CN110769803A - Cosmetic containing titanium dioxide powder - Google Patents

Abstract

The present invention provides a powder cosmetic which has excellent makeup durability, makeup appearance and usability, maintains covering power, and has an excellent function of transmitting light in a long wavelength region (red light selective transmission function). The powder cosmetic is characterized by comprising: 1 to 30 mass% of a titanium dioxide powder having an apparent average particle diameter of 100nm or more and less than 500nm, an average crystallite diameter of 15 to 30nm as measured by an X-ray diffraction method, and a specific surface area of 10 to 30m²/g、And particles having a shape in which needle-like protrusions protruding radially are coagulated, and the ratio of the short diameter to the long diameter (long diameter/short diameter) of the shape is 1.0 to 2.5; and 0.1 to 10 mass% of hydrophobized zinc oxide.

Description

Cosmetics mixed with titanium dioxide powder

Affiliate application

This application claims priority from Japanese Patent Application No. 2017-124681 filed on June 26, 2017, which is incorporated herein by reference.

technical field

The present invention relates to powder cosmetics incorporating hydrophobized zinc oxide, in particular to titanium dioxide suitable for use in the powder cosmetics.

Background technique

Titanium dioxide is widely used as a white pigment for paints, plastics, etc. due to its high refractive index and excellent whiteness, hiding power, and tinting power. In addition, titanium dioxide can be used as a substance that shields ultraviolet rays by controlling its particle size and photoactivity, and can also be used as an ultraviolet absorber or ultraviolet shielding agent in cosmetics, catalysts, and other applications, so in recent years, research in these applications has been flourishing. development.

It is known that if a titanium dioxide powder with an apparent specific average particle diameter formed by small spherical particles of titanium dioxide with a specific average primary particle diameter in a coccoid shape formed of many titanium dioxides is used in cosmetics, it is known that the conventional titanium dioxide can be added to the powder. A functional material with excellent smoothness or excellent light resistance which is not available (Patent Document 1).

In addition, it is known to contain 1 to 15 mass % of rutile-type titanium oxide agglomerated particles having an average particle diameter of 0.2 to 0.4 μm and an average friction coefficient (MIU value) of 0.4 to 0.6, and 1 to 40 mass % of rutile-type titanium oxide aggregated particles. A solid oil-based lip cosmetic, which has luster, suppresses conspicuous lip wrinkles, and is excellent in long-lasting makeup (Patent Document 2).

In addition, it is known that, as a colorant used in cosmetics, by blending a colorant with a low absorption rate of light on the long-wavelength side (wavelength 630 to 700 nm) even in the visible light region, the light transmittance inside the skin is known to be close to that of the skin without makeup. , a natural makeup can be achieved (Patent Document 3).

In this way, as titanium dioxide for improving the transmittance of light on the long wavelength side of light, it is known to develop a rutile-type titanium oxide in which rod-like particles are oriented and aggregated into a bundle, and the surface of the oriented and aggregated particles is known. The apparent average major axis length is 80 to 300 nm, the apparent mean minor axis length of the particles formed by orientation aggregation is 30 to 150 nm, and the apparent mean axis ratio expressed by the apparent mean major axis length/apparent mean minor axis length is 1.1 to 4, with a specific surface area of 120 to 180 m ² /g, that is, rutile-type titanium oxide in the form of short strips or straw bundles, and high in transparency and ultraviolet shielding ability (Patent Document 4).

However, since this titanium dioxide is an aggregate of rod-shaped particles, and there are many voids in the secondary aggregate, the apparent refractive index decreases, and the hiding power is insufficient when actually mixed into a cosmetic. In addition, since the target is focused on UV protection, the apparent particle size of the secondary agglomerates is also less than 100 nm, which is significantly smaller than the particle size that maximizes the scattering effect of titanium oxide based on the Mie theory, so this also becomes a mask The main reason for the low power.

In addition, powder cosmetics typified by powder foundations are cosmetics formed by adding an oily component as a binder to powder components, mixing them, and then filling them into a container and molding. Powder components are mainly composed of inorganic pigments, organic pigments, and resin powders, and pigments are further classified into colored/pearl pigments for adjusting color tone and gloss, and extender pigments. The representative of extender pigments is talc, mica, kaolin and other plate powders, which account for most of the powder components and have a great impact on the formability, adhesion, and usability of cosmetics. Therefore, by adding characteristic extender pigments such as boron nitride, synthetic fluorphlogopite, and barium sulfate to these basic extender pigments, the characteristics of powder cosmetics can be roughly formed.

Conventional titanium dioxide has a high covering power for skin spots, etc., but conversely, when a large amount of titanium dioxide is added to improve the covering power, an unnatural makeup will be formed, and the unevenness on the skin may be higher than that of the skin without makeup. more conspicuous.

In view of such a situation, it is desired to develop powder cosmetics that incorporate titanium dioxide, are excellent in usability and uniform makeup, and form a natural makeup when applied to the skin.

prior art literature

Patent Literature

Patent Document 1: Japanese Patent Laid-Open No. 2000-191325;

Patent Document 2: Japanese Patent Laid-Open No. 2010-24189;

Patent Document 3: Japanese Patent Laid-Open No. 2006-265134;

Patent Document 4: Japanese Patent Laid-Open No. 2010-173863.

SUMMARY OF THE INVENTION

The problem to be solved by the invention

Therefore, the present invention has been made in view of the above-mentioned prior art, and the problem to be solved is to provide powder cosmetics which are blended with hydrophobized zinc oxide and titanium dioxide, have excellent makeup retention, and provide a natural makeup when applied to the skin.

means of solving problems

The inventors of the present invention have conducted intensive studies in order to solve the above-mentioned problems, and as a result, have found that titanium dioxide obtained by firing a specific titanium dioxide to obtain a specific particle size, a specific crystallite diameter, and a specific specific surface area has sufficient properties required for cosmetics. Excellent hiding power and selective transmission of red light. Furthermore, it was found that a compound obtained by blending hydrophobized zinc oxide with this titanium dioxide has excellent makeup retention and usability, and has natural makeup and no whitening when applied to the skin.

That is, the powder cosmetic according to the present invention is characterized by containing:

1 to 30 mass % of titanium dioxide powder having an apparent average particle diameter of 100 nm or more and less than 500 nm, an average crystallite diameter measured by X-ray diffractometry of 15 to 30 nm, and a specific surface area of 10 -30 m ² /g and having a shape in which radially protruding needle-like protrusions agglomerate, and the ratio of the minor axis to the major axis (major axis/minor axis) of the shape is 1.0 or more and less than 2.5; and

0.1 to 10 mass % of hydrophobized zinc oxide.

In the above-mentioned powder cosmetic, the ratio of the short diameter to the long diameter (long diameter/short diameter) of the shape of the titanium dioxide powder is preferably 1.0 to 2.0.

The powder cosmetic according to the present invention is characterized by comprising:

1 to 30 mass % of titanium dioxide powder having an apparent average particle diameter of 100 nm or more and less than 500 nm, an average crystallite diameter measured by X-ray diffractometry of 15 to 30 nm, and a specific surface area of 10 -30 m ² /g particles having a shape in which radially protruding needle-like protrusions agglomerate; and

0.1 to 10 mass % of hydrophobized zinc oxide.

The powder cosmetic according to the present invention is characterized by comprising:

1-30 mass % rutile-type titanium dioxide powder, the rutile-type titanium dioxide powder has an average crystallite diameter measured by X-ray diffraction method of 15-30 nm, a specific surface area of 10-30 m ² /g, and a reflectance of 450 nm is 1.3 times or more the value of the reflectance at 650 nm, and the chromatic aberration (ΔE) is 22 or less; and

0.1 to 10 mass % of hydrophobized zinc oxide.

It should be noted that the color difference (ΔE) is obtained by dispersing and mixing titanium dioxide powder in a nitrocellulose varnish so that the concentration becomes 5%, and the obtained dispersion is 0.101 μm on the black and white coverage test paper JIS-K5400. The thickness of the film was coated and dried to obtain a test sample. The obtained test samples were colorimetrically measured on the surfaces of the coating films on white and black paper using a spectrophotometer. Calculate the color difference (ΔE) in the Hunter Lab color space.

