excellent fine particle metal oxide dispersion composition in all items of “goodness of spread”. On the other hand, Comparative Example 11 in which dimethylpolysiloxane was blended instead of liquid paraffin and Comparative Example 12 in which decamethylcyclopentasiloxane was blended had all of “dispersibility”, “stability over time”, and “goodness of spread”. The item was inferior.

Examples 19 to 21 and Comparative Examples 13 to 15: Water-in-oil emulsified cosmetics Water-in-oil emulsified cosmetics having the compositions shown in Table 8 were prepared by the following production method. The stability of the product and the “goodness of the cosmetics” were evaluated, and the results are also shown in Table 8.

(Production method)
What uniformly mixed component (10)-(14) was added to what mixed component (1)-(9) uniformly, it emulsified, and defoamed, and the water-in-oil emulsion cosmetic was obtained.

(Evaluation Method 4) Stability over time in cosmetics If the cosmetics have good stability, the change in viscosity of the cosmetics before and after the acceleration test shown below is small, and if the stability is poor, the viscosity changes before and after the acceleration test Becomes larger. The accelerated test here is to store in a constant temperature bath at 50 ° C. for 4 weeks. Viscosity value measured with a B-type viscometer after being stored in a 30 ° C constant temperature bath for 1 day after manufacturing the cosmetic, and measured after being stored in a 30 ° C constant temperature bath for 4 weeks after being stored in a 50 ° C constant temperature bath The viscosity values were compared and judged according to the following criteria.

(Evaluation criteria for stability over time in cosmetics)
(Evaluation): (Judgment)
Viscosity change is 0 mPa · s or more and less than ± 10000 mPa · s;
Viscosity change is ± 10000 mPa · s or more and less than ± 20000 mPa · s;
Viscosity change is ± 20000 mPa · s or more and less than ± 40000 mPa · s;
Viscosity change is ± 40000 mPa · s or more; ×

(Evaluation Method 5) Goodness of Spreading in Cosmetics The cosmetics were tested for use by 20 panelists specializing in cosmetics evaluation. Ask each panel to use each sample, evaluate it in 6 grades according to the following absolute evaluation criteria, give a score, calculate the average value from the total scores of all the panel members of each sample, and according to the following 4 criteria Judged.

Absolute Evaluation Criteria (Score): (Evaluation)
6 points: Very good 5 points: Good 4 points: Slightly good 3 points: Normal 2 points: Slightly bad 1 point: Bad 4 grade criteria (judgment): (Average score)
◎: Over 5 points ○: Over 5 points and under 5 points △: Over 2 points over 3.5 points ×: Up to 2 points

  As shown in Table 8, Example 19 in which a fine particle metal oxide surface-treated with isopropyl triisostearoyl titanate, a fine particle metal oxide dispersion composition containing polyhydroxystearic acid and liquid paraffin was blended, In all items of “stability over time” and “excellence in cosmetics”. Examples 20 and 21 in which a fine particle metal oxide surface-treated with isopropyl triisostearoyl titanate and a (dimethicone / methicone) copolymer, a fine particle metal oxide dispersion composition containing polyhydroxystearic acid and liquid paraffin were blended are also described in “Cosmetics”. It was excellent in all items of “stability over time in cosmetics” and “excellence in spreading in cosmetics”. Comparative Example 13, which does not contain polyhydroxystearic acid and contains a fine particle metal oxide dispersion composition composed only of liquid paraffin and a fine particle metal oxide surface-treated with isopropyl triisostearoyl titanate, is in a non-uniform emulsified state. Yes, it was inferior in all items of “stability over time in cosmetics” and “excellent spread in cosmetics”. Comparative Example 14 in which a particulate metal oxide dispersion composition containing particulate metal oxide, polyhydroxystearic acid and liquid paraffin, which had no surface treatment, was not fluid, and “stable over time in cosmetics” ”And“ goodness of cosmetics ”were inferior in all items. Comparative Example 15 in which a fine particle metal oxide dispersion composition containing silicone oil instead of liquid paraffin was blended was in a non-uniform emulsified state, and “Stability over time in cosmetics”, “Non-enhanced in cosmetics” It was inferior in all items of “goodness”.

