CN110769803A - Cosmetic containing titanium dioxide powder - Google Patents
Cosmetic containing titanium dioxide powder Download PDFInfo
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- CN110769803A CN110769803A CN201880041563.1A CN201880041563A CN110769803A CN 110769803 A CN110769803 A CN 110769803A CN 201880041563 A CN201880041563 A CN 201880041563A CN 110769803 A CN110769803 A CN 110769803A
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/27—Zinc; Compounds thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/29—Titanium; Compounds thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
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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
Related application
The present application claims priority from japanese patent application No. 2017-124681, filed on 26/6/2017, and is incorporated herein.
Technical Field
The present invention relates to a powdery cosmetic containing hydrophobized zinc oxide blended therein, and particularly to titanium dioxide suitably used for the powdery cosmetic.
Background
Titanium dioxide has a high refractive index and is excellent in whiteness, hiding power, and coloring power, and thus is widely used as a white pigment for paints, plastics, and the like. Further, titanium dioxide is used as a substance for shielding ultraviolet rays, as an ultraviolet absorber or an ultraviolet shielding agent, and also used for cosmetics, catalysts, and the like by controlling the particle diameter or the photoactivity thereof, and thus, research and development have been actively carried out in these applications in recent years.
It is known that titanium dioxide powder having an apparent specific average particle diameter, which is formed of spherical particles of titanium dioxide having a specific average primary particle diameter and formed of a large number of titanium dioxide particles, is used in cosmetics as a functional material capable of imparting good smoothness and excellent light resistance, which have not been obtained with conventional titanium dioxide (patent document 1).
It is also known that the content of 1 to 15 mass% of the particles has an average particle diameter of 0.2 to 0.4μA lip cosmetic comprising aggregated particles of Rutile (Rutile) titanium oxide having an average friction coefficient (MIU value) of 0.4 to 0.6 and 1 to 40 mass% of a semisolid oil component, which is glossy, has reduced conspicuousness of lip marks, and has excellent long-lasting makeup properties (patent document 2).
Further, it is known that a coloring material used as a cosmetic can achieve natural makeup by blending a coloring material having a low absorption of light (wavelength of 630 to 700nm) in a long wavelength region in a visible light region to make the light transmittance inside the skin close to that of a makeup-free skin (patent document 3).
As such, as titanium dioxide for improving the transmittance of light on the long wavelength side of light, the following rutile-type titanium oxide has been known: the particles are in the form of rod-like particles which are oriented and agglomerated, the particles are oriented and agglomerated and have an apparent average major axis length of 80 to 300nm, the particles oriented and agglomerated have an apparent average minor axis length of 30 to 150nm, an apparent average axial ratio of the apparent average major axis length/the apparent average minor axis length of 1.1 to 4, and a specific surface area of 120 to 180m2The rutile titanium oxide is in the form of short strands or straw bundles, and has high transparency and ultraviolet shielding ability (patent document 4).
However, since this titanium dioxide is an aggregate of rod-like particles and many voids are present in the secondary aggregate, the apparent refractive index is lowered, and the hiding power is insufficient when the titanium dioxide is actually blended in a cosmetic. In addition, since the focus is on the protection against ultraviolet rays, the apparent particle diameter of the secondary agglomerate is also less than 100nm, which is significantly smaller than the particle diameter based on Mie theory to maximize the scattering effect of titanium oxide, and this also becomes a factor of reducing the hiding power.
In addition, Powder cosmetics represented by Powder Foundation (Powder Foundation) are cosmetics obtained by adding an oil component as a binder to a Powder component, mixing the mixture, filling the mixture into a container, and molding the mixture. The powder component is mainly composed of inorganic pigments, organic pigments, and resin powders, and the pigments are further classified into color/pearl pigments for adjusting hue or gloss and extender pigments other than these. The extender pigment is typically a plate-like powder such as talc, mica, kaolin, etc., and occupies most of the powder components, and has a great influence on the moldability, adhesion, usability, etc. of the cosmetic. Therefore, the addition of a characteristic extender pigment such as boron nitride, synthetic fluorophlogopite, barium sulfate to these basic extender pigments has been made to have the characteristic of a powder cosmetic.
In the conventional titanium dioxide, the hiding power of spots and the like on the skin is high, but conversely, when a large amount of titanium dioxide is blended in order to increase the hiding power, unnatural makeup is formed, and unevenness on the skin may be more conspicuous than makeup-free skin.
In view of such circumstances, it is desired to develop a powder cosmetic which incorporates titanium dioxide, is excellent in usability and uniform makeup, and forms a natural makeup when applied to the skin.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2000-191325;
patent document 2: japanese patent laid-open publication No. 2010-24189;
patent document 3: japanese patent laid-open publication No. 2006-265134;
patent document 4: jp 2010-173863 a.
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made in view of the above-described conventional techniques, and an object of the present invention is to provide a powder cosmetic which is excellent in makeup retention and forms a natural makeup when applied to the skin, by blending hydrophobized zinc oxide and titanium dioxide.
Means for solving the problems
The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that: specifically disclosed is a titanium dioxide which is obtained by firing a specific titanium dioxide to have a specific particle diameter, a specific crystallite diameter and a specific surface area, has a sufficient covering power required for cosmetics, and has an excellent red light selective transmission function. It is also found that a substance obtained by blending hydrophobized zinc oxide with this titanium dioxide is excellent in makeup retention and usability, and has natural makeup appearance and no whitening when applied to the skin.
That is, the powder cosmetic according to the present invention 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 and an average particle diameter measured by an X-ray diffraction methodThe diameter of the microcrystal is 15-30 nm, and the specific surface area is 10-30 m2Particles having a shape in which radially protruding needle-like protrusions are coagulated, the ratio of the short diameter to the long diameter (long diameter/short diameter) of the shape being 1.0 or more and less than 2.5; and
0.1 to 10 mass% of hydrophobized zinc oxide.
In the above-mentioned powdery cosmetic, the ratio of the minor axis to the major axis (major axis/minor axis) 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 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 30m2Particles each having a shape in which needle-like protrusions protruding radially are aggregated; and
0.1 to 10 mass% of hydrophobized zinc oxide.
The powder cosmetic according to the present invention is 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 dispersing and mixing 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 for color with a spectrophotometer, respectively, to calculate the color difference in the Hunter Lab color space (△ E).
The powder cosmetic according to the present invention is characterized by comprising:
1 to 30 mass% of a titanium dioxide powder obtained by firing rutile titanium dioxide having acicular protrusions on the particle surface and satisfying the following requirements (a) to (c), wherein the rutile titanium dioxide 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 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。
The powder cosmetic according to the present invention is 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。
In the above powder cosmetic, the firing temperature of titanium dioxide is suitably 500 to 800 ℃.
In the above powdery cosmetic, the firing temperature of titanium dioxide is preferably 550 to 750 ℃.
Effects of the invention
According to the present invention, a powder cosmetic excellent in makeup and usability, maintaining hiding power, and further having an excellent function of transmitting light in a long wavelength region (red light selective transmission function) can be provided.
Drawings
FIG. 1 shows a method for calculating an apparent average particle diameter.
FIG. 2 is a graph showing the spectral reflectance of rutile type pigmentary titanium oxide (. multidot.1), titanium oxide B (unfired), and a substance obtained by firing titanium oxide B at 700 ℃ and 900 ℃.
FIG. 3 is a view showing changes in the shape of titania B fired at each firing temperature by TEM observation.
FIG. 4 is a graph showing the change in the covering power of titanium oxide B due to the change in the firing temperature in a Rotary Kiln (Rotary Kiln).