The powder cosmetic according to the present invention is characterized by comprising:

1 to 30 mass % of titanium dioxide powder obtained by firing rutile-type titanium dioxide having needle-like protrusions on the particle surface satisfying the following (a) to (c), The apparent average particle diameter is 100 nm or more and less than 500 nm, the average crystallite diameter measured by X-ray diffractometry is 15 to 30 nm, and the specific surface area is 10 to 30 m ² /g; and

0.1 to 10 mass % of hydrophobized zinc oxide;

(a) The apparent average particle diameter is 100 nm or more and less than 500 nm,

(b) The average crystallite diameter measured by X-ray diffractometry is 1 to 25 nm,

(c) The specific surface area is 40 to 200 m ² /g.

The powder cosmetic according to the present invention is characterized by comprising:

1 to 30% by mass of titanium dioxide powder characterized by being obtained by firing rutile-type titanium dioxide having needle-like protrusions on particle surfaces satisfying the following (a) to (c) powder, and the specific surface area of the rutile-type titanium dioxide powder after firing is 8 to 50% relative to that before firing; and

0.1 to 10 mass % of hydrophobized zinc oxide;

(a) The apparent average particle diameter is 100 nm or more and less than 500 nm,

(b) The average crystallite diameter measured by X-ray diffractometry is 1 to 25 nm,

(c) The specific surface area is 40 to 200 m ² /g.

In the above powder cosmetic, the firing temperature of titanium dioxide is preferably 500 to 800°C.

In the above powder cosmetic, the firing temperature of titanium dioxide is preferably 550 to 750°C.

Invention effect

ADVANTAGE OF THE INVENTION According to this invention, the powder cosmetics excellent in the function (red light selective transmission function) excellent in the function (red light selective transmission function) which are excellent in make-up and usability, maintain hiding power, and can transmit the light of the long wavelength range more can be provided.

Description of drawings

[ Fig. 1 ] It is a calculation method of the apparent average particle diameter.

2 is a graph showing the spectral reflectance of rutile-type pigment grade titanium oxide (*1), titanium oxide B (unfired), and titanium oxide B fired at 700 and 900°C.

[ Fig. 3] Fig. 3 is a graph showing a change in shape of titanium dioxide B fired at each firing temperature by TEM observation.

[ Fig. 4] Fig. 4 is a graph showing a change in the hiding power of titanium oxide B due to a change in the firing temperature in a rotary kiln (Rotary Kiln).

[ Fig. 5] Fig. 5 is a graph showing a change in red transmittance due to a change in the firing temperature of titanium oxide B due to a change in the firing temperature in the rotary kiln.

Detailed ways

The titanium dioxide powder according to the present invention is characterized by calcining titanium dioxide having needle-like protrusions on the surface of the particles obtained by aggregating rod-shaped or needle-shaped particles in a radial orientation at 500 to 800°C, more preferably 550 to 750°C The obtained titanium dioxide powder has an average crystallite diameter of 15 to 30 nm as measured by X-ray diffractometry, and an apparent average particle diameter of titanium dioxide of 100 nm or more and less than 500 nm, more preferably 200 to 400 nm. The surface area is 10 to 30 m ² /g.

[Titanium dioxide for parent nucleus]

The crystal forms of titanium dioxide used for the mother nucleus are anatase type and rutile type due to the difference in crystal structure. Here, since the crystal form of titanium dioxide used in the present invention has low photocatalytic activity and high refractive index, it needs to be a rutile type with high hiding power.

For the titanium dioxide used for the parent core, titanium dioxide with red light transmission function is used. Considering that a shrinkage phenomenon generally occurs after firing, from the viewpoint of realizing the hiding power and excellent red light transmission function due to the scattering of titanium dioxide obtained in the present invention, the apparent appearance of titanium dioxide used for the mother core is The average particle diameter is desirably preferably 100 nm or more and less than 500 nm, and more preferably 200 to 400 nm.

As a shape of the rutile-type titanium dioxide used for a mother nucleus, a cocoon shape, a straw bundle shape, a short strip shape, a spherical shape, a needle shape, a rod shape, etc. are mentioned, for example. In the present invention, it is preferable that the rod-shaped or needle-shaped particles are aggregated in a radial orientation and have needle-shaped protrusions on the particle surface.

The specific surface area of the titanium dioxide used for the mother core is desirably 40 to 200 m ² /g from the viewpoint of efficiently increasing the apparent refractive index by firing.

The rutile-type titanium dioxide used for the mother core preferably has an average crystallite diameter of 1 to 25 nm as measured by X-ray diffractometry.

Titanium dioxide used for the parent core may be commercially available. For example, ST700 series manufactured by Titanium Industry Co., Ltd. is mentioned. Among these, ST710 etc. are mentioned.

[Titanium dioxide powder used in the present invention]

The titanium dioxide powder used in the present invention can be obtained by firing the titanium dioxide used for the mother core.

The firing temperature is desirably the following temperature conditions depending on the device for firing: the needle-like protrusions that protrude radially from the surface of the particles existing before firing are particles that are agglomerated by firing. The voids existing between the needle-shaped particles are reduced, the needle-shaped particles are sintered with each other, and the average crystallite diameter measured by the X-ray diffraction method does not increase excessively. Thereby, sufficient hiding power and the red light selective transmission function can be achieved at the same time.

The titanium dioxide powder used in the present invention is characterized in that the needle-like protrusions that protrude radially from the surface of the particles before firing are in the shape of particles coagulated by firing. Furthermore, it is characterized in that the ratio of the short axis to the long axis (long axis/short axis) of the particles is 1.0 or more and less than 2.5. More preferably, it is 1.0-2.0.

The appropriate firing temperature varies depending on the firing apparatus, but when firing is performed in a muffle furnace or a rotary kiln, which is a general firing furnace, it is desirably 500 to 800° C., more preferably 550 to 750° C. range for firing. When the temperature is lower than 500°C, the voids existing before firing are not sufficiently reduced, so that the hiding power is insufficient. When the temperature exceeds 800°C, the sintering proceeds excessively and the selective transmission function of red light is lost.

The titanium dioxide of the present invention needs to have an average crystallite diameter of 15 to 30 nm as measured by X-ray diffractometry.

When the said crystallite diameter is less than 15 nm, since sufficient hiding power cannot be acquired, it is unpreferable. In addition, when it exceeds 30 nm, sintering progresses, and the sufficient selective transmission function of red light is lost, which is not preferable from this point of view.

In addition, the titanium dioxide powder of the present invention needs to have an apparent average particle diameter of 100 nm or more and less than 500 nm, more preferably 200 nm, from the viewpoint of effectively realizing the hiding power due to scattering and the excellent red transmission function. ~400nm.

The specific surface area of the titanium dioxide powder used in the present invention is an index showing the reduction of the porosity of the obtained titanium oxide particles and the progress of sintering, and the specific surface area of the titanium dioxide powder serving as the mother nucleus after firing is the same as that before firing (100 %) is preferably in the range of 8 to 50%. More preferably, it is 8 to 30%.

In addition, the specific surface area of the titanium dioxide powder of the present invention needs to be 10 to 30 m ² /g. If it is less than 10 m ² /g, sintering will proceed, and a sufficient selective transmission function of red light will be lost, which is not preferable from this point of view. On the other hand, when it exceeds 30 m ² /g, there are excessive voids, and sufficient hiding power cannot be achieved, which is not preferable from this point of view.

The titanium dioxide powder of the present invention may be surface-treated after firing. By performing the surface treatment, the viscosity, dispersibility to oil, and makeup retention along with water repellency can be improved, and titanium dioxide excellent in usability can be obtained.

Examples of inorganic substances that can be used as surface treatment agents include hydrated oxides or oxides of metals such as aluminum, silicon, zinc, titanium, zirconium, iron, cerium, and tin. The above-mentioned metal salts that can be used here are not particularly limited.

Examples of organic substances that can be used as surface treatment agents include stearic acid, oleic acid, isohard acid, etc., after surface treatment with metal oxides such as aluminum hydroxide and alumina, and metal hydroxides in order to add lipophilicity. Fatty acid, myristic acid, palmitic acid, behenic acid and other fatty acids; methyl hydrogen polysiloxane, polydimethylsiloxane, alkyl (C8-C18, etc.) trialkoxy Silane, amino-modified siloxane, carboxyl-modified siloxane and other organosilicon compounds; fluorine compounds such as perfluoroalkyl alkyl phosphates; dextrin myristate, dextrin palmitate, lauroyl lysine, Amino acid derivatives such as lauroyl glutamate, etc.

When these surface treatment agents are contained in an amount of 1 to 10 mass % with respect to the titanium dioxide powder, the shielding power is high, which is preferable.

