JP2006233221A - Treated powder - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silicone-coated treated powder which can be applied to a cosmetic and have excellent in water repellency and dispersibility. <P>SOLUTION: The treated powder is obtained by coating the surface of a powder with a silicone compound having Si-H groups (for example, methylhydrogenpolysiloxane and phenylhydrogenpolysiloxane) and adding a compound which can be reacted with the Si-H groups to the parts of unreacted Si-H groups of the silicone compound in a density of more than 100 μmol/g. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a treated powder. More specifically, the present invention relates to a treated powder imparted with a function of high water repellency and excellent dispersibility by adding functional groups, particularly alkyl groups, at high density to the silicone-coated treated powder.

  A technique for modifying a powder by coating a silicone compound having Si—H on the powder surface and adding an unsaturated compound to an unreacted Si—H group has been reported (for example, Patent Document 1). However, the addition amount is generally less than about 100 μmol / g per powder, and only an amount necessary for changing the hydrophobicity and dispersion preference is added. When manufacturing powder cosmetics etc. using such a processed powder, it is difficult to obtain sufficient oil-and-oil dispersibility, Therefore It is necessary to add the oil component and to improve the dispersibility in a system.

  On the other hand, powder cosmetics, especially solid powder cosmetics, tend to solidify with the use of oils and fats on the cosmetic surface as they are used. The realization of a solid powder cosmetic that was not desired was desired. However, until now, in the production of solid powder cosmetics, no oil-free cosmetics containing no oil have been obtained.

Japanese Patent Publication No. 1-54380

  The present invention has been made in view of the above circumstances, and an object thereof is to provide a treated powder having high water repellency and excellent dispersibility in a safe and simple manner.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have uniformly coated the surface of the powder with a silicone compound, and further introduced functional groups at a high density of a predetermined density or higher on the powder surface. The present inventors have found that a treated powder having a high water content and excellent dispersibility can be obtained, and the present invention has been completed.

  That is, in the present invention, the powder surface is coated with a silicone compound having a Si—H group, and a compound capable of reacting with the Si—H group is added to an unreacted Si—H group portion of the silicone compound. The present invention relates to a treated powder added at a density of 100 μmol / g or more.

  According to the present invention, a functional powder, particularly an alkyl group, is added to the silicone-coated powder at a higher density than in the past to obtain a treated powder having a high water repellency and excellent dispersibility. be able to. Further, by using this treated powder, a solid powder cosmetic material containing substantially no oil can be obtained.

  Hereinafter, the present invention will be described in detail.

  The powder used in the present invention is not particularly limited, but generally means any object having a particle diameter of 10 mm or less (sometimes larger than 10 mm may be included), specifically, an organic pigment. Examples thereof include inorganic pigments, metal oxides and metal hydroxides, mica, pearly luster materials, metals, carbon, magnetic powder, silicate minerals, and porous materials. These powders may be used alone or in combination, and may be an aggregate, a molded body, a molded body, or the like. Moreover, you may contain the other substance (For example, a coloring agent, UV absorber, a pharmaceutical, various additives) on or in the powder. According to the present invention, any powder including an ultrafine powder having a particle size of 0.02 μm or less can be modified (treated).

  Examples of organic pigments include red 201, red 202, red 204, red 205, red 220, red 226, red 228, red 305, orange 203, orange 204, yellow 205, Yellow 401 and blue 404, red 3, red 104, red 106, red 227, red 230, red 401, red 505, orange 205, yellow 4, yellow 5, Yellow 202, yellow 203, green 3 and blue 1 and the like, and these organic pigments may be zirconium lake, barium lake or aluminum lake.

  Examples of inorganic pigments include bitumen, ultramarine, manganese violet, (oxide) titanium-coated mica, and bismuth oxychloride.

Examples of the metal oxide and metal hydroxide include magnesium oxide, magnesium hydroxide, calcium oxide, calcium hydroxide, aluminum oxide, aluminum hydroxide, silica, iron oxide (α-Fe ₂ O ₃ , γ-Fe ₂ O ₃ , Fe ₃ O ₄ , FeO, etc.), yellow iron oxide (especially rod-shaped), red iron oxide, black iron oxide, iron hydroxide, titanium oxide (especially titanium dioxide having a particle size of 0.001 to 0.1 μm). , Low-order titanium oxide, zirconium oxide, chromium oxide, chromium hydroxide, manganese oxide, cobalt oxide, nickel oxide, and composite oxides and hydroxides of combinations of two or more thereof, such as silica alumina, iron titanate , Cobalt titanate, lithium cobalt titanate, cobalt aluminate and the like.

