WO2014123111A1 - Procédé de production pour des microparticules d'oxyde inorganique à surface modifiée - Google Patents

Procédé de production pour des microparticules d'oxyde inorganique à surface modifiée Download PDF

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Publication number
WO2014123111A1
WO2014123111A1 PCT/JP2014/052535 JP2014052535W WO2014123111A1 WO 2014123111 A1 WO2014123111 A1 WO 2014123111A1 JP 2014052535 W JP2014052535 W JP 2014052535W WO 2014123111 A1 WO2014123111 A1 WO 2014123111A1
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fine particles
inorganic oxide
oxide fine
modified
modified inorganic
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Japanese (ja)
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坂西裕一
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株式会社ダイセル
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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
    • A61K8/0241—Containing particulates characterized by their shape and/or structure
    • 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
    • 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
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/86—Polyethers
    • 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
    • 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
    • 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
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3072—Treatment with macro-molecular organic compounds
    • 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
    • C09C1/3676—Treatment with macro-molecular organic compounds
    • 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
    • C09C1/40—Compounds of aluminium
    • 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
    • A61K2800/60—Particulates further characterized by their structure or composition
    • A61K2800/61—Surface treated
    • A61K2800/62—Coated
    • A61K2800/622—Coated by organic compounds
    • 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
    • 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
    • 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
    • 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
    • A61Q1/08—Preparations containing skin colorants, e.g. pigments for cheeks, e.g. rouge
    • 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
    • A61Q1/10—Preparations containing skin colorants, e.g. pigments for eyes, e.g. eyeliner, mascara
    • 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
    • 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
    • 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
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values

Definitions

  • the present invention relates to a method for producing surface-modified inorganic oxide fine particles imparted with water dispersibility while maintaining the properties of the inorganic oxide fine particles such as transparency, ultraviolet shielding properties, weather resistance, and light discoloration resistance.
  • Inorganic oxides such as titanium oxide are known to exhibit different characteristics depending on their particle sizes. For example, fine particles having an average particle size of 200 nm or less have excellent transparency and ultraviolet shielding properties compared to pigment grade particles having an average particle size of more than 200 nm. Therefore, the characteristics, paints, sunscreen cosmetics, and resins are utilized. It is used in fields such as compositions.
  • titanium oxide fine particles and the like are coated with various inorganic compounds to improve their properties or impart new properties.
  • titanium oxide fine particles have a smaller specific particle size than pigment grade titanium oxide particles, and thus have a large specific surface area and high photoactivity. Therefore, it is inferior in terms of weather resistance and light discoloration resistance as compared with pigment grade titanium oxide particles. Therefore, it has been proposed to provide weather resistance and light discoloration resistance to titanium oxide fine particles by coating the surface with zirconium oxide and hydrated oxide, and aluminum oxide and hydrated oxide. (Patent Documents 1 and 2).
  • Patent Documents 3 and 4 It has also been proposed to improve the transparency and UV shielding properties of titanium oxide fine particles by coating the surface of titanium oxide fine particles with silicon oxide and aluminum oxide, and the fields of packaging materials, paints, inks, etc.
  • an object of the present invention is to provide a method for producing surface-modified inorganic oxide particles provided with water dispersibility while maintaining the properties of the inorganic oxide particles such as transparency, ultraviolet shielding properties, weather resistance, and light discoloration resistance. Is to provide.
  • Another object of the present invention is to provide surface-modified inorganic oxide fine particles obtained by the production method.
  • Still another object of the present invention is to provide a sunscreen cosmetic containing the surface-modified inorganic oxide fine particles.
  • the present inventors have modified the surface of the inorganic oxide fine particles with polyglycerin, so that the properties of the inorganic oxide fine particles as the modification (for example, transparency, ultraviolet shielding property, It has been found that hydrophilicity can be imparted without impairing the weather resistance, light discoloration resistance, etc., and the dispersibility in water and polar organic solvents can be remarkably improved.
  • the present invention has been completed based on these findings.
