WO2000042112A1 - Preparation cosmetique, particules d'oxyde metallique enrobees d'un sol de silice rendues hydrophobes en surface, oxyde metallique revetu de sol de silice et procedes de production - Google Patents
Preparation cosmetique, particules d'oxyde metallique enrobees d'un sol de silice rendues hydrophobes en surface, oxyde metallique revetu de sol de silice et procedes de production Download PDFInfo
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- WO2000042112A1 WO2000042112A1 PCT/JP2000/000088 JP0000088W WO0042112A1 WO 2000042112 A1 WO2000042112 A1 WO 2000042112A1 JP 0000088 W JP0000088 W JP 0000088W WO 0042112 A1 WO0042112 A1 WO 0042112A1
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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
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/58—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
- A61K8/585—Organosilicon compounds
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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
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/0212—Face masks
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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
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/11—Encapsulated compositions
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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
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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
- A61K8/25—Silicon; 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
- A61K8/27—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
- A61K8/28—Zirconium; 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
- 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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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0004—Preparation of sols
- B01J13/0047—Preparation of sols containing a metal oxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0052—Preparation of gels
- B01J13/0069—Post treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/20—After-treatment of capsule walls, e.g. hardening
- B01J13/22—Coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/04—Compounds of zinc
- C09C1/043—Zinc oxide
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
- C09C1/3684—Treatment with organo-silicon compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/06—Treatment with inorganic compounds
- C09C3/063—Coating
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/12—Treatment with organosilicon compounds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/20—Chemical, physico-chemical or functional or structural properties of the composition as a whole
- A61K2800/26—Optical properties
- A61K2800/262—Transparent; Translucent
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/41—Particular ingredients further characterized by their size
- A61K2800/413—Nanosized, i.e. having sizes below 100 nm
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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
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
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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
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
- A61Q1/04—Preparations containing skin colorants, e.g. pigments for lips
- A61Q1/06—Lipsticks
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
Definitions
- the present invention relates to a cosmetic, a surface-hydrophobized silica-coated metal oxide particle, a silica-coated metal oxide sol, and a method for producing the same, more specifically, a cosmetic, particularly a UV-shielding cosmetic, and Surface-hydrophobized silica-coated metal oxide particles suitable for use, a method for producing the same, and a dense and practical silica film having a specific infrared absorption spectrum peak. In addition, it has good dispersibility with a smaller primary particle size and is suitable for cosmetics, especially UV shielding cosmetics.
- the present invention relates to a metal oxide sol coated with a surface-hydrophobic silica coated with a hydrophobicity-imparting agent and a method for producing the same. More specifically, the present invention provides a cosmetic composition which is excellent in use feeling during makeup, has high UV shielding ability, has low phototoxicity, and has excellent storage stability, and a specific infrared absorption spectrum peak.
- the present invention also has a high ultraviolet shielding ability, a high effect of suppressing photocatalytic activity, excellent storage stability, and excellent use feeling and transparency during makeup.
- the present invention relates to a cosmetic containing the above-mentioned silicic acid-coated metal oxide sol and Z or a surface-hydrophobized silicic acid-coated metal oxide sol. Background art
- metal oxide particles when these metal oxide particles are directly incorporated into cosmetics, the feeling of use becomes worse, or the photocatalytic activity of the metal oxide particles adversely affects the human body and skin. It is known that some coating of metal oxide particles is required. In particular, coating with an inorganic substance that is not easily chemically changed by a photocatalytic reaction is preferably performed.
- inorganic-coated metal oxide particles have a high photocatalytic activity inhibitory effect when compounding cosmetics, they do not easily lose their makeup due to oily cosmetics, w / o dispersed cosmetics, or sweat and water.
- dispersion in a hydrophobic base material is not sufficient and the above-mentioned excellent powder properties cannot be sufficiently exhibited.
- metal oxide particles such as titania and zinc oxide, which are widely used as inorganic ultraviolet shielding materials with excellent ultraviolet shielding ability and high safety as described above, are directly incorporated into cosmetics
- Metal oxide particles coated with alumina, silica, etc. are available on the market, but the coating reduces the photocatalytic activity and gives a good feeling of use when blended into cosmetics. Both satisfactory products have not been known.
- the present inventors considered that 1150 to 1250 cm ⁇ 1 and 10000 to 110
- I 1 is the maximum absorption peak intensity within the range of 1150 to 1250 cm—1, and I 2 is within the range of 10000 to 1100 cm-1. Represents the maximum absorption peak intensity.
- the invention discloses a silica-coated metal oxide particle having a silica film, a method for producing the same, and a cosmetic containing the same. Film thickness
- UV shielding cosmetics have been required to have not only high UV shielding ability but also good feeling of use and high transparency. Therefore, the primary particle size is smaller and the dispersibility is higher than before so that the metal oxide particles used as an ultraviolet shielding material can have a good feeling of use and transparency at the time of formulation of the cosmetic.
- the silica-coated metal oxide particles based on the invention of the present inventors have excellent properties such as suppression of photocatalytic activity and feeling of use, but in order to enhance transparency when compounding cosmetics, Further refinement and improvement in dispersibility have been desired.
- a first object of the present invention is to provide a good dispersion of metal oxide particles in an oily base material, an excellent feeling in use during makeup, a high ultraviolet shielding ability, a low phototoxicity, and an excellent storage stability.
- it is intended to provide cosmetics, and is a metal oxide coated with a dense and practical silica film with specific characteristics, high shape following properties, and a hydrophobic surface. It is to provide particles and an economical method for their production.
- a second object of the present invention is to provide an economical production method of the above-mentioned metal oxide sol coated with a silica, which is covered with a dense and practical silica film, and further has dispersibility and transparency.
- An object of the present invention is to provide a sol of a metal oxide having improved odor, and to provide an ultraviolet shielding cosmetic in which a silica-coated metal oxide is well dispersed in the cosmetic, and which is particularly excellent in transparency. Disclosure of the invention
- the present invention that achieves the above object is in the following inventions. (1) to (21) particularly relate to the first object, and (22) to (48) particularly relate to the second object.
- a cosmetic comprising surface-modified hydrophobized metal oxide particles obtained by further surface-treating the silicon-coated metal oxide particles with a hydrophobicity-imparting agent.
- a cosmetic comprising the surface-hydrophobized silica-coated metal oxide particles according to (1), wherein the metal film has a thickness of 0.1 to 100 nm.
- hydrophobicity-imparting agent is one or more hydrophobicity-imparting agents selected from the group consisting of silicone oils, organic alkoxysilanes, and higher fatty acid salts.
- the photocatalytic activity measured by the tetralamine autoxidation method was 60%.
- the surface-hydrophobized silica-coated metal oxide particles have a primary particle diameter of 5 to 500 nm and a secondary particle diameter of 0.5 to 10 m.
- the surface-hydrophobic silica-coated metal oxide particles have a primary particle diameter of 5 to 120 nm and a silica film thickness of 0.5 to 25 nm.
- the cosmetic according to (5) The cosmetic according to (5).
- the metal oxide is one or more metal oxides selected from the group consisting of titanium oxide, zinc oxide, cerium oxide, zirconium oxide and iron oxide.
- I I i ZI 2 : In the formula, 1! is the absorption peak intensity of 1150 to 1250 cm 1 , and I 2 is 1 0 0 0 represent 1 1 0 0 absorption peak intensity cm 1. ) Is 0.2 or more and the refractive index is 1.435 or more.
- the surface is characterized by being subjected to a surface treatment with a metal oxide particle coated with a silicon oxide film and a hydrophobicity imparting agent. Hydrophobic silicide coated metal oxide particles.
- the hydrophobicity-imparting agent is one or more hydrophobicity-imparting agents selected from the group consisting of silicone oils, organic alkoxysilanes, and higher fatty acid salts.
- the metal oxide particles are brought into contact with the composition for forming a silicon film having a silicon concentration in the range of 0.001 to 5 mol liter, and the silica is formed on the surface of the metal oxide particles.
- a method for producing surface-hydrophobized silica-coated metal oxide particles characterized by further treating the surface of the silica-coated metal oxide particles obtained by selective deposition with a hydrophobicity-imparting agent.
- the hydrophobicity imparting agent is a surface treatment with one or more hydrophobic agents selected from the group consisting of silicone oils, organic alkoxysilanes, and higher fatty acid salts.
- the metal oxide particles are brought into contact with the composition for forming a silicon oxide film in the range of Z liters, and the silicon oxide particles are selectively deposited on the surface of the metal oxide particles.
- the water / organic solvent ratio is in the range of 0.1 to 10 by adding the alkoxysilane, and the silicon concentration derived from the alkylalkoxysilane is in the range of 0.001 to 5 mol / liter.
- the surface treatment of the silica-coated metal oxide particles with the reaction product of the alkylalkoxysilane, and the surface treatment with the silica-coated metal and the alkylalkoxysilane are continuously performed. (16) to (18), characterized in that the surface hydrophobizing varnish is applied.
- the method for producing metal oxide particles is continuously performed.
- (22) b) Metal oxide sol generated by hydrolysis, mouth) silicic acid or a precursor capable of producing silicic acid, c) alkali, 2) organic solvent and, if necessary, e) water Irrespective of the order, metal oxides are added so that the water-Z organic solvent ratio after addition is in the range of 0.1 to 10 and the silicon concentration is in the range of 0.001 to 5 mol / liter.
- (23) a) Alkali, mouth) organic solvent and c) to a mixture of water, 2) metal oxide sol generated by hydrolysis, and e) silicic acid or a precursor capable of producing silicic acid.