Examples 22 to 24 and Comparative Examples 16 to 18; oil-in-water emulsified cosmetics Oil-in-water emulsified cosmetics having the composition shown in Table 9 were prepared by the following production method. “Stability” and “Goodness in cosmetics” were evaluated, and the results are also shown in Table 9.

(Production method)
What uniformly mixed component (9)-(15) was added to what mixed component (1)-(8) uniformly, and it emulsified, defoamed, and obtained the oil-in-water type emulsion cosmetic.

  As shown in Table 9, Example 22 in which a fine particle metal oxide surface-treated with isopropyl triisostearoyl titanate, a fine particle metal oxide dispersion composition containing polyhydroxystearic acid and liquid paraffin was blended, In all items of “stability over time” and “excellence in cosmetics”. Examples 23 and 24 in which a particulate metal oxide surface-treated with isopropyl triisostearoyl titanate and (dimethicone / methicone) copolymer and a particulate metal oxide dispersion composition containing polyhydroxystearic acid and liquid paraffin were formulated, It was excellent in all items of “stability over time in cosmetics” and “excellence in spreading in cosmetics”. Comparative Example 16 containing a particulate metal oxide dispersion composition containing only liquid paraffin and a particulate metal oxide surface-treated with isopropyl triisostearoyl titanate and containing no polyhydroxystearic acid was in a non-uniform emulsified state. Yes, it was inferior in all items of “stability over time in cosmetics” and “excellent spread in cosmetics”. Comparative Example 17 in which a fine particle metal oxide not subjected to surface treatment with isopropyl triisostearoyl titanate, a fine particle metal oxide dispersion composition containing polyhydroxystearic acid and liquid paraffin was blended was described as “Stability over time in cosmetics. It was inferior in "sex". Comparative Example 18, in which a fine particle metal oxide dispersion composition containing silicone oil instead of liquid paraffin was blended, was in a non-uniform emulsified state, and “Stability over time in cosmetics”, “Non-enhanced in cosmetics” It was inferior in all items of “goodness”.

Example 25: Water-in-oil type emulsion sunscreen cosmetic (component) (%)
1.2,4,6-tris [4- (2-ethylhexyloxycarbonyl)
Anilino] -1,3,5-triazine 1
2. Octyl methoxycinnamate 7
3. Isononyl isononanoate 5
4). Diglyceryl triisostearate 5
5. Partially cross-linked organopolysiloxane elastomer (Note 7) 5
6). Fine particle metal oxide dispersion composition of Example 10 10
7). Light liquid isoparaffin 15
8). PEG-30 dipolyhydroxystearic acid 8
9. Purified water balance 10. Glycerin 10
11. Sodium chloride 1
12 Preservative appropriate amount13. Perfume appropriate amount (Note 7): KSG43 (manufactured by Shin-Etsu Chemical Co., Ltd.)

(Production method)
A: Components 1 to 4 are heated to 90 ° C. and dissolved and mixed.
B: Components 5 to 8 and 13 are added to A and mixed.
C: Components 9 to 12 are dissolved.
D: C is added to B and emulsified.
E: Defoamed to obtain a water-in-oil emulsified sunscreen cosmetic.

  Example 25 was a water-in-oil emulsified sunscreen cosmetic with excellent stability over time and good usability.