  • the present invention provides a surface modification in which inorganic oxide fine particles having an average particle size of 200 nm or less are reacted with polyglycerol while heating under reduced pressure, and the surface of the inorganic oxide fine particles is modified with polyglycerol.
  • a method for producing surface-modified inorganic oxide fine particles for obtaining inorganic oxide fine particles is provided.
  • the present invention also provides a method for producing the surface-modified inorganic oxide fine particles as described above, wherein the inorganic oxide is titanium oxide, silicon oxide, aluminum oxide, zirconium oxide, or zinc oxide.
  • the present invention also provides a surface-modified inorganic oxide fine particle obtained by the method for producing a surface-modified inorganic oxide fine particle, wherein the surface of the inorganic oxide fine particle having an average particle diameter of 200 nm or less is modified with polyglycerin. provide.
  • the present invention also provides a sunscreen cosmetic containing the surface-modified inorganic oxide fine particles.
  • the present invention relates to the following.
  • a sunscreen cosmetic comprising the surface-modified inorganic oxide fine particles according to (5) or (6).
  • surface-modified inorganic oxide fine particles can be efficiently obtained using an inexpensive and highly safe compound as a raw material.
  • surface-modified inorganic oxide fine particles can be obtained without causing lumps even when the reaction is carried out in the absence of a solvent.
  • the obtained surface-modified inorganic oxide fine particles have the above-mentioned configuration, water is not impaired without impairing the properties (transparency, ultraviolet shielding property, weather resistance, light discoloration resistance) of the inorganic oxide fine particles that are to be modified. And excellent dispersibility and dispersion stability in polar organic solvents. Therefore, even when water is used as a dispersion medium, it does not aggregate and a stable dispersion state can be maintained.
  • the surface-modified inorganic oxide fine particles of the present invention can be suitably used for environmentally friendly water-based paints, sunscreen cosmetics, resin compositions, and the like.
  • the method for producing the surface-modified inorganic oxide fine particles of the present invention comprises reacting inorganic oxide fine particles having an average particle diameter of 200 nm or less with polyglycerin while heating under reduced pressure, so that the surface of the inorganic oxide fine particles is poly. Surface-modified inorganic oxide fine particles modified with glycerin are obtained.
  • inorganic oxide fine particles examples include silicon oxide, titanium oxide, aluminum oxide, zirconium oxide, and zinc oxide.
  • the inorganic oxide fine particles of the present invention are preferably titanium oxide fine particles and zinc oxide fine particles, particularly preferably titanium oxide fine particles (most preferably rutile-type or anatase-type titanium oxide, more preferably spindles) because they are excellent in UV protection ability. (Like rutile-type titanium oxide) fine particles.
  • the inorganic oxide fine particles may be fine particles composed of one kind of inorganic oxide or fine particles containing two or more kinds of inorganic oxides. Specifically, inorganic oxide fine particles (fine particles selected from silicon oxide fine particles, titanium oxide fine particles, aluminum oxide fine particles, zirconium oxide fine particles, zinc oxide fine particles, etc.) are coated with other inorganic oxides. And the improvement of the characteristic or the other characteristic may be provided by coat
  • Examples of the inorganic compound that covers the surface of the titanium oxide fine particles include inorganic oxides such as Al 2 O 3 , SiO 2 , ZrO 2 , SnO 2 , Sb 2 O 3 , and hydrated inorganic substances corresponding to the inorganic oxides.
  • An oxide etc. can be mentioned.
  • a compound obtained by coating the surface of titanium oxide fine particles with Al 2 O 3 and / or SiO 2 has much more excellent transparency and ultraviolet shielding properties than titanium oxide fine particles before coating.
  • a compound obtained by coating the surface of titanium oxide fine particles with at least one selected from ZrO 2 , hydrated ZrO 2 , Al 2 O 3 , and hydrated Al 2 O 3 is in addition to transparency and ultraviolet shielding properties.
  • Has weather resistance and light discoloration resistance is in addition to transparency and ultraviolet shielding properties.
