WO2020067417A1 - Particules d'oxyde métallique traitées en surface, dispersion liquide, produit cosmétique et procédé de production de particules d'oxyde métallique traitées en surface - Google Patents

Particules d'oxyde métallique traitées en surface, dispersion liquide, produit cosmétique et procédé de production de particules d'oxyde métallique traitées en surface Download PDF

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WO2020067417A1
WO2020067417A1 PCT/JP2019/038132 JP2019038132W WO2020067417A1 WO 2020067417 A1 WO2020067417 A1 WO 2020067417A1 JP 2019038132 W JP2019038132 W JP 2019038132W WO 2020067417 A1 WO2020067417 A1 WO 2020067417A1
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oxide particles
metal oxide
treated
treated metal
dispersion
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PCT/JP2019/038132
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English (en)
Japanese (ja)
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浩和 松下
藤橋　岳
直 根矢
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住友大阪セメント株式会社
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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
    • 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
    • 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
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/14—Methods for preparing oxides or hydroxides in general
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/04—Compounds of zinc
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/12—Treatment with organosilicon compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D17/00—Pigment pastes, e.g. for mixing in paints

Definitions

  • the present invention relates to a surface-treated metal oxide particle, a dispersion, a cosmetic, and a method for producing a surface-treated metal oxide particle.
  • Ultraviolet shielding metal oxide particles such as zinc oxide and titanium oxide are used in cosmetics such as sunscreens and foundations.
  • surface treatment of the metal oxide particles is performed in order to adjust the surface state of the metal oxide particles to the properties of the cosmetic or to suppress the catalytic activity of the metal oxide particles.
  • the surface treatment agent for such metal oxide particles include metal soaps such as magnesium stearate, silicone oils such as dimethicone and hydrogen dimethicone, and silane coupling agents having an alkoxy group such as octyltriethoxysilane. (For example, see Patent Documents 1 and 2).
  • the metal oxide particles surface-treated with the silane coupling agent have high stability because the silane coupling agent, which is a surface treatment agent, is chemically bonded to the surface of the metal oxide particles. Furthermore, the properties of the metal oxide particles as described above can be easily changed by using surface treatment agents having different substituents. In the following description, metal oxide particles surface-treated with a silane coupling agent are referred to as surface-treated metal oxide particles.
  • Such surface-treated metal oxide particles are blended into cosmetics as they are, or blended into cosmetics in the form of a dispersion dispersed in a dispersion medium.
  • the above-mentioned surface-treated metal oxide particles sometimes have poor ultraviolet shielding properties when blended in cosmetics, and have a problem that the quality relating to ultraviolet shielding properties is difficult to stabilize.
  • the ultraviolet shielding properties of the surface treated metal oxide particles are significantly reduced. was there.
  • the present invention has been made in view of the above circumstances, and has as its object to provide surface-treated metal oxide particles exhibiting a stable and high ultraviolet shielding property. Another object of the present invention is to provide a dispersion, a composition, and a cosmetic containing such surface-treated metal oxide particles. Another object of the present invention is to provide a method for producing such surface-treated metal oxide particles.
  • a first aspect of the present invention is a metal oxide particle surface-treated with a silane coupling agent having an alkoxy group, wherein the metal oxide particle has an ultraviolet shielding property and the surface-treated metal oxide 105 ° C. of the object particles, drying loss at 3 hours is not more than 0.15 mass%, the surface-treated metal oxide particles, 900cm -1 ⁇ 1300cm -1 measured by a Fourier transform type infrared spectrophotometer
  • the present invention provides surface-treated metal oxide particles in which a peak derived from the alkoxy group is not detected in the reflection spectrum of the above.
  • a second aspect of the present invention provides a dispersion containing the above-mentioned surface-treated metal oxide particles and a dispersion medium.
  • a third aspect of the present invention provides a cosmetic containing at least one selected from the group consisting of the above-mentioned surface-treated metal oxide particles and the above-mentioned dispersion.
  • a fourth aspect of the present invention is a method for producing metal oxide particles surface-treated with a silane coupling agent having an alkoxy group, wherein the metal oxide particles have an ultraviolet shielding property and the surface treatment is performed. and the metal oxide particles, in the reflection spectrum at 900cm -1 ⁇ 1300cm -1 measured by a Fourier transform type infrared spectrophotometer, comprising the step of determining that the peak derived from the alkoxy group is not detected, the surface treatment Provided is a method for producing metal oxide particles.
  • the present invention it is possible to provide surface-treated metal oxide particles that exhibit high ultraviolet shielding properties stably. Further, according to the present invention, a dispersion and a cosmetic containing such surface-treated metal oxide particles can be provided. According to the present invention, a method for producing such surface-treated metal oxide particles can be provided.
  • FIG. 4 is a view showing the results of FT-IR measurement of surface-treated zinc oxide particles of Example 1 and Comparative Example 1, and octyltriethoxysilane.
  • FIG. 2 is a view showing an optical microscope image of surface-treated zinc oxide particles of Example 1.
  • FIG. 4 is a view showing an optical microscope image of surface-treated zinc oxide particles of Comparative Example 2.
  • the surface-treated metal oxide particles may be abbreviated as “surface-treated particles”.
  • the surface-treated metal oxide particles of this embodiment are ultraviolet-shielding metal oxide particles surface-treated with a silane coupling agent having an alkoxy group.
  • the metal oxide particles have an ultraviolet shielding property, and a loss on drying of the surface-treated metal oxide particles at 105 ° C. for 3 hours is 0.15% by mass or less.
  • the surface-treated metal oxide particles in the reflection spectrum at 900cm -1 ⁇ 1300cm -1 measured by a Fourier transform type infrared spectrophotometer (FT-IR), a peak derived from the alkoxy group is detected Not done.
  • FT-IR Fourier transform type infrared spectrophotometer
  • a peak derived from the alkoxy group, a silane coupling agent having an alkoxy group with FT-IR, as measured by the ATR method generally, the peak detected in the range of 900cm -1 ⁇ 1300cm -1
  • the peak of the alkoxy group is identified by using the “identification method by the spectrum of the organic compound, sixth edition”. I just need.
  • a peak derived from the alkoxy group is preferably not detected, 1170cm -1, 1100cm -1, which is 1080 cm -1, and 950 cm -1. Preferably, at least one of these peaks is not detected, more preferably not all peaks are detected.
  • octyltriethoxysilane is a silane coupling agent having an alkoxy group as measured by FT-IR, a peak detected in the range of 900cm -1 ⁇ 1300cm -1.