- the mixed solution consisting of the organic solvent and, if necessary, the organic solvent and, if necessary, the water) is added, the water-to-organic solvent ratio after the addition is in the range of 0.1 to 10 and the silicon concentration is 0.0000.
- (22) wherein the metal oxide sol particles are added so as to be in a range of from about 5 mol Z liter to form a silicide film on the surface of the metal oxide sol particles.
- the organic solvent is at least methanol, ethanol, propanol, pentanol, tetrahydrofuran, 1,4-dioxane or acetone. Characterized by being selected from at least one of them The method for producing a silicon oxide metal oxide sol according to any one of (22) to (24).
- a silica-coated metal oxide sol obtained by a method for producing a silica-coated metal oxide sol, wherein silica is deposited on the surface of the metal oxide sol particles to form a silica film.
- the silicate force-coated metal oxide particles are further hydrophobically treated.
- hydrophobicity imparting agent is one or more selected from the group consisting of silicone oils, organic alkoxysilanes and higher fatty acid salts.
- the hydrophobicity imparting agent is one or more selected from the group consisting of silicone oils, organic alkoxysilanes and higher fatty acid salts.
- the organic alkoxysilane has the following structural formula R 1 (R 2) n S ⁇ X 3-n
- the silicon-coated metal oxide particles are further used as a hydrophobicity imparting agent.
- (40) b) Metal oxide sol generated by hydrolysis, mouth) silicic acid or a precursor capable of producing silicic acid, c) alkali, 2) organic solvent and, if necessary, e) water Irrespective of the order, the metal is added so that the water-Z organic solvent ratio after the addition is in the range of 0.1 to 10 and the silicon concentration is in the range of 0.001 to 5 mol / liter.
- the silicon metal particles are further coated with a hydrophobicity-imparting agent.
- the surface-hydrophobic silicic acid-coated metal oxide sol obtained by the method for producing a surface-hydrophobic silicic acid-coated metal oxide sol which is characterized in that it is subjected to a solid-liquid separation, dried, and Surface hydrophobized silica coating obtained by pulverization according to the surface Genus oxide particles.
- the above-mentioned metal oxide-coated metal oxide particles are further used as a hydrophobicity imparting agent.
- Cosmetic characterized by containing a surface-hydrophobicized silica force-coated metal oxide sol obtained by the method for producing surface-hydrophobicized silica force-coated metal oxide zone le to Toku ⁇ to surface treatment.
- the silica-coated metal oxide particles obtained by drying and, if necessary, pulverizing, and Z or the metal oxide sol generated by hydrolysis are: a) Silicic acid or a precursor capable of producing silicic acid, Mouth) Alkali, c) organic solvent and, if necessary, 2) water in any order.
- the water / organic solvent ratio after the addition is in the range of 0.1 to 10 and the silicon concentration is in the range of 0.01 to 5 mol / liter, and the metal oxide sol is added.
- the silicon oxide metal particles are further surface-treated with a hydrophobicity imparting agent.
- the surface-hydrophobic silicic acid-coated metal oxide sol obtained by the method for producing a surface-hydrophobic silicic acid-coated metal oxide sol is solid-liquid separated, dried, and pulverized as necessary.
- a cosmetic comprising the obtained surface-hydrophobicized silica-coated metal oxide particles.
- the average primary particle diameter of metal oxide particles in a metal oxide sol coated with silica and a metal oxide sol coated with surface-hydrophobic silica is 1 to 10 Qnm.
- metal oxide described above wherein the metal oxide is one or more metal oxides selected from the group consisting of titanium oxide, zinc oxide, cerium oxide, zirconium oxide, and iron oxide.
- metal oxide is one or more metal oxides selected from the group consisting of titanium oxide, zinc oxide, cerium oxide, zirconium oxide, and iron oxide.
- “Dense” in the present invention means that the formed silica film has a refractive index of 1.435 or more.
- the denseness and refractive index of a silicon film Is positively correlated (for example, JEFFEREY BRINKER, Saul-GEL SCIENCE, 581-583, ACADEMIC PRESS C 1990)), and the silica film obtained by the ordinary sol-gel method has a refractive index if fired.
- the value is 1.435 or more, but if firing is not performed, the value is less than 1.435 and the density is low. However, in the present invention, this value is achieved without firing.
- silica has a strong covering power on the base metal oxide, does not substantially separate the coating, and has an appropriate degree of hydrophilicity.
- “appropriate hydrophilicity” means a case where this value is 0.2 or more.
- the silicon film obtained by the ordinary sol-gel method has an I value of 0.2 or more unless firing is performed, but as described above, the film is densely reduced.
- the density is improved, but the I value is less than 0.2, the hydrophilicity is reduced, and the hydrophilicity is not sufficient. That is, since the silica coating of the present invention has an appropriate hydrophilicity, it must be baked while maintaining good surface physical properties (smoothness and slipperiness) when blended in cosmetics. If the thickness is as small as 0.1 nm, it is impossible to obtain a dense and strong coating, and the ability to suppress the photocatalytic activity of metal oxide is maintained at a high level.
- the cosmetic contains surface-hydrophobized coated metal oxide particles that have been surface-treated with a hydrophobicity-imparting agent.
- the surface-hydrophobized metal oxide particles are effective as long as the surface is hydrophobicized.
- the present inventor has proposed a cosmetic composition having desired properties by coating metal oxide particles with a silica film and blending the surface-hydrophobicized silica-coated metal oxide particles obtained by hydrophobizing the surface. Was obtained.
- 1 1 5 0 ⁇ 1 2 5 0 cm 1 and 1 0 0 0 ⁇ 1 1 0 0 cm 1 of the ratio of the absorption peak intensity of the infrared absorption scan Bae-vector 1 (1 1! / I 2:
- II represents an absorption peak intensity of 1150 to 1250 cm 1
- I 2 represents an absorption peak intensity of 1100 to 1100 cm 1
- Such suitable surface-hydrophobized silicon-coated metal oxide particles include: i) silicic acid or a precursor capable of producing silicic acid, mouth) water, c) alkali, and 2) an organic solvent. Metal oxide particles were added to a silica coating forming composition having a solvent ratio in the range of 0.1 to 10 and a silicon concentration in the range of 0.01 to 5 mol / liter. It is possible to obtain silicide-coated metal oxide particles obtained by contacting and selectively depositing silicon on the surface of metal oxide particles by roughly treating the surface with a hydrophobicity-imparting agent. .
- the present invention will be described, in particular, metal oxide particles coated with silica having a surface hydrophobicized.
- the metal oxide particles may be formed without hydrophobizing the silica-coated metal oxide particles according to the second aspect of the present invention.
- the case where the sol is coated with silica is also explained.
- a second aspect of the present invention contains silicic acid or a precursor capable of producing silicic acid, water, an alkali and an organic solvent, and the water-Z organic solvent ratio is in the range of 0.1 to 10 in volume ratio.
- the metal oxide particles are brought into contact with a composition for forming a silicon film having a silicon concentration in the range of 0.001 to 5 mol.
- a silica-coated metal oxide sol is produced by using a metal oxide sol generated by hydrolysis of a composition for forming a silicon film as metal oxide particles.
- the method for producing the silica-coated metal oxide sol includes: a) a metal oxide sol generated by hydrolysis, a mouth) silicic acid or a precursor capable of producing silicic acid, c) an alkali, and 2) an organic solvent. And, if necessary, e) regardless of the order of the water, the water-Z organic solvent ratio after the addition is in the range of 0.1 to 10 and the silicon concentration is in the range of 0.001 to 5 mol. It is characterized in that silica is deposited on the surface of the metal oxide sol particles to form a silica film.
- the surface of the obtained silica-coated metal oxide sol can be further hydrophobized.
- the silica-coated metal oxide sol according to the second aspect of the present invention uses a metal oxide sol as a raw material and is produced by only a liquid treatment without a drying step in the middle. Since the properties and the small primary particle size are maintained, a more transparent cosmetic can be obtained. In addition, it is economical because it has a large specific surface area, has a high ultraviolet shielding ability per unit mass, and requires only a small amount of addition. Further, in the present invention, the fine particles of the silica-coated metal oxide in the silica-coated metal oxide sol are further dispersed. Also includes a metal oxide sol coated with a surface-hydrophobicized silica treated with a water-based imparting agent.
- silica-coated sols and surface-hydrophobic silica-coated sols are not known.
- the silicic acid used in the composition for forming a silica film used in the composition for forming a silica film
- ortho-silicic acid and its polymer which are shown in the section of “silicic acid” in the Chemical Dictionary (Kiritsu Shuppan Co., Ltd., published on March 15, 1969, No. 7) Mesosilicic acid, mesotrisilicic acid, mesotetrasilicic acid, etc. It should be noted that this “silicic acid” does not contain organic or halogen groups.
- Compositions containing silicic acid include, for example, tetraalkoxysilane (Si (0R) 4 , wherein R is a hydrocarbon group, specifically tetramethoxyxylan, tetraethoxysilane, tetratetrasilane.
- R is a hydrocarbon group, specifically tetramethoxyxylan, tetraethoxysilane, tetratetrasilane.
- Water, alkali, and organic solvent are added to n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, etc.), stirred, and the hydrolysis reaction proceeds. This method is preferred because it is easy to handle or operate and practical. Of these, tetraethoxysilane is a preferred material.
- a composition containing silicic acid can be obtained by using a method of adding an organic solvent.
- the tetraalkoxysilane, tetrahalogenated silane, and water glass used as raw materials for silicic acid are not particularly limited, and may be those widely used for industrial purposes or as reagents. Preferably, a higher purity is suitable.
- the formation of a solder coating of the composition The composition for use may contain an unreacted material of the above-mentioned raw material of silicic acid.