Examples of mica include muscovite, phlogopite, biotite, sericite, iron mica, red mica, lithia mica, chinwald mica, soda mica, artificial mica, or KAl ₂ (Al, Si ₃ ) O ₁₀ F ₂ , KMg ₃ (Al, Si ₃ ) O ₁₀ F ₂ , mica represented by K (Mg, Fe ₃ ) (Al, Si ₃ ) O ₁₀ F ₂ , and the like.

  Examples of the pearl luster material include mica titanium-based composite material, mica iron oxide-based composite material, bismuth oxychloride, guanine, and mica coated with a titanium compound containing titanium oxynitride and / or low-order titanium oxide. Is mentioned. The titanium of the mica titanium-based composite material may be any of titanium dioxide, low-order titanium oxide, and titanium oxynitride. Further, for example, iron oxide, bitumen, chromium oxide, carbon black, carmine or ultramarine may be further mixed with mica titanium-based composite material or bismuth oxychloride.

  Examples of the metal include aluminum, iron, nickel, cobalt, chromium, gold, silver, copper, platinum, zinc, indium, tin, antimony, tungsten, zirconium, molybdenum, silicon, and titanium.

Examples of the magnetic powder include γ-Fe ₂ O ₃ , magnetite (Fe ₃ O ₄ ), beltlite-type iron oxide (FeO _x ; 1.33 <x <1.5), or cobalt, manganese, nickel, Those modified with zinc, chromium or the like, needle-like iron or iron powder containing Al, B, Co, Cr, Cu, Mo, Mn, Ni, P, Si, Sn, Zn, CrO ₂ or Ba Examples thereof include ferrite.

  Further, the powder may be iron, nickel, cobalt or oxide thereof coated on mica, but is not limited thereto.

  Silicate minerals include phyllosilicate minerals (eg kaolin, montmorillonite, clay mica, chlorite, serpentine) and tectosilicate minerals (eg zeolite), pyrophyllite, talc, Chlorite, chrysotile, antigolite, lizardite, kaolinite, decaitite, nacrite, halosite, montmorillonite, nontronite, saponite, sauconite, bentonite, soda zeolite, mesolite, scolite, Thomsonite, etc. And pyroxenes such as pyroxenes, zeolitics and chabazite, and zeolites such as zeolitic, heavy cross-zeolite, chalceolite, chabazite and gmelinite.

  Furthermore, in the present invention, the porous material can be treated well. Examples of the porous material include porous glass beads, hollow silica or zeolite, or metal oxide, metal nitride, silicate mineral, carbonic acid. Examples thereof include those obtained by granulating or molding a salt mineral, sulfate mineral, or phosphate mineral, or those obtained by granulating or molding the mineral and then firing it, metal, cellulose, fiber, or synthetic resin.

  As the silicone compound having an Si—H group used in the present invention, any compound can be used as long as it is a silicone compound having an Si—H group. For example, silicone oil, silicone resin, silicone wax and the like can be mentioned. Especially, the following general formula (I)

(R ¹ HSiO) _a (R ² R ³ SiO) _b (R ⁴ R ⁵ R ⁶ SiO _1/2 ) _c (I)

[Wherein, R ¹ , R ² and R ³ are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which can be substituted with at least one halogen atom (provided that R ¹ , R ² and R ³ are not hydrogen atoms at the same time; R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom or 1 to 10 carbon atoms which can be substituted with at least one halogen atom. A is an integer of 1 or more, b is 0 or an integer of 1 or more, c is 0 or 2 (provided that 3 ≦ a + b + c ≦ 10000); and It shall contain at least one Si-H group moiety]
Is preferably used.

  Here, when c = 0, the following general formula (III)

(R ¹ HSiO) _a (R ² R ³ SiO) _b (III)

[Wherein R ¹ , R ² , R ³ , a, and b are as defined in the general formula (I). However, R ¹ , R ² and R ³ are preferably each independently a lower alkyl group having 1 to 4 carbon atoms or an aryl group (for example, a phenyl group) that can be substituted with at least one halogen atom (especially a fluorine atom). Yes; a + b is 3 or more, preferably 10 to 1000, particularly 20 to 500]
It is the cyclic silicone compound represented by these. Preferably, one having two or more hydrogen atoms in one molecule is desirable. Specific examples of the compound of the general formula (III) include cyclic methyl hydrogen polysiloxane, 1,3,5,7, -tetramethylcyclotetrasiloxane and the like.