  • peak is not detected means that the reflectance at the peak top is 1% or less (-1% or more and 0% or less) in absolute value when the reflectance of the baseline is 0%.
  • the peak at 950 cm -1 is not detected, it means that the peak that contains the 950 cm -1 in the range is not detected. That is, this does not mean that a peak having a peak top at 950 cm ⁇ 1 is not detected.
  • 1170cm -1, 1100cm -1 The same applies to the 1080 cm -1.
  • “Fourier transform infrared spectrophotometer” may be abbreviated as “FT-IR”.
  • the surface treatment of the metal oxide particles is performed by a hydrolysis reaction of a silane coupling agent containing an alkoxy group. Therefore, the fact that the alkoxy group does not remain indicates that almost all of the alkoxy group in the silane coupling agent undergoes a hydrolysis reaction and reacts with the OH group on the surface of the metal oxide particle. As a result, it is inferred that the number of OH groups remaining in the surface-treated metal oxide particles is reduced or not remaining. Further, when the surface metal oxide particles are stored, the alkoxy groups remaining in the particles are hydrolyzed by atmospheric moisture, and as a result, the OH groups in the surface metal oxide particles increase. , Can be prevented.
  • the surface-treated metal oxide particles of the present embodiment have a loss on drying at 105 ° C. for 3 hours of 0.15% by mass or less, preferably 0.13% by mass or less, and more preferably 0.10% by mass or less. More preferred.
  • the lower limit of the loss on drying can be arbitrarily selected, but may be, for example, 0.00% by mass, 0.01% by mass, or 0.03% by mass.
  • the loss on drying at 105 ° C. for 3 hours does not exceed 0.15% by mass, the dispersion stability in a composition containing an aqueous volatile component and an oil component is maintained, and the composition containing the surface-treated metal oxide particles. Even when the object is applied to an object (in the case of cosmetics, skin), high ultraviolet shielding properties can be exhibited.
  • the present inventors have in the reflection spectrum at 900cm -1 ⁇ 1300cm -1 measured by FT-IR, not detected peak derived from an alkoxy group, and, loss on drying at 105 ° C. 3 hours 0.15 wt% With the following surface-treated metal oxide particles, they have found that the UV-shielding properties of the surface-treated metal oxide particles are very high when blended in cosmetics.
  • the cosmetic is generally used in an oil-in-water (W / O type) or water-in-oil (O / W type) dosage form.
  • W / O type oil-in-water
  • O / W type water-in-oil
  • OH in the surface-treated metal oxide particles is reduced.
  • Many bases For this reason, during the process of being applied to the skin and dried, it is presumed that the surface-treated metal oxide particles tend to agglomerate in the oil phase, making it difficult to impart a desired ultraviolet shielding property to the skin.
  • having an ultraviolet shielding property means having an effect of shielding at least any range in an ultraviolet (10 to 400 nm) region.
  • An example of a method for evaluating the presence or absence of the ultraviolet shielding property is to measure a transmission spectrum in a wavelength region of 250 to 450 nm of a coating film containing 10% by mass of metal oxide particles.
  • the surface-treated metal oxide particles of the above embodiment are preferably primary particles.
  • the primary particles may aggregate to form secondary particles.
  • the specific surface area of the surface-treated metal oxide particles can be arbitrarily selected, but is preferably 1.5 m 2 / g or more, more preferably 2.5 m 2 / g or more, and more preferably 4 m 2 / g or more. It is more preferred that there be.
  • the specific surface area of the surface-treated metal oxide particles is preferably 65 m 2 / g or less, more preferably 60 m 2 / g or less. If necessary, it may be 50 m 2 / g or less, 30 m 2 / g or less, or 10 m 2 / g or less.
  • the upper and lower limits of the specific surface area of the surface-treated metal oxide particles can be arbitrarily combined.
  • the specific surface area of the surface-treated metal oxide particles is 1.5 m 2 / g or more and 65 m 2 / g or less, transparency and ultraviolet shielding properties are excellent when blended in cosmetics.
  • the specific surface area of the surface-treated metal oxide particles is preferably 8 m 2 / g or more, more preferably 15 m 2 / g or more, More preferably, it is 20 m 2 / g or more.
  • the specific surface area of the surface-treated metal oxide particles is preferably less than 8 m 2 / g, and is preferably 7.5 m 2 / g or less. More preferably, it is more preferably 7.0 m 2 / g or less.
  • the specific surface area of the surface-treated metal oxide particles means a value measured by a BET method using a fully automatic specific surface area measuring device (trade name: Macsorb HM Model-1201, manufactured by Mountech Corporation).
  • the average primary particle diameter of the surface-treated metal oxide particles of the present embodiment can be arbitrarily selected, but is preferably 15 nm or more, and more preferably 20 nm or more.
  • the average primary particle diameter of the surface-treated metal oxide particles is preferably 715 nm or less, and more preferably 650 nm or less.
  • the average primary particle diameter of the surface-treated metal oxide particles is 15 nm or more and 715 nm or less, when blended in a cosmetic, transparency and ultraviolet shielding properties are excellent.
  • the average primary particle diameter of the surface-treated metal oxide particles is preferably 135 nm or less, more preferably 100 nm or less, and more preferably 50 nm or less.
  • the primary particle diameter of the surface-treated metal oxide particles is preferably more than 135 nm, more preferably 140 nm or more, and more preferably 150 nm or more. Is more preferable.
  • the average primary particle diameter of the surface-treated metal oxide particles can be calculated by equation (1) using the specific surface area of the surface-treated metal oxide particles.
  • Average primary particle diameter (nm) 6000 / (specific surface area (m 2 / g) ⁇ ⁇ (g / cm 3 ) (1) (Where ⁇ is the density of the metal oxide particles.)
  • ⁇ of zinc oxide is 5.61 g / cm 3
  • ⁇ of titanium oxide is 4.23 g / cm 3 .
  • the average primary particle diameter of the surface-treated metal oxide particles may be determined by the following method.
  • TEM transmission electron microscope
  • a predetermined number of the surface-treated metal oxide particles for example, 200 or 100 are selected. Then, the longest linear portion (maximum major axis) of each of the surface-treated metal oxide particles is measured, and the measured values are arithmetically averaged.
  • the surface-treated metal oxide particles are aggregated, the aggregated particle diameter of the aggregate is not measured.
  • a predetermined number of the surface-treated metal oxide particles (primary particles) constituting the aggregate are measured to obtain an average primary particle diameter.