The titanium dioxide powder used in the present invention can be widely blended in cosmetics, pigments, inks, paints, and the like.

The blending amount of the titanium dioxide used in the present invention is 1 to 30% by mass, more preferably 5 to 15% by mass, with respect to the total weight of the powder cosmetic. If it is less than 1 mass %, the effect by the blending of the titanium dioxide of the present invention may not be obtained, and if it exceeds 30 mass %, the makeup may become unnatural.

[Hydrophobic treatment of zinc oxide]

The blending amount of the hydrophobized zinc oxide (particularly preferably dextrin palmitate-treated zinc oxide) used in the present invention is 0.1 to 10 mass %, more preferably 2 to 5 mass % with respect to the total weight of the powder cosmetic %. If it is less than 0.1 mass %, the makeup holding effect may not be obtained, and if it exceeds 10 mass %, the usability may be deteriorated.

Examples of the hydrophobized zinc oxide include zinc oxide treated with dextrin palmitate, zinc oxide treated with n-octyltriethoxysilane, zinc oxide treated with perfluoroalkyl phosphate, and the like. In the present invention, it is a low-temperature sintered product of particulate zinc oxide, and as the hydrophobization treatment, dextrin palmitate treatment is preferably used.

The hydrophobized zinc oxide can be produced by, for example, coating a fatty acid on a zinc oxide fired at a low temperature using the method described in JP 5-3844.

As a commercial item of the hydrophobized zinc oxide, WSX-MZ-700 of TAYCA Co., Ltd. is mentioned.

[other ingredients]

In the powder cosmetic according to the present invention, other ingredients such as inorganic powder, organic powder, ester, anionic surfactant, cationic surfactant, Amphoteric surfactants, nonionic surfactants, moisturizing agents, water-soluble polymers, thickeners, film agents, UV absorbers, metal ion blocking agents, lower alcohols, polyols, sugars, amino acids, organic amines, polymers Emulsions, pH adjusters, skin nutrients, vitamins, antioxidants, antioxidant aids, fragrances, water, etc., can be produced by conventional methods depending on the intended dosage form.

Specific ingredients that can be blended are listed below, and powder cosmetics can be prepared by blending the above-mentioned essential ingredients and any one or two or more of the following ingredients.

Examples of the inorganic powder include talc, boron nitride, sericite, natural mica, calcined mica, synthetic mica, synthetic sericite, alumina, mica, kaolin, bentonite, montmorillonite, calcium carbonate, magnesium carbonate, Calcium phosphate, silicic anhydride, magnesium oxide, tin oxide, iron oxide, yttrium oxide, chromium oxide, zinc oxide, cerium oxide, aluminum oxide, magnesium oxide, chromium hydroxide, cyanine (Prussian blue), ultramarine blue, calcium phosphate, hydrogen Alumina, barium sulfate, magnesium sulfate, silicic acid, magnesium aluminum silicate, calcium silicate, barium silicate, magnesium silicate, aluminum silicate, strontium silicate, silicon carbide, magnesium fluoride, metal tungstate, aluminum Magnesium Oxide, Magnesium AluminoMetasilicate, Aluminum Chlorohydroxyl, Clay, Zeolite, Hydroxyapatite, Ceramic Powder, Spinel, Mullite, Cordierite, Aluminum Nitride, Titanium Nitride, Nitride Silicon, Lanthanum, Samarium, Tantalum, Terbium, Europium, Neodymium, Mn-Zn Ferrite, Ni-Zn Ferrite, Silicon Carbide, Cobalt Titanate, Barium Titanate, Iron Titanate, Lithium Titanate Cobalt, cobalt aluminate, tin oxide containing antimony, indium oxide containing tin, magnetite, aluminum powder, gold powder, silver powder, platinum powder, copper powder, precious metal colloid, iron powder, zinc powder, cobalt blue, cobalt violet, cobalt green , Subvalent Titanium Oxide, Particulate Titanium Oxide, Butterfly Barium Sulfate, Petal Zinc Oxide, Tetrapod Zinc Oxide, Particulate Zinc Oxide; As Pearl Pigments: Titanium Oxide Coated Mica, Titanium Oxide Coated Mica, Oxide Titanium-coated synthetic mica, titanium oxide-coated silica, titanium oxide-coated synthetic mica, titanium oxide-coated talc, zinc oxide-coated silica, titanium oxide-coated colored mica, iron oxide red-coated titanium mica, iron oxide red/iron oxide black Coated mica titanium, carmine coated mica titanium, cyanine coated mica titanium, etc.

Organic powders include (for example, silicone elastomer powder, silicone powder, silicone resin-coated silicone elastomer powder, polyamide resin powder (nylon powder), polyethylene powder, polymethyl methacrylate powder (for example, , methyl methacrylate cross-linked polymer), polystyrene powder, copolymer resin powder of styrene and acrylic acid, benzoguanamine resin powder, polytetrafluoroethylene powder, cellulose powder, etc.); zirconium, barium Or organic pigments such as aluminum lakes (for example, Red No. 201, Red No. 202, Red No. 204, Red No. 205, Red No. 220, Red No. 226, Red No. 228, Red No. 405, Orange No. 203, Orange 204, yellow 205, yellow 401, and blue 404 and other organic pigments, etc.).

Examples of anionic surfactants include fatty acid soaps (eg, sodium laurate, sodium palmitate, etc.); higher alkyl sulfate salts (eg, sodium lauryl sulfate, potassium lauryl sulfate, etc.); alkyl ethers Sulfate salts (eg, POE-lauryl sulfate triethanolamine, POE-sodium lauryl sulfate, etc.); N-acyl sarcosine (eg, sodium lauroyl sarcosinate, etc.); higher fatty acid amide sulfonates (eg, N-myristoyl-N-methyl taurate sodium, coconut oil fatty acid sodium methyl taurate, sodium lauryl methyl taurate, etc.); Phosphate ester salts (POE-sodium oleyl ether phosphate, POE- Stearyl ether phosphate, etc.); sulfosuccinates (eg, sodium di-2-ethylhexyl sulfosuccinate, sodium monolauroyl monoethanolamide polyoxyethylene sulfosuccinate, lauryl polypropylene glycol sulfonate sodium succinate, etc.); alkylbenzene sulfonates (for example, linear sodium dodecylbenzenesulfonate, linear dodecylbenzenesulfonic acid triethanolamine, linear dodecylbenzenesulfonic acid, etc.) ; Higher fatty acid ester sulfate salts (for example, hydrogenated coconut fatty acid sodium glycerol sulfate, etc.); N-acyl glutamate salts (for example, N-lauroyl glutamate monosodium, N-stearoyl glutamate di- sodium, N-myristoyl-L-glutamate monosodium, etc.); sulfated oils (eg, turkey red oil, etc.); POE-alkyl ether carboxylic acids; POE-alkyl allyl ether carboxylates; α -Olefin sulfonate; Higher fatty acid ester sulfonate; Secondary alcohol sulfate; Higher fatty acid alkanolamide sulfate; Sodium lauroyl monoethanolamide succinate; N-palmitoyl aspartic acid bis(tris) Ethanolamine); sodium caseinate, etc.

Examples of cationic surfactants include: alkyltrimethylammonium salts (for example, stearyltrimethylammonium chloride, lauryltrimethylammonium chloride, etc.); alkylpyridinium salts (for example, Cetylpyridinium chloride, etc.); distearyldimethylammonium chloride dialkyldimethylammonium salt; poly(N,N'-dimethyl-3,5-methylenepiperyl chloride) pyridinium); alkyl quaternary ammonium salts; alkyl dimethyl benzyl ammonium salts; alkyl isoquinolinium salts; dialkyl morpholinium salts; POE-alkylamines; alkylamine salts; polyamine fatty acids Derivatives; amyl alcohol fatty acid derivatives; Benzalkonium Chloride (Benzalkonium Chloride); Benzethonium Chloride (Benzethonium Chloride) and the like.

Examples of the amphoteric surfactant include imidazoline-based amphoteric surfactants (for example, sodium 2-undecyl-N,N,N-(hydroxyethylcarboxymethyl)-2-imidazoline, 2- - Cocoyl-2-imidazolinium hydroxide-1-carboxyethoxy disodium salt, etc.); betaine-based surfactants (for example, 2-heptadecyl-N-carboxymethyl-N- Hydroxyethylimidazolinium betaine, lauryl dimethylaminoacetic acid betaine, alkyl betaine, amido betaine, sulfobetaine, etc.) and the like.