  When c = 2, the following general formula (IV)

(R ¹ HSiO) _a (R ² R ³ SiO) _b (R ⁴ R ⁵ R ⁶ SiO _1/2 ) ₂ (IV)

[Wherein, R ^{1 to} R ⁶ , a and b are as defined in the general formula (I). Preferably, however, R ^{1 to} R ⁶ are each independently a lower alkyl group having 1 to 4 carbon atoms or an aryl group (for example, a phenyl group) that can be substituted with at least one halogen atom (particularly a fluorine atom); a + b Is 10 to 1000, particularly 20 to 500]
It is the chain silicone compound represented by these. Specific examples of the general formula (IV) include methyl hydrogen polysiloxane, phenyl hydrogen polysiloxane, 1,1,1,3,5,7,7-octamethyltetrasiloxane, 1,1,1, 3,5,7,9,9,9-nonamethylpentasiloxane, 1,1,1,3,5,7,9,11,11,11-decamethylhexasiloxane and the like.

  Any compound capable of reacting with the Si—H group used in the present invention (Si—H group reactive compound) can be used as long as it can react with the unreacted Si—H group of the silicone compound. These compounds can optionally be used.

  This Si—H group reactive compound is added to the unreacted Si—H portion of the silicone compound to introduce a desired pendant group into the silicone compound. Therefore, various functions can be imparted to the powder by appropriately selecting the Si—H reactive compound and introducing a desired pendant group. Here, the “pendant group” is a residue of a compound that can react with the Si—H group moiety, and means a group that is introduced into the silicone compound by the addition reaction of the compound. This pendant group imparts various properties and functions to the powder. Hydrophobicity can be further enhanced by adjusting the type or length of the hydrocarbon group of the unsaturated compound to be added.

  The pendant group can be arbitrarily selected. For example, an alkyl group has a high water repellency and is well dispersed in oils and fats. By adding an ultraviolet absorber, an ultraviolet-absorbing powder having no percutaneous absorption can be obtained. If a group having an antibacterial action is added, an antibacterial powder without percutaneous absorption can be obtained. Those to which an epoxy group is added can react with the resin, form a strong resin / powder composite, and become a hard composite that does not expand by heat.

  As such a Si—H group reactive compound, for example, a compound having an OH group or an SH group, such as an amino acid (cysteine or the like) can be used. Furthermore, an unsaturated compound (vinyl compound) having at least one carbon-carbon double bond or triple bond and capable of reacting with the Si-H group moiety can be used.

  Suitable unsaturated compounds include the following general formula (II)

(Wherein R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, halogen atom, hydroxyl group, mercapto group, acyloxy group, alkoxy group, amino group, nitro group, carboxyl group, sulfo group, or carbon. Is a substituted or unsubstituted hydrocarbon group having 1 to 30 atoms; or R ⁷ and R ⁹ form a carbon-carbon bond, and together with —C═C— form a carbon-carbon triple bond Or R ⁸ and R ¹⁰ can form a carbon-carbon bond and together with —C═C— can form an alicyclic group).
The compound etc. which are represented by these are mentioned.

  In the above, examples of the substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms include, for example, an aliphatic group (for example, alkyl group, alkenyl group, alkynyl group, etc.), an aromatic group (for example, phenyl group, naphthyl group). Etc.), heterocyclic groups (for example, those containing one or more nitrogen, oxygen or sulfur atoms as heteroatoms), alicyclic groups (for example, cycloalkyl groups, cycloalkenyl groups, cycloalkynyl groups, etc.) ), A spiro compound residue or a terpene compound residue.

The hydrocarbon groups R ^{7 to} R ¹⁰ are one or more unsaturated hydrocarbon groups (for example, the above-mentioned general hydrocarbon groups) unless they adversely affect the addition reaction by a double bond or triple bond in the compound of the general formula (II). As exemplified by the definition of formula (II)) and / or one or more functional groups. Representative examples of functional groups include halogen atoms, amino groups, carboxyl groups, sulfo groups, mercapto groups, epoxy groups, cyano groups, nitro groups, hydroxyl groups, alkoxy groups, alkoxycarbonyl groups, acyl groups, acyloxy groups, and quaternary ammonium. Group, polyalkylene ether group and the like.