  • the metal oxide particles used as a raw material in the present embodiment are not particularly limited as long as they have an ultraviolet shielding property.
  • the metal oxide particles for example, zinc oxide particles, titanium oxide particles, cerium oxide particles, and the like can be used. Zinc oxide particles and titanium oxide particles are more preferred because they are commonly used in cosmetics. Zinc oxide particles are more preferred in that they have excellent ultraviolet shielding properties in the UV-A region.
  • the specific surface area of the metal oxide particles in the present embodiment can be arbitrarily selected, but is preferably 1.5 m 2 / g or more, more preferably 2.5 m 2 / g or more, and more preferably 4 m 2 / g or more. Is more preferable.
  • the specific surface area of the metal oxide particles is preferably 65 m 2 / g or less, more preferably 60 m 2 / g or less. If necessary, it may be 50 m 2 / g or less, 30 m 2 / g or less, or 10 m 2 / g or less.
  • the upper and lower limits of the specific surface area of the metal oxide particles can be arbitrarily combined.
  • the specific surface area of the metal oxide particles is 1.5 m 2 / g or more and 65 m 2 / g or less, transparency and ultraviolet shielding properties are excellent when blended in cosmetics. If it is desired to increase the transparency of when incorporated into cosmetics, it is preferable that the specific surface area of the metal oxide particles is 8m 2 / g or more, more preferably 15 m 2 / g or more, 20 m 2 / g or more is more preferable. On the other hand, when it is desired to increase the ultraviolet shielding property when blended in a cosmetic, the specific surface area of the metal oxide particles is preferably less than 8 m 2 / g, and is 7.5 m 2 / g or less. Is more preferable, and it is still more preferable that it is 7.0 m ⁇ 2 > / g or less.
  • the specific surface area of the metal oxide particles in the present embodiment means a value measured by a BET method using a fully automatic specific surface area measuring device (trade name: Macsorb HM Model-1201, manufactured by Mountech Corporation).
  • the average primary particle diameter of the metal oxide particles of the present embodiment can be arbitrarily selected, but is preferably 15 nm or more, and more preferably 20 nm or more.
  • the average primary particle diameter of the surface-treated metal oxide particles is preferably 715 nm or less, and more preferably 650 nm or less.
  • the average primary particle diameter of the metal oxide particles is 15 nm or more and 715 nm or less, transparency and ultraviolet shielding properties are excellent when blended in cosmetics.
  • the average primary particle diameter of the metal oxide particles is preferably 135 nm or less, more preferably 100 nm or less, and more preferably 50 nm or less. More preferred.
  • the primary particle diameter of the metal oxide particles is preferably more than 135 nm, more preferably 140 nm or more, and more preferably 150 nm or more. Is more preferable.
  • the average primary particle diameter of the metal oxide particles can be calculated by the equation (1) using the specific surface area of the metal oxide particles, similarly to the average primary particle diameter of the surface-treated metal oxide particles.
  • the average primary particle diameter of the metal oxide particles may be determined by the following method. That is, when the metal oxide particles are observed using a transmission electron microscope (TEM) or the like, a predetermined number of metal oxide particles, for example, 200 or 100 are selected. Then, the longest linear portion (maximum major axis) of each of the metal oxide particles is measured, and the measured values are arithmetically averaged. When the metal oxide particles are aggregated, the aggregate particle diameter of the aggregate is not measured. A predetermined number of metal oxide particles (primary particles) constituting this aggregate are measured and defined as an average primary particle diameter.
  • TEM transmission electron microscope
  • the surface treatment of the metal oxide particles tends to reduce the specific surface area of the surface-treated metal oxide particles, but they are substantially the same size.
  • the average primary particle diameter tends to increase when the metal oxide particles surface, but they are substantially the same size.
  • the silane coupling agent having an alkoxy group used in the present embodiment is not particularly limited as long as it is a silane coupling agent usable for cosmetics.
  • a silane coupling agent among the silane coupling agents represented by the general formula (2), those that can be used in cosmetics are listed.
  • R 1 Si (OR 2 ) 3 ... (2) R 1 represents an alkyl group having 1 to 18 carbon atoms, a fluoroalkyl group or a phenyl group, and R 2 represents an alkyl group having 1 to 4 carbon atoms.
  • silane coupling agent used for the surface treatment methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, Ethyl tributoxy silane, n-propyl trimethoxy silane, n-propyl triethoxy silane, n-propyl tripropoxy silane, n-propyl tributoxy silane, isopropyl trimethoxy silane, isopropyl triethoxy silane, isopropyl tripropoxy silane, isopropyl tri Butoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltributoxysilane, n-octy
  • silane coupling agent used for the surface treatment a siloxane skeleton such as dimethoxydiphenylsilane-triethoxycaprylylsilane crosspolymer, triethoxysilylethyl polydimethylsiloxyethyl dimethicone, triethoxysilylethyl polydimethylsiloxyethylhexyl dimethicone, etc. is used.
  • a polymer silane coupling agent having an alkoxy group and an acrylic group in the molecular structure.
  • silane coupling agents may be used alone, or two or more thereof may be used in combination.
  • silane coupling agents a silane coupling agent having an octyl group in the molecule is preferable. More specifically, octyltriethoxysilane, octyltrimethoxysilane, dimethoxydiphenylsilane-triol, which has a moderate polarity of the functional groups and is compatible with a wide range of oil phases from natural oils and ester oils to silicone oils. Ethoxycaprylylsilane crosspolymer can be particularly preferably used.
  • One of these silane coupling agents may be used alone, or two or more thereof may be used in combination.
  • the amount of surface treatment with the silane coupling agent may be appropriately adjusted according to desired characteristics.
  • the amount of the silane coupling agent is preferably 2 parts by mass or more and 15 parts by mass or less, more preferably 3 parts by mass or more and 15 parts by mass or less, based on 100 parts by mass of the metal oxide particles. It is more preferable that the amount be 4 parts by mass or more and 12 parts by mass or less.
  • the surface treatment of the metal oxide particles with a silane coupling agent in the above range is preferable because surface-treated particles having excellent dispersibility and excellent ultraviolet shielding properties are easily obtained.
  • the amount of the silane coupling agent may be an amount added and used at the time of production.
  • a surface treatment agent used for cosmetics other than the silane coupling agent, may be used.
  • the oxide particles may be surface-treated.