FIG. 5 is a graph showing the change in red transmittance due to the change in the firing temperature of titanium oxide B caused by the change in the firing temperature in the rotary kiln.
Detailed Description
The titanium dioxide powder is characterized in that it is obtained by firing titanium dioxide having acicular protrusions on the particle surface, which is obtained by aggregating rod-like or acicular particles in a radial orientation, at 500 to 800 ℃, more preferably 550 to 750 ℃, and has an average crystallite diameter of 15 to 30nm as measured by an X-ray diffraction method, an apparent average particle diameter of 100nm or more and less than 500nm, more preferably 200 to 400nm, and a specific surface area of 10 to 30m2/g。
[ titanium dioxide for mother nucleus ]
The crystal form of titanium dioxide used for the mother nucleus is, due to the difference in crystal structure, Anatase Type (antase Type) and Rutile Type (Rutile Type). The crystal form of titanium dioxide used in the present invention needs to be a rutile type having a high covering power because of its low photocatalytic activity and high refractive index.
Titanium dioxide having a red light-transmitting function is used as titanium dioxide for the mother core. Considering that a shrinkage phenomenon generally occurs after firing, the apparent average particle diameter of the titanium dioxide used for the mother core is preferably 100nm or more and less than 500nm, and more preferably 200 to 400nm, from the viewpoint of achieving the covering power due to scattering of the titanium dioxide obtained by the present invention and the excellent red light transmitting function.
Examples of the shape of the rutile type titanium dioxide used for the mother core include: cocoon-shaped, straw bundle-shaped, short strip-shaped, spherical, needle-shaped, rod-shaped and the like. In the present invention, the rod-like or needle-like particles are preferably aggregated in a radial orientation and have needle-like projections on the particle surface.
The specific surface area of the titanium dioxide used for the matrix is preferably 40 to 200m from the viewpoint of efficiently increasing the apparent refractive index by firing2/g。
The rutile titanium dioxide used for the mother nucleus preferably has an average crystallite diameter of 1 to 25nm as measured by X-ray diffraction.
The titanium dioxide used for the parent nucleus may be a commercially available product. For example, ST700 series manufactured by titanium industries, Ltd. Among them, ST710 and the like can be given.
[ titanium dioxide powder for use in the invention ]
The titanium dioxide powder used in the present invention can be obtained by firing titanium dioxide used for the mother core.
The firing temperature is preferably the following temperature conditions depending on the apparatus for firing: the acicular protrusions radially protruding from the surface of the particles existing before firing are particles agglomerated by firing, and the agglomeration occurs by firing to reduce the voids existing between the acicular particles and sinter the acicular particles to each other, so that the average crystallite diameter measured by an X-ray diffraction method does not excessively increase. This makes it possible to achieve both sufficient hiding power and a red light selective transmission function.
The titanium dioxide powder used in the present invention is characterized in that acicular protrusions radially protruding from the surface of particles existing before firing are in the shape of particles coagulated by firing. The ratio of the minor axis to the major axis (major axis/minor axis) of the particles is 1.0 or more and less than 2.5. More preferably 1.0 to 2.0.
The appropriate firing temperature varies depending on the firing apparatus, and when firing is performed in a muffle furnace (mufflefuranace) or a rotary kiln, which is a general firing furnace, it is desirable to perform firing at 500 to 800 ℃, more preferably at 550 to 750 ℃. If the temperature is less than 500 ℃, voids existing before firing are not sufficiently reduced, so that the hiding power is insufficient, and if the temperature exceeds 800 ℃, sintering excessively proceeds, and the red light selective transmission function is lost.
The titanium dioxide of the present invention has an average crystallite diameter of 15 to 30nm as measured by an X-ray diffraction method.
When the crystallite diameter is less than 15nm, sufficient hiding power cannot be obtained, which is not preferable. When the particle diameter exceeds 30nm, the sintering proceeds, and the red light selective transmission function is not sufficiently exhibited, which is not preferable.
In addition, the titanium dioxide powder of the present invention needs to have an apparent average particle diameter of 100nm or more and less than 500nm, more preferably 200 to 400nm, from the viewpoint of effectively realizing the covering power by scattering and the excellent red light transmission function.
The specific surface area of the titanium dioxide powder used in the present invention is an index indicating the decrease in porosity and the progress of sintering of the obtained titanium oxide particles, and the specific surface area of the titanium dioxide powder serving as the matrix after firing is preferably in the range of 8 to 50% as compared with that before firing (100%). More preferably 8 to 30%.
In addition, the specific surface area of the titanium dioxide powder of the invention needs to be 10-30 m2(ii) in terms of/g. If it is less than 10m2In the case of the red light selective transmission, the red light selective transmission function is not sufficiently exhibited. In addition, if it exceeds 30m2However, the presence of voids is not preferable because sufficient covering power cannot be achieved.
The titanium dioxide powder of the present invention may be subjected to surface treatment after firing. By performing the surface treatment, titanium dioxide having improved makeup retention properties associated with viscosity, oil dispersibility, and water repellency and excellent usability can be obtained.
Examples of the inorganic substance usable as the surface treatment agent include: hydrated oxides or oxides of metals such as aluminum, silicon, zinc, titanium, zirconium, iron, cerium, and tin. The metal salt usable herein is not particularly limited.
Examples of the organic material that can be used as the surface treatment agent include, after surface treatment with a metal oxide or metal hydroxide such as aluminum hydroxide or aluminum oxide, for example, in order to impart lipophilicity: fatty acids such as stearic acid, oleic acid, isostearic acid, myristic acid, palmitic acid, behenic acid (behenic acid), and the like; organosilicon compounds such as methylhydrogenpolysiloxanes, polydimethylsiloxanes, alkyl (C8-C18) trialkoxysilanes, amino-modified siloxanes and carboxyl-modified siloxanes; fluorine compounds such as perfluoroalkyl alkyl phosphates; dextrin myristate, dextrin palmitate, lauroyl lysine, lauroyl glutamate and like amino acid derivatives, and the like.
It is preferable that the surface treatment agent is 1 to 10% by mass based on the titanium dioxide powder because the masking force is high.
The titanium dioxide powder used in the present invention can be widely blended in cosmetics, pigments, inks, paints, and the like.
The amount of titanium dioxide used in the present invention is 1 to 30% by mass, more preferably 5 to 15% by mass, based on the total weight of the powder cosmetic. If the content is less than 1% by mass, the effect of blending the titanium dioxide of the present invention may not be obtained, and if the content exceeds 30% by mass, the cosmetic appearance may be unnatural.
[ hydrophobization of Zinc oxide ]
The amount of the hydrophobized zinc oxide (particularly dextrin palmitate treated zinc oxide) used in the present invention is 0.1 to 10% by mass, more preferably 2 to 5% by mass, based on the total weight of the powder cosmetic. If the amount is less than 0.1% by mass, cosmetic effects may not be obtained, and if the amount exceeds 10%, usability may be deteriorated.
Examples of the hydrophobized zinc oxide include: dextrin palmitate treated zinc oxide, n-octyltriethoxysilane treated zinc oxide, perfluoroalkyl phosphate treated zinc oxide, and the like. In the present invention, the particulate zinc oxide which is a low-temperature fired product is preferably subjected to a dextrin palmitate treatment as the hydrophobic treatment.
The hydrophobized zinc oxide can be produced by coating a low-temperature-fired zinc oxide with a fatty acid by the method described in Japanese examined patent publication (Kokoku) No. 5-3844, for example.