- the amount of the silicic acid is not particularly limited, but is preferably in the range of 0.001 to 5 mol / liter as the silicon concentration. If the silicon concentration is less than 0.001 mol liter, the formation rate of the silicon film is extremely low and is not practical. On the other hand, if it exceeds 5 mol Z liter, silicide particles may be formed in the composition without forming a film.
- the silicon concentration can be calculated from the addition amount of a raw material of silicic acid, for example, tetraethoxysilane, but the composition can also be measured by atomic absorption analysis.
- a spectrum of silicon having a wavelength of 251.6 nm is used as an analysis line, and a frame made of acetylene / nitrous oxide may be used.
- the water used in the composition for forming a silicon film is not particularly limited, but is preferably water from which particles have been removed by filtration or the like. If particles are included in the water, they are not preferable because they are mixed as impurities in the product.
- Water is preferably used in such an amount that the water Z organic solvent ratio is in the range of 0.1 to 10 in volume ratio. Outside this range, the film cannot be formed, or the film forming speed may be extremely reduced. More preferably, the organic solvent Z water ratio is in the range of 0.1 to 0.5 in volume ratio.
- the type of alkali used is not limited. When the ratio deviates from this, that is, when the water-Z organic solvent ratio is 0.5 or more, it is preferable to form a film using an alkali not containing an alkali metal, for example, ammonia, ammonium hydrogencarbonate, ammonium carbonate, or the like. Good.
- the alkali used in the composition for forming a silicon film is not particularly limited.
- inorganic alkalis such as ammonium, sodium hydroxide, hydroxylating lime, ammonium carbonate, ammonium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate, etc.
- Inorganic salts monomethylamine, dimethylamine, trimethylamine, monoethylamine, getylamine, triethylamine, pyridine, aniline, colin Organic alcohols such as tetramethylammonium hydroxide oxide, guanidine, etc., ammonium formate, ammonium acetate, monomethyl formate, dimethyl acetate, pyrazine lactate, guanidinoacetic acid, Organic acid alkali salts such as aniline acetate can be used. Among these, ammonia, ammonium carbonate, ammonium hydrogen carbonate, ammonium formate, ammonium acetate, sodium carbonate, and sodium hydrogen carbonate are particularly preferred. Alkali can be used alone or in combination of two or more from these groups.
- the purity of the alkali used in the present composition is not particularly limited, and may be those widely used for industrial purposes or as reagents, but preferably those having higher purity are suitable.
- a small amount of about 0.02 mol / liter can be used to form a film, but a large amount of about 1 mol / liter can be added. It doesn't matter. However, it is not preferable to add a solid alloy in an amount exceeding the solubility because it is mixed as an impurity into the metal oxide particles.
- alkali metal that does not contain alkali metal As a main component, it is possible to produce silicon-coated metal oxide particles having a low alkali metal content.
- ammonia Particularly preferred are ammonia, hydrogencarbonate and hydrogencarbonate.
- the organic solvent used in the film-forming composition is preferably one in which the composition forms a homogeneous solution.
- alcohols such as methanol, ethanol, propanol and pentanole; ether-acetals such as tetrahydrofuran, 1,4-dioxane; and acetoaldehydes.
- aldehydes ketones such as acetone, diaceton alcohol, and methyl ketone
- polyhydric alcohols such as ethylene glycol, propylene glycol, and diethylene glycol. Derivatives and the like can be used.
- alcohols are preferred, and ethanol is particularly preferred.
- the organic solvent one kind selected from these groups, or a mixture of two or more kinds can be used.
- the purity of the organic solvent used in the present composition is not particularly limited, and may be those widely used for industrial purposes or as reagents, but preferably those having higher purity are suitable.
- a general solution preparation method can be applied to the preparation of the composition for forming a silicon film.
- a method of adding a predetermined amount of alkali and water to an organic solvent, stirring the mixture, and then adding and stirring tetraethoxysilane may be used. Is possible.
- water and tetraethoxysilane it is preferable to dilute both with an organic solvent from the viewpoint of controllability of the reaction.
- silicic acid or a precursor capable of producing silicic acid containing c) an alkali and 2) an organic solvent, a water / organic solvent ratio in the range of 0.1 to 10 and silicon
- the composition for forming a silicon film which satisfies the condition that the concentration is in the range of 0.001 to 5 mol / liter, is a stable composition. Real No sedimentation, no sedimentation. After contacting the metal oxide particles with the composition, the silica begins to selectively deposit on the surface of the metal oxide particles.
- the expression that the surface helical force of the metal oxide particles is selectively deposited means that the liquid itself of the composition for forming a silica film is formed while the metal oxide particles are in contact with the composition for forming a silica film. Is stable, substantially free of deposition and precipitation (ie, silica deposition), and is thus transparent, but so to speak, but only from the liquid composition in contact with the surface of the metal oxide particles.
- silica is selectively deposited to form a solid silica coating. That is, after solid silica (particles and the like) is generated in the liquid of the silica film forming composition, the solid silica moves to the surface of the metal oxide particles and deposits (adheres).
- the method does not dry the gel of the composition for forming a silicon oxide film that has produced the solid silica to cause the solid silica to adhere to the surface of the metal oxide particles.
- the contact between the composition for forming a silicon film and the metal oxide particles may be performed after the composition for forming a silicon film that satisfies the above-mentioned conditions or after the composition for forming a silicon film is formed.
- the remaining components of the composition for forming a silicon dioxide film are added to obtain a composition for forming a silicon dioxide film that satisfies the above-mentioned conditions. Either may be prepared or may be prepared.
- a part of the composition for forming a silicon film or a component thereof is deposited or precipitated (ie, (Precipitation of silica) can be prevented.
- the silica-coated metal oxide particles of the present invention (in the present specification, the term “silica-coated metal oxide particles” is used to refer to, in principle, the silica-coated metal oxide particles according to the second aspect of the present invention. Silicon oxide particles constituting the oxide sol or silicon oxide particles derived from silicon oxide metal sol although it is meant to include metal oxide particles coated with metal, sol-coated metal oxide sols should be mentioned when special explanation is required.
- the metal oxide used as the raw material in (1) is preferably one or more metal oxides selected from the group consisting of titania, zinc oxide, cerium oxide, zirconium oxide, and iron oxide.
- the method for producing the metal oxide particles as these raw materials is not particularly limited, and any method may be used. If for example, titania powder, hot vapor-phase oxidation of T i C 1 4, T i C 1 vapor hydrolytic 4, and Mochiiruko even those produced by sulfuric acid method, any method for producing chlorine method Can be. '
- the crystallinity of the metal oxide may be any crystal type.
- titania it may be any of amorphous, rutile, anatase, and bukkaite types, and may be a mixture thereof.
- the metal oxide particles have as few impurities as possible, and that the particles have less agglomeration are preferable in terms of controlling the secondary particle diameter.
- a general solution preparation method can be applied to the preparation of the composition for forming a die used for producing the die-coated metal oxide sol of the present invention.
- water and tetraethoxysilane it is preferable to dilute both with an organic solvent from the viewpoint of controllability of the reaction.
- the composition for forming a resilient film formed in this manner is also a stable composition, as described above, and is in contact with the metal oxide sol. Substantially no sedimentation or sedimentation occurs prior to immersion. After contacting the metal oxide sol with the composition, The surface helical force of the metal oxide sol begins to selectively deposit.
- the dispersion of the metal oxide sol obtained by such a method can be used as it is or, if necessary, by removing unreacted substances, adjusting the pH, removing the metal oxide sol, water and organic solvent. It can be used for a composition for forming a silica film after concentration adjustment or the like.
- the crystallinity of the metal oxide sol may be any crystal type.
- titania sol it may be any of amorphous, rutile, anatase, and buquettes, and may be a mixture thereof.
- the metal oxide sol has as little impurities as possible, and that the metal oxide sol has less cohesiveness for the purpose of the present invention.
- a metal oxide sol having low cohesion can be obtained by appropriately setting the conditions of the electrolyte and pH.
- the average primary particle diameter of the fine particles of the metal oxide constituting the metal oxide sol is preferably from 1 to 100 nm, more preferably from 5 to 20 nm.
- the average primary particle size can be controlled by appropriately setting reaction conditions such as temperature, concentration, and aging time.
- the surface of the metal oxide particles in the sol 1 1 5 0 ⁇ 1 2 5 0 cm - 1 and 1 0 0 0 ⁇ 1 1 0 0 cm 1 in the infrared absorption scan
- the ratio of the peak intensity I (I I i ZI 2 : I i 1 1 5 0 to the maximum absorption peak intensity in 1 2 5 0 in the range of cm 1, I 2 1 0 0 0 to 1 1 0 0 cm
- ) is 0.2 or more and the refractive index is 1.435 or more. Can be used.
- the above silica-coated metal oxide sol that can be used in the cosmetic of the present invention is obtained by adding silicic acid or a precursor capable of producing the silicic acid to a metal oxide sol generated by hydrolysis, an alkali, an organic solvent and If necessary, regardless of the order of water, the water-Z organic solvent ratio after the addition is within the range of 0.1 to 10 by volume, and the silicon concentration is within the range of 0.001 to 5 mol. It is obtained by a method in which silicon is deposited on the surface of the metal oxide sol to form a silicic coating.
- a metal oxide sol generated by hydrolysis is added to a mixture of an alkali, an organic solvent and, if necessary, water, and further, silicic acid or a precursor capable of producing silicic acid, an organic solvent and
- the water / organic solvent ratio after addition of the mixed solution composed of water is in the range of 0.1 to 10 and the silicon concentration is in the range of 0.001 to 5 mol / liter, depending on the And a method of depositing a silicon force on the surface of the metal oxide sol particles to form a silicon film.