Examples of lipophilic nonionic surfactants include sorbitan fatty acid esters (for example, sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurin acid ester, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan trioleate, sorbitan penta-2-ethyl diglyceryl hexanoate, sorbitan tetra-2-ethylhexanoate diglyceride, etc.); glycerol polyglycerol fatty acids (eg, glycerol mono-cottonseed oil fatty acid, glycerol monoerucate, sesquioleic acid) Glycerides, glycerol monostearate, α , α' -oleic acid pyroglutamate, glycerol malate monostearate, etc.); propylene glycol fatty acid esters (eg, propylene glycol monostearate, etc.) ; Hydrogenated castor oil derivatives; Glycerol alkyl ethers, etc.

Examples of hydrophilic nonionic surfactants include POE-sorbitan fatty acid esters (for example, POE-sorbitan monooleate, POE-sorbitan monostearate, POE-sorbitan monooleate, POE-sorbitan tetraoleate, etc.); POE-sorbitan fatty acid esters (eg, POE-sorbitan monolaurate, POE-sorbitol monooleate, POE-sorbitan pentaoleate, POE-sorbitol monostearate, etc.); POE-glycerol fatty acid esters (eg, POE-glycerol monostearate, POE-glycerol monostearate, etc.) Isostearates, POE-monooleate of POE-glyceryl triisostearate, etc.); POE-fatty acid esters (for example, POE-distearate, POE-monodioleate ( POE-monodioleate), ethylene glycol distearate, etc.); POE-alkyl ethers (eg, POE-lauryl ether, POE-oleyl ether, POE-stearyl ether, POE-docosane base ether, POE-2-octyldodecyl ether, POE-cholestanol ether (POE-cholestanol ether, etc.); Pluronic type (for example, Pluronic etc.); POE/POP-alkyl ethers ( For example, POE/POP-cetyl ether, POE/POP-2-decyltetradecyl ether, POE/POP-monobutyl ether, POE/POP-hydrogenated lanolin, POE/POP-glyceryl ether, etc. ); tetra-POE/tetra-POP-ethylenediamine condensates (for example, Tetronic, etc.); POE-castor oil hydrogenated castor oil derivatives (for example, POE-castor oil, POE-hydrogenated castor oil, POE-hydrogenated castor oil mono Isostearate, POE-hydrogenated castor oil triisostearate, POE-hydrogenated castor oil monopyroglutamic acid monoisostearate diester, POE-hydrogenated castor oil maleate, etc.); POE- Beeswax/lanolin derivatives (eg, POE-sorbitol beeswax, etc.); alkanolamides (eg, coconut oil fatty acid diethanolamide, lauric acid monoethanolamide, fatty acid isopropanolamide, etc.); POE-propylene glycol fatty acid ester; POE-alkylamine; POE-fatty acid amide; sucrose fatty acid ester; alkyl ethoxy dimethyl amine oxide; trioleyl phosphate, etc.

As a moisturizing agent, for example, polyethylene glycol, propylene glycol, glycerin, 1,3-butanediol, xylitol, sorbitol, maltitol, chondroitin sulfate, hyaluronic acid, mucin sulfate, cardamom Charonic Acid, Atelocollagen, Cholesteryl 12-Hydroxystearate, Sodium Lactate, Bile Salt, d1-Pyrrolidone Carboxylate, Alkylene Oxide Derivatives, Short-chain soluble collagen, diglycerol (EO) PO adduct, prickly pear extract, yarrow extract, cloverleaf extract, etc.

Examples of natural water-soluble polymers include plant-based polymers (eg, gum arabic, gum tragacanth, galactan, guar gum, carob gum, karaya gum, carrageenan, fruit Gum, agar, quince seeds (Marmelo), algal colloid (brown algae extract), starch (rice, corn, potato, wheat), glycyrrhizic acid, etc.); microbial polymers (for example, xanthan gum, glucan, succinylglycan, pullulan, etc.); animal-based macromolecules (eg, collagen, casein, albumin, gelatin, etc.), and the like.

Examples of semisynthetic water-soluble polymers include starch-based polymers (for example, carboxymethyl starch, methylhydroxypropyl starch, etc.); cellulose-based polymers (methyl cellulose, ethyl cellulose, etc.) , methyl hydroxypropyl cellulose, hydroxyethyl cellulose, sodium cellulose sulfate, hydroxypropyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, crystalline cellulose, cellulose powder, etc.); seaweed Acid-based polymers (such as sodium alginate, propylene glycol alginate, etc.) and the like.

Examples of synthetic water-soluble polymers include vinyl-based polymers (for example, polyvinyl alcohol, polyvinyl methyl ether, polyvinylpyrrolidone, carboxyvinyl polymers, etc.); polyoxyethylene-based polymers (for example, Polyoxyethylene polyoxypropylene copolymer of polyethylene glycol 20,000, 40,000, 60,0000, etc.); acrylic polymer (for example, sodium polyacrylate, polyethyl acrylate, polyacrylamide, etc.); polyethyleneimine; Cationic polymers, etc.

Examples of thickeners include gum arabic, carrageenan, karaya gum, tragacanth gum, carob gum, quince seed (Marmelo), casein, dextrin, gelatin, sodium pectate, Sodium Alginate, Methyl Cellulose, Ethyl Cellulose, CMC, Hydroxyethyl Cellulose, Hydroxypropyl Cellulose, PVA, PVM, PVP, Sodium Polyacrylate, Carboxyvinyl Polymer, Locust Bean Gum, Guar Gum, Tamarind Gum, Dialkyldimethylammonium Cellulose Sulfate, Xanthan Gum, Magnesium Aluminum Silicate, Bentonite, Hectorite, AlMg Silicate (Veegum), Laponite, Silicic Anhydride Wait.

Examples of the ultraviolet absorber include: benzoic acid-based ultraviolet absorbers (for example, p-aminobenzoic acid (hereinafter abbreviated as PABA), PABA monoglyceride, N,N-dipropoxy PABA ethyl ester, N,N -diethoxy PABA ethyl ester, N,N-dimethyl PABA ethyl ester, N,N-dimethyl PABA butyl ester, N,N-dimethyl PABA ethyl ester, etc.); anthranilic acid ultraviolet Absorbers (eg, homomenthyl N-acetylanthranilate, etc.); salicylic acid-based UV absorbers (eg, amyl salicylate, menthyl salicylate, homomenthyl salicylate, salicylic acid) octyl acid, phenyl salicylate, benzyl salicylate, p-isopropanol phenyl salicylate, etc.); cinnamic acid-based UV absorbers (eg, octyl methoxycinnamate, ethyl-4 cinnamate) -Isopropyl, methyl-2,5-diisopropyl cinnamate, ethyl-2,4-diisopropyl cinnamate, methyl-2,4-diisopropyl cinnamate, p-methoxy Propyl p-methoxycinnamate, isopropyl p-methoxycinnamate, isoamyl p-methoxycinnamate, octyl p-methoxycinnamate (2-ethylhexyl p-methoxycinnamate), p-methyl 2-Ethoxyethyl oxycinnamate, cyclohexyl p-methoxycinnamate, ethyl α -cyano- β -phenylcinnamate, 2-ethyl α -cyano- β -phenylcinnamate ethyl hexyl ester, mono-2-ethylhexanoyl-di-p-methoxycinnamate glyceride, etc.); benzophenone-based ultraviolet absorbers (for example, 2,4-dihydroxybenzophenone, 2,2 '-Dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxydi Benzophenone, 2-Hydroxy-4-methoxybenzophenone, 2-Hydroxy-4-methoxy-4'-methylbenzophenone, 2-Hydroxy-4-methoxybenzophenone Keto-5-sulfonate, 4-phenylbenzophenone, 2-ethylhexyl-4'-phenyl-benzophenone-2-carboxylate, 2-hydroxy-4-n-octyloxy Benzophenone, 4-hydroxy-3-carboxybenzophenone, etc.); 3-(4'-methylbenzylidene)-d,1-camphor, 3-benzylidene-d,1-camphor; 2-phenyl-5-methylbenzoxazole; 2,2'-hydroxy-5-methylphenylbenzotriazole;2-(2'-hydroxy-5'-tert-octylphenyl)benzeneTriazole;2-(2'-Hydroxy-5'-methylphenyl)benzotriazole;Dibenzalazine; Dianisoyl Methane; 4-Methoxy- 4'-tert-butyldibenzoylmethane; 5-(3,3-dimethyl-2-norbornylidene)-3-pentan-2-one, dimorpholinopyridazinone (ジモルホリノ)ピリダジノ); 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate; 2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]-benzene yl}-6-(4-methoxyphenyl)-(1,3,5)-triazine and the like.