As a commercially available product of hydrophobized zinc oxide, WSX-MZ-700 from TAYCA K.K. can be mentioned.
[ other ingredients ]
The powder cosmetic according to the present invention may contain, as necessary, other components, for example: inorganic powder, organic powder, ester, anionic surfactant, cationic surfactant, amphoteric surfactant, nonionic surfactant, humectant, water-soluble polymer, thickener, coating agent, ultraviolet absorbent, metal ion blocking agent, lower alcohol, polyhydric alcohol, sugar, amino acid, organic amine, polymer emulsion, pH regulator, skin nutrient, vitamin, antioxidant auxiliary, perfume, water, etc., and can be produced by a conventional method according to the desired formulation.
Specific blending-required components are listed below, and the powder cosmetic can be prepared by blending the above-mentioned essential blending components with any 1 or 2 or more of the following components.
Examples of the inorganic powder include: talc, boron nitride, sericite, natural mica, calcined 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, alumina, magnesium oxide, chromium hydroxide, prussian blue, ultramarine, calcium phosphate, aluminum hydroxide, barium sulfate, magnesium sulfate, silicic acid, aluminum magnesium silicate, calcium silicate, barium silicate, magnesium silicate, aluminum silicate, strontium silicate, silicon carbide, magnesium fluoride, metal tungstate, magnesium aluminate, magnesium metasilicate aluminate, chlorohydroxyaluminum, clay, zeolite, hydroxyapatite, ceramic powder, spinel, Mullite (mullilite), cordierite, aluminum nitride, titanium nitride, silicon nitride, lanthanum, samarium, tantalum, terbium, europium, neodymium, Mn-Zn ferrite, Ni — Zn ferrite, Silicon Carbide (Silicon Carbide), cobalt titanate, barium titanate, iron titanate, lithium cobalt titanate, cobalt aluminate, antimony-containing tin Oxide, tin-containing indium Oxide, magnetite, aluminum powder, gold powder, silver powder, platinum powder, copper powder, noble metal colloid, iron powder, Zinc powder, cobalt blue, cobalt violet, cobalt green, titanium suboxide, particulate titanium Oxide, barium sphenoid sulfate, petaloid Zinc Oxide, Tetrapod Zinc Oxide (particulate Zinc Oxide), particulate Zinc Oxide; as pearl pigments: titanium oxide-coated mica, titanium oxide-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 mica titanium, iron oxide red/iron oxide black-coated mica titanium, carmine-coated mica titanium, beryl blue-coated mica titanium, and the like.
Examples of the organic powder include (for example, silicone elastomer powder, silicone resin-coated silicone elastomer powder, polyamide resin powder (nylon powder), polyethylene powder, polymethyl methacrylate powder (for example, methyl methacrylate crosslinked polymer), polystyrene powder, copolymer resin powder of styrene and acrylic acid, benzoguanamine resin powder, polytetrafluoroethylene powder, cellulose powder, and the like); examples of the organic pigment such as zirconium, barium or aluminum lake include (for example, organic pigments such as red 201, red 202, red 204, red 205, red 220, red 226, red 228, red 405, orange 203, orange 204, yellow 205, yellow 401 and blue 404).
Examples of the anionic surfactant include: fatty acid soaps (e.g., sodium laurate, sodium palmitate, etc.); higher alkyl sulfate ester salts (e.g., sodium lauryl sulfate, potassium lauryl sulfate, etc.); alkyl ether sulfate ester salts (e.g., POE-triethanolamine lauryl sulfate, POE-sodium lauryl sulfate, etc.); n-acyl sarcosines (e.g., sodium lauroyl sarcosinate, etc.); higher fatty acid amide sulfonates (e.g., sodium N-myristoyl-N-methyltaurate, sodium coconut fatty acid methyltaurate, sodium lauryl methyltaurate, etc.); phosphate ester salts (POE-oleyl ether sodium phosphate, POE-stearyl ether phosphate, etc.); sulfosuccinates (e.g., di-2-ethylhexyl sulfosuccinateSodium peroxodisulfate, monolauryl monoethanolamide polyoxyethylene sodium sulfosuccinate, sodium lauryl polypropylene glycol sulfosuccinate, etc.); alkyl benzene sulfonates (e.g., linear sodium dodecylbenzene sulfonate, linear triethanolamine dodecylbenzene sulfonate, linear dodecylbenzene sulfonic acid, etc.); higher fatty acid ester sulfate salts (e.g., sodium hydrogenated coconut oil fatty acid glycerol sulfate); n-acyl glutamates (e.g., monosodium N-lauroyl glutamate, disodium N-stearoyl glutamate, monosodium N-myristoyl-L-glutamate, etc.); sulfated oils (e.g., turkish red oil, etc.); POE-alkyl ether carboxylic acids; POE-alkyl allyl ether carboxylate;α-an olefin sulfonate; higher fatty acid ester sulfonates; secondary alcohol sulfate salts; higher fatty acid alkanolamide sulfate salts; lauroyl monoethanolamide sodium succinate; n-palmitoyl aspartic acid di (triethanolamine); sodium caseinate, and the like.
Examples of the cationic surfactant include: alkyltrimethylammonium salts (e.g., stearyltrimethylammonium chloride, lauryltrimethylammonium chloride, etc.); alkylpyridinium salts (e.g., cetylpyridinium chloride, etc.); distearyldimethylammonium chloride dialkyldimethylammonium salts; poly (N, N' -dimethyl-3, 5-methylenepiperidinium) chloride; alkyl quaternary ammonium salts; alkyl dimethyl benzyl ammonium salts; an alkylisoquinolinium salt; a dialkyl morpholinium salt; POE-alkylamine; an alkylamine salt; polyamine fatty acid derivatives; a pentanol fatty acid derivative; benzalkonium Chloride (Benzalkonium Chloride); benzethonium chloride (benzethonium chloride), and the like.
Examples of the amphoteric surfactant include: imidazoline-based amphoteric surfactants (e.g., 2-undecyl-N, N, N- (hydroxyethylcarboxymethyl) -2-imidazolinium sodium, 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethoxy disodium salt, etc.); betaine-type surfactants (e.g., 2-heptadecyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, lauryl dimethylaminoacetic acid betaine, alkyl betaine, amidobetaine, sulfobetaine, etc.), and the like.
Examples of the lipophilic nonionic surfactant include: sorbitan fatty acid esters (e.g., sorbitan monooleate)Sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan trioleate, sorbitan penta-2-ethylhexanoate diglyceride, sorbitan tetra-2-ethylhexanoate, and the like); glycerol polyglycerin fatty acids (e.g., cottonseed oil fatty acid glyceride, erucic acid glyceride, sesquioleic acid glyceride, glyceryl monostearate, glycerol monostearate,α,α' -glyceryl pyroglutamate oleate, glyceryl malic acid monostearate, etc.); propylene glycol fatty acid esters (e.g., propylene glycol monostearate); hydrogenated castor oil derivatives; glycerol alkyl ethers, and the like.
