WO2019088130A1 - Zinc oxide powder, dispersion, cosmetic material, and method for producing zinc oxide powder - Google Patents

Zinc oxide powder, dispersion, cosmetic material, and method for producing zinc oxide powder Download PDF

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Publication number
WO2019088130A1
WO2019088130A1 PCT/JP2018/040401 JP2018040401W WO2019088130A1 WO 2019088130 A1 WO2019088130 A1 WO 2019088130A1 JP 2018040401 W JP2018040401 W JP 2018040401W WO 2019088130 A1 WO2019088130 A1 WO 2019088130A1
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Prior art keywords
zinc oxide
oxide powder
present
dispersion
mass
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PCT/JP2018/040401
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French (fr)
Japanese (ja)
Inventor
俊輔 須磨
西田　健一郎
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住友大阪セメント株式会社
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Priority to JP2019550430A priority Critical patent/JP7173033B2/en
Publication of WO2019088130A1 publication Critical patent/WO2019088130A1/en

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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
    • 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
    • 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
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/02—Oxides; Hydroxides

Definitions

  • the present invention relates to a zinc oxide powder, a dispersion, a cosmetic, and a method for producing zinc oxide powder.
  • Priority is claimed on Japanese Patent Application No. 2017-211195, filed Oct. 31, 2017, the content of which is incorporated herein by reference.
  • Zinc oxide powder has an ultraviolet shielding function, a gas permeation suppressing function, and the like, and also has high transparency. Therefore, they are used in applications requiring transparency, such as ultraviolet shielding films, ultraviolet shielding glasses, cosmetics, and gas barrier films (see, for example, Patent Documents 1 to 7).
  • zinc oxide powder can suppress spreading of sebum by solidifying sebum. For this reason, it is known that makeup collapse by sebum can be suppressed by using for foundation etc. (for example, refer to patent documents 8).
  • the present invention has been made in view of the above-mentioned circumstances, and zinc oxide powder capable of shortening the time for which sebum solidifies more than before, and dispersion liquid containing zinc oxide powder, cosmetics, and zinc oxide powder
  • the purpose is to provide a method of manufacturing the body.
  • S in the S—O bonded state of the zinc oxide powder measured by X-ray photoelectron spectroscopy is 0.1 atm% or more and 1.0 atm%. It is below.
  • the dispersion liquid which is the 2nd aspect of this invention contains the zinc oxide powder of the 1st aspect of this invention, and a dispersion medium.
  • the cosmetic according to the third aspect of the present invention comprises at least one selected from the group consisting of the zinc oxide powder of the first aspect of the present invention and the dispersion according to the second aspect of the present invention, and a cosmetic base And an agent raw material.
  • the method for producing zinc oxide powder according to the fourth aspect of the present invention comprises the steps of mixing zinc oxide powder and an aqueous solution containing SO 4 .
  • the proportion of S in the S—O bond state is 0.1 atm% or more and 1.0 atm% or less, which is measured by X-ray photoelectron spectroscopy.
  • the time required for solidification of sebum can be shortened.
  • the time required for solidification of sebum can be shortened.
  • the cosmetic of the third aspect of the present invention at least one selected from the group consisting of the zinc oxide powder of the first aspect of the present invention and the dispersion of the second aspect of the present invention, and cosmetics Since the base material is contained, makeup breakdown can be further suppressed.
  • zinc oxide powder excellent in sebum solidifying property can be produced.
  • the zinc oxide powder, the dispersion, the cosmetic and the method for producing the zinc oxide powder of the present embodiment which are preferable examples of the present invention, will be described below.
  • the following examples are specifically described for better understanding of the gist of the invention, and do not limit the present invention unless otherwise specified. Modifications, omissions, substitutions, additions, and other modifications are possible without departing from the spirit of the present invention.
  • Zinc oxide powder In the zinc oxide powder of the present embodiment, S in an S—O bond state measured by X-ray photoelectron spectroscopy is 0.1 atm% or more and 1.0 atm% or less. Due to this feature, the zinc oxide powder of the present embodiment can shorten the time required for solidification of sebum when used in cosmetics.
  • the present inventors have found that zinc oxide powder in which S in an S-O bond state measured by X-ray photoelectron spectroscopy is 0.1 atm% or more and 1.0 atm% or less can shorten the sebum solidification time.
  • a zinc oxide powder for example, an aqueous solution containing SO 4
  • the ratio (atomic percentage) of S in S—O bonded state obtained by measuring the zinc oxide powder (zinc oxide particles) of the present embodiment by X-ray photoelectron spectroscopy is 0.1 atm% or more and 1.0 atm % Or less and preferably 0.2 atm% or more and 0.9 atm% or less.
  • S is 0.1 atm% or more, sebum solidification time can be shortened.
  • S exceeds 1.0 atm%, the amount of impurities in the zinc oxide powder increases, which is not preferable.
  • the S-bonded state of S which is measured by X-ray photoelectron spectroscopy, can be obtained, for example, by the following method. Specifically, preferably using a scanning X-ray photoelectron spectroscopy (XPS: X-Ray Photoelectron Spectroscopy / ESCA: Electron Spectroscopy for Chemical) PHI 5000 (manufactured by ULVAC-PHI, Inc.), etc., preferably measure according to the following method. Can. In the measurement, AlK ⁇ (monochrome: 50 W, 15 kV) 1486.6 eV is used as an X-ray source. The analysis area is 0.4 ⁇ 0.4 mm 2 .
  • an appropriate amount of zinc oxide powder is fixed on an aluminum pan and introduced into a scanning X-ray photoelectron spectrometer.
  • qualitative analysis (performed with a wide spectrum) is performed on the surface of the zinc oxide powder. By scanning a wide energy range, it is possible to confirm to some extent what elements are present.
  • O is measured for O1s (525 eV to 540 eV).
  • Zn is measured for Zn2p (1015 eV to 1030 eV).
  • S is measured for S2p (160 eV to 175 eV).
  • C is measured for C1s (280 eV to 295 eV).
  • Qualitative analysis can be performed with binding energy values in an appropriate range, for example, 0 to 1100 eV.
  • the atomic concentration on the surface of the zinc oxide powder is calculated from the area of the peaks detected in the measurement range for the elements detected by qualitative analysis and S and C. We use ULVAC-PHI's handbook and relative sensitivity factors for state analysis and quantitative calculations.
  • the content of SO 4 in the zinc oxide powder is preferably 100 ppm or more and 10000 ppm or less.
  • SO 4 may be present in any state in zinc oxide powder or zinc oxide particles in the powder. For example, it may be on the surface only, or may be inside the particle as well as the surface. These states may be controlled by manufacturing conditions and the like.
  • SO 4 may be a part constituting a compound such as a sulfate, may be in an ionic state such as SO 4 2-, or may be bonded to a zinc atom or the like on the particle surface.
  • the content of the SO 4 is used in the preparation remained in or surface of the final product, the SO 4 in the molecular structure of the compounds such as sulfuric acid or sulfates, be a value attributed mainly good.
  • the content of SO 4 is in the above range, zinc oxide powder excellent in sebum solidifying property can be obtained.
  • the content of SO 4 in the zinc oxide powder can be measured by an ICP emission spectrometer.
  • zinc oxide particles are included, and further, zinc sulfate, beryllium sulfate, magnesium sulfate, calcium sulfate, on the surface, near the surface, and / or in the particles of the particles.
  • the sulfate is zinc sulfate, magnesium sulfate or calcium sulfate. It is also preferable that these powders have an SO 4 content of 100 ppm or more and 10000 ppm or less.
  • the content of SO 4 in the zinc oxide powder is 100 ppm or more and 10000 ppm or less
  • the zinc oxide powder contains the sulfate salt on the particle surface or in the vicinity of the surface And zinc oxide powder, wherein the sulfate contains SO 4 in the molecular structure, and the amount of SO 4 in the sulfate is included in the content of SO 4 in the zinc oxide powder.
  • the sulfate may be attributable to the material used to make the zinc oxide powder, such as the material used to make the aqueous solution containing SO 4 .
  • the zinc oxide powder of the present invention is not limited to only the zinc oxide powder of the above example.
  • the zinc oxide powder of the present embodiment preferably, the zinc oxide powder obtained by mixing the aqueous solution containing SO 4 and the zinc oxide powder as a raw material is obtained by measurement by X-ray photoelectron spectroscopy. Since S in the SO-bonded state to be treated is in the above range, the time required for the sebum to solidify can be shortened. However, the details of this mechanism are unknown. However, it is inferred as follows. When the aqueous solution containing SO 4 and the zinc oxide powder are mixed, SO 4 or a compound containing SO 4 is uniformly present on the surface of the zinc oxide powder.
  • the SO 4 in the aqueous solution may be contained in the aqueous solution as an ion such as SO 4 2- or may be contained as a part constituting a compound in the aqueous solution.
  • fatty acids mainly oleic acid
  • sebum components which are oil components causing makeup breakdown, are solidified among sebum components, while they are contained in emollient components in sebum and cosmetics. It is known that preference is given to oil components that do not solidify them (Fragrance Journal, December 2015, pages 42-46).
  • the zinc oxide powder of the present embodiment is excellent in the solidifying property of oleic acid, though the reason is not clear.
  • the zinc oxide powder of the present embodiment has solidifying properties for cyclopentasiloxane, tri (caprylic acid / capric acid) glyceryl, squalane, olive oil, etc. which are generally blended as oils in cosmetics. Do not have. That is, the zinc oxide powder of the present embodiment also has an effect of being able to selectively solidify a fatty acid (oleic acid).
  • the specific surface area of the zinc oxide powder of the present embodiment can be arbitrarily selected according to the required characteristics. For example, from the viewpoint of transparency, it is preferable that the specific surface area is less than 8m 2 / g or more and 65 m 2 / g, more preferably 15 m 2 / g or more and 60 m 2 / g or less, 20 m 2 / More preferably, it is g or more and 50 m 2 / g or less, and most preferably 25 m 2 / g or more and 45 m 2 / g or less. When the specific surface area of the zinc oxide powder is in the above range, the transparency of the dispersion containing the zinc oxide powder and cosmetics can be increased.
  • the feel of the zinc oxide powder is preferably 1 m 2 / g or more and 8m 2 / g, more preferably 2m 2 / g or more and 7m 2 / g or less, 3m More preferably, it is 2 / g or more and 7 m 2 / g or less.
  • the specific surface area of the zinc oxide powder is in the above range, the feel of a cosmetic containing this zinc oxide powder can be improved.
  • the specific surface area of the zinc oxide powder means a value measured by the BET method.
  • the apparatus used for measuring the specific surface area include a fully automatic specific surface area measuring apparatus (trade name: Macsorb HM Model-1201, manufactured by Mountech Co., Ltd.).
  • the method for producing zinc oxide powder of the present embodiment includes the step of mixing zinc oxide powder and an aqueous solution containing SO 4 .
  • zinc oxide powder it is preferable to use high purity zinc oxide powder used in cosmetics.
  • zinc oxide powder of high purity an increase in the amount of impurities in the zinc oxide powder can be suppressed.
  • the zinc oxide powder may be used after being washed with pure water or alcohol.
  • the aqueous solution containing SO 4 not particularly limited as long as it contains a SO 4.
  • An aqueous solution containing SO 4 can be obtained, for example, by dissolving a compound containing SO 4 in water.
  • a compound containing SO 4 for example, sulfuric acid or sulfate can be used alone or in combination of two or more.
  • the sulfate is not particularly limited, and examples thereof include zinc sulfate, beryllium sulfate, magnesium sulfate, calcium sulfate, strontium sulfate, barium sulfate, aluminum sulfate, cerium sulfate, sodium sulfate, potassium sulfate and ammonium sulfate. These sulfates contain SO 4 in the molecular structure. It is preferable to use zinc sulfate, magnesium sulfate, and calcium sulfate in that the sebum solidification time is further shortened.
  • the concentration of the aqueous solution containing SO 4 is such that S in the S—O bonded state of the resulting zinc oxide powder, as measured by X-ray photoelectron spectroscopy, within the range of solubility of sulfate, falls within the above range It may be adjusted and is not particularly limited.
  • an aqueous solution having a concentration of sulfate of 0.01% by mass or more and 50% by mass or less can be used.
  • the above-mentioned aqueous solution and zinc oxide powder as a raw material are prepared such that the mass ratio of zinc oxide and a compound containing SO 4 is in the range of 1: 0.001 to 1: 0.1. , Just mix it.
  • a method of mixing zinc oxide powder as a raw material and an aqueous solution containing SO 4 it is possible to use a method of mixing so that a compound containing SO 4 uniformly exists (adheres) on the surface of zinc oxide powder.
  • a compound containing SO 4 uniformly exists (adheres) on the surface of zinc oxide powder.
  • an aqueous solution containing SO 4 it may be stirred zinc oxide powder, spraying an aqueous solution containing SO 4 in the zinc oxide powder (particle) in a spray, stirring the zinc oxide powder in a Henschel mixer You may
  • the method for producing the zinc oxide powder of the present embodiment may further include the step of drying the zinc oxide powder after being mixed with the aqueous solution containing SO 4 .
  • the mixed zinc oxide powder may be naturally dried or may be dried at a temperature of 80 ° C. to 150 ° C. by a dryer.
  • the zinc oxide powder of the present embodiment can be produced by the above steps.
  • the compound containing SO 4 that may be present on the surface of the zinc oxide powder of the present embodiment is the same as the compound containing SO 4 that can be used for producing the zinc oxide powder of the present embodiment, It may be different.
  • zinc oxide powder and an aqueous solution containing SO 4 were mixed.
  • the method for producing the zinc oxide powder of the present embodiment is not limited to this.
  • a compound containing SO 4 may be present (adhered) on the surface of zinc oxide powder (zinc oxide particles). Therefore, at some stage of the manufacturing process of the zinc oxide powder of interest, a SO 4, i.e. a compound containing SO 4 in the structure and / or a material containing SO 4 ions to form zinc oxide powder It is speculated that the ingredients may be mixed. Therefore, when producing zinc oxide powder by a vapor phase method, it is speculated that the zinc oxide powder of the present embodiment can be obtained by mixing a gas containing SO 4 and a gas containing zinc.
  • a raw material (zinc oxalate, zinc hydroxide, zinc carbonate, basic zinc carbonate, etc.) of zinc oxide powder and an aqueous solution containing SO 4 are mixed. By doing this, it is presumed that the zinc oxide powder of the present embodiment can be obtained.
  • the method for producing the zinc oxide powder of the present embodiment when used in a cosmetic, it is possible to produce a zinc oxide powder having excellent sebum solidifying properties.
  • At least a part of the surface of the zinc oxide powder of the present embodiment may be surface-treated with at least one of an inorganic component and an organic component.