Examples of metal ion blocking agents include 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid tetrasodium salt, disodium edetate, edetate Trisodium acid, tetrasodium edetate, sodium citrate, sodium polyphosphate, sodium metaphosphate, gluconic acid, phosphoric acid, citric acid, ascorbic acid, succinic acid, edetate, trisodium ethylenediamine hydroxyethyltriacetate Wait.

Examples of lower alcohols include ethanol, propanol, isopropanol, isobutanol, and tert-butanol.

Examples of polyhydric alcohols include dihydric alcohols (eg, ethylene glycol, propylene glycol, trimethylene glycol, 1,2-butanediol, 1,3-butanediol, tetramethylene glycol, 2,3-butanediol, pentamethylene glycol, 2-butene-1,4-diol, hexylene glycol, caprylyl glycol, etc.); trihydric alcohols (eg, glycerol, trimethylolpropane) etc.); tetrahydric alcohols (for example, pentaerythritol, such as 1,2,6-hexanetriol, etc.); pentahydric alcohols (for example, xylitol, etc.); hexahydric alcohols (for example, sorbitol, mannitol, etc.) sugar alcohols, etc.); polyol polymers (eg, diethylene glycol, dipropylene glycol, triethylene glycol, polypropylene glycol, tetraethylene glycol, diglycerol, polyethylene glycol, triglycerol, tetraglycerol, polyglycerol, etc.) ; Dihydric alcohol alkyl ethers (eg, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monohexyl ether, ethylene glycol mono 2-methylhexyl ether, ethylene glycol isoamyl ether, ethylene glycol benzyl ether, ethylene glycol isopropyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, etc.); two Alcohol alkyl ethers (eg, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol butyl ether, diethylene glycol Alcohol methyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol isobutyl ether, propylene glycol isopropyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, Dipropylene glycol butyl ether, etc.); glycol ether esters (eg, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol mono Phenyl ether acetate, ethylene glycol diadipate, ethylene glycol disuccinate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monophenyl ether acetate, etc.); glycerol monoalkyl ethers (for example, Chimyl Alcohol, Selachyl Alcohol, Selachyl Alcohol Batyl Alcohol, etc.); sugar alcohols (for example, sorbitol, maltitol, maltotriose, mannitol, sucrose, erythritol, glucose, fructose, amylolytic sugar, maltose, xylitol, Amylolytic sugar reducing alcohol, etc.); Glysolid (グリソリッド); Tetrahydrofurfuryl alcohol; POE-tetrahydrofurfuryl alcohol; POP-butyl ether; POP/POE-butyl ether; Tripolyoxypropylene glyceryl ether; POP-glyceryl ether; POP-glyceryl ether phosphate; POP/POE-pentaerythritol ether, polyglycerol, etc.

Examples of monosaccharides include three-carbon sugars (for example, D-glyceraldehyde, dihydroxyacetone, etc.); four-carbon sugars (for example, D-erythrose, D-erythrulose, D-threose, erythritol, etc.); five-carbon sugars (for example, L-arabinose, D-xylose, L-lyxose, D-arabinose, D-ribose, D-ribulose, D-xylulose, L-xylulose, etc.); six-carbon sugars (eg, D-glucose, D-talose, D-psicose, D-galactose, D-fructose, L-galactose, L-mannose, D-tagatose (D-tagatose); heptose (e.g., heptanose, heptulose, etc.); eight-carbon sugar (e.g., caprylose, etc.); Deoxysugars (eg, 2-deoxy-D-ribose, 6-deoxy-L-galactose, 6-deoxy-L-mannose, etc.); Amino sugars (eg, D-glucosamine, D-galactosamine, sialic acid, aminouronic acid, muramic acid, etc.); uronic acid (eg D-glucuronic acid, D-mannuronic acid, L-guluronic acid, D-galacturonic acid, L- iduronic acid, etc.) etc.

Examples of oligosaccharides include sucrose, gentiotriose, Umbelliferose, lactose, Planteose, isolychnose, α , α -trehalose ( α -trehalose) , α -trehalose), Raffinose, Lychnose, Umbilicin, Stachyose, Verbascose, etc.

Examples of polysaccharides include cellulose, quince seeds, chondroitin sulfate, starch, galactan, dermatan sulfate (Dermatan Sulfate), glycogen (Glycogen), gum arabic, and heparan sulfate (Heparan Sulfate). , Hyaluronic Acid, Gum Tragacanth, Keratan Sulfate, Chondroitin, Xanthan Gum, Mucoitin Sulfate, Guar Gum, Dextran, Keratosulfate, Locust Bean Gum, Amber acylglycan, caronin acid, etc.

As amino acids, neutral amino acids (for example, threonine, cysteine, etc.); basic amino acids (for example, hydroxylysine, etc.), etc. are mentioned, for example. In addition, examples of amino acid derivatives include sodium acyl sarcosinate (sodium lauroyl sarcosinate), acyl glutamate, sodium acyl beta -alanine, glutathione, pyrrolidone carboxylic acid, and the like.

Examples of organic amines include monoethanolamine, diethanolamine, triethanolamine, morpholine, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol, and 2-amino-2-methyl -1-Propanol, etc.

As a polymer emulsion, an acrylic resin emulsion, a polyethyl acrylate emulsion, an acrylic resin solution, a polyalkyl acrylate emulsion, a polyvinyl acetate resin emulsion, a natural rubber latex etc. are mentioned, for example.

As a pH adjuster, buffers, such as lactic acid-sodium lactate, citric acid-sodium citrate, and succinic acid-sodium succinate, etc. are mentioned, for example.

Examples of vitamins include vitamins A, B1, B2, B6, C, E and derivatives thereof, pantothenic acid and derivatives thereof, biotin, and the like.

As antioxidants, tocopherols, dibutylhydroxytoluene, butylhydroxyanisole, gallic acid esters, etc. are mentioned, for example.

Examples of antioxidant adjuvants include phosphoric acid, citric acid, ascorbic acid, maleic acid, malonic acid, succinic acid, fumaric acid, cephalin, hexametaphosphate, and phytic acid. , EDTA, etc.

Examples of other ingredients that can be blended include: preservatives (ethyl p-hydroxybenzoate, butyl p-hydroxybenzoate, chlorphenesin, phenoxyethanol, etc.); anti-inflammatory agents (for example, glycyrrhizic acid derivatives) , glycyrrhetic acid derivatives, salicylic acid derivatives, hinokitiol, zinc oxide, allantoin, etc.); whitening agents (eg, placenta extract, saxifrage extract, arbutin, etc.); various extracts (For example, Cork, Coptis, Comfrey, Paeonia, Birch, Sage, Loquat, Ginseng, Aloe, Mallow, Orris, Grape, Coix Seed, Loofah, Lily, Saffron, Chuanxiong, Pine ball, forsythia, formonone, garlic, pepper, dried tangerine peel, angelica, seaweed, etc.); activators (activators) (for example, royal jelly, photosensin, cholesterol derivatives, etc.); blood circulation enhancers (for example, Vanillamide pelargonate, benzyl nicotinate, β -butoxyethyl nicotinate, capsaicin, zingerone, Cantharides Tincture, Ichthammol, tannic acid, alpha -Cetyl alcohol ( α -borneol, α -borneol), tocopherol nicotinate, inositol hexanicotinate, Cyclandelate, Cinnarizine, Tolazoline, Acetylcholine ( Acetylcholine), Verapamil (Verapamil), Cepharanthine (Cepharanthine), γ -oryzanol ( γ -oryzanol), etc.); antiseborrhea (eg, sulfur, Thianthol, etc.); anti-inflammatory Drugs (for example, tranexamic acid, thiotaurine, hypotaurine (Hypotaurine, hypotaurine), etc.) and the like.

Moreover, it can also be properly blended: disodium edetate, trisodium edetate, sodium citrate, sodium polyphosphate, sodium metaphosphate, gluconic acid, malic acid and other metal blockers, caffeine, tannin, vitamin Lapamil, tranexamic acid and its derivatives, extracts of various herbs (crude medicines) such as licorice, karin, Japanese staghorn, tocopherol acetate, glycyrrhetinic acid, licorice Medicinal products such as acid (グリチルリチンacid) and derivatives or salts thereof, whitening agents such as vitamin C, magnesium ascorbyl phosphate, ascorbyl glucoside, arbutin, kojic acid, amino acids such as arginine and lysine, and the like Derivatives, sugars such as fructose, mannose, erythritol, trehalose, xylitol, etc.

