WO2012169611A1 - 丸み状過酸化亜鉛粒子、丸み状酸化亜鉛粒子、それらの製造方法、化粧料及び放熱性フィラー - Google Patents
丸み状過酸化亜鉛粒子、丸み状酸化亜鉛粒子、それらの製造方法、化粧料及び放熱性フィラー Download PDFInfo
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- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/04—Metal peroxides or peroxyhydrates thereof; Metal superoxides; Metal ozonides; Peroxyhydrates thereof
- C01B15/047—Metal peroxides or peroxyhydrates thereof; Metal superoxides; Metal ozonides; Peroxyhydrates thereof of heavy metals
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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
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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
- 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
- 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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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
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- 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
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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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
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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
- A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2004/00—Particle morphology
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- C01P2004/32—Spheres
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- C01P2004/00—Particle morphology
- C01P2004/54—Particles characterised by their aspect ratio, i.e. the ratio of sizes in the longest to the shortest dimension
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- 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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- 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
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
Definitions
- the present invention relates to round zinc peroxide particles, round zinc oxide particles, a production method thereof, a cosmetic, and a heat dissipating filler.
- Zinc peroxide is used as a carboxyl group cross-linking agent, deodorant, bactericidal agent, bleaching agent, curing agent, photocatalyst and the like during the production of nitrile rubber.
- As an oxidizing agent it may be added to fireworks. Furthermore, since it becomes zinc oxide when fired, it can also be used as an intermediate raw material for zinc oxide production.
- As a method for producing such zinc peroxide particles zinc oxide precipitates obtained by adding a basic solution to a solution containing a zinc salt are dispersed in hydrogen peroxide water and subjected to a heat treatment to produce zinc oxide.
- Patent Document 1 describes a method for obtaining a fine particle-dispersed sol.
- zinc oxide particles are used in many applications such as UV screening agents for cosmetics and heat-dissipating fillers.
- a lot of zinc oxide particles having a particle diameter of 0.1 ⁇ m or less for example, Patent Documents 2 and 3
- zinc oxide particles having a particle diameter exceeding 1.0 ⁇ m have been studied.
- round shaped zinc oxide particles having a particle diameter of about 0.04 to 1.0 ⁇ m have not been studied much, and the production method thereof has not been sufficiently established.
- round zinc oxide particles having a particle size of 0.04 to 1.0 ⁇ m are used as a heat-dissipating filler in combination with particles having a large particle size for the purpose of increasing heat conduction, and thus the aspect ratio. Since it is small and close to a spherical shape, heat conduction can be improved more efficiently than when zinc oxide particles having a similar particle size and not a round shape are blended.
- the present invention has an excellent performance in that it has an average particle size of 0.04 ⁇ m or more, an aspect ratio as small as 2.0 or less, and a round shape close to a spherical shape.
- Round zinc peroxide particles having a particle diameter larger than that of zinc oxide particles, round zinc oxide particles obtained by firing the same, methods for producing them, and cosmetics containing such round zinc oxide particles is provided.
- an object of the present invention is to provide a heat dissipating filler composed of such round zinc oxide particles.
- the present invention is round zinc peroxide particles having an average particle size of 0.04 ⁇ m or more and an aspect ratio of 2.0 or less.
- the round zinc peroxide particles are preferably obtained by the step (1) of treating zinc oxide particles with hydrogen peroxide.
- the present invention is also round zinc oxide particles having an average particle diameter of 0.04 ⁇ m or more and an aspect ratio of 2.0 or less obtained by pyrolyzing the round zinc peroxide particles described above.
- the round zinc oxide particles preferably have a D90 / D10 of 3.0 or less in the particle size distribution.
- the round zinc oxide particles preferably have a specific surface area of 30 m 2 / g or less.
- the present invention is also a method for producing the rounded zinc peroxide particles described above, which comprises the step (1) of treating zinc oxide particles with hydrogen peroxide.
- the present invention includes the step (1) of treating zinc oxide particles with hydrogen peroxide and the round shape described above, which includes the step (2) of thermally decomposing the round zinc peroxide particles obtained by the step (1) by firing. It is also a method for producing zinc oxide particles.
- the present invention is also a cosmetic comprising the round zinc oxide particles described above.
- the present invention is also a heat dissipating filler comprising the rounded zinc oxide particles described above.
- the round zinc peroxide particles of the present invention have a large particle size, an average particle size of 0.04 ⁇ m or more, an aspect ratio as small as 2.0 or less, a round shape close to a spherical shape, and zinc peroxide. Since the reactivity of is appropriately controlled, it has excellent effects in various applications.
- the round zinc oxide particles of the present invention have excellent ultraviolet shielding properties and are excellent in transparency, and therefore can be suitably used as an ultraviolet shielding agent for cosmetics. Furthermore, it has the advantage that it is excellent in the uniformity of a particle diameter and a shape. Further, when used as a heat dissipating filler, it exhibits excellent heat dissipating performance especially in combination with other heat dissipating fillers having a large particle size.
- FIG. 2 is a transmission electron micrograph of round zinc peroxide particles of the present invention obtained in Example 1.
- FIG. 2 is a scanning electron micrograph of round zinc peroxide particles of the present invention obtained in Example 1.
- FIG. 2 is an X-ray diffraction spectrum of the round zinc peroxide particles of the present invention obtained in Example 1.
- FIG. 3 is a transmission electron micrograph of round zinc oxide particles of the present invention obtained in Example 2.
- FIG. 2 is a scanning electron micrograph of round zinc oxide particles of the present invention obtained in Example 2.
- FIG. 2 is an X-ray diffraction spectrum of the round zinc oxide particles of the present invention obtained in Example 2.
- FIG. 4 is a transmission electron micrograph of round zinc peroxide particles of the present invention obtained in Example 3.
- FIG. 6 is a transmission electron micrograph of round zinc peroxide particles of the present invention obtained in Example 5.
- FIG. 4 is a transmission electron micrograph of round zinc peroxide particles of the present invention obtained in Example 6.
- FIG. 4 is a transmission electron micrograph of zinc oxide particles (SF-15, manufactured by Sakai Chemical Industry Co., Ltd.) used in Comparative Example 1.
- 4 is a transmission electron micrograph of zinc oxide particles (fine zinc oxide manufactured by Sakai Chemical Industry Co., Ltd.) used in Comparative Example 2.
- 4 is a transmission electron micrograph of zinc oxide particles (Zinc oxide, 1 type, manufactured by Sakai Chemical Industry Co., Ltd.) used in Comparative Example 3.
- Comparative Example 4 is a transmission electron micrograph of zinc oxide particles (FINEX-50 manufactured by Sakai Chemical Industry Co., Ltd.) used in Comparative Example 4.
- 6 is a transmission electron micrograph of particles obtained in Comparative Example 5.
- 6 is an X-ray diffraction spectrum of particles obtained in Comparative Example 5.
- the present invention is described in detail below.
- the zinc peroxide particles of the present invention are round zinc peroxide particles having an average particle diameter of 0.04 ⁇ m or more and an aspect ratio of 2.0 or less.
- Conventional zinc peroxide particles are likely to be fine particles, and those having a particle size of less than 0.04 ⁇ m can be easily manufactured, but particles having an arbitrary particle size exceeding that cannot be manufactured.
- An object of the present invention is to solve such problems and to provide round zinc peroxide particles having an average particle diameter of 0.04 ⁇ m or more.
- the average particle diameter is more preferably 0.045 ⁇ m or more, and further preferably 0.05 ⁇ m or more.
