JP5584005B2 - Iron oxide / organopolysiloxane hybrid powder, method for producing the same, and cosmetics containing the same - Google Patents

Description

  The present invention relates to an iron oxide / organopolysiloxane hybrid powder and a method for producing the same, and further relates to a cosmetic containing the powder.

  Various inorganic pigments are blended in cosmetics for the purpose of imparting chromaticity, covering properties, spreadability, adhesion and the like. Some inorganic pigments have low dispersibility in solvents and tend to aggregate, and such inorganic pigments are difficult to be stably blended in cosmetics. Moreover, when it mix | blends in cosmetics in large quantities with the shape and physical property, there exists a thing which is unpreferable on use feeling.

  For example, iron oxides such as yellow iron oxide, red iron oxide, and black iron oxide are highly cohesive and have low dispersibility in oils. Therefore, cosmetics containing these have poor storage stability or a uniform cosmetic film. It was difficult to get. In addition, iron oxide is difficult to obtain a smooth feeling of use, and furthermore, since it has a high solid surface activity, it promotes rancidity in oil-based cosmetics and promotes the oxidation of sebum on the skin. Had.

  In order to solve such problems, the surface of an inorganic pigment is modified by treating it with a hydrophobizing agent such as organopolysiloxane. However, a sufficient modification effect may not be obtained only by surface treatment.

  On the other hand, development of an organic-inorganic hybrid powder in which an organic substance is more uniformly fused with an inorganic pigment is also under development. For example, after seed particles are swollen with a swelling solvent containing a polymerizable metal alkoxide, An organic-inorganic hybrid powder obtained by polymerizing with an unsaturated double bond, and then hydrolyzing and condensing an alkoxy group of a metal alkoxide is disclosed (Patent Document 1). The applicant also hydrolyzes the metal alkoxide to form a sol, and a reactive organosiloxane is added to the sol to form a hybrid sol solution. The hybrid sol solution is then mixed with an aqueous ammonia solution and an organic solvent. There has already been proposed a metal oxide / organopolysiloxane hybrid powder obtained by dropping into a mixed solution (Patent Document 2).

  As described above, in the production of the organic-inorganic hybrid material, since the reactivity is high, it is general to employ a sol-gel reaction using a metal alkoxide as a starting material. However, if the production method of Patent Document 1 is applied to a hybrid powder of iron oxide, iron alkoxide is expensive, and therefore the cost becomes very high. Moreover, since iron alkoxide is instantly oxidized in the air, the yield is low, and there is a restriction that the reaction must be performed in an inert gas atmosphere in order to produce it stably. In the latter method of Patent Document 2, ammonia is used as a catalyst to hydrolyze the reactive organosiloxane after the metal alkoxide is hydrolyzed and to condense them, thereby generating odor. In some cases, it was problematic in terms of workability.

JP-A-7-265686 Japanese Patent No. 3843387

  Therefore, there is a need for a production method that can obtain a hybrid powder of iron oxide and organopolysiloxane at a low cost, stably and in a high yield, with no problem in workability, and the present invention provides such a production. It is an object to provide a method.

  As a result of intensive studies, the inventor of the present invention can use iron chloride as a starting material, and can react with an organopolysiloxane having a specific structure at a specific ratio, whereby it can be stably produced in air. It has been found that the condensation reaction proceeds rapidly without using a catalyst, and an iron oxide / organopolysiloxane hybrid powder can be obtained in a high yield, and the present invention has been completed.

That is, the present invention comprises (A) iron (III) chloride reacted with an alkali to obtain (a) iron hydroxide (III). (1)
(In the formula, R may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X represents an optionally bonded ether bond (—O—) having 2 to 4 carbon atoms. Represents an alkylene group, and n is 1 to 12.
An iron oxide / organopolysiloxane hybrid powder characterized by being added and reacted at a molar ratio ((a) :( B)) of 10: 0.05 to 10: 1.5 It is a manufacturing method.

  Moreover, this invention is an iron oxide and organopolysiloxane hybrid powder obtained by the said manufacturing method.

  Furthermore, the present invention is a cosmetic comprising the above iron oxide / organopolysiloxane hybrid powder.

  According to the production method of the present invention, an iron oxide / organopolysiloxane hybrid powder can be obtained at a low cost and in a high yield in a good production environment without generation of odor or the like. In addition, the iron oxide / organopolysiloxane hybrid powder of the present invention exhibits good dispersibility in an oil agent, has excellent blocking ability in the UV-A and B regions due to blue shift, and has low solid catalyst activity. is there. Therefore, a cosmetic containing this iron oxide / organopolysiloxane hybrid powder has excellent dispersion stability of the powder, uniformity of the cosmetic film, and feeling of use, and has an excellent UV protection effect. It is possible to suppress deterioration of oil and sebum inside.

2 is an electron micrograph of iron oxide / organopolysiloxane hybrid powders of Production Examples 1 to 4 and Production Comparative Example 1. FIG. It is a figure which shows the light transmittance of 320-700 nm of the iron oxide * organopolysiloxane hybrid powder of manufacture Examples 1-3, and red iron oxide.

  In the production method of the present invention, first, (A) iron (III) chloride is used as a starting material, and this is reacted with an alkali to obtain (a) iron (III) hydroxide. When iron alkoxide is used as a starting material, especially iron methoxide and ethoxide are unstable in the air and thus need to be reacted in a nitrogen atmosphere, but iron (III) chloride has higher stability than this. It can be reacted in air. Examples of the alkali used in the reaction include sodium hydroxide and potassium hydroxide, and it is preferable to add these in an equivalent amount or more with respect to (A) iron (III) chloride. Specifically, for example, a 1 mol / L iron (III) chloride aqueous solution may be dropped into a 3 mol / L sodium hydroxide aqueous solution and reacted at 30 to 100 ° C. for about 0.5 to 5 hours.

  Next, (B) the organopolysiloxane represented by the following general formula (1) is added to (a) iron hydroxide (III) and reacted.

  In the above formula (1), R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. However, because of high reactivity, an alkyl group having 1 to 4 carbon atoms is preferable, and in particular, having 1 to 3 carbon atoms. Alkyl groups are preferred. Moreover, although R may be the same or different, it is preferable that all are the same. X is a C2-C4 alkylene group which may have an ether bond (—O—), and preferably a C3-C3 alkylene group. On the other hand, n is in the range of 1-12, preferably 4-10. If it is this range, the particle | grains excellent in the dispersibility, the usability | use_condition, etc. can be obtained. Examples of such commercially available organopolysiloxanes include X-24-9050 (manufactured by Shin-Etsu Chemical Co., Ltd .; in the above formula (1), R is all methyl groups, X is an alkylene group having 3 carbon atoms, n = 8) and the like. Can be mentioned. The organopolysiloxane of the above formula (1) can be obtained, for example, by reacting dimethylpolysiloxane having Si—H at both ends with allyltrialkoxysilane using chloroplatinic acid as a catalyst.

  The organopolysiloxane of the above (B) is used in a molar ratio ((a) :( B)) of 10: 0.05 to 10: 1.5 with respect to (a) iron hydroxide (III), preferably 10: 0. 0.05 to 10: 1.0. If it is this range, the particle | grains excellent in the dispersibility, the usability | use_condition, etc. will be obtained.

  (B) is preferably added dropwise to (a) iron hydroxide (III) as a solution of an appropriate organic solvent. As the organic solvent, 2-propanol, 1-butanol, 1-pentanol and the like can be used, but 2-propanol is preferable because of the high solubility of (B).