Examples of the hydrophilic nonionic surfactant include: POE-sorbitan fatty acid esters (e.g., POE-sorbitan monooleate, POE-sorbitan monostearate, POE-sorbitan monooleate, POE-sorbitan tetraoleate, etc.); POE-sorbitol fatty acid esters (e.g., POE-sorbitol monolaurate, POE-sorbitol monooleate, POE-sorbitol pentaoleate, POE-sorbitol monostearate, etc.); POE-glycerin fatty acid esters (for example, POE-monooleate such as POE-glycerin monostearate, POE-glycerin monoisostearate and POE-glycerin triisostearate); POE-fatty acid esters (e.g., POE-distearate, POE-monooleate (POE-monodioleate), ethylene glycol distearate, etc.); POE-alkyl ethers (e.g., POE-lauryl ether, POE-oleyl ether, POE-stearyl ether, POE-behenyl ether, POE-2-octyldodecyl ether, POE-cholestanol ether (POE-cholestanol ether), etc.); pluronic types (e.g., Pluronic, etc.); POE/POP-alkyl ethers (e.g., POE/POP-cetyl ether, POE/POP-2-decyltetradecyl ether, POE/POP-monobutyl ether, POE/POP-hydrogenated lanolin, POE/POP-glyceryl ether, etc.); tetrapolye/tetrapod-ethylenediamine condensates (for example, Tetronic); POE-castor oil hydrogenated castor oil derivatives (e.g., POE-castor oil, POE-hydrogenated castor oil monoisostearate, POE-hydrogenated castor oil triisostearate, POE-hydrogenated castor oil monopyroglutamic acid monoisostearic acid diester, POE-hydrogenated castor oil maleate, etc.); POE-beeswax/lanolin derivatives (e.g., POE-sorbitol beeswax, etc.); alkanolamides (e.g., 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; triolein phosphate and the like.
Examples of the humectant include: polyethylene glycol, propylene glycol, glycerol, 1, 3-butylene glycol, xylitol, sorbitol, maltitol, chondroitin sulfate, hyaluronic Acid, mucin sulfate, caronic Acid (Charonic Acid), Atelocollagen (Atelocollagen ), 12-hydroxystearic Acid cholesteryl ester, sodium lactate, bile Acid salt, d 1-pyrrolidone carboxylate, alkylene oxide derivative, short-chain soluble collagen, diglycerol (EO) PO adduct, rosa roxburghii extract, yarrow extract, melilotus officinalis extract, and the like.
Examples of the natural water-soluble polymer include: plant-based polymers (e.g., gum arabic, gum tragacanth, galactan, guar gum, carob gum, karaya gum, carrageenan, pectin, agar, quince seed (Marmelo), algae colloid (brown algae extract), starch (rice, corn, potato, wheat), glycyrrhizic acid, etc.); microbial polymers (e.g., xanthan gum, dextran, succinoglycan, pullulan, etc.); animal polymers (e.g., collagen, casein, albumin, gelatin, etc.), and the like.
Examples of the semisynthetic water-soluble polymer include: starch-based polymers (e.g., carboxymethyl starch, methylhydroxypropyl starch, etc.); cellulose polymers (methyl cellulose, ethyl cellulose, methylhydroxypropyl cellulose, hydroxyethyl cellulose, sodium cellulose sulfate, hydroxypropyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, crystalline cellulose, cellulose powder, etc.); alginic acid polymers (e.g., sodium alginate, propylene glycol alginate, etc.), and the like.
Examples of the water-soluble polymer to be synthesized include: vinyl polymers (e.g., polyvinyl alcohol, polyvinyl methyl ether, polyvinyl pyrrolidone, carboxyvinyl polymer, etc.); polyoxyethylene polymers (e.g., polyoxyethylene polyoxypropylene copolymers of polyethylene glycol 20,000, 40,000, 60,0000, etc.); acrylic polymers (for example, sodium polyacrylate, polyethylacrylate, polyacrylamide, etc.); a polyethyleneimine; cationic polymers, and the like.
Examples of the thickener 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, dialkyl dimethyl ammonium cellulose sulfate, xanthan gum, magnesium aluminum silicate, bentonite, hectorite, silicic acid A1Mg (Veegum), Laponite (Laponite), silicic anhydride, and the like.
Examples of the ultraviolet absorber include: benzoic acid-based ultraviolet absorbers (e.g., p-aminobenzoic acid (hereinafter abbreviated as PABA), PABA monoglyceride, N-dipropoxypPABA ethyl ester, N-diethoxypPABA ethyl ester, N-dimethylpPABA butyl ester, N-dimethylpPABA ethyl ester, etc.); anthranilic acid-based ultraviolet absorbers (e.g., N-acetyl anthranilic acid homomenthyl ester); salicylic acid-based ultraviolet absorbers (e.g., amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropyl alcohol phenyl salicylate, etc.); cinnamic acid-based ultraviolet absorbers (for example, octyl methoxycinnamate, ethyl-4-isopropyl cinnamate, methyl-2, 5-diisopropyl cinnamate, ethyl-2, 4-diisopropyl cinnamate, methyl-2, 4-diisopropyl cinnamate, propyl p-methoxycinnamate, isopropyl p-methoxycinnamate, isoamyl p-methoxycinnamate, octyl p-methoxycinnamate (2-ethylhexyl p-methoxycinnamate), 2-ethoxyethyl p-methoxycinnamate, cyclohexyl p-methoxycinnamate, ethyl p-methoxycinnamate, isopropyl p-methoxycinnamate,α-cyano-β-ethyl phenylcinnamate,α-cyano-β2-ethylhexyl phenylcinnamate, mono-2-ethylhexanoyl-di-p-methoxycinnamate, etc.); benzophenone-based ultraviolet absorbers (e.g., 2, 4-dihydroxybenzophenone, 2 ' -dihydroxy-4-methoxybenzophenone, 2 ' -dihydroxy-4, 4 ' -dimethoxybenzophenone, 2 ', 4,4 ' -tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4 ' -methylbenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 4-phenylbenzophenone, 2-ethylhexyl-4 ' -phenyl-benzophenone-2-carboxylate, 2-hydroxy-4-n-octyloxybenzophenone, 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) benzotriazole; 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole; dibenzylidene azine (dibenzazine); dianisicyl Methane (Dianisoyl Methane); 4-methoxy-4' -tert-butyl dibenzoylmethane; 5- (3, 3-dimethyl-2-norbornylene) -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]-phenyl } -6- (4-methoxyphenyl) - (1,3,5) -triazine and the like.
Examples of the metal ion-blocking agent include: 1-hydroxyethane-1, 1-diphosphonic acid, 1-hydroxyethane-1, 1-diphosphonic acid tetrasodium salt, edetate disodium, edetate trisodium, edetate tetrasodium, sodium citrate, sodium polyphosphate, sodium metaphosphate, gluconic acid, phosphoric acid, citric acid, ascorbic acid, succinic acid, edetic acid, ethylenediamine hydroxyethyltriacetic acid trisodium salt, and the like.
Examples of the lower alcohol include: ethanol, propanol, isopropanol, isobutanol, tert-butanol, and the like.
Examples of the polyhydric alcohol include: dihydric alcohols (e.g., 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, octanediol, etc.); trihydric alcohols (e.g., glycerin, trimethylolpropane, etc.); tetrahydric alcohols (e.g., pentaerythritol such as 1,2, 6-hexanetriol); pentahydric alcohols (e.g., xylitol, etc.); hexahydric alcohols (e.g., sorbitol (ソルビトール), mannitol, etc.); polyol polymers (e.g., diethylene glycol, dipropylene glycol, triethylene glycol, polypropylene glycol, tetraethylene glycol, diglycerin, polyethylene glycol, triglycerol, tetraglycerol, polyglycerin, and the like); dihydric alcohol alkyl ethers (e.g., ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monohexyl ether, ethylene glycol 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.); glycol alkyl ethers (e.g., diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol butyl ether, diethylene glycol methyl ethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol isobutyl ether, propylene glycol isopropyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol butyl ether, etc.); glycol ether esters (e.g., ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, ethylene glycol diadipate, ethylene glycol disuccinate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monophenyl ether acetate, etc.); glycerol monoalkyl ethers (e.g., Chimyl Alcohol (Chimyl Alcohol), Selachyl Alcohol (Selactiyl Alcohol), Batyl Alcohol (Batyl Alcohol), etc.); sugar alcohols (e.g., 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; glyceryl triphenoxide ether; POP-glyceryl ether; POP-glyceryl ether phosphate; POP/POE-pentaerythritol ether, polyglycerol, etc.
