WO2020067417A1 - Surface-treated metal oxide particles, liquid dispersion, cosmetic, and method for producing surface-treated metal oxide particles - Google Patents

Surface-treated metal oxide particles, liquid dispersion, cosmetic, and method for producing surface-treated metal oxide particles Download PDF

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Publication number
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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Prior art keywords
oxide particles
metal oxide
treated
treated metal
dispersion
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PCT/JP2019/038132
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French (fr)
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

Surface-treated metal oxide particles which are metal oxide particles each surface-treated with a silane coupling agent having an alkoxy group, wherein the metal oxide particles have ultraviolet ray blocking properties, the loss on drying of the surface-treated metal oxide particles at 105ºC for 3 hours is 0.15% by mass or less, and a peak attributed to the alkoxy group is not detected in a spectra of the surface-treated metal oxide particles as measured with a Fourier transform infrared spectrometer.

Description

表面処理金属酸化物粒子、分散液、化粧料および表面処理金属酸化物粒子の製造方法Surface-treated metal oxide particles, dispersion, cosmetic, and method for producing surface-treated metal oxide particles
　本発明は、表面処理金属酸化物粒子、分散液、化粧料および表面処理金属酸化物粒子の製造方法に関する。
　本願は、２０１８年９月２８日に、日本に出願された特願２０１８－１８３４８６号、及び２０１９年７月５日に、日本に出願された特願２０１９－１２６２９２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 surface-treated metal oxide particle, a dispersion, a cosmetic, and a method for producing a surface-treated metal oxide particle.
This application claims priority based on Japanese Patent Application No. 2018-183486 filed in Japan on September 28, 2018 and Japanese Patent Application No. 2019-126292 filed in Japan on July 5, 2019. , The contents of which are incorporated herein.
　酸化亜鉛や酸化チタン等の紫外線遮蔽性を有する金属酸化物粒子は、日焼け止め、ファンデーション等の化粧料に使用されている。
　これらの金属酸化物粒子を化粧料に適用する場合、金属酸化物粒子の表面状態を化粧品の性状に合わせたり、金属酸化物粒子の触媒活性を抑えたりするために、金属酸化物粒子の表面処理が行われている。このような金属酸化物粒子の表面処理剤としては、例えば、ステアリン酸マグネシウム等の金属石鹸、ジメチコンやハイドロゲンジメチコン等のシリコーンオイル、オクチルトリエトキシシラン等のアルコキシ基を有するシランカップリング剤等が用いられている（例えば、特許文献１、２参照）。 Ultraviolet shielding metal oxide particles such as zinc oxide and titanium oxide are used in cosmetics such as sunscreens and foundations.
When these metal oxide particles are applied to cosmetics, 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. Has been done. Examples of 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).
　中でも、上記シランカップリング剤で表面処理した金属酸化物粒子は、表面処理剤であるシランカップリング剤が金属酸化物粒子の表面に化学的に結合しているため安定性が高い。
　さらに、上記のような金属酸化物粒子は、置換基が異なる表面処理剤を用いることにより、粒子表面の性質を容易に変更可能である。以下の説明では、シランカップリング剤で表面処理した金属酸化物粒子を表面処理金属酸化物粒子と称する。 Above all, 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.
　このような表面処理金属酸化物粒子は、そのまま化粧料に配合されたり、分散媒に分散させた分散液の状態で化粧料に配合されたりしている。 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.
特開２００２－３６２９２５号公報JP-A-2002-362925 特開２００１－１８１１３６号公報JP 2001-181136 A
　しかしながら、上記表面処理金属酸化物粒子は、化粧料に配合したときの紫外線遮蔽性が悪い場合があり、紫外線遮蔽性に関する品質が安定し難いという課題があった。特に、比表面積が大きい金属酸化物粒子を用いた場合や、表面処理剤の量を増やした場合や、長期保管した場合には、表面処理金属酸化物粒子の紫外線遮蔽性が大きく低下するという課題があった。 However, 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. In particular, when metal oxide particles having a large specific surface area are used, when the amount of the surface treatment agent is increased, or when the metal oxide particles are stored for a long period of time, the ultraviolet shielding properties of the surface treated metal oxide particles are significantly reduced. was there.
　本発明は上記事情に鑑みてなされたものであって、安定的に高い紫外線遮蔽性を示す表面処理金属酸化物粒子を提供することを目的とする。また、このような表面処理金属酸化物粒子を含む分散液、組成物、化粧料を提供することをあわせて目的とする。また、このような表面処理金属酸化物粒子の製造方法を提供することをあわせて目的とする。 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.
　上記の課題を解決するため、本発明は、以下の表面処理金属酸化物粒子、分散液、及び化粧料を提供する。
　本発明の第一の態様は、アルコキシ基を有するシランカップリング剤で表面処理された金属酸化物粒子であって、前記金属酸化物粒子は紫外線遮蔽性を有し、前記表面処理された金属酸化物粒子の１０５℃、３時間における乾燥減量が０．１５質量％以下であり、前記表面処理された金属酸化物粒子を、フーリエ変換式赤外分光光度計で測定した９００ｃｍ－１～１３００ｃｍ－１における反射スペクトルにおいて、前記アルコキシ基に由来するピークが検出されない表面処理金属酸化物粒子を提供する。 In order to solve the above-mentioned problems, the present invention provides the following surface-treated metal oxide particles, a dispersion, and a cosmetic.
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.
　本発明の第二の態様は、上記の表面処理金属酸化物粒子と、分散媒と、を含有する分散液を提供する。 第二 A second aspect of the present invention provides a dispersion containing the above-mentioned surface-treated metal oxide particles and a dispersion medium.
　本発明の第三の態様は、上記の表面処理金属酸化物粒子および上記の分散液からなる群から選ばれる少なくとも１種を含有する化粧料を提供する。 第三 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.
　本発明の第四の態様は、アルコキシ基を有するシランカップリング剤で表面処理された金属酸化物粒子の製造方法であって、前記金属酸化物粒子は紫外線遮蔽性を有し、前記表面処理された金属酸化物粒子を、フーリエ変換式赤外分光光度計で測定した９００ｃｍ－１～１３００ｃｍ－１における反射スペクトルにおいて、前記アルコキシ基に由来するピークが検出されないことを判定する工程を含む、表面処理金属酸化物粒子の製造方法を提供する。 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.
　本発明によれば、安定的に高い紫外線遮蔽性を示す表面処理金属酸化物粒子を提供することができる。また、本発明によれば、このような表面処理金属酸化物粒子を含む分散液、化粧料を提供することができる。また、本発明によれば、このような表面処理金属酸化物粒子を製造する方法を提供することができる。 According to 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.
実施例１と比較例１の表面処理酸化亜鉛粒子と、オクチルトリエトキシシランのＦＴ－ＩＲの測定結果を示す図である。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. 実施例１の表面処理酸化亜鉛粒子の光学顕微鏡像を示す図である。FIG. 2 is a view showing an optical microscope image of surface-treated zinc oxide particles of Example 1. 比較例２の表面処理酸化亜鉛粒子の光学顕微鏡像を示す図である。FIG. 4 is a view showing an optical microscope image of surface-treated zinc oxide particles of Comparative Example 2.
　本発明の表面処理金属酸化物粒子、分散液、化粧料および表面処理金属酸化物粒子の製造方法の、好ましい実施の形態について説明する。
　なお、本実施の形態は、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。例えば、特に制限の無い限り、材料、量、種類、数、サイズ、比率、温度などの条件などを、必要に応じて変更、追加、及び省略してもよい。以下に述べる実施形態間において、互いの好ましい例を交換したり、共有しても良い。 Preferred embodiments of the method for producing surface-treated metal oxide particles, dispersion liquid, cosmetics and surface-treated metal oxide particles of the present invention will be described.
The present embodiment is specifically described for better understanding of the spirit of the present invention, and does not limit the present invention unless otherwise specified. For example, unless otherwise specified, conditions such as materials, amounts, types, numbers, sizes, ratios, and temperatures may be changed, added, or omitted as necessary. Preferred embodiments may be exchanged or shared between the embodiments described below.
　以下の説明においては、表面処理金属酸化物粒子を「表面処理粒子」と略称することがある。 に お い て In the following description, the surface-treated metal oxide particles may be abbreviated as “surface-treated particles”.
［表面処理金属酸化物粒子］
　本実施形態の表面処理金属酸化物粒子は、アルコキシ基を有するシランカップリング剤で表面処理された紫外線遮蔽性を有する金属酸化物粒子である。前記金属酸化物粒子は紫外線遮蔽性を有し、かつ、表面処理された金属酸化物粒子の１０５℃、３時間における乾燥減量が０．１５質量％以下である。さらに、この表面処理された金属酸化物粒子を、フーリエ変換式赤外分光光度計（ＦＴ－ＩＲ）で測定した９００ｃｍ－１～１３００ｃｍ－１における反射スペクトルにおいて、前記アルコキシ基に由来するピークが検出されない。 [Surface treated metal oxide 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. Further, 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.
　（表面処理金属酸化物粒子の反射スペクトル）
　前記アルコキシ基に由来するピークとは、アルコキシ基を有するシランカップリング剤をＦＴ－ＩＲで、ＡＴＲ法で測定した場合に、一般的に、９００ｃｍ－１～１３００ｃｍ－１の範囲で検出されるピークを意味する。
　ピークの有無の検出については、詳細には、アルコキシ基を有するシランカップリング剤の構造を考慮し、「有機化合物のスペクトルによる同定法、第６版」を用いて、アルコキシ基のピークを同定すればよい。 (Reflection spectrum of surface-treated metal oxide particles)
Wherein 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 Means
Regarding the detection of the presence or absence of the peak, in detail, considering the structure of the silane coupling agent having an alkoxy group, 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.