  Thus, (a) iron hydroxide (III) and (B) the organopolysiloxane represented by the above general formula (1) are added and reacted to prepare an iron oxide / organosiloxane hybrid. The reaction is carried out at 30 to 110 ° C., preferably 40 to 100 ° C., for about 2 to 10 hours. The reaction is preferably performed in the presence of water. In the organopolysiloxane of the above general formula (1), when R is an alkyl group having 1 to 4 carbon atoms, that is, when an alkoxy group is included, the alkoxy group is first hydrolyzed to become an OH group, Next, (a) it is considered that a condensation reaction occurs with the OH group of iron (III) hydroxide. Accordingly, it is preferable to use water equal to or more than the alkoxy group in (B) the organopolysiloxane. For example, when (B) the organopolysiloxane is one in which all R are methyl groups, It is preferable to use 6 mol or more of water with respect to 1 mol. Then, (B) the OH group of the organopolysiloxane and (a) the OH group of iron (III) hydroxide undergo a condensation reaction to form Fe—O—Si— bonds, and iron oxide / organosiloxane hybrid gel particles are formed. It is thought. In this reaction, a catalyst such as ammonia may be used. However, in the production method of the present invention, the reaction can proceed rapidly without using such a catalyst.

  The solid content is separated from the obtained iron oxide / organosiloxane hybrid gel particle dispersion by known solid-liquid separation means such as filtration, suction filtration, centrifugation, decantation, etc., and if necessary, washed with 2-propanol or the like. Then, it is dried at about 100 to 150 ° C. for about 2 to 6 hours, and further pulverized as necessary to obtain an iron oxide / organosiloxane hybrid powder.

  Thus, since the production method of the present invention can be stably produced in the air using inexpensive iron chloride (III) as a starting material, it is less expensive and has a higher yield than the production method using iron alkoxide. An iron oxide / organosiloxane hybrid powder can be obtained.

  The iron oxide / organosiloxane hybrid powder of the present invention thus obtained is a homogeneous composite of iron oxide and organopolysiloxane. For example, when this powder is observed with an optical microscope, the iron oxide phase and the organopolysiloxane are mixed. The siloxane phase cannot be distinguished. The particle size is preferably about 0.01 to 50.0 μm, more preferably about 0.05 to 10.0 μm, by crushing. Iron oxide has a low dispersibility with respect to the oil agent and easily aggregates, but the iron oxide / organosiloxane hybrid powder of the present invention exhibits a good dispersibility with respect to the oil agent. In addition, iron oxide is known to have high solid catalyst activity, but the hybrid powder of the present invention has reduced solid catalyst activity, and further improved the UV blocking ability in the UV-A and B regions by blue shift. It is a thing. Here, blue shift refers to a phenomenon in which the absorption wavelength of a compound containing a transition metal shifts to a lower wavelength side.

  The cosmetic of the present invention is obtained by blending the above-mentioned iron oxide / organosiloxane hybrid powder and preparing it by a conventional method, and is an optional blend that is usually blended in cosmetics as long as the effects of the present invention are not impaired. Ingredients can be blended.

  Examples of such optional components include powder components other than the above iron oxide / organosiloxane hybrid powder for the purpose of feeling adjustment and coloring, oily components such as base materials and emollient components, aqueous components such as moisturizing components, alkaline components Agent, emulsification, powder dispersion, surfactant for adjusting feel, UV absorber, moisturizer, water-soluble film-forming resin, anti-fading agent, antioxidant, antifoaming agent, cosmetic ingredients, antiseptic, fiber And fragrances.

  As a powder component, as long as it is a powder generally used in cosmetics, it is not particularly limited by the shape of a plate, spindle, needle, etc., particle diameter, particle structure such as porous, nonporous, etc. Inorganic powders, glitter powders, organic powders, pigment powders, composite powders and the like can be mentioned. Specifically, salmon, ultramarine, titanium oxide, zinc oxide, titanium / titanium oxide sintered product, cerium oxide, magnesium oxide, zirconium oxide, antimony oxide, magnesium carbonate, calcium carbonate, chromium oxide, chromium hydroxide, carbon black , Aluminum silicate, magnesium silicate, calcium silicate, barium silicate, magnesium aluminum silicate, magnesium magnesium metasilicate, mica, synthetic mica, synthetic sericite, sericite, talc, muscovite, phlogopite, red mica, Inorganic powders such as biotite, kaolin, barium sulfate, bentonite, smectite, diatomaceous earth, hydroxyapatite, boron nitride, bismuth oxychloride, titanium mica, titanium dioxide coated bismuth oxychloride, iron oxide coated mica, iron oxide coated Mica titanium, Blue coated mica titanium, carmine coated mica titanium, organic pigment coated mica titanium, iron oxide / titanium oxide coated synthetic phlogopite, fish phosphorus foil, titanium dioxide coated glass flake, polyethylene terephthalate / aluminum / epoxy laminated powder, polyethylene terephthalate / polyolefin laminated Bright powder such as film powder, polyethylene terephthalate / polymethylmethacrylate laminated film powder, polyamide resin, polyethylene resin, polyacrylic resin, polyester resin, fluorine resin, cellulose resin, polystyrene resin, styrene -Copolymer resins such as acrylic copolymer resins, organic polymer resin powders such as polypropylene resins, silicone resins and urethane resins, organic powders such as N-acyl lysine, starches, silk powders, cellulose powders, etc. Organic powder, organic tar pigments, pigment powders such as organic pigment lake pigments, metal powders such as aluminum powder, gold powder, silver powder, fine titanium oxide coated mica titanium, fine zinc oxide coated mica titanium, barium sulfate coating Examples include composite powders such as titanium mica, titanium oxide-containing silicon dioxide, and zinc oxide-containing silicon dioxide. These can be used alone or in combination. In addition, these powders may be a composite of two or more types, such as fluorine compounds, silicone compounds, metal soaps, lecithin, hydrogenated lecithin, collagen, higher fatty acids, higher alcohols, esters, waxes, The surface treatment may be performed by a known method using one or more of wax, fats and oils, hydrocarbons, surfactants, amino acid compounds, water-soluble polymers and the like.

  Oily components include hydrocarbons, fats and oils, waxes, and hardened oils, regardless of the origin, such as animal oil, vegetable oil, synthetic oil, and the properties of solid oil, semi-solid oil, liquid oil, volatile oil, etc. Ester oils, fatty acids, higher alcohols, silicone oils, fluorinated oils, lanolin derivatives, oily gelling agents and the like. Specifically, hydrocarbons such as liquid paraffin, squalane, petrolatum, polyisobutylene, polybutene, paraffin wax, ceresin wax, microcrystalline wax, polyethylene wax, ethylene / propylene copolymer, montan wax, Fischer-Tropsch wax, moscow, olive oil Oils such as castor oil, jojoba oil, mink oil, macadamian nut oil, waxes such as beeswax, carnauba wax, candelilla wax, gallow, cetyl isooctanoate, isopropyl myristate, isopropyl palmitate, myristic acid Octyldodecyl, glyceryl trioctanoate, polyglyceryl diisostearate, diglyceryl triisostearate, diisostearyl malate, glyceride tribehenate Rosin, pentaerythritol ester of rosin acid, neopentyl glycol dioctanoate, cholesterol fatty acid ester, N-lauroyl-L-glutamate di (cholesteryl, behenyl, octyldodecyl), stearic acid, lauric acid, myristic acid, behen Acids, fatty acids such as isostearic acid, oleic acid, 12-hydroxystearic acid, higher alcohols such as stearyl alcohol, cetyl alcohol, lauryl alcohol, oleyl alcohol, isostearyl alcohol, behenyl alcohol, low degree of polymerization dimethylpolysiloxane, high polymerization Dimethylpolysiloxane, methylphenylpolysiloxane, decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, cross-linked organopolysiloxane, Silicones such as elementally modified polysiloxanes, fluorine oils such as perfluorodecane, perfluorooctane, perfluoropolyether, lanolin, lanolin acetate, lanolin fatty acid isopropyl, lanolin derivatives such as lanolin alcohol, dextrin fatty acid ester, sucrose fatty acid Examples thereof include oily gelling agents such as esters, starch fatty acid esters, aluminum isostearate and calcium stearate.