Examples of the monosaccharide include: three-carbon sugars (e.g., D-glyceraldehyde, dihydroxyacetone, etc.); four carbon sugars (e.g., D-erythrose, D-erythrulose, D-threose, erythritol, etc.); five-carbon sugars (e.g., L-arabinose, D-xylose, L-lyxose, D-arabinose, D-ribose, D-ribulose, D-xylulose, L-xylulose, etc.); a six-carbon sugar (e.g., D-glucose, D-talose, D-psicose, D-galactose, D-fructose, L-galactose, L-mannose, D-tagatose); seven-carbon sugars (e.g., aldoheptose, ketoheptose (ヘプロ - ス), etc.); eight-carbon sugars (e.g., octulose, etc.); deoxy sugars (e.g., 2-deoxy-D-ribose, 6-deoxy-L-galactose, 6-deoxy-L-mannose, etc.); aminosugars (e.g., D-glucosamine, D-galactosamine, sialic acid, aminouronic acid, muramic acid, etc.); uronic acids (e.g., D-glucuronic acid, D-mannuronic acid, L-guluronic acid, D-galacturonic acid, L-iduronic acid, etc.) and the like.
Examples of the oligosaccharide include: sucrose, gentiotriose, Umbelliferose, lactose, plantago (Planteose), Isochrysosporane (Isolyhnose), sucrose, gentianose, Umbelliferose, lactose, sucrose, lactose, sucrose,α,αtrehalose (c)α,αTrehalose), Raffinose (Raffinose), lychose (lychloro), Umbilicin (ウンビリシン), Stachyose (Stachyose), Verbascose (verbasose), and the like.
Examples of the polysaccharide include: cellulose, quince seed, chondroitin Sulfate, starch, galactan, Dermatan Sulfate (Dermatan Sulfate), Glycogen (Glycogen), gum arabic, Heparan Sulfate (Heparan Sulfate), hyaluronic acid, tragacanth gum, Keratan Sulfate (Keratan Sulfate), chondroitin, xanthan gum, mucin Sulfate (mucoitin Sulfate), guar gum, dextran, cutin Sulfate (Keratan Sulfate), locust bean gum, succinoglycan, caronin acid, and the like.
Examples of the amino acid include: neutral amino acids (e.g., threonine, cysteine, etc.); basic amino acids (e.g., hydroxylysine, etc.), and the like. Examples of the amino acid derivative include: sodium acyl sarcosinate (sodium lauroyl sarcosinate), acyl glutamate, and acyl groupβSodium alaninate, glutathione, pyrrolidone carboxylic acid, and the like.
Examples of the organic amine include: monoethanolamine, diethanolamine, triethanolamine, morpholine, triisopropanolamine, 2-amino-2-methyl-1, 3-propanediol, 2-amino-2-methyl-1-propanol, and the like.
Examples of the polymer emulsion include: acrylic resin emulsion, polyethylacrylate emulsion, acrylic resin solution, polyalkylacrylate emulsion, polyvinyl acetate resin emulsion, natural rubber latex, etc.
Examples of the pH adjuster include: and buffers such as sodium lactate-lactate, sodium citrate-citrate, and sodium succinate-succinate.
Examples of the vitamins include: vitamins A, B1, B2, B6, C, E and derivatives thereof, pantothenic acid and derivatives thereof, biotin, and the like.
Examples of the antioxidant include: tocopherols, dibutylhydroxytoluene, butylhydroxyanisole, gallic acid esters, etc.
Examples of the antioxidant auxiliary include: phosphoric Acid, citric Acid, ascorbic Acid, maleic Acid, malonic Acid, succinic Acid, fumaric Acid, cephalin, hexametaphosphate, Phytic Acid (Phytic Acid), ethylenediaminetetraacetic Acid, and the like.
Examples of other components that can be blended include: preservatives (ethyl p-hydroxybenzoate, butyl p-hydroxybenzoate, chlorphenesin, phenoxyethanol, and the like); anti-inflammatory agents (e.g., glycyrrhizic acid derivatives, glycyrrhetinic acid derivatives, salicylic acid derivatives, hinokitiol, zinc oxide, allantoin, etc.); whitening agents (e.g., placenta extract, saxifrage extract, arbutin, etc.); various extracts (e.g., phellodendron amurense, coptis chinensis, lithospermum, paeonia lactiflora, swertia japonica, Birch (Birch), sage, loquat, ginseng, aloe, mallow, orris, grape, coix seed, luffa, lily, saffron, ligusticum wallichii, pinecone, hypericum erectum, formononetin, garlic, capsicum, dried orange peel, angelica, seaweed, etc.); activators (activators) (e.g., royal jelly, photoreceptors, cholesterol derivatives, etc.); blood circulation promoter (e.g., vanillylnonanamide (ノニル acid ワレニルアミド), benzyl nicotinate, nicotinic acidβ-butoxyethyl ester, capsaicin, zingerone, Tincture of sting (cantaraides tinture),Ichthammol, tannic acid,α-alcohol of arrowhead: (α-at least one ice flake,α-borneol), tocopheryl nicotinate, inositol hexanicotinate, Cyclandelate, Cinnarizine (Cinnarizine), Tolazoline (Tolazoline), Acetylcholine (Acetylcholine), Verapamil (Verapail), Cepharanthine (cephaloranthine), and mixtures thereof,γ-oryzanol: (γ-oryzanol), etc.); anti-lipemic agents (e.g., sulfur, dithiane (thiantohol), etc.); anti-inflammatory agents (e.g., tranexamic acid, thiotaurine, Hypotaurine (Hypotaurine), etc.) and the like.
Further, it is also possible to appropriately blend: metal-blocking agents such as disodium edetate, trisodium edetate, sodium citrate, sodium polyphosphate, sodium metaphosphate, gluconic acid, malic acid, etc., agents such as caffeine, tannin, verapamil, tranexamic acid and derivatives thereof, various herbal (crude drug) extracts of licorice, pyrus ussuriensis (カリン), pyrola japonica, etc., tocopheryl acetate, glycyrrhetinic acid (グリチルレジン acid), glycyrrhizic acid (グリチルリチン acid) and derivatives thereof or salts thereof, whitening agents such as vitamin C, magnesium ascorbyl phosphate, ascorbyl glucoside, arbutin, kojic acid, etc., amino acids and derivatives thereof such as arginine, lysine, etc., saccharides such as fructose, mannose, erythritol, trehalose, xylitol, etc., and the like.
As the product form of the powder cosmetic according to the present invention, any product form within the powder cosmetic category can be adopted. Specifically, products such as foundation, eye shadow, blush, toilet Powder (Body Powder), Powder perfume (PerfumePowder), Baby toilet Powder (Baby Powder), Pressed Powder (Pressed Powder), deodorant Powder (DeodorantPowder), and face Powder can be used.