  • the inorganic compound coating the surface of zinc oxide particles for example, include inorganic oxides such as SiO 2, Al 2 O 3.
  • a compound obtained by coating the surface of zinc oxide fine particles with SiO 2 and / or Al 2 O 3 has much more excellent transparency and ultraviolet shielding properties than the zinc oxide fine particles before coating.
  • the inorganic oxide fine particles have one or two chemical groups (for example, —NH 2 , —OH, —COOH, —P ( ⁇ O) —OH, —SH, etc.) capable of reacting with polyglycerol on the surface. It is preferable to have the above, and in particular, it is preferable to have an —OH group.
  • the inorganic oxide fine particles may originally have the chemical group or may newly add the chemical group.
  • the average particle diameter of the inorganic oxide fine particles is 200 nm or less.
  • the upper limit of the average particle diameter (volume average diameter) of the inorganic oxide fine particles is preferably 150 nm, more preferably 130 nm, particularly preferably 120 nm, and most preferably 100 nm.
  • the lower limit is preferably 1 nm, more preferably 3 nm, still more preferably 5 nm, particularly preferably 7 nm, and most preferably 10 nm.
  • the inorganic oxide fine particles having an average particle diameter in the above range have excellent transparency and ultraviolet shielding properties. In the case of spindle-shaped inorganic oxide fine particles, the average particle diameter is the average major axis length.
  • the chemical groups possessed by the inorganic oxide fine particles and the average particle diameter of the inorganic oxide fine particles can be controlled by adjusting the production method, production conditions, classification operation conditions after production, and the like.
  • trade name “STR-100A” spindle-shaped rutile type titanium oxide fine particles coated with SiO 2 / Al 2 O 3 , long axis average length: 130 nm, short axis average length: 16 nm
  • STR-100A spindle-shaped rutile type titanium oxide fine particles coated with SiO 2 / Al 2 O 3 , long axis average length: 130 nm, short axis average length: 16 nm
  • Commercially available products such as Sakai Chemical Industry Co., Ltd.
  • Commercially available inorganic oxide fine particles may be further chemically modified before reacting with polyglycerol.
  • Polyglycerin Polyglycerin is represented by the following formula (1). HO— (C 3 H 6 O 2 ) n —H (1)
  • C 3 H 6 O 2 in parentheses in the formula (1) has both structures represented by the following formulas (2) and (3).
  • n represents the number average polymerization degree of polyglycerol, and is 2 to 100, for example.
  • the upper limit of the number average degree of polymerization of polyglycerol is preferably 40, particularly preferably 20, and most preferably 15.
  • the lower limit is preferably 3, particularly preferably 5, and most preferably 10. If the number average degree of polymerization of the polyglycerol is too small, it is difficult to prevent the particles from aggregating due to insufficient repulsion between the inorganic oxide fine particles, and it is difficult to maintain a stable dispersion state in water. There is.
  • the number average degree of polymerization of polyglycerin is too large, the polyglycerin chains are entangled between the surface-modified inorganic oxide fine particles and the fine particles are easily aggregated. Properties, UV shielding properties, weather resistance, light discoloration resistance, etc.) tend to be diluted.
  • the number average degree of polymerization here is defined by the number of glycerol units constituting the polyglycerol.
  • the polyglycerin includes a polyglycerin having a linear structure, a branched chain structure, and a cyclic structure.
  • a polycyclic structure having a branched structure particularly, a highly branched structure in which the ratio of primary hydroxyl groups to the total hydroxyl groups of polyglycerol is 50% or more, particularly preferably 60% or more, and most preferably 70% or more.
  • the use of glycerin is preferable in that the surface-modified inorganic oxide fine particles having further excellent water dispersibility can be obtained.
  • PGL10PS primary hydroxyl group ratio: 76%, number average polymerization degree: 10, highly branched polyglycerin
  • PGL20P primary hydroxyl group ratio: 75%, number average
  • reaction conditions The reaction between the inorganic oxide fine particles and polyglycerol is carried out under reduced pressure (for example, about 0.01 to 10 kPa, preferably 0.01 to 1 kPa).