  The aqueous component may be any component that is soluble in water, for example, alcohols such as ethyl alcohol and isopropyl alcohol, glycols such as propylene glycol, 1,3-butylene glycol, dipropylene glycol, and polyethylene glycol. Glycerols such as glycerin, diglycerin, polyglycerin, saccharides such as sorbitol, maltitol, sucrose, starch sugar, lactitol, guar gum, sodium chondroitin sulfate, sodium hyaluronate, gum arabic, sodium alginate, carrageenan, methylcellulose, hydroxy Water-soluble polymers such as ethyl cellulose, carboxymethyl cellulose, carboxyvinyl polymer, polyvinyl alcohol, polyvinyl pyrrolidone, sodium polyacrylate, salts Examples thereof include salts such as sodium chloride, magnesium chloride and sodium lactate, and plant extracts such as aloe vera, witch hazel, hamamelis, cucumber, lemon, lavender and rose.

  Examples of the alkali agent include inorganic alkali agents such as sodium hydroxide and potassium hydroxide, basic amino acids such as L-arginine, and organic alkali agents such as triethanolamine, ammonia and aminomethylpropanol.

  As the surfactant, any surfactant that is generally used in cosmetics can be used. Nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, etc. Is mentioned. Examples of the nonionic surfactant include glycerin fatty acid ester and its alkylene glycol adduct, polyglycerin fatty acid ester and its alkylene glycol adduct, propylene glycol fatty acid ester and its alkylene glycol adduct, sorbitan fatty acid ester and its alkylene glycol addition. Sorbitol fatty acid ester and its alkylene glycol adduct, polyalkylene glycol fatty acid ester, sucrose fatty acid ester, polyoxyalkylene alkyl ether, glycerin alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene hydrogenated castor oil, lanolin alkylene Glycol adduct, polyoxyalkylene alkyl co-modified silicone, polyether-modified silicone And the like. Examples of the anionic surfactant include inorganic and organic salts of fatty acids such as stearic acid and lauric acid, alkylbenzene sulfate, alkyl sulfonate, α-olefin sulfonate, dialkyl sulfosuccinate, and α-sulfonated fatty acid. Salt, acylmethyl taurate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl phenyl ether sulfate, alkyl phosphate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl phenyl ether phosphate, N-acyl amino acid salt , O-alkyl substituted malates, alkylsulfosuccinates and the like. Examples of the cationic surfactant include alkylamine salts, polyamines and alkanolamine fatty acid derivatives, alkyl quaternary ammonium salts, and cyclic quaternary ammonium salts. Examples of amphoteric surfactants include amino acid type and betaine type carboxylic acid types, sulfate ester types, sulfonic acid types, and phosphate ester types, and those that are safe for the human body can be used. For example, N, N-dimethyl-N-alkyl-N-carboxylmethyl ammonium betaine, N, N-dialkylaminoalkylene carboxylic acid, N, N, N-trialkyl-N-sulfoalkylene ammonium betaine, N, N-dialkyl -N, N-bis (polyoxyethylene sulfate) ammonium betaine, 2-alkyl-1-hydroxyethyl-1-carboxymethylimidazolinium betaine, lecithin and the like can be mentioned.

  Examples of ultraviolet absorbers include benzophenone-based, PABA-based, cinnamic acid-based, salicylic acid-based, 4-tert-butyl-4'-methoxydibenzoylmethane, and oxybenzone. Examples of humectants include protein, mucopolysaccharide, and collagen. , Elastin, keratin, etc., for example, α-tocopherol, ascorbic acid, etc., cosmetic ingredients, eg, vitamins, anti-inflammatory agents, herbal medicines, etc., antiseptics, eg, paraoxybenzoic acid esters, 1, 2 -Pentanediol, phenoxyethanol and the like.

  Examples of the fibers include synthetic fibers such as nylon and polyester, artificial fibers such as rayon, natural fibers such as cellulose, semi-synthetic fibers such as acetate silk, and these fibers include general oils, silicone oils, fluorine compounds, Those treated with a surfactant or the like can also be used. Among these, when nylon is used, the length is preferably 0.3 to 3 mm, the thickness is preferably 0.1 to 20 denier, and more preferably 0.5 to 10 denier. .

  Examples of the dosage form of the cosmetic of the present invention include a powder type, an oily type, an O / W type, a W / O type, an aqueous type, and a multilayer type. Examples of the type include foundation, makeup base, white powder, concealer, sunscreen, eye color, cheek red, lipstick, mascara, eyeliner, body lotion, and the like. Among these, the powder type, the oily type, the O / W type, and the W / O type are preferable as the dosage form because the effects of the present invention are more exerted, and the types of cosmetics include foundation and makeup. A base and white powder are preferred.

  Since iron oxides such as yellow iron oxide, red iron oxide, and black iron oxide have low dispersibility in oils, cosmetics containing these have poor dispersion stability and it is difficult to obtain a uniform cosmetic film. However, the cosmetic containing the iron oxide / organosiloxane hybrid powder of the present invention is excellent in dispersion stability and uniformity of the cosmetic film, and can obtain a smoother feeling in use. In addition, iron oxide has a high solid catalyst activity, and thus there has been a problem that the oxidation of fats and oils in cosmetics and the decomposition of pigments are promoted. Occurrence is suppressed and storage stability is excellent. Furthermore, iron oxide has a low ultraviolet blocking ability, and even if it is blended, a sufficient effect cannot be obtained. However, the cosmetic of the present invention has a high blocking ability in the UV-A and B regions, and has excellent ultraviolet light. It has a protective effect.

  The iron oxide / organopolysiloxane hybrid powder of the present invention can also be used in inks and paints. Furthermore, since the solid catalyst activity is low and the ultraviolet blocking ability is excellent, it is possible to suppress the deterioration of the resin as a resin filler or to impart an ultraviolet protection function to the resin.

  EXAMPLES Next, although an Example etc. demonstrate this invention in detail, this invention is not restrict | limited to these Examples etc. at all. Unless otherwise specified,% means mass%.

Production Example 1 (Molar ratio Fe: Si ((a) :( B)) = 10: 1.5 hybrid powder)
To 50 ml of 3.0 mol / L aqueous sodium hydroxide solution, 50 ml of 1.0 mol / L iron (III) chloride aqueous solution was added dropwise at a dropping rate of 100 ml / h, and the reaction was carried out at 40 ° C. for 1 hour. Iron (III) oxide was prepared. To this iron hydroxide (III), 0.0075 mol of reactive organopolysiloxane X-24-9050 (manufactured by Shin-Etsu Chemical Co., Ltd .; in the above general formula (1), all R is a methyl group and X is an alkylene having 3 carbon atoms. A solution prepared by dissolving the group, n = 8) in 50 ml of 2-propanol was gradually added dropwise, and then reacted at 60 ° C. for 2 hours. The obtained dispersion was separated by suction filtration and washed several times with 2-propanol to obtain a brown slurry. This was dried at 100 ° C. for 2 hours to obtain an iron oxide / organopolysiloxane hybrid powder in a yield of 7.00 g (yield 55.1%).

Production Example 2 (Molar ratio Fe: Si ((a) :( B)) = 10: 1.0 hybrid powder)
To 50 ml of 3.0 mol / L aqueous sodium hydroxide solution, 50 ml of 1.0 mol / L iron (III) chloride aqueous solution was dropped at a dropping rate of 100 ml / h, and the reaction was carried out at 40 ° C. for 1 hour. Iron (III) oxide was prepared. A solution prepared by dissolving 0.005 mol of a reactive organopolysiloxane X-24-9050 in 50 ml of 2-propanol in this iron (III) hydroxide was gradually added dropwise, followed by reaction at 60 ° C. for 2 hours. I let you. The obtained dispersion was separated by suction filtration and washed several times with 2-propanol to obtain a brown slurry. This was dried at 100 ° C. for 2 hours to obtain an iron oxide / organopolysiloxane hybrid powder in a yield of 7.85 g (yield 76.6%).

Production Example 3 (Molar ratio Fe: Si ((a) :( B)) = 10: 0.5 hybrid powder)
To 50 ml of 3.0 mol / L aqueous sodium hydroxide solution, 50 ml of 1.0 mol / L iron (III) chloride aqueous solution was added dropwise at a dropping rate of 100 ml / h, and the reaction was carried out at 40 ° C. for 1 hour. Iron (III) oxide was prepared. A solution prepared by dissolving 0.0025 mol of a reactive organopolysiloxane X-24-9050 in 50 ml of 2-propanol in this iron (III) hydroxide was gradually added dropwise, followed by reaction at 60 ° C. for 2 hours. I let you. The obtained dispersion was separated by suction filtration and washed several times with 2-propanol to obtain a brown slurry. This was dried at 100 ° C. for 2 hours to obtain an iron oxide / organopolysiloxane hybrid powder in a yield of 5.70 g (yield 73.1%).