  • the atomic concentration of S in the S—O bonded state of the at least partially surface-treated zinc oxide powder is within the above range. It is preferable to add a step of the surface treatment after the process of mixing the aqueous solution containing zinc oxide powder and SO 4 as a raw material.
  • the zinc oxide powder thus surface-treated with at least one of the inorganic component and the organic component is referred to as a surface-treated zinc oxide powder.
  • the surface-treated zinc oxide powder can further suppress the surface activity of zinc oxide, and can improve the dispersibility in the dispersion medium.
  • An inorganic component and an organic component are suitably selected according to the use of zinc oxide powder.
  • the inorganic component and the organic component used for the surface treatment are not particularly limited.
  • the surface treatment agent generally used for cosmetics is mentioned.
  • the inorganic component include silica, alumina and the like.
  • One of these inorganic components may be used alone, or two or more thereof may be used in combination.
  • organic component examples include silicone compounds, organopolysiloxanes, fatty acids, fatty acid soaps, fatty acid esters, polyolefins, N-acyl amino acids or salts thereof, N-acyl-N-alkyl amino acids or salts thereof, hydrogenated lecithin or salts thereof And at least one selected from the group consisting of organic titanate compounds.
  • One of these organic components may be used alone, or two or more of these organic components may be used in combination.
  • surfactant as an inorganic component and an organic component.
  • zinc oxide powder is surface-treated using at least one selected from such inorganic components and organic components, the surface activity of zinc oxide is suppressed, or the zinc oxide powder is dispersed in a dispersion medium. It is possible to improve the
  • silicone compounds used for surface treatment include silicone oils such as methylhydrogenpolysiloxane, dimethylpolysiloxane and methylphenylpolysiloxane; methyltrimethoxysilane, ethyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane Alkylsilanes such as octyltriethoxysilane; fluoroalkylsilanes such as trifluoromethylethyltrimethoxysilane and heptadecafluorodecyltrimethoxysilane; methicone, dimethicone, hydrogen dimethicone, triethoxysilylethyl polydimethylsiloxyethyl dimethicone, triethoxy Silylethyl polydimethylsiloxyethyl hexyl dimethicone, (acreates / tride
  • silicone compounds may be used alone, or two or more thereof may be used in combination. Moreover, as a silicone compound, you may use the copolymer of these silicone compounds. Among these silicone compounds, methicone, dimethicone and hydrogen dimethicone are preferable, and hydrogen dimethicone is particularly preferable, from the viewpoint of hardly inhibiting the sebum solidifying property of zinc oxide powder.
  • the example of the organic component is further described.
  • the fatty acid include palmitic acid, isostearic acid, stearic acid, lauric acid, myristic acid, behenic acid, oleic acid, rosin acid, 12-hydroxystearic acid, polyhydroxystearic acid and the like.
  • fatty acid soaps include aluminum stearate, calcium stearate, aluminum 12-hydroxystearate and the like.
  • the fatty acid ester include dextrin fatty acid ester, cholesterol fatty acid ester, sucrose fatty acid ester, starch fatty acid ester and the like.
  • N-acyl amino acids examples include N-lauroyl glutamic acid, N-myristoyl glutamic acid, N-palmitoyl glutamic acid, N-cocoyl glutamic acid, N-lauroyl lysine, N-stearoyl glutamic acid, dilauroyl glutamic acid lysine and the like.
  • salts of N-acyl amino acids sodium salts, potassium salts, magnesium salts, calcium salts, aluminum salts, zinc salts of N-acyl amino acids and the like can be mentioned.
  • a gemini amphiphilic amino acid including an N-acyl amino acid salt such as lysine sodium dilauroyl glutamate may be used.
  • organic titanate compound for example, isopropyl triisostearoyl titanate, isopropyl dimethacryl isostearoyl titanate, isopropyl tri (dodecyl) benzene sulfonyl titanate, neopentyl (diallyl) oxy-tri (dioctyl) phosphate titanate, neopentyl (diallyl) oxy- trineododeca Noyl titanate etc. are mentioned.
  • the surface-treated zinc oxide powder of the present embodiment is used in industrial applications such as a UV shielding film or a gas barrier film, particles are dispersed in addition to or instead of the inorganic component and the organic component used in the cosmetic.
  • a common dispersant used in the process can be appropriately selected and used.
  • a dispersing agent an anionic dispersing agent, a cationic dispersing agent, a nonionic dispersing agent, a silane coupling agent, a wetting dispersing agent etc. are mentioned, for example.
  • the method for producing the surface-treated zinc oxide powder is not particularly limited, and may be appropriately carried out by a known method according to the components used for the surface treatment.
  • the dispersion liquid of the present embodiment contains the zinc oxide powder of the present embodiment and a dispersion medium.
  • the zinc oxide powder may be surface-treated zinc oxide powder.
  • the dispersion liquid of the present embodiment can shorten the time required for solidification of sebum.
  • the dispersion liquid of the present embodiment may be a paste-like dispersion having a high viscosity.
  • the content of the zinc oxide powder in the dispersion may be appropriately adjusted in accordance with the desired characteristics.
  • content of the zinc oxide powder in a dispersion liquid can be selected arbitrarily.
  • the content is preferably 30% by mass to 90% by mass, more preferably 40% by mass to 85% by mass, and still more preferably 50% by mass to 80% by mass.
  • the content of the zinc oxide powder in the dispersion for example, by setting the content in the range of 30% by mass to 90% by mass, the zinc oxide powder is contained in the dispersion at a high concentration it can. Therefore, the degree of freedom in formulation can be improved, and the viscosity of the dispersion can be made easy to handle.
  • content of a zinc oxide powder is not limited only to the said range.
  • 10 mass%, 20 mass%, 40 mass%, 60 mass% etc. can be mentioned preferably.
  • 95 mass%, 90 mass%, 85 mass%, 75 mass% etc. can be mentioned preferably.
  • the viscosity of the dispersion of the present embodiment can be selected arbitrarily. For example, it is preferably 5 Pa ⁇ s or more and 300 Pa ⁇ s or less, more preferably 8 Pa ⁇ s or more and 100 Pa ⁇ s or less, still more preferably 10 Pa ⁇ s or more and 80 Pa ⁇ s or less, 15 Pa It is most preferable that s or more and 60 Pa ⁇ s or less.
  • a dispersion which is easy to handle can be obtained, even when the solid content (zinc oxide powder) is contained at a high concentration.
  • the dispersion medium contained in the dispersion liquid is appropriately selected according to the application of the dispersion liquid.
  • suitable dispersion media are exemplified below, the dispersion media in the dispersion are not limited to these.
  • the dispersion medium for example, alcohols such as water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, octanol, glycerin and the like; ethyl acetate, butyl acetate, ethyl lactate, propylene glycol monomethyl ether Esters such as acetate, propylene glycol monoethyl ether acetate and ⁇ -butyrolactone; diethyl ether, ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (ethyl cellosolve), ethylene glycol monobutyl ether (butyl cellosolve), diethylene glycol mono
  • ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, cyclohexanone and the like; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and the like; cyclic hydrocarbons such as cyclohexane; And amides such as N-dimethylacetoacetamide and N-methylpyrrolidone; linear polysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane and diphenylpolysiloxane; and the like.
  • One of these dispersion media may be used alone, or two or more thereof may be mixed and used.
  • cyclic polysiloxanes such as octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane, dodecamethyl cyclohexane siloxane, etc .; amino-modified polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, fluorine-modified Modified polysiloxanes such as polysiloxane are used.
  • One of these dispersion media may be used alone, or two or more thereof may be mixed and used.
  • a hydrophobic dispersion medium such as a higher alcohol such as stearyl alcohol may be used.
  • One of these dispersion media may be used alone, or two or more thereof may be mixed and used.
  • the above-mentioned dispersion media can be used in any combination according to the required properties.
  • the amount of the dispersion medium can be arbitrarily selected, but for example, it is generally 5% by mass or more and 90% by mass or less, preferably 10% by mass or more and 70% by mass or less based on the total amount of the dispersion. More preferably, it is 15% by mass or more and 60% by mass or less.
  • the dispersion of the present embodiment may contain commonly used additives as long as the properties of the dispersion are not impaired.
  • the additive for example, a dispersant, a stabilizer, a water soluble binder, a thickener, an oil soluble preservative, a UV absorber, an oil soluble drug, an oil soluble pigment, an oil soluble protein, a vegetable oil, an animal oil etc.
  • the The amount of each additive can be selected arbitrarily, but for example, it is generally 0.1% by mass or more and 80% by mass or less, preferably 0.5% by mass or more and 50% by mass with respect to the total amount of the dispersion. % Or less, more preferably 1% by mass or more and 40% by mass or less. As another example, if necessary, it may be 0.1 to 2% by mass, 2 to 5% by mass, or 5 to 10% by mass.
  • the method for producing the dispersion is not particularly limited.
  • a method of mechanically dispersing zinc oxide powder and a dispersion medium with a known dispersing device can be mentioned.
  • a dispersion apparatus a stirrer, a self-revolution type
  • the dispersion liquid of the present embodiment can be used for a composition having an ultraviolet shielding function, a gas permeation suppressing function, and the like other than cosmetics.
  • the time required for solidification of sebum can be shortened when used for cosmetics.
  • the cosmetic of the present embodiment contains at least one selected from the group consisting of the zinc oxide powder of the present embodiment and the dispersion of the present embodiment, and a cosmetic base material.
  • the cosmetic of the present embodiment can contain the zinc oxide powder of the present embodiment, a cosmetic base material, and, if necessary, a dispersion medium.
  • the cosmetic of the present embodiment can suppress makeup collapse.
  • the cosmetic base material means various raw materials forming the main body of the cosmetic, and can be selected arbitrarily.
  • cosmetic base materials include oily materials, aqueous materials, surfactants, and powder materials. These can be used in combination as needed.
  • oils and oils As an oil-based raw material, fats and oils, higher fatty acids, higher alcohols, ester oils etc. are mentioned, for example.
  • aqueous material examples include purified water, alcohol, thickener and the like.
  • a powder raw material a colored pigment, a white pigment, a pearlescent agent, an extender pigment etc. are mentioned, for example.
  • the cosmetic of the present embodiment mixes the zinc oxide powder or the dispersion of the present embodiment with cosmetic base materials such as milk, cream, foundation, lipstick, blush, and eye shadow by a known method.
  • cosmetic base materials such as milk, cream, foundation, lipstick, blush, and eye shadow.
  • the cosmetic may be prepared by blending the zinc oxide powder of the present embodiment in an oil phase or an aqueous phase, as an O / W type or W / O type emulsion, and then blending with a cosmetic base material. Can also be obtained.
  • the content of the zinc oxide powder in the cosmetic of the present embodiment may be appropriately adjusted according to the desired characteristics.
  • the lower limit of the content of the zinc oxide powder may be 0.01% by mass or more, 0.1% by mass or more, or 1% by mass or more.
  • the upper limit of the content of the zinc oxide powder may be 50% by mass or less, 40% by mass or less, or 30% by mass or less. 20 mass% or less, 10 mass% or less, 5 mass% or less may be sufficient.
  • the cosmetic of the present embodiment contains at least one selected from the group consisting of the zinc oxide powder of the present embodiment and the dispersion of the present embodiment, and a cosmetic base material, so that the cosmetic collapse is caused. Can be further suppressed.
  • Example 1 30 g of zinc oxide powder A (Sumitomo Osaka Cement, BET specific surface area 45.1 m 2 / g) was added to 150 g of an aqueous solution containing 0.3 mass% zinc sulfate (ZnSO 4 ), and the mixture was stirred for 30 minutes. The mixed solution was subjected to solid-liquid separation by centrifugation, and the obtained zinc oxide powder was dried at 105 ° C. for 3 hours to obtain the zinc oxide powder of Example 1.
  • ZnSO 4 0.3 mass% zinc sulfate
  • the amount of S present on the surface of the zinc oxide powder of Example 1 was measured by the following method using a scanning X-ray photoelectron spectrometer PHI5000 (manufactured by ULVAC-PHI, Inc.). In the measurement, AlK ⁇ (monochrome: 50 W, 15 kV) 1486.6 eV was used as an X-ray source. The analysis area was 0.4 ⁇ 0.4 mm 2 . The zinc oxide powder was fixed to a pan made of aluminum and introduced into a scanning X-ray photoelectron spectrometer. Next, qualitative analysis (wide spectrum) of the zinc oxide powder was performed.
  • state analysis is performed for the element (O, Zn) detected by qualitative analysis, the element (S) to be measured, and the reference element (C), and the peak area of the spectrum obtained for these
  • the surface atomic concentration was calculated from Since C and S have low intensities, energy resolution was lowered and sensitivity was prioritized.
  • O was measured for O1s (525 eV to 540 eV).
  • Zn was measured for Zn2p (1015 eV to 1030 eV).
  • S was measured for S2p (160 eV to 175 eV).
  • C was measured for C1s (280 eV to 295 eV).
  • the amount of SO 4 contained in the zinc oxide powder of Example 1 was measured by the following method using an ICP emission spectrometer ICP-AES 700-ES (manufactured by Varian). 0.5 g of the zinc oxide powder of Example 1 was weighed into a 200 mL beaker. Subsequently, 50 mL of pure water and 5 mL of 60 mass% concentrated nitric acid were added to a beaker containing this zinc oxide powder, and the mixture was stirred to dissolve the zinc oxide powder of Example 1. This solution was adjusted to 200 mL with pure water using a volumetric flask. This solution was diluted twice to prepare a test solution. To this test solution, 1000 ppm of Y (yttrium) was added as an internal standard substance.
  • a calibration curve was prepared using an elemental standard solution of known concentration.
  • 1000 ppm of Y as an internal standard substance and nitric acid were added to the elemental standard solution for preparing a calibration curve so as to have the same concentration as the test solution.
  • the test solution was measured by an ICP emission spectrophotometer and quantified by a calibration curve method.
  • the amount of SO 4 contained in the zinc oxide powder was 0.64 mass% (6400 ppm). The results are shown in Table 2.
  • An artificial sebum was prepared by mixing 10 g of oleic acid (manufactured by Kanto Chemical Co., Ltd.), 10 g of squalane (manufactured by Kanto Chemical Co., Ltd.), and 10 g of olive oil (trade name: EX virgin oil, manufactured by BOSCO).
  • Example 1 0.5 g of the zinc oxide powder of Example 1 and 4 g of artificial sebum were mixed and stirred by a stirrer. In the state of stirring, the time from the end of the stirring to the solidification of the artificial sebum was measured to evaluate the sebum solidifying property. As a result, the zinc oxide powder of Example 1 solidified in 5 seconds.