  • a surface treatment agent other than the silane coupling agent for example, inorganic materials such as silica and alumina, and organic materials such as silicone compounds, fatty acids, fatty acid soaps, fatty acid esters, and organic titanate compounds can be used.
  • the method for producing the surface-treated metal oxide particles of the present embodiment is not particularly limited, and can be arbitrarily selected. Depending on the components used for the surface treatment, the production of the particles can be appropriately performed by a known method such as a dry treatment or a wet treatment.
  • a method of performing a surface treatment by the following operation may be mentioned.
  • a silane coupling agent is added by dropping or spraying while a metal oxide particle as a raw material is stirred in a mixer such as a Henschel mixer or a super mixer, and then the mixture is vigorously stirred for a certain period of time at high speed.
  • a heat treatment is performed at a temperature of 70 to 200 ° C. while stirring is continued.
  • the heating temperature and the stirring time can be selected as needed depending on the material used and the silane coupling agent.
  • a method of performing a surface treatment by the following method may, for example, be mentioned.
  • the metal oxide particles, the silane coupling agent, and the solvent are mixed at 25 ° C. to 100 ° C. for several hours while stirring. Thereafter, solid-liquid separation and washing are performed, and the obtained washed product is subjected to a heat treatment at 70 to 200 ° C.
  • the water for hydrolysis of the silane coupling agent may use water attached to the metal oxide particles, and may be added together with or separately from the silane coupling agent as necessary. May be.
  • the silane coupling agent may be diluted with a solvent that can be mixed with the silane coupling agent before use.
  • a solvent examples include alcohols such as methanol, ethanol, and isopropanol, n-hexane, toluene, xylene, and the like.
  • One or more solvents can be used.
  • a polar solvent such as alcohol having high compatibility with water is preferably used among these solvents.
  • the method for producing surface-treated metal oxide particles of the present embodiment is as follows.
  • the metal oxide particles surface-treated with a silane coupling agent having an alkoxy group are measured with a Fourier transform infrared spectrophotometer at 900 cm ⁇ 1 to 1300 cm ⁇ . And a step of judging that no peak derived from the alkoxy group is detected in the reflection spectrum of 1 .
  • a step of preparing metal oxide particles surface-treated with a silane coupling agent having an alkoxy group, manufactured by an arbitrarily selected method, and a step of measuring the particles with a Fourier transform infrared spectrophotometer. It is also preferable to include in the production method.
  • the method for producing surface-treated metal oxide particles of the present embodiment includes the above-described determination step. Therefore, the amount of unreacted alkoxy groups of the surface-treated particles can be quantitatively confirmed, and whether or not surface-treated metal oxide particles having excellent ultraviolet shielding properties are obtained is easily confirmed after production. be able to. Therefore, a product with stable quality can be provided by including the steps up to this determination step in the manufacturing operation.
  • the method for producing surface-treated metal oxide particles of the present embodiment preferably further includes the following step when the peak derived from the alkoxy group is confirmed in the above-described determination step.
  • the method may include a step of heating the metal oxide particles surface-treated with the silane coupling agent having the alkoxy group until the peak disappears, that is, heating the surface-treated metal oxide particles.
  • the heating conditions in this heating step can be arbitrarily selected.
  • the temperature may be the same as that at the time of producing the particles, for example, a temperature of 70 ° C to 200 ° C.
  • the amount of unreacted alkoxy groups remaining on the surface-treated particles can be quantitatively controlled so as to be within a preferable range. For this reason, surface-treated metal oxide particles having excellent ultraviolet shielding properties can be stably produced.
  • the method for producing surface-treated metal oxide particles of the present embodiment there is a step of confirming the presence of a residual alkoxy group. Therefore, the amount of unreacted alkoxy groups can be quantitatively confirmed, and whether or not surface-treated metal oxide particles having excellent ultraviolet shielding properties can be confirmed. Further, according to the method for producing surface-treated metal oxide particles of the present embodiment, a heating step is preferably included. This makes it possible to quantitatively control the amount of the alkoxy group remaining on the surface-treated particles. For this reason, surface-treated metal oxide particles having excellent ultraviolet shielding properties can be stably produced.
  • the method for producing surface-treated metal oxide particles according to the present embodiment includes a second determination step of determining that the loss on drying of the surface-treated metal oxide particles at 105 ° C. for 3 hours is 0.15% by mass or less. May be included.
  • the second determination step can be performed in the same manner as the above-described method for measuring the loss on drying of the surface-treated metal oxide particles at 105 ° C. for 3 hours.
  • the second determination step may be performed before or after the determination step using a Fourier transform infrared spectrophotometer.
  • a step of heating until the loss on drying becomes 0.15% by mass or less may be included.
  • the heating conditions in this heating step can be arbitrarily selected.
  • the temperature may be the same as that at the time of production of the particles, for example, a temperature of 70 to 200 ° C.
  • the surface-treated metal is used until a peak derived from an alkoxy group is not detected in the first determination step and the loss on drying is 0.15% by mass or less in the second determination step. It is preferable to include a step of heating the oxide particles. Further, when the desired characteristics are not satisfied in the first determination step and / or the second determination step, it is preferable to heat at a temperature of 70 ° C. to 200 ° C. until these characteristics are satisfied.
  • the dispersion of the present embodiment contains the surface-treated metal oxide particles of the present embodiment and a dispersion medium.
  • the dispersion of the present embodiment also includes a paste-like dispersion having a high viscosity.
  • the dispersion medium is not particularly limited as long as it can be formulated into cosmetics and can disperse the surface-treated particles.
  • the dispersion medium include water; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, octanol and glycerin; ethyl acetate, butyl acetate, ethyl lactate, propylene glycol monomethyl ether acetate; Esters such as 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 monomethyl ether, diethylene glycol Ethers such as monoethyl ether; natural oil, ester
  • Other dispersion media include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone and cyclohexanone; aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; cyclic hydrocarbons such as cyclohexane; dimethylformamide; Amides such as N, N-dimethylacetoacetamide and N-methylpyrrolidone; and linear polysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane and diphenylpolysiloxane.
  • ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone and cyclohexanone
  • aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene
  • dispersion media include cyclic polysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexanesiloxane; amino-modified polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, and fluorine-modified Modified polysiloxanes such as polysiloxane are used.
  • cyclic polysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexanesiloxane
  • amino-modified polysiloxane polyether-modified polysiloxane
  • alkyl-modified polysiloxane alkyl-modified polysiloxane
  • fluorine-modified Modified polysiloxanes such as polysiloxane
  • dispersing media include hydrocarbon oils such as liquid paraffin, squalane, isoparaffin, branched light paraffin, petrolatum, and ceresin; and ester oils such as isopropyl myristate, cetyl isooctanoate, and glyceryl trioctanoate.