Production Example 4 (Molar ratio Fe: Si ((a) :( B)) = 10: 0.05 hybrid powder)
To 50 ml of 3.0 mol / L aqueous sodium hydroxide solution, 50 ml of 1.0 mol / L iron (III) chloride aqueous solution was dropped at a dropping rate of 100 ml / h, and the reaction was carried out at 40 ° C. for 1 hour. Iron (III) oxide was prepared. A solution obtained by dissolving 0.00025 mol of reactive organopolysiloxane X-24-9050 in 50 ml of 2-propanol in this iron (III) hydroxide was gradually added dropwise, followed by reaction at 60 ° C. for 2 hours. I let you. The obtained dispersion was separated by suction filtration and washed several times with 2-propanol to obtain a brown slurry. This was dried at 100 ° C. for 2 hours to obtain an iron oxide / organopolysiloxane hybrid powder in a yield of 4.80 g (yield 85.9%).

Production Comparative Example 1 (Molar ratio Fe: Si ((a) :( B)) = 10: 2)
To 50 ml of 3.0 mol / L aqueous sodium hydroxide solution, 50 ml of 1.0 mol / L iron (III) chloride aqueous solution was dropped at a dropping rate of 100 ml / h, and the reaction was carried out at 40 ° C. for 1 hour. Iron (III) oxide was prepared. A solution prepared by dissolving 0.01 mol of reactive organopolysiloxane X-24-9050 in 50 ml of 2-propanol in this iron (III) hydroxide was gradually added dropwise, followed by reaction at 60 ° C. for 2 hours. I let you. The obtained dispersion was separated by suction filtration and washed several times with 2-propanol to obtain a brown slurry. This was dried at 100 ° C. for 2 hours to obtain 7.05 g (yield 52.4%) of iron oxide / organopolysiloxane hybrid powder. When force was applied to the powder, it was somewhat sticky.

Test example 1
Observation by electron microscope:
The powders obtained in Production Examples 1 to 4 were sufficiently ground in a mortar and observed with a scanning electron microscope. The powder obtained in Production Comparative Example 1 was similarly observed with a microscope. An electron micrograph of each powder is shown in FIG.

Test example 2
Evaluation of solid catalyst activity (1):
The iron oxide / organopolysiloxane hybrid powders obtained in Production Examples 1 to 4 were evaluated by the solid catalyst activity evaluation method for powders using carotenoid dyes described in JP-A-2009-222702. That is, 2 g of each powder was added to 24 g of a 0.025 g / L astaxanthin / tri-2-ethyl glyceryl solution, dispersed by ultrasonication for 1 hour, and then half of the solution was centrifuged to obtain astaxanthin (absorbance Absorbance measurement (manufactured by UV-2500 SHIMADZU) was performed. Half of the solution was stored in a thermostat at 50 ° C. for 1 week, and the absorbance was measured in the same manner. The discoloration rate (%) of astaxanthin due to the solid catalyst activity was calculated by the following formula using the absorbance immediately after dispersion as an initial value.

Fading rate (%) = (A−B) / A × 100
A: Absorbance of astaxanthin immediately after dispersion
B: Absorbance of astaxanthin after 1 week at 50 ° C

  Moreover, solid catalyst activity was determined based on the following criteria. Table 1 shows the fading rate. Note that yellow iron oxide and black iron oxide were similarly evaluated. Further, these were also evaluated in the same manner for those treated with silicone by the following method. The determination criteria were set as follows based on the fact that it was determined that there was no problem with the fading rate of less than 40% from the presence or absence of odor and discoloration in the product blended with each powder.

(Method for producing silicone-treated 2% yellow iron oxide and silicone-treated 2% black iron oxide)
While gradually adding 10 parts by mass of a 20% solution of dimethylpolysiloxane / methylhydrogenpolysiloxane in isopropyl alcohol to 98 parts by mass of yellow iron oxide or black iron oxide, the mixture is mixed using a Henschel mixer. Next, after drying at 125 ° C., a silicone-treated product is obtained.
(Criteria)
A: The fading rate is less than 30%.
○: The fading rate is 30% or more and less than 40%.
Δ: The fading rate is 40% or more and less than 60%.
X: The fading rate is 60% or more.

  From the results shown in Table 1, the iron oxide / organopolysiloxane hybrid powder of the production example has a solid catalyst activity as compared with yellow iron oxide, black iron oxide, silicone-treated yellow iron oxide, and silicone-treated black iron oxide. It was shown to be low.

Test example 3
Evaluation of solid catalyst activity (2):
A deterioration test was performed on oleic acid, which is a sebum component. Oleic acid and the iron oxide / organopolysiloxane hybrid powder obtained in Production Examples 1 to 4 were mixed at a ratio of 10: 1 and dispersed for 1 hour using an ultrasonic machine (BRANSONIC 1510J-DTH 42 kHz). These and only oleic acid that does not contain powder as a standard product were stored in a thermostatic bath at 50 ° C. for 1 week, and then the odor was evaluated in comparison with the standard product to confirm the effect of suppressing deterioration. Deterioration suppression was determined based on the following criteria. For comparison, yellow iron oxide and black iron oxide and these silicone-treated products prepared in Test Example 2 were used. The results are shown in Table 2.

(Criteria)
A: No change from standard products.
○: Slightly different odor than standard product, but hardly changed.
Δ: It is understood that there was a slight odor change and a change from the standard product.
X: It can be seen that the odor changed considerably from the standard product.

  From Table 2, the iron oxide / organopolysiloxane hybrid powders of Production Examples 1 to 4 are compared with yellow iron oxide, black iron oxide, silicone-treated yellow iron oxide, and silicone-treated black iron oxide, and oxidative deterioration of sebum. It was shown to be effectively suppressed.

Test example 4
Evaluation of powder dispersibility:
The dispersibility of the iron oxide / organopolysiloxane hybrid powders obtained in Production Examples 1 to 4 in an oil was evaluated. For comparison, the iron oxide / organopolysiloxane hybrid powder obtained in Production Comparative Example 1, red iron oxide, yellow iron oxide, black iron oxide, and these silicone-treated products treated in the same manner as in Test Example 2 were used. . As an oil agent, 0.5 part by mass of each sample was added to 20 parts by mass of glyceryl 2-ethylhexanoate and dispersed. After dispersing for 1 hour by ultrasonic waves, the mixture was placed in a settling tube, and the liquid level was adjusted to 25 cm. Based on the following criteria, the dispersibility was evaluated from the thickness of the dispersion layer after 3 days. The results are shown in Table 3.

(Criteria) Dispersibility determination method A: The dispersion layer is 15 cm or more.
○: The dispersed layer is 10 cm or more and less than 15 cm.
(Triangle | delta): A dispersion layer is 5 cm or more and less than 10 cm.
X: The dispersion layer is less than 5 cm.

  From Table 3, it was shown that the iron oxide / organopolysiloxane hybrid powders of the production examples had higher dispersibility than red iron oxide, yellow iron oxide, and black iron oxide.

Test Example 5
Evaluation of the UV blocking ability of the powder dispersion:
(Preparation method of powder dispersion)
A powder dispersion having the formulation shown below was prepared by dispersing each component with three rollers. As the powder, the iron oxide / organopolysiloxane hybrid powder, red iron oxide, and yellow iron oxide obtained in Production Examples 1 to 4 and Production Comparative Example 1 were used.
(Component) (parts by mass)
1. 1,3-Butyl call 2
2. Sorbitan sesquioleate 0.2
3. Polyoxyethylene (E, O.20) sorbitan monooleate 0.4
4). Lecithin 0.3
5. Powder 2

(Transmittance measurement)
Each of the obtained powder dispersions was applied to a quartz plate with a doctor blade (6 μm), and the transmittance of 320 nm to 700 nm was measured with an absorbance measuring device (manufactured by UV-2500 SHIMADZU). The measurement results of Production Examples 1 to 3 and red iron oxide are shown in FIG. Further, the transmittance at a wavelength of 360 nm was determined based on the following criteria for determining the ultraviolet blocking ability. The results are shown in Table 4.