- the metal oxide sol used as the raw material of the silicon oxide metal oxide sol is selected from the group consisting of titanium oxide, zinc oxide, cerium oxide, zirconium oxide, and iron oxide as the metal oxide constituting the sol. One or two or more of them may be mentioned.
- the method for producing these metal oxide sols is not particularly limited. Examples thereof include alkoxides of metal elements, acetyl acetate, organic acid salts such as acetates and oxalates, chlorides, oxychlorides, and nitrates. Any of the methods for hydrolyzing the above-mentioned inorganic compound can be used. Preferably, they are produced by a method of hydrolyzing metal alkoxides and metal chlorides.
- the metal oxide particles are immersed in the composition for forming a silica film, and are kept at a predetermined temperature to selectively deposit silicon on the surface of the metal oxide.
- a method of preparing a film-forming composition in advance and then charging the metal oxide particles to form a silicon film may be used, or the metal oxide particles may be suspended in a solvent in advance and then other raw material components may be added.
- a method of forming a coating film forming composition to form a silicon film may be used. That is, the raw materials of the composition for forming a film,
- the order in which the metal oxide particles are charged is not particularly limited, and a film can be formed in any order.
- a highly dense silicone is obtained. It is preferable since a force film can be formed and an industrially useful continuous process can be constructed.
- a metal oxide sol is added to a mixture of an organic solvent, water, and alkali, and a tetraalkoxysilane diluted with an organic solvent and, in some cases, water is added thereto. It is preferable that the silica film is charged over time because a dense silica film can be formed, and a continuous process that is industrially useful can be constructed.
- the film thickness of the silicon film can be increased by increasing the film formation time.
- the metal oxide particles are held for a predetermined time in a film-forming composition to which a silicic acid equivalent to a desired silicon film thickness is added, and a silicon film is formed to consume the silicic acid. After the metal oxide particles are taken out of the system, silicic acid corresponding to the consumption amount is additionally added, so that the composition can be subsequently used for forming a film on the next metal oxide particles.
- a continuous process with high productivity can be constructed.
- the temperature at the time of film formation is not particularly limited, but is preferably in the range of 10 ° C to 100 ° C, more preferably in the range of 20 ° C to 50 ° C.
- the higher the temperature the higher the deposition rate.
- the temperature is too high, it is difficult to maintain a constant solution composition due to volatilization of the components in the composition. Also low temperature If it is too much, the film forming rate becomes slow and is not practical.
- the pH at the time of film formation may be an alkaline pH.
- a metal oxide whose solubility depends on the pH is coated with the silicon, it is preferable to control the pH of the film-forming composition.
- the pH of the film-forming composition For example, in the production of silica-coated zinc oxide particles, it is preferable to reduce the amount of alkali added and control the pH during film formation to 11 or less. If the pH exceeds 11, the yield of the silica coated product may decrease.
- the film formation rate is reduced due to the decrease in the amount of force, it is preferable to maintain a practical film formation rate by increasing the film formation temperature or increasing the silicon concentration.
- the solid-liquid separation is carried out to obtain the silica coating metal oxide particles.
- general separation methods such as filtration, centrifugal sedimentation, and centrifugation can be used.
- Drying is performed after the solid-liquid separation, whereby silica-coated metal oxide particles having a low water content can be obtained.
- General drying methods such as natural drying, hot air drying, vacuum drying, and spray drying can be used.
- firing is not necessarily required.
- the silica film obtained by the above-described manufacturing method is not easily attached to the complicated shape of the metal oxide particles of the base material, and has good coverage even with a thin film of about 0.5 nm. Has a high ability to conceal the photocatalytic activity.
- the silicon oxide film since it is possible to form a silicon coating having a very low metal content, the silicon oxide film does not dissolve even in a high-temperature and high-humidity atmosphere, and the physical properties of the silicon oxide-coated metal oxide particles are reduced. It does not change.
- the silicon oxide metal oxide sol according to the second aspect of the present invention when forming the silicon oxide metal oxide sol according to the second aspect of the present invention, after forming the coating, the unreacted raw materials, alkali, and organic solvent are removed. Then, if necessary, concentration is performed to obtain a silicon oxide film metal oxide sol.
- concentration is performed to obtain a silicon oxide film metal oxide sol.
- general separation methods such as evaporation, distillation, and membrane separation can be used.
- the medium of the silica-coated sol of the present invention is not particularly limited, but is usually selected from dermatologically harmless media.
- dermatologically harmless media For example, water, natural oil, and silicone oil are used. Changing from an aqueous system to another medium can be performed by general solvent replacement, membrane separation, and the like.
- the silica-coated metal oxide sol can be obtained by drying the solid-liquid separated metal oxide sol after solid-liquid separation.
- a method for solid-liquid separation general separation methods such as filtration, centrifugal sedimentation, and centrifugation can be used.
- a drying method a general drying method such as natural drying, hot air drying, vacuum drying, spray drying and the like can be used. If particles are agglomerated by drying, they can be ground. Since the silica-coated metal oxide sol of the present invention has a high covering power of the base metal oxide particles, the silica coating is crushed by pulverization, and the effect of suppressing the photocatalytic activity is reduced or used. The feeling does not deteriorate.
- the grinding method is not particularly limited, and a jet mill, a high-speed rotation mill, or the like can be used.
- Siri mosquito film obtained by the above manufacturing method even when using a metal oxide particles, even when using a metal oxide sol, 1 1 5 0-1 2 5 0 cm one 1 1 0 0 0-1 1 0 0 cm- 1 ratio of the absorption peak intensity of the infrared absorption scan Bae click preparative Le I (II i ZI z: maximum peak intensity in the absorption range of 1 1 5 0 ⁇ 1 2 5 0 cm- ', I 2 represents the maximum absorption peak intensity in the range of 1000 to 1100 cm- 1 .) Can be 0.2 or more, and the refractive index can be 1.435 or more.
- the above-mentioned silicon film has good coverage with the complicated shape of the metal oxide particles of the base material, and has good coatability and photocatalytic activity even with a thin film of about 0.1 nm. The ability to conceal is high.
- the silicon coating since it is possible to form a silicon coating having an extremely small content of alkali metal, the silicon coating does not dissolve even in a high-temperature and high-humidity atmosphere, and the physical properties of the silicon oxide coating metal oxide sol do not change. Things are obtained.
- the preferred film thickness of the silica film is 0.1 to 100 nm, more preferably 1 to 20 nm.
- the silica-coated metal oxide particles are surface-treated with a hydrophobicity-imparting agent in the first aspect, but if desired, the silica-coated metal oxide sol obtained in the second aspect is also hydrophobic.
- Surface treatment can be performed with a property imparting agent.
- Known methods can be used for the surface treatment of the silicic acid-coated metal oxide particles with a hydrophobicity-imparting agent, as long as they can be applied.
- Conventional dry, wet, and spray methods can be used.
- a hydrophobicity-imparting agent or an organic solvent solution of a hydrophobicity-imparting agent is sprayed into metal oxide particles that are being stirred by a mixer such as a V-type mixer or a Hensil mixer. It is possible to use a method in which the powder is added, the mixture is further mixed, and the powder is uniformly adhered to the surface of the powder, dried, and, if necessary, heated to adhere firmly.
- a method is used in which metal oxide particles are dispersed in water or an organic solvent, a hydrophobicity-imparting agent, a reaction catalyst, and the like are added thereto, and the mixture is further stirred, and then filtered and dried. I can do it. Further, in the spraying method, a method of spraying a hydrophobicity imparting agent or a solution thereof onto high-temperature metal oxide particles to cover the surface can be used.
- Known methods can also be used for the surface treatment of the silicon oxide metal oxide sol with a hydrophobicity-imparting agent.
- a hydrophobicity-imparting agent or a solution thereof and a reaction catalyst are added to a liquid in which a metal oxide sol is dispersed in water or an organic solvent or a mixed solvent, and the surface is treated after further stirring.
- a method can be used.
- the silica-coated metal oxide particles can be directly hydrophobized using a dry method or a spray method.
- the method can be a known method similar to the above.
- the hydrophobicity-imparting agent used in the present invention is not particularly limited, and examples thereof include mouth, higher fatty acid triglyceride, higher fatty acid, higher fatty acid polyvalent metal salt, and higher aliphatic sulfur oxide polyvalent metal salt.
- Higher fatty acids, higher alcohols or their derivatives, organic or fluorine compounds such as perfluoro- or partially fluorinated higher fatty acids and higher alcohols, silicone oils, organic alkoxysilanes , Organic chlorosilanes, and organosilicon compounds such as silazanes can be used.
- Polyvalent metal salts of higher fatty acids, silicone oil, silane coupling agents, and alkoxysilanes are preferably used, but alkoxysilanes and silane coupling are particularly preferred in terms of practical effects. Agents are preferably used.
- the silicone oils used in the present invention are not particularly limited, and examples thereof include dimethylpolysiloxane, methylhydrodiethanolpolysiloxane, methylphenylpolysiloxane, and cyclic polydimethylsiloxane. .
- modified silicone oils such as alkyl-modified, polyether-modified, amino-modified, mercapto-modified, epoxy-modified, and fluorine-modified may be used.
- the chlorosilane used in the present invention is not particularly limited, and may be selected from trimethyl chlorosilane, dimethyldichlorosilane, methyltrichlorosilane, and methyltrichlorosilane.
- the silazane used in the present invention is not particularly limited, but may be hexamethyldisilazane, N, N'-bis (trimethylsilyl) urea, or N-trimethylsilyl acetate. Amido, dimethyltrimethylsilinoreamin, getyltrimethylsilylamine and trimethylsilylimidazole.