  • the reaction between the inorganic oxide fine particles and polyglycerol is carried out at a temperature of, for example, about 50 to 180 ° C. (preferably 80 to 150 ° C., particularly preferably 100 to 150 ° C.).
  • the reaction time is, for example, about 1 minute to 48 hours, preferably 5 minutes to 24 hours, particularly preferably 10 minutes to 10 hours.
  • the reaction between the inorganic oxide fine particles and polyglycerin may be performed in the presence of a catalyst or may be performed in the absence of a catalyst.
  • a catalyst examples of the catalyst that can be used include acidic catalysts such as trifluoroboron etherate, acetic acid, and phosphoric acid; basic catalysts such as triethylamine, pyridine, dimethylaminopyridine, and triphenylphosphine.
  • the amount of the catalyst used is, for example, about 0.01 to 0.1 parts by weight, preferably 0.02 to 0.05 parts by weight with respect to 100 parts by weight of the inorganic oxide fine particles.
  • the reaction between the inorganic oxide fine particles and polyglycerin is performed in the presence or absence of a solvent.
  • the modified inorganic oxide fine particles do not become lumps.
  • the atmosphere of the reaction between the inorganic oxide fine particles and polyglycerin is not particularly limited as long as the reaction is not inhibited, and may be any of an air atmosphere, a nitrogen atmosphere, an argon atmosphere, and the like.
  • separation / purification means such as concentration, precipitation, centrifugation, filtration, extraction, washing, drying, or a combination of two or more of these separation / purification means.
  • the degree of polymerization of the polyglycerin chain can be easily controlled within a desired range, and a desired water content can be obtained by introducing a minimum amount of the polyglycerin chain.
  • Surface-modified inorganic oxide fine particles having dispersibility can be obtained efficiently.
  • the surface-modified inorganic oxide fine particles obtained by the above method are characterized in that the surface of the inorganic oxide fine particles having an average particle diameter of 200 nm or less is modified with a group containing polyglycerol.
  • the surface of the inorganic oxide fine particles is modified with a group containing polyglycerin means that the polyglycerin is bonded to all or part of the chemical groups present on the surface of the inorganic oxide fine particles. Indicates.
  • the amount of polyglycerin introduced is not particularly limited as long as high dispersibility in water is obtained, but it is, for example, 4 to 750 parts by weight with respect to the weight (100 parts by weight) of the inorganic oxide fine particle part. Degree.
  • the upper limit of the amount of polyglycerol introduced is preferably 380 parts by weight, more preferably 150 parts by weight, particularly preferably 100 parts by weight, most preferably 85 parts by weight, and still more preferably less than 70 parts by weight.
  • the lower limit is preferably 9 parts by weight, particularly preferably 13 parts by weight, more preferably 20 parts by weight, and most preferably 30 parts by weight.
  • the amount of polyglycerin introduced When the amount of polyglycerin introduced is below the above range, the amount of modification on the surface of the inorganic oxide fine particles is insufficient, so that it is difficult to prevent aggregation of the particles and it is difficult to maintain a stable dispersion state in water. Tend.
  • the amount of polyglycerol introduced exceeds the above range, the fine particles tend to aggregate due to the entanglement of the polyglycerol chains between the surface-modified inorganic oxide fine particles.
  • the properties of the inorganic oxide fine particles themselves for example, transparency, ultraviolet shielding properties, weather resistance, light discoloration resistance, etc.
  • the weight ratio between the polyglycerin introduced on the surface and the inorganic oxide fine particle portion is the weight change during heat treatment of the surface modified inorganic oxide fine particles using a differential thermal balance analyzer (TG-DTA), or the composition ratio by elemental analysis. It can be determined by measuring.
  • TG-DTA differential thermal balance analyzer
  • a branched structure in all the introduced polyglycerin (particularly, a highly branched structure in which the ratio of primary hydroxyl groups to all hydroxyl groups of polyglycerol is 50% or more, particularly preferably 60% or more, and most preferably 70% or more. ) Is preferably 10% by weight or more (in particular, 20% or more, particularly 30% or more) from the viewpoint of further excellent water dispersibility.