Example 26: Water-in-oil type emulsified base (component) (%)
1. Dextrin palmitate 2
2. Titanium oxide 3
3. Fine zinc oxide 3
4). (Alkyl acrylate / dimethicone) copolymer (Note 8) 2
5. PEG-9 polydimethylsiloxyethyl dimethicone (Note 9) 1
6). Dimethyl distearyl ammonium hectorite 1
7). Decamethylcyclopentasiloxane 10
8). Diethylaminohydroxybenzoylhexyl benzoate 3
9. Fine particle metal oxide dispersion composition of Example 6 15
10. Decamethylcyclopentasiloxane 3
11. PEG-30 dipolyhydroxystearic acid 3
12 Polyglyceryl diisostearate 2
13. Purified water balance 14. Ethanol 5
15.1,2-Pentanediol 1
(Note 8): KP-540 (manufactured by Shin-Etsu Chemical)
(Note 9): KF-6028 (manufactured by Shin-Etsu Chemical)

(Production method)
A: Components 1 to 7 are heated to 90 ° C. and dispersed with a three-roller.
B: Components 8 to 12 are added to A, and the mixture is heated to 90 ° C. and dispersed.
C: Cool B to 45 ° C.
D: D is added to E: C where components 13 to 15 are mixed, and emulsified.
F: Defoamed to obtain a water-in-oil type emulsion base.

  Example 26 was a water-in-oil type emulsified base having excellent stability over time and good usability.

Example 27: Oil-in-water emulsified serum
(Ingredient) (%)
1. Propylene glycol dicaprate 3
2. Dimethylpolysiloxane (2cs) 5
3. Fine particle metal oxide dispersion composition of Example 6 20
4). Methyl trimethicone 5
5. Stearic acid 1.5
6). Cetanol 1.5
7). Glyceryl monostearate 1
8). Butylene glycol 10
9. Cetyl phosphate 1
10. Polyethylene glycol monostearate (55 EO) 0.5
11. Purified water balance 12. Xanthan gum 0.2
13. Ethanol 5
14.1,2-Pentanediol 1

(Production method)
A: Components 1 to 7 are heated to 75 ° C. and mixed.
B: Components 8 to 14 are heated to 75 ° C and mixed.
C: A is added to B and emulsified.
D: C is cooled to 30 ° C.
E: D was defoamed to obtain an oil-in-water emulsified cosmetic liquid.

  Example 27 was an oil-in-water emulsified cosmetic solution with excellent stability over time and good usability.

Example 28: Wood lacquer
(Ingredient) (%)
1. H1 / 4 nitrified cotton 7.5
2. Isopropyl alcohol 22.5
3. 3. Butyl acetate balance 4. Ethyl acetate 15
5. Butanol 10
6). Toluene 25
7). Particulate metal oxide dispersion composition of Example 1 3

(Production method)
Ingredients 1-7 were mixed at 25 ° C. to obtain a wood lacquer.

  Example 28 was a wood lacquer having excellent stability over time and good stretch.

Claims (5)

The following components (a) to (c):
Particulate metal oxide dispersion composition comprising (a) fine particle metal oxide surface-treated with alkyl titanate and (dimethicone / methicone) copolymer (b) polyhydroxystearic acid (c) non-silicone oil agent Because
The amount of surface treatment with the alkyl titanate of component (a) is surface treatment agent / particulate metal oxide = 0.02 to 0.25 in terms of mass ratio,
The amount of surface treatment with the component (a) (dimethicone / methicone) copolymer is (surface treatment agent) / (particulate metal oxide surface-treated with alkyl titanate) = 0.01 to 0.15 in mass ratio. Fine particle metal oxide dispersion composition. Particulate metal oxide dispersion composition according to claim 1, content, characterized in that 30 to 70% by weight of component (a). The fine particle metal oxide dispersion composition according to claim 1 or 2 , wherein the mass ratio (b) / (a) of the component (a) and the component (b) is 0.01 to 0.5. . The particulate metal oxide dispersion composition according to any one of claims 1 to 3 , wherein the non-silicone oil agent of component (c) is a hydrocarbon oil or an ester oil. A cosmetic comprising the fine-particle metal oxide dispersion composition according to any one of claims 1 to 4 .