(Criteria)
A: The transmittance (%) at 360 nm is less than 5%.
A: The transmittance (%) at 360 nm is 5% or more and less than 10%.
Δ: The transmittance (%) at 360 nm is 10% or more and less than 15%.
X: The transmittance (%) at 360 nm is 15% or more.

  Table 4 shows that the iron oxide / organopolysiloxane hybrid powders of Production Examples 1 to 4 are superior in ultraviolet blocking ability compared to the hybrid powder, red iron oxide, and yellow iron oxide of Production Comparative Example 1. It was done. Further, from FIG. 2, the blocking region of red iron oxide is from about 560 nm to 320 nm and the transmittance is about 15%, but the blocking region of the hybrid powders of Production Examples 2 and 3 is larger than that. Shifted to the lower wavelength side (blue shift), from 400 nm to 320 nm, the transmittance is as low as about 0.5%, and has excellent blocking ability in the UV-A and B regions compared to red iron oxide. I understood that. It was also found that the hybrid powder of Production Example 1 has a higher blocking ability than red iron oxide from around 400 nm to 320 nm.

Examples 1-4 and Comparative Examples 1-4
The O / W type base | substrate of the prescription shown in following Table 5 was prepared with the following manufacturing methods. About the obtained O / W type groundwork, each of the 20 panelists specializing in cosmetics evaluation evaluated each item of “uniformity of makeup film” and “smooth use feeling” according to the following evaluation criteria. Further, using the average score of all the panels, the determination was made according to the following criteria. The results are also shown in Table 5. The calculated values of iron content and Fe content in the product are shown in the table.

[Evaluation criteria]
(Evaluation result): (Score)
Very good: 6 points Good: 5 points Somewhat good: 4 points Normal: 3 points Somewhat bad: 2 points Bad: 1 point Very bad: 0 points

[Criteria]
(Average score): (Judgment)
5.0 or more: ◎ Very good 3.5 or more to less than 5.0: ○ Good 1.5 or more to less than 3.5: △ Defect Less than 1.5: × Very poor

(UV protection effect)
Moreover, the SPF value by In-Vitro was measured with respect to each O / W type | mold base using the SPF analyzer (UV-2000S by Labsphere). Measurement conditions were determined according to the following evaluation criteria by measuring about 0.2 g of each O / W type substrate uniformly on a transpore tape (3M company), measuring the SPF value in the range of 280-400 nm. The results are also shown in Table 5.

(Evaluation criteria)
A: SPF value is 15 or more.
○: SPF value is 10 or more and less than 15.
Δ: SPF value is 5 or more and less than 10.
X: SPF value is less than 5.

* 1: CARBOPOL 940 (LUBRISOL ADVANCED MATERIALS A)
* 2: Pemulen TR-1 (Noveon)
* 3: Lecithin CLO (manufactured by J-Oil Mills)

(Manufacturing method)
(1) Components 1 to 4 are uniformly dissolved at 80 ° C.
(2) Components 5 to 9 are uniformly dissolved at 80 ° C.
(3) Add (1) to (2) and emulsify at 80 ° C., then add component 10 and mix.
(4) The components 11-21 are processed with a roller.
(5) Add (4) to cooled (3) and mix.
(6) Defoam (5) and fill the container.

The O / W type substrates of Examples 1 to 4 were O / W type substrates excellent in “ultraviolet ray blocking effect”, “uniformity of decorative film”, and “smooth use feeling”. The O / W type grounds of Comparative Examples 1 to 3 were inferior in all of the ultraviolet blocking effect, the uniformity of the decorative film, and the smooth feeling of use. Although the O / W type base of Comparative Example 4 was excellent in ultraviolet blocking ability, it was inferior in the uniformity of the decorative film and smooth use feeling because of the large amount of iron oxide.
The Fe content contained in the O / W type substrate of Example 1 is lower than the Fe content contained in the O / W type substrates of Comparative Examples 2 and 3, but the UV protection effect is low. It was expensive. This is because the blue-shifted hybrid powder of Production Example 1 has a higher blocking ability in the UV-A and B regions, and the uniformity (dispersibility) of the decorative film is superior to conventional iron oxide. It is possible.

Example 5 O / W type foundation An O / W type foundation having the following formulation was prepared by the following method.
(Ingredient) (%)
1. Monooleic acid polyoxyethylene sorbitan (20EO) 0.5
2. Sorbitan sesquioleate 0.5
3. 1,3-butylene glycol 10.0
4). Silicone-treated titanium oxide * 4 10.0
5. Silicone-treated Bengala * 4 0.4
6). Hybrid powder of Production Example 1 2.0
7). Silicone-treated black iron oxide * 4 0.1
8). Silicone-treated talc * 4 5.0
9. Carboxyvinyl polymer * 1 0.3
10. Triethanolamine 1.0
11. Purified water remaining amount 12. Ethanol 2.0
13. Stearic acid 1.0
14 Behenyl alcohol 0.5
15. Liquid paraffin 2.0
16. Glyceryl tri-2-ethylhexanoate 2.0
17. 2-Ethylhexyl paramethoxycinnamate 2.0
18. Vaseline 0.5
19. Preservative (methyl paraoxybenzoate) 0.1
20. Fragrance 0.05
* 4: Treatment with 5% dimethylpolysiloxane / methylhydrogenpolysiloxane (mixed in a Henschel mixer while gradually adding a solution of dimethylpolysiloxane / methylhydrogenpolysiloxane dissolved in isopropyl alcohol to each powder. And then dried at 125 ° C.)

(Manufacturing method)
(1) Components 1 to 8 are uniformly dispersed with a roller.
(2) Mix components 9-11 uniformly.
(3) Add (1) to (2) and mix uniformly.
(4) Components 13 to 19 are mixed and dissolved at 80 ° C.
(5) Add (4) to (3) at 80 ° C., emulsify, add component 12 and mix.
(6) (5) was cooled, component 20 was added, and an O / W type foundation was obtained.

  The obtained O / W type foundation was excellent in powder dispersibility, was an O / W type foundation excellent in ultraviolet blocking effect, uniform cosmetic film without color unevenness, and smooth use feeling.

Example 6 W / O type foundation A W / O type foundation having the following formulation was prepared by the following method.
(Ingredient) (%)
1. Polyoxyethylene methylsiloxane / polyoxypropylene oleyl methylsiloxane / dimethylsiloxane copolymer * 5 2.0
2. PEG-3 dimethicone * 6 1.0
3. Decamethylcyclopentasiloxane 20.0
4). Hybrid powder of Production Example 2 3.0
5. Silicone-treated red iron oxide * 7 0.5
6). Silicone-treated yellow iron oxide * 7 0.5
7). Silicone-treated black iron oxide * 7 0.5
8). Silicone-treated titanium oxide * 4 10.0
9. Silicone-treated talc * 4 5.0
10. Glyceryl tri-2-ethylhexanoate 10.0
11. Sorbitan sesquioleate 0.5
12 Purified water remaining amount 13. Sodium chloride 0.5
14.1,3-Butylene glycol 10.0
15. Ethanol 5.0
16. Preservative (methyl paraoxybenzoate) 0.1
17. Fragrance 0.05
* 5: KF-6026 (Shin-Etsu Chemical Co., Ltd.)
* 6: KF-6015 (manufactured by Shin-Etsu Chemical Co., Ltd.)
* 7: Treatment with 3% dimethylpolysiloxane (mixed in a Henschel mixer while gradually adding a solution of dimethylpolysiloxane dissolved in isopropyl alcohol to each powder and then dried at 125 ° C)

(Manufacturing method)
(1) Components 1 to 3 are mixed uniformly.
(2) Components 4 to 11 are uniformly dispersed with a roller.
(3) Add (2) to (1) and mix uniformly.
(4) Components 12 to 17 were added to (3) and emulsified to obtain a W / O type foundation.