  • the surface-modified inorganic oxide fine particles of the present invention have the above properties, the properties of the inorganic oxide fine particles such as transparency, ultraviolet shielding properties, weather resistance, and light discoloration resistance are maintained, and dispersion in water and polar organic solvents is performed. Excellent in stability and dispersion stability. Therefore, in addition to the field of cosmetics and the like, it can be used in engineering application fields such as abrasives for CMP and dresser materials. Among these, it can be preferably used as a sunscreen cosmetic.
  • the sunscreen cosmetic obtained by dispersing the surface-modified inorganic oxide fine particles of the present invention with water has a fresh feel, has a good stretch, and can be easily washed away with water.
  • the sunscreen cosmetic of the present invention is characterized by containing the surface-modified inorganic oxide fine particles.
  • the sunscreen cosmetics in the present invention are cosmetics having an ultraviolet protection effect, for example, basic cosmetics such as skin lotion, milky lotion, cream, and cosmetic liquid; lip gloss, lipstick, mascara, foundation, eye color, eye Makeup cosmetics such as liners, eyebrows and cheek colors; creamy, milky or gel sunscreens are included.
  • the content of the surface-modified inorganic oxide fine particles in the total amount (100% by weight) of the sunscreen cosmetic is, for example, about 0.1 to 30% by weight, preferably 1 to 20% by weight.
  • the sunscreen cosmetic of the present invention can be prepared by adding the surface-modified inorganic oxide fine particles to a cosmetic raw material.
  • the cosmetic raw material examples include components used in normal cosmetics, such as water, surfactants, viscosity modifiers, moisturizing components (eg, polyols), oils (eg, squalane, jojoba oil, olive oil, high grades). Alcohol, lanolin, ester, silicone, etc.), amide, foam increasing agent, preservative, water-soluble polymer, pH adjuster, pearling agent, antioxidant, fragrance, dye and the like. These can be suitably blended within a range not impairing the effects of the present invention.
  • components used in normal cosmetics such as water, surfactants, viscosity modifiers, moisturizing components (eg, polyols), oils (eg, squalane, jojoba oil, olive oil, high grades). Alcohol, lanolin, ester, silicone, etc.), amide, foam increasing agent, preservative, water-soluble polymer, pH adjuster, pearling agent, antioxidant, fragrance, dye and the like. These can be suitably blended within a range not impairing the effects
  • the sunscreen cosmetic of the present invention contains the surface-modified inorganic oxide fine particles, it has an excellent ultraviolet protection effect. In addition, since it has excellent dispersion stability and transparency, it can be finished naturally without whitening even when applied to the skin.
  • Example 1 ⁇ Production of polyglycerol-modified titanium oxide fine particles>
  • Raw material titanium oxide fine particles (trade name “STR-100A”, spindle-shaped rutile type titanium oxide, long axis average length: 75 nm, short axis average length: 15 nm, coating treatment with SiO 2 / AI 2 O 3 , Sakai Chemical Industry (Made by Corporation
  • PGL10PS highly branched polyglycerin, number average degree of polymerization: 10, primary hydroxyl group ratio: 76%, Inc.
  • the reaction solution is mixed with methanol, centrifuged (5000 rpm, 90 minutes, 20 ° C.) to remove the supernatant, methanol added to the precipitate, stirred and dispersed, and centrifuged (5000 rpm, 60 minutes, 20 ° C.) twice.
  • the supernatant liquid was removed repeatedly, methanol was added to the precipitate and dispersed by stirring, the fourth centrifugation (5000 rpm, 60 minutes, 20 ° C.) was performed, and after drying, a yellow precipitate was obtained.
  • the polyglycerin-modified titanium oxide fine particles obtained in the examples were evaluated for water dispersibility and ultraviolet / visible light absorption characteristics by the following methods.
  • aqueous solution having a total amount of 10 g was prepared by adding 50.0 mg of polyglycerin-modified titanium oxide fine particles obtained in Examples to a screw tube.