- the upper limit of the average particle diameter is not particularly limited, but is preferably 100 ⁇ m or less, and more preferably 50 ⁇ m or less.
- the average particle diameter of the round zinc peroxide particles is a fixed diameter (with the particles sandwiched) in a field of view of 2000 to 100000 times that of a transmission electron microscope (TEM, JEM-1200EX II, manufactured by JEOL Ltd.).
- TEM transmission electron microscope
- ⁇ m The distance between two parallel lines in a certain direction (measured in a certain direction for particles of any shape on the image) ( ⁇ m), which is 250 particles in a TEM photograph.
- the constant direction diameter was measured, and the average value of the cumulative distribution was obtained.
- the round zinc peroxide particles of the present invention preferably have an aspect ratio of 2.0 or less.
- the aspect ratio is more preferably 1.8 or less, and further preferably 1.5 or less.
- the “rounded shape” refers to a rounded shape as a whole, and refers to a spherical shape, an elliptical spherical shape, or the like.
- the aspect ratio of the round zinc peroxide particles is such that the major axis of the round zinc peroxide particles is 2,000 to 100,000 times larger than that of a transmission electron microscope (TEM, JEM-1200EX II, manufactured by JEOL Ltd.). And the ratio of the length of the minor axis passing through the center of the major axis; the major axis / minor axis, the aspect ratio of 250 particles in the TEM photograph was measured, and the average value of the cumulative distribution was obtained.
- TEM transmission electron microscope
- the production method of the round zinc peroxide particles having such an average particle diameter is not particularly limited.
- the zinc oxide particles used as a raw material (hereinafter referred to as “raw zinc oxide particles”) It can be obtained by treating in an aqueous hydrogen oxide solution.
- the method for treating the raw material zinc oxide particles in an aqueous hydrogen peroxide solution is not particularly limited.
- An example is a method in which a hydrogen peroxide aqueous solution having a concentration of 1 to 500 g / l as hydrogen peroxide is added to the particle slurry and stirred.
- the concentration of the raw material zinc oxide particles is preferably 10 to 1500 g / l with respect to the total amount of the slurry. Further, the treatment amount of hydrogen peroxide is preferably 0.7 times or more, more preferably equivalent or more, as the number of moles relative to the raw material zinc oxide.
- raw material zinc oxide particles are used. Although it does not specifically limit as said raw material zinc oxide particle, It is preferable that a particle diameter is 0.01 micrometer or more.
- the particle diameter of the raw material zinc oxide particles corresponds to the diameter of a sphere having the same surface area as that obtained by the BET method. That is, the particle diameter of the raw material zinc oxide particles is obtained from the following calculation formula from the specific surface area: Sg and the true specific gravity of zinc oxide: ⁇ determined by measuring with a fully automatic BET specific surface area measuring device Macsorb (manufactured by Mounttech). Value.
- Particle diameter ( ⁇ m) [6 / (Sg ⁇ ⁇ )] (Sg (m 2 / g): specific surface area, ⁇ (g / cm 3 ): true specific gravity of particles) Note that the true specific gravity of the particles: ⁇ was 5.6, which is the value of the true specific gravity of zinc oxide.
- the zinc oxide manufactured by the well-known method can be used.
- Examples of commercially available products include FINEX-75, FINEX-50, FINEX-30, fine zinc oxide, SF-15, and one type of zinc oxide manufactured by Sakai Chemical Industry.
- the round zinc peroxide particles obtained by treating the raw material zinc oxide particles with hydrogen peroxide have higher uniformity in particle shape and particle size distribution than the raw material zinc oxide particles.
- the zinc particles may have low uniformity in particle shape and particle size distribution.
- the particle diameter, shape, etc. of the raw material zinc oxide particles are not particularly limited, and may be appropriately selected according to the physical properties of the target zinc peroxide.
- Examples of the particle shape include a needle shape, a rod shape, a plate shape, and a spherical shape. That is, according to the production method of the present invention, round zinc peroxide particles having an aspect ratio of 2.0 or less can be obtained regardless of the shape of the raw material zinc oxide particles.
- the particle diameter of the raw material zinc oxide particles is not particularly limited, but in order to obtain round zinc peroxide particles having an average particle diameter of 0.04 ⁇ m or more according to the present invention, the particle diameter is 0.01 ⁇ m. It is preferable to use the raw material zinc oxide particles as described above. In the production method of the present invention, the average particle diameter of round zinc peroxide particles obtained after the hydrogen peroxide treatment can be arbitrarily controlled by the particle diameter of the raw material zinc oxide particles.
- the treatment temperature and treatment time of the hydrogen peroxide treatment of the present invention are not particularly limited, and examples include conditions of treatment temperature: 10 to 100 ° C., treatment time: 0.5 to 12 hours. Moreover, in the said process, you may add additives, such as a dispersing agent, in the range which does not impair the objective of invention as needed.
- the round zinc peroxide particles thus obtained may be subjected to post-treatment such as filtration, washing with water, and drying as necessary. Moreover, you may classify by a sieve as needed. Examples of the classification method using a sieve include wet classification and dry classification. Further, a treatment such as wet pulverization or dry pulverization may be performed.
- the round zinc peroxide particles of the present invention can also be used as a raw material for round zinc oxide particles. That is, the round zinc peroxide particles as described above are thermally decomposed by firing at 220 to 700 ° C. to obtain round zinc oxide particles.
- the round zinc oxide particles obtained by such a manufacturing method have the property that the particle shape and the particle size are more uniform than the raw material zinc oxide particles used as a raw material, and further, aggregation between particles is less likely to occur. Is. For this reason, it can be suitably used as a cosmetic or a heat dissipating filler.
- Such round zinc oxide particles are also one aspect of the present invention.
- the average particle diameter of the round zinc oxide particles of the present invention is preferably 0.04 ⁇ m or more.
- the average particle diameter is more preferably 0.045 ⁇ m or more, and further preferably 0.05 ⁇ m or more.
- the average particle diameter of the round zinc oxide particles is not particularly limited as to the upper limit of the particle diameter, but is preferably 10 ⁇ m or less, and more preferably 1 ⁇ m or less.
- the average particle diameter of the round zinc oxide particles is a constant direction diameter (constant across the particles) in a field of view of 2000 to 100,000 times that of a transmission electron microscope (TEM, JEM-1200EX II, manufactured by JEOL Ltd.).
- the particle size ( ⁇ m) defined by the interval between two parallel lines in the direction (measured in a certain direction for particles of any shape on the image), and a fixed number of 250 particles in the TEM photograph.
- the direction diameter is measured, and the average value of the cumulative distribution is obtained.
- the round zinc oxide particles of the present invention preferably have an aspect ratio of 2.0 or less.
- the aspect ratio 2.0 or less it is preferable in that it can be particularly excellent in dispersibility and transparency, particularly when used in cosmetics.
- the aspect ratio is more preferably 1.8 or less, and further preferably 1.5 or less.
- the aspect ratio of the round zinc oxide particles is as follows: the transmission axis of the transmission electron microscope (TEM, JEM-1200EX II, manufactured by JEOL Ltd.) has a long diameter of the round zinc oxide particles, The ratio of the length of the minor axis passing through the center of the major axis; the major axis / minor axis, the aspect ratio of 250 particles in the TEM photograph was measured, and the average value of the cumulative distribution was obtained.
- TEM transmission electron microscope
- the round zinc oxide particles of the present invention have a specific surface area measured by the BET method of 30 m 2 / g or less.