  The obtained W / O type foundation was excellent in powder dispersibility, was a W / O type foundation excellent in ultraviolet blocking effect, uniform cosmetic film without color unevenness, and smooth usability.

Example 7 Oily solid foundation An oily solid foundation having the following formulation was prepared by the following method.
(Ingredient) (%)
1. Talc 15.0
2. Mica 10.0
3. Silicone-treated titanium oxide * 4 15.0
4). Hybrid powder of Production Example 3 5.0
5. Silicone-treated Bengala * 4 0.2
6). Silicone-treated yellow iron oxide * 7 0.5
7). Silicone-treated black iron oxide * 7 0.2
8). Polyethylene wax 7.0
9. Microcrystalline wax 6.0
10. 10. glyceryl tri-2-ethylhexanoate remaining 11 Dimethylpolysiloxane * 8 10.0
12 Liquid paraffin 20.0
13. Polyoxyethylene methylsiloxane / polyoxypropylene oleyl methylsiloxane / dimethylsiloxane copolymer * 5 2.0
14 Preservative (methyl paraoxybenzoate) 0.1
15. Perfume 0.02
* 8: KF-96 (20CS) (Shin-Etsu Chemical Co., Ltd.)

(Manufacturing method)
(1) Components 8 to 14 are dissolved by heating at 90 ° C.
(2) Components 1 to 7 are added to (1) and dispersed uniformly with a roller.
(3) Component 15 was added to (2), dissolved at 80 ° C., and then filled into a metal pan to obtain an oily solid foundation.

  The obtained oily solid foundation was an oily solid foundation having excellent powder dispersibility, an ultraviolet blocking effect, a uniform cosmetic film without color unevenness, and a smooth feeling of use.

Example 8 Solid powder foundation A solid powder foundation having the following formulation was prepared by the following production method.
(Ingredient) (%)
1. Silicone-treated titanium oxide * 4 15.0
2. 2. Talc remaining amount Hybrid powder of Production Example 3 3.0
4). Silicone-treated Bengala * 4 0.3
5. Silicone-treated yellow iron oxide * 7 0.5
6). Silicone-treated black iron oxide * 7 0.1
7). Mica 20.0
8). Nylon powder 2.0
9. Glyceryl tri-2-ethylhexanoate 3.0
10. Liquid paraffin 3.0
11. 2-Ethylhexyl paramethoxycinnamate 3.0
12 Preservative (Methyl paraoxybenzoate) 0.2
13. Fragrance 0.15

(Manufacturing method)
(1) Components 1 to 8 are mixed uniformly.
(2) Add components 9 to 13 to (1) and mix uniformly.
(3) Grind (2) with a pulverizer.
(4) A metal pan was filled with (3) to obtain a solid powder type foundation.

The obtained solid powder foundation was a solid powder foundation having excellent powder dispersibility, an ultraviolet blocking effect, a uniform cosmetic film without color unevenness, and a smooth feeling of use.

Example 9 Powdery Foundation A powdery foundation having the following formulation was prepared by the following production method.
(Ingredient) (%)
1. Cross-linked methylpolysiloxane mixture * 9 7.0
2. Dimethylpolysiloxane * 10 1.0
3. Preservative (Methyl paraoxybenzoate) 0.2
4). Lauroyl-L-lysine 40.0
5. Nylon powder 10.0
6). 6. Talc remaining Titanium oxide 7.0
8). Hybrid powder of Production Example 4 1.5
9. Red iron oxide 0.1
10. Yellow iron oxide 0.5
11. Black iron oxide 0.1
12 Boron nitride 5.0
13. Fragrance 0.1
* 9: KSG-16 (manufactured by Shin-Etsu Chemical Co., Ltd.)
* 10: KF-96 (6CS) (manufactured by Shin-Etsu Chemical Co., Ltd.)

(Manufacturing method)
(1) Components 1 and 2 are mixed with a desper mixer to prepare a gel.
(2) Components 3 to 13 are mixed and dispersed with a super mixer.
(3) Add (1) to (2) and stir.
(4) (3) was filled into a container to obtain a powdery foundation.

  The obtained powdery foundation was excellent in powder dispersibility, was a powdery foundation excellent in ultraviolet blocking effect, uniform cosmetic film without color unevenness, and smooth use feeling.

Example 10 Oily Eyeshadow An oily eyeshadow having the following formulation was prepared by the following method.
(Ingredient) (%)
1. Palmitic acid / 2-ethylhexanoic acid dextrin * 11 2.0
2. Diisostearyl malate 2.5
3.2 Cetyl 2-ethylhexanoate 15.0
4). Dextrin palmitate * 12 12.0
5. Liquid paraffin 6 Hydrogenated polyisobutene 1.5
7). Silica anhydride 6.0
8). Nylon powder 5.0
9. Silicone-treated talc * 4 0.5
10. Hybrid powder of Production Example 1 5.0
11. Red No. 202 0.05
12 Yellow No. 4 aluminum lake 0.05
13. Blue No. 1 aluminum rake 0.05
14 Mica titanium 1.5
15. Fragrance 0.2
* 11: Leopard TT (manufactured by Chiba Flour Mills)
* 12: Leopard KL (manufactured by Chiba Flour Mills)

(Manufacturing method)
(1) Components 1 to 6 are dissolved and mixed at 100 ° C.
(2) Add components 7 to 15 to (1) and uniformly disperse with three rollers.
(3) (2) was poured into a container at 80 ° C. and solidified by cooling to obtain an oily eye shadow.

  The obtained oily eyeshadow was an oily eyeshadow with excellent powder dispersibility, an ultraviolet blocking effect, a uniform cosmetic film without color unevenness, and a smooth feeling of use.

Example 11 Solid Powder Eyeshadow A solid powder eye shadow having the following formulation was prepared by the following production method.
(Ingredient) (%)
1. Mica titanium 30.0
2. 2. Talc remaining amount Hybrid powder of Production Example 2 5.0
4). Yellow 401 No. 1.0
5. Red No. 202 0.5
6). Nylon powder 2.0
7). Glyceryl tri-2-ethylhexanoate 4.0
8). Liquid paraffin 4.0
9. Vaseline 1.0
10. Preservative (methyl paraoxybenzoate) 0.3
11. Fragrance 0.2

(Manufacturing method)
(1) Components 1 to 6 are mixed uniformly.
(2) Add components 7 to 11 to (1) and mix uniformly.
(3) Grind (2) with a pulverizer.
(4) A metal pan was filled with (3) to obtain a solid powder eye shadow.

  The obtained solid powder eye shadow was a solid powder eye shadow having excellent powder dispersibility, an ultraviolet blocking effect, a uniform cosmetic film having no color unevenness, and a smooth use feeling.

Example 12 Water Gel Foundation A water gel foundation having the following formulation was prepared by the following production method.
(Ingredient) (%)
1. Gellan gum * 15 0.5
2. Propylene glycol 5.0
3. 1,3-butylene glycol 10.0
4). Glycerin 3.0
5. Hydrogenated lecithin * 16 1.0
6). Squalane 1.0
7). Nylon powder 10.0
8). Titanium oxide 8.0
9. Hybrid powder of Production Example 3 2.0
10. Yellow iron oxide 0.2
11. Bengala 0.05
12 Black iron oxide 0.01
13. Preservative (Methyl paraoxybenzoate) 0.2
14 Fragrance 0.05
15. Purified water remaining amount * 15: Kelcogel LT100 (Dainippon Sumitomo Pharma Co., Ltd.)
* 16: Basis LS-60HR (Nisshin Oillio Group)

(Manufacturing method)
(1) Components 1, 2, and 15 are dissolved by heating.
(2) Components 3 to 13 are kneaded.
(3) (2) was added to (1) and cooled, and component 14 was added to obtain an aqueous gel-like foundation.

  The obtained water-based gel-like foundation was a water-based gel-like foundation having excellent powder dispersibility, an ultraviolet blocking effect, a uniform cosmetic film without color unevenness, and a smooth feeling of use.