  • Example 2 The zinc oxide powder of Example 2 was obtained in the same manner as Example 1, except that the concentration of the aqueous solution containing ZnSO 4 was changed to 0.2% by mass. As a result of evaluation in the same manner as in Example 1, the amount of S in the S—O bonded state present on the surface of the zinc oxide powder was 0.4 atm%. The amount of SO 4 contained in the zinc oxide powder was 0.42% by mass (4200 ppm). The time required for the sebum to solidify was 2 minutes and 30 seconds. The results are shown in Tables 1 and 2.
  • Comparative Example 1 30 g of zinc oxide powder A and 0.45 g of ZnSO 4 (powder) were mixed in a mortar. That is, the powders were simply mixed to prepare a sample. The obtained mixture was evaluated in the same manner as in Example 1. As a result, the amount of S in the S—O bonded state present on the surface of the zinc oxide powder was below the detection limit ( ⁇ 0.1 atm%). The amount of SO 4 contained in the zinc oxide powder was 0.68% by mass (6800 ppm). Moreover, the time required for sebum solidification was 30 minutes. The results are shown in Tables 1 and 2.
  • the zinc oxide powder A was used as the zinc oxide powder of Comparative Example 2. That is, untreated zinc oxide powder A itself was used as a sample. As a result of evaluation in the same manner as in Example 1, the amount of S present on the surface of the zinc oxide powder was below the detection limit ( ⁇ 0.1 atm%). The amount of SO 4 in the SO-bonded state contained in the zinc oxide powder was 0.005% by mass (50 ppm). As a result of measuring the time required for sebum solidification as in Example 1, the sebum was not solidified even after 30 minutes. The results are shown in Table 2.
  • Reference Example 2 The zinc oxide powder of Reference Example 2 was obtained in the same manner as Reference Example 1 except that CaSO 4 was changed to MgSO 4 .
  • Reference Example 3 The zinc oxide powder of Reference Example 3 was obtained in the same manner as in Reference Example 1 except that CaSO 4 was changed to Na 2 SO 4 .
  • Reference Example 4 The zinc oxide powder of Reference Example 4 was obtained in the same manner as in Reference Example 1 except that CaSO 4 was changed to CaCl 2 .
  • Reference Example 5 The zinc oxide powder of Reference Example 5 was obtained in the same manner as Reference Example 1 except that CaSO 4 was changed to MgCl 2 .
  • the sebum solidification property was evaluated in the same manner as Example 1. If the solidification time is 5 minutes or less, “ ⁇ " (excellent), if the solidification time is more than 5 minutes to 20 minutes or less, “ ⁇ " (good), the solidification time exceeds 20 minutes to 30 minutes or less In the case where the solidification time was more than 30 minutes, it was evaluated as "poor". The shorter the setting time, the better the sebum setting property.
  • the present invention can provide a zinc oxide powder capable of shortening the time for which sebum solidifies, a dispersion containing zinc oxide powder, a cosmetic, and a method for producing zinc oxide powder.

Abstract

Provided is zinc oxide powder in which S in a S-O bonding state of the zinc oxide powder is 0.1-1.0 atm%, as measured by X-ray photoelectron spectroscopy.

Description

酸化亜鉛粉体、分散液、化粧料、および酸化亜鉛粉体の製造方法Zinc oxide powder, dispersion liquid, cosmetic, and method for producing zinc oxide powder
　本発明は、酸化亜鉛粉体、分散液、化粧料、および酸化亜鉛粉体の製造方法に関する。
　本願は、２０１７年１０月３１日に、日本に出願された特願２０１７－２１１１９５号に基づき優先権を主張し、その内容をここに援用する。 The present invention relates to a zinc oxide powder, a dispersion, a cosmetic, and a method for producing zinc oxide powder.
Priority is claimed on Japanese Patent Application No. 2017-211195, filed Oct. 31, 2017, the content of which is incorporated herein by reference.
　酸化亜鉛粉体は、紫外線遮蔽機能やガス透過抑制機能等を有し、かつ透明性も高い。このため、紫外線遮蔽フィルム、紫外線遮蔽ガラス、化粧料やガスバリアフィルム等、透明性が必要な用途に用いられている（例えば、特許文献１～特許文献７参照）。 Zinc oxide powder has an ultraviolet shielding function, a gas permeation suppressing function, and the like, and also has high transparency. Therefore, they are used in applications requiring transparency, such as ultraviolet shielding films, ultraviolet shielding glasses, cosmetics, and gas barrier films (see, for example, Patent Documents 1 to 7).
　また、酸化亜鉛粉体は、皮脂を固化させることによって皮脂の広がりを抑制できる。このため、ファンデーション等に使用することで、皮脂による化粧崩れを抑制できることが知られている（例えば、特許文献８参照）。 Moreover, zinc oxide powder can suppress spreading of sebum by solidifying sebum. For this reason, it is known that makeup collapse by sebum can be suppressed by using for foundation etc. (for example, refer to patent documents 8).
特開昭５７－２０５３１９号公報Japanese Patent Application Laid-Open No. 57-205319 特開昭６０－２５５６２０号公報Japanese Patent Application Laid-Open No. 60-255620 特開昭６３－２８８９１３号公報Japanese Patent Application Laid-Open No. 63-288913 特開昭６３－２８８９１４号公報Japanese Patent Application Laid-Open No. 63-288914 特開平３－１９９１２１号公報Unexamined-Japanese-Patent No. 3-199121 特開平７－２３２９１９号公報Japanese Patent Application Laid-Open No. 7-232919 特開２００２－２０１３８２号公報Japanese Patent Application Publication No. 2002-201382 特開２０１１－２６２６４号公報JP, 2011-26264, A
　しかしながら、酸化亜鉛粉体が皮脂を固化するまでには一定以上の時間を要するため、酸化亜鉛粉体のみで化粧崩れを抑制することは困難であった。 However, since it takes a certain amount of time or more for the zinc oxide powder to solidify the sebum, it has been difficult to suppress makeup breakdown with only the zinc oxide powder.
　本発明は、上記事情に鑑みてなされたものであって、皮脂が固化する時間を従来よりも短縮できる酸化亜鉛粉体、並びに、酸化亜鉛粉体を含む分散液、化粧料、および酸化亜鉛粉体の製造方法を提供することを目的とする。 The present invention has been made in view of the above-mentioned circumstances, and zinc oxide powder capable of shortening the time for which sebum solidifies more than before, and dispersion liquid containing zinc oxide powder, cosmetics, and zinc oxide powder The purpose is to provide a method of manufacturing the body.
　すなわち、本発明の第一の態様である酸化亜鉛粉体は、Ｘ線光電子分光法により測定される酸化亜鉛粉体のＳ－Ｏ結合状態のＳが、０．１ａｔｍ％以上かつ１．０ａｔｍ％以下である。 That is, in the zinc oxide powder according to the first aspect of the present invention, S in the S—O bonded state of the zinc oxide powder measured by X-ray photoelectron spectroscopy is 0.1 atm% or more and 1.0 atm%. It is below.
　本発明の第二の態様である分散液は、本発明の第一の態様の酸化亜鉛粉体と、分散媒と、を含有する。 The dispersion liquid which is the 2nd aspect of this invention contains the zinc oxide powder of the 1st aspect of this invention, and a dispersion medium.
　本発明の第三の態様である化粧料は、本発明の第一の態様の酸化亜鉛粉体および本発明の第二の態様の分散液からなる群から選択される少なくとも１種と、化粧品基剤原料と、を含有する。 The cosmetic according to the third aspect of the present invention comprises at least one selected from the group consisting of the zinc oxide powder of the first aspect of the present invention and the dispersion according to the second aspect of the present invention, and a cosmetic base And an agent raw material.
　本発明の第四の態様の酸化亜鉛粉体の製造方法は、酸化亜鉛粉体と、ＳＯ４を含む水溶液と、を混合する工程を有する。 The method for producing zinc oxide powder according to the fourth aspect of the present invention comprises the steps of mixing zinc oxide powder and an aqueous solution containing SO 4 .
　本発明の第一の態様の酸化亜鉛粉体によれば、Ｘ線光電子分光法により測定される、Ｓ－Ｏ結合状態のＳの割合を、０．１ａｔｍ％以上かつ１．０ａｔｍ％以下としたため、皮脂の固化に要する時間を短縮することができる。 According to the zinc oxide powder of the first aspect of the present invention, the proportion of S in the S—O bond state is 0.1 atm% or more and 1.0 atm% or less, which is measured by X-ray photoelectron spectroscopy. The time required for solidification of sebum can be shortened.
　本発明の第二の態様の分散液によれば、本発明の酸化亜鉛粉体と、分散媒と、を含有するため、皮脂の固化に要する時間を短縮することができる。 According to the dispersion liquid of the second aspect of the present invention, since the zinc oxide powder of the present invention and the dispersion medium are contained, the time required for solidification of sebum can be shortened.
　本発明の第三の態様の化粧料によれば、本発明の第一の態様の酸化亜鉛粉体および本発明の第二の態様の分散液からなる群から選択される少なくとも１種と、化粧品基剤原料と、を含有するため、化粧崩れをより抑制することができる。 According to the cosmetic of the third aspect of the present invention, at least one selected from the group consisting of the zinc oxide powder of the first aspect of the present invention and the dispersion of the second aspect of the present invention, and cosmetics Since the base material is contained, makeup breakdown can be further suppressed.
　本発明の第四の態様の酸化亜鉛粉体の製造方法によれば、皮脂固化性に優れる酸化亜鉛粉体を作製することができる。 According to the method for producing zinc oxide powder of the fourth aspect of the present invention, zinc oxide powder excellent in sebum solidifying property can be produced.
　本発明の好ましい例である、本実施形態の酸化亜鉛粉体、分散液、化粧料および酸化亜鉛粉体の製造方法について以下に説明する。
　なお、以下の例は、発明の趣旨をより良く理解させるために具体的に説明するものであり、特に指定のない限り、本発明を限定するものではない。本発明の趣旨を逸脱しない範囲で、変更、省略、置換、追加、その他の変更が可能である。 The zinc oxide powder, the dispersion, the cosmetic and the method for producing the zinc oxide powder of the present embodiment, which are preferable examples of the present invention, will be described below.
The following examples are specifically described for better understanding of the gist of the invention, and do not limit the present invention unless otherwise specified. Modifications, omissions, substitutions, additions, and other modifications are possible without departing from the spirit of the present invention.
［酸化亜鉛粉体］
　本実施形態の酸化亜鉛粉体は、Ｘ線光電子分光法により測定される、Ｓ－Ｏ結合状態のＳが、０．１ａｔｍ％以上かつ１．０ａｔｍ％以下である。この特徴により、本実施形態の酸化亜鉛粉体は、化粧料に用いた場合に、皮脂の固化に要する時間を短縮することができる。 [Zinc oxide powder]
In the zinc oxide powder of the present embodiment, S in an S—O bond state measured by X-ray photoelectron spectroscopy is 0.1 atm% or more and 1.0 atm% or less. Due to this feature, the zinc oxide powder of the present embodiment can shorten the time required for solidification of sebum when used in cosmetics.
　本発明者等は、Ｘ線光電子分光法により測定されるＳ－Ｏ結合状態のＳが０．１ａｔｍ％以上かつ１．０ａｔｍ％以下となる酸化亜鉛粉体は、皮脂固化時間を短縮できることを見出した。そして、そのような酸化亜鉛粉体は、例えば、ＳＯ４を含む水溶液と、原料としての酸化亜鉛粉体を混合することにより、前記酸化亜鉛粉体の表面に、ＳＯ４を存在（付着）させて得ることができることを見出した。そして本発明を完成するに至った。 The present inventors have found that zinc oxide powder in which S in an S-O bond state measured by X-ray photoelectron spectroscopy is 0.1 atm% or more and 1.0 atm% or less can shorten the sebum solidification time. The Then, such a zinc oxide powder, for example, an aqueous solution containing SO 4, by mixing zinc oxide powder as a raw material, the surface of the zinc oxide powder, in the presence of SO 4 (attached) I found that I could get it. And it came to complete the present invention.
（Ｓ－Ｏ結合状態にあるＳ、およびその測定）
　本実施形態の酸化亜鉛粉体（酸化亜鉛粒子）をＸ線光電子分光法により測定して得られる、Ｓ－Ｏ結合状態のＳの割合（原子百分率）は、０．１ａｔｍ％以上かつ１．０ａｔｍ％以下であり、０．２ａｔｍ％以上かつ０．９ａｔｍ％以下であることが好ましい。
　Ｓが０．１ａｔｍ％以上であることにより、皮脂固化時間を短縮することができる。一方で、Ｓが１．０ａｔｍ％を超えると、酸化亜鉛粉体中の不純物量が多くなるため、好ましくない。 (S in S-O bound state, and its measurement)
The ratio (atomic percentage) of S in S—O bonded state obtained by measuring the zinc oxide powder (zinc oxide particles) of the present embodiment by X-ray photoelectron spectroscopy is 0.1 atm% or more and 1.0 atm % Or less and preferably 0.2 atm% or more and 0.9 atm% or less.
When S is 0.1 atm% or more, sebum solidification time can be shortened. On the other hand, when S exceeds 1.0 atm%, the amount of impurities in the zinc oxide powder increases, which is not preferable.
　Ｘ線光電子分光法により測定される、前記Ｓ－Ｏ結合状態のＳは、例えば、以下の方法で得ることができる。具体的には、走査型Ｘ線光電子分光分析装置（ＸＰＳ：Ｘ－Ｒａｙ　Ｐｈｏｔｏｅｌｅｃｔｒｏｎ　Ｓｐｅｃｔｒｏｓｃｏｐｙ／ＥＳＣＡ：Ｅｌｅｃｔｒｏｎ　Ｓｐｅｃｔｒｏｓｃｏｐｙ　ｆｏｒ　Ｃｈｅｍｉｃａｌ）ＰＨＩ５０００（アルバック・ファイ社製）などを用いて、以下の方法により好ましく測定することができる。
　測定において、Ｘ線源として、ＡｌＫα（モノクロ：５０Ｗ、１５ｋＶ）１４８６．６ｅＶを用いる。分析領域は、０．４×０．４ｍｍ２とする。 The S-bonded state of S, which is measured by X-ray photoelectron spectroscopy, can be obtained, for example, by the following method. Specifically, preferably using a scanning X-ray photoelectron spectroscopy (XPS: X-Ray Photoelectron Spectroscopy / ESCA: Electron Spectroscopy for Chemical) PHI 5000 (manufactured by ULVAC-PHI, Inc.), etc., preferably measure according to the following method. Can.
In the measurement, AlKα (monochrome: 50 W, 15 kV) 1486.6 eV is used as an X-ray source. The analysis area is 0.4 × 0.4 mm 2 .