　前記アルコキシ基に由来するピークであって、検出されないことが好ましいピークは、１１７０ｃｍ－１、１１００ｃｍ－１、１０８０ｃｍ－１、および９５０ｃｍ－１である。これらのピークの少なくとも１つが検出されないことが好ましく、全てのピークが検出されないことがより好ましい。
　これらのピークは、アルコキシ基を有するシランカップリング剤であるオクチルトリエトキシシランをＦＴ－ＩＲで測定したときに、９００ｃｍ－１～１３００ｃｍ－１の範囲で検出されるピークである。 A peak derived from the alkoxy group, the peak 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.
These peaks, 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.
　本明細書において「ピークが検出されない」とは、ベースラインの反射率を０％としたときに、ピークトップの反射率が絶対値で１％以下（－１％以上０％以下）であることを意味する。
　また、本明細書において、９５０ｃｍ－１においてピークが検出されないとは、９５０ｃｍ－１を範囲に含むピークが検出されないことを意味する。すなわち、９５０ｃｍ－１をピークトップとするピークが検出されない、という意味ではない。１１７０ｃｍ－１、１１００ｃｍ－１、１０８０ｃｍ－１についても同様である。
　なお、「フーリエ変換式赤外分光光度計」を「ＦＴ－ＩＲ」と略記する場合がある。 In this specification, "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%. Means
In this specification, 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.
Note that “Fourier transform infrared spectrophotometer” may be abbreviated as “FT-IR”.
　フーリエ変換式赤外分光光度計で測定したスペクトルにおいて、アルコキシ基由来のピークが検出されないことの技術的意義について以下に説明する。
　アルコキシ基を有するシランカップリング剤で表面処理された金属酸化物粒子をＦＴ－ＩＲを測定した時に、このアルコキシ基に由来するピークが観察されないということは、シランカップリング剤のアルコキシ基が残留していないことを意味する。 The technical significance of not detecting a peak derived from an alkoxy group in a spectrum measured by a Fourier transform infrared spectrophotometer will be described below.
When a metal oxide particle surface-treated with a silane coupling agent having an alkoxy group was subjected to FT-IR measurement, no peak derived from the alkoxy group was observed, which means that the alkoxy group of the silane coupling agent remained. Not mean.
　本実施形態では、アルコキシ基を含むシランカップリング剤を加水分解反応させることにより、金属酸化物粒子の表面処理をしている。そのため、アルコキシ基が残留していないということは、シランカップリング剤中のアルコキシ基のほぼ全てが加水分解反応して、金属酸化物粒子表面にあるＯＨ基と反応していると推測される。その結果、表面処理金属酸化物粒子に残存するＯＨ基は少なくなっている、又は残存していない、と推測される。また、表面金属酸化物粒子を保管した場合に、前記粒子中に残留したアルコキシ基が大気中の水分により加水分解されて、その結果、表面金属酸化物粒子中のＯＨ基が増えてしまうことを、防止することができる、と推測される。 In the present embodiment, 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.
　（表面処理金属酸化物粒子の乾燥減量）
　本実施形態の表面処理金属酸化物粒子は、１０５℃、３時間における乾燥減量が０．１５質量％以下であり、０．１３質量％以下がより好ましく、０．１０質量％以下であることがさらに好ましい。乾燥減量の下限値は任意に選択できるが、例えば０．００質量％や、０．０１質量％や０．０３質量％であってもよい。 (Dry weight loss of surface treated metal oxide particles)
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.
　１０５℃、３時間における乾燥減量が０．１５質量％を超えないと、水系の揮発成分と油系の成分を含む組成物への分散安定性が保たれ、表面処理金属酸化物粒子を含む組成物が対象物（化粧料の場合、肌）に塗布されても高い紫外線遮蔽性を示すことができる。 When 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.
　表面処理金属酸化物粒子の１０５℃、３時間における乾燥減量は、以下の方法により得ることができる。まず、表面処理金属酸化物粒子２ｇを用意する。この表面処理金属酸化物粒子は、乾燥条件下で保管されている粒子であることが好ましい。この粒子を１０５℃に設定した乾燥機で３時間加熱し、加熱後の質量を測定し、その質量減少率を乾燥減量（質量％）とすることができる。
　すなわち、乾燥減量は、表面処理金属酸化物粒子の乾燥減量（質量％）＝（加熱前の表面処理金属酸化物粒子の質量－加熱後の表面処理金属酸化物粒子の質量）／加熱前の表面処理金属酸化物粒子の質量×１００、の式より得ることができる。 The loss on drying of the surface-treated metal oxide particles at 105 ° C. for 3 hours can be obtained by the following method. First, 2 g of surface-treated metal oxide particles are prepared. The surface-treated metal oxide particles are preferably particles stored under dry conditions. The particles are heated in a dryer set at 105 ° C. for 3 hours, the mass after heating is measured, and the mass reduction rate can be regarded as the loss on drying (% by mass).
That is, the loss on drying is determined by the loss on drying (% by mass) of the surface-treated metal oxide particles = (the mass of the surface-treated metal oxide particles before heating−the mass of the surface-treated metal oxide particles after heating) / the surface before heating. It can be obtained from the formula of mass of treated metal oxide particles × 100.
　（表面処理金属酸化物粒子の紫外線遮蔽性）
　本発明者等は、ＦＴ－ＩＲで測定した９００ｃｍ－１～１３００ｃｍ－１における反射スペクトルにおいて、アルコキシ基に由来するピークが検出されず、かつ、１０５℃３時間における乾燥減量が０．１５質量％以下の表面処理金属酸化物粒子であれば、化粧料に配合されたときに、表面処理金属酸化物粒子の紫外線遮蔽性が非常に高いことを見出した。 (Ultraviolet shielding properties of surface-treated metal oxide particles)
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.
　その理由は次のように推測される。
　化粧料は、一般に水中油型（ｏｉｌ　ｉｎ　ｗａｔｅｒ：Ｗ／Ｏ型）または油中水型（ｗａｔｅｒ　ｉｎ　ｏｉｌ：Ｏ／Ｗ型）の剤型で用いられる。アルコキシ基由来のピークが検出され、かつ、上記乾燥減量が０．１５質量％を超える表面処理金属酸化物粒子が、油相に配合された化粧料においては、表面処理金属酸化物粒子中のＯＨ基数が多い。このため、肌に塗布されて乾燥される過程で、油相中で表面処理金属酸化物粒子同士が凝集しやすく、肌に所望の紫外線遮蔽性を付与することが難しくなる、と推測される。 The reason is presumed as follows.
The cosmetic is generally used in an oil-in-water (W / O type) or water-in-oil (O / W type) dosage form. In cosmetics in which a peak derived from an alkoxy group is detected and the above-mentioned loss on drying exceeds 0.15% by mass is contained in an oil phase, 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.
　しかし、上記アルコキシ基由来のピークが検出されず、かつ、乾燥減量が０．１５質量％以下の、本実施形態の表面処理金属酸化物粒子であれば、表面処理金属酸化物粒子中のＯＨ基が少なく、かつ、積極的に増えることはない。このため、安定的に高い紫外線遮蔽性を示すことができる、と推測される。
　なお本発明において、紫外線遮蔽性を有するとは、紫外線（１０～４００ｎｍ）領域中の、少なくとも何れかの範囲を、遮蔽する効果を有することを意味する。　紫外線遮蔽性の有無を評価する方法の例を挙げると、金属酸化物粒子を１０質量％含む塗膜の２５０～４５０ｎｍの波長領域における透過スペクトルを測定することが挙げられる。紫外線遮蔽性を有する場合、２５０～４００ｎｍの波長領域における透過率が、４５０ｎｍにおける透過率よりも低くなる領域がある。
　なお上記実施形態の表面処理金属酸化物粒子は、一次粒子であることが好ましい。ただし、これのみに限定されない。例えば、一次粒子同士が凝集して二次粒子を形成していてもよい。 However, if the peak derived from the alkoxy group is not detected, and the loss on drying is 0.15% by mass or less, the OH group in the surface-treated metal oxide particle may be used. Is small and does not increase positively. For this reason, it is presumed that high ultraviolet shielding properties can be stably exhibited.
In the present invention, 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. In the case of having an ultraviolet shielding property, there is a region where the transmittance in the wavelength region of 250 to 400 nm is lower than the transmittance in the wavelength region of 450 nm.
The surface-treated metal oxide particles of the above embodiment are preferably primary particles. However, it is not limited to this. For example, the primary particles may aggregate to form secondary particles.
　[表面処理金属酸化物粒子の比表面積]
　前記表面処理金属酸化物粒子の比表面積は任意に選択できるが、１．５ｍ２／ｇ以上であることが好ましく、２．５ｍ２／ｇ以上であることがより好ましく、４ｍ２／ｇ以上であることがさらに好ましい。また、表面処理金属酸化物粒子の比表面積は、６５ｍ２／ｇ以下であることが好ましく、６０ｍ２／ｇ以下であることがより好ましい。必要に応じて、５０ｍ２／ｇ以下や、３０ｍ２／ｇ以下や、１０ｍ２／ｇ以下であってもよい。表面処理金属酸化物粒子の比表面積の上記上限値および下限値は、任意に組み合わせることができる。
　表面処理金属酸化物粒子の比表面積が１．５ｍ２/ｇ以上６５ｍ２/ｇ以下であれば、化粧料に配合した場合に透明性と紫外線遮蔽性に優れる。
　化粧料に配合した場合の透明性を高くしたい場合には、前記表面処理金属酸化物粒子の比表面積は８ｍ２/ｇ以上であることが好ましく、１５ｍ２/ｇ以上であることがより好ましく、２０ｍ２/ｇ以上であることがさらに好ましい。一方で、化粧料に配合した場合の紫外線遮蔽性を大きくしたい場合には、前記表面処理金属酸化物粒子の比表面積は８ｍ２/ｇ未満であることが好ましく、７．５ｍ２/ｇ以下であることがより好ましく、７．０ｍ２/ｇ以下であることがさらに好ましい。 [Specific surface area of surface-treated metal oxide 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. In addition, 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.
When 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.
When it is desired to increase the transparency when blended in a cosmetic, 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. 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 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.