- the specific surface area is more preferably 28 m 2 / g or less, and still more preferably 27 m 2 / g or less. Setting the specific surface area within the above range is preferable in that round zinc oxide particles having an average particle diameter of 0.04 ⁇ m or more are mainly obtained.
- the round zinc oxide particles of the present invention preferably have a D90 / D10 in the particle size distribution of 3.0 or less.
- D10 means 10% cumulative particle size on a volume basis
- D90 means 90% cumulative particle size on a volume basis. That is, D90 / D10 of 3.0 or less means that the number of coarse particles having an extremely large particle diameter and extremely small particles having an extremely small particle diameter with respect to the average particle diameter is small.
- the rounded zinc oxide particles having a D90 / D10 of 3.0 or less are excellent because they have very large coarse particles and extremely small fine particles with respect to the average particle size and a very sharp particle size distribution. Further, it is particularly preferable for use in cosmetics in that visible light transparency can be stably obtained.
- D10 and D90 of the round zinc oxide particles are values measured by a laser diffraction / scattering particle size distribution analyzer LA-750 (manufactured by Horiba, Ltd.). Mayonnaise 75 ml in volume with 0.5 g of round zinc oxide particles, 20 ml of sodium hexametaphosphate aqueous solution having a concentration of 0.025% by weight as sodium hexametaphosphate, and 88 g of zirconia beads (crushed balls made by Toray Industries, Inc.) of ⁇ 0.3 mm After putting in a bottle and stirring well, it was fixed to a paint conditioner 5410 type (manufactured by RED DEVIL), and dispersed by applying vibration for 45 minutes to prepare a slurry, and measurement was performed using the slurry. Measurements were made with a relative refractive index of 1.5.
- the method and apparatus for performing the firing are not particularly limited, and can be performed by any known method.
- the method of baking with a stationary furnace or a rotary furnace can be mentioned.
- the surface may be subjected to surface coating such as silica treatment, alumina treatment, zirconia treatment or the like.
- surface coating treatment is performed on the round zinc oxide particles of the present invention, the surface of the zinc peroxide powder is coated with a silicon compound, an aluminum compound, a zirconium compound, etc. It is preferable to obtain surface-coated round zinc oxide particles by firing.
- the surface-coated round zinc oxide particles thus obtained are preferred in that the particles are less likely to aggregate and the particle diameter and particle distribution are controlled.
- the round zinc oxide particles obtained by firing the round zinc peroxide particles that have not been surface-treated can also be surface-treated.
- the surface treatment method of the round zinc peroxide particles or the round zinc oxide particles obtained by firing the round zinc peroxide particles is not particularly limited, and can be performed, for example, by the method described in detail below. .
- the round zinc peroxide particles or the round zinc oxide particles obtained by firing the round zinc peroxide particles is 0.1 to 20% by weight, preferably Has a high-density coating layer made of silicon oxide in the range of 0.2 to 15% by weight.
- the silicon oxide is not limited, but is preferably a hydrous silicon oxide.
- the proportion of silicon oxide in the round zinc peroxide particle composition or the round zinc oxide particle composition obtained by firing the round zinc peroxide particles is less than 0.1% by weight, When the surface activity of zinc oxide particles or round zinc oxide particles cannot be sufficiently suppressed, on the other hand, when it exceeds 20% by weight, the obtained round zinc peroxide particle composition is fired to obtain round zinc oxide.
- the particle composition is used, the content of zinc oxide in the round zinc oxide particle composition is lowered, and sufficient ultraviolet light shielding properties cannot be obtained.
- the same method can be used when performing alumina treatment, zirconia treatment, or the like.
- Firing of the round zinc peroxide particles subjected to the surface treatment can be performed by the same method as the firing of the round zinc peroxide particles described above.
- various parameters such as the particle diameter and the particle size distribution are the same as those for the round zinc peroxide described above. It is preferably within the range of values for the particles and round zinc oxide particles.
- the round zinc oxide particles (including the surface-coated round zinc oxide particles) of the present invention may be subjected to a surface treatment after firing.
- the surface treatment is not particularly limited, and examples include a surface treatment with a surface treatment agent selected from an organosilicon compound, an organoaluminum compound, an organotitanium compound, a higher fatty acid, a higher fatty acid ester, a metal soap, a polyhydric alcohol, or an alkanolamine. be able to.
- a surface treating agent can set a processing amount suitably according to the particle diameter of the said round zinc oxide particle or the surface covering round zinc oxide particle.
- Such round zinc oxide particles of the present invention can be used as a cosmetic ingredient. Such cosmetics are also part of the present invention.
- the round zinc oxide particles of the present invention are excellent in transparency since they have a small aspect ratio, and also have excellent performance in ultraviolet shielding properties, and therefore can be suitably used in cosmetics.
- Examples of the cosmetic of the present invention include foundations, makeup bases, eye shadows, blushers, mascara, lipsticks, sunscreen agents, and the like.
- the cosmetics of the present invention can be in any form of oily cosmetics, aqueous cosmetics, O / W type cosmetics, and W / O type cosmetics. Especially, it can be used especially suitably in a sunscreen agent.
- the cosmetic of the present invention may be used in combination with any aqueous component or oily component that can be used in the cosmetic field, in addition to the components constituting the mixture.
- the aqueous component and the oil component are not particularly limited, and examples thereof include oils, surfactants, moisturizers, higher alcohols, sequestering agents, natural and synthetic polymers, water-soluble and oil-soluble polymers, UV shielding agents, Various extracts, inorganic and organic pigments, various powders such as inorganic and organic clay minerals, inorganic and organic pigments treated with metal soap or silicone, organic dyes and other colorants, preservatives, antioxidants, dyes, You may contain components, such as a thickener, a pH adjuster, a fragrance
- the compounding amounts of these compounding components are not
- the oil content is not particularly limited.
- the lipophilic nonionic surfactant is not particularly limited, and examples thereof include sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan trioleate.
- Sorbate fatty acid esters such as diglycerol sorbitan tetra-2-ethylhexylate, diglycerol sorbitan tetra-2-ethylhexylate, mono-cotton oil fatty acid glycerin, glyceryl monoerucate, glyceryl sesquioleate, glyceryl monostearate, ⁇ , ⁇ Glycerol polyglycerin fatty acids such as glycerin monooleate, glyceryl monostearate, and propylene glycol monostearate It can be exemplified glycol fatty acid esters, hardened castor oil derivatives, glycerin alkyl ether.
- the hydrophilic nonionic surfactant is not particularly limited, and examples thereof include POE sorbitan fatty acid esters such as POE sorbitan monooleate, POE sorbitan monostearate, POE sorbitan tetraoleate, POE sorbite monolaurate, and POE sorbite mono.
- POE sorbitan fatty acid esters such as POE sorbitan monooleate, POE sorbitan monostearate, POE sorbitan tetraoleate, POE sorbite monolaurate, and POE sorbite mono.