　まず適当な量の酸化亜鉛粉体を、アルミニウム製の皿に固定し、走査型Ｘ線光電子分光分析装置に導入する。
　次いで、酸化亜鉛粉体の表面について、定性分析（ワイドスペクトルで実施）、を行う。広いエネルギー範囲を走査することで、どのような元素が存在するかをある程度確認できる。
　次いで、前記酸化亜鉛粉体の表面について、前記定性分析で検出された元素（通常は、亜鉛（Ｚｎ）と酸素（Ｏ）が検出）と、測定したい元素である硫黄（Ｓ）と、基準元素である炭素（Ｃ）とについて状態分析（ナロースペクトルで実施）を行う。なお酸化亜鉛粉末の測定では微量の炭素（Ｃ）も観察されることが多いが、大気への暴露による炭化水素系有機物の付着等が原因の一つと考えられる。得られたスペクトルの各ピーク面積から、酸化亜鉛粉体の表面における原子濃度（ａｔｍ％）を算出する。なお、ＣとＳは強度が低いため、エネルギー分解能を落し、感度を優先して測定する。 First, an appropriate amount of zinc oxide powder is fixed on an aluminum pan and introduced into a scanning X-ray photoelectron spectrometer.
Next, qualitative analysis (performed with a wide spectrum) is performed on the surface of the zinc oxide powder. By scanning a wide energy range, it is possible to confirm to some extent what elements are present.
Then, for the surface of the zinc oxide powder, an element detected by the qualitative analysis (usually, zinc (Zn) and oxygen (O) are detected), sulfur (S) which is an element to be measured, and a reference element Perform state analysis (implemented with narrow spectrum) for carbon (C) that is In addition, although a trace amount carbon (C) is also observed in the measurement of zinc oxide powder in many cases, it is thought that one of the causes is adhesion of hydrocarbon-based organic substances due to exposure to the air. The atomic concentration (atm%) on the surface of the zinc oxide powder is calculated from each peak area of the obtained spectrum. In addition, since C and S are low in intensity, energy resolution is lowered and sensitivity is prioritized and measured.
　状態分析（ナロースペクトル）において、Ｏは、Ｏ１ｓ（５２５ｅＶ～５４０ｅＶ）について測定する。Ｚｎは、Ｚｎ２ｐ（１０１５ｅＶ～１０３０ｅＶ）について測定する。Ｓは、Ｓ２ｐ（１６０ｅＶ～１７５ｅＶ）について測定する。Ｃは、Ｃ１ｓ（２８０ｅＶ～２９５ｅＶ）について測定する。定性分析（ワイドスペクトル）は、結合エネルギー値を適正な範囲で、例えば０～１１００ｅＶなどで、行うことができる。
　定性分析で検出された元素と、Ｓ、Ｃについて、測定範囲で検出されたピークの面積から、酸化亜鉛粉体の表面における原子濃度を算出する。状態分析と定量計算には、アルバック・ファイ社のハンドブックと相対感度係数を用いる。 In the state analysis (narrow spectrum), O is measured for O1s (525 eV to 540 eV). Zn is measured for Zn2p (1015 eV to 1030 eV). S is measured for S2p (160 eV to 175 eV). C is measured for C1s (280 eV to 295 eV). Qualitative analysis (wide spectrum) can be performed with binding energy values in an appropriate range, for example, 0 to 1100 eV.
The atomic concentration on the surface of the zinc oxide powder is calculated from the area of the peaks detected in the measurement range for the elements detected by qualitative analysis and S and C. We use ULVAC-PHI's handbook and relative sensitivity factors for state analysis and quantitative calculations.
（ＳＯ４の含有量）
　本実施形態の酸化亜鉛粉体は、この酸化亜鉛粉体中のＳＯ４の含有量が１００ｐｐｍ以上かつ１００００ｐｐｍ以下であることが好ましい。ＳＯ４は、酸化亜鉛粉体や、前記粉体中の酸化亜鉛粒子に、どのような状態で存在していても良い。例えば、表面のみにあっても良いし、表面だけでなく粒子の内部に入っていても良い。これらの状態は、製造条件等でコントロールしてよい。なおＳＯ４は、硫酸塩などの化合物を構成する一部であっても良く、ＳＯ４ ２－などのイオン状態であってもよく、粒子表面の亜鉛原子等と結合していても良い。また前記ＳＯ４の含有量は、製造に使用されて最終生成物の中や表面に残った、硫酸や硫酸塩などの化合物の分子構造中のＳＯ４に、主に起因する値であっても良い。
　ＳＯ４の含有量が上記範囲であることにより、皮脂固化性に優れた酸化亜鉛粉体を得ることができる。 (Content of SO 4 )
In the zinc oxide powder of the present embodiment, the content of SO 4 in the zinc oxide powder is preferably 100 ppm or more and 10000 ppm or less. SO 4 may be present in any state in zinc oxide powder or zinc oxide particles in the powder. For example, it may be on the surface only, or may be inside the particle as well as the surface. These states may be controlled by manufacturing conditions and the like. SO 4 may be a part constituting a compound such as a sulfate, may be in an ionic state such as SO 4 2-, or may be bonded to a zinc atom or the like on the particle surface. The content of the SO 4 is used in the preparation remained in or surface of the final product, the SO 4 in the molecular structure of the compounds such as sulfuric acid or sulfates, be a value attributed mainly good.
When the content of SO 4 is in the above range, zinc oxide powder excellent in sebum solidifying property can be obtained.
　酸化亜鉛粉体中のＳＯ４の含有量は、ＩＣＰ発光分光分析装置で測定することができる。
　なお本実施形態の酸化亜鉛粉体の例として、酸化亜鉛粒子を含み、更に、この粒子の表面上、表面付近、及び／または、粒子中に、硫酸亜鉛、硫酸ベリリウム、硫酸マグネシウム、硫酸カルシウム、硫酸ストロンチウム、硫酸バリウム、硫酸アルミニウム、硫酸セリウム、硫酸ナトリウム、硫酸カリウム、及び硫酸アンモニウムからなる群から選択される、少なくとも一つの硫酸塩を含む、酸化亜鉛粉体を好ましく挙げられる。前記硫酸塩が、硫酸亜鉛、硫酸マグネシウム、または硫酸カルシウムであることも好ましい。これらの粉体は、ＳＯ４の含有量が１００ｐｐｍ以上かつ１００００ｐｐｍ以下であることも好ましい。
　例えば、本実施形態では、酸化亜鉛粉体中のＳＯ４の含有量が１００ｐｐｍ以上かつ１００００ｐｐｍ以下であり、前記酸化亜鉛粉体が、前記硫酸塩を粒子表面上又は表面近傍に含む前記酸化亜鉛粒子を含み、前記硫酸塩は分子構造中にＳＯ４を含み、前記硫酸塩のＳＯ４の量が前記酸化亜鉛粉体中のＳＯ４の含有量に含まれる、酸化亜鉛粉体も好ましく使用できる。前記硫酸塩は、酸化亜鉛粉体の製造に使用される材料、例えばＳＯ４を含む水溶液の製造に用いられる物質に起因しても良い。なお本発明の酸化亜鉛粉体は、上記例の酸化亜鉛粉体のみに限定されない。 The content of SO 4 in the zinc oxide powder can be measured by an ICP emission spectrometer.
As an example of the zinc oxide powder of the present embodiment, zinc oxide particles are included, and further, zinc sulfate, beryllium sulfate, magnesium sulfate, calcium sulfate, on the surface, near the surface, and / or in the particles of the particles. Preferred are zinc oxide powders comprising at least one sulfate selected from the group consisting of strontium sulfate, barium sulfate, aluminum sulfate, cerium sulfate, sodium sulfate, potassium sulfate and ammonium sulfate. It is also preferred that the sulfate is zinc sulfate, magnesium sulfate or calcium sulfate. It is also preferable that these powders have an SO 4 content of 100 ppm or more and 10000 ppm or less.
For example, in the present embodiment, the content of SO 4 in the zinc oxide powder is 100 ppm or more and 10000 ppm or less, and the zinc oxide powder contains the sulfate salt on the particle surface or in the vicinity of the surface And zinc oxide powder, wherein the sulfate contains SO 4 in the molecular structure, and the amount of SO 4 in the sulfate is included in the content of SO 4 in the zinc oxide powder. The sulfate may be attributable to the material used to make the zinc oxide powder, such as the material used to make the aqueous solution containing SO 4 . The zinc oxide powder of the present invention is not limited to only the zinc oxide powder of the above example.
（酸化亜鉛粉体の特性について）
　本実施形態の酸化亜鉛粉体、好ましくは、ＳＯ４を含む水溶液と、原料としての酸化亜鉛粉体を混合することで得られた酸化亜鉛粉体は、Ｘ線光電子分光法により測定して得られるＳ－Ｏ結合状態のＳが上記範囲であるので、皮脂が固化するまでに要する時間を短縮できる。しかしながら、このメカニズムの詳細は不明である。しかしながら、次のように推測される。
　ＳＯ４を含む水溶液と酸化亜鉛粉体を混合すれば、ＳＯ４、またはＳＯ４を含む化合物が、酸化亜鉛粉体の表面に均一に存在することとなる。この酸化亜鉛粉体表面に存在するＳＯ４が反応点となり、酸化亜鉛と脂肪酸の反応が促進されるため、皮脂を固化する時間を短縮することができると考えられる。なお前記水溶液中のＳＯ４は、ＳＯ４ ２－等のイオンとして水溶液中に含まれてもよく、又は水溶液中の化合物を構成する一部として含まれても良い。 (On the characteristics of zinc oxide powder)
The zinc oxide powder of the present embodiment, preferably, the zinc oxide powder obtained by mixing the aqueous solution containing SO 4 and the zinc oxide powder as a raw material is obtained by measurement by X-ray photoelectron spectroscopy. Since S in the SO-bonded state to be treated is in the above range, the time required for the sebum to solidify can be shortened. However, the details of this mechanism are unknown. However, it is inferred as follows.
When the aqueous solution containing SO 4 and the zinc oxide powder are mixed, SO 4 or a compound containing SO 4 is uniformly present on the surface of the zinc oxide powder. Since SO 4 present on the surface of the zinc oxide powder serves as a reaction point to accelerate the reaction between zinc oxide and fatty acid, it is considered that the time for solidifying sebum can be shortened. The SO 4 in the aqueous solution may be contained in the aqueous solution as an ion such as SO 4 2- or may be contained as a part constituting a compound in the aqueous solution.
　皮脂固化性については、皮脂成分の中でも、化粧崩れの原因となる油分である脂肪酸（主にオレイン酸）についてはこれらを固化させ、一方で、皮脂中のエモリエント成分や、化粧料中に含まれる油分についてはこれらを固化させないという、選択性があることが好ましいことが知られている（Ｆｒａｇｒａｎｃｅ　Ｊｏｕｒｎａｌ，２０１５年１２月号、４２頁～４６頁）。
　本実施形態の酸化亜鉛粉体は、理由は明確でないが、オレイン酸の固化性に優れる。一方、本実施形態の酸化亜鉛粉体は、化粧料中に油分として一般的に配合されているシクロペンタシロキサン、トリ（カプリル酸／カプリン酸）グリセリル、スクワラン、およびオリーブオイル等については固化性を有さない。すなわち、本実施形態の酸化亜鉛粉体は、脂肪酸（オレイン酸）を選択的に固化できる効果も得られる。 Among sebum components, fatty acids (mainly oleic acid), which are oil components causing makeup breakdown, are solidified among sebum components, while they are contained in emollient components in sebum and cosmetics. It is known that preference is given to oil components that do not solidify them (Fragrance Journal, December 2015, pages 42-46).
The zinc oxide powder of the present embodiment is excellent in the solidifying property of oleic acid, though the reason is not clear. On the other hand, the zinc oxide powder of the present embodiment has solidifying properties for cyclopentasiloxane, tri (caprylic acid / capric acid) glyceryl, squalane, olive oil, etc. which are generally blended as oils in cosmetics. Do not have. That is, the zinc oxide powder of the present embodiment also has an effect of being able to selectively solidify a fatty acid (oleic acid).
（酸化亜鉛粉体の比表面積）
　本実施形態の酸化亜鉛粉体の比表面積は、求められる特性に応じて任意に選択可能である。例えば、透明性の観点からは、比表面積が８ｍ２／ｇ以上かつ６５ｍ２／ｇ以下であることが好ましく、１５ｍ２／ｇ以上かつ６０ｍ２／ｇ以下であることがより好ましく、２０ｍ２／ｇ以上かつ５０ｍ２／ｇ以下であることがさらに好ましく、２５ｍ２／ｇ以上かつ４５ｍ２／ｇ以下であることが最も好ましい。
　酸化亜鉛粉体の比表面積が上記範囲であることにより、この酸化亜鉛粉体を含有する分散液や、化粧料の透明性を高くすることができる。 (Specific surface area of zinc oxide powder)
The specific surface area of the zinc oxide powder of the present embodiment can be arbitrarily selected according to the required characteristics. For example, from the viewpoint of transparency, it is preferable that the specific surface area is less than 8m 2 / g or more and 65 m 2 / g, more preferably 15 m 2 / g or more and 60 m 2 / g or less, 20 m 2 / More preferably, it is g or more and 50 m 2 / g or less, and most preferably 25 m 2 / g or more and 45 m 2 / g or less.
When the specific surface area of the zinc oxide powder is in the above range, the transparency of the dispersion containing the zinc oxide powder and cosmetics can be increased.
　一方、酸化亜鉛粉体の感触を向上させる観点からは、１ｍ２／ｇ以上かつ８ｍ２／ｇであることが好ましく、２ｍ２／ｇ以上かつ７ｍ２／ｇ以下であることがより好ましく、３ｍ２／ｇ以上かつ７ｍ２／ｇ以下であることがさらに好ましい。
　酸化亜鉛粉体の比表面積が上記範囲であることにより、この酸化亜鉛粉体を含有する化粧料の感触を向上することができる。 On the other hand, from the viewpoint of improving the feel of the zinc oxide powder is preferably 1 m 2 / g or more and 8m 2 / g, more preferably 2m 2 / g or more and 7m 2 / g or less, 3m More preferably, it is 2 / g or more and 7 m 2 / g or less.
When the specific surface area of the zinc oxide powder is in the above range, the feel of a cosmetic containing this zinc oxide powder can be improved.
　したがって、分散液や化粧料に求められる透明性や感触を考慮して、酸化亜鉛粉体の比表面積を選択することが好ましい。 Therefore, it is preferable to select the specific surface area of the zinc oxide powder in consideration of the transparency and feel required for the dispersion liquid and the cosmetic.