Example 13 Solid powder face color A solid powder face color having the following formulation was prepared by the following production method.
(Ingredient) (%)
1. Mica 30.0
2. 2. Talc remaining amount Synthetic phlogopite 10.0
4). Hybrid powder of production example 4 1.0
5. Red 226 0.2
6). Liquid paraffin 4.0
7). Glyceryl tri-2-ethylhexanoate 4.0
8). Preservative (Methyl paraoxybenzoate) 0.2
9. Fragrance 0.2

(Manufacturing method)
(1) Mix components 1 to 5 uniformly.
(2) Add components 6 to 9 to (1) and mix uniformly.
(3) Grind (2) with a pulverizer.
(4) (3) was filled in a metal pan to obtain a solid powder face color.

  The obtained solid powder face color was excellent in powder dispersibility, was a solid powder face color excellent in ultraviolet blocking effect, uniform cosmetic film without color unevenness, and smooth use feeling.

Example 14 Stick-shaped lipstick A stick-shaped lipstick having the following formulation was prepared by the following method.
(Ingredient) (%)
1. Polyethylene wax 7.0
2. Microcrystalline wax 3.0
3. Paraffin wax 2.0
4). Glyceryl tri-2-ethylhexanoate 20.0
5. Tetra-2-ethylhexanoic acid pentaerythrit 10.0
6). Dimethylpolysiloxane * 8 3.0
7. Cetyl 2-ethylhexanoate Remaining 8. Hybrid powder of production example 1 4.0
9. Red 202 0.5
10. Yellow 4 2.0
11. Titanium oxide 0.1
12 Titanium oxide-treated synthetic phlogopite * 17 3.0
* 17: Prominence YF (Nippon Koken Kogyo Co., Ltd.)

(Manufacturing method)
(1) Components 1 to 7 are uniformly dissolved and mixed at 100 ° C.
(2) Components 8 to 12 are added to (1) and dispersed uniformly with three rollers.
(3) After heating (2) to 85 ° C., it was poured into a container and cooled to obtain a stick-shaped lipstick.

  The obtained stick-shaped lipstick was excellent in powder dispersibility, a UV-blocking effect, a uniform cosmetic film having no color unevenness, and a stick-shaped lipstick excellent in smooth use feeling.

Example 15 Oily Eyeliner An oily eyeliner having the following formulation was prepared by the following method.
(Ingredient) (%)
1. Paraffin wax 8.0
2. Polyisobutylene 16.0
3. Polyethylene wax 8.0
4). Hydrogenated microcrystalline wax 3.0
5. Light liquid isoparaffin 6 Hybrid powder of Production Example 2 15.0
7). Silicone-treated black iron oxide * 7 1.0
8). Silicone-treated talc * 4 5.0

(Manufacturing method)
(1) Components 1 to 4 are heated to 100 ° C. and mixed uniformly.
(2) Components 5-8 are mixed uniformly.
(3) Add (2) to (1) and mix uniformly.
(4) (3) was processed with a roller to obtain an oily eyeliner.

  The obtained oily eyeliner was an oily eyeliner excellent in powder dispersibility, an ultraviolet blocking effect, a uniform cosmetic film without color unevenness, and a smooth feeling of use.

Example 16 Eyebrow An eyebrow having the following formulation was prepared by the following production method.
(Ingredient) (%)
1. Alkyl acrylate copolymer emulsion * 18 30.0
2. L-Arginine 1.0
3. Purified water remaining amount 4. Ethanol 15.0
5. Monooleic acid polyoxyethylene sorbitan (20EO) 0.5
6.1,3-Butylene glycol 3.0
7). Hybrid powder of Production Example 3 3.0
8). Black iron oxide 0.01
9. Yellow iron oxide 0.01
10. Bengala 0.01
11. Antiseptic (1,2-pentanediol) 0.2
12 Fragrance 0.1
* 18: Iodosol GH41F (manufactured by Akzo Nobel)

(Manufacturing method)
(1) Components 1 to 4 are mixed uniformly.
(2) Components 5 to 10 are processed with a roller.
(3) After adding (2) and components 11 and 12 to (1), they were mixed uniformly to obtain an eyebrow.

  The obtained eyebrow was an eyebrow excellent in powder dispersibility, an ultraviolet blocking effect, a uniform cosmetic film having no color unevenness, and a smooth use feeling.

Example 17 Nonaqueous Mascara A nonaqueous mascara having the following formulation was prepared by the following method.
(Ingredient) (%)
1. Rosin acid pentaerythritol 10.0
2. Candelilla resin * 19 3.0
3. Beeswax 2.0
4). Paraffin wax 1.0
5. Microcrystalline wax 0.6
6). Polyethylene wax 0.4
7). Dextrin palmitate * 12 2.0
8). Trimethylsiloxysilicic acid * 20 6.0
9. Dimethyl distearyl ammonium hectorite 5.0
10. Propion carbonate 1.0
11. Light liquid isoparaffin remaining amount 12. Hybrid powder of production example 4 7.0
13. Silica 3.0
14 Talc 5.0
* 19: Candelilla resin E-1 (Nippon Natural Products)
* 20: Silicon KF-9021 (manufactured by Shin-Etsu Chemical Co., Ltd.)

(Manufacturing method)
(1) Ingredients 1-7 are heated to 110 ° C.
(2) Add components 8 to 11 to (1) and mix.
(3) Add components 12 to 14 to (2) and mix.
(4) (3) was processed with three rollers to obtain a non-aqueous mascara.

  The obtained non-aqueous mascara was a non-aqueous mascara having excellent powder dispersibility, an ultraviolet blocking effect, a uniform cosmetic film without color unevenness, and a smooth feeling of use.

Example 18 O / W type mascara An O / W type mascara having the following formulation was prepared by the following method.
(Ingredient) (%)
1. Stearic acid 2.0
2. Beeswax 10.0
3. Cetostearyl alcohol 1.0
4). Monooleic acid polyoxyethylene sorbitan (20EO) 1.5
5. Sorbitan sesquioleate 0.5
6). Hybrid powder of production example 1 7.0
7). Silicic anhydride 3.0
8). Purified water remaining amount 9.1,3-butylene glycol 10.0
10. Triethanolamine 1.5
11. Alkyl acrylate copolymer emulsion * 18 30.0
13. Preservative (1,2-pentanediol) 0.2
14 Fragrance 0.2

(Manufacturing method)
(1) Components 1 to 7 are mixed uniformly at 80 ° C.
(2) Components 8 to 14 are uniformly mixed at 80 ° C.
(3) Add (2) to (1) and emulsify.
(4) (3) was cooled to obtain an O / W type mascara.

  The obtained O / W type mascara was an O / W type mascara having excellent powder dispersibility, an ultraviolet blocking effect, a uniform decorative film without color unevenness, and a smooth feeling of use.

Example 19 W / O Sunscreen The following formula W / O sunscreen was prepared by the following method.
(Ingredient) (%)
1. Zinc oxide 10.0
2. Silicone-treated fine particle titanium oxide * 4 5.0
3. Hybrid powder of Production Example 2 5.0
4). Sorbitan sesquiisostearate 1.0
5. Glyceryl tri-2-ethylhexanoate 10.0
6). 2-ethylhexyl palmitate 5.0
7). Decamethylcyclopentasiloxane 10.0
8). 2-Ethylhexyl paramethoxycinnamate 10.0
9. Methyl polysiloxane, cetyl methyl polysiloxane, poly (oxyethylene,
Oxypropylene) methylpolysiloxane copolymer * 21 2.0
10. Purified water remaining amount 11. Sodium chloride 0.2
12 Ethanol 5.0
13. Preservative (Methyl paraoxybenzoate) 0.2
14 Fragrance 0.1
* 21: ABIL EM90 (Evonic Goldschmidt GMBH)

(Manufacturing method)
(1) Components 1 to 5 are uniformly dispersed with three rollers.
(2) Add components 6 to 9 to (1) and mix uniformly.
(3) Emulsified while adding components 10 to 14 to (2) to obtain a W / O sunscreen.