　前記表面処理金属酸化物粒子の比表面積とは、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）を用い、ＢＥＴ法により測定された値を意味する。 比 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).
　本実施形態の表面処理金属酸化物粒子の平均一次粒子径は任意に選択できるが、１５ｎｍ以上であることが好ましく、２０ｎｍ以上であることがより好ましい。また、前記表面処理金属酸化物粒子の平均一次粒子径は７１５ｎｍ以下であることが好ましく、６５０ｎｍ以下であることがより好ましい。
　表面処理金属酸化物粒子の平均一次粒子径が１５ｎｍ以上７１５ｎｍ以下であれば、化粧料に配合した場合に透明性と紫外線遮蔽性に優れる。
　化粧料に配合した場合の透明性を高くしたい場合には、前記表面処理金属酸化物粒子の平均一次粒子径は１３５ｎｍ以下であることが好ましく、１００ｎｍ以下であることがより好ましく、５０ｎｍ以下であることがさらに好ましい。一方で、化粧料に配合した場合の紫外線遮蔽性を大きくしたい場合には、前記表面処理金属酸化物粒子の一次粒子径は１３５ｎｍを超えることが好ましく、１４０ｎｍ以上であることがより好ましく、１５０ｎｍ以上であることがさらに好ましい。 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.
When 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.
When it is desired to increase the transparency when blended in a cosmetic, 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. Is more preferable. On the other hand, when it is desired to increase the ultraviolet shielding property when blended in a cosmetic, 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.
　前記表面処理金属酸化物粒子の平均一次粒子径は、前記表面処理金属酸化物粒子の比表面積を用いて（１）式によって算出することができる。
　平均一次粒子径（ｎｍ）＝６０００/（比表面積（ｍ２/ｇ）×ρ（ｇ/ｃｍ３）・・・（１）
　　（式中、ρは金属酸化物粒子の密度である。）
　例えば、酸化亜鉛のρは５．６１ｇ/ｃｍ３であり、酸化チタンのρは４．２３ｇ/ｃｍ３である。
　または、前記表面処理金属酸化物粒子の平均一次粒子径は、以下の方法で求めてもよい。すなわち、前記表面処理金属酸化物粒子を、透過型電子顕微鏡（ＴＥＭ）等を用いて観察した場合に、表面処理金属酸化物粒子を所定数、例えば、２００個、あるいは１００個を選び出す。そして、これら表面処理金属酸化物粒子各々の最長の直線部分（最大長径）を測定し、これらの測定値を算術平均する。
　なお、表面処理金属酸化物粒子同士が凝集している場合には、この凝集体の凝集粒子径を測定するのではない。この凝集体を構成している表面処理金属酸化物粒子（一次粒子）を所定数測定し、平均一次粒子径とする。 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) × ρ (g / cm 3 ) (1)
(Where ρ is the density of the metal oxide particles.)
For example, ρ of zinc oxide is 5.61 g / cm 3 , and ρ of titanium oxide is 4.23 g / cm 3 .
Alternatively, the average primary particle diameter of the surface-treated metal oxide particles may be determined by the following method. That is, when the surface-treated metal oxide particles are observed using a transmission electron microscope (TEM) or the like, 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.
When 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.
［金属酸化物粒子］
　本実施形態における、原料として使用される金属酸化物粒子は、紫外線遮蔽性を有していれば特に限定されない。金属酸化物粒子としては、例えば、酸化亜鉛粒子、酸化チタン粒子、酸化セリウム粒子等を用いることができる。化粧料に一般的に使用されているため、酸化亜鉛粒子と酸化チタン粒子がより好ましい。ＵＶ－Ａ領域の紫外線遮蔽性に優れる点において、酸化亜鉛粒子がさらに好ましい。 [Metal oxide particles]
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. As 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.
　本実施形態における金属酸化物粒子の比表面積は任意に選択できるが、１．５ｍ２／ｇ以上であることが好ましく、２．５ｍ２／ｇ以上であることがより好ましく、４ｍ２／ｇ以上であることがさらに好ましい。また、金属酸化物粒子の比表面積は、６５ｍ２／ｇ以下であることが好ましく、６０ｍ２／ｇ以下であることがより好ましい。必要に応じて、５０ｍ２／ｇ以下や、３０ｍ２／ｇ以下や、１０ｍ２／ｇ以下であってもよい。
金属酸化物粒子の比表面積の上記上限値および下限値は、任意に組み合わせることができる。
　前記金属酸化物粒子の比表面積が１．５ｍ２/ｇ以上６５ｍ２/ｇ以下であれば、化粧料に配合した場合に透明性と紫外線遮蔽性に優れる。
　化粧料に配合した場合の透明性を高くしたい場合には、金属酸化物粒子の比表面積は８ｍ２/ｇ以上であることが好ましく、１５ｍ２/ｇ以上であることがより好ましく、２０ｍ２/ｇ以上であることがさらに好ましい。一方で、化粧料に配合した場合の紫外線遮蔽性を大きくしたい場合には、前記金属酸化物粒子の比表面積は８ｍ２/ｇ未満であることが好ましく、７．５ｍ２/ｇ以下であることがより好ましく、７．０ｍ２/ｇ以下であることがさらに好ましい。 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.
When 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.
　本実施形態における金属酸化物粒子の比表面積とは、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）を用い、ＢＥＴ法により測定された値を意味する。 比 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).
　本実施形態の金属酸化物粒子の平均一次粒子径は任意に選択できるが、１５ｎｍ以上であることが好ましく、２０ｎｍ以上であることがより好ましい。また、前記表面処理金属酸化物粒子の平均一次粒子径は７１５ｎｍ以下であることが好ましく、６５０ｎｍ以下であることがより好ましい。
　金属酸化物粒子の平均一次粒子径が１５ｎｍ以上７１５ｎｍ以下であれば、化粧料に配合した場合に透明性と紫外線遮蔽性に優れる。
　化粧料に配合した場合の透明性を高くしたい場合には、前記金属酸化物粒子の平均一次粒子径は１３５ｎｍ以下であることが好ましく、１００ｎｍ以下であることがより好ましく、５０ｎｍ以下であることがさらに好ましい。一方で、化粧料に配合した場合の紫外線遮蔽性を大きくしたい場合には、前記金属酸化物粒子の一次粒子径は１３５ｎｍを超えることが好ましく、１４０ｎｍ以上であることがより好ましく、１５０ｎｍ以上であることがさらに好ましい。 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.
When 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.
When it is desired to increase the transparency when blended in a cosmetic, 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. On the other hand, when it is desired to increase the ultraviolet shielding property when blended in a cosmetic, 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.
　前記金属酸化物粒子の平均一次粒子径は、上記表面処理金属酸化物粒子の平均一次粒子径と同様に、前記金属酸化物粒子の比表面積を用いて（１）式によって算出することができる。
　または、前記金属酸化物粒子の平均一次粒子径は、以下の方法で求めてもよい。すなわち、前記金属酸化物粒子を、透過型電子顕微鏡（ＴＥＭ）等を用いて観察した場合に、金属酸化物粒子を所定数、例えば、２００個、あるいは１００個を選び出す。そして、これら金属酸化物粒子各々の最長の直線部分（最大長径）を測定し、これらの測定値を算術平均する。
　なお、金属酸化物粒子同士が凝集している場合には、この凝集体の凝集粒子径を測定するのではない。この凝集体を構成している金属酸化物粒子（一次粒子）を所定数測定し、平均一次粒子径とする。 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.
Alternatively, 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.
　本実施形態では、金属酸化物粒子に表面処理することにより、表面処理金属酸化物粒子の比表面積が小さくなる傾向はあるが、実質的には同程度の大きさである。同様に、金属酸化物粒子に表面することにより、平均一次粒子径は大きくなる傾向はあるが、実質的には同程度の大きさである。 In the present embodiment, 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. Similarly, the average primary particle diameter tends to increase when the metal oxide particles surface, but they are substantially the same size.
　本実施形態における金属酸化物粒子は、化粧料中での分散安定性を向上させる観点において、高純度の金属酸化物粒子を用いることが好ましい。 金属 From the viewpoint of improving the dispersion stability of the metal oxide particles in the present embodiment, it is preferable to use high-purity metal oxide particles.
［シランカップリング剤］
　本実施形態において使用されるアルコキシ基を有するシランカップリング剤は、化粧料に使用可能なシランカップリング剤であれば特に限定されない。
　例えば、シランカップリング剤としては、一般式（２）で表されるシランカップリング剤のうち、化粧料に使用可能なものが挙げられる。
　Ｒ１Ｓｉ（ＯＲ２）３　　・・・（２）
（Ｒ１は、炭素数１～１８のアルキル基、フルオロアルキル基またはフェニル基、Ｒ２は、炭素数１～４のアルキル基を示す。） [Silane coupling agent]
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.
For example, as the 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.)
　具体的には、表面処理に用いるシランカップリング剤として、メチルトリメトキシシラン、メチルトリエトキシシラン、メチルトリプロポキシシラン、メチルトリブトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、エチルトリプロポキシシラン、エチルトリブトキシシラン、ｎ－プロピルトリメトキシシラン、ｎ－プロピルトリエトキシシラン、ｎ－プロピルトリプロポキシシラン、ｎ－プロピルトリブトキシシラン、イソプロピルトリメトキシシラン、イソプロピルトリエトキシシラン、イソプロピルトリプロポキシシラン、イソプロピルトリブトキシシラン、フェニルトリメトキシシラン、フェニルトリエトキシシラン、フェニルトリプロポキシシラン、フェニルトリブトキシシラン、ｎ－オクチルトリメトキシシラン、ｎ－オクチルトリエトキシシラン（トリエトキシカプリリルシラン）、ｎ－オクタデシルトリメトキシシラン等のアルキルアルコキシシラン；トリフルオロプロピルトリメトキシシラン、パーフルオロオクチルトリエトキシシラン、トリデカフルオロオクチルトリエトキシシラン等のフルオロアルコキシシラン、フルオロアルキルアルコキシシラン；が挙げられる。 Specifically, as a 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-octyltrimethoxy Alkylalkoxysilanes such as silane, n-octyltriethoxysilane (triethoxycaprylylsilane) and n-octadecyltrimethoxysilane; trifluoropropyltrimethoxysilane, perfluorooctyltriethoxysilane, tridecafluorooctyltriethoxysilane and the like Of fluoroalkoxysilane and fluoroalkylalkoxysilane.