[ method for producing solid powder cosmetic according to the present invention ]
Dry-type manufacturing method
The inorganic powder component, the oily component and other components were mixed in a Henschel Mixer (Henschel Mixer) in advance, and then pulverized 2 times by a Pulverizer (Pulverizer). Then, the obtained mixture is filled in a resin-made medium-sized container and dry press-molded by a known method to obtain a solid powdery cosmetic containing the titanium oxide of the present invention blended in the cosmetic.
Other manufacturing methods
As a method for producing a cosmetic containing the titanium oxide of the present invention, a known method can be used. For example, it can be suitably obtained by the following production method: a production method of drying a slurry using a volatile solvent described in japanese patent No. 5422092, and a production method of filling a slurry using a volatile solvent and removing the filled slurry described in japanese patent No. 5972437.
Examples
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Unless otherwise specified, the blending amount is expressed as mass% relative to the system in which the components are blended.
Before the examples are explained, the evaluation method of the test of titanium dioxide used in the present invention will be explained.
Evaluation (1): method for measuring average crystallite diameter
The sample was measured by an X-ray diffraction apparatus (Geigerflex, manufactured by chem motors), and the average crystallite diameter was calculated by applying Scherrer's formula.
Evaluation (2): evaluation of hiding Power
Titanium dioxide powder was dispersed and mixed in nitrocellulose varnish so as to have a concentration of 5%, and the resulting dispersion was subjected to black-and-white coverage test paper JIS-K5400 at 0.101μThe test samples were measured for color of the surface of the coating film on white and black paper with a spectrophotometer (CM-2600, manufactured by Konica Minolta Co., Ltd.) the color difference in Hunter Lab color space (△ E) was calculated and evaluated as the hiding power, and it was noted that the higher △ E indicates the smaller hiding power and the lower △ E indicates the larger hiding power.
ΔE＝
(evaluation criteria)
×：25<△E
△：22<△E≤25
○：△E≤22
Evaluation (3): evaluation of Red transmittance
The red transmittance is a ratio of reflectance at a wavelength of 450nm to reflectance at a wavelength of 650nm (reflectance at a wavelength of 450 nm/reflectance at a wavelength of 650 nm: R450/R650) calculated from the spectral reflectance at each wavelength measured on the black paper in the same manner as the above-mentioned hiding power.
The higher R450/R650 indicates higher red transmittance, and the lower R450/R650 indicates lower 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): method for measuring specific surface area
The specific surface area per unit mass can be determined by a nitrogen adsorption method known as the BET (Brunauer-Emmet-Teller) method described in the journal of the American Chemical Society, volume 60, page 309, and month 2 1938 corresponding to International Standard ISO 5794/1 (appendix D).
Evaluation (5): method for measuring apparent average particle diameter
The average of the lengths of the major axis and the minor axis of the particle was obtained by the method shown in fig. 1.
[ selection of titanium oxide for mother nucleus ]
First, the present inventors evaluated the titanium oxide of rutile type and anatase type, which are commercially available pigment grades, by the above-described evaluation method. The results are shown in Table 1.
[ Table 1]
*1: tipaque CR-50 (product of Stone industries, average apparent particle size: 200nm, shape: amorphous)
*2: bayer A (average particle diameter: 400nm, shape: amorphous, manufactured by Bayer Co., Ltd.)
Both rutile type and anatase type pigment-grade titanium oxides have low red transmittance. Further, even when they are fired at a high temperature, red transmittance is low.
The present inventors have studied whether a product having excellent hiding power can be produced by using rutile titanium oxide having high red transmittance.
The present inventors synthesized titanium dioxide having acicular particles aggregated in radial orientation and having acicular protrusions on the particle surface, which is different in 2 kinds of particle sizes, by using the method of patent document (jp 2010-173863 a).
The titanium oxides thus obtained were each referred to as titanium oxide A (specific surface area: 101 m)2(iv)/g, crystallite diameter: 5nm, apparent average particle diameter: 0.2 to 0.3μm, acicular projection shape), titanium oxide B (specific surface area: 117m2(iv)/g, crystallite diameter: 11nm, apparent average particle diameter: 0.3μm, needle-like projection shape).
Titanium dioxide having acicular protrusions on the particle surface, which is obtained by aggregating acicular particles as a commercially available product (ST-730: manufactured by titanium industries, Ltd.) in radial orientation, is called titanium oxide C (specific surface area: 98 m)2(iv)/g, crystallite diameter: 6nm, apparent average particle diameter: 0.5μm, needle-like projection shape).
Titanium dioxide having acicular protrusions on the particle surface, which is obtained by aggregating acicular particles as a commercially available product (ST-750: manufactured by titanium industries, Ltd.) in radial orientation, is referred to as titanium oxide D (84 m)2(iv)/g, crystallite diameter: 8.6nm, apparent average particle diameter: 1.0μm, needle-like projection shape).
Titanium oxide having needle-like particles as a commercially available product (MT 062; manufactured by Tayca industries, Ltd.) is referred to as titanium oxide E (specific surface area)Product: 47m2(iv)/g, crystallite diameter: 23.3nm, apparent average particle diameter: 65nm, acicular projection shape).
Using each titanium dioxide, a titanium dioxide powder was obtained by the following method. The obtained titanium dioxide powder was evaluated by the above evaluation method, and the relationship between the kind of titanium dioxide before firing and the firing temperature was examined. The results are shown in tables 2 to 6.
(method for producing titanium dioxide powder)
100g of titanium dioxide for the mother core was put in a crucible made of quartz, and firing was performed in a muffle furnace at each temperature for 1 hour, thereby obtaining a titanium dioxide powder.
Titanium oxide A (specific surface area: 101 m)2(iv)/g, crystallite diameter: 5nm, apparent average particle diameter: 0.2 to 0.3μm, needle-like projection shape)
[ Table 2]
Titanium oxide B (specific surface area: 117 m)2(iv)/g, crystallite diameter: 11nm, apparent average particle diameter: 0.3μm, needle-like projection shape)
[ Table 3]
Titanium oxide C (specific surface area: 98 m)2(iv)/g, crystallite diameter: 6nm, apparent average particle diameter: 0.5μm, needle-like projection shape)
[ Table 4]
Titanium oxide D (84 m)2(iv)/g, crystallite diameter: 8.6nm, apparent average particle diameter: 1μm, needle-like projection shape)
[ Table 5]
Titanium oxide E (specific surface area: 47 m)2(iv)/g, crystallite diameter: 23.3nm, apparent average particle diameter: 65nm, needle-like projection shape)
[ Table 6]
| Test examples | 5-1 | 5-2 | 5-3 | 5-4 |
| Shape of | Needle-like shape | Needle-like shape | Needle-like shape | Needle-like shape |
| Ratio of minor diameter to major 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/. degree.C | - | 350 | 630 | 720 |
| Permeability of red | ◎ | ◎ | ◎ | ◎ |
| Hiding power | × | × | × | × |
In each of the titanium oxides a to C, the hiding power is improved by increasing the firing temperature. Since the specific surface area decreases with an increase in temperature, it is known that the acicular particles aggregated in the radial orientation existing before firing are agglomerated with each other, and thus voids existing in the particles are reduced. This results in an increase in the apparent refractive index and an increase in hiding power. However, the red transmittance gradually decreases. In particular, excessive sintering occurs during firing at high temperatures, and the initial red transmittance is significantly reduced.
In particular, titanium oxide C having a large average particle diameter almost loses red transmittance at 700 ℃.
In addition, in the case of titanium oxide D in which acicular particles are aggregated in a radial orientation as in the case of titanium oxides a to C, the specific surface area decreases as the firing temperature increases as in the case of titanium oxides a to C, but the apparent particle diameter is significantly large, and therefore the improvement in hiding power is extremely small. In addition, since the apparent particle size is significantly large, the red transmittance is low both before and after firing, and the desired red transmittance cannot be obtained.