As the product form of the powder cosmetic according to the present invention, any product form within the category of powder cosmetic can be adopted. Specifically, foundation, eye shadow, blush, body powder, Perfume Powder, Baby Powder, Pressed Powder, Deodorant Powder, dusting powder and other products can be used form.

[The production method of the solid powder cosmetic according to the present invention]

<Dry production method>

The inorganic powder component, oily component, and other components were mixed in advance in a Henschel mixer, and then pulverized twice with a pulverizer. Then, the obtained mixture is filled in a resin medium-sized container, and dry press-molding is performed by a known method to obtain a powder cosmetic in a solid form in which the titanium oxide of the present invention is blended into the cosmetic.

<Other manufacturing methods>

As a manufacturing method of mixing the titanium oxide of this invention into cosmetics, a well-known method can be used. For example, the following production methods can be suitably obtained: the production method described in Japanese Patent No. 5422092 by drying a slurry using a volatile solvent, and the production method described in Japanese Patent No. 5972437 using a volatile solvent. The manufacturing method which removes and manufactures after filling the slurry.

Example

The present invention will be described in more detail below by way of Examples, but the present invention is not limited to these Examples. Unless otherwise specified, the blending amount is represented by mass % with respect to the system in which the components are blended.

Before explaining the Example, the evaluation method of the test of the titanium dioxide used by this invention is demonstrated.

Evaluation (1): Method for Measuring Average Crystalline Diameter

The sample was measured with an X-ray diffractometer (Geigerflex, manufactured by Rigaku Electric Co., Ltd.), and the average crystallite diameter was calculated by applying the Scherrer formula.

Evaluation (2): Evaluation of Hiding Power

The titanium dioxide powder was dispersed and mixed in the nitrocellulose varnish so as to have a concentration of 5%, and the obtained dispersion was applied on a black and white coverage test paper JIS-K5400 with a film thickness of 0.101 μm and dried to obtain a test sample. . The obtained test samples were each color-measured on the surfaces of the coating films on white and black paper using a spectrophotometer (CM-2600, manufactured by Konica Minolta). The color difference (ΔE) in the Hunter Lab color space was calculated and evaluated as the hiding power. It should be noted that the higher the ΔE, the smaller the hiding power, and the lower the ΔE, the greater the hiding power.

ΔE=

(Evaluation Criteria)

×: 25<△E

△: 22<△E≤25

○: △E≤22

Evaluation (3): Evaluation of red permeability

The red transmittance refers to the ratio of the reflectance at a wavelength of 450 nm to the reflectance at a wavelength of 650 nm (wavelength: Reflectance at 450 nm/wavelength reflectance at 650 nm: R450/R650).

The higher the R450/R650, the higher the red transmittance, and the lower the R450/R650, the lower the red transmittance.

(Evaluation Criteria)

×: R450/R650≤1.3

△: 1.3<R450/R650≤1.35

○: 1.35<R450/R650≤1.4

◎: 1.4<R450/R650

Evaluation (4): Measurement method of specific surface area

The specific surface area per unit mass can be determined by BET (Brunauer-Emmet-Teller) described in The Journal of the American Chemical Society, Vol. 60, page 309, February 1938 as equivalent to International Standard ISO 5794/1 (Appendix D). It can be obtained by the well-known nitrogen adsorption method.

Evaluation (5): Method for Measuring the Apparent Average Particle Size

By the method shown in FIG. 1, the average value of the lengths of the long axis and the short axis of the particles was obtained.

[Selection of titanium oxide for parent nucleus]

First, the present inventors evaluated by the above-described evaluation method using pigment-grade rutile-type and anatase-type titanium oxides available as commercial products. The results are shown in Table 1.

[Table 1]

*1: Tipaque CR-50 (manufactured by Ishihara Sangyo Co., Ltd., apparent average particle size: 200 nm, shape: indeterminate)

*2: Bayertitan A (manufactured by Bayer Corporation, apparent average particle diameter: 400 nm, shape: indeterminate)

Both the rutile-type pigment-grade titanium oxide and the anatase-type pigment-grade titanium oxide have low red transmittance. In addition, even if they are fired at high temperature, the red transmittance is low.

The inventors of the present invention have studied whether or not a product excellent in hiding power can be produced by using rutile-type titanium oxide with high red permeability.

The present inventors used the method of the patent document (JP-A-2010-173863 ) to synthesize two types of titanium dioxide having needle-like protrusions on the particle surface, in which needle-like particles were aggregated in a radial orientation, with different particle sizes.

The obtained titanium oxides are referred to as titanium oxide A (specific surface area: 101 m ² /g, crystallite diameter: 5 nm, apparent average particle size: 0.2 to 0.3 μm , needle-like protrusion shape), titanium oxide B ( Specific surface area: 117 m ² /g, crystallite diameter: 11 nm, apparent average particle diameter: 0.3 μm , needle-like protrusion shape).

In addition, titanium dioxide having needle-like protrusions on the particle surface obtained by agglomeration of needle-like particles as a commercial product (ST-730: manufactured by Titanium Industry Co., Ltd.) in a radial orientation is referred to as titanium oxide C (specific surface area: 98 m ² / g, crystallite diameter: 6 nm, apparent average particle diameter: 0.5 μm , needle-like protrusion shape).

In addition, titanium dioxide having needle-like protrusions on the particle surface obtained by agglomeration of needle-like particles as a commercial product (ST-750: manufactured by Titanium Industry Co., Ltd.) in a radial orientation is referred to as titanium oxide D (84 m ² /g, micro Crystal diameter: 8.6 nm, apparent average particle diameter: 1.0 μm , needle-like protrusion shape).

In addition, titanium oxide whose particles are needle-shaped as a commercial item (MT062; manufactured by Tayca Industries Co., Ltd.) is referred to as titanium oxide E (specific surface area: 47 m ² /g, crystallite diameter: 23.3 nm, and the apparent average Particle size: 65 nm, needle-like protrusion shape).

Using each titanium dioxide, titanium dioxide powder was obtained by the following method. The obtained titanium dioxide powder was evaluated by the above-mentioned evaluation method, and the relationship between the type of titanium dioxide before firing and the firing temperature was investigated. The results are shown in Tables 2 to 6.

(Manufacturing method of titanium dioxide powder)

Titanium dioxide powder was obtained by putting 100 g of titanium dioxide used for the mother nucleus in a crucible made of quartz, and firing in a muffle furnace at each temperature for 1 hour.

Titanium oxide A (specific surface area: 101 m ² /g, crystallite diameter: 5 nm, apparent average particle size: 0.2 to 0.3 μm , needle-like protrusion shape)

[Table 2]

Titanium oxide B (specific surface area: 117 m ² /g, crystallite diameter: 11 nm, apparent average particle diameter: 0.3 μm , needle-like protrusion shape)

[table 3]

Titanium oxide C (specific surface area: 98 m ² /g, crystallite diameter: 6 nm, apparent average particle diameter: 0.5 μm , needle-like protrusion shape)

[Table 4]

Titanium oxide D (84 m ² /g, crystallite diameter: 8.6 nm, apparent average particle diameter: 1 μm , needle-like protrusion shape)

[table 5]

Titanium oxide E (specific surface area: 47 m ² /g, crystallite diameter: 23.3 nm, apparent average particle size: 65 nm, needle-like protrusion shape)

[Table 6]

Test example 5-1 5-2 5-3 5-4 shape acicular acicular acicular acicular ratio of short diameter to long diameter 3.3 3.3 3.3 3.2 Apparent particle size/nm 65 65 65 65 Crystallite diameter/nm 23.3 23.3 24.3 26.9 Specific surface area/m²/g 47 44 40 19 Firing temperature/℃ - 350 630 720 red permeability ◎ ◎ ◎ ◎ hiding power × × × ×

In all of titanium oxides A to C, the hiding power is improved by raising the firing temperature. Since the specific surface area decreases as the temperature rises, it can be seen that the acicular particles aggregated in the radial orientation existing before the firing are coagulated with each other, thereby reducing the voids existing in the particles. This results in an increase in the apparent refractive index and an increase in hiding power. However, the red transmittance gradually decreases. In particular, when fired at high temperature, excessive sintering occurs, and the initial red transmittance is remarkably reduced.