  More preferred unsaturated compounds are alkenes or alkynes having one or more unsaturated bonds (double bonds, triple bonds) at the terminal or at any position, such as acetylene, ethylene, propylene, butene, octene, decene, octadecene, etc. Is mentioned. Alkenes and the like have an unsaturated bond and undergo an addition reaction with the Si—H group moiety at that position, so that cyclic structures such as cyclohexane, benzene, and naphthalene may exist at other positions.

  Also, butadiene, isoprene, etc. having two or more double bonds can be used.

In the present invention, in the general formula (II), in the general formula (II), R ⁸ , R ⁹ and R ¹⁰ are hydrogen atoms, and R ⁷ has 1 to 30 carbon atoms, preferably 8 carbon atoms. Those having an alkyl group of ˜18 are preferably used. Thus, when an alkyl group is used as a pendant group, a treated powder having particularly high water repellency and high dispersibility can be obtained.

  In the present invention, the powder surface is uniformly coated with a silicone compound having a Si—H group, and a compound having a pendant group on the unreacted Si—H group of the silicone compound is 100 μmol / g or more per powder. It is characterized in that it is added at a high density. By introducing functional groups into the powder at a high density in this way, not only the functionality can be sufficiently exhibited, but also performance different from the conventional one can be exhibited. The functional powder of the present invention can be applied to various fields such as cosmetics, paints and composite materials. Particularly in cosmetics, it is possible to provide a powder cosmetic that does not contain any oil that has been conventionally required.

  The powder coating method and functional group addition method of the silicone compound having Si-H groups can be performed by conventional means.

  Regarding the powder coating method of the silicone compound having Si-H groups, for example, the silicone compound is dissolved in an organic solvent (chloroform, hexane, benzene, toluene, acetone, etc.), and the powder is dispersed in this. The powder can be coated with a silicone compound coating by preparing a dispersion, heating the dispersion to evaporate the solvent, and forming a coating on the powder surface. Alternatively, the dispersion is poured into a poor solvent of the silicone compound, or the poor solvent is poured into the dispersion to adhere an insolubilized silicone compound onto the powder surface to form a film. The body may be covered. Furthermore, the powder may be encapsulated with a silicone compound coating by monomer polymerization of the silicone compound in the presence of a catalyst on the surface of the powder as in the in-situ polymerization method. Alternatively, it is possible to coat using active sites that are widely distributed over substantially the entire surface of the powder.

  Further, the silicone compound may be sprayed on the powder as it is, or after the powder is dispersed in a solvent, the silicone compound may be sprayed.

Alternatively, the powder is preferably coated with the silicone compound in water or an aqueous solution. The aqueous solution means a solution containing water as a main component and containing about 80% by weight or more of water. Examples of components other than water include alcohols such as ethanol, methanol, and isopropanol, sodium hydroxide, potassium hydroxide, calcium hydroxide, hydrochloric acid, sulfuric acid, and mixtures thereof. In addition, as water contained in this aqueous solution, ion exchange water, distilled water, etc. are mentioned, However, The inorganic ion may exist in this water. Examples of inorganic ions include Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ , Mg ⁺⁺ , Ca ⁺ , HSO 4 ⁻ , Cl ^{− and the} like. By changing the content of these ions, the pH of the aqueous system can be controlled, and as a result, the addition reaction of the pendant group in the aqueous system can be controlled. That is, if the pH value is increased by increasing the amount of inorganic ions, the crosslinking of Si-H groups can be promoted. On the other hand, if the pH value is decreased by decreasing the amount of inorganic ions, the degree of crosslinking can be suppressed. . Therefore, if the pH value is decreased to make it difficult to cause cross-linking of Si—H groups and the remaining Si—H groups are increased, the addition density of pendant groups by a hydrosilylation reaction described later can be increased. In the present invention, in order to add a compound having a pendant group at a high density of 100 μmol / g or more per powder, the pH is preferably controlled to about 5 to 8.

  The ratio of the silicone compound and the aqueous solution varies depending on the powder mixing method, but it is preferably 0.1 to 100 (weight ratio) with respect to the silicone 1, and more preferably 5 to 50. The mixing method can be performed by a conventional method using a commonly used mixer. In the case of wet mixing, the amount of water used is slightly larger, and in the case of dry mixing, the amount of water is slightly smaller.