  The obtained W / O-type sunscreen was a W / O-type sunscreen with excellent powder dispersibility, an ultraviolet blocking effect, a uniform cosmetic film without color unevenness, and a smooth use feeling.

Example 20 Aqueous Gel Eyeshadow An aqueous gel eyeshadow having the following formulation was prepared by the following method.
(Ingredient) (%)
1. Silicone-treated talc * 4 2.0
2. Lecithin * 3 0.2
3. Sorbitan sesquioleate 0.1
4). Polyoxyethylene monooleate (EO20) sorbitan 0.2
5. Preservative (Methyl paraoxybenzoate) 0.2
6). Hybrid powder of Production Example 3 2.0
7.1,3-Butylene glycol 2.0
8). Synthetic phlogopite 15.0
9. Fluorine-treated mica titanium * 22 15.0
10. Fluorine-treated glass powder * 23 3.0
11. (Polyethylene terephthalate / polymethyl methacrylate) Laminated powder * 24
3.0
12 Gellan gum * 15 0.5
13.1,3-Butylene glycol 13.0
14 Purified water remaining amount 15. Chelating agent (disodium edetate) 0.2
16. Fragrance 0.2
* 22: Perfluorooctyltriethoxysilane treated with 2% * 23: Metashine MC1080TY treated with 2% perfluorooctyltriethoxysilane (manufactured by Nippon Sheet Glass)
* 24: Aurora Flakes Violet 0.05 (Kakuhachi Fish Scale)

(Manufacturing method)
(1) Components 12 to 15 are mixed uniformly and swollen at 80 ° C.
(2) Components 1 to 7 are uniformly dispersed with three rollers.
(3) Add (2) to (1) and disperse uniformly.
(4) Components 8 to 11 are added to (3) and dispersed uniformly.
(5) Component 16 was added to (4), and after defoaming, the container was filled to obtain an aqueous gel eyeshadow.

  The obtained water-based gel eye shadow was a water-based gel eye shadow having excellent powder dispersibility, an ultraviolet blocking effect, a uniform cosmetic film having no color unevenness, and a smooth use feeling.

Example 21 Oil-Based Pigment Ink Composition An oil-based pigment ink composition having the following formulation was prepared by the following production method.
(Dispersant A)
(Ingredient) (%)
1. Hybrid powder of Production Example 1 25.0
2. Dispersant * 25 25.0
3. Ethylene glycol monobutyl ether acetate 50.0
* 25: SOLPERSE 32550 (made by Lubrizol)
(Manufacturing method)
(1) Components 1 to 3 were dispersed for 2 hours with a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) using zirconia beads having a diameter of 0.3 mm to obtain dispersion A.

(Composition)
(Ingredient) (%)
1. Dispersion A 12.0
2. Vinyl chloride resin * 26 1.7
3. Propylene glycol diacetate (organic solvent) 21.3
4.3-Methoxybutyl acetate (organic solvent) 20.0
5. Dipropylene glycol dimethyl ether (organic solvent) 25.0
6). N-methyl-2-pyrrolidone (organic solvent) 20.0
* 26: UCAR Solution Vinyl Resin VYHD (molecular weight 22000, manufactured by Dow Chemical Company)
(Manufacturing method)
(1) Components 1 to 6 are stirred with a magnetic stirrer for 30 minutes.
(2) Suction filtration was performed using glass fiber filter paper GFP (manufactured by Kiriyama Seisakusho Co., Ltd., supplemental particles 0.8 μm) to prepare an oily brown ink composition.

  The obtained oil-based pigment ink composition was excellent in powder dispersibility, excellent in fixability and storage stability.

Example 22 Paint A paint having the following formulation was prepared by the following production method.
(Ingredient) (%)
1. Methyl methacrylate resin * 27 30.0
2. Dispersant * 25 14.0
3. Ethyl acetate 26.0
4). Hybrid powder 30.0 of Production Example 2
* 27: Parapet G (Kuraray)
(Manufacturing method)
(1) Components 1 to 4 were dispersed for 2 hours with a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) using zirconia beads having a diameter of 0.3 mm to obtain a paint.

  The obtained paint was excellent in powder dispersibility and excellent in ultraviolet blocking effect.

Example 23 Resin sheet to which a resin deterioration preventing filler was added A resin sheet was formed by the following method.
(Ingredient) (%)
1. Soft polyvinyl chloride 98.0
2. Hybrid powder of Production Example 3 2.0
(Manufacturing method)
(1) Components 1 and 2 were mixed and rolled into a heated roll to form a 0.24 mm sheet.

  The obtained molded sheet was excellent in powder dispersibility and excellent in ultraviolet blocking effect.

  The production method of the present invention is useful as a method capable of obtaining an iron oxide / organopolysiloxane hybrid powder at low cost and high yield. Further, the iron oxide / organopolysiloxane hybrid powder of the present invention is excellent in powder dispersibility, has a good feeling in use, and has an excellent ultraviolet protection ability, and therefore can be advantageously used as a raw material for cosmetics. Furthermore, it can be used for inks and paints, and since it has low solid catalyst activity, it can also be used as a filler agent for preventing deterioration of resins.

Claims (9)

(A) Iron (III) chloride is reacted with an alkali to obtain (a) iron hydroxide (III). (A) Iron (III) hydroxide is converted into (B) the following general formula (1)
(In the formula, R may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X represents an optionally bonded ether bond (—O—) having 2 to 4 carbon atoms. Represents an alkylene group, and n is 1 to 12.
The organopolysiloxane represented by formula (1) is added at a molar ratio ((a) :( B)) of 10: 0.05 to 10: 1.5, and (B) the organopolysiloxane represented by the above general formula (1) siloxane (a) method for producing iron oxide-organopolysiloxane hybrid powder, wherein Rukoto by condensation reaction of iron hydroxide (III). (B) The condensation reaction of the organopolysiloxane represented by the general formula (1) and (a) iron hydroxide (III) is carried out by the condensation reaction between the OH group of (B) and the OH group of (a). 2. The method for producing an iron oxide / organopolysiloxane hybrid powder according to claim 1, which forms an O-Si- bond . R in the general formula (1) of (B) is an alkyl group having 1 to 4 carbon atoms, the OR group in the general formula (1) is hydrolyzed to become an OH group, and the OH group of (a) The method for producing an iron oxide / organopolysiloxane hybrid powder according to claim 2, which undergoes a condensation reaction . (A) any one of claim wherein of claims 1 to condensation reaction is performed at 30 to 110 ° C. with organopolysiloxane represented by iron (III) hydroxide and (B) the general formula (1) 3 Of producing iron oxide / organopolysiloxane hybrid powder. (A) Iron (III) chloride is reacted with an alkali to obtain (a) iron hydroxide (III). (A) Iron (III) hydroxide is converted into (B) the following general formula (1)
(In the formula, R may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X represents an optionally bonded ether bond (—O—) having 2 to 4 carbon atoms. Represents an alkylene group, and n is 1 to 12.
And (B) the above general formula is added in a molar ratio ((a) :( B)) of 10: 0.05 to 10: 1.0 ( excluding 10: 1). An iron oxide / organopolysiloxane hybrid powder obtained by condensation reaction of an organopolysiloxane represented by the formula (1) and (a) iron (III) hydroxide . (B) The condensation reaction of the organopolysiloxane represented by the general formula (1) and (a) iron hydroxide (III) is carried out by the condensation reaction between the OH group of (B) and the OH group of (a). The iron oxide / organopolysiloxane hybrid powder according to claim 5, which forms an O—Si— bond . R in the general formula (1) of (B) is an alkyl group having 1 to 4 carbon atoms, the OR group in the general formula (1) is hydrolyzed to become an OH group, and the OH group of (a) The iron oxide / organopolysiloxane hybrid powder according to claim 6, which undergoes a condensation reaction . A cosmetic comprising the iron oxide / organopolysiloxane hybrid powder according to any one of claims 5 to 7 . Cosmetics which mix | blend the iron oxide and organopolysiloxane hybrid powder obtained by the manufacturing method in any one of Claims 1 thru | or 4.