In particular, about titanium oxide C having a large average particle size, the red transmittance was almost lost at 700°C.

In addition, as with titanium oxides A to C, titanium oxide D in which needle-shaped particles are aggregated in a radial orientation has a specific surface area that decreases as the firing temperature increases, as with titanium oxides A to C, but due to the apparent appearance The particle size is significantly larger, so the increase in hiding power is minimal. Furthermore, with regard to the red transmittance, since the apparent particle size was remarkably large, the red transmittance was low even before and after firing, and the desired red transmittance could not be obtained.

In addition, with regard to titanium oxide E, which has a small average particle size before firing and is composed of single needle-shaped particles, there is no significant change in shape after firing, and although the red transmittance is maintained, the hiding power is not improved at all. .

Also, different shapes of titanium dioxide were investigated.

In addition, titanium dioxide whose particles are granular as a commercial item (TT055(A); manufactured by Ishihara Sangyo Co., Ltd.) is referred to as titanium oxide F (specific surface area: 37 m ² /g, crystallite diameter: 24.8 nm, apparent Average particle size: 50 nm, granular).

In addition, the titanium dioxide in which the rod-shaped particles as a commercial item (ST643; manufactured by Titanium Industry Co., Ltd.) are aggregated in a straw-like orientation is referred to as titanium oxide G (specific surface area: 132 m ² /g, crystallite diameter: 8.6 nm, Apparent average particle diameter: 200 nm, straw bundle shape).

Titanium oxide F (specific surface area: 37 m ² /g, crystallite diameter: 24.8 nm, apparent average particle size: 50 nm, granular)

[Table 7]

Test example 6-1 6-2 6-3 6-4 shape granular granular granular granular ratio of short diameter to long diameter 1.7 1.7 1.7 1.7 apparent particle size 50 50 50 50 crystallite diameter 24.8 25.1 24.8 26.5 specific surface area 37 38 32 35 firing temperature - 350 630 720 red permeability ◎ ◎ ◎ ◎ hiding power × × × ×

From Test Examples 6-1 to 6-4, when the granular titanium oxide was fired at 350 to 720° C., the crystallite diameter did not change, and neither the specific surface area nor the crystallite diameter could achieve the present invention. of fired titanium oxide.

Therefore, although it has red transmittance, desired hiding power cannot be obtained.

Titanium oxide G (specific surface area: 132 m ² /g, crystallite diameter: 8.6 nm, apparent average particle diameter: 200 nm, straw bundle shape)

[Table 8]

Test example 7-1 7-2 7-3 7-4 shape straw bunch straw bunch straw bunch straw bunch ratio of short diameter to long diameter 2.5 2.5 2.5 2.5 apparent particle size 200 200 200 200 crystallite diameter 8.6 8.7 9.9 11.1 specific surface area 132 79 34 39 firing temperature - 350 630 720 red permeability △ △ △ △ hiding power × △ △ △

The titanium oxide used in Test Example 7-1 satisfies (a) the apparent average particle diameter, (b) the average crystallite diameter measured by X-ray diffraction, and (c) the same as the titanium dioxide used for the mother core of the present invention. ) specific surface area, but the particle surface does not have needle-like protrusions. Furthermore, since the ratio of the short diameter to the long diameter is as large as 2.5, sufficient red transmittance and hiding power cannot be achieved even after firing.

From these studies, it has been found that titanium oxide B suitable for use as a mother core in the present invention is titanium oxide B having a wide allowable temperature range from the viewpoints of improving hiding properties and maintaining red transmittance.

The results of measuring the spectral reflectance of rutile-type pigment-grade titanium oxide (*1) and titanium oxide B (unfired, firing temperature: 700° C., 900° C.) are shown in FIG. 2 . It should be noted that the measurement was performed by dispersing and mixing titanium dioxide powder in a nitrocellulose varnish at a concentration of 5%, and carrying out the obtained dispersion on a black and white coverage test paper JIS-K5400 with a film thickness of 0.101 μm . It was coated and dried to obtain a test sample. Using a spectrophotometer (CM-2600, manufactured by Konica Minolta), the obtained test samples were each color-measured on the surface of the coating film on the black paper to obtain the spectral reflectance.

Then, with respect to titanium dioxide B, TEM images of unfired and fired (fired temperature: 300° C., 500° C., 700° C., 900° C.) were photographed. The results are shown in FIG. 3 .

In addition, with respect to titanium dioxide B, the shielding power and red transmittance based on the change in the firing temperature of the rotary kiln were measured. The results are shown in Figs. 4 and 5, respectively.

From the above results, in the case of firing in a muffle furnace, a suitable temperature is 500 to 800°C, and more preferably 500 to 700°C.

Next, the present inventors carefully studied the firing temperature in the range of 500 to 800°C using titanium oxide B as the mother nucleus. That is, the present inventors evaluated the titanium dioxide powder whose firing temperature was changed by the above-mentioned evaluation method. The results are shown in Table 5 and Table 6.

Firing is performed in a rotary-type firing furnace (rotary kiln) that is closer to mass production and has high firing efficiency.

In general, a rotary-type firing furnace has high firing efficiency, and it is known that the same firing state can be obtained at a temperature lower than that of firing in a muffle furnace that is fired at rest.

[Table 9]

[Table 10]

The specific surface area is an index indicating the reduction of the porosity of the obtained titanium oxide particles and the progress of sintering, and the titanium dioxide used in the present invention is preferably made by sintering the titanium dioxide powder serving as the mother nucleus so that the specific surface area becomes lower than that in the sintering. The front (100%) is in the range of 8 to 30%.

From these results, it is understood that the calcination temperature is preferably 550 to 700°C, and more preferably 575 to 660°C, for excellent hiding power and red permeability.

[Solid Powder Cosmetics]

Furthermore, the present inventors used the titanium dioxide obtained at the firing temperature of 660° C. in Table 6, obtained the hydrophobized titanium dioxide by the following surface treatment method, and carried out the solid powder cosmetic mixed with the titanium dioxide by the conventional method, respectively. Adjustment. Then, the obtained cosmetic was evaluated by the following evaluation method.

[Surface treatment method of titanium dioxide powder]

The obtained titanium dioxide powder was dispersed in ion-exchanged water, and after heating, 3 mass % of stearic acid was adsorbed, followed by dehydration, washing, and drying to obtain surface-treated titanium dioxide.

[Manufacturing method of solid powder cosmetic]

<Dry production method>

The inorganic powder component, the oily component, and other components were preliminarily mixed in a Henschel mixer, and then pulverized twice with a pulverizer. Then, the obtained mixture is filled in a medium-sized resin container, and dry press-molding is performed by a known method to obtain a powder cosmetic in a solid form in which the titanium oxide of the present invention is blended into the cosmetic.

[Evaluation method of solid powder cosmetics]

Evaluation (6): Natural makeup

Ten professional panelists applied the sample to the face, and evaluated the feeling of use after application.

A: More than 7 out of 10 judges answered as natural makeup

B: More than 5 and less than 7 out of 10 judges answered as natural makeup

C: Less than 5 out of 10 judges answered as natural makeup

Evaluation (7): No whitening

Ten professional panelists applied the sample to the face, and evaluated the feeling of use after application.

A: More than 7 out of 10 reviewers answered that they were not whitened

B: More than 5 and less than 7 out of 10 reviewers answered no whitening

C: Less than 5 out of 10 reviewers answered no blushing

Evaluation (8): Covering of spots and freckles

Ten professional panelists applied the sample to the face, and evaluated the feeling of use after application.

A: More than 7 out of 10 reviewers answered as having covered spots and freckles

B: More than 5 and less than 7 out of 10 reviewers answered that there were covered spots and freckles

C: Less than 5 out of 10 reviewers answered as having covered spots, freckles

Evaluation (9): Conspicuous texture

Ten professional panelists applied the sample to the face, and evaluated the feeling of use after application.

A: More than 7 out of 10 reviewers answered that the texture was not conspicuous

B: More than 5 and less than 7 of the 10 reviewers answered that the texture was inconspicuous

C: Less than 5 out of 10 reviewers answered that the texture was inconspicuous

Evaluation (10): Longevity

Ten professional panelists applied the samples to the face and evaluated the makeup lasting after 3 hours of application.

A: 7 or more out of 10 panelists answered that the makeup was good after 3 hours of application

B: 5 or more and less than 7 out of 10 panelists answered that the makeup was good after 3 hours of application

C: Less than 5 out of 10 panelists answered that the makeup was good after 3 hours of application

Evaluation (11): No card powder

Ten professional panelists applied the sample to the face, and evaluated the feeling of use during application.