  The amount of the silicone compound based on the powder is preferably 2 to 20% by weight, more preferably 3 to 10% by weight. If the amount of silicone is less than 2% by weight, pendant groups cannot be introduced to such an extent that the effects of the present invention can be obtained. Further, the Si—H group reactive compound is preferably 0.5 to 3 equivalents, more preferably 1 to 2 equivalents, of the Si—H groups of the silicone compound of the entire system. Water is mixed at the ratio described above with respect to the amount of the silicone compound and used as a reaction solution.

  The silicone-coated powder thus produced has an unreacted Si—H group portion, and becomes slightly unstable under severe conditions such as alkali and acid.

  Next, a compound capable of reacting with the Si—H group is added to the unreacted Si—H group of the silicone compound coated with the powder. Thereby, a Si-H reactive compound is added to the unreacted Si-H part of the silicone compound, and a pendant group derived from the Si-H reactive compound is introduced into the silicone compound. By appropriately selecting a Si—H reactive compound and introducing a desired pendant group, various functions can be imparted to the powder.

  More specifically, in the above-described first stage coating step, cross-linking of Si—H groups occurs on the powder surface to form a network structure, and the powder surface is coated with a silicone compound coating. Due to steric hindrance and the like, crosslinking is not completely performed. For this reason, residual Si—H groups exist, and tend to be slightly unstable under severe conditions such as alkali and acid. By adding a Si-H reactive compound (for example, an unsaturated compound such as alkene or alkylene) to the remaining Si-H group by a hydrosilylation reaction to form a Si-C bond, an alkali or acid is added. In contrast, a more stable powder can be obtained.

  Therefore, various functions can be imparted to the powder by appropriately selecting a Si—H reactive compound (unsaturated compound, etc.) and introducing a desired pendant group. Here, the “pendant group” is a residue of a compound that can react with the Si—H group moiety, and means a group that is introduced into the silicone compound by the addition reaction of the compound. This pendant group imparts various properties and functions to the powder. Hydrophobicity can be further enhanced by adjusting the type or length of the hydrocarbon group of the unsaturated compound to be added.

  In the present invention, the Si—H reactive compound having a pendant group is added to 100 μmol / g or more, preferably 150 μmol / g or more to 1 g of the powder.

  The silicone compound coating and the pendant group addition reaction may both be carried out in an aqueous solution. For example, a predetermined amount of a silicone compound having a Si-H group, a compound capable of reacting with the Si-H group, and water are charged into a mixer, and after mixing, the mixture is sprayed onto the powder in the form of a mist. A method of heating and mixing and further adding a catalyst can be mentioned. In addition, after adding a water-based solvent to a kneader containing powder and thoroughly stirring and mixing, a silicone compound having a Si—H group and a compound capable of reacting with the Si—H group are added and mixed by heating to prepare a catalyst. It can be added and coated and added simultaneously. This contact reaction is preferably performed while heating because the reaction time is shortened.

  Further, it may be supplied in the form of gas, or may be stirred and mixed together with the powder by a ball mill or the like. When supplying in the form of gas, a low boiling point is desirable.

  In addition, although heating temperature can be performed in the range of 50-120 degreeC, the reaction rate is large and the reaction is complete | finished in a short time at high temperature.

  Next, a catalyst is added to promote the hydrosilylation reaction between the Si—H group and the pendant group of the silicone compound.

  As a catalyst for promoting the hydrosilation reaction, a platinum group catalyst, that is, a compound of ruthenium, rhodium, palladium, osmium, iridium, or platinum is suitable, and a compound of palladium and platinum is particularly suitable. In the palladium system, palladium (II) chloride, ammonium tetraaminepalladium (II) chloride, palladium (II) oxide, palladium (II) hydroxide and the like can be mentioned. Platinum-based platinum (II) chloride, tetrachloroplatinic acid (II), platinum chloride (IV), hexachloroplatinic acid (IV), ammonium hexachloroplatinate (IV), platinum (II) oxide, platinum (II) hydroxide Platinum (IV) dioxide, platinum (IV) oxide, platinum (IV) disulfide, platinum (IV) sulfide, potassium hexachloroplatinate (IV), and the like. In addition, amine catalysts such as tributylamine or polymerization initiators can be used.

  Solid powder cosmetics containing no oil content can be made by mixing only the high addition density powder thus produced or other powders.