　また、表面処理に用いるシランカップリング剤として、ジメトキシジフェニルシラン－トリエトキシカプリリルシランクロスポリマー、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等、シロキサン骨格を主鎖とし、分子構造内にアルコキシ基とアクリル基とを有するポリマー型シランカップリング剤等が挙げられる。 As the 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. And a polymer silane coupling agent having an alkoxy group and an acrylic group in the molecular structure.
　これらのシランカップリング剤は、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。 は One of these silane coupling agents may be used alone, or two or more thereof may be used in combination.
　上記シランカップリング剤の中でも、分子内にオクチル基を有するシランカップリング剤が好ましい。具体的には、官能基の極性が中程度であり、ナチュラルオイルやエステル油からシリコーンオイルまでの幅広い極性の油相に対応可能な、オクチルトリエトキシシラン、オクチルトリメトキシシラン、ジメトキシジフェニルシラン－トリエトキシカプリリルシランクロスポリマーを特に好適に用いることができる。
　これらのシランカップリング剤は、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。 Among the 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.
　上記シランカップリング剤による表面処理量は、所望の特性に応じて適宜調整すればよい。金属酸化物粒子１００質量部に対して、シランカップリング剤の量は、２質量部以上かつ１５質量部以下であることが好ましく、３質量部以上かつ１５質量部以下であることがより好ましく、４質量部以上かつ１２質量部以下であることがさらに好ましい。
　上記範囲で金属酸化物粒子をシランカップリング剤で表面処理することにより、分散性に優れ、紫外線遮蔽性に優れる表面処理粒子が得られやすいため好ましい。上記シランカップリング剤の量は、製造時に加えられて使用される量であっても良い。 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.
　なお、本実施形態の表面処理粒子の特性を阻害しない範囲であれば、シランカップリング剤に加え、化粧料に用いられる表面処理剤であって、シランカップリング剤以外のものを用いて、金属酸化物粒子を表面処理してもよい。 In addition, as long as the properties of the surface-treated particles of the present embodiment are not impaired, in addition to the silane coupling agent, a surface treatment agent used for cosmetics, other than the silane coupling agent, may be used. The oxide particles may be surface-treated.
　シランカップリング剤以外の表面処理剤としては、例えば、シリカ、アルミナ等の無機材料や、シリコーン化合物、脂肪酸、脂肪酸石鹸、脂肪酸エステルおよび有機チタネート化合物等の有機材料を用いることができる。 表面 As 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.
　本実施形態の表面処理金属酸化物粒子によれば、安定的に高い紫外線遮蔽性を示す表面処理金属酸化物粒子が得られる。 表面 According to the surface-treated metal oxide particles of the present embodiment, surface-treated metal oxide particles exhibiting a stable high ultraviolet shielding property can be obtained.
［表面処理金属酸化物粒子の製造方法］
　本実施形態の表面処理金属酸化物粒子の製造方法は、特に限定されず、任意に選択できる。表面処理に用いる成分に応じて、乾式処理や湿式処理等の公知の方法で、前記粒子の製造を適宜実施することができる。 [Method for producing surface-treated metal oxide particles]
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.
　例えば、乾式処理の場合は、例えば、以下のような作業よって、表面処理を行う方法が挙げられる。まず、原料としての金属酸化物粒子をヘンシェルミキサーやスーパーミキサー等のミキサー中で撹拌しながら、シランカップリング剤を液滴下あるいはスプレー噴霧にて加え、その後、一定時間高速強撹拌する。その後、撹拌を続けながら、７０℃から２００℃の温度にて、加熱処理する。なお加熱温度や攪拌時間は、用いる材料やシランカップリング剤によって、必要に応じて選択できる。 For example, in the case of dry processing, a method of performing a surface treatment by the following operation may be mentioned. First, 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. Thereafter, 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.
　例えば、湿式処理の場合は、例えば、以下の方法によって表面処理を行う方法が挙げられる。まず、金属酸化物粒子とシランカップリング剤と溶媒とを撹拌しながら、２５℃から１００℃で数時間混合する。この後、固液分離し、洗浄し、得られたこの洗浄物を７０℃から２００℃で加熱処理する。 For example, in the case of a wet treatment, a method of performing a surface treatment by the following method may, for example, be mentioned. First, 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.
　前記乾式処理や湿式処理等の方法においては、シランカップリング剤の加水分解用の水分は、金属酸化物粒子の付着水を用いてもよく、必要に応じてシランカップリング剤と共にまたは別々に添加してもよい。 In the methods such as the dry treatment and the wet treatment, 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.
　　前記乾式処理や湿式処理等の方法においては、シランカップリング剤は、シランカップリング剤と混合可能な溶媒で希釈して用いてもよい。このような溶媒としては、例えば、メタノール、エタノール、イソプロパノール等のアルコールや、ｎ－ヘキサン、トルエン、キシレン等が挙げられる。溶媒は、１種又は２種以上を用いることができる。加水分解用の水分を添加して表面処理する場合には、これらの溶媒の中でも、水との相溶性が高いアルコール等の極性溶媒が好適に用いられる。 In the methods such as the dry treatment and the wet treatment, the silane coupling agent may be diluted with a solvent that can be mixed with the silane coupling agent before use. Examples of such a solvent include alcohols such as methanol, ethanol, and isopropanol, n-hexane, toluene, xylene, and the like. One or more solvents can be used. When surface treatment is performed by adding water for hydrolysis, a polar solvent such as alcohol having high compatibility with water is preferably used among these solvents.
　本実施形態の表面処理金属酸化物粒子の製造方法は、アルコキシ基を有するシランカップリング剤で表面処理された金属酸化物粒子をフーリエ変換式赤外分光光度計で測定した９００ｃｍ－１～１３００ｃｍ－１における反射スペクトルにおいて、前記アルコキシ基に由来するピークが検出されないことを判定する工程を有する。任意に選択される方法で製造された、アルコキシ基を有するシランカップリング剤で表面処理された金属酸化物粒子を用意する工程や、この粒子をフーリエ変換式赤外分光光度計で測定する工程を、前記製造方法に含むことも好ましい。 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.
　物の製造方法においては、同一条件で製造した物であっても、全く同一の物を製造することはなかなか困難である。原料ロットの変更、製造日の温湿度、製造量等、様々な条件により、表面処理金属酸化物粒子の特性は変化する可能性がある。しかし、本実施形態の表面処理金属酸化物粒子の製造方法は、上記判定工程を有する。このため、表面処理粒子の未反応のアルコキシ基の量を定量的に確認することができ、紫外線遮蔽性に優れる表面処理金属酸化物粒子が得られているか否かを、製造後に簡易に確認することができる。よってこの判定工程までを製造作業に含めることにより、品質の安定した製品を提供することができる。 In the method of manufacturing a product, it is difficult to manufacture exactly the same product even if manufactured under the same conditions. The characteristics of the surface-treated metal oxide particles may change due to various conditions such as a change in the raw material lot, the temperature and humidity on the production day, and the production amount. However, 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.
　本実施形態の表面処理金属酸化物粒子の製造方法は、上記判定工程において、前記アルコキシ基由来のピークが確認された場合、さらに次の工程を含むことが好ましい。具体的には、前記ピークが消失するまで、前記アルコキシ基を有するシランカップリング剤で表面処理された金属酸化物粒子を、すなわち、前記表面処理金属酸化物粒子を、加熱する工程を含むことが好ましい。この加熱工程の加熱条件は任意に選択できる。例えば、前記粒子の製造時と同じ温度、例えば７０℃から２００℃の温度、であってもよい。この加熱工程を含むことにより、表面処理粒子に残留する未反応のアルコキシ基の量が好ましい範囲にあるように、定量的に管理することができる。このため、紫外線遮蔽性に優れる表面処理金属酸化物粒子を安定的に製造することができる。 製造 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. Specifically, 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. preferable. The heating conditions in this heating step can be arbitrarily selected. For example, 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. By including this heating step, 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.
　本実施形態の表面処理金属酸化物粒子の製造方法によれば、残留するアルコキシ基の存在を確認する工程を有する。このため、未反応のアルコキシ基の量を定量的に確認することができ、紫外線遮蔽性に優れる表面処理金属酸化物粒子が得られているか否かを確認することができる。また、本実施形態の表面処理金属酸化物粒子の製造方法によれば、加熱工程を好ましく含む。このことにより、表面処理粒子に残留するアルコキシ基の量を定量的に管理することができる。このため、紫外線遮蔽性に優れる表面処理金属酸化物粒子を安定的に製造することができる。 According to 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.
　本実施形態の表面処理金属酸化物粒子の製造方法は、表面処理された金属酸化物粒子の１０５℃、３時間における乾燥減量が０．１５質量％以下であることを判定する第２の判定工程を含んでもよい。 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.
　第２の判定工程は、上述の表面処理金属酸化物粒子の１０５℃、３時間における乾燥減量の測定方法と同様に行うことができる。
　第２の判定工程は、フーリエ変換式赤外分光光度計を用いた判定工程より先に行ってもよく、後に行ってもよい。
　第２の判定工程において乾燥減量が０．１５質量％を超えていた場合は、乾燥減量が０．１５質量％以下となるまで加熱する工程を含んでもよい。この加熱工程の加熱条件は任意に選択できる。例えば、前記粒子の製造時と同じ温度、例えば７０℃から２００℃の温度、であってもよい。 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.
When the loss on drying exceeds 0.15% by mass in the second determination step, 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. For example, 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.