- the organic alkoxysilanes used in the present invention are not particularly limited, and examples thereof include vinyltrichlorosilane, vinyltris (/ 3-methoxyethoxyethoxy) silane, and vinyltrichlorosilane.
- an alkylalkoxysilane represented by the following formula is preferably used.
- R 2 is a hydrogen group or an alkyl group or phenyl group having 1 to 4 carbon atoms
- X is an alkoxyl group having 1 to 4 carbon atoms
- n is 0. It is an integer of ⁇ 2.
- the surface treatment with the alkoxysilanes can be performed by any of a liquid phase method and a dry method, but the liquid phase method is preferably used from the following points. That is, after the metal oxide particles are brought into contact with the composition for forming a silicon film and coated with silica, a hydrophobicity-imparting agent is added without separating the powder, and if necessary, an alkali is added. ⁇ , water and a solvent can be added, and the surface treatment of the silicide-coated metal oxide can be continuously performed with a hydrophobicity-imparting agent.
- This method can omit an intermediate separation and purification step, and is an industrially advantageous production method.
- the liquid phase method is particularly preferred. That is, after the silica is coated with the metal oxide particles in the sol according to the method described above, a hydrophobicity-imparting agent is added without separating the silica-coated metal oxide particles, and Water, an organic solvent and an alkali, and the water-organic solvent ratio is in the range of 0.1 to 10 and the silicon concentration derived from the alkylalkoxysilane is 0.0001 to 5 mol / l.
- the surface treatment can be performed by selectively depositing the reaction product on the surface of the silica-coated metal oxide particles. Since this method has no drying step, it does not impair the dispersibility and small primary particle size of the raw material sol, and can omit an intermediate solid separation step, which is industrially advantageous.
- the hydrophobizing composition in the method for producing a metal zole coated with a surface hydrophobizing agent using an alkylalkoxysilane has a water-Z organic solvent ratio in the range of 0.1 to 10 in volume ratio and an alkylalkoxysilane. Is in the range of 0.001 to 5 mol Z liter.
- the silicon concentration, water, water-to-organic solvent ratio, alkali, organic solvent, temperature, pH, and separation / purification step in the present composition the description of the silica film-forming composition can be applied as it is.
- the present composition can be obtained by adding alkylalkoxysilanes to the composition for forming a silicon film after the formation of the silicon film, instead of the precursor for producing silicic acid.
- the compositions and conditions do not necessarily have to be the same. For example, if the reaction rate of the alkylalkoxysilane is different from that of the precursor that produces silicic acid, alkali, water, or a solvent may be added as necessary. Reaction conditions such as a water / organic solvent ratio, silicon concentration, pH, and temperature can be selected so as to give a practical reaction rate within the range.
- the coating amount of the hydrophobicity-imparting agent may be not less than the minimum coating amount that allows the hydrophobicity-imparting agent to completely cover the surface of the raw material metal oxide particles. This amount is
- Metal oxide particle mass (g) X specific surface area (m 2 Z g)
- the upper limit of the amount of the hydrophobicity-imparting agent cannot be unconditionally determined. It is not economical because the amount of precipitation outside increases. Usually, it is preferably at most 30% by mass, more preferably at most 20% by mass, based on the silica-coated metal oxide particles.
- the silica film thickness of the silica-coated metal oxide particles and the surface-hydrophobic silica-coated metal oxide particles of the present invention (including those of the silica-coated metal oxide sol. The same applies hereinafter). It is from l to 100 nm, preferably from 0.5 to 25 nm. Below this range, it may not be possible to obtain a cosmetic that has a sufficient photocatalytic activity-suppressing effect, and above this range, it may not be possible to obtain a cosmetic having sufficient ultraviolet shielding ability, and it may not be economical.
- the photocatalytic activity of the silica-coated metal oxide particles of the present invention and the surface-hydrophobic silica-coated metal oxide particles of the present invention is not more than 60 Pa / min. Beyond this range, a sufficient masking effect of the photocatalytic activity may not be obtained.
- the surface-hydrophobic silica-coated metal oxide particles used in the present invention have a primary particle diameter of 5 to 500 nm, preferably 5 to 12 O nm, The diameter is 0.5 to 10111.
- the silica-coated metal oxide particles of the silica-coated metal oxide sol of the present invention have a primary particle diameter of 1-1.
- the primary particles and secondary particles referred to in the present invention are those defined by Kubo Teruichiro et al., “Powder,” p. 56-66, published in 1979.
- the powder kinetic friction coefficient of the silica-coated metal oxide particles and the surface-hydrophobic silica-coated metal oxide particles used in the present invention measured by the glass plate method is 0.554 or less. Preferable, more preferably 0 4 9 or less. If it exceeds 0.54, a cosmetic having a good feeling in use may not be obtained.
- the dye-fading rate of the silica-coated metal oxide particles and the surface-hydrophobic silica-coated metal oxide particles used in the present invention is preferably 0.06 or less. And even more preferably less than 0.02. If it exceeds 0.06, the masking effect of the photocatalytic activity may not be sufficient, and a cosmetic having high storage stability may not be obtained.
- the decomposition rate of the organic ultraviolet absorber as measured by the parasol method of the silica-coated metal oxide particles and the surface-hydrophobic silica-coated metal oxide particles used in the present invention is preferably 0.02 or less, more preferably 0.01 or less. If it is less than 0.02, the effect of concealing the photocatalytic activity is not sufficient, and a cosmetic composition in which the organic UV absorber is less decomposed may not be obtained.
- the silica-coated metal oxide particles used in the present invention do not particularly need to be fired. Of course, it is also possible to use it after firing.
- the silica-coated metal oxide particles and the surface-hydrophobic silica-coated metal oxide particles obtained from the silica-coated metal oxide sol of the present invention have a small primary particle size and low cohesiveness. Since it has good dispersibility, it has high ultraviolet shielding ability and high visible light transmittance. In addition, since it is coated with a dense and practical silica film, the effect of suppressing photocatalytic activity is high, and there is little modification of other cosmetic ingredients, and the feel and slipperiness are good.
- silica-coated metal oxide sol and surface-hydrophobic silica-coated metal oxide sol or silica-coated metal oxide sol and surface-hydrophobic silicon sol By blending the silica-coated metal oxide particles obtained from the metal-coated metal oxide sol and the silica-coated metal oxide particles with a surface-hydrophobicized material, the storage stability is good, safe, transparent, and used. An ultraviolet shielding cosmetic with excellent feeling can be obtained.
- oil-based cosmetics, W / 0 emulsified cosmetics, and repellent with less makeup collapse due to water and sweat It is preferably used for water-based cosmetics.
- the cosmetic obtained from the silicon-coated metal oxide sol of the present invention is the above-mentioned silicon-coated metal oxide sol and / or the surface-hydrophobic silicon-coated metal oxide sol or the silicon-coated metal oxide sol and the surface.
- the cosmetic of the present invention contains the above-mentioned silica-coated metal oxide particles and surface-hydrophobic silica-coated metal oxide particles (including the silica-coated metal oxide sol; the same applies hereinafter). At the same time, it can be manufactured by a normal manufacturing method using a normal raw material that can be blended with the cosmetic.
- the cosmetic of the present invention is not particularly limited as long as it contains a powder and an oil component, and includes a dispersion of the powder in a solvent or a solution.
- a powder and an oil component for example, white powder, foundation, powder, lipstick, eye shadow, lipstick, eye liner, mascara, eyebrow, cream, essence, lotion, lotion, emulsion, lotion And the like.
- oil-based cosmetics, WZO emulsified cosmetics, and water-repellent cosmetics that are less likely to lose their makeup due to water and sweat are preferred.
- a powder component and an oil component constitute the cosmetic of the present invention.
- those that constitute the powder component include silica-coated metal oxide particles and surface-hydrophobicized silica-coated metal oxide particles, as well as extender pigments (for example, myric, talc, kaolin, Calcium carbonate, magnesium carbonate, silicic anhydride, aluminum oxide, barium sulfate, etc., white pigments (eg, titanium dioxide, zinc oxide, etc.), and coloring pigments (eg, red iron oxide, yellow iron oxide, black iron oxide) , Chromium oxide, ultramarine, navy blue, carbon black, etc.), and these can be appropriately blended.
- a spherical powder for example, a nylon powder, a polymethylmethacrylate powder, etc.
- a spherical powder for example, a nylon powder, a polymethylmethacrylate powder, etc.
- the oil components to be incorporated in the cosmetic of the present invention include liquid paraffin, scoran, castor oil, glycerinoresilisostearate, glyceryl triisostearate, and glycerol. Lutely 2 -ethylhexanoate, isopropyl myristate, glycerol olenotrisoleate, dimethylpolysiloxane, methylphenylpolysiloxane, cellulose, Examples include diisostearyl maleate and purified lanolin.
- the blending amount of the oil component with respect to the solid powder cosmetic is preferably 3% by mass or more, and more preferably 10 to 90% by mass.
- an organic ultraviolet absorber may be blended in the oil.
- the organic UV absorber refers to an organic compound that has a function of protecting skin by absorbing ultraviolet rays and converting the energy into heat, vibration, fluorescence, radicals, and the like.
- the ultraviolet absorbent that can be used in the cosmetic of the present invention is not particularly limited, and examples thereof include benzophenone-based, salicylic acid-based, PABA-based, gay-sinnic acid-based, dibenzoylmethane-based, and perocanoic acid. UV absorbers such as UV absorbers.
- the compounding amount is in the range of 0.1 to 10% by mass, but it is desirable to make the compounding amount appropriate depending on the ultraviolet absorbing ability of the absorbent.