- POE sorbite fatty acid esters such as oleate, POE sorbite pentaoleate, POE sorbite monostearate, POE glycerin fatty acid esters such as POE glycerin monostearate, POE glycerin monoisostearate, POE glycerin triisostearate, POE POE fatty acid esters such as monooleate, POE distearate, POE monodiolate, ethylene glycol stearate, POE lauryl ether, POE POE alkyl ethers such as yl ether, POE stearyl ether, POE behenyl ether, POE 2-octyldodecyl ether, POE cholestanol ether, POE alkyl phenyl ethers such as POE octyl phenyl ether, POE nonyl phenyl ether, POE dinonyl
- surfactants examples include anionic surfactants such as fatty acid soaps, higher alkyl sulfates, POE lauryl sulfate triethanolamine, alkyl ether sulfates, alkyltrimethylammonium salts, alkylpyridinium salts, alkyl quaternary salts. Stabilizes cationic surfactants such as ammonium salts, alkyldimethylbenzylammonium salts, POE alkylamines, alkylamine salts, polyamine fatty acid derivatives, and amphoteric surfactants such as imidazoline-based amphoteric surfactants and betaine-based surfactants. And you may mix
- anionic surfactants such as fatty acid soaps, higher alkyl sulfates, POE lauryl sulfate triethanolamine, alkyl ether sulfates, alkyltrimethylammonium salts, al
- the humectant is not particularly limited, and examples thereof include xylitol, sorbitol, maltitol, chondroitin sulfate, hyaluronic acid, mucoitin sulfate, caronic acid, atelocollagen, cholesteryl-12-hydroxystearate, sodium lactate, bile salt, dl- Examples include pyrrolidone carboxylate, short-chain soluble collagen, diglycerin (EO) PO adduct, Isaiyobara extract, yarrow extract, and merirot extract.
- EO diglycerin
- the higher alcohol is not particularly limited, and examples thereof include linear alcohols such as lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetostearyl alcohol, monostearyl glycerin ether (batyl alcohol), 2-decyl.
- linear alcohols such as lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetostearyl alcohol, monostearyl glycerin ether (batyl alcohol), 2-decyl.
- branched chain alcohols such as tetradecinol, lanolin alcohol, cholesterol, phytosterol, hexyldodecanol, isostearyl alcohol, octyldodecanol, and the like.
- the sequestering agent is not particularly limited.
- examples thereof include sodium, gluconic acid, phosphoric acid, citric acid, ascorbic acid, succinic acid, edetic acid and the like.
- the natural water-soluble polymer is not particularly limited.
- the semi-synthetic water-soluble polymer is not particularly limited.
- starch-based polymers such as carboxymethyl starch and methylhydroxypropyl starch, methylcellulose, nitrocellulose, ethylcellulose, methylhydroxypropylcellulose, hydroxyethylcellulose, sodium cellulose sulfate, Examples thereof include cellulose polymers such as hydroxypropylcellulose, sodium carboxymethylcellulose (CMC), crystalline cellulose, and cellulose powder, and alginic acid polymers such as sodium alginate and propylene glycol alginate.
- CMC carboxymethylcellulose
- crystalline cellulose cellulose powder
- alginic acid polymers such as sodium alginate and propylene glycol alginate.
- the synthetic water-soluble polymer is not particularly limited, and examples thereof include vinyl polymers such as polyvinyl alcohol, polyvinyl methyl ether, and polyvinyl pyrrolidone, and polyoxyethylene polymers such as polyethylene glycol 20,000, 40,000, and 60,000. Examples thereof include polymers, polyoxyethylene polyoxypropylene copolymer copolymer polymers, acrylic polymers such as sodium polyacrylate, polyethyl acrylate and polyacrylamide, polyethyleneimine, and cationic polymers.
- the inorganic water-soluble polymer is not particularly limited, and examples thereof include bentonite, silicate A1Mg (beegum), laponite, hectorite, and silicic anhydride.
- the UV screening agent is not particularly limited.
- paraaminobenzoic acid hereinafter abbreviated as PABA
- PABA paraaminobenzoic acid
- PABA monoglycerin ester N, N-dipropoxy PABA ethyl ester, N, N-diethoxy PABA ethyl ester, N, N-dimethyl
- Benzoic acid UV screening agents such as PABA ethyl ester and N, N-dimethyl PABA butyl ester
- Anthranilic acid UV screening agents such as homomenthyl-N-acetylanthranylate
- Amyl salicylate Menthyl salicylate, Homomentil salicylate
- Salicylic acid UV screening agents such as phenyl salicylate, benzyl salicylate, p-isopropanol phenyl salicylate; octylcinnamate, ethyl-4-isopropylcinnamate,
- Other drug components are not particularly limited and include, for example, vitamin A oil, retinol, retinol palmitate, inosit, pyridoxine hydrochloride, benzyl nicotinate, nicotinamide, nicotinic acid DL- ⁇ -tocopherol, magnesium ascorbate phosphate, 2 Vitamins such as -O- ⁇ -D-glucopyranosyl-L-ascorbic acid, vitamin D2 (ergocaciferol), dl- ⁇ -tocopherol, dl- ⁇ -tocopherol acetate, pantothenic acid, biotin; estradiol, ethinylestradiol, etc.
- Hormones such as arginine, aspartic acid, cystine, cysteine, methionine, serine, leucine and tryptophan; anti-inflammatory agents such as allantoin and azulene; whitening agents such as arbutin; astringents such as tannic acid; L Menthol, cooling agents and sulfur camphor such as, lysozyme chloride, can be mentioned pyridoxine chloride, and the like.
- Examples of the various powders include bengara, yellow iron oxide, black iron oxide, titanium mica, iron oxide-coated mica titanium, titanium oxide-coated glass flakes and other bright colored pigments, mica, talc, kaolin, sericite, titanium dioxide,
- examples thereof include inorganic powders such as silica and organic powders such as polyethylene powder, nylon powder, crosslinked polystyrene, cellulose powder, and silicone powder.
- a part or all of the powder component is hydrophobized by a known method with a substance such as silicones, fluorine compounds, metal soaps, oils, acyl glutamates in order to improve sensory characteristics and cosmetic durability. Used. Moreover, you may mix and use the other zinc oxide particle which does not correspond to this invention.
- the round zinc oxide particles of the present invention can also be used as a heat dissipating filler.
- the round zinc oxide particles of the present invention are used as a heat-dissipating filler, either a single use or a combination with other heat-dissipating fillers can be used.
- the heat dissipating filler of the present invention is 10 to 90% by volume based on the total amount of the heat dissipating composition such as the resin composition and the grease composition. It is preferable to use in proportions.
- the round zinc oxide particle of this invention when using the round zinc oxide particle of this invention as a heat dissipation filler, it can also be used in combination with the heat dissipation filler from which a particle diameter differs.
- the heat dissipating filler that can be used in combination is not particularly limited, and examples thereof include metal oxides such as magnesium oxide, titanium oxide, and aluminum oxide, aluminum nitride, boron nitride, silicon carbide, silicon nitride, titanium nitride, and metal silicon. And diamond. Furthermore, it can also be used in combination with zinc oxide other than the round zinc oxide particles described above.
- the heat dissipating filler used in combination may have an arbitrary shape such as a spherical shape, a needle shape, a rod shape, or a plate shape.
- the resin used may be a thermoplastic resin or a thermosetting resin, and an epoxy resin, a phenol resin, a polyphenylene sulfide (PPS) resin, a polyester resin, polyamide, polyimide, polystyrene, polyethylene, Polypropylene, polyvinyl chloride, polyvinylidene chloride, fluororesin, polymethyl methacrylate, ethylene / ethyl acrylate copolymer (EEA) resin, polycarbonate, polyurethane, polyacetal, polyphenylene ether, polyetherimide, acrylonitrile-butadiene-styrene
- the resin include polymer (ABS) resin, liquid crystal resin (LCP), silicone resin, and acrylic resin.
- the heat dissipating resin composition of the present invention comprises (1) a thermoforming resin composition obtained by kneading a thermoplastic resin and the rounded zinc oxide particles in a molten state, and (2) a thermosetting resin.