  • the total wavelength light transmittance of the obtained aqueous solution was measured using an ultraviolet-visible spectrophotometer (trade name “UV-2450”, manufactured by Shimadzu Corporation). As a result, it was confirmed that light having a wavelength of 380 nm or less in the ultraviolet region was hardly transmitted.
  • the surface-modified inorganic oxide fine particles can be efficiently obtained using a safe and inexpensive compound as a raw material.
  • surface-modified inorganic oxide fine particles can be obtained without causing lumps even when the reaction is carried out in the absence of a solvent.
  • the obtained surface-modified inorganic oxide fine particles can be used for water or a polar organic solvent without impairing the properties (transparency, ultraviolet shielding property, weather resistance, light discoloration resistance) of the inorganic oxide fine particles that are to be modified. Excellent dispersibility and dispersion stability are imparted.
  • the surface-modified inorganic oxide fine particles of the present invention can be suitably used for environmentally friendly water-based paints, sunscreen cosmetics, resin compositions, and the like.

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  • Animal Behavior & Ethology (AREA)
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Abstract

L'invention concerne : des microparticules d'oxyde inorganique à surface modifiée qui sont modifiées de façon à être dispersibles dans l'eau tout en maintenant d'autres propriétés des microparticules d'oxyde inorganique telles que la transparence, la résistance aux intempéries et à la décoloration, et des propriétés de blocage de rayonnement UV ; un procédé de production pour des microparticules d'oxyde inorganique à surface modifiée ; et un produit cosmétique d'écran solaire qui contient les microparticules d'oxyde inorganique à surface modifiée. Les microparticules d'oxyde inorganique à surface modifiée selon la présente invention sont obtenues par modification des surfaces des microparticules d'oxyde inorganique ayant une dimension moyenne de particule de 200 nm ou moins avec des groupes qui contiennent un polyglycérol. De préférence, l'oxyde inorganique est l'oxyde de titane, l'oxyde de silicium, l'oxyde d'aluminium, l'oxyde de zirconium ou l'oxyde de zinc.
PCT/JP2014/052535 2013-02-08 2014-02-04 Procédé de production pour des microparticules d'oxyde inorganique à surface modifiée WO2014123111A1 (fr)

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WO2015037493A1 (fr) * 2013-09-12 2015-03-19 株式会社ダイセル Composition contenant des particules d'oxyde inorganiques dispesées et produit cosmétique à base d'eau

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JPS6430637A (en) * 1987-07-24 1989-02-01 Shiseido Co Ltd Emulsion composition
JPH01180811A (ja) * 1988-01-08 1989-07-18 Nippon Oil & Fats Co Ltd 化粧用粉体
JPH02191211A (ja) * 1988-06-20 1990-07-27 Shiseido Co Ltd 固型粉末化粧料
JP2002256169A (ja) * 2001-02-28 2002-09-11 Mitsubishi Materials Corp シリカ粉末及びその製造方法
JP2007277414A (ja) * 2006-04-07 2007-10-25 Toyo Tire & Rubber Co Ltd ランフラットタイヤの安全支持体用潤滑組成物
JP2008015527A (ja) * 2006-06-30 2008-01-24 Dongwoo Fine-Chem Co Ltd 硬化性樹脂組成物、コーティングフィルム、このコーティングフィルムを備えた偏光板及び表示装置
JP2008094956A (ja) * 2006-10-12 2008-04-24 Shin Etsu Chem Co Ltd シリコーンコーティング組成物、その製造方法及び被覆物品
JP2011001277A (ja) * 2009-06-17 2011-01-06 Daicel Chemical Industries Ltd 新規なポリグリセリン誘導体又はその塩、及びその製造方法
JP2013014554A (ja) * 2011-07-06 2013-01-24 Hakuto Co Ltd 化粧料

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015037493A1 (fr) * 2013-09-12 2015-03-19 株式会社ダイセル Composition contenant des particules d'oxyde inorganiques dispesées et produit cosmétique à base d'eau

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