- the silica-coated metal oxide particles used in the present invention have a high photocatalytic activity shielding effect, they are used in combination with an organic ultraviolet absorber. Even so, the decomposition of the absorbent is suppressed, and a cosmetic having high ultraviolet shielding ability can be obtained.
- An existing emulsifier can also be added to the cosmetic of the present invention at a general concentration.
- Cosmetic Ingredients Standard 2nd Edition Comment, Japan Official Church, edited by Japan Pharmaceutical Daily, 1984 (Yakuji Nippo) , Supplementary Standards for Non-standard Cosmetic Ingredients, supervised by Ministry of Health and Welfare Pharmaceutical Affairs Bureau, 1993 (Yakuji Nippo) All emulsifiers described in, and Cosmetic Ingredient Dictionary, 1991 (Nikko Chemicals), etc. can be used.
- tocofuryl phosphates can also be used as an emulsifier.
- an existing anti-inflammatory component or anti-inflammatory component can be used in combination or in combination to help prevent inflammation due to ultraviolet rays.
- anti-inflammatory components that can be added to the cosmetic of the present invention, but aniline derivative anti-inflammatory agents, salicylic acid derivative anti-inflammatory agents, pyrazolone-derived anti-inflammatory agents, and indomethacin Antiphlogistics, Mefhamic acid antiphlogistics, anti-gout agents, antitussives, antitussives, expectorants, bronchodilators, respiratory improvers, antihistamines, antiallergic agents, antiinflammatory enzymes Agents and the like.
- a cosmetic containing the silica-coated metal oxide particles and the surface-hydrophobic silica-coated metal oxide particles of the present invention is used together with an antioxidant, which is a substance having an antioxidant action, generation of free radicals due to ultraviolet rays
- an antioxidant which is a substance having an antioxidant action, generation of free radicals due to ultraviolet rays
- the antioxidant used in the cosmetic of the present invention which has the effect of suppressing the photocatalytic activity to a low level, is not particularly limited.
- vitamin A for example, vitamin A, / 3-potassin, astaxanthin, vitamin B, Biyu Min C, L—ascorbic acid 12—magnesium phosphate, L—ascorbic acid—2—sodium phosphate, L—ascorbic acid—2—sodium magnesium phosphate, L Ascorbic acid-2-glucoside, L-Ascorbic acid-2-Phosphoric acid-5, 6-Benzylidene, Natural vitamin E, dl-Hitokofue, dl-Hito Coferyl acetate, dl—Hydrogen sodium sodium, ubiquinone and their vitamin derivatives, cystine, glutathione, glutathione peroxide, S 0 D, catalase, cunic acid, phosphoric acid, polyphenol, catechin, tea extract, kojic acid, nucleic acid, hydroquinone, arbutin and the like.
- One or more antioxidants selected from these groups can be blended.
- the cosmetics according to the present invention include components other than the above, which are generally blended in compositions such as cosmetics, such as fats and oils, waxes, hydrocarbons, fatty acids, alcohols, polyhydric alcohols, and the like.
- Cosmetics such as fats and oils, waxes, hydrocarbons, fatty acids, alcohols, polyhydric alcohols, and the like.
- the compounding amount of the silica-coated metal oxide particles and the surface-hydrophobized silica-coated metal oxide particles in the cosmetic of the present invention is preferably 1 to 50% by mass relative to the cosmetic, and more preferably.
- the content should be within the range of 5 to 30% by mass.
- titania having a higher ratio of rutile type having lower photocatalytic activity than anatase type it is preferable to use titania having a higher ratio of rutile type having lower photocatalytic activity than anatase type as the silica-coated titania particles.
- the silica-coated titania particles and the surface-hydrophobic silica-coated titania particles used in the cosmetic of the present invention suppress the generation of free radicals due to ultraviolet rays, and are therefore phototoxic regardless of the crystal type. Low-cost cosmetics can be obtained.
- Silicon coated metal oxide particles and surface hydrophobized silicon coated particles according to the present invention
- Cosmetic products containing a coated metal oxide not only have a high ultraviolet shielding ability, but also have excellent feeling in use, without squeaky feeling even when metal oxide particles are blended at a high concentration. I have.
- the cosmetic of the present invention has high transparency and does not have a pale makeup finish unlike the case of containing conventional titania particles.
- the composition since the photocatalytic activity of the metal oxide is sufficiently suppressed, the composition does not promote the change of other components in the composition and has excellent storage stability. It can contain an organic ultraviolet absorber, and can achieve higher ultraviolet shielding ability.
- the thickness and the refractive index of the silica film are determined by using the silica film formed on the silicon wafer immersed in the system when synthesizing the silica-coated metal oxide particles. It can be carried out. The same silicon film as that on the metal oxide particles is formed on this silicon wafer.
- the refractive index of the silicon film can be measured by an ellipsometer (made by ULVAC; LASSERELLIPS OM ETERESM-1A). A step gauge can be used for measuring the film thickness.
- Surface-hydrophobic silica coating The transmission infrared absorption spectrum (FT-IR-800, manufactured by JASCO) of metal oxide particles in a silica film can be measured using the KBr method. Yes o
- the primary particle diameter and the thickness of the silicon oxide-coated metal oxide particles and the surface-hydrophobic silicon oxide-coated metal oxide particles can be determined from transmission electron microscope images.
- the secondary particle size can be measured by a laser single light scattering method (Nikkiso's Micro Track II).
- the total alkali metal content is measured by dissolving the silica-coated metal oxide particles and the surface-hydrophobic silica-coated metal oxide particles in hydrofluoric acid, and then performing flame analysis.
- the photocatalytic activity of the silicon oxide-coated metal oxide particles and the surface-hydrophobized silicon oxide-coated metal oxide particles was determined by the tetralamine autoxidation method (manabu Kiyono, titan oxide-physical properties and applied technology, Gihodo Shuppan, pp. 196-197, 1991).
- the measurement conditions were as follows: temperature: 40 ° C, tetralin: 20 m 1, and metal oxide particles: Q.02 g.
- the light transmittance of the silica-coated metal oxide particles and the surface-hydrophobic silicon-coated metal oxide particles of the present invention are as follows. It is measured by the Cosmole method, the balazol method, the glass plate method, the Sunset Toy Yellow method, and the methanol solution method described in this specification, respectively.
- Solution 3 was added to Suspension 3 being stirred with stirring blades at a constant speed over 9 hours, and then aged for 12 hours. Silica film formation and aging were performed at 45 ° C. Thereafter, the solid content was separated by centrifugal filtration and vacuum-dried at 50 ° C. for 12 hours to obtain silica-coated zinc oxide particles.
- the surface-hydrophobic silica-coated titanium particles obtained in Production Examples 1b to 5b were also used for the primary particle diameter, secondary particles, silica film thickness, and photocatalytic activity by tetralin autoxidation. The degree and the water repellency were measured. Table 1 shows the results Shown in
- aqueous titanium dioxide water
- Suspension liquid 1 was prepared by dispersing 8.83 kg of a titania concentration of 20.0% by mass, a primary particle diameter of 16 nm, and a specific surface area of 13.6 g / m 2 .
- a solution 2 was prepared by mixing 2.30 kg of tetraethoxysilane (manufactured by Nacalai Tesque) and 990 g of ethanol.
- Solution 2 was added to Suspension 1 stirred by a stirring blade at a constant rate over 9 hours, and then aged for 12 hours. The formation and aging of the silica coating were performed at 25 ° C. Thereafter, ammonia and ethanol were removed by distillation to obtain a silica-coated titania sol.
- Solution 2 was added to Suspension 1 stirred by a stirring blade at a constant speed over 9 hours, and then aged for 12 hours. Silicon film formation and aging were performed at 45 ° C. Thereafter, ammonia and ethanol were removed by distillation to obtain a silica-coated zinc oxide sol.
- Cerium oxide sol, zirconium oxide sol, and bengalazol were used instead of the titania sol of Production Example 6, and the other production conditions were the same, and the silica-coated cerium oxide sol, the silica-coated zirconium oxide sol, and the silicon-coated film were used. Bengalazol was obtained.
- the average primary particle size of the silicon oxide film metal oxide sol obtained in Production Examples 6 to 10 the thickness of the silicon oxide film, the ratio of the absorption peak intensity of the infrared absorption spectrum (I value), The refractive index of the film and the BET specific surface area were measured. Table 2 summarizes the results.
- Solution 2 was added to stirring suspension 1 at a constant rate over 9 hours, and then aged for 12 hours. Surface coating and aging were performed at 645 ° C. Thereafter, ammonia and ethanol were removed by distillation to obtain a zinc oxide sol having a surface-hydrophobic silicic acid coating.
- the water repellency of the metal oxide sol having a hydrophobized surface-coated silica obtained in Production Examples 11 to 15 was measured by the methyl method. That is, put 10 g of a 20% aqueous methanol solution into a test tube, and adjust the test substance to 1% by mass. In addition, the mixture was agitated vigorously and allowed to stand, and after 1 hour, the water repellency was determined. All showed good water repellency. In addition, the primary particle size, the silica film thickness, and the BET specific surface area were measured. Table 2 summarizes the results.
- the solid content of the silica-coated metal oxide sol obtained in Production Examples 6 to 10 and the solid content of the surface-hydrophobic silica-coated metal oxide sol obtained in Production Examples 11 to 15 were separated by centrifugal filtration. , Vacuum-dried at 50 ° C for 12 hours, further pulverized with a jet mill, and oxidized metal oxide derived from silica-coated metal oxide sol and surface-hydrophobic silica-coated metal oxide sol. Substance particles were obtained.