- the resin component can be freely selected depending on the application. For example, when adhering and adhering to a heat source and a heat sink, a resin having high adhesiveness and low hardness such as silicone resin or acrylic resin may be selected.
- the resin when the heat radiating resin composition of the present invention is a resin composition for paint, the resin may be curable or non-curable.
- the paint may be a solvent-based one containing an organic solvent or a water-based one in which a resin is dissolved or dispersed in water.
- the said round zinc oxide particle When using the said round zinc oxide particle as a heat dissipation filler, it can also be used as a heat dissipation grease mixed with the base oil containing mineral oil or synthetic oil.
- ⁇ -olefin, diester, polyol ester, trimellitic acid ester, polyphenyl ether, alkylphenyl ether, etc. can be used as synthetic oil. It can also be used as a heat dissipating grease mixed with silicone oil.
- the round zinc oxide particles of the present invention can be used in combination with other components when used as a heat-dissipating filler.
- Other components that can be used in combination include metal oxides such as magnesium oxide, titanium oxide, and aluminum oxide, and oxidation of aluminum nitride, boron nitride, silicon carbide, silicon nitride, titanium nitride, metal silicon, diamond, etc. Examples include heat dissipating fillers other than zinc, resins, and surfactants.
- the round zinc oxide particles of the present invention in combination with zinc oxide particles having a smaller particle diameter and other heat dissipating fillers, more excellent heat dissipating performance can be obtained.
- the zinc oxide particles having a small particle diameter used in combination are preferably those having a spherical shape, a needle shape, a rod shape, a plate shape, or the like.
- the round zinc oxide particles of the present invention are used in the fields of rubber vulcanization accelerators, paint / ink pigments, electronic parts such as ferrite and varistors, pharmaceuticals, etc. in addition to the cosmetics and heat dissipating fillers described above. can do.
- Example 1 16.28 g of SF-15 (manufactured by Sakai Chemical Industry Co., Ltd., particle size: 0.08 ⁇ m) was repulped in water to prepare 500 ml of slurry so that the concentration as zinc oxide was 0.4 mol / l. Subsequently, 20.77 g of hydrogen peroxide solution (hydrogen peroxide content: 30.0 to 35.5 wt% manufactured by Wako Pure Chemical Industries, Ltd.) was added to the water, and the concentration as hydrogen peroxide was 0.4 mol. 500 ml of an aqueous hydrogen peroxide solution was prepared so as to be / l.
- hydrogen peroxide solution hydrogen peroxide content: 30.0 to 35.5 wt% manufactured by Wako Pure Chemical Industries, Ltd.
- TEM transmission electron microscope
- JEM-1200EX II manufactured by JE
- Example 3 16.28 g of fine zinc oxide (manufactured by Sakai Chemical Industry Co., Ltd., particle size: 0.11 ⁇ m) was repulped into water to prepare 500 ml of slurry so that the concentration as zinc oxide was 0.4 mol / l. Subsequently, 20.77 g of hydrogen peroxide solution (hydrogen peroxide content: 30.0 to 35.5 wt% manufactured by Wako Pure Chemical Industries, Ltd.) was added to the water, and the concentration as hydrogen peroxide was 0.4 mol. 500 ml of an aqueous hydrogen peroxide solution was prepared so as to be / l.
- Example 5 16.28 g of one kind of zinc oxide (manufactured by Sakai Chemical Industry Co., Ltd., particle size 0.31 ⁇ m) was repulped into water to prepare 500 ml of slurry so that the concentration as zinc oxide was 0.4 mol / l. Subsequently, 20.77 g of hydrogen peroxide solution (hydrogen peroxide content: 30.0 to 35.5 wt% manufactured by Wako Pure Chemical Industries, Ltd.) was added to the water, and the concentration as hydrogen peroxide was 0.4 mol. 500 ml of an aqueous hydrogen peroxide solution was prepared so as to be / l.
- hydrogen peroxide solution hydrogen peroxide content: 30.0 to 35.5 wt% manufactured by Wako Pure Chemical Industries, Ltd.
- Example 6 FINEX-50 (manufactured by Sakai Chemical Industry Co., Ltd., particle size 0.02 ⁇ m) was repulped in water to prepare 500 ml of slurry so that the concentration as zinc oxide was 0.4 mol / l. Subsequently, 20.77 g of hydrogen peroxide solution (hydrogen peroxide content: 30.0 to 35.5 wt% manufactured by Wako Pure Chemical Industries, Ltd.) was added to the water, and the concentration as hydrogen peroxide was 0.4 mol. 500 ml of an aqueous hydrogen peroxide solution was prepared so as to be / l.
- the average particle diameter is a constant diameter in a field of view of 2000 to 100000 times that of a transmission electron microscope (TEM, JEM-1200EXII, manufactured by JEOL Ltd.) (two parallel in a fixed direction across the particle).
- the particle diameter ( ⁇ m) defined by the interval between the lines; measured in a certain direction for particles of any shape on the image, and measuring the constant direction diameter of 250 particles in the TEM photograph, The average value of the cumulative distribution is obtained.
- D50, D90, D10, D90 / D10 are values measured by a laser diffraction / scattering particle size distribution analyzer LA-750 (manufactured by Horiba, Ltd.).
- D50 means 50% cumulative particle size on a volume basis
- D90 means 90% cumulative particle size on a volume basis
- D10 means 10% cumulative particle size on a volume basis.
- a ratio of D90 / D10 is calculated as an index of the sharpness of the particle size distribution. A larger value means that the particle size distribution is broader, and a smaller value means that the particle size distribution is sharper. That is, the smaller the value of D90 / D10, the smaller the number of particles having an extremely large particle diameter, the smaller the number of particles having an extremely small particle diameter, and the uniform particle size.
- Zinc oxide particles 2 g of the above examples and comparative examples Zinc oxide particles 2 g of the above examples and comparative examples, varnish 10 g (manufactured by Acridic A-801-P DIC), butyl acetate 5 g (reagent special grade, manufactured by Wako Pure Chemical Industries, Ltd.), xylene 5 g (genuine special grade, produced by Junsei Chemical Co., Ltd.) ), Put 38 g of glass beads (1.5 mm Potters Barotini) into a mayonnaise bottle with a volume of 75 ml, stir well, and fix to paint conditioner type 5410 (made by RED DEVIL) and give vibration for 90 minutes. A paint was prepared by dispersion treatment.
- a coating film was prepared by Yasuda Seiki Seisakusho. The prepared coating film was dried at 20 ° C. for 12 hours, and then used for measurement of total light transmittance 1, total light transmittance 2, total light transmittance 3, parallel light transmittance 1, and parallel light transmittance 2.
- Total light transmittance 1 Total light transmittance 2, Total light transmittance 3, Parallel light transmittance 1, Parallel light transmittance 2
- total light transmittance 1 (%), total light transmittance 2 (%), total light transmittance 3 (%), parallel light transmittance 1 (%), and parallel light transmittance 2 (%) are:
- the measured value of the prepared coating film was measured with a spectrophotometer V-570 (manufactured by JASCO Corporation).
- the value of total light transmittance 1 (%) is the value of total light transmittance at a wavelength of 310 nm
- the value of total light transmittance 2 (%) is the value of total light transmittance at a wavelength of 350 nm
- the total light transmittance 3 ( %) Is the value of total light transmittance at a wavelength of 375 nm
- the value of parallel light transmittance 1 (%) is the value of parallel light transmittance at a wavelength of 500 nm
- the value of parallel light transmittance 2 (%) is at a wavelength of 700 nm.