  • hydrocarbon oils such as liquid paraffin, squalane, isoparaffin, branched light paraffin, petrolatum, and ceresin
  • ester oils 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 decanol, iso-
  • a hydrophobic dispersion medium such as a higher alcohol such as stearyl alcohol may be used. The above dispersion medium may be used singly or as a mixture of two or more.
  • the dispersion of the present embodiment may contain a commonly used additive as long as its properties are not impaired.
  • additives for example, preservatives, dispersants, dispersing aids, stabilizers, water-soluble binders, thickeners, oil-soluble drugs, oil-soluble pigments, oil-soluble proteins, UV absorbers and the like are preferably used.
  • preservatives for example, preservatives, dispersants, dispersing aids, stabilizers, water-soluble binders, thickeners, oil-soluble drugs, oil-soluble pigments, oil-soluble proteins, UV absorbers and the like are preferably used.
  • the particle diameter (d50) of the surface-treated metal oxide particles can be arbitrarily selected, but is preferably 300 nm or less, preferably 250 nm or less. Is more preferable, and further preferably 200 nm or less.
  • the lower limit value of d50 is not particularly limited, and may be, for example, 50 nm or more, 100 nm or more, or 150 nm or more.
  • the upper limit and the lower limit of d50 can be arbitrarily combined.
  • the particle size (d90) when the cumulative volume percentage of the particle size distribution in the dispersion of this embodiment is 90% can be arbitrarily selected, but is preferably 400 nm or less, more preferably 350 nm or less. , And 300 nm or less.
  • the lower limit of d90 is not particularly limited, and may be, for example, 100 nm or more, 150 nm or more, or 200 nm or more.
  • the upper limit and the lower limit of d90 can be arbitrarily combined.
  • the dispersion has a d50 of 300 nm or less, when the cosmetic prepared using the dispersion is applied to the skin, the surface-treated particles are easily distributed uniformly and the ultraviolet shielding effect is improved, which is preferable.
  • the d90 of the dispersion is 400 nm or less, the transparency of the dispersion is high, and the transparency of the cosmetic prepared using this dispersion is also high, which is preferable.
  • a dispersion having excellent transparency and excellent ultraviolet shielding properties can be obtained.
  • cosmetics produced using this dispersion are also excellent in transparency and ultraviolet shielding properties.
  • the cumulative volume percentage of the particle size distribution in the dispersion can be measured using a dynamic light scattering type particle size distribution measuring device.
  • the content of the surface-treated metal oxide particles in the dispersion of the present embodiment may be appropriately adjusted according to desired characteristics.
  • the content of the surface-treated metal oxide particles in the dispersion can be arbitrarily selected, but is preferably 10% by mass or more, and more preferably 20% by mass or more. More preferably, the content is more preferably 30% by mass or more. Further, the content of the surface-treated metal oxide particles in the dispersion is preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less. The upper and lower limits of the content of the surface-treated metal oxide particles in the dispersion can be arbitrarily combined.
  • the content of the surface-treated metal oxide particles in the dispersion is within the above range, the surface-treated metal oxide particles are contained at a high concentration. For this reason, the degree of freedom of formulation can be improved, and the viscosity of the dispersion can be reduced to a level that facilitates handling.
  • the viscosity of the dispersion of the present embodiment can be arbitrarily selected, but is preferably 5 Pa ⁇ s or more, more preferably 8 Pa ⁇ s or more, still more preferably 10 Pa ⁇ s or more, and more preferably 15 Pa ⁇ s or more. It is most preferred that it is s or more. Further, the viscosity of the dispersion is preferably 300 Pa ⁇ s or less, more preferably 100 Pa ⁇ s or less, further preferably 80 Pa ⁇ s or less, and most preferably 60 Pa ⁇ s or less. . The upper and lower limits of the viscosity of the dispersion can be arbitrarily combined.
  • the dispersion of the present embodiment is applied by applying a dispersion containing 10% by mass of the surface-treated particles onto a predetermined substrate so that the thickness after drying becomes 12 ⁇ m and naturally drying for 15 minutes.
  • the physical property value measured for the coating film is preferably in the following range. That is, the transmittance of the coating film at 450 nm is preferably 40% or more, more preferably 45% or more, and even more preferably 50% or more.
  • the upper limit of the transmittance is not particularly limited, and may be 100% or less, 90% or less, or 80% or less.
  • the upper limit and the lower limit of the transmittance at 450 nm of the coating film can be arbitrarily combined.
  • the transmittance at 450 nm is preferably higher.
  • the average transmittance of the coating film at 290 nm to 320 nm is preferably 10% or less, more preferably 7% or less, and even more preferably 5% or less.
  • the lower limit is not particularly limited, and may be 0% or more, 0.5% or more, or 1% or more.
  • the upper limit and the lower limit of the average transmittance of the coating film at 290 nm to 320 nm can be arbitrarily combined.
  • the SPF value of the coating film is preferably 30 or more, more preferably 35 or more, and even more preferably 40 or more.
  • the upper limit is not particularly limited, and may be 150 or less, 100 or less, or 80 or less.
  • the upper and lower limits of the SPF value of the coating film can be arbitrarily combined.
  • the critical wavelength (Critical Wavelength) of the coating film is preferably 370 nm or more.
  • the coating film can shield a wide range of ultraviolet light including long wavelength ultraviolet light (UVA) and short wavelength ultraviolet light (UVB).
  • UVA long wavelength ultraviolet light
  • UVB short wavelength ultraviolet light
  • the cosmetic containing the dispersion of the present embodiment has a critical wavelength of 370 nm or more, and the film formed on the skin by the cosmetic has a wide range of ultraviolet light of long wavelength ultraviolet (UVA) and short wavelength ultraviolet (UVB). Can be shielded.
  • the “critical wavelength” is a value obtained by measuring the coating film coated with the dispersion. Specifically, the absorption spectrum of the coating film in the ultraviolet region of 290 nm or more and 400 nm or less is measured, and the obtained absorption spectrum is integrated from 290 nm to the longer wavelength side. At this time, the wavelength at which the integrated area is 90% of the integrated area in the entire region of 290 nm or more and 400 nm or less is defined as the “critical wavelength”.