- the metal oxide particles coated with a surface-hydrophobic silica of the present invention exhibit good water repellency. In contrast, conventional silica-coated metal oxide particles do not exhibit water repellency.
- test substance was dispersed in polyglyceryl triisostearate (Cosmo 43) to prepare a 1% concentration slurry, and the slurry was 0.1 mm thick quartz.
- the sample was placed in a cell, and the light transmittance was measured with a spectrophotometer (SHIMADZUUV-160).
- Tables 3 and 4 show the absorbance at a wavelength of 360 nm (A360), the absorbance at a wavelength of 530 nm (A530), and the ratio of the two (A360 / A530). Show.
- the surface-hydrophobicized silicon oxide-coated metal oxide particles and the silicon oxide-coated metal oxide sol of the present invention have improved dispersibility in liquid, and as a result, compared to conventional silicon oxide-coated metal oxide particles in the ultraviolet region.
- the shielding ability (A360) of the glass increases, and the transparency in the visible light region increases (1 / A530). Therefore, the surface-hydrophobized silica-coated titania particles and the silica-coated metal oxide sol were used. In the cosmetic of the present invention used, it can be expected that higher ultraviolet shielding ability and visible light transparency can be obtained (A360ZA530).
- Antioxidant mixture (/ 3—Carotene 5%, Astaxanthin 5%, L—Ascorbic acid—2—Magnesium phosphate 20%, L—Ascorbic acid—2—Sodium phosphate 1 0%, L—ascorbic acid 12—glucoside 10%, L—ascorbic acid—2_phosphoric acid—5, 6—benzylidene 10%, natural vitamin E 10%, dl— ⁇ -tocophere mouth—5%, dl— ⁇ —tocopheryl acetate 5%, ⁇ I-a-sodium tocopheryl phosphate 5%, citrate 5%, A mixture of 5% of phosphoric acid and 5% of epigallocatechin: ratio was mass%) was prepared.
- the antioxidant mixture was mixed with the silica-coated titania particles of Production Example 1 at a mass ratio of 1: 1. Only the titania-coated titania particles of Production Example 1 and the uncoated titania powder alone were titania-concentrated. Equivalent (0.5%) aqueous suspension, DMPO as radical trapping agent, electron spin resonance measurement method for hydroxy radical under light irradiation. The amount generated was measured.
- the amount of hydroxyradicals generated was lowest when silica-coated titania particles were mixed with an antioxidant, then low when silica-coated titania particles were used alone, and low when non-coated titania particles were used. The highest and the highest.
- silica-coated metal oxide sols obtained in Production Examples 6 to 10 and five kinds of surface-hydrophobic silica-coated metal oxides obtained in Examples 11 to 15 were obtained.
- the decomposition rate of the organic UV absorber was measured by the parasol method using the sol as the test substance.
- the mixture was stirred to extract parasol 178 9 into the hexane phase, and the absorbance of the hexane phase at an optical path length of 1 mm (340 nm) was measured with a spectrophotometer (SHI MA DZUUV-160). (3 points at 0, 5 and 10 hours after UV irradiation). The decreasing rate of the absorbance at 340 nm ( ⁇ 340 / h) was determined. The results are shown in Tables 5 and 6.
- Both the surface-hydrophobized silica-coated metal oxide particles and the silica-coated metal oxide sol that can be used in the present invention are less than 0.01 ( ⁇ 340 / h), It shows the same degradability as the silica-coated metal oxide particles. Therefore, it is clear that the cosmetic containing the surface-hydrophobic silica-coated metal oxide particles and the silica-coated metal oxide sol can be used in combination with an organic ultraviolet shielding material. It can be said that the surface treatment with the hydrophobicity imparting agent does not impair the low decomposability of the UV absorber of the conventional silica-coated surface-treated metal oxide particles.
- the powder of the test substance is dispersed on a 100 x 200 mm glass plate so as to have a concentration of 10 mg / cm 2, and the glass plate is placed on a test table of a surface texture measuring device (HEIDON).
- the dynamic friction coefficient was measured under the conditions of a load of 22.2 g / cm 2 , a moving speed of 200 mmZm in. And a moving distance of 20 mm. The results are shown in Tables 5 and 6.
- the cosmetics containing the metal oxide particles derived from the silica-coated metal oxide sol of the present invention and the metal oxide particles derived from the surface-hydrophobic silica-coated metal oxide sol of the present invention are more than ever. It is suggested that they have a better feeling of use.
- Sansetto Perro a pigment for cosmetics
- the test substance was dispersed to a concentration of 0.067% by mass, and the dispersion was irradiated with ultraviolet light (ultraviolet light intensity: 1.65 mWZ cm 2 ).
- the absorbance at 490 nm which is the maximum absorption wavelength of the oscilloscope at an optical path length of 1 mm, is measured over time with a spectrophotometer (SHI MA DZUUV-160), and the rate of decrease in the absorbance ( ⁇ ⁇ 490 / h) was calculated.
- SHI MA DZUUV-160 spectrophotometer
- the dye-fading rate of the surface-hydrophobized silica-coated metal oxide particles and the silica-coated metal oxide sol used in the present invention is 0.060 (m A490 / h) or less. It shows a dye fading rate equivalent to that of conventional silica-coated metal oxide particles. It is about 110,000 for uncoated metal oxide particles and about 100 for conventional surface-treated titania particles, and the decomposition of pigment is kept low.
- the surface-hydrophobized silicon oxide-coated metal oxide particles and the silicon oxide-coated metal oxide particles derived from the silicon oxide-coated metal oxide sol used in the present invention can maintain the conventional silicon oxide-coated metal oxide particles even after the surface treatment with the hydrophobicity imparting agent. It is clear that the low pigment-degrading properties of the force-coated metal oxide particles are maintained, and a cosmetic product with high storage stability can be provided.
- a foundation having the following formulation was produced by a standard method.
- As the surface-hydrophobicized silica-coated metal oxide particles three types of surface-hydrophobicized silica-coated metal oxide particles obtained in Production Examples 2b to 4b were used. During manufacture, the surface-hydrophobic silica-coated titania particles and other surface-hydrophobic silica-coated metal oxide particles were well dispersed.
- a WZ0 emulsion type emulsion having the following formulation was produced by a conventional method. During manufacture, the surface-hydrophobized silica-coated titania particles were well dispersed.
- a sunscreen cream having the following formulation was produced by a conventional method.
- the dispersion of the surface-hydrophobic silica-coated titania particles during the production was good.
- Silicon-hydrophobized silicone-coated titania particles (Production example: lb) 3.0% by mass Microcrystalline wax 1.0% by mass Beeswax 2.0% by mass Lanolin 2.0% by mass Liquid paraffin 1 8.0% by mass Sulfurane 10.0% by mass Polyoxyethylene sorbitan fatty acid ester 1.0% by mass Sorbitan sesquioleate 4.0% by mass Porropyrene glycol 7.0% % Purified water 52.0% by mass Perfume Appropriate amount Preservative Appropriate amount A sensory test was carried out on the above emulsion, and a good feeling of use was obtained.
- a cream having the following formulation was obtained by a standard method. Manufactured. During production, the surface-hydrophobic silica-coated titania particles and the surface-hydrophobic silica-coated zinc oxide particles obtained in Production Example 2b were well dispersed.
- a cream having the following formulation was produced by a conventional method. During the production, the surface-hydrophobated silica-coated titania particles and the surface-hydrophobic silica-coated zinc oxide particles obtained in Production Example 2b were well dispersed.
- a pack having the following formulation was produced by an ordinary method. During manufacture, the surface-hydrophobic silica-coated titania particles were well dispersed.
- a lipstick having the following formulation was produced by an ordinary method. During manufacture, the surface-hydrophobic silica-coated titania particles were well dispersed.
- Formulation of sensory test foundation Test substance 6.0% by mass Silicone-treated talc 180% by mass Silicone-treated my power 390% by mass Silicone-treated iron oxide (red) 10% by mass Silicone-treated iron oxide (yellow) 30 Wt% Silicone treated iron oxide (black) 0 3 wt% Silicone treated titania 150 wt% Zinc stearate 0 2 wt% Nye mouth Powder 20 wt% Squalane 40 wt% Solid paraffin 0 5% by mass Dimethylpolysiloxane 40% by mass Glycerin triisooctanoate 50% by mass Antioxidant mixture 20% by mass Antiseptic agent Perfume Weekly amount Antioxidant As a mixture, y8—Carotin 5%, Astaxanthin 5%, L-ascorbic acid—2—magnesium phosphate 20%, L—Ascorbic acid—2—sodium phosphate 10% , L—ascorbic acid-2—glucoside 10%, L—ascorbic acid
- Table 8 shows the results.
- the feeling of use of the foundation containing the metal oxide particles coated with the silicic acid coating according to the present invention is extremely good (++).
- the foundry containing the conventional silicide-coated metal oxide particles is ordinary (ten).
- a production example of the metal oxide coated with surface-hydrophobized silica of the present invention will be further described.
- titania particles coated with surface-hydrophobic silica were obtained under the same production conditions as in Production Example 1b.
- the surface-coated metal oxide particles obtained in Production Examples 1a to 5a were surface-treated by a dry method. That is, 100 g of the above-mentioned silica-coated metal oxide particles was put into a Hensil type stirring mixer (manufactured by Fukae Kogyo Co., Ltd., LFS-GS-1J), and rotated at a rotation speed of 300 rpm. The hydrophobic additive described in Table 7 or a solution thereof was sprayed in an amount corresponding to 10% by mass of the metal oxide particles to uniformly adhere to the surface of the silica-coated metal oxide particles. It was dried at 0 to 105 ° C. The results are shown in Table 10. Table 10
- a sunscreen emulsion having the following formulation was produced by a conventional method. That is, polyethylene glycol was added to purified water, and after heating and dissolving, the test substance and beegam were added, and the mixture was uniformly dispersed with a homomixer, and then 70. Keep at C (aqueous phase). Mix other ingredients, heat and maintain at 70 ° C (oil phase). The oil phase was added to the aqueous phase, and the mixture was uniformly emulsified and dispersed with a homomixer. After emulsification, the mixture was cooled to 35 ° C with stirring. The test substance was formulated as a sunscreen emulsion using the three types of silica-coated metal oxide sols prepared in Preparation Examples 6 to 8 at a solid content of 10%.