- the value of parallel light transmittance It means that the smaller the value of total light transmittance 1 (%), the higher the ultraviolet shielding effect against UVB wavelength ultraviolet light.
- total light transmittance 2 (%) and total light transmittance 3 (%) are The smaller the value, the higher the ultraviolet shielding effect against ultraviolet rays having a wavelength of UVA.
- the value of the total light transmittance 3 (%) is small, it means that the shielding region with respect to ultraviolet rays having a wavelength of UVA is spread over a wider area.
- visible light transparency is so high that the value of parallel light transmittance 1 (%) and parallel light transmittance 2 (%) is large.
- the round zinc peroxide particles of the present invention can be obtained even if the shape of the raw material zinc oxide particles is indefinite. Moreover, it is clear that the round zinc peroxide particles and round zinc oxide particles of the present invention have a very small aspect ratio. Moreover, it was shown that the round zinc oxide particle of an Example has a very sharp particle size distribution compared with the zinc oxide particle of a comparative example. Further, the round zinc oxide particles having an average particle diameter of 0.10 ⁇ m in Example 2 and the round zinc oxide particles having an average particle diameter of 0.12 ⁇ m in Example 4 are 0.11 ⁇ m shown in Comparative Example 2. It is also clear that superior transparency can be obtained compared to conventional amorphous zinc oxide particles having an average particle size.
- the round zinc oxide particles of Examples 2 and 4 have a low total light transmittance 3 (%) and an excellent ultraviolet shielding property even in the UVA wavelength region of 375 nm.
- the conventional zinc oxide particles of Comparative Examples 1, 3, and 4 have a total light transmittance 3 (%) higher than that of Examples 2 and 4, and UV shielding in the wavelength region of 375 nm UVA. It was not possible to obtain sufficient sex.
- the round zinc peroxide particles of the present invention can be used for a crosslinking agent, a deodorant, a bactericidal agent, a bleaching agent, an oxidizing agent, a photocatalyst and the like.
- the round zinc oxide particles of the present invention can be used as a component of cosmetics, heat dissipating fillers, heat dissipating resin compositions, heat dissipating greases and heat dissipating coating compositions.
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Abstract
Description
上記丸み状過酸化亜鉛粒子は、酸化亜鉛粒子を過酸化水素で処理する工程(1)によって得られたものであることが好ましい。
上記丸み状酸化亜鉛粒子は、粒度分布におけるD90/D10が3.0以下であることが好ましい。
上記丸み状酸化亜鉛粒子は、比表面積が30m2/g以下であることが好ましい。
本発明は、酸化亜鉛粒子を過酸化水素で処理する工程(1)と、工程(1)により得られた丸み状過酸化亜鉛粒子を焼成により熱分解する工程(2)を含む上述した丸み状酸化亜鉛粒子の製造方法でもある。
本発明は、上述した丸み状酸化亜鉛粒子を含有することを特徴とする化粧料でもある。
本発明は、上述した丸み状酸化亜鉛粒子からなることを特徴とする放熱性フィラーでもある。
本発明の丸み状酸化亜鉛粒子は、優れた紫外線遮蔽性を有し、透明性においても優れることから、化粧料の紫外線遮蔽剤として好適に使用することができる。更に、粒子径及び形状の均一性に優れるものであるという利点も有する。また、放熱性フィラーとして使用した場合には、特に、粒子径が大きい他の放熱性フィラーとの併用において優れた放熱性能を発揮するものである。
本発明の過酸化亜鉛粒子は、平均粒子径が0.04μm以上、アスペクト比が2.0以下の丸み状過酸化亜鉛粒子である。従来の過酸化亜鉛粒子は、微粒子になり易く、0.04μm未満の粒子径を有するものは容易に製造できるが、それを超えた任意の粒子径のものを製造することはできなかった。
上記平均粒子径は、0.045μm以上であることがより好ましく、0.05μm以上であることが更に好ましい。上記平均粒子径の上限は特に限定されるものではないが、100μm以下であることが好ましく、50μm以下であることがより好ましい。
粒子径(μm)=[6/(Sg×ρ)]
(Sg(m2/g):比表面積、ρ(g/cm3):粒子の真比重)
なお、粒子の真比重:ρは、酸化亜鉛の真比重の値である5.6を上記計算に用いた。
上記原料酸化亜鉛粒子を過酸化水素処理することによって得られる丸み状過酸化亜鉛粒子は、原料酸化亜鉛粒子よりも粒子形状や粒径分布の均一性が高くなることから、使用する原料としての酸化亜鉛粒子は、粒子形状や粒径分布において均一性が低いものであってもよい。
上記パラメータにおいて、D10とは体積基準での10%積算粒径、D90とは体積基準での90%積算粒径であることを意味する。すなわち、D90/D10が3.0以下であるとは、平均粒子径に対して粒子径が極端に大きい粗大粒子と極端に小さい微細粒子の数が少ないことを意味するものである。
上記D90/D10が3.0以下である丸み状酸化亜鉛粒子は、平均粒子径に対して極端に大きい粗大粒子や極端に小さい微細粒子が少なく粒度分布が非常にシャープなものであるため、優れた可視光透明性を安定して得ることができるという点で化粧料への使用に際して特に好ましいものである。