  • the method for producing the dispersion of the present embodiment is not particularly limited. For example, there is a method of mechanically dispersing the surface-treated particles of the present embodiment and the dispersion medium using a known dispersion apparatus.
  • the dispersion device can be selected as required, and examples thereof include a stirrer, a self-revolving mixer, a homomixer, an ultrasonic homogenizer, a sand mill, a ball mill, and a roll mill.
  • the dispersion of the present embodiment can be used for paints having an ultraviolet shielding function, a gas permeation suppression function, and the like, in addition to cosmetics.
  • the dispersion of the present embodiment since it contains the surface-treated metal oxide particles of the present embodiment, it exhibits a stable and high ultraviolet shielding property.
  • composition of the present embodiment contains the surface-treated particles of the present embodiment and a polymer.
  • the content of the surface-treated particles in the composition of the present embodiment may be appropriately adjusted according to desired characteristics.
  • the content is, for example, preferably 10% by mass or more and 40% by mass or less, and more preferably 20% by mass or more and 30% by mass or less.
  • the content of the surface-treated particles in the composition is within the above range, the solid content (surface-treated metal oxide particles) is contained at a high concentration, so that the properties of the surface-treated particles are sufficiently obtained, and Can be obtained.
  • the polymer in the composition of the present embodiment is not particularly limited, and for example, a water-soluble polymer, a semi-synthetic polymer, a synthetic polymer, a resin, and the like can be used.
  • a water-soluble polymer for example, gelatin, casein, collagen, hyaluronic acid, albumin, starch and the like can be used.
  • the semi-synthetic polymer for example, methyl cellulose, ethyl cellulose, methyl hydroxypropyl cellulose, carboxymethyl cellulose, hydroxymethyl cellulose, hydroxypropyl cellulose, sodium carboxymethyl cellulose, propylene glycol alginate and the like can be used.
  • synthetic polymer for example, polyvinyl alcohol, polyvinylpyrrolidone, carbomer (carboxyvinyl polymer), polyacrylate, polyethylene oxide and the like can be used.
  • the resin is not particularly limited as long as it is generally used in industrial applications, and examples thereof include an acrylic resin, an epoxy resin, a urethane resin, a polyester resin, and a silicone resin. When used for cosmetics, it is preferable to use a silicone resin.
  • the content of the polymer in the composition of the present embodiment is not particularly limited, and is appropriately adjusted according to the characteristics of the target composition.
  • the composition of the present embodiment may include a dispersion medium.
  • the dispersion medium is not particularly limited as long as it is generally used in industrial applications.
  • examples include water, alcohols such as methanol, ethanol, and propanol, methyl acetate, ethyl acetate, toluene, methyl ethyl ketone, and methyl isobutyl ketone. Is mentioned.
  • the dispersion medium may include one kind or a combination of two or more kinds.
  • the content of the dispersion medium in the composition of the present embodiment is not particularly limited, and is appropriately adjusted according to the characteristics of the target composition.
  • composition of the present embodiment may contain a commonly used additive as long as its properties are not impaired.
  • additives include a polymerization initiator, a dispersant, a preservative, a thickener, a higher fatty acid, and the like.
  • the method for producing the composition of the present embodiment is not particularly limited, and examples thereof include a method of mechanically mixing the surface-treated particles of the present embodiment and a polymer with a known mixing device.
  • Examples of the mixing device include a stirrer, a self-revolving mixer, a homomixer, and an ultrasonic homogenizer.
  • composition of the present embodiment a roll coating method, a flow coating method, a spray coating method, a screen printing method, a brush coating method, and a dipping method, etc., by a normal coating method, a substrate arbitrarily selected, for example,
  • a coating film can be formed.
  • These coating films can be used as arbitrarily selected applications, for example, as an ultraviolet shielding film or a gas barrier film.
  • the composition of the present embodiment since the composition contains the surface-treated metal oxide particles of the present embodiment, the composition exhibits a stable and high ultraviolet shielding property.
  • the cosmetic of one embodiment of the present embodiment contains at least one selected from the group consisting of the surface-treated metal oxide particles of the present embodiment, the dispersion of the present embodiment, and the composition of the present embodiment. Become.
  • the cosmetic of another embodiment includes a cosmetic base material and at least one selected from the group consisting of the surface-treated particles of the present embodiment, the dispersion of the present embodiment, and the composition of the present embodiment. It contains.
  • the cosmetic base material refers to various materials that form the main body of the cosmetic.
  • an oily raw material an aqueous raw material, a surfactant, a powder raw material and the like can be mentioned as examples.
  • the oily raw material can be arbitrarily selected, and examples thereof include oils and fats, higher fatty acids, higher alcohols, and ester oils.
  • the aqueous raw material can be arbitrarily selected and includes purified water, alcohol, thickener and the like.
  • the powder raw material can be arbitrarily selected and includes colored pigments, white pigments, pearling agents, extender pigments and the like.
  • the dispersion of the present embodiment is obtained by blending the dispersion of the present embodiment with a cosmetic base material such as a milky lotion, cream, foundation, lipstick, blusher, eye shadow, etc.
  • a cosmetic base material such as a milky lotion, cream, foundation, lipstick, blusher, eye shadow, etc.
  • the cosmetic of the present embodiment is obtained, for example, by blending the surface-treated particles of the present embodiment with an oil phase or an aqueous phase to form an O / W or W / O emulsion, and It is obtained by blending.
  • the content of the surface-treated metal oxide particles in the cosmetic of the present embodiment may be appropriately adjusted according to desired characteristics.
  • the lower limit of the content of the surface-treated particles 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 surface-treated particles may be 50% by mass or less, 40% by mass or less, or 30% by mass or less.
  • the upper limit and the lower limit of the content of the surface-treated particles in the cosmetic can be arbitrarily combined.
  • the sunscreen cosmetics In order to effectively block ultraviolet rays, especially long-wavelength ultraviolet rays (UVA), and to obtain a good feeling of use with less powderiness and squeaking in sunscreen cosmetics, it is necessary to include surface-treated metal oxide particles. Adjusting the amount is also preferred.
  • the lower limit of the content of the surface-treated metal oxide particles in the sunscreen cosmetic is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and more preferably 1% by mass or more. It is more preferred that there be.
  • the upper limit of the content of the surface-treated particles in the sunscreen cosmetic may be 50% by mass or less, 40% by mass or less, or 30% by mass or less.
  • the upper limit and the lower limit of the content of the surface-treated particles in the sunscreen cosmetics can be arbitrarily combined. In the above range, a preferable range such as 5 to 15% by mass or 10 to 20% by mass can be selected.