（酸化亜鉛粉体における比表面積の測定）
　本実施形態において、酸化亜鉛粉体における比表面積とは、ＢＥＴ法により測定された値を意味する。比表面積の測定に用いられる装置としては、例えば、全自動比表面積測定装置（商品名：Ｍａｃｓｏｒｂ　ＨＭ　Ｍｏｄｅｌ－１２０１、マウンテック社製）が挙げられる。 (Measurement of specific surface area of zinc oxide powder)
In the present embodiment, the specific surface area of the zinc oxide powder means a value measured by the BET method. Examples of the apparatus used for measuring the specific surface area include a fully automatic specific surface area measuring apparatus (trade name: Macsorb HM Model-1201, manufactured by Mountech Co., Ltd.).
　本実施形態の酸化亜鉛粉体によれば、Ｘ線光電子分光法により測定されるＳ－Ｏ結合状態のＳを０．１ａｔｍ％以上かつ１．０ａｔｍ％以下としたため、化粧料に用いた場合に、皮脂の固化に要する時間を短縮することができる。 According to the zinc oxide powder of the present embodiment, since S in an S-O bonded state measured by X-ray photoelectron spectroscopy is 0.1 atm% or more and 1.0 atm% or less, when used in cosmetics The time required for solidification of sebum can be shortened.
［酸化亜鉛粉体の製造方法］
　本実施形態の酸化亜鉛粉体の製造方法は、酸化亜鉛粉体と、ＳＯ４を含む水溶液とを混合する工程を有する。 [Method of producing zinc oxide powder]
The method for producing zinc oxide powder of the present embodiment includes the step of mixing zinc oxide powder and an aqueous solution containing SO 4 .
　酸化亜鉛粉体としては、化粧料で用いられる高純度な酸化亜鉛粉体を用いることが好ましい。高純度の酸化亜鉛粉体を用いることで、酸化亜鉛粉体中における不純物量の増加を抑制することができる。
　酸化亜鉛粉体中に不純物量が多い場合には、酸化亜鉛粉体を純水やアルコール等で洗浄してから用いればよい。 As zinc oxide powder, it is preferable to use high purity zinc oxide powder used in cosmetics. By using zinc oxide powder of high purity, an increase in the amount of impurities in the zinc oxide powder can be suppressed.
When the amount of impurities in the zinc oxide powder is large, the zinc oxide powder may be used after being washed with pure water or alcohol.
　ＳＯ４を含む水溶液とは、ＳＯ４を含んでいれば特に限定されない。ＳＯ４を含む水溶液は、例えば、ＳＯ４を含む化合物を水に溶解することにより得ることができる。ＳＯ４を含む化合物としては、例えば、硫酸や硫酸塩を、単独で又は２種以上を組み合わせて、用いることができる。 The aqueous solution containing SO 4, not particularly limited as long as it contains a SO 4. An aqueous solution containing SO 4 can be obtained, for example, by dissolving a compound containing SO 4 in water. As a compound containing SO 4 , for example, sulfuric acid or sulfate can be used alone or in combination of two or more.
　硫酸塩としては、特に限定されないが、例えば、硫酸亜鉛、硫酸ベリリウム、硫酸マグネシウム、硫酸カルシウム、硫酸ストロンチウム、硫酸バリウム、硫酸アルミニウム、硫酸セリウム、硫酸ナトリウム、硫酸カリウム、及び硫酸アンモニウム等が挙げられる。これら硫酸塩はＳＯ４を分子構造中に含む。
　皮脂固化時間がより短縮する点において、硫酸亜鉛、硫酸マグネシウム、硫酸カルシウムを用いることが好ましい。 The sulfate is not particularly limited, and examples thereof include zinc sulfate, beryllium sulfate, magnesium sulfate, calcium sulfate, strontium sulfate, barium sulfate, aluminum sulfate, cerium sulfate, sodium sulfate, potassium sulfate and ammonium sulfate. These sulfates contain SO 4 in the molecular structure.
It is preferable to use zinc sulfate, magnesium sulfate, and calcium sulfate in that the sebum solidification time is further shortened.
　ＳＯ４を含む水溶液の濃度は、硫酸塩の溶解度の範囲内で、Ｘ線光電子分光法により測定される、得られる酸化亜鉛粉体のＳ－Ｏ結合状態のＳが、上記範囲となるように調整すればよく、特に限定されない。例えば、硫酸塩の濃度が０．０１質量％以上かつ５０質量％以下の水溶液を用いることができる。好ましい混合の例としては、前記水溶液と、原料としての酸化亜鉛粉体を、酸化亜鉛とＳＯ４を含む化合物が質量比で、１：０．００１～１：０．１の範囲となるように、混合すればよい。 The concentration of the aqueous solution containing SO 4 is such that S in the S—O bonded state of the resulting zinc oxide powder, as measured by X-ray photoelectron spectroscopy, within the range of solubility of sulfate, falls within the above range It may be adjusted and is not particularly limited. For example, an aqueous solution having a concentration of sulfate of 0.01% by mass or more and 50% by mass or less can be used. As a preferable example of mixing, the above-mentioned aqueous solution and zinc oxide powder as a raw material are prepared such that the mass ratio of zinc oxide and a compound containing SO 4 is in the range of 1: 0.001 to 1: 0.1. , Just mix it.
　原料としての酸化亜鉛粉体と、ＳＯ４を含む水溶液とを混合する方法としては、酸化亜鉛粉体の表面に、ＳＯ４を含む化合物が均一に存在（付着）するように混合する方法であればよく、特に限定されない。例えば、ＳＯ４を含む水溶液中で、酸化亜鉛粉体を撹拌してもよいし、ＳＯ４を含む水溶液をスプレーで酸化亜鉛粉体（粒子）に吹き付け、その酸化亜鉛粉体をヘンシェルミキサーで撹拌してもよい。 As a method of mixing zinc oxide powder as a raw material and an aqueous solution containing SO 4 , it is possible to use a method of mixing so that a compound containing SO 4 uniformly exists (adheres) on the surface of zinc oxide powder. There is no particular limitation. For example, in an aqueous solution containing SO 4, it may be stirred zinc oxide powder, spraying an aqueous solution containing SO 4 in the zinc oxide powder (particle) in a spray, stirring the zinc oxide powder in a Henschel mixer You may
　本実施形態の酸化亜鉛粉体の製造方法は、ＳＯ４を含む水溶液と混合した後の酸化亜鉛粉体を、乾燥する工程をさらに有していてもよい。
　混合後の酸化亜鉛粉体は、自然乾燥させてもよいし、乾燥機により８０℃～１５０℃の温度で乾燥させてもよい。
　以上の工程により、本実施形態の酸化亜鉛粉体を作製することができる。なお本実施形態の酸化亜鉛粉体の表面にあってよいＳＯ４を含む化合物は、本実施形態の酸化亜鉛粉体の製造に用いることができるＳＯ４を含む化合物と、同じであっても、異なっていても良い。 The method for producing the zinc oxide powder of the present embodiment may further include the step of drying the zinc oxide powder after being mixed with the aqueous solution containing SO 4 .
The mixed zinc oxide powder may be naturally dried or may be dried at a temperature of 80 ° C. to 150 ° C. by a dryer.
The zinc oxide powder of the present embodiment can be produced by the above steps. The compound containing SO 4 that may be present on the surface of the zinc oxide powder of the present embodiment is the same as the compound containing SO 4 that can be used for producing the zinc oxide powder of the present embodiment, It may be different.
　なお、本実施形態では、酸化亜鉛粉体と、ＳＯ４を含む水溶液とを混合した。しかし、本実施形態の酸化亜鉛粉体の製造方法は、これのみに限定されない。例えば、酸化亜鉛粉体（酸化亜鉛粒子）の表面にＳＯ４を含む化合物が存在（付着）させることができればよい。このため、目的の酸化亜鉛粉体の作製工程のどこかの段階で、ＳＯ４を、すなわちＳＯ４を構造中に含む化合物及び／又はＳＯ４イオンを含む材料を、酸化亜鉛粉体を形成するための原料に、混合してもよいと推測される。
　したがって、気相法で酸化亜鉛粉体を作製する場合には、ＳＯ４を含むガスと、亜鉛を含むガスを混合することにより、本実施形態の酸化亜鉛粉体が得られると推測される。
　また、熱分解法で酸化亜鉛粉体を作製する場合には、酸化亜鉛粉体の原料（シュウ酸亜鉛、水酸化亜鉛、炭酸亜鉛、塩基性炭酸亜鉛等）と、ＳＯ４を含む水溶液を混合することにより、本実施形態の酸化亜鉛粉体が得られると推測される。 In the present embodiment, zinc oxide powder and an aqueous solution containing SO 4 were mixed. However, the method for producing the zinc oxide powder of the present embodiment is not limited to this. For example, a compound containing SO 4 may be present (adhered) on the surface of zinc oxide powder (zinc oxide particles). Therefore, at some stage of the manufacturing process of the zinc oxide powder of interest, a SO 4, i.e. a compound containing SO 4 in the structure and / or a material containing SO 4 ions to form zinc oxide powder It is speculated that the ingredients may be mixed.
Therefore, when producing zinc oxide powder by a vapor phase method, it is speculated that the zinc oxide powder of the present embodiment can be obtained by mixing a gas containing SO 4 and a gas containing zinc.
Moreover, when producing zinc oxide powder by a thermal decomposition method, a raw material (zinc oxalate, zinc hydroxide, zinc carbonate, basic zinc carbonate, etc.) of zinc oxide powder and an aqueous solution containing SO 4 are mixed. By doing this, it is presumed that the zinc oxide powder of the present embodiment can be obtained.
　本実施形態の酸化亜鉛粉体の製造方法によれば、化粧料に用いた場合に、皮脂固化性に優れる酸化亜鉛粉体を作製することができる。 According to the method for producing the zinc oxide powder of the present embodiment, when used in a cosmetic, it is possible to produce a zinc oxide powder having excellent sebum solidifying properties.
［表面処理された酸化亜鉛粉体］
　本実施形態の酸化亜鉛粉体は、その表面の少なくとも一部が、無機成分および有機成分の少なくとも一方で表面処理されていてもよい。
前記少なくとも一部が表面処理された酸化亜鉛粉体の、Ｓ－Ｏ結合状態のＳの原子濃度は、前記範囲内である。原料である酸化亜鉛粉体とＳＯ４を含む水溶液とを混合する処理の後に表面処理をする工程を加えることが好ましい。
このように無機成分および有機成分の少なくとも一方で表面処理されている酸化亜鉛粉体を、表面処理酸化亜鉛粉体と言う。表面処理酸化亜鉛粉体は、酸化亜鉛の表面活性をより抑制することができ、また、分散媒への分散性を向上することができる。
　無機成分と有機成分は、酸化亜鉛粉体の用途に応じて、適宜選択される。 [Surface-treated zinc oxide powder]
At least a part of the surface of the zinc oxide powder of the present embodiment may be surface-treated with at least one of an inorganic component and an organic component.
The atomic concentration of S in the S—O bonded state of the at least partially surface-treated zinc oxide powder is within the above range. It is preferable to add a step of the surface treatment after the process of mixing the aqueous solution containing zinc oxide powder and SO 4 as a raw material.
The zinc oxide powder thus surface-treated with at least one of the inorganic component and the organic component is referred to as a surface-treated zinc oxide powder. The surface-treated zinc oxide powder can further suppress the surface activity of zinc oxide, and can improve the dispersibility in the dispersion medium.
An inorganic component and an organic component are suitably selected according to the use of zinc oxide powder.
　表面処理酸化亜鉛粉体が、化粧料に用いられる場合、表面処理に用いられる無機成分および有機成分は、特に限定されない。無機成分および有機成分としては、一般的に化粧料に用いられる表面処理剤が挙げられる。
　無機成分としては、例えば、シリカ、アルミナ等が挙げられる。これらの無機成分は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 When the surface-treated zinc oxide powder is used in a cosmetic, the inorganic component and the organic component used for the surface treatment are not particularly limited. As an inorganic component and an organic component, the surface treatment agent generally used for cosmetics is mentioned.
Examples of the inorganic component include silica, alumina and the like. One of these inorganic components may be used alone, or two or more thereof may be used in combination.
　有機成分としては、例えば、シリコーン化合物、オルガノポリシロキサン、脂肪酸、脂肪酸石鹸、脂肪酸エステル、ポリオレフィン、Ｎ－アシルアミノ酸またはその塩、Ｎ－アシル－Ｎ－アルキルアミノ酸またはその塩、水添レシチンまたはその塩、および有機チタネート化合物からなる群から選択される少なくとも１種が挙げられる。これらの有機成分は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Examples of the organic component include silicone compounds, organopolysiloxanes, fatty acids, fatty acid soaps, fatty acid esters, polyolefins, N-acyl amino acids or salts thereof, N-acyl-N-alkyl amino acids or salts thereof, hydrogenated lecithin or salts thereof And at least one selected from the group consisting of organic titanate compounds. One of these organic components may be used alone, or two or more of these organic components may be used in combination.
　また、無機成分や有機成分としては、界面活性剤を用いてもよい。
　このような無機成分および有機成分から選択される少なくとも１種を使用して、酸化亜鉛粉体を表面処理した場合、酸化亜鉛の表面活性を抑制したり、酸化亜鉛粉体の分散媒への分散性を向上したりすることができる。 Moreover, you may use surfactant as an inorganic component and an organic component.
When zinc oxide powder is surface-treated using at least one selected from such inorganic components and organic components, the surface activity of zinc oxide is suppressed, or the zinc oxide powder is dispersed in a dispersion medium. It is possible to improve the
　表面処理に用いられるシリコーン化合物としては、例えば、メチルハイドロジェンポリシロキサン、ジメチルポリシロキサン、メチルフェニルポリシロキサン等のシリコーンオイル；メチルトリメトキシシラン、エチルトリメトキシシラン、ヘキシルトリメトキシシラン、オクチルトリメトキシシラン、オクチルトリエトキシシラン等のアルキルシラン；トリフルオロメチルエチルトリメトキシシラン、ヘプタデカフルオロデシルトリメトキシシラン等のフルオロアルキルシラン、メチコン、ジメチコン、ハイドロゲンジメチコン、トリエトキシシリルエチルポリジメチルシロキシエチルジメチコン、トリエトキシシリルエチルポリジメチルシロキシエチルヘキシルジメチコン、（アクリレーツ／アクリル酸トリデシル／メタクリル酸トリエトキシシリルプロピル／メタクリル酸ジメチコン）コポリマー、トリエトキシカプリリルシラン等が挙げられる。 Examples of silicone compounds used for surface treatment include silicone oils such as methylhydrogenpolysiloxane, dimethylpolysiloxane and methylphenylpolysiloxane; methyltrimethoxysilane, ethyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane Alkylsilanes such as octyltriethoxysilane; fluoroalkylsilanes such as trifluoromethylethyltrimethoxysilane and heptadecafluorodecyltrimethoxysilane; methicone, dimethicone, hydrogen dimethicone, triethoxysilylethyl polydimethylsiloxyethyl dimethicone, triethoxy Silylethyl polydimethylsiloxyethyl hexyl dimethicone, (acreates / tridecyl acrylate / tri methacrylate) Butoxy silylpropyl / methacrylic acid dimethicone) copolymer, triethoxysilane caprylyl silane, and the like.