- Test substance 7 0.0% by weight Stearic acid 2.0% by weight Cetyl alcohol 1.0% by weight Vaseline 5.0% by weight Silicon oil 2.0% by weight Liquid paraffin 10.0 Glycerin monostearate (self-emulsifying type) 1.0% by mass Polyoxyethylene (25 mol) monooleate 1.0% by mass Polyethylene glycol 15.05.0% by mass Bi-gum 0.5% by mass Purified water 2.2% by mass Fragrance 0.1% by mass Preservative 0.2% by mass
- the sunscreen emulsion containing the silica-coated metal oxide sol of the present invention has a very good feeling of use and transparency both (++).
- the feeling of use is extremely good (++) or good (+), but the transparency is normal (ten-) or good (-). +).
- the sunscreen emulsion containing the silica-coated metal oxide sol of the present invention has particularly improved transparency compared to the sunscreen emulsion containing the conventional silica-coated metal oxide powder. It is. Table 11 1 Sensory test results (sunscreen emulsion)
- silicide-coated metal oxide particles derived from the two types of silicide-coated metal oxide sols obtained in Production Examples 16 to 17 were used.
- the foundation containing silicon-coated metal oxide particles derived from the silicon-coated metal oxide sol of the present invention is a conventional foundation containing conventional silicon-coated metal oxide powder. It is evident that the transparency is particularly improved as compared with the case of using
- a foundation having the following formulation was produced by a standard method.
- the silicon-coated metal oxide sol any one of the four silicon-coated metal oxide sols derived from the four types of silicon-coated metal oxide sols obtained in Production Examples 17 to 20 was used. Using.
- Titania powder (Production Example 16) 10.0% by mass
- a lotion having the following formulation was produced by an ordinary method.
- An emulsion having the following formulation was produced by a conventional method.
- Silica-coated titania sol (Production Example 6) 30.0% by mass Apogado oil 11.0% by mass Behenyl alcohol 0.6% by mass Stearyl acid 0.4% by mass Glycerin fatty acid ester 0.9 % By mass Polyoxyethylene sorbitan fatty acid ester 1.1% by mass Polyoxyethylene alkyl ether 0.4% by mass
- a cream having the following formulation was manufactured by a conventional method.
- Silicon oxide cerium oxide sol (Production example 8) 30% by mass Sulfur 11 1% by mass Stearic acid 78% by mass Stearyl alcohol 60% by mass Beeswax 19% by mass Propylene glycol Mono stearate 3 1% by mass Polyoxyethylene cetyl ether 1 1% by mass
- a cream having the following formulation was manufactured by a conventional method.
- Silica-coated zinc oxide sol 35.0% by mass squalane 15.2% by mass Stearic acid 7.8% by mass Stearyl alcohol 6.0% by mass Beeswax 1 9% by mass Propylene glycol monostearate 31 1% by mass Polyoxyethylene styrene ester 1 1% by mass
- a cream having the following formulation was produced by an ordinary method.
- Silica-coated zirconium oxide sol 150% by mass Sulfurane 400% by mass Glyceryl diisostearate 30% by mass Oxybenzene 30% by mass Organically modified montmorillonite 15 mass%
- Test substance 7.0% by mass Polyvinyl alcohol 14.5% by mass Carboxymethyl cellulose sodium 4.8% by mass
- Production Example 2 Using the five types of surface-hydrophobic silicon oxide-coated metal oxide sols obtained in 1 to 25 as silica test-coated metal oxide particles as the test substance, a dual-purpose fan of the following formulation was used in a conventional manner. Production. At the time of manufacture, all of the silica-coated metal oxide particles were well dispersed.
- Test substance 60% by mass Silicone-treated tanolek 190% by mass Silicone-treated my power 3 96% by mass Silicone-treated iron oxide (red) 0% by mass Silicone-treated iron oxide (yellow) 30% by mass Silicone-treated iron oxide (black) 0 3% by mass Silicone-treated titania 1 50% by mass Zinc stearate 0 2% by mass Nye mouth Powder 20% by mass Squalane 4 0% by mass Solid Balaffin 0 5% by mass Dimethylpolysiloxane 40% by mass Glycerin triisooctanoate 50% by mass Antioxidant 0 2% by mass Preservative 0 1% by mass Perfume 0 1% % Cosmetic examples 53 Sensory tests were performed on the three-use foundations of 3 to 57.
- the following formula was prepared by a standard method.
- the surface-hydrophobic silicic acid-coated titania sol and the silica-coated metal oxide particles derived from zinc oxide sol obtained in Production Examples 21 and 22 were obtained in Production Examples 17 to 20, respectively.
- Four types of surface-hydrophobic silica-coated metal oxide sols were used. During the production, both the silica-coated titania particles and the silica-coated zinc oxide particles were well dispersed.
- Silica-coated zinc oxide particles (Production Example 22) 5.0% by mass Talc 17.5% by mass Kaolin 15.0% by mass Zinc white 15.0% by mass Iron oxide (red) 1. Q mass % Iron oxide (yellow) 3.0% by mass Iron oxide (black) 0.2% by mass Solid paraffin 3.0% by mass Microcrystalline rinse 6.0% by mass Mitsurou 2.0% by mass Vaseline 1 2.0 % By weight Lanolin acetate 1.0% by weight Sulfane 6.0% by weight Isopropyl palmitate 1 8.0% by weight Antioxidant 0.2% by weight Fragrance 0.1% by weight When a sensory test was performed on the foundations, all of the foundations had extremely good feeling of use and extremely good transparency.
- I I i / I 2:
- I represents an absorption peak intensity of 1150 to 1250 cm— ′
- I 2 represents an absorption peak intensity of 1100 to 1100 cm- 1 .
- a cosmetic comprising a surface-hydrophobic silicic acid-coated metal oxide particle having a photocatalytic activity of 60 Pa Zmin or less as measured by a tetralin autoxidation method.
- This cosmetic has a good dispersion of metal oxide particles in a cosmetic base material, a high ultraviolet shielding ability, a high transparency of a cosmetic finish, an excellent feeling in use during makeup, and a suppression of photocatalytic activity. Since it is highly effective and has excellent storage stability, it is useful as a practical cosmetic.
- an economical method for producing a silica-coated metal oxide sol which is coated with a dense and practical silica film, and has improved dispersibility and transparency.
- the present invention provides a metal oxide sol having excellent dispersibility of the silica-coated metal oxide particles, and a particularly excellent transparency.
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Description
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Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/889,048 US6534044B1 (en) | 1999-01-11 | 2000-01-11 | Cosmetic preparation, surface-hydrophobized silica-coated metal oxide particles, sol of silica-coated metal oxide, and processes for producing these |
AT00900179T ATE492260T1 (de) | 1999-01-11 | 2000-01-11 | Kosmetische zusammensetzung, mit oberflächenhydrophobierter kieselsäure beschichtete metalloxidteilchen, sol von mit oberflächenhydrophobierter kieselsäure beschichtete kieselsäurebeschichteten metalloxiden und verfahren zur herstellung derselben. |
EP00900179A EP1167462B1 (en) | 1999-01-11 | 2000-01-11 | Cosmetic preparation, surface-hydrophobized silica-coated metal oxide particles, sol of surface-hydrophobized silica-coated metal oxide, and processes for producing these |
JP2000593672A JP4740458B2 (ja) | 1999-01-11 | 2000-01-11 | 化粧料、表面疎水化シリカ被覆金属酸化物粒子、シリカ被覆金属酸化物ゾル、及びこれらの製法 |
AU18930/00A AU750973B2 (en) | 1999-01-11 | 2000-01-11 | Cosmetic material, surface-hydrophobicized silica-coated metal oxide particles, silica-coated metal oxide sol and process for their preparation |
DE60045414T DE60045414D1 (de) | 1999-01-11 | 2000-01-11 | Kosmetische zusammensetzung, mit oberflächenhydrophobierter kieselsäure beschichtete metalloxidteilchen, sol von mit oberflächenhydrophobierter kieselsäure beschichtete kieselsäurebeschichteten metalloxiden und verfahren zur herstellung derselben. |
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JP11/4613 | 1999-01-11 | ||
JP461399 | 1999-01-11 | ||
US11755199P | 1999-01-28 | 1999-01-28 | |
US60/117,551 | 1999-01-28 | ||
JP31231899 | 1999-11-02 | ||
JP11/312318 | 1999-11-02 |
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PCT/JP2000/000088 WO2000042112A1 (fr) | 1999-01-11 | 2000-01-11 | Preparation cosmetique, particules d'oxyde metallique enrobees d'un sol de silice rendues hydrophobes en surface, oxyde metallique revetu de sol de silice et procedes de production |
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US (1) | US6534044B1 (ja) |
EP (1) | EP1167462B1 (ja) |
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Cited By (34)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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CN1312233C (zh) | 2007-04-25 |
US6534044B1 (en) | 2003-03-18 |
CN1340086A (zh) | 2002-03-13 |
EP1167462B1 (en) | 2010-12-22 |
EP1167462A1 (en) | 2002-01-02 |
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