　本実施形態の製造方法は、第１の判定工程でアルコキシ基に由来するピークが検出されず、かつ、第２の判定工程で乾燥減量が０．１５質量％以下となるまで、前記表面処理金属酸化物粒子を加熱する工程を含むことが好ましい。
　また、第１の判定工程および/又は第２の判定工程で所望の特性を満たしていない場合には、それらの特性を満たすまで、７０℃から２００℃の温度で加熱することが好ましい。 In the production method of the present embodiment, 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.
［分散液］
　本実施形態の分散液は、本実施形態の表面処理金属酸化物粒子と、分散媒と、を含有する。
　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も含む。 [Dispersion]
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.
　分散媒は、化粧料に処方することが可能で、表面処理粒子が分散できるものであれば、特に限定されない。
　分散媒としては、例えば、水；メタノール、エタノール、ｎ－プロパノール、イソプロパノール、ｎ－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；ナチュラルオイル、エステル油、シリコーンオイル等が好適に用いられる。 The dispersion medium is not particularly limited as long as it can be formulated into cosmetics and can disperse the surface-treated particles.
Examples of 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 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, diethylene glycol Ethers such as monoethyl ether; natural oil, ester oil, silicone oil, etc. It is preferably 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。 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.
　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。 Other 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.
　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。
　なお、上記上げた分散媒は、１種のみ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。 Other 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. 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.
　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。 分散 The dispersion of the present embodiment may contain a commonly used additive as long as its properties are not impaired.
　添加剤としては、例えば、防腐剤、分散剤、分散助剤、安定剤、水溶性バインダー、増粘剤、油溶性薬剤、油溶性色素類、油溶性蛋白質類、ＵＶ吸収剤等が好適に用いられる。 As the 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. Can be
　本実施形態の分散液における粒度分布の累積体積百分率が５０％のときの、表面処理金属酸化物粒子の粒径（ｄ５０）は、任意に選択できるが、３００ｎｍ以下であることが好ましく、２５０ｎｍ以下であることがより好ましく、２００ｎｍ以下であることがさらに好ましい。 When the cumulative volume percentage of the particle size distribution in the dispersion of the present embodiment is 50%, 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.
　ｄ５０の下限値は特に限定されず、例えば、５０ｎｍ以上であってもよく、１００ｎｍ以上であってもよく、１５０ｎｍ以上であってもよい。ｄ５０の上限値および下限値は、任意に組み合わせることができる。 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.
　また、本実施形態の分散液における粒度分布の累積体積百分率が９０％のときの粒径（ｄ９０）は、任意に選択できるが、４００ｎｍ以下であることが好ましく、３５０ｎｍ以下であることがより好ましく、３００ｎｍ以下であることがさらに好ましい。 In addition, 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.
　ｄ９０の下限値は特に限定されず、例えば、１００ｎｍ以上であってもよく、１５０ｎｍ以上であってもよく、２００ｎｍ以上であってもよい。ｄ９０の上限値および下限値は、任意に組み合わせることができる。 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.
　分散液のｄ５０が３００ｎｍ以下の場合には、この分散液を用いて作製した化粧料を皮膚に塗布した場合に、表面処理粒子が均一に分布しやすく、紫外線遮蔽効果が向上するため好ましい。また、分散液のｄ９０が４００ｎｍ以下の場合には、分散液の透明性が高く、この分散液を用いて作製された化粧料の透明性も高くなるため好ましい。 (4) When 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. When 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.
　すなわち、本実施形態における分散液のｄ５０とｄ９０が上記範囲であることにより、透明性に優れ、紫外線遮蔽性に優れる分散液を得ることができる。また、この分散液を用いて作製した化粧料も、透明性と紫外線遮蔽性に優れる。 That is, when the d50 and d90 of the dispersion in the present embodiment are within the above ranges, a dispersion having excellent transparency and excellent ultraviolet shielding properties can be obtained. In addition, cosmetics produced using this dispersion are also excellent in transparency and ultraviolet shielding properties.
　分散液における粒度分布の累積体積百分率は、動的光散乱式粒径分布測定装置を用いて測定することができる。 累積 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.
　本実施形態の分散液における表面処理金属酸化物粒子の含有量は、所望の特性に合わせて適宜調整すればよい。 含有 The content of the surface-treated metal oxide particles in the dispersion of the present embodiment may be appropriately adjusted according to desired characteristics.
　本実施形態の分散液を化粧料に用いる場合には、分散液における表面処理金属酸化物粒子の含有量は、任意に選択できるが、１０質量％以上であることが好ましく、２０質量％以上であることがより好ましく、３０質量％以上であることがさらに好ましい。また、分散液における表面処理金属酸化物粒子の含有量は、９０質量％以下であることが好ましく、８５質量％以下であることがより好ましく、８０質量％以下であることがさらに好ましい。分散液における表面処理金属酸化物粒子の含有量の上限値および下限値は、任意に組み合わせることができる。 When the dispersion of this embodiment is used for cosmetics, 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.
　分散液における表面処理金属酸化物粒子の含有量が上記範囲であることにより、表面処理金属酸化物粒子が高濃度で含有される。このため、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。 に よ り When 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.
　本実施形態の分散液の粘度は、任意に選択できるが、５Ｐａ・ｓ以上であることが好ましく、８Ｐａ・ｓ以上であることがより好ましく、１０Ｐａ・ｓ以上であることがさらに好ましく、１５Ｐａ・ｓ以上であることが最も好ましい。また、分散液の粘度は、３００Ｐａ・ｓ以下であることが好ましく、１００Ｐａ・ｓ以下であることがより好ましく、８０Ｐａ・ｓ以下であることがさらに好ましく、６０Ｐａ・ｓ以下であることが最も好ましい。分散液の粘度の上限値および下限値は、任意に組み合わせることができる。 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.
　分散液の粘度が上記の範囲であることにより、固形分（表面処理金属酸化物粒子）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。 に よ り When the viscosity of the dispersion is within the above range, a dispersion that is easy to handle can be obtained even when the dispersion contains a high concentration of solids (surface-treated metal oxide particles).
　本実施形態の分散液は、表面処理粒子を１０質量％含有させた分散液を、所定の基板の上に、乾燥後の厚さが１２μｍとなるように塗布して１５分間自然乾燥させて塗膜を形成した場合、当該塗膜について測定される物性値が、次の範囲であることが好ましい。
　すなわち、上記塗膜の４５０ｎｍにおける透過率が、４０％以上であることが好ましく、４５％以上であることがより好ましく、５０％以上であることがさらに好ましい。透過率の上限値は特に限定されず、１００％以下であってもよく、９０％以下であってもよく、８０％以下であってもよい。塗膜の４５０ｎｍにおける透過率の上限値および下限値は、任意に組み合わせることができる。 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 μm and naturally drying for 15 minutes. When a film is formed, 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.
　上記塗膜の４５０ｎｍにおける透過率が大きいほど透明性に優れる。このため、４５０ｎｍにおける透過率は高いほうが好ましい。 透明 The greater the transmittance of the coating film at 450 nm, the better the transparency. Therefore, the transmittance at 450 nm is preferably higher.
　また、上記塗膜の２９０ｎｍ～３２０ｎｍにおける平均透過率は、１０％以下であることが好ましく、７％以下であることがより好ましく、５％以下であることがさらに好ましい。下限値は特に限定されず、０％以上であってもよく、０．５％以上であってもよく、１％以上であってもよい。塗膜の２９０ｎｍ～３２０ｎｍにおける平均透過率の上限値および下限値は、任意に組み合わせることができる。 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.
　上記塗膜の２９０ｎｍ～３２０ｎｍにおける平均透過率が小さいほど紫外線遮蔽性に優れる。このため、２９０ｎｍ～３２０ｎｍにおける平均透過率は小さいほうが好ましい。 (4) The smaller the average transmittance of the coating film at 290 nm to 320 nm is, the more excellent the ultraviolet shielding property is. Therefore, it is preferable that the average transmittance in the range of 290 nm to 320 nm is small.
　また、上記塗膜のＳＰＦ値は、３０以上であることが好ましく、３５以上であることがより好ましく、４０以上であることがさらに好ましい。上限値は特に限定されず、１５０以下であってもよく、１００以下であってもよく、８０以下であってもよい。上記塗膜のＳＰＦ値の上限値および下限値は、任意に組み合わせることができる。 Further, 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.
　上記塗膜のＳＰＦ値が大きいほど、紫外線Ｂ波を防ぐ効果が大きい。このため、ＳＰＦ値は大きいほうが好ましい。 効果 The greater the SPF value of the coating film, the greater the effect of preventing ultraviolet B waves. Therefore, it is preferable that the SPF value is large.
　上記塗膜の臨界波長（Ｃｒｉｔｉｃａｌ　Ｗａｖｅｌｅｎｇｔｈ）は、３７０ｎｍ以上であることが好ましい。塗膜の臨界波長が３７０ｎｍ以上であることにより、塗膜は長波長紫外線（ＵＶＡ）および短波長紫外線（ＵＶＢ）の広範囲の紫外線を遮蔽することができる。したがって、本実施形態の分散液を含有する化粧料は、臨界波長が３７０ｎｍ以上となり、化粧料によって皮膚上に形成された膜は長波長紫外線（ＵＶＡ）および短波長紫外線（ＵＶＢ）の広範囲の紫外線を遮蔽することができる。 臨界 The critical wavelength (Critical Wavelength) of the coating film is preferably 370 nm or more. When the critical wavelength of the coating film is 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). Accordingly, 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.
　なお、本明細書において上記「臨界波長」とは、分散液を塗布した前記塗膜を測定することで求められる値である。具体的には、上記塗膜について、２９０ｎｍ以上かつ４００ｎｍ以下の紫外線領域の吸収スペクトルを測定し、得られた吸収スペクトルにおいて２９０ｎｍから長波長側に積分する。このとき、積分面積が２９０ｎｍ以上かつ４００ｎｍ以下の全領域での積分面積の、９０％となる波長を、求める「臨界波長」とする。 In the present specification, 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”.
　本実施形態の分散液の製造方法は、特に限定されない。例えば、本実施形態の表面処理粒子と、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。 製造 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.