  Powders that can be blended in addition to this powder are talc, kaolin, mica, sericite (sericite), muscovite, phlogopite, synthetic mica, biotite, phlogopite, lithia mica, permiculite, magnesium carbonate, calcium carbonate, Aluminum silicate, barium silicate, calcium silicate, magnesium silicate, strontium silicate, metal tungstate, magnesium, silica, zeolite, barium sulfate, calcined calcium sulfate (baked gypsum), calcium phosphate, fluorapatite, hydroxyapatite, ceramic Powder, metal soap (zinc myristate, calcium palmitate, aluminum stearate), inorganic powder such as boron nitride, polyamide resin powder (nylon powder), polyethylene powder, polymethyl methacrylate powder, polystyrene powder, Organic powder components such as copolymer resin powder of tylene and acrylic acid, benzoguanamine resin powder, silicone powder, polytetrafluoroethylene powder, cellulose powder; inorganic white pigments such as titanium dioxide and zinc oxide, iron oxide (Bengara), Inorganic red pigments such as iron titanate, inorganic brown pigments such as γ-iron oxide, inorganic yellow pigments such as yellow iron oxide and ocher, inorganic black pigments such as black iron oxide, carbon black, low-order titanium oxide, Inorganic purple pigments such as mango violet and cobalt violet, inorganic green pigments such as chromium oxide, chromium hydroxide and cobalt titanate, inorganic blue pigments such as ultramarine and bitumen, titanium oxide coated mica, titanium oxide coated bismuth oxychloride , Titanium oxide coated talc, colored titanium oxide coated mica, bismuth oxychloride, fish scale foil, etc. Pigment powder, metal powder pigment such as aluminum powder, copper powder, red 201, red 202, red 204, red 205, red 220, red 226, red 228, red 305, orange 203, Orange No. 204, Yellow No. 205, Yellow No. 401 and Blue No. 404, Red No. 3, Red No. 104, Red No. 106, Red No. 227, Red No. 230, Red No. 401, Red No. 505, Orange No. 205, Examples include organic pigments such as zirconium, barium or aluminum lakes such as yellow No. 4, yellow No. 5, yellow No. 202, yellow No. 203, green No. 3 and blue No. 1.

  In addition to these powders, antioxidants, preservatives and the like can be added.

  These powders can be mixed using an ordinary mixer, but it is desirable to use those having a high shearing force.

  By using the above-described high-density processed powder to which pendant groups are added according to the present invention, or by mixing other powders, a solid powder cosmetic containing substantially no oil can be obtained. As used herein, the term “oil” means a liquid that is in a liquid state at room temperature. Specifically, avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk Oil, sesame oil, persic oil, wheat germ oil, sasanqua oil, castor oil, flaxseed oil, safflower oil, cottonseed oil, eno oil, soybean oil, peanut oil, tea seed oil, kaya oil, rice bran oil, cinnagiri oil, Japanese kiri Liquid oils such as oil, jojoba oil, germ oil, glycerin trioctanoate, glycerin triisopalmitate; hydrocarbons such as liquid paraffin, squalene, squalane, pristane, fatty acids such as oleic acid, tall oil, isostearic acid; lauryl alcohol, Liquid higher alcohols such as oleyl alcohol, isostearyl alcohol, octyldodecanol; methyl Liquid silicones such as resiloxane, methylphenyl polysiloxane, methyl hydrogen polysiloxane, decamethyl polysiloxane; isopropyl myristate, isopropyl palmitate, hexyl laurate, oleyl oleate, decyl oleate, octyldodecyl myristate, dimethyloctane Examples include esters such as hexyldecyl acid, diethyl phthalate, and dibutyl phthalate. Therefore, the cosmetic substantially free of oil means a cosmetic substantially free of any of these liquid oils.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, it goes without saying that the scope of the present invention is not limited by these examples.

Example 1-1 Treatment of sericite 291 g of sericite and 190 g of ion-exchanged water were placed in a 1 L kneader and sufficiently stirred and mixed at room temperature. Thereafter, 12 g of “silicone KF-99” (manufactured by Shin-Etsu Chemical Co., Ltd.), which is a silicone compound having a Si—H group, is added, the temperature is raised while stirring and mixing, and water is evaporated at 100 ° C. for 5 hours. Reacted. Next, the remaining water was removed by a vacuum dryer to obtain silicone-treated sericite.

  Thereafter, 250 g of ion-exchanged water was added to the silicone-treated sericite and stirred and mixed well. Then, 50 g of tetradecene and 15 mg of chloroplatinic acid were added, the temperature was raised while stirring and mixing were continued, and water was evaporated at 100 ° C. while evaporating the water. Reacted for hours. Next, after remaining water and unreacted tetradecene were removed by a vacuum dryer, the coated powder was taken out. The obtained treated powder showed remarkable hydrophobicity. The amount of tetradecene added per powder was measured by elemental analysis and found to be 382 μmol / g.