  • Sunscreen cosmetics include hydrophobic dispersion media, inorganic fine particles and inorganic pigments other than surface-treated metal oxide particles, hydrophilic dispersion media, oils and fats, surfactants, humectants, thickeners, and pH adjustment. Agents, nutrients, antioxidants, fragrances and the like.
  • hydrophobic dispersion medium examples include liquid oils such as liquid paraffin, squalane, isoparaffin, branched light paraffin, petrolatum, and ceresin; and ester oils such as isopropyl myristate, cetyl isooctanoate, and glyceryl trioctanoate.
  • liquid oils such as liquid paraffin, squalane, isoparaffin, branched light paraffin, petrolatum, and ceresin
  • ester oils 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 decanol, And higher alcohols such as stearyl alcohol.
  • inorganic fine particles and inorganic pigments other than the surface-treated metal oxide particles contained in the cosmetic for example, calcium carbonate, calcium phosphate (apatite), magnesium carbonate, calcium silicate, magnesium silicate, aluminum silicate, kaolin, talc,
  • examples include titanium oxide, aluminum oxide, yellow iron oxide, ⁇ -iron oxide, cobalt titanate, cobalt violet, and silicon oxide.
  • Sunscreen cosmetics may further contain at least one organic ultraviolet absorber.
  • organic UV absorbers examples include benzotriazole UV absorbers, benzoylmethane UV absorbers, benzoic UV absorbers, anthranilic UV absorbers, salicylic UV absorbers, and cinnamic UV absorbers. Agents, silicone-based cinnamate UV absorbers, and other organic-based UV absorbers.
  • benzotriazole-based ultraviolet absorber examples include, for example, 2,2′-hydroxy-5-methylphenylbenzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 2- (2′- Hydroxy-5'-methylphenylbenzotriazole and the like.
  • benzoylmethane-based ultraviolet absorber examples include dibenzalazine, dianisylmethane, 4-tert-butyl-4′-methoxydibenzoylmethane, 1- (4′-isopropylphenyl) -3-phenylpropane-1,3- Dione and 5- (3,3′-dimethyl-2-norbornylidene) -3-pentan-2-one.
  • benzoic acid-based ultraviolet absorber examples include para-aminobenzoic acid (PABA), PABA monoglycerin ester, N, N-dipropoxy PABA ethyl ester, N, N-diethoxy PABA ethyl ester, N, N-dimethyl PABA ethyl ester, N, N-dimethyl PABA butyl ester, N, N-dimethyl PABA methyl ester and the like can be mentioned.
  • PABA para-aminobenzoic acid
  • anthranilic acid-based ultraviolet absorber examples include homomenthyl-N-acetylanthranilate and the like.
  • salicylic acid-based ultraviolet absorber examples include amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, and p-2-propanol phenyl salicylate.
  • cinnamic acid-based ultraviolet absorbers examples include octyl methoxycinnamate (ethylhexyl methoxycinnamate), glyceryl di-paramethoxycinnamate-mono-2-ethylhexanoate, octyl cinnamate, and ethyl-4-isopropyl cinnamate Mate, methyl-2,5-diisopropylcinnamate, ethyl-2,4-diisopropylcinnamate, methyl-2,4-diisopropylcinnamate, propyl-p-methoxycinnamate, isopropyl-p-methoxycinnamate, isoamyl- p-methoxycinnamate, octyl-p-methoxycinnamate (2-ethylhexyl-p-methoxycinnamate), 2-ethoxyethy
  • silicone-based cinnamic acid ultraviolet absorber examples include [3-bis (trimethylsiloxy) methylsilyl-1-methylpropyl] -3,4,5-trimethoxycinnamate and [3-bis (trimethylsiloxy) methylsilyl- 3-methylpropyl] -3,4,5-trimethoxycinnamate, [3-bis (trimethylsiloxy) methylsilylpropyl] -3,4,5-trimethoxycinnamate, [3-bis (trimethylsiloxy) methyl [Silylbutyl] -3,4,5-trimethoxycinnamate, [3-tris (trimethylsiloxy) silylbutyl] -3,4,5-trimethoxycinnamate, [3-tris (trimethylsiloxy) silyl-1-methyl Propyl] -3,4-dimethoxycinnamate.
  • organic ultraviolet absorbers other than those described above include, for example, 3- (4′-methylbenzylidene) -d, l-camphor, 3-benzylidene-d, l-camphor, urocanic acid, urocanic acid ethyl ester, 2-phenyl Examples thereof include -5-methylbenzoxazole, 5- (3,3'-dimethyl-2-norbornylidene) -3-pentan-2-one, a silicone-modified ultraviolet absorber, and a fluorine-modified ultraviolet absorber.
  • the ultraviolet absorber may be used alone or in combination of two or more.
  • the critical wavelength of the cosmetic of the present embodiment is preferably 370 nm or more.
  • a wide range of long-wave ultraviolet (UVA) and short-wave ultraviolet (UVB) ultraviolet can be blocked.
  • the cosmetic contains at least one selected from the group consisting of the surface-treated metal oxide particles of the present embodiment, the dispersion of the present embodiment, and the composition of the present embodiment. For this reason, it is possible to stably exhibit high ultraviolet shielding properties.
  • Example 1 "Production of surface-treated metal oxide particles" 100 parts by mass of zinc oxide particles (specific surface area S: 30 m 2 / g, manufactured by Sumitomo Osaka Cement Co., Ltd.), 8 parts by mass of octyltriethoxysilane (trade name: KBE-3083, manufactured by Shin-Etsu Chemical Co., Ltd.), and 0. A mixed solution of 6 parts by mass and 34.2 parts by mass of isopropyl alcohol was mixed in a Henschel mixer. Then, the mixture was dried at 80 ° C. until isopropyl alcohol was removed.
  • Example 1 The obtained dried product was crushed by a hammer mill, and the crushed powder was dried at 120 ° C. for 3 hours to obtain surface-treated zinc oxide particles of Example 1.
  • Example 2 Surface-treated zinc oxide particles of Example 2 were obtained in the same manner as in Example 1, except that drying was performed at 120 ° C. for 3 hours instead of drying at 120 ° C. for 3 hours.
  • a dispersion liquid of Example 2 was obtained in the same manner as in Example 1 except that the surface-treated zinc oxide particles of Example 2 were used instead of using the surface-treated zinc oxide particles obtained in Example 1.