　分散装置は、必要に応じて選択でき、例えば、撹拌機、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 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.
　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塗料等に用いることができる。 分散 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.
　本実施形態の分散液によれば、本実施形態の表面処理金属酸化物粒子を含むため、安定的に高い紫外線遮蔽性を示すものとなる。 分散 According to 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.
［組成物］
　本実施形態の組成物は、本実施形態の表面処理粒子と、高分子と、を含有してなる。 [Composition]
The composition of the present embodiment contains the surface-treated particles of the present embodiment and a polymer.
　本実施形態の組成物における表面処理粒子の含有量は、所望の特性に合わせて適宜調整すればよい。前記含有量は、例えば、１０質量％以上かつ４０質量％以下であることが好ましく、２０質量％以上かつ３０質量％以下であることが好ましい。 含有 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.
　組成物における表面処理粒子の含有量が上記範囲であることにより、固形分（表面処理金属酸化物粒子）を高濃度に含むため、表面処理粒子の特性が充分に得られ、かつ、表面処理粒子を均一に分散した組成物を得ることができる。 When 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.
　本実施形態の組成物における高分子としては特に限定されず、例えば、水溶性高分子、半合成高分子、合成高分子、樹脂等を用いることができる。
　水溶性高分子としては、例えば、ゼラチン、カゼイン、コラーゲン、ヒアルロン酸、アルブミン、デンプン等を用いることができる。
　半合成高分子としては、例えば、メチルセルロース、エチルセルロース、メチルヒドロキシプロピルセルロース、カルボキシメチルセルロース、ヒドロキシメチルセルロース、ヒドロキシプロピルセルロース、カルボキシメチルセルロースナトリウム、アルギン酸プロピレングリコールエステル等を用いることができる。
　合成高分子としては、例えば、ポリビニルアルコール、ポリビニルピロリドン、カルボマー（カルボキシビニルポリマー）、ポリアクリル酸塩、ポリエチレンオキシド等を用いることができる。 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.
As the water-soluble polymer, for example, gelatin, casein, collagen, hyaluronic acid, albumin, starch and the like can be used.
As 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.
As the synthetic polymer, for example, polyvinyl alcohol, polyvinylpyrrolidone, carbomer (carboxyvinyl polymer), polyacrylate, polyethylene oxide and the like can be used.
　樹脂としては、工業用途で一般的に用いられるものであれば特に限定されないが、例えば、アクリル樹脂、エポキシ樹脂、ウレタン樹脂、ポリエステル樹脂、シリコーン樹脂等が挙げられる。化粧料用途で用いる場合には、シリコーン樹脂を用いることが好ましい。 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.
　本実施形態の組成物における高分子の含有量は、特に限定されず、目的とする組成物の特性に応じて適宜調整される。 高分子 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.
　本実施形態の組成物は、分散媒を含んでもよい。
　分散媒としては、工業用途で一般的に用いられるものであれば特に限定されないが、例えば、水、メタノール、エタノール、プロパノール等のアルコール類、酢酸メチル、酢酸エチル、トルエン、メチルエチルケトン、メチルイソブチルケトン等が挙げられる。分散媒は、１種を、または２種以上を組み合わせて、含んでも良い。 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.
　本実施形態の組成物における分散媒の含有量は、特に限定されず、目的とする組成物の特性に応じて適宜調整される。 分散 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.
　本実施形態の組成物は、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、重合開始剤、分散剤、防腐剤、増粘剤、高級脂肪酸等が挙げられる。 The composition of the present embodiment may contain a commonly used additive as long as its properties are not impaired.
Examples of the additives include a polymerization initiator, a dispersant, a preservative, a thickener, a higher fatty acid, and the like.
　本実施形態の組成物の製造方法は、特に限定されないが、例えば、本実施形態の表面処理粒子と、高分子とを、公知の混合装置で、機械的に混合する方法が挙げられる。 製造 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.
　また、上述した分散液と、高分子とを、公知の混合装置で、機械的に混合する方法が挙げられる。 方法 Further, there is a method of mechanically mixing the above-mentioned dispersion liquid and a polymer with a known mixing device.
　混合装置としては、例えば、撹拌機、自公転式ミキサー、ホモミキサー、超音波ホモジナイザー等が挙げられる。 Examples of the mixing device include a stirrer, a self-revolving mixer, a homomixer, and an ultrasonic homogenizer.
　本実施形態の組成物を、ロールコート法、フローコート法、スプレーコート法、スクリーン印刷法、はけ塗り法、及び浸漬法等の、通常の塗布方法により、任意に選択される基材、例えば、ポリエステルフィルム等のプラスチック基材に塗布することにより、塗膜を形成することができる。これらの塗膜は、任意に選択される用途、例えば、紫外線遮蔽膜やガスバリア膜として活用することができる。 The 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, By applying the composition to a plastic substrate such as a polyester film, 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.
　本実施形態の組成物によれば、本実施形態の表面処理金属酸化物粒子を含むため、安定的に高い紫外線遮蔽性を示すものとなる。 According to 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.
［化粧料］
　本実施形態の一実施形態の化粧料は、本実施形態の表面処理金属酸化物粒子、本実施形態の分散液および本実施形態の組成物からなる群から選択される少なくとも１種を含有してなる。 [Cosmetics]
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.
　別の一実施形態の化粧料は、化粧品基剤原料と、本実施形態の表面処理粒子、本実施形態の分散液および本実施形態の組成物からなる群から選択される少なくとも１種と、を含有してなる。 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.
　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のことを指す。例えば、油性原料、水性原料、界面活性剤、粉体原料等が例として挙げられる。
　油性原料としては、任意に選択でき、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。 Here, the cosmetic base material refers to various materials that form the main body of the cosmetic. For example, 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.
　水性原料としては、任意に選択でき、精製水、アルコール、増粘剤等が挙げられる。 The aqueous raw material can be arbitrarily selected and includes purified water, alcohol, thickener and the like.
　粉末原料としては、任意に選択でき、有色顔料、白色顔料、パール剤、体質顔料等が挙げられる。 The powder raw material can be arbitrarily selected and includes colored pigments, white pigments, pearling agents, extender pigments and the like.
　本実施形態の化粧料を得る方法としては、例えば、本実施形態の分散液を、乳液、クリーム、ファンデーション、口紅、頬紅、アイシャドー等の化粧品基剤原料に、従来通りに配合することにより得られる。 As a method for obtaining the cosmetic of the present embodiment, for example, 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. Can be
　また、本実施形態の化粧料は、例えば、上記本実施形態の表面処理粒子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、化粧品基剤原料と配合することにより得られる。 In addition, 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.
　本実施形態の化粧料における表面処理金属酸化物粒子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、前記表面処理粒子の含有量の下限は、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、表面処理粒子の含有量の上限は、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。化粧料における表面処理粒子の含有量の上限値および下限値は、任意に組み合わせることができる。 含有 The content of the surface-treated metal oxide particles in the cosmetic of the present embodiment may be appropriately adjusted according to desired characteristics. For example, 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.
　以下、日焼け止め化粧料について具体的に説明する。
　日焼け止め化粧料において、紫外線を、特に長波長紫外線（ＵＶＡ）を効果的に遮蔽し、かつ、粉っぽさやきしみの少ない良好な使用感を得るためには、表面処理金属酸化物粒子の含有量を調整することも好ましい。例えば、日焼け止め化粧料における表面処理金属酸化物粒子の含有量の下限は、０．０１質量％以上であることが好ましく、０．１質量％以上であることがより好ましく、１質量％以上であることがさらに好ましい。また、日焼け止め化粧料における表面処理粒子の含有量の上限は、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。日焼け止め化粧料における表面処理粒子の含有量の上限値および下限値は、任意に組み合わせることができる。また上記範囲の中で、５～１５質量％や、１０～２０質量％など、好ましい範囲を選択することができる。 Hereinafter, the sunscreen cosmetics will be specifically described.
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. For example, 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. Further, 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.
　日焼け止め化粧料は、必要に応じて、疎水性分散媒、表面処理金属酸化物粒子以外の無機微粒子や無機顔料、親水性分散媒、油脂、界面活性剤、保湿剤、増粘剤、ｐＨ調整剤、栄養剤、酸化防止剤、香料等を含んでいてもよい。 Sunscreen cosmetics, if necessary, 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.
　疎水性分散媒としては、例えば、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が挙げられる。 Examples of the hydrophobic dispersion medium 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. , 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.
　化粧料に含まれる表面処理金属酸化物粒子以外の無機微粒子や無機顔料としては、例えば、炭酸カルシウム、リン酸カルシウム（アパタイト）、炭酸マグネシウム、ケイ酸カルシウム、ケイ酸マグネシウム、ケイ酸アルミニウム、カオリン、タルク、酸化チタン、酸化アルミニウム、黄酸化鉄、γ－酸化鉄、チタン酸コバルト、コバルトバイオレット、酸化ケイ素等が挙げられる。 As 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, γ-iron oxide, cobalt titanate, cobalt violet, and silicon oxide.
　日焼け止め化粧料は、さらに有機系紫外線吸収剤を少なくとも１種含有していてもよい。 Sunscreen cosmetics may further contain at least one organic ultraviolet absorber.
　有機系紫外線吸収剤としては、例えば、ベンゾトリアゾール系紫外線吸収剤、ベンゾイルメタン系紫外線吸収剤、安息香酸系紫外線吸収剤、アントラニル酸系紫外線吸収剤、サリチル酸系紫外線吸収剤、ケイ皮酸系紫外線吸収剤、シリコーン系ケイ皮酸紫外線吸収剤、これら以外の有機系紫外線吸収剤等が挙げられる。 Examples of organic UV absorbers 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.
　ベンゾトリアゾール系紫外線吸収剤としては、例えば、２，２’－ヒドロキシ－５－メチルフェニルベンゾトリアゾール、２－（２’－ヒドロキシ－５’－ｔ－オクチルフェニル）ベンゾトリアゾール、２－（２’－ヒドロキシ－５’－メチルフェニルベンゾトリアゾール等が挙げられる。 Examples of the benzotriazole-based ultraviolet absorber include, for example, 2,2′-hydroxy-5-methylphenylbenzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 2- (2′- Hydroxy-5'-methylphenylbenzotriazole and the like.