また、本発明の丸み状過酸化亜鉛粒子及び丸み状酸化亜鉛粒子がこのような表面処理を施したものである場合も、粒子径、粒度分布等の各種パラメータは、上述した丸み状過酸化亜鉛粒子及び丸み状酸化亜鉛粒子についての値の範囲内のものであることが好ましい。
本発明の化粧料としては、ファンデーション、化粧下地、アイシャドウ、頬紅、マスカラ、口紅、サンスクリーン剤等を挙げることができる。本発明の化粧料は、油性化粧料、水性化粧料、O/W型化粧料、W/O型化粧料の任意の形態とすることができる。なかでも、特にサンスクリーン剤において特に好適に使用することができる。
脂肪酸アミド、ショ糖脂肪酸エステル、POE ノニルフェニルホルムアルデヒド縮合物、アルキルエトキシジメチルアミンオキシド、トリオレイルリン酸等を挙げることができる。
SF-15(堺化学工業社製 粒子径0.08μm)16.28gを水にリパルプし、酸化亜鉛としての濃度が0.4mol/lとなるよう500mlのスラリーを調製した。続いて、過酸化水素水(和光純薬工業社製 過酸化水素の含有量:30.0~35.5重量%)20.77gを水に添加し、過酸化水素としての濃度が0.4mol/lとなるよう500mlの過酸化水素水溶液を調製した。続いて、上記SF-15のスラリー500mlを攪拌し、そこへ上記過酸化水素水溶液500mlを添加し、処理温度を25℃に設定して6時間攪拌処理した。攪拌処理後、ろ過、水洗し、110℃で12時間乾燥することにより、平均粒子径が0.11μmの丸み状過酸化亜鉛粒子を得た。得られた粒子のサイズ・形態を透過型電子顕微鏡(TEM、JEM-1200EX II、日本電子社製)で観察した。得られた電子顕微鏡写真を図1に示した。また、走査型電子顕微鏡(SEM、JSM-7000F、日本電子社製)で観察した。得られた電子顕微鏡写真を図2に示した。また、得られた粒子のX線回折のスペクトルを図3に示した。また、得られた粒子の物性の評価結果を表1に示した。
実施例1で得られた丸み状過酸化亜鉛粒子10gを、アルミナ製るつぼ(縦・横・高さ=100mm・100mm・35mm)に入れ、電気マッフル炉(東洋製作所社製)で500℃で2時間静置焼成することにより、平均粒子径が0.10μmの丸み状酸化亜鉛粒子を得た。得られた粒子のサイズ・形態を透過型電子顕微鏡(TEM、JEM-1200EX II、日本電子社製)で観察した。得られた電子顕微鏡写真を図4に示した。また、走査型電子顕微鏡(SEM、JSM-7000F、日本電子社製)で観察した。得られた電子顕微鏡写真を図5に示した。また、得られた粒子のX線回折のスペクトルを図6に示した。また、得られた粒子の物性、及び塗膜の物性の評価結果を表1に示した。
微細酸化亜鉛(堺化学工業社製 粒子径0.11μm)16.28gを水にリパルプし、酸化亜鉛としての濃度が0.4mol/lとなるよう500mlのスラリーを調製した。続いて、過酸化水素水(和光純薬工業社製 過酸化水素の含有量:30.0~35.5重量%)20.77gを水に添加し、過酸化水素としての濃度が0.4mol/lとなるよう500mlの過酸化水素水溶液を調製した。続いて、上記微細酸化亜鉛のスラリー500mlを攪拌し、そこへ上記過酸化水素水溶液500mlを添加し、処理温度を25℃に設定して6時間攪拌処理した。攪拌処理後、ろ過、水洗し、110℃で12時間乾燥することにより、平均粒子径が0.13μmの丸み状過酸化亜鉛粒子を得た。得られた粒子のサイズ・形態を透過型電子顕微鏡(TEM、JEM-1200EX II、日本電子社製)で観察した。得られた電子顕微鏡写真を図7に示した。得られた粒子の物性の評価結果を表1に示した。
実施例3で得られた丸み状過酸化亜鉛粒子10gを、アルミナ製るつぼ(縦・横・高さ=100mm・100mm・35mm)に入れ、電気マッフル炉(東洋製作所社製)で500℃で2時間静置焼成することにより、平均粒子径が0.12μmの丸み状酸化亜鉛粒子を得た。得られた粒子の物性、及び塗膜の物性の評価結果を表1に示した。
酸化亜鉛1種(堺化学工業社製 粒子径0.31μm)16.28gを水にリパルプし、酸化亜鉛としての濃度が0.4mol/lとなるよう500mlのスラリーを調製した。続いて、過酸化水素水(和光純薬工業社製 過酸化水素の含有量:30.0~35.5重量%)20.77gを水に添加し、過酸化水素としての濃度が0.4mol/lとなるよう500mlの過酸化水素水溶液を調製した。続いて、上記酸化亜鉛1種のスラリー500mlを攪拌し、そこへ上記過酸化水素水溶液500mlを添加し、処理温度を25℃に設定して6時間攪拌処理した。攪拌処理後、ろ過、水洗し、110℃で12時間乾燥することにより、平均粒子径が0.36μmの丸み状過酸化亜鉛粒子を得た。得られた粒子のサイズ・形態を透過型電子顕微鏡(TEM、JEM-1200EX II、日本電子社製)で観察した。得られた電子顕微鏡写真を図8に示した。得られた粒子の物性の評価結果を表1に示した。
FINEX-50(堺化学工業社製 粒子径0.02μm)16.28gを水にリパルプし、酸化亜鉛としての濃度が0.4mol/lとなるよう500mlのスラリーを調製した。続いて、過酸化水素水(和光純薬工業社製 過酸化水素の含有量:30.0~35.5重量%)20.77gを水に添加し、過酸化水素としての濃度が0.4mol/lとなるよう500mlの過酸化水素水溶液を調製した。続いて、上記FINEX-50のスラリー500mlを攪拌し、そこへ上記過酸化水素水溶液500mlを添加し、処理温度を25℃に設定して6時間攪拌処理した。攪拌処理後、ろ過、水洗し、110℃で12時間乾燥することにより、平均粒子径が0.05μmの丸み状過酸化亜鉛粒子を得た。得られた粒子のサイズ・形態を透過型電子顕微鏡(TEM、JEM-1200EX II、日本電子社製)で観察した。得られた電子顕微鏡写真を図9に示した。得られた粒子の物性の評価結果を表1に示した。
(比較例1)
SF-15(堺化学工業社製 粒子径0.08μm)について実施例と同様の評価を行った。電子顕微鏡写真を図10に示した。また、粒子の物性の評価結果を表1に示した。
微細酸化亜鉛(堺化学工業社製 粒子径0.11μm)について実施例と同様の評価を行った。電子顕微鏡写真を図11に示した。また、粒子の物性、及び塗膜の物性の評価結果を表1に示した。
酸化亜鉛1種(堺化学工業社製 粒子径0.31μm)について実施例と同様の評価を行った。電子顕微鏡写真を図12に示した。また、粒子の物性の評価結果を表1に示した。
FINEX-50(堺化学工業社製 粒子径0.02μm)について実施例と同様の評価を行った。電子顕微鏡写真を図13に示した。また、粒子の物性の評価結果を表1に示した。
SF-15(堺化学工業社製 粒子径0.08μm)16.28gを水にリパルプし、酸化亜鉛としての濃度が0.4mol/lとなるよう500mlのスラリーを調製した。続いて、過酸化水素水(和光純薬工業社製 過酸化水素の含有量:30.0~35.5重量%)10.38gを水に添加し、過酸化水素としての濃度が0.2mol/lとなるよう500mlの過酸化水素水溶液を調製した。続いて、上記SF-15の水スラリー500mlを攪拌し、そこへ上記過酸化水素水溶液500mlを添加し、処理温度を25℃に設定して6時間攪拌処理した。攪拌処理後、ろ過、水洗し、110℃で12時間乾燥することにより、粒子を得た。得られた粒子のサイズ・形態を透過型電子顕微鏡(TEM、JEM-1200EX II、日本電子社製)で観察した。得られた電子顕微鏡写真を図14に示した。また、得られた粒子のX線回折のスペクトルを図15に示した。また、得られた粒子の物性の評価結果を表1に示した。電子顕微鏡写真から、得られた粒子は丸み状粒子と不定形粒子とが混在しており、X線回折のスペクトルからは酸化亜鉛と過酸化亜鉛との混合物であることがわかった。これらの結果より、上記条件においては、原料酸化亜鉛粒子であるSF-15と過酸化水素との反応が充分に進行せず、原料酸化亜鉛粒子が残っているものと考えられる。
本明細書において、平均粒子径は、透過型電子顕微鏡(TEM、JEM-1200EXII、日本電子社製)写真の2000~100000倍の視野での定方向径(粒子を挟む一定方向の二本の平行線の間隔;画像上のどのような形状の粒子についても、一定方向で測定した)で定義される粒子径(μm)であって、TEM写真内の粒子250個の定方向径を計測し、その累積分布の平均値を求めたものである。
透過型電子顕微鏡(TEM、JEM-1200EX II、日本電子社製)写真の2000~100000倍の視野において、過酸化亜鉛粒子、又は酸化亜鉛粒子の長径と、長径の中心を通る短径の長さの比;長径/短径であって、TEM写真内の粒子250個のアスペクト比を計測し、その累積分布の平均値を求めたものである。