  • Comparative Example 1 Surface-treated zinc oxide particles of Comparative Example 1 were obtained in the same manner as in Example 1 except that drying was performed at 100 ° C. for 1 hour instead of drying at 120 ° C. for 3 hours. A dispersion liquid of Comparative Example 1 was obtained in the same manner as in Example 1 except that the surface-treated zinc oxide particles of Comparative Example 1 were used instead of using the surface-treated zinc oxide particles obtained in Example 1.
  • Example 2 surface-treated zinc oxide particles of Comparative Example 2 were obtained in the same manner as in Example 1, except that drying was performed at 120 ° C. for 3 hours and air drying was performed. A dispersion liquid of Comparative Example 2 was obtained in the same manner as in Example 1 except that the surface-treated zinc oxide particles of Comparative Example 2 were used instead of using the surface-treated zinc oxide particles obtained in Example 1.
  • Comparative Example 3 The surface-treated zinc oxide particles of Comparative Example 3 were obtained by allowing the surface-treated zinc oxide particles obtained in Example 1 to stand at 85 ° C. and 90% RH for 72 hours to absorb water. .
  • a dispersion liquid of Comparative Example 3 was obtained in the same manner as in Example 1 except that the surface-treated zinc oxide particles of Comparative Example 3 were used instead of using the surface-treated zinc oxide particles obtained in Example 1.
  • Example 3 The surface-treated zinc oxide particles of Example 3 were obtained by drying the surface-treated zinc oxide particles obtained in Comparative Example 3 at 120 ° C. for 3 hours. A dispersion liquid of Example 3 was obtained in the same manner as in Example 1 except that the surface-treated zinc oxide particles of Example 3 were used instead of using the surface-treated zinc oxide particles obtained in Example 1.
  • Comparative Example 1 the surface treated zinc oxide particles of Comparative Example 2, 1170cm -1, 1100cm -1, 1080cm -1, and peaks in 950 cm -1 was detected. That is, in Examples, unreacted octyltriethoxysilane was not detected on the particle surface, and it was confirmed that in Comparative Examples 1 and 2, unreacted octyltriethoxysilane remained.
  • FIG. 1 shows the results of FT-IR measurement of Example 1, Comparative Example 1, and octyltriethoxysilane.
  • Examples 1 to 3 1170cm -1, 1100cm -1, 1080cm -1, and a peak in any of the 950 cm -1 it is not detected Comparative Example 1 in which these peaks are detected, compared with Comparative Example 2 Also, it was confirmed that the maximum aggregation diameter was small and the SPF value was high. In Examples 1 to 3 in which the loss on drying at 105 ° C. for 3 hours was 0.15% by mass or less, the maximum agglomeration was larger than that in Comparative Examples 1 to 3 in which the loss on drying exceeded 0.15% by mass. It was confirmed that the diameter was small and the SPF value was high.
  • the surface-treated metal oxide particles of the present invention exhibit a stable and high ultraviolet shielding property. Therefore, the surface-treated metal oxide particles of the present invention can easily ensure design quality when applied to dispersions, compositions, paints, and cosmetics, and have large industrial value.

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Abstract

La présente invention concerne des particules d'oxyde métallique traitées en surface qui sont des particules d'oxyde métallique, chacune de celles-ci étant traitée en surface avec un agent de couplage silane comprenant un groupe alcoxy, les particules d'oxyde métallique présentant des propriétés de blocage de rayons ultraviolets, la perte au séchage des particules d'oxyde métallique traitées en surface à 105 °C pendant 3 heures étant inférieure ou égale à 0,15 % en masse, et un pic attribué au groupe alcoxy n'étant pas détecté dans un spectre des particules d'oxyde métallique traitées en surface tel que mesuré avec un spectromètre infrarouge à transformée de Fourier.
PCT/JP2019/038132 2018-09-28 2019-09-27 Particules d'oxyde métallique traitées en surface, dispersion liquide, produit cosmétique et procédé de production de particules d'oxyde métallique traitées en surface WO2020067417A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001181136A (ja) * 1999-12-27 2001-07-03 Daito Kasei Kogyo Kk 化粧料用顔料およびその顔料を含む化粧料
JP2006299126A (ja) * 2005-04-21 2006-11-02 Nissan Motor Co Ltd ナノフィラーの表面改質方法、ポリマーナノコンポジット及びポリマーナノコンポジットの製造方法
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JP2009001750A (ja) * 2007-06-25 2009-01-08 Nippon Paint Co Ltd 無機有機複合コーティング組成物の製造方法
JP2009019075A (ja) * 2007-07-10 2009-01-29 Nippon Paint Co Ltd 無機有機複合コーティング組成物
JP2009208988A (ja) * 2008-03-03 2009-09-17 Hyogo Prefecture 酸化チタンナノチューブを用いた機能性材料
JP2013037747A (ja) * 2011-08-09 2013-02-21 Asahi Glass Co Ltd 波長選択回折素子及びこれを用いた光ヘッド装置
WO2017221940A1 (fr) * 2016-06-24 2017-12-28 東レ・ダウコーニング株式会社 Agent de traitement de poudre pour cosmétique, poudre pour cosmétique, et cosmétique formulé en utilisant ladite poudre

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001181136A (ja) * 1999-12-27 2001-07-03 Daito Kasei Kogyo Kk 化粧料用顔料およびその顔料を含む化粧料
JP2006299126A (ja) * 2005-04-21 2006-11-02 Nissan Motor Co Ltd ナノフィラーの表面改質方法、ポリマーナノコンポジット及びポリマーナノコンポジットの製造方法
JP2008303231A (ja) * 2007-06-05 2008-12-18 Nippon Paint Co Ltd 無機有機複合コーティング組成物
JP2009001750A (ja) * 2007-06-25 2009-01-08 Nippon Paint Co Ltd 無機有機複合コーティング組成物の製造方法
JP2009019075A (ja) * 2007-07-10 2009-01-29 Nippon Paint Co Ltd 無機有機複合コーティング組成物
JP2009208988A (ja) * 2008-03-03 2009-09-17 Hyogo Prefecture 酸化チタンナノチューブを用いた機能性材料
JP2013037747A (ja) * 2011-08-09 2013-02-21 Asahi Glass Co Ltd 波長選択回折素子及びこれを用いた光ヘッド装置
WO2017221940A1 (fr) * 2016-06-24 2017-12-28 東レ・ダウコーニング株式会社 Agent de traitement de poudre pour cosmétique, poudre pour cosmétique, et cosmétique formulé en utilisant ladite poudre

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