　ベンゾイルメタン系紫外線吸収剤としては、例えば、ジベンザラジン、ジアニソイルメタン、４－ｔｅｒｔ－ブチル－４’－メトキシジベンゾイルメタン、１－（４’－イソプロピルフェニル）－３－フェニルプロパン－１，３－ジオン、５－（３，３’－ジメチル－２－ノルボルニリデン）－３－ペンタン－２－オン等が挙げられる。 Examples of the benzoylmethane-based ultraviolet absorber 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.
　安息香酸系紫外線吸収剤としては、例えば、パラアミノ安息香酸（ＰＡＢＡ）、ＰＡＢＡモノグリセリンエステル、Ｎ，Ｎ－ジプロポキシＰＡＢＡエチルエステル、Ｎ，Ｎ－ジエトキシＰＡＢＡエチルエステル、Ｎ，Ｎ－ジメチルＰＡＢＡエチルエステル、Ｎ，Ｎ－ジメチルＰＡＢＡブチルエステル、Ｎ，Ｎ－ジメチルＰＡＢＡメチルエステル等が挙げられる。 Examples of the benzoic acid-based ultraviolet absorber 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.
　アントラニル酸系紫外線吸収剤としては、例えば、ホモメンチル－Ｎ－アセチルアントラニレート等が挙げられる。 Examples of the anthranilic acid-based ultraviolet absorber include homomenthyl-N-acetylanthranilate and the like.
　サリチル酸系紫外線吸収剤としては、例えば、アミルサリシレート、メンチルサリシレート、ホモメンチルサリシレート、オクチルサリシレート、フェニルサリシレート、ベンジルサリシレート、ｐ－２－プロパノールフェニルサリシレート等が挙げられる。 Examples of the salicylic acid-based ultraviolet absorber include amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, and p-2-propanol phenyl salicylate.
　ケイ皮酸系紫外線吸収剤としては、例えば、オクチルメトキシシンナメート（メトキシケイヒ酸エチルヘキシル）、ジ－パラメトキシケイ皮酸－モノ－２－エチルヘキサン酸グリセリル、オクチルシンナメート、エチル－４－イソプロピルシンナメート、メチル－２，５－ジイソプロピルシンナメート、エチル－２，４－ジイソプロピルシンナメート、メチル－２，４－ジイソプロピルシンナメート、プロピル－ｐ－メトキシシンナメート、イソプロピル－ｐ－メトキシシンナメート、イソアミル－ｐ－メトキシシンナメート、オクチル－ｐ－メトキシシンナメート（２－エチルヘキシル－ｐ－メトキシシンナメート）、２－エトキシエチル－ｐ－メトキシシンナメート、シクロヘキシル－ｐ－メトキシシンナメート、エチル－α－シアノ－β－フェニルシンナメート、２－エチルヘキシル－α－シアノ－β－フェニルシンナメート、グリセリルモノ－２－エチルヘキサノイル－ジパラメトキシシンナメート等が挙げられる。 Examples of cinnamic acid-based ultraviolet absorbers 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-ethoxyethyl-p-methoxycinnamate, cyclohexyl-p-methoxycinnamate, ethyl-α-cyano β- phenyl cinnamate, 2-ethylhexyl -α- cyano -β- phenyl cinnamate, glyceryl mono-2-ethyl hexanoyl - di p-methoxycinnamate, and the like.
　シリコーン系ケイ皮酸紫外線吸収剤としては、例えば、［３－ビス（トリメチルシロキシ）メチルシリル－１－メチルプロピル］－３，４，５－トリメトキシシンナメート、［３－ビス（トリメチルシロキシ）メチルシリル－３－メチルプロピル］－３，４，５－トリメトキシシンナメート、［３－ビス（トリメチルシロキシ）メチルシリルプロピル］－３，４，５－トリメトキシシンナメート、［３－ビス（トリメチルシロキシ）メチルシリルブチル］－３，４，５－トリメトキシシンナメート、［３－トリス（トリメチルシロキシ）シリルブチル］－３，４，５－トリメトキシシンナメート、［３－トリス（トリメチルシロキシ）シリル－１－メチルプロピル］－３，４－ジメトキシシンナメート等が挙げられる。 Examples of the silicone-based cinnamic acid ultraviolet absorber 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.
　上記以外の有機系紫外線吸収剤としては、例えば、３－（４’－メチルベンジリデン）－ｄ，ｌ－カンファー、３－ベンジリデン－ｄ，ｌ－カンファー、ウロカニン酸、ウロカニン酸エチルエステル、２－フェニル－５－メチルベンゾキサゾール、５－（３，３’－ジメチル－２－ノルボルニリデン）－３－ペンタン－２－オン、シリコーン変性紫外線吸収剤、フッ素変性紫外線吸収剤等が挙げられる。上記紫外線吸収剤は１種を用いても良く、２種以上を組み合わせて使用してもよい。 Examples of 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.
　本実施形態の化粧料の臨界波長は、３７０ｎｍ以上であることが好ましい。化粧料の臨界波長が３７０ｎｍ以上であることにより、長波長紫外線（ＵＶＡ）及び短波長紫外線（ＵＶＢ）の広範囲の紫外線を遮蔽することができる。 臨界 The critical wavelength of the cosmetic of the present embodiment is preferably 370 nm or more. When the critical wavelength of the cosmetic is 370 nm or more, a wide range of long-wave ultraviolet (UVA) and short-wave ultraviolet (UVB) ultraviolet can be blocked.
　本実施形態の化粧料によれば、本実施形態の表面処理金属酸化物粒子、本実施形態の分散液および本実施形態の組成物からなる群から選択される少なくとも１種を含む。このため、安定的に高い紫外線遮蔽性を示すものとなる。 According to the cosmetic of the present embodiment, 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.
　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に限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.
［実施例１］
「表面処理金属酸化物粒子の作製」
　酸化亜鉛粒子（比表面積Ｓ：３０ｍ２／ｇ、住友大阪セメント社製）１００質量部と、オクチルトリエトキシシラン（商品名：ＫＢＥ－３０８３、信越化学社製）８質量部と、純水０．６質量部と、イソプロピルアルコール３４．２質量部と、の混合液をヘンシェルミキサー内で混合した。
　次いで、その混合液を８０℃でイソプロピルアルコールが除去されるまで乾燥した。 [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.
　次いで、得られた乾燥物をハンマーミルにて解砕し、この解砕粉を１２０℃で３時間乾燥することで、実施例１の表面処理酸化亜鉛粒子を得た。 Next, 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.
「分散液の作製」
　実施例１の表面処理酸化亜鉛粒子を１０質量部と、ＰＥＧ－９ポリジメチルシロキシエチルジメチコン（商品名：ＫＦ－６０２８、信越化学社製）を２質量部と、デカメチルシクロペンタシロキサン（商品名：ＳＨ２４５、東レ・ダウコーニング社製）８８質量部とを、攪拌機を用いて４０００ｒｐｍで撹拌し、実施例１の分散液を得た。
　なおＰＥＧ－９ポリジメチルシロキシエチルジメチコンは、表面処理酸化亜鉛粒子をデカメチルシクロペンタシロキサンに分散させるための分散剤として、混合物に加えられている。 "Preparation of dispersion liquid"
10 parts by mass of the surface-treated zinc oxide particles of Example 1, 2 parts by mass of PEG-9 polydimethylsiloxyethyl dimethicone (trade name: KF-6028, manufactured by Shin-Etsu Chemical Co., Ltd.), and decamethylcyclopentasiloxane (trade name) : SH245, manufactured by Dow Corning Toray Co., Ltd.) was stirred at 4000 rpm using a stirrer to obtain a dispersion of Example 1.
PEG-9 polydimethylsiloxyethyl dimethicone was added to the mixture as a dispersant for dispersing the surface-treated zinc oxide particles in decamethylcyclopentasiloxane.
［実施例２］
　実施例１において、１２０℃で３時間乾燥する替わりに、１２０℃で２時間乾燥した以外は、実施例１と同様にして、実施例２の表面処理酸化亜鉛粒子を得た。
　実施例１で得られた表面処理酸化亜鉛粒子を用いる替わりに、実施例２の表面処理酸化亜鉛粒子を用いた以外は実施例１と同様にして、実施例２の分散液を得た。 [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.
［比較例１］
　実施例１において、１２０℃で３時間乾燥する替わりに、１００℃で１時間乾燥した以外は、実施例１と同様にして、比較例１の表面処理酸化亜鉛粒子を得た。
　実施例１で得られた表面処理酸化亜鉛粒子を用いる替わりに、比較例１の表面処理酸化亜鉛粒子を用いた以外は実施例１と同様にして、比較例１の分散液を得た。 [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.
［比較例２］
　実施例１において、１２０℃で３時間の乾燥を行わず、自然乾燥をした以外は、実施例１と同様にして、比較例２の表面処理酸化亜鉛粒子を得た。
　実施例１で得られた表面処理酸化亜鉛粒子を用いる替わりに、比較例２の表面処理酸化亜鉛粒子を用いた以外は実施例１と同様にして、比較例２の分散液を得た。 [Comparative Example 2]
In Example 1, 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.
［比較例３］
　実施例１で得られた表面処理酸化亜鉛粒子を、８５℃、９０％ＲＨの条件下に７２時間静置することで、水を吸収させて、比較例３の表面処理酸化亜鉛粒子を得た。
　実施例１で得られた表面処理酸化亜鉛粒子を用いる替わりに、比較例３の表面処理酸化亜鉛粒子を用いた以外は実施例１と同様にして、比較例３の分散液を得た。 [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.