In addition, titanium oxide E having a small average particle size before firing and consisting of single needle-like particles did not change its shape after firing, and the red transmittance was maintained, but the hiding power was not improved at all.
Also, titanium dioxide of various shapes was studied.
Further, titanium dioxide in which the particles as a commercially available product (TT055 (A); manufactured by Shidaikon K.K.) were granular was referred to as titanium oxide F (specific surface area: 37 m)2(iv)/g, crystallite diameter: 24.8nm, apparent average particle diameter: 50nm, granular).
Further, titanium dioxide obtained by aggregating rod-like particles as a commercially available product (ST 643; manufactured by titanium industries, Ltd.) in a straw-like orientation is referred to as titanium oxide G (specific surface area: 132 m)2(iv)/g, crystallite diameter: 8.6nm, apparent average particle diameter: 200nm, straw bundle shape).
Titanium oxide F (specific surface area: 37 m)2(iv)/g, crystallite diameter: 24.8nm, apparent average particle diameter: 50nm, granular)
[ Table 7]
| Test examples | 6-1 | 6-2 | 6-3 | 6-4 |
| Shape of | Granular form | Granular form | Granular form | Granular form |
| Ratio of minor diameter to major diameter | 1.7 | 1.7 | 1.7 | 1.7 |
| |
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 |
| Permeability of red | ◎ | ◎ | ◎ | ◎ |
| Hiding power | × | × | × | × |
As is clear from test examples 6-1 to 6-4, when the granular titanium oxide was fired at 350 to 720 ℃, the crystallite diameter was not changed, and neither the specific surface area nor the crystallite diameter became the titanium oxide after firing according to the present invention.
Therefore, the desired hiding power cannot be obtained despite the red transmittance.
Titanium oxide G (specific surface area: 132 m)2(iv)/g, crystallite diameter: 8.6nm, apparent average particle diameter: 200nm straw bundle shape)
[ Table 8]
| Test examples | 7-1 | 7-2 | 7-3 | 7-4 |
| Shape of | Straw bundle | Straw bundle | Straw bundle | Straw bundle |
| Ratio of minor diameter to major 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 |
| Permeability of red | △ | △ | △ | △ |
| Hiding power | × | △ | △ | △ |
The titanium oxide used in test example 7-1 satisfied (a) an apparent average particle diameter, (b) an average crystallite diameter measured by an X-ray diffraction method, and (c) a specific surface area in the same manner as the titanium dioxide for a matrix of the present invention, but the particle surface did not have needle-like projections. Further, since the ratio of the minor axis/major axis is as large as 2.5, sufficient red transmittance and hiding power cannot be achieved even after firing.
From these studies, it was found that titanium oxide suitable as a matrix for use in the present invention is titanium oxide B having a wide allowable temperature range in terms of improvement of covering properties and maintenance of red transmittance.
The results of measuring the spectral reflectance of rutile type pigmentary titanium oxide (. apprxeq.1) and titanium oxide B (unfired, fired temperature: 700 ℃ C., 900 ℃ C.) are shown in FIG. 2. In the measurement, titanium dioxide powder was dispersed and mixed in nitrocellulose varnish so that the concentration thereof became 5%, and the resulting dispersion was measured on black-and-white coverage test paper JIS-K5400 at 0.101μm is coated and dried to obtain a testAnd (3) sampling. The color of the surface of the coating film on the black paper was measured with a spectrophotometer (CM-2600, manufactured by Konica Minolta Co., Ltd.) to obtain a spectral reflectance.
Then, TEM images of the unfired and fired titania B (firing temperature: 300 ℃, 500 ℃, 700 ℃, 900 ℃) were taken. The results are shown in FIG. 3.
Further, with respect to titanium dioxide B, the shielding force and red transmittance were measured by the change in firing temperature of the rotary kiln. The results are shown in fig. 4 and 5, respectively.
From the above results, in the case of firing in a muffle furnace, the temperature is preferably 500 to 800 ℃, and more preferably 500 to 700 ℃.
Next, the present inventors carefully studied the firing temperature in the range of 500 to 800 ℃ with titanium oxide B as a mother nucleus. That is, the present inventors evaluated the titanium dioxide powder having a changed firing temperature by the above-described evaluation method. The results are shown in tables 5 and 6.
Firing is performed in a rotary firing furnace (rotary kiln) which is more similar to mass production and has high firing efficiency.
In general, the rotary firing furnace has high firing efficiency, and it is known that the same firing state can be obtained at a temperature lower than that in the case of firing in a muffle furnace in which firing is performed with standing.
[ Table 9]
[ Table 10]
The specific surface area is an index indicating the decrease in porosity and the progress of sintering of the obtained titanium oxide particles, and the titanium dioxide used in the present invention is preferably such that the specific surface area is in the range of 8 to 30% as compared with that before firing (100%).
From these results, it is found that the firing temperature is preferably 550 to 700 ℃, more preferably 575 to 660 ℃ in order to obtain excellent hiding power and red transmittance.
[ solid powder cosmetics ]
Further, the present inventors used the titanium dioxide obtained at the firing temperature of 660 ℃ in Table 6 and obtained hydrophobized titanium dioxide by the surface treatment method described below, and adjusted solid powder cosmetics blended with the titanium dioxide by a conventional method, respectively. Then, the obtained cosmetic was evaluated by the following evaluation method.
[ method for surface treatment of titanium dioxide powder ]
The obtained titanium dioxide powder was dispersed in ion exchange water, heated to adsorb stearic acid by 3 mass%, and then dehydrated, washed and dried to obtain surface-treated titanium dioxide.
[ method for producing solid powder cosmetic ]
Dry-type manufacturing method
The inorganic powder component, oily component and other components were mixed in a Henschel mixer in advance, and then pulverized 2 times by a pulverizer. Then, the obtained mixture is filled in a resin-made medium-sized container and dry press-molded by a known method to obtain a solid powdery cosmetic containing the titanium oxide of the present invention blended in the cosmetic.
[ evaluation method of solid powder cosmetic ]
Evaluation (6): natural makeup
10 professional panelists applied the samples to the face and evaluated the feeling of use after application.
A: more than 7 of 10 panelists responded naturally as makeup
B: more than 5 and less than 7 of 10 panelists responded as makeup naturally
C: among 10 panelists, less than 5 were answered with makeup naturally
Evaluation (7): without whitening
10 professional panelists applied the samples to the face and evaluated the feeling of use after application.
A: of 10 panelists, 7 or more answered no whitening
B: no whitening in 5 or more and less than 7 out of 10 panelists
C: among 10 panelists, less than 5 answers were non-whitening
Evaluation (8): covering of spots and freckles
10 professional panelists applied the samples to the face and evaluated the feeling of use after application.
A: among 10 panelists, 7 or more answered with masked spots and freckles
B: among 10 panelists, 5 or more and less than 7 were answered with masked spots and freckles
C: less than 5 out of 10 panelists answered with masked spots, freckles
Evaluation (9): the obvious appearance of texture
10 professional panelists applied the samples to the face and evaluated the feeling of use after application.
A: of 10 panelists, 7 or more answers were unobtrusive in texture
B: of 10 panelists, 5 or more and less than 7 answers were unobtrusive in texture
C: less than 5 out of 10 panelists answered unobtrusively for texture
Evaluation (10): make-up keeping property
10 professional panelists applied the samples to the face and evaluated the makeup retention 3 hours after application.