　これらのシリコーン化合物は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
　また、シリコーン化合物としては、これらのシリコーン化合物の共重合体を用いてもよい。
　これらのシリコーン化合物の中でも、酸化亜鉛粉体の皮脂固化性をほとんど阻害しない点から、メチコン、ジメチコン、およびハイドロゲンジメチコンが好ましく、ハイドロゲンジメチコンが特に好ましい。 One of these silicone compounds may be used alone, or two or more thereof may be used in combination.
Moreover, as a silicone compound, you may use the copolymer of these silicone compounds.
Among these silicone compounds, methicone, dimethicone and hydrogen dimethicone are preferable, and hydrogen dimethicone is particularly preferable, from the viewpoint of hardly inhibiting the sebum solidifying property of zinc oxide powder.
　有機成分の例について、さらに説明する。
　脂肪酸としては、例えば、パルミチン酸、イソステアリン酸、ステアリン酸、ラウリン酸、ミリスチン酸、ベヘニン酸、オレイン酸、ロジン酸、１２－ヒドロキシステアリン酸、ポリヒドロキシステアリン酸等が挙げられる。
　脂肪酸石鹸としては、例えば、ステアリン酸アルミニウム、ステアリン酸カルシウム、１２－ヒドロキシステアリン酸アルミニウム等が挙げられる。
　脂肪酸エステルとしては、例えば、デキストリン脂肪酸エステル、コレステロール脂肪酸エステル、ショ糖脂肪酸エステル、デンプン脂肪酸エステル等が挙げられる。 The example of the organic component is further described.
Examples of the fatty acid include palmitic acid, isostearic acid, stearic acid, lauric acid, myristic acid, behenic acid, oleic acid, rosin acid, 12-hydroxystearic acid, polyhydroxystearic acid and the like.
Examples of fatty acid soaps include aluminum stearate, calcium stearate, aluminum 12-hydroxystearate and the like.
Examples of the fatty acid ester include dextrin fatty acid ester, cholesterol fatty acid ester, sucrose fatty acid ester, starch fatty acid ester and the like.
　Ｎ－アシルアミノ酸としては、例えば、Ｎ－ラウロイルグルタミン酸、Ｎ－ミリストイルグルタミン酸、Ｎ－パルミトイルグルタミン酸、Ｎ－ココイルグルタミン酸、Ｎ－ラウロイルリシン、Ｎ－ステアロイルグルタミン酸、ジラウロイルグルタミン酸リシン等が挙げられる。
　Ｎ－アシルアミノ酸の塩としては、Ｎ－アシルアミノ酸のナトリウム塩、カリウム塩、マグネシウム塩、カルシウム塩、アルミニウム塩、亜鉛塩等が挙げられる。
　また、Ｎ－アシルアミノ酸またはその塩の代わりに、ジラウロイルグルタミン酸リシンナトリウムのような、Ｎ－アシルアミノ酸塩を含むジェミニ型両親媒性アミノ酸を用いてもよい。 Examples of N-acyl amino acids include N-lauroyl glutamic acid, N-myristoyl glutamic acid, N-palmitoyl glutamic acid, N-cocoyl glutamic acid, N-lauroyl lysine, N-stearoyl glutamic acid, dilauroyl glutamic acid lysine and the like.
As salts of N-acyl amino acids, sodium salts, potassium salts, magnesium salts, calcium salts, aluminum salts, zinc salts of N-acyl amino acids and the like can be mentioned.
Also, instead of the N-acyl amino acid or a salt thereof, a gemini amphiphilic amino acid including an N-acyl amino acid salt such as lysine sodium dilauroyl glutamate may be used.
　有機チタネート化合物としては、例えば、イソプロピルトリイソステアロイルチタネート、イソプロピルジメタクリルイソステアロイルチタネート、イソプロピルトリ（ドデシル）ベンゼンスルホニルチタネート、ネオペンチル（ジアリル）オキシートリ（ジオクチル）ホスフェイトチタネート、ネオペンチル（ジアリル）オキシートリネオドデカノイルチタネート等が挙げられる。 As an organic titanate compound, for example, isopropyl triisostearoyl titanate, isopropyl dimethacryl isostearoyl titanate, isopropyl tri (dodecyl) benzene sulfonyl titanate, neopentyl (diallyl) oxy-tri (dioctyl) phosphate titanate, neopentyl (diallyl) oxy- trineododeca Noyl titanate etc. are mentioned.
　本実施形態の表面処理酸化亜鉛粉体が、紫外線遮蔽フィルムやガスバリア性フィルム等の工業用途で用いられる場合、化粧料に用いられる無機成分や有機成分の他に、あるいは代わりに、粒子を分散させる際に用いられる一般的な分散剤も、適宜選択して用いることができる。このような分散剤としては、例えば、アニオン系分散剤、カチオン系分散剤、ノニオン系分散剤、シランカップリング剤、湿潤分散剤等が挙げられる。
　このような分散剤を用いた表面処理を行うことにより、酸化亜鉛粉体の表面活性を抑制したり、酸化亜鉛粉体の分散媒への分散性を向上したりすることができる。 When the surface-treated zinc oxide powder of the present embodiment is used in industrial applications such as a UV shielding film or a gas barrier film, particles are dispersed in addition to or instead of the inorganic component and the organic component used in the cosmetic. A common dispersant used in the process can be appropriately selected and used. As such a dispersing agent, an anionic dispersing agent, a cationic dispersing agent, a nonionic dispersing agent, a silane coupling agent, a wetting dispersing agent etc. are mentioned, for example.
By performing surface treatment using such a dispersing agent, the surface activity of the zinc oxide powder can be suppressed, and the dispersibility of the zinc oxide powder in the dispersion medium can be improved.
　表面処理酸化亜鉛粉体の製造方法は、特に限定されず、表面処理に用いる成分に応じて、公知の方法で適宜実施すればよい。 The method for producing the surface-treated zinc oxide powder is not particularly limited, and may be appropriately carried out by a known method according to the components used for the surface treatment.
［分散液］
　本実施形態の分散液は、本実施形態の酸化亜鉛粉体と、分散媒と、を含有する。
　酸化亜鉛粉体は、表面処理酸化亜鉛粉体であってもよい。
　本実施形態の分散液は、皮脂の固化に要する時間を短縮することができる。
　なお、本実施形態の分散液は、粘度が高いペースト状の分散体であってもよい。 [Dispersion liquid]
The dispersion liquid of the present embodiment contains the zinc oxide powder of the present embodiment and a dispersion medium.
The zinc oxide powder may be surface-treated zinc oxide powder.
The dispersion liquid of the present embodiment can shorten the time required for solidification of sebum.
The dispersion liquid of the present embodiment may be a paste-like dispersion having a high viscosity.
　分散液における酸化亜鉛粉体の含有量は、所望の特性に合わせて適宜調整すればよい。
　分散液を化粧料に用いる場合には、分散液における酸化亜鉛粉体の含有量は任意に選択できる。例えば、３０質量％以上かつ９０質量％以下であることが好ましく、４０質量％以上かつ８５質量％以下であることがより好ましく、５０質量％以上かつ８０質量％以下であることがさらに好ましい。
　分散液における酸化亜鉛粉体の含有量を限定することにより、例えば、３０質量％以上かつ９０質量％以下の範囲とすることにより、酸化亜鉛粉体が高濃度で分散液に含有されることができる。そのため、処方の自由度を向上することができるとともに、分散液の粘度を、取り扱いが容易な程度とすることができる。なお、酸化亜鉛粉体の含有量は、前記範囲のみに限定されない。下限の例として、１０質量％や、２０質量％や、４０質量％や６０質量％等を好ましく挙げることができる。上限の例として、９５質量％や、９０質量％や、８５質量％や、７５質量％等を好ましく挙げることができる。 The content of the zinc oxide powder in the dispersion may be appropriately adjusted in accordance with the desired characteristics.
When using a dispersion liquid for cosmetics, content of the zinc oxide powder in a dispersion liquid can be selected arbitrarily. For example, the content is preferably 30% by mass to 90% by mass, more preferably 40% by mass to 85% by mass, and still more preferably 50% by mass to 80% by mass.
By limiting the content of the zinc oxide powder in the dispersion, for example, by setting the content in the range of 30% by mass to 90% by mass, the zinc oxide powder is contained in the dispersion at a high concentration it can. Therefore, the degree of freedom in formulation can be improved, and the viscosity of the dispersion can be made easy to handle. In addition, content of a zinc oxide powder is not limited only to the said range. As an example of a minimum, 10 mass%, 20 mass%, 40 mass%, 60 mass% etc. can be mentioned preferably. As an example of an upper limit, 95 mass%, 90 mass%, 85 mass%, 75 mass% etc. can be mentioned preferably.
　本実施形態の分散液の粘度は任意に選択できる。例えば、５Ｐａ・ｓ以上かつ３００Ｐａ・ｓ以下であることが好ましく、８Ｐａ・ｓ以上かつ１００Ｐａ・ｓ以下であることがより好ましく、１０Ｐａ・ｓ以上かつ８０Ｐａ・ｓ以下であることがさらに好ましく、１５Ｐａ・ｓ以上かつ６０Ｐａ・ｓ以下であることが最も好ましい。
　分散液の粘度が上記範囲であることにより、例えば、固形分（酸化亜鉛粉体）を高濃度に含んでいても、取り扱いが容易な分散液を得ることができる。 The viscosity of the dispersion of the present embodiment can be selected arbitrarily. For example, it is preferably 5 Pa · s or more and 300 Pa · s or less, more preferably 8 Pa · s or more and 100 Pa · s or less, still more preferably 10 Pa · s or more and 80 Pa · s or less, 15 Pa It is most preferable that s or more and 60 Pa · s or less.
When the viscosity of the dispersion is in the above-mentioned range, for example, a dispersion which is easy to handle can be obtained, even when the solid content (zinc oxide powder) is contained at a high concentration.
　分散液に含まれる分散媒は、分散液の用途に応じて、適宜選択される。好適な分散媒を以下に例示するが、分散液における分散媒は、これらのみに限定されない。
　分散媒としては、例えば、水、メタノール、エタノール、１－プロパノール、２－プロパノール、１－ブタノール、２－ブタノール、オクタノール、グリセリン等のアルコール類；酢酸エチル、酢酸ブチル、乳酸エチル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、γ－ブチロラクトン等のエステル類；ジエチルエーテル、エチレングリコールモノメチルエーテル（メチルセロソルブ）、エチレングリコールモノエチルエーテル（エチルセロソルブ）、エチレングリコールモノブチルエーテル（ブチルセロソルブ）、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル等のエーテル類が用いられる。
　これらの分散媒は、１種を単独で用いてもよく、２種以上を混合して用いてもよい。 The dispersion medium contained in the dispersion liquid is appropriately selected according to the application of the dispersion liquid. Although suitable dispersion media are exemplified below, the dispersion media in the dispersion are not limited to these.
As the dispersion medium, for example, alcohols such as water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, octanol, glycerin and the like; ethyl acetate, butyl acetate, ethyl lactate, propylene glycol monomethyl ether Esters such as acetate, propylene glycol monoethyl ether acetate and γ-butyrolactone; diethyl ether, ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (ethyl cellosolve), ethylene glycol monobutyl ether (butyl cellosolve), diethylene glycol monomethyl ether Ethers such as diethylene glycol monoethyl ether are used.
One of these dispersion media may be used alone, or two or more thereof may be mixed and used.
　また、他の分散媒としては、アセトン、メチルエチルケトン、メチルイソブチルケトン、アセチルアセトン、シクロヘキサノン等のケトン類；ベンゼン、トルエン、キシレン、エチルベンゼン等の芳香族炭化水素；シクロヘキサン等の環状炭化水素；ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアセトアミド、Ｎ－メチルピロリドン等のアミド類；ジメチルポリシロキサン、メチルフェニルポリシロキサン、ジフェニルポリシロキサン等の鎖状ポリシロキサン類等が用いられる。
　これらの分散媒は、１種を単独で用いてもよく、２種以上を混合して用いてもよい。 Further, as other dispersion media, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, cyclohexanone and the like; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and the like; cyclic hydrocarbons such as cyclohexane; And amides such as N-dimethylacetoacetamide and N-methylpyrrolidone; linear polysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane and diphenylpolysiloxane; and the like.
One of these dispersion media may be used alone, or two or more thereof may be mixed and used.
　また、他の分散媒としては、オクタメチルシクロテトラシロキサン、デカメチルシクロペンタシロキサン、ドデカメチルシクロヘキサンシロキサン等の環状ポリシロキサン類；アミノ変性ポリシロキサン、ポリエーテル変性ポリシロキサン、アルキル変性ポリシロキサン、フッ素変性ポリシロキサン等の変性ポリシロキサン類等が用いられる。
　これらの分散媒は、１種を単独で用いてもよく、２種以上を混合して用いてもよい。 Further, as other dispersion media, cyclic polysiloxanes such as octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane, dodecamethyl cyclohexane siloxane, etc .; amino-modified polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, fluorine-modified Modified polysiloxanes such as polysiloxane are used.
One of these dispersion media may be used alone, or two or more thereof may be mixed and used.
　また、他の分散媒としては、流動パラフィン、スクワラン、イソパラフィン、分岐鎖状軽パラフィン、ワセリン、セレシン等の炭化水素油、イソプロピルミリステート、セチルイソオクタノエート、グリセリルトリオクタノエート等のエステル油、デカメチルシクロペンタシロキサン、ジメチルポリシロキサン、メチルフェニルポリシロキサン等のシリコーン油、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸等の高級脂肪酸、ラウリルアルコール、セチルアルコール、ステアリルアルコール、ヘキシルドデカノール、イソステアリルアルコール等の高級アルコール等の疎水性の分散媒を用いてもよい。
　これらの分散媒は、１種を単独で用いてもよく、２種以上を混合して用いてもよい。 As other dispersion media, liquid paraffin, squalane, isoparaffin, branched chain light paraffin, hydrocarbon oil such as vaseline and ceresin, ester oil such as isopropyl myristate, cetyl isooctanoate and glyceryl trioctanoate , Silicone oils such as decamethylcyclopentasiloxane, dimethylpolysiloxane and methylphenylpolysiloxane, higher fatty acids such as lauric acid, myristic acid, palmitic acid and stearic acid, lauryl alcohol, cetyl alcohol, stearyl alcohol, hexyl dodecanol, iso A hydrophobic dispersion medium such as a higher alcohol such as stearyl alcohol may be used.