本明細書において、D50、D90及びD10は、レーザー回折/散乱式粒度分布測定装置LA-750(堀場製作所社製)によって測定した値である。実施例、比較例の酸化亜鉛粒子0.5g、ヘキサメタりん酸ナトリウムとしての濃度が0.025重量%のヘキサメタりん酸ナトリウム水溶液20ml、φ0.3mmのジルコニアビーズ(東レ社製 粉砕ボール)88gを容積75mlのマヨネーズ瓶に入れ、良くかき混ぜた後、ペイントコンディショナー5410型(RED DEVIL社製)に固定し、45分間振動を与えて分散処理することにより、スラリーを調製し、そのスラリーを用いて測定を行った。相対屈折率を1.5として測定を行った。D50とは、体積基準での50%積算粒径、D90とは、体積基準での90%積算粒径、D10とは、体積基準での10%積算粒径を意味する。粒度分布のシャープさの指標として、D90/D10の比を算出する。この値が大きい程粒度分布がブロードであることを意味し、この値が小さい程粒度分布がシャープであることを意味する。すなわち、D90/D10の値が小さい程、粒子径が極端に大きい粒子の数が少なく、粒子径が極端に小さい粒子の数が少なく、粒子サイズが揃っていることを意味する。
上記実施例、比較例の酸化亜鉛粒子2g、ワニス10g(アクリディック A-801-P DIC社製)、酢酸ブチル5g(試薬特級 和光純薬工業社製)、キシレン5g(純正特級 純正化学社製)、ガラスビーズ38g(1.5mm ポッターズ・バロティーニ社製)を容積75mlのマヨネーズ瓶に入れ、良くかき混ぜた後、ペイントコンディショナー5410型(RED DEVIL社製)に固定し、90分間振動を与えて分散処理することにより塗料を作成した。次に、作成した塗料をスライドガラス(縦・横・厚み=76mm・26mm・0.8~1.0mm 松浪硝子工業社製)の上に少量滴下し、バーコーター(No.579 ROD No.6 安田精機製作所社製)で塗膜を作成した。作成した塗膜を20℃で12時間乾燥した後、全光線透過率1、全光線透過率2、全光線透過率3、平行光線透過率1、平行光線透過率2の測定に用いた。
本明細書において、全光線透過率1(%)、全光線透過率2(%)、全光線透過率3(%)及び平行光線透過率1(%)、平行光線透過率2(%)は、作成した塗膜を分光光度計V-570(日本分光社製)で測定した値である。なお、全光線透過率1(%)の値は波長310nmにおける全光線透過率の値、全光線透過率2(%)の値は波長350nmにおける全光線透過率の値、全光線透過率3(%)の値は波長375nmにおける全光線透過率の値、平行光線透過率1(%)の値は波長500nmにおける平行光線透過率の値、平行光線透過率2(%)の値は波長700nmにおける平行光線透過率の値である。全光線透過率1(%)の値が小さい程、UVBの波長の紫外線に対する紫外線遮蔽効果が高いことを意味し、全光線透過率2(%)と全光線透過率3(%)の値が小さい程、UVAの波長の紫外線に対する紫外線遮蔽効果が高いことを意味する。特に、全光線透過率3(%)の値が小さい場合、UVAの波長の紫外線に対する遮蔽領域がより広域に渡っていることを意味する。また、平行光線透過率1(%)、平行光線透過率2(%)の値が大きい程、可視光透明性が高いことを意味する。
図3、図6、図15に示すX線回折のスペクトル、及び表1における得られた粒子の組成は、銅管球をもつX線回折装置UltimaIII(リガク社製)により分析した結果を示したものである。
本発明の丸み状酸化亜鉛粒子は、化粧料、放熱性フィラー、放熱性樹脂組成物、放熱性グリース及び放熱性塗料組成物の成分として使用することができる。
Claims (9)
- 平均粒子径が0.04μm以上、アスペクト比が2.0以下の丸み状過酸化亜鉛粒子。
- 酸化亜鉛粒子を過酸化水素で処理する工程(1)によって得られたものである請求項1記載の丸み状過酸化亜鉛粒子。
- 請求項1又は2記載の丸み状過酸化亜鉛粒子を熱分解することによって得られた平均粒子径が0.04μm以上、アスペクト比が2.0以下の丸み状酸化亜鉛粒子。
- 粒度分布におけるD90/D10が3.0以下となる請求項3に記載の丸み状酸化亜鉛粒子。
- 比表面積が30m2/g以下となる請求項3又は4に記載の丸み状酸化亜鉛粒子。
- 酸化亜鉛粒子を過酸化水素で処理する工程(1)を有することを特徴とする請求項1又は2記載の丸み状過酸化亜鉛粒子の製造方法。
- 酸化亜鉛粒子を過酸化水素で処理する工程(1)と、工程(1)により得られた過酸化亜鉛を焼成により熱分解する工程(2)を含む請求項3、4又は5に記載の丸み状酸化亜鉛粒子の製造方法。
- 請求項3、4又は5に記載の丸み状酸化亜鉛粒子を含有することを特徴とする化粧料。
- 請求項3、4又は5に記載の丸み状酸化亜鉛粒子からなることを特徴とする放熱性フィラー。
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- 2012-06-08 WO PCT/JP2012/064777 patent/WO2012169611A1/ja active Application Filing
- 2012-06-08 CN CN201280017073.0A patent/CN103502142A/zh active Pending
- 2012-06-08 US US14/123,874 patent/US9376319B2/en active Active
- 2012-06-08 ES ES12796264.5T patent/ES2694570T3/es active Active
- 2012-06-08 JP JP2013519539A patent/JP5967087B2/ja active Active
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Cited By (7)
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JP2014148426A (ja) * | 2013-01-31 | 2014-08-21 | Ishihara Sangyo Kaisha Ltd | 放熱性組成物 |
JP2014221708A (ja) * | 2013-05-14 | 2014-11-27 | テイカ株式会社 | 酸化亜鉛および酸化亜鉛の製造方法並びにこの酸化亜鉛を用いた化粧料、樹脂組成物、塗料組成物、無機粉体 |
KR20180044276A (ko) * | 2015-08-28 | 2018-05-02 | 스미토모 오사카 세멘토 가부시키가이샤 | 산화 아연 분체, 분산액, 조성물, 및 화장료 |
JPWO2017038635A1 (ja) * | 2015-08-28 | 2018-06-14 | 住友大阪セメント株式会社 | 酸化亜鉛粉体、分散液、組成物、及び化粧料 |
KR102547489B1 (ko) | 2015-08-28 | 2023-06-23 | 스미토모 오사카 세멘토 가부시키가이샤 | 산화 아연 분체, 분산액, 조성물, 및 화장료 |
WO2018124639A3 (ko) * | 2016-12-27 | 2018-11-29 | 롯데첨단소재(주) | 열가소성 수지 조성물 및 이로부터 제조된 성형품 |
US11091624B2 (en) | 2016-12-27 | 2021-08-17 | Lotte Advanced Materials Co., Ltd. | Thermoplastic resin composition and article produced therefrom |
Also Published As
Publication number | Publication date |
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US20140212669A1 (en) | 2014-07-31 |
CN103502142A (zh) | 2014-01-08 |
ES2694570T3 (es) | 2018-12-21 |
EP2719659A4 (en) | 2015-03-04 |
KR20140024865A (ko) | 2014-03-03 |
EP2719659A1 (en) | 2014-04-16 |
KR101907940B1 (ko) | 2018-10-16 |
JPWO2012169611A1 (ja) | 2015-02-23 |
US9376319B2 (en) | 2016-06-28 |
JP5967087B2 (ja) | 2016-08-10 |
EP2719659B1 (en) | 2018-10-10 |
CA2837441A1 (en) | 2012-12-13 |
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