A: More than 7 out of 10 reviewers answered that they are not stuck in use

B: More than 5 and less than 7 of the 10 reviewers answered that they are not stuck in use

C: Less than 5 out of 10 reviewers answered that they are not stuck in use

[Table 11]

Test example 8-1 8-2 8-3 8-4 8-5 8-6 8-7 Branched alkyl siloxane (ethoxy functional group) treated talc (*1) to 100% to 100% to 100% to 100% to 100% to 100% to 100% Synthetic fluorophlogopite iron (*2) 12 12 12 12 12 12 12 Synthetic Fluorphlogopite (*3) 12 12 12 12 12 12 12 Pigment grade titanium dioxide (*4) 9.5 9.5 Titanium dioxide of the present invention (after firing) 9.5 9.5 9.5 0.3 32 Titanium dioxide before firing 9.5 Particulate titanium dioxide (*5) 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Silicone treated iron oxide red 0.35 0.35 0.35 0.35 0.35 0.35 0.35 Silicone treated iron oxide yellow 1.8 1.8 1.8 1.8 1.8 1.8 1.8 Silicone treated iron oxide black 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Spherical (diphenyl dimethicone/vinyl diphenyl dimethicone/silsesquioxane) crosspolymer (*6) 4 4 4 4 4 4 4 Spherical nylon powder (*7) 4 4 4 4 4 4 4 Spherical (Vinyl Dimethicone/Methicone Silsesquioxane) Crosspolymer (*8) 4 4 4 4 4 4 4 Dextrin fatty acid ester treated particulate zinc oxide 4 11 0.01 4 4 4 4 preservative Moderate Moderate Moderate Moderate Moderate Moderate Moderate Dimethicone (*9) 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Methylphenylpolysiloxane (*10) 2.3 2.3 2.3 2.3 2.3 2.3 2.3 Triglyceride 2-ethylhexanoate (*11) 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Octyl Methoxycinnamate (*12) 5 5 5 5 5 5 5 Antioxidants Moderate Moderate Moderate Moderate Moderate Moderate Moderate total 100 100 100 100 100 100 100 natural makeup A A A B A B C not whitened A A A C A A C Covering spots and freckles A A A A C C A Conspicuous texture A A A A C B B Make-up A A C A A A A Non-card powder in use A C A A A A A

(*1) BAE-Talc JA68R manufactured by Miyoshi Chemical Co., Ltd.

(*2) PDM-FE manufactured by Topy Industry Co., Ltd.

(*3) PDM-9WA manufactured by Topy Industry Co., Ltd.

(*4) Tipaque CR-50 manufactured by Ishihara Sangyo Co., Ltd.

(*5) MT-100TV manufactured by Tayca Co., Ltd.

(*6) KSP-300 manufactured by Shin-Etsu Chemical Industry Co., Ltd.

(*7) Nylon SP-500 manufactured by Toray Co., Ltd.

(*8) KSP-100 manufactured by Shin-Etsu Chemical Co., Ltd.

(*9) KF-96A-6T manufactured by Shin-Etsu Chemical Industry Co., Ltd.

(*10)Silicon KF-56 manufactured by Shin-Etsu Chemical Co., Ltd.

(*11) RA-G-308 manufactured by Nippon Seika Co., Ltd.

(*12)Parsol MCR-XR by DSM Nutrition Japan Co., Ltd.

From Test Example 8-1, it was found that the solid powder cosmetic using the titanium dioxide and hydrophobized zinc oxide of the present invention was excellent in longevity and usability, and had natural makeup and no whitening when applied to the skin. In addition, a low-temperature fired product of fine particles is particularly preferred, and the hydrophobization treatment is preferably a dextrin palmitate treatment.

From Test Example 8-2, it can be seen that when the hydrophobized zinc oxide is blended beyond the range of the present invention, the makeup holding property is good, but it is inferior in terms of non-stickiness during use.

From Test Example 8-3, it was found that when the amount of the hydrophobized zinc oxide was less than the range of the present invention, the makeup retention was poor.

From Test Example 8-4, even if conventional pigment-grade titanium was used, it was inferior in that it did not whiten when applied to the skin.

As can be seen from Test Example 8-5, when the titanium dioxide used for the mother nucleus is used as it is, the coverage of spots and freckles and the conspicuous texture of the texture are inferior.

From Test Examples 8-6, when the amount of titanium dioxide of the present invention is smaller than the range of the present invention, the coverage of spots and freckles is poor, and a natural makeup cannot be obtained.

From Test Examples 8-7, it can be seen that if the amount of titanium dioxide of the present invention is larger than the range of the present invention, the makeup is natural and not whitened.

Claims (8)

1. A powder cosmetic characterized by comprising:

1 to 30 mass% of a titanium dioxide powder characterized by having an apparent average particle diameter of 100nm or more and less than 500nm, an average crystallite diameter of 15 to 30nm as measured by an X-ray diffraction method, and a specific surface area of 10 to 30m²Particles having a shape in which radially protruding needle-like protrusions are coagulated, and the ratio of the short diameter to the long diameter of the shape, i.e., the long diameter/short diameter, is 1.0 or more and less than 2.5; and

0.1 to 10 mass% of hydrophobized zinc oxide.

2. A powdery cosmetic preparation according to claim 1, wherein the shape of the titanium dioxide powder has a ratio of a short diameter to a long diameter, i.e., a long diameter/short diameter, of 1.0 to 2.0.

3. A powder cosmetic characterized by comprising:

1 to 30 mass% of titanium dioxide powder, the titanium dioxideThe titanium powder has an apparent average particle diameter of 100nm or more and less than 500nm, an average crystallite diameter of 15 to 30nm as measured by an X-ray diffraction method, and a specific surface area of 10 to 30m²Particles each having a shape in which needle-like protrusions protruding radially are aggregated; and

0.1 to 10 mass% of hydrophobized zinc oxide.

4. A powder cosmetic characterized by comprising:

1 to 30 mass% of rutile titanium dioxide powder having an average crystallite diameter of 15 to 30nm as measured by X-ray diffraction method and a specific surface area of 10 to 30m²A reflectance value at 450nm of 1.3 times or more the reflectance value at 650nm and a color difference △ E of 22 or less, and

0.1 to 10 mass% of hydrophobized zinc oxide;

the color difference △ E was obtained by mixing and dispersing titanium dioxide powder in nitrocellulose varnish so as to have a concentration of 5%, and the obtained dispersion was subjected to black-and-white coverage test paper JIS-K5400 at 0.101μm, and then dried to obtain test samples, and the surfaces of the coating films on the white and black papers were measured with a spectrophotometer to calculate a color difference △ E in the Hunter Lab color space.

5. A powder cosmetic characterized by comprising:

1 to 30 mass% of a titanium dioxide powder obtained by firing rutile titanium dioxide having acicular protrusions on particle surfaces, wherein acicular particles satisfying the following (a) to (c) are aggregated in a radial orientation, and the rutile titanium dioxide powder has an apparent average particle diameter of 100nm or more and less than 500nm, an average crystallite diameter measured by an X-ray diffraction method of 15 to 30nm, and a specific surface area of 10 to 30m²(ii)/g; and

0.1 to 10 mass% of hydrophobized zinc oxide;

(a) an apparent average particle diameter of 100nm or more and less than 500nm,

(b) An average crystallite diameter of 1 to 25nm as measured by an X-ray diffraction method,

(c) The specific surface area is 40-200 m²/g。

6. A powder cosmetic characterized by comprising:

1 to 30 mass% of a titanium dioxide powder obtained by firing rutile titanium dioxide having needle-like protrusions on the particle surface, the rutile titanium dioxide powder satisfying the following (a) to (c), and the rutile titanium dioxide powder having a specific surface area after firing being 8 to 50% relative to that before firing; and

0.1 to 10 mass% of hydrophobized zinc oxide;

(a) an apparent average particle diameter of 100nm or more and less than 500nm,

(b) An average crystallite diameter of 1 to 25nm as measured by an X-ray diffraction method,

(c) The specific surface area is 40-200 m²/g。

7. A powdery cosmetic preparation according to claim 5 or 6, wherein the firing temperature of titanium dioxide is 500 to 800 ℃.

8. A powdery cosmetic preparation according to claim 7, wherein the firing temperature of titanium dioxide is 550 to 750 ℃.

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