［実施例３］
　比較例３で得られた表面処理酸化亜鉛粒子を、１２０℃で３時間乾燥することで、実施例３の表面処理酸化亜鉛粒子を得た。
　実施例１で得られた表面処理酸化亜鉛粒子を用いる替わりに、実施例３の表面処理酸化亜鉛粒子を用いた以外は実施例１と同様にして、実施例３の分散液を得た。 [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.
「評価」
（フーリエ変換式赤外分光光度計（ＦＴ－ＩＲ）の測定）
　実施例１～実施例３および比較例１、比較例２で得られた表面処理酸化亜鉛粒子について、フーリエ変換式赤外分光光度計ＦＴ／ＩＲ６７０Ｐｌｕｓ（日本分光社製）で６００ｃｍ－１から１５００ｃｍ－１のスペクトルをＡＴＲ法で測定した。また、参考例として、オクチルトリエトキシシランのスペクトルを測定した。
　その結果、実施例１～実施例３で得られた表面改質酸化亜鉛粒子については、１１７０ｃｍ－１、１１００ｃｍ－１、１０８０ｃｍ－１、および９５０ｃｍ－１にピークが検出されなかった。それに対して、比較例１、比較例２の表面処理酸化亜鉛粒子は、１１７０ｃｍ－１、１１００ｃｍ－１、１０８０ｃｍ－１、および９５０ｃｍ－１にピークが検出された。すなわち、実施例では粒子表面には、未反応のオクチルトリエトキシシランは検出されず、比較例１、比較例２では未反応のオクチルトリエトキシシランが残留していることが確認された。
　実施例１と比較例１とオクチルトリエトキシシランのＦＴ－ＩＲの測定結果を図１に示す。 "Evaluation"
(Measurement of Fourier transform infrared spectrophotometer (FT-IR))
The surface-treated zinc oxide particles obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were measured with a Fourier transform infrared spectrophotometer FT / IR670Plus (manufactured by JASCO Corporation) at 600 cm −1 to 1500 cm −. 1 was measured by the ATR method. As a reference example, the spectrum of octyltriethoxysilane was measured.
As a result, the surface modification of zinc oxide particles obtained in Examples 1 to 3, 1170cm -1, 1100cm -1, 1080cm -1, and peaks in 950 cm -1 was not detected. In contrast, 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.
（乾燥減量の測定）
　実施例１～実施例３および比較例１～比較例３で得られた表面処理酸化亜鉛粒子について、それぞれ２ｇを１０５℃に設定した乾燥機で３時間加熱した。加熱前後の質量を測定し、質量減少率を得て、乾燥減量（質量％）とした。すなわち、表面処理金属酸化物粒子の乾燥減量（質量％）＝（加熱前の表面処理金属酸化物粒子の質量－加熱後の表面処理金属酸化物粒子の質量）／加熱前の表面処理金属酸化物粒子の質量×１００で得られる値とした。結果を表１に示す。 (Measurement of loss on drying)
About 2 g of each of the surface-treated zinc oxide particles obtained in Examples 1 to 3 and Comparative Examples 1 to 3 was heated for 3 hours by a dryer set at 105 ° C. The mass before and after the heating was measured to obtain a mass reduction rate, which was defined as a loss on drying (% by mass). That is, loss on drying of surface-treated metal oxide particles (% by mass) = (mass of surface-treated metal oxide particles before heating−mass of surface-treated metal oxide particles after heating) / surface-treated metal oxide before heating The value was obtained by multiplying the mass of particles by 100. Table 1 shows the results.
（ＳＰＦ値の測定）
　実施例１～実施例３および比較例１～比較例３で得られた分散液を、それぞれ石英ガラス板上に分散液の厚さが１２μｍとなるように塗布し、１５分間自然乾燥させて塗膜を形成した。
　得られた塗膜について、ＳＰＦアナライザーＵＶ－２０００Ｓ（Ｌａｂｓｐｈｅｒｅ社製）を用いて測定し、ＳＰＦ値を求めた。結果を表１に示す。 (Measurement of SPF value)
Each of the dispersions obtained in Examples 1 to 3 and Comparative Examples 1 to 3 was applied on a quartz glass plate so that the thickness of the dispersion became 12 μm, and the coating was dried naturally for 15 minutes. A film was formed.
The SPF value of the obtained coating film was determined using an SPF analyzer UV-2000S (manufactured by Labsphere). Table 1 shows the results.
（凝集径の測定）
　実施例１～実施例３および比較例１～比較例３で得られた分散液３質量部と、デカメチルシクロペンタシロキサン（商品名：ＳＨ２４５、東レ・ダウコーニング社製）２７質量部を、目視で均一となるまで手振りで混合した。
　この液状の混合物を２枚のスライドガラスで挟み、光学顕微鏡で観察した。
　その結果、観察された表面処理酸化亜鉛粒子の凝集物のうち、最大の粒子径を表１に示す。
　また、実施例１の表面処理酸化亜鉛粒子の光学顕微鏡像を図２に、比較例２の表面処理酸化亜鉛粒子の光学顕微鏡像を図３に示す。 (Measurement of aggregation diameter)
3 parts by mass of the dispersions obtained in Examples 1 to 3 and Comparative Examples 1 to 3 and 27 parts by mass of decamethylcyclopentasiloxane (trade name: SH245, manufactured by Dow Corning Toray) were visually observed. And mixed by hand until uniform.
This liquid mixture was sandwiched between two slide glasses and observed with an optical microscope.
As a result, among the observed aggregates of the surface-treated zinc oxide particles, Table 1 shows the maximum particle diameter.
FIG. 2 shows an optical microscope image of the surface-treated zinc oxide particles of Example 1, and FIG. 3 shows an optical microscope image of the surface-treated zinc oxide particles of Comparative Example 2.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　実施例１～実施例３は、１１７０ｃｍ－１、１１００ｃｍ－１、１０８０ｃｍ－１、および９５０ｃｍ－１のいずれにもピークが検出されず、これらのピークが検出される比較例１、比較例２よりも、最大凝集径が小さく、ＳＰＦ値が高いことが確認された。
　また、１０５℃、３時間における乾燥減量が０．１５質量％以下である実施例１～実施例３は、乾燥減量が０．１５質量％を超える比較例１～比較例３よりも、最大凝集径が小さく、ＳＰＦ値が高いことが確認された。　 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.
　本発明の表面処理金属酸化物粒子は、安定的に高い紫外線遮蔽性を示す。従って、本発明の表面処理金属酸化物粒子は、分散液、組成物、塗料および化粧料へ適用した場合の設計品質を担保し易く、その工業的価値は大きい。 表面 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.

Claims (7)

  1. 　アルコキシ基を有するシランカップリング剤で表面処理された金属酸化物粒子であって、
    　前記金属酸化物粒子は紫外線遮蔽性を有し、
    　前記表面処理された金属酸化物粒子の１０５℃、３時間における乾燥減量が０．１５質量％以下であり、
    　前記表面処理された金属酸化物粒子を、フーリエ変換式赤外分光光度計で測定した９００ｃｍ－１～１３００ｃｍ－１における反射スペクトルにおいて、前記アルコキシ基に由来するピークが検出されないことを特徴とする表面処理金属酸化物粒子。     Metal oxide particles surface-treated with a silane coupling agent having an alkoxy group,
    The metal oxide particles have an ultraviolet shielding property,
    The surface-treated metal oxide particles have a loss on drying at 105 ° C. for 3 hours of 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, a peak derived from the alkoxy group is characterized in that no detected surface Treated metal oxide particles.
  2. 　前記アルコキシ基に由来するピークが、１１７０ｃｍ－１、１１００ｃｍ－１、１０８０ｃｍ－１、および９５０ｃｍ－１であることを特徴とする請求項１に記載の表面処理金属酸化物粒子。 The peak derived from the alkoxy group, 1170cm -1, 1100cm -1, 1080cm -1, and surface-treated metal oxide particles according to claim 1, wherein the 950cm -1.
  3. 　請求項１または２に記載の表面処理金属酸化物粒子と、分散媒と、を含有することを特徴とする分散液。 (4) A dispersion comprising the surface-treated metal oxide particles according to (1) or (2) and a dispersion medium.
  4. 　請求項１または２に記載の表面処理金属酸化物粒子、および請求項３に記載の分散液からなる群から選ばれる少なくとも１種を含有することを特徴とする化粧料。 化粧 A cosmetic comprising at least one selected from the group consisting of the surface-treated metal oxide particles according to claim 1 and the dispersion according to claim 3.
  5. 　アルコキシ基を有するシランカップリング剤で表面処理された金属酸化物粒子の製造方法であって、
    　前記金属酸化物粒子は紫外線遮蔽性を有し、
    　前記表面処理された金属酸化物粒子を、フーリエ変換式赤外分光光度計で測定した９００ｃｍ－１～１３００ｃｍ－１における反射スペクトルにおいて、前記アルコキシ基に由来するピークが検出されないことを判定する工程、を含むことを特徴とする表面処理金属酸化物粒子の製造方法。     A method for producing metal oxide particles surface-treated with a silane coupling agent having an alkoxy group,
    The metal oxide particles have an ultraviolet shielding property,
    Step of determining that the surface-treated metal oxide particles, in the reflection spectrum at 900cm -1 ~ 1300cm -1 measured by a Fourier transform type infrared spectrophotometer, a peak derived from the alkoxy group is not detected, A method for producing surface-treated metal oxide particles, comprising:
  6. 　前記アルコキシ基に由来するピークが検出されないことを判定する工程において、前記アルコキシ基に由来するピークが確認された場合、前記ピークが消失するまで、表面処理金属酸化物粒子を加熱する工程を含むことを特徴とする請求項５に記載の表面処理金属酸化物粒子の製造方法。 In the step of determining that the peak derived from the alkoxy group is not detected, if a peak derived from the alkoxy group is confirmed, the method may include a step of heating the surface-treated metal oxide particles until the peak disappears. The method for producing surface-treated metal oxide particles according to claim 5, characterized in that:
  7. 　前記アルコキシ基に由来するピークが、１１７０ｃｍ－１、１１００ｃｍ－１、１０