Example 1-2
A similar treatment was performed by replacing the sericite of Example 1-1 with titanium dioxide to obtain a treated powder. The amount of tetradecene added was 330 μmol / g.

Example 1-3
A similar treatment was performed by replacing the sericite of Example 1-1 with silica gel to obtain a treated powder. The amount of tetradecene added was 318 μmol / g.

Example 1-4
A similar treatment was performed by replacing the sericite of Example 1-1 with talc to obtain a treated powder. The amount of tetradecene added was 355 μmol / g.

Example 1-5
A similar treatment was performed by replacing the sericite of Example 1-1 with zinc white to obtain a treated powder. The amount of tetradecene added was 348 μmol / g.

Example 1-6
A similar treatment was performed by replacing the sericite of Example 1-1 with titanium mica to obtain a treated powder. The amount of tetradecene added was 311 μmol / g.

Example 1-7
A similar treatment was performed by replacing the sericite of Example 1-1 with Bengala to obtain a treated powder. The amount of tetradecene added was 287 μmol / g.

Example 1-8
A similar treatment was performed by replacing the sericite of Example 1-1 with yellow iron oxide to obtain a treated powder. The amount of tetradecene added was 364 μmol / g.

Example 1-9
A similar treatment was performed by replacing the sericite of Example 1-1 with black iron oxide to obtain a treated powder. The amount of tetradecene added was 303 μmol / g.

Example 2
Sericite 50kg, mica powder 20kg, titanium dioxide 10kg, talc 15kg, red iron oxide 1kg, yellow iron oxide 3.2kg, black iron oxide 0.2kg, fine titanium dioxide 0.6kg and ion-exchanged water 60kg into a 200L kneader The mixture was mixed well, and the temperature was raised while adding 3.5 kg of “Silicone KF-99” (manufactured by Shin-Etsu Chemical Co., Ltd.) in the same manner as in Example 1, and the mixture was reacted at 100 ° C. for 8 hours. Next, the remaining water was removed by a vacuum dryer to obtain a silicone-treated composite powder.

  After that, 100 kg of ion-exchanged water was added to the silicone-treated composite powder and stirred and mixed well. Then, 8 kg of tetradecene and 3.5 g of chloroplatinic acid were added, and the temperature was raised while stirring and mixing, and water was evaporated at 100 ° C. And allowed to react for 2 hours. Next, after remaining water and unreacted tetradecene were removed by a vacuum dryer, the coated powder was taken out. The obtained treated powder showed remarkable hydrophobicity. The amount of tetradecene added was measured by elemental analysis and found to be 402 μmol / g.

Example 3
Put 150g of sericite, 100g of mica powder, 30g of titanium dioxide, 45g of talc, 3g of red iron oxide, 10g of yellow iron oxide, 0.6g of black iron oxide, 1.8g of fine titanium dioxide and 180g of ion-exchanged water in a 1L kneader. The mixture was mixed well, and the temperature was raised while gradually adding 7.5 g of “Silicone KF-99” (manufactured by Shin-Etsu Chemical Co., Ltd.) in the same manner as in Example 1 and reacted at 100 ° C. for 8 hours. Next, the remaining water was removed by drying under reduced pressure to obtain a silicone-treated composite powder.

  Thereafter, 300 g of ion-exchanged water was added to the silicone-treated composite powder and stirred and mixed well. Then, 15 g of tetradecene and 10 mg of chloroplatinic acid were added, and the temperature was increased while stirring and mixing were continued. Reacted for hours. Next, after remaining water and unreacted tetradecene were removed by a vacuum dryer, the coated powder was taken out. The obtained treated powder showed remarkable hydrophobicity. The amount of tetradecene added was measured by elemental analysis and found to be 210 μmol / g.

Comparative Example 1
In Example 3, a treated powder composite was obtained in the same manner as in Example 3 except that the amount of “silicone KF-99” (manufactured by Shin-Etsu Chemical Co., Ltd.) was changed to 3.0 g. The obtained treated composite powder was hydrophobic, and the amount of tetradecene added was 85 μmol / g.