One of these dispersion media may be used alone, or two or more thereof may be mixed and used.
　前述の分散媒は、求められる特性に応じて、任意に組み合わせて用いることが可能である。分散媒の量は任意に選択できるが、例えば、分散液の総量に対して、５質量％以上かつ９０質量％以下が一般的であり、好ましくは１０質量％以上かつ７０質量％以下であり、より好ましくは１５質量％以上かつ６０質量％以下である。 The above-mentioned dispersion media can be used in any combination according to the required properties. The amount of the dispersion medium can be arbitrarily selected, but for example, it is generally 5% by mass or more and 90% by mass or less, preferably 10% by mass or more and 70% by mass or less based on the total amount of the dispersion. More preferably, it is 15% by mass or more and 60% by mass or less.
　本実施形態の分散液は、その特性を損なわない範囲において、一般的に用いられる添加剤を含んでいてもよい。
　添加剤としては、例えば、分散剤、安定剤、水溶性バインダー、増粘剤、油溶性防腐剤、紫外線吸収剤、油溶性薬剤、油溶性色素類、油溶性蛋白質類、植物油、動物油等から選択される少なくとも１つが挙げられる。各添加剤の量は任意に選択できるが、例えば、分散液の総量に対して、０．１質量％以上かつ８０質量％以下が一般的であり、好ましくは０．５質量％以上かつ５０質量％以下であり、より好ましくは１質量％以上かつ４０質量％以下である。その他の例として、必要に応じて、０．１～２質量％であったり、２～５質量％であったり、５～１０質量％であったりしてもよい。 The dispersion of the present embodiment may contain commonly used additives as long as the properties of the dispersion are not impaired.
As the additive, for example, a dispersant, a stabilizer, a water soluble binder, a thickener, an oil soluble preservative, a UV absorber, an oil soluble drug, an oil soluble pigment, an oil soluble protein, a vegetable oil, an animal oil etc. And at least one of the The amount of each additive can be selected arbitrarily, but for example, it is generally 0.1% by mass or more and 80% by mass or less, preferably 0.5% by mass or more and 50% by mass with respect to the total amount of the dispersion. % Or less, more preferably 1% by mass or more and 40% by mass or less. As another example, if necessary, it may be 0.1 to 2% by mass, 2 to 5% by mass, or 5 to 10% by mass.
　分散液の製造方法は、特に限定されない。例えば、酸化亜鉛粉体と、分散媒とを、公知の分散装置で、機械的に分散する方法が挙げられる。
　分散装置としては、例えば、攪拌機、自公転式ミキサー、ホモミキサー、超音波ホモジナイザー、サンドミル、ボールミル、ロールミル等が挙げられる。 The method for producing the dispersion is not particularly limited. For example, a method of mechanically dispersing zinc oxide powder and a dispersion medium with a known dispersing device can be mentioned.
As a dispersion apparatus, a stirrer, a self-revolution type | formula mixer, a homomixer, an ultrasonic homogenizer, a sand mill, a ball mill, a roll mill etc. are mentioned, for example.
　本実施形態の分散液は、化粧料の他、紫外線遮蔽機能やガス透過抑制機能等を有する組成物等に用いることができる。 The dispersion liquid of the present embodiment can be used for a composition having an ultraviolet shielding function, a gas permeation suppressing function, and the like other than cosmetics.
　本実施形態の分散液によれば、本実施形態の酸化亜鉛粉体と、分散媒と、を含有するため、化粧料に用いた場合に、皮脂の固化に要する時間を短縮することができる。 According to the dispersion liquid of the present embodiment, since the zinc oxide powder of the present embodiment and the dispersion medium are contained, the time required for solidification of sebum can be shortened when used for cosmetics.
［化粧料］
　本実施形態の化粧料は、本実施形態の酸化亜鉛粉体および本実施形態の分散液からなる群から選択される少なくとも１種と、化粧品基剤原料と、を含有する。言い換えると、本実施形態の化粧料は、本実施形態の酸化亜鉛粉体と、化粧品基剤原料と、さらに必要に応じて分散媒とを、含有することができる。
　本実施形態の化粧料は、化粧崩れを抑制することができる。 [Cosmetics]
The cosmetic of the present embodiment contains at least one selected from the group consisting of the zinc oxide powder of the present embodiment and the dispersion of the present embodiment, and a cosmetic base material. In other words, the cosmetic of the present embodiment can contain the zinc oxide powder of the present embodiment, a cosmetic base material, and, if necessary, a dispersion medium.
The cosmetic of the present embodiment can suppress makeup collapse.
　ここで、化粧品基剤原料とは、化粧品の本体を形成する諸原料を意味し、任意に選択することができる。化粧品基剤原料としては、例えば、油性原料、水性原料、界面活性剤、及び粉体原料等が挙げられる。これらは必要に応じて組み合わせて使用することができる。 Here, the cosmetic base material means various raw materials forming the main body of the cosmetic, and can be selected arbitrarily. Examples of cosmetic base materials include oily materials, aqueous materials, surfactants, and powder materials. These can be used in combination as needed.
　油性原料としては、例えば、油脂、高級脂肪酸、高級アルコール、エステル油類等が挙げられる。
　水性原料としては、例えば、精製水、アルコール、増粘剤等が挙げられる。
　粉末原料としては、例えば、有色顔料、白色顔料、パール剤、体質顔料等が挙げられる。 As an oil-based raw material, fats and oils, higher fatty acids, higher alcohols, ester oils etc. are mentioned, for example.
Examples of the aqueous material include purified water, alcohol, thickener and the like.
As a powder raw material, a colored pigment, a white pigment, a pearlescent agent, an extender pigment etc. are mentioned, for example.
　本実施形態の化粧料は、例えば、本実施形態の酸化亜鉛粉体や分散液を、乳液、クリーム、ファンデーション、口紅、頬紅、及びアイシャドー等の化粧品基剤原料に、公知の方法で配合することにより、得ることができる。
　また、化粧料は、本実施形態の酸化亜鉛粉体を、油相または水相に配合して、Ｏ／Ｗ型またはＷ／Ｏ型のエマルションとしてから、次に化粧品基剤原料と配合することにより、得ることもできる。 For example, the cosmetic of the present embodiment mixes the zinc oxide powder or the dispersion of the present embodiment with cosmetic base materials such as milk, cream, foundation, lipstick, blush, and eye shadow by a known method. Can be obtained by
In addition, the cosmetic may be prepared by blending the zinc oxide powder of the present embodiment in an oil phase or an aqueous phase, as an O / W type or W / O type emulsion, and then blending with a cosmetic base material. Can also be obtained.
　本実施形態の化粧料における酸化亜鉛粉体の含有量は、所望の特性に応じて、適宜調整すればよい。例えば、酸化亜鉛粉体の含有量の下限は、０．０１質量％以上であってもよく、０．１質量％以上であってもよく、１質量％以上であってもよい。また、酸化亜鉛粉体の含有量の上限は、５０質量％以下であってもよく、４０質量％以下であってもよく、３０質量％以下であってもよい。２０質量％以下や、１０質量％以下や、５質量％以下であってもよい。 The content of the zinc oxide powder in the cosmetic of the present embodiment may be appropriately adjusted according to the desired characteristics. For example, the lower limit of the content of the zinc oxide powder may be 0.01% by mass or more, 0.1% by mass or more, or 1% by mass or more. Further, the upper limit of the content of the zinc oxide powder may be 50% by mass or less, 40% by mass or less, or 30% by mass or less. 20 mass% or less, 10 mass% or less, 5 mass% or less may be sufficient.
　本実施形態の化粧料によれば、本実施形態の酸化亜鉛粉体および本実施形態の分散液からなる群から選択される少なくとも１種と、化粧品基剤原料と、を含有するため、化粧崩れをより抑制することができる。 The cosmetic of the present embodiment contains at least one selected from the group consisting of the zinc oxide powder of the present embodiment and the dispersion of the present embodiment, and a cosmetic base material, so that the cosmetic collapse is caused. Can be further suppressed.
　以下、実施例および比較例により本発明をさらに具体的に説明するが、本発明は以下の実施例のみに限定されるものではない。 Hereinafter, the present invention will be more specifically described by way of examples and comparative examples, but the present invention is not limited to only the following examples.
［実施例１］
　０．３質量％の硫酸亜鉛（ＺｎＳＯ４）を含む水溶液１５０ｇに、酸化亜鉛粉体Ａ（住友大阪セメント製、ＢＥＴ比表面積４５．１ｍ２／ｇ）を３０ｇ添加し、３０分撹拌した。
　この混合液を遠心分離により固液分離し、得られた酸化亜鉛粉体を１０５℃で３時間乾燥することにより、実施例１の酸化亜鉛粉体を得た。 Example 1
30 g of zinc oxide powder A (Sumitomo Osaka Cement, BET specific surface area 45.1 m 2 / g) was added to 150 g of an aqueous solution containing 0.3 mass% zinc sulfate (ZnSO 4 ), and the mixture was stirred for 30 minutes.
The mixed solution was subjected to solid-liquid separation by centrifugation, and the obtained zinc oxide powder was dried at 105 ° C. for 3 hours to obtain the zinc oxide powder of Example 1.
（酸化亜鉛粉体の評価）
　走査型Ｘ線光電子分光分析装置　ＰＨＩ５０００（アルバック・ファイ社製）を用いて、以下の方法で、実施例１の酸化亜鉛粉体の表面に存在するＳ量を測定した。測定において、Ｘ線源として、ＡｌＫα（モノクロ：５０Ｗ、１５ｋＶ）１４８６．６ｅＶを用いた。
分析領域は０．４×０．４ｍｍ２とした。
　酸化亜鉛粉体をアルミニウム製の皿に固定し、走査型Ｘ線光電子分光分析装置に導入した。
　次いで、酸化亜鉛粉体の定性分析（ワイドスペクトル）を行った。
　次いで、定性分析で検出された元素（Ｏ、Ｚｎ）と、測定したい元素（Ｓ）と、基準元素（Ｃ）と、について状態分析（ナロースペクトル）を行い、これらについて得られたスペクトルのピーク面積から、表面原子濃度を算出した。なお、ＣとＳは強度が低いため、エネルギー分解能を落し、感度を優先した。
　ＯはＯ１ｓ（５２５ｅＶ～５４０ｅＶ）について測定した。ＺｎはＺｎ２ｐ（１０１５ｅＶ～１０３０ｅＶ）について測定した。ＳはＳ２ｐ（１６０ｅＶ～１７５ｅＶ）について測定した。ＣはＣ１ｓ（２８０ｅＶ～２９５ｅＶ）について測定した。 (Evaluation of zinc oxide powder)
The amount of S present on the surface of the zinc oxide powder of Example 1 was measured by the following method using a scanning X-ray photoelectron spectrometer PHI5000 (manufactured by ULVAC-PHI, Inc.). In the measurement, AlKα (monochrome: 50 W, 15 kV) 1486.6 eV was used as an X-ray source.
The analysis area was 0.4 × 0.4 mm 2 .
The zinc oxide powder was fixed to a pan made of aluminum and introduced into a scanning X-ray photoelectron spectrometer.
Next, qualitative analysis (wide spectrum) of the zinc oxide powder was performed.
Next, state analysis (narrow spectrum) is performed for the element (O, Zn) detected by qualitative analysis, the element (S) to be measured, and the reference element (C), and the peak area of the spectrum obtained for these The surface atomic concentration was calculated from Since C and S have low intensities, energy resolution was lowered and sensitivity was prioritized.
O was measured for O1s (525 eV to 540 eV). Zn was measured for Zn2p (1015 eV to 1030 eV). S was measured for S2p (160 eV to 175 eV). C was measured for C1s (280 eV to 295 eV).
　測定した結果、Ｓ２ｐは、１６８～１６９ｅＶ付近にピークが検出された。このとき、Ｓ－Ｏ状態が主体であることが確認された。
　Ｏ、Ｚｎ、Ｓ、Ｃについて、測定範囲で検出されたピークの面積から、表面原子濃度を算出した。結果を表１に示す。
　なお、状態分析と定量計算には、アルバック・ファイ社のハンドブックと相対感度係数を用いた。
　計算により得られた酸化亜鉛粉体の表面に存在するＳ－Ｏ結合状態のＳ量は、０．６ａｔｍ％であった。 As a result of measurement, a peak was detected in the vicinity of 168 to 169 eV for S2p. At this time, it was confirmed that the S-O state is the subject.
The surface atomic concentration was calculated from the area of the peak detected in the measurement range for O, Zn, S, and C. The results are shown in Table 1.
In addition, the handbook of ULVAC-PHI and relative sensitivity factor were used for state analysis and quantitative calculation.
The amount of S in the S—O bond state existing on the surface of the zinc oxide powder obtained by the calculation was 0.6 atm%.
　ＩＣＰ発光分光分析装置　ＩＣＰ－ＡＥＳ　７００－ＥＳ（バリアン社製）を用いて、以下の方法で、実施例１の酸化亜鉛粉体中に含まれるＳＯ４量を測定した。
　実施例１の酸化亜鉛粉体を０．５ｇ、２００ｍＬビーカーに秤量した。次いで、この酸化亜鉛粉体を含むビーカーに、純水５０ｍＬと、６０質量％の濃硝酸を５ｍＬとを加えて攪拌し、実施例１の酸化亜鉛粉体を溶解させた。
　この溶解液を、メスフラスコで、純水で２００ｍＬに定容した。
　この定容した液を２倍に希釈して、検液とした。
　この検液に、内標準物質としてＹ（イットリウム）を１０００ｐｐｍ加えた。
　濃度既知の元素標準液により、検量線を作成した。なお、検量線作成用の元素標準液にも、内標準物質としてＹを１０００ｐｐｍと、硝酸とを、検液と同濃度になるように加えた。
　検液をＩＣＰ発光分光分析装置で測定し、検量線法により定量した。
　その結果、粉体に含まれる各元素の定量結果から、酸化亜鉛粉体中に含まれるＳＯ４量は、０．６４質量％（６４００ｐｐｍ）であった。結果を表２に示す。 The amount of SO 4 contained in the zinc oxide powder of Example 1 was measured by the following method using an ICP emission spectrometer ICP-AES 700-ES (manufactured by Varian).
0.5 g of the zinc oxide powder of Example 1 was weighed into a 200 mL beaker. Subsequently, 50 mL of pure water and 5 mL of 60 mass% concentrated nitric acid were added to a beaker containing this zinc oxide powder, and the mixture was stirred to dissolve the zinc oxide powder of Example 1.