A: among 10 panelists, 7 or more answers were good makeup retention after 3 hours of application
B: among 10 panelists, 5 or more and less than 7 answers were good in makeup retention after 3 hours of application
C: among 10 panelists, less than 5 answers were good make-up after 3 hours of application
Evaluation (11): non-sticking powder
10 professional panelists applied the samples to the face and evaluated the feeling of use during application.
A: among 10 panelists, 7 or more answers were no calorie in use
B: the 10 panelists answered no calorie in use in 5 or more and less than 7 answers
C: less than 5 out of 10 panelists answered no calorie in use
[ Table 11]
| Test examples | 8-1 | 8-2 | 8-3 | 8-4 | 8-5 | 8-6 | 8-7 |
| Branched alkylsiloxane (ethoxy functionality) treated talc (. 1) | To 100 percent | To 100 percent | To 100 percent | To 100 percent | To 100 percent | To 100 percent | To 100 percent |
| Synthetic iron fluorophlogopite (. dot.2) | 12 | 12 | 12 | 12 | 12 | 12 | 12 |
| Synthetic fluorophlogopite (. about.3) | 12 | 12 | 12 | 12 | 12 | 12 | 12 |
| Pigmentary titanium dioxide (. 4) | 9.5 | 9.5 | |||||
| The invention titanium dioxide (after firing) | 9.5 | 9.5 | 9.5 | 0.3 | 32 | ||
| Titanium dioxide before firing | 9.5 | ||||||
| Fine particle titanium dioxide (. 5) | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
| Organosilicon treated iron oxide red | 0.35 | 0.35 | 0.35 | 0.35 | 0.35 | 0.35 | 0.35 |
| Organosilicon treated yellow iron oxide | 1.8 | 1.8 | 1.8 | 1.8 | 1.8 | 1.8 | 1.8 |
| Organosilicon treated black iron oxide | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Spherical (Diphenylpolydimethylsiloxane/Vinyldiphenylpolydimethylsiloxane/silsesquioxane) crosslinked Polymer (. 6) | 4 | 4 | 4 | 4 | 4 | 4 | 4 |
| Spherical nylon powder (. 7) | 4 | 4 | 4 | 4 | 4 | 4 | 4 |
| Spherical (vinyl polydimethylsiloxane/polymethylsilsesquioxane) crosslinked polymer (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 | Proper amount of | Proper amount of | Proper amount of | Proper amount of | Proper amount of | Proper amount of | Proper amount of |
| Dimethylpolysiloxane (. 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 |
| Tri 2-ethylhexanoic acid glycerol ester (. about 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 |
| Antioxidant agent | Proper amount of | Proper amount of | Proper amount of | Proper amount of | Proper amount of | Proper amount of | Proper amount of |
| Total up to | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Natural makeup | A | A | A | B | A | B | C |
| Without whitening | A | A | A | C | A | A | C |
| Covering of spots and freckles | A | A | A | A | C | C | A |
| The obvious appearance of texture | A | A | A | A | C | B | B |
| Make-up keeping property | A | A | C | A | A | A | A |
| Non-sticking powder in use | A | C | A | A | A | A | A |
(x 1) BAE-Talc JA68R, manufactured by Sanko Kabushiki Kaisha
(X2) PDM-FE manufactured by Topy industries Ltd
(X3) PDM-9WA manufactured by Topy industries Ltd
(4) Tipaque CR-50 available from Stone industries Ltd
(5) MT-100TV manufactured by Tayca K.K
(6) KSP-300 manufactured by shin-Etsu chemical Co., Ltd
(7) Nylon SP-500 manufactured by Toray corporation
(8) KSP-100 manufactured by shin-Etsu chemical Co., Ltd
(9) KF-96A-6T manufactured by shin-Etsu chemical Co., Ltd
(10) Silicon KF-56 available from shin-Etsu chemical Co., Ltd
(. 11) RA-G-308, manufactured by Nippon Kogyo Co., Ltd
(. 12) Parsol MCR-XR manufactured by DSM Nutrition Japan K.K
From test example 8-1, it is seen that the solid powder cosmetic using the titanium dioxide and the hydrophobized zinc oxide of the present invention is excellent in makeup retention and in use, and has natural makeup appearance and no whitening when applied to the skin. In addition, low-temperature firing of fine particles is particularly preferable, and dextrin palmitate treatment is preferable for the hydrophobization treatment.
From test example 8-2, it is understood that when the hydrophobized zinc oxide is blended beyond the range of the present invention, the make-up retention is good, but the powder sticking during use is poor.
From test examples 8 to 3, it is clear that blending hydrophobized zinc oxide in a smaller amount than the range of the present invention is inferior in the aspect of the makeup retention property.
From test examples 8 to 4, it is clear that even when conventional pigment-grade titanium is used, it is inferior in that whitening does not occur when it is applied to the skin.
It is understood from test examples 8 to 5 that titanium dioxide used for the parent nucleus is inferior in the coverage of spots and freckles and the conspicuousness of the texture when used as it is.
From test examples 8 to 6, it is understood that 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 natural makeup cannot be obtained.
As is clear from test examples 8 to 7, when the amount of titanium dioxide of the present invention is larger than the range of the present invention, the natural makeup appearance is poor and whitening is not caused.
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 ℃.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017124681A JP7017326B2 (en) | 2017-06-26 | 2017-06-26 | Cosmetics containing titanium dioxide powder |
| JP2017-124681 | 2017-06-26 | ||
| PCT/JP2018/020373 WO2019003755A1 (en) | 2017-06-26 | 2018-05-28 | Cosmetic containing titanium dioxide powder |
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| Publication Number | Publication Date |
|---|---|
| CN110769803A true CN110769803A (en) | 2020-02-07 |
| CN110769803B CN110769803B (en) | 2023-01-03 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201880041563.1A Active CN110769803B (en) | 2017-06-26 | 2018-05-28 | Cosmetic containing titanium dioxide powder |
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|---|---|
| JP (1) | JP7017326B2 (en) |
| CN (1) | CN110769803B (en) |
| TW (1) | TW201904874A (en) |
| WO (1) | WO2019003755A1 (en) |
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| KR20230111431A (en) | 2022-01-18 | 2023-07-25 | 이범재 | Exercise equipment to train the lower body |
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| JP3053667B2 (en) * | 1991-06-10 | 2000-06-19 | 株式会社資生堂 | Photochromic ultraviolet shielding powder, method for producing the same, and external preparation for skin |
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| JP4018770B2 (en) * | 1997-02-28 | 2007-12-05 | チタン工業株式会社 | Fan-shaped titanium oxide, method for producing fan-shaped or plate-shaped titanium oxide, and use thereof |
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- 2018-05-28 WO PCT/JP2018/020373 patent/WO2019003755A1/en active Application Filing
- 2018-05-28 CN CN201880041563.1A patent/CN110769803B/en active Active
- 2018-06-04 TW TW107119169A patent/TW201904874A/en unknown
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| JPH10182397A (en) * | 1996-12-27 | 1998-07-07 | Kose Corp | Ultraviolet-protecting cosmetic |
| JP2000191325A (en) * | 1998-12-25 | 2000-07-11 | Tayca Corp | Spherical titanium dioxide aggregate formed from fine spherical particles of titanium dioxide and its production |
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| WO2019003755A1 (en) | 2019-01-03 |
| JP2019006716A (en) | 2019-01-17 |
| CN110769803B (en) | 2023-01-03 |
| JP7017326B2 (en) | 2022-02-08 |
| TW201904874A (en) | 2019-02-01 |
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