Example 4: Foundation
Compounding ingredients Weight%
(1) Processed powder of Example 1-1 40.0
(2) Processed powder of Example 1-2 13.0
(3) Treated powder of Example 1-4 34.7
(4) Processed powder of Example 1-7 1.0
(5) Processed powder of Example 1-8 2.5
(6) Processed powder of Example 1-9 0.1
(7) Spherical silica 3.0
(8) Spherical silicone powder 2.0
(9) Spherical polyethylene powder 3.5
(10) Ethylparaben 0.2
Manufacturing method The said component (1)-(9) was mixed, it grind | pulverized to the average particle diameter of 1-5 micrometers through a grinder, and after adjusting the particle diameter through the sieve, it compression-molded and the cake type foundation was obtained. The obtained foundation was able to be molded in spite of not containing any oil, had a good stretch, was easy to use and had good makeup.

Example 5: Foundation
Compounding ingredients Weight%
(1) Treated powder of Example 2 85.0
(2) Spherical nylon powder 3.0
(3) Spherical silicone powder 2.0
(4) Spherical polyethylene powder 9.8
(5) Ethylparaben 0.2
Manufacturing method The said component (1)-(5) was mixed, it grind | pulverized to the average particle diameter of 1-5 micrometers through the grinder, and after forming the particle size through the sieve, it compression-molded and the cake type foundation was obtained. The obtained foundation was able to be molded in spite of not containing any oil, had a good stretch, was easy to use and had good makeup.

Example 6: Foundation
Compounding ingredients Weight%
(1) Processed powder of Example 3 85.0
(2) Spherical nylon powder 3.0
(3) Spherical silicone powder 2.0
(4) Spherical polyethylene powder 9.8
(5) Ethylparaben 0.2
Manufacturing method The said component (1)-(5) was mixed, it grind | pulverized to the average particle diameter of 1-5 micrometers through the grinder, and after forming the particle size through the sieve, it compression-molded and the cake type foundation was obtained. The obtained foundation was able to be molded in spite of not containing any oil, had a good stretch, was easy to use and had good makeup.

Comparative Example 2
In Example 5, instead of the treated powder of Example 2, a foundation was produced using the same other ingredients except that the treated powder of Comparative Example 1 was used. The obtained foundation was completely powdery and could not be molded.

Claims (7)

  The powder surface is coated with a silicone compound having a Si—H group, and a compound capable of reacting with the Si—H group is added to the unreacted Si—H group portion of the silicone compound at a concentration of 100 μmol / g or more. Processed powder added by density. The silicone compound having the Si-H group is represented by the following general formula (I):
(R ¹ HSiO) _a (R ² R ³ SiO) _b (R ⁴ R ⁵ R ⁶ SiO _1/2 ) _c (I)
[Wherein, R ¹ , R ² and R ³ are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which can be substituted with at least one halogen atom (provided that R ¹ , R ² and R ³ are not hydrogen atoms at the same time; R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom or one carbon atom which can be substituted with at least one halogen atom. A is an integer of 1 or more, b is 0 or an integer of 1 or more, c is 0 or 2 (provided that 3 ≦ a + b + c ≦ 10000); and The compound shall contain at least one Si-H group moiety)
The treated powder according to claim 1, which is a silicone compound represented by the formula:   The treated powder according to claim 1 or 2, wherein the silicone compound is methyl hydrogen polysiloxane.   The compound capable of reacting with the Si-H group is an unsaturated compound having at least one carbon-carbon double bond or triple bond and capable of reacting with the Si-H group. The treated powder according to any one of the above. The compound capable of reacting with the Si-H group is represented by the following general formula (II)

(Wherein R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, halogen atom, hydroxyl group, mercapto group, acyloxy group, alkoxy group, amino group, nitro group, carboxyl group, sulfo group, or carbon. Is a substituted or unsubstituted hydrocarbon group having 1 to 30 atoms; or R ⁷ and R ⁹ form a carbon-carbon bond, and together with —C═C— form a carbon-carbon triple bond Or R ⁸ and R ¹⁰ can form a carbon-carbon bond and together with —C═C— can form an alicyclic group).
The processing powder of any one of Claims 1-4 which is a compound represented by these. The treated powder according to claim 5, wherein, in the general formula (II), R ⁸ , R ⁹ and R ¹⁰ are hydrogen atoms, and R ⁷ is a hydrocarbon group having 1 to 30 carbon atoms. The treated powder according to claim 6, wherein, in the general formula (II), R ⁸ , R ⁹ and R ¹⁰ are hydrogen atoms, and R ⁷ is an alkyl group having 1 to 30 carbon atoms.