This solution was adjusted to 200 mL with pure water using a volumetric flask.
This solution was diluted twice to prepare a test solution.
To this test solution, 1000 ppm of Y (yttrium) was added as an internal standard substance.
A calibration curve was prepared using an elemental standard solution of known concentration. In addition, 1000 ppm of Y as an internal standard substance and nitric acid were added to the elemental standard solution for preparing a calibration curve so as to have the same concentration as the test solution.
The test solution was measured by an ICP emission spectrophotometer and quantified by a calibration curve method.
As a result, from the quantitative result of each element contained in the powder, the amount of SO 4 contained in the zinc oxide powder was 0.64 mass% (6400 ppm). The results are shown in Table 2.
（皮脂固化性の評価）
「人工皮脂の作製」
　オレイン酸（関東化学社製）１０ｇ、スクワラン１０ｇ（関東化学社製）、及びオリーブオイル１０ｇ（商品名：ＥＸバージンオイル、ＢＯＳＣＯ社製）を混合して、人工皮脂を作製した。 (Evaluation of sebum solidification)
"Production of artificial sebum"
An artificial sebum was prepared by mixing 10 g of oleic acid (manufactured by Kanto Chemical Co., Ltd.), 10 g of squalane (manufactured by Kanto Chemical Co., Ltd.), and 10 g of olive oil (trade name: EX virgin oil, manufactured by BOSCO).
　実施例１の酸化亜鉛粉体０．５ｇと、人工皮脂４ｇとを混合し、スターラーで攪拌した。攪拌した状態で、攪拌が終了してから人工皮脂が固化するまでの時間を測定し、皮脂固化性を評価した。
　その結果、実施例１の酸化亜鉛粉体は５秒で固化した。 0.5 g of the zinc oxide powder of Example 1 and 4 g of artificial sebum were mixed and stirred by a stirrer. In the state of stirring, the time from the end of the stirring to the solidification of the artificial sebum was measured to evaluate the sebum solidifying property.
As a result, the zinc oxide powder of Example 1 solidified in 5 seconds.
［実施例２］
　ＺｎＳＯ４を含む水溶液の濃度を０．２質量％に変更したこと以外は、実施例１と同様にして、実施例２の酸化亜鉛粉体を得た。
　実施例１と同様に評価した結果、酸化亜鉛粉体の表面に存在するＳ－Ｏ結合状態のＳ量は０．４ａｔｍ％であった。また、酸化亜鉛粉体中に含まれるＳＯ４量は、０．４２質量％（４２００ｐｐｍ）であった。
　また、皮脂固化に要した時間は２分３０秒であった。結果を表１と表２に示す。 Example 2
The zinc oxide powder of Example 2 was obtained in the same manner as Example 1, except that the concentration of the aqueous solution containing ZnSO 4 was changed to 0.2% by mass.
As a result of evaluation in the same manner as in Example 1, the amount of S in the S—O bonded state present on the surface of the zinc oxide powder was 0.4 atm%. The amount of SO 4 contained in the zinc oxide powder was 0.42% by mass (4200 ppm).
The time required for the sebum to solidify was 2 minutes and 30 seconds. The results are shown in Tables 1 and 2.
［比較例１］
　酸化亜鉛粉体Ａを３０ｇと、ＺｎＳＯ４（粉体）０．４５ｇとを、乳鉢で混合した。すなわち、粉体同士を単に混合して、サンプルとした。
　得られた混合物を、実施例１と同様に評価した結果、酸化亜鉛粉体の表面に存在するＳ－Ｏ結合状態のＳ量は、検出限界以下（＜０．１ａｔｍ％）であった。また、酸化亜鉛粉体中に含まれるＳＯ４量は、０．６８質量％（６８００ｐｐｍ）であった。
　また、皮脂固化に要した時間は３０分であった。結果を表１と表２に示す。 Comparative Example 1
30 g of zinc oxide powder A and 0.45 g of ZnSO 4 (powder) were mixed in a mortar. That is, the powders were simply mixed to prepare a sample.
The obtained mixture was evaluated in the same manner as in Example 1. As a result, the amount of S in the S—O bonded state present on the surface of the zinc oxide powder was below the detection limit (<0.1 atm%). The amount of SO 4 contained in the zinc oxide powder was 0.68% by mass (6800 ppm).
Moreover, the time required for sebum solidification was 30 minutes. The results are shown in Tables 1 and 2.
［比較例２］
　酸化亜鉛粉体Ａを、比較例２の酸化亜鉛粉体とした。すなわち未処理の酸化亜鉛粉体Ａ自体を、サンプルとした。
　実施例１と同様に評価した結果、酸化亜鉛粉体の表面に存在するＳ量は検出限界以下（＜０．１ａｔｍ％）であった。また、酸化亜鉛粉体に含まれるＳ－Ｏ結合状態のＳＯ４量は、０．００５質量％（５０ｐｐｍ）であった。
　実施例１と同様に皮脂固化に必要な時間を測定した結果、３０分経過後も皮脂は固化していなかった。結果を表２に示す。 Comparative Example 2
The zinc oxide powder A was used as the zinc oxide powder of Comparative Example 2. That is, untreated zinc oxide powder A itself was used as a sample.
As a result of evaluation in the same manner as in Example 1, the amount of S present on the surface of the zinc oxide powder was below the detection limit (<0.1 atm%). The amount of SO 4 in the SO-bonded state contained in the zinc oxide powder was 0.005% by mass (50 ppm).
As a result of measuring the time required for sebum solidification as in Example 1, the sebum was not solidified even after 30 minutes. The results are shown in Table 2.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表１および表２の結果から、Ｘ線光電子分光法により測定されるＳ－Ｏ結合状態のＳを０．４ａｔｍ％以上とすることにより、皮脂固化性が向上することが確認された。
　また、比較例１のように、粉体同士を単に混合した場合には、酸化亜鉛粉体に含まれるＳＯ４量が６８００ｐｐｍであっても、酸化亜鉛粉体の表面に存在するＳ量は検出限界以下となり、皮脂固化性を向上する効果が得られなかった。 From the results in Table 1 and Table 2, it was confirmed that sebum solidifying property is improved by setting S in the S-O bonded state measured by X-ray photoelectron spectroscopy to 0.4 atm% or more.
Further, as in Comparative Example 1, when the powders are simply mixed, the amount of S present on the surface of the zinc oxide powder is detected even if the amount of SO 4 contained in the zinc oxide powder is 6800 ppm. It became below the limit, and the effect of improving sebum solidification was not obtained.
［参考実験］
　硫酸亜鉛以外であっても、ＳＯ４を含む化合物であれば、それらを用いて、所望の皮脂固化性を有する酸化亜鉛粉体が得られることを確認するために、以下の実験を行った。 [Reference experiment]
The following experiment was conducted to confirm that zinc oxide powder having desired sebum solidifying properties can be obtained using a compound other than zinc sulfate as long as it is a compound containing SO 4 .
［参考例１］
　酸化亜鉛粉体Ａを３０ｇと、ＣａＳＯ４を０．２質量％含む水溶液１５０ｇを用意しこれらを混ぜ、３０分撹拌した。
　この混合液を遠心分離により固液分離し、得られた酸化亜鉛粉体を１０５℃で３時間乾燥することにより、参考例１の酸化亜鉛粉体を得た。 [Reference Example 1]
30 g of zinc oxide powder A and 150 g of an aqueous solution containing 0.2% by mass of CaSO 4 were prepared, mixed, and stirred for 30 minutes.
The mixed solution was subjected to solid-liquid separation by centrifugation, and the obtained zinc oxide powder was dried at 105 ° C. for 3 hours to obtain a zinc oxide powder of Reference Example 1.
［参考例２］
　ＣａＳＯ４をＭｇＳＯ４に変更したこと以外は、参考例１と同様にして、参考例２の酸化亜鉛粉体を得た。 [Reference Example 2]
The zinc oxide powder of Reference Example 2 was obtained in the same manner as Reference Example 1 except that CaSO 4 was changed to MgSO 4 .
［参考例３］
　ＣａＳＯ４をＮａ２ＳＯ４に変更したこと以外は、参考例１と同様にして、参考例３の酸化亜鉛粉体を得た。 [Reference Example 3]
The zinc oxide powder of Reference Example 3 was obtained in the same manner as in Reference Example 1 except that CaSO 4 was changed to Na 2 SO 4 .
［参考例４］
　ＣａＳＯ４をＣａＣｌ２に変更したこと以外は、参考例１と同様にして、参考例４の酸化亜鉛粉体を得た。 [Reference Example 4]
The zinc oxide powder of Reference Example 4 was obtained in the same manner as in Reference Example 1 except that CaSO 4 was changed to CaCl 2 .
［参考例５］
　ＣａＳＯ４をＭｇＣｌ２に変更したこと以外は、参考例１と同様にして、参考例５の酸化亜鉛粉体を得た。 [Reference Example 5]
The zinc oxide powder of Reference Example 5 was obtained in the same manner as Reference Example 1 except that CaSO 4 was changed to MgCl 2 .
　参考例１～参考例５の酸化亜鉛粉体について、実施例１と同様に皮脂固化性を評価した。
　固化時間が５分以下である場合を「◎」（優）、固化時間が５分を超えて２０分以下である場合を「○」（良）、固化時間が２０分を超えて３０分以下である場合を「△」（可）、固化時間が３０分を超える場合を「×」（不可）と評価した。固化時間が短いほど、皮脂固化性が良好であることを意味する。 With respect to the zinc oxide powders of Reference Example 1 to Reference Example 5, the sebum solidification property was evaluated in the same manner as Example 1.
If the solidification time is 5 minutes or less, "◎" (excellent), if the solidification time is more than 5 minutes to 20 minutes or less, "○" (good), the solidification time exceeds 20 minutes to 30 minutes or less In the case where the solidification time was more than 30 minutes, it was evaluated as "poor". The shorter the setting time, the better the sebum setting property.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表３の結果から、硫酸塩を酸化亜鉛粉体の表面に存在させることにより、皮脂固化性が向上することが確認された。
　また、第１族元素の硫酸塩より、第２族元素の硫酸塩の方が、皮脂固化性が向上しやすいことが確認された。 From the results in Table 3, it was confirmed that sebum solidifying properties are improved by the presence of the sulfate on the surface of the zinc oxide powder.
Moreover, it was confirmed that sebum solidification property is more easily improved in the case of the sulfate of the group 2 element than in the sulfate of the group 1 element.
　上記の皮脂固化性の評価により、Ｓ－Ｏ結合状態のＳ量が０．１ａｔｍ％以上かつ１．０ａｔｍ％以下である酸化亜鉛粉体は、皮脂を固化できる時間が短縮されることが確認された。その結果、この酸化亜鉛粉体を化粧料に用いた場合、化粧崩れを抑制できると考えられる。 According to the above evaluation of sebum solidification, it has been confirmed that zinc oxide powder in which the amount of S in the S-O bound state is 0.1 atm% or more and 1.0 atm% or less can shorten the time for which sebum can be solidified. The As a result, when this zinc oxide powder is used for cosmetics, it is thought that makeup collapse can be suppressed.
　本発明の酸化亜鉛粉体は、皮脂固化性に優れるため、化粧料に用いられた場合の工業的価値は大きい。本発明は、皮脂が固化する時間を従来よりも短縮できる酸化亜鉛粉体、並びに、酸化亜鉛粉体を含む分散液、化粧料、および酸化亜鉛粉体の製造方法を提供できる。 Since the zinc oxide powder of the present invention is excellent in sebum solidifying properties, it has a large industrial value when used in cosmetics. The present invention can provide a zinc oxide powder capable of shortening the time for which sebum solidifies, a dispersion containing zinc oxide powder, a cosmetic, and a method for producing zinc oxide powder.

Claims (9)

  1. 　Ｘ線光電子分光法により測定される、酸化亜鉛粉体のＳ－Ｏ結合状態のＳが、０．１ａｔｍ％以上かつ１．０ａｔｍ％以下であることを特徴とする酸化亜鉛粉体。 What is claimed is: 1. A zinc oxide powder characterized in that S in a S-O bonded state of zinc oxide powder, which is measured by X-ray photoelectron spectroscopy, is 0.1 atm% or more and 1.0 atm% or less.
  2. 　前記酸化亜鉛粉体中のＳＯ４の含有量が１００ｐｐｍ以上かつ１００００ｐｐｍ以下であることを特徴とする請求項１に記載の酸化亜鉛粉体。 The zinc oxide powder according to claim 1, wherein the content of SO 4 in the zinc oxide powder is 100 ppm or more and 10000 ppm or less.
  3. 　無機成分および有機成分の少なくとも一方で表面処理されたことを特徴とする請求項１または２に記載の酸化亜鉛粉体。 The zinc oxide powder according to claim 1 or 2, which is surface-treated with at least one of an inorganic component and an organic component.
  4. 　請求項１から３のいずれか１項に記載の酸化亜鉛粉体と、分散媒と、を含有することを特徴とする分散液。 A dispersion comprising the zinc oxide powder according to any one of claims 1 to 3 and a dispersion medium.
  5. 　請求項１から３のいずれか１項に記載の酸化亜鉛粉体と、化粧品基剤原料と、を含有することを特徴とする化粧料。 A cosmetic comprising the zinc oxide powder according to any one of claims 1 to 3 and a cosmetic base material.
  6. さらに分散媒を含有することを特徴とする請求項５に記載の化粧料。 The cosmetic according to claim 5, further comprising a dispersion medium.
  7. 　酸化亜鉛粉体と、ＳＯ４を含む水溶液と、を混合する工程を有することを特徴とする酸化亜鉛粉体の製造方法。 A process for producing a zinc oxide powder comprising the steps of mixing a zinc oxide powder and an aqueous solution containing SO 4 .
  8. 　原料としての酸化亜鉛粉体と、硫酸塩または硫酸を含む水溶液とを混合し、さらに乾燥して得られた、請求項１に記載の酸化亜鉛粉体。 The zinc oxide powder according to claim 1, which is obtained by mixing zinc oxide powder as a raw material with an aqueous solution containing sulfate or sulfuric acid and further drying it.
  9. 　前記酸化亜鉛粉体が、酸化亜鉛粒子と、前記粒子に付着したＳＯ４を含む化合物とを含むことを特徴とする、請求項１に記載の酸化亜鉛粉体。 The zinc oxide powder according to claim 1, wherein the zinc oxide powder comprises zinc oxide particles and a compound containing SO 4 attached to the particles.
PCT/JP2018/040401 2017-10-31 2018-10-30 Zinc oxide powder, dispersion, cosmetic material, and method for producing zinc oxide powder WO2019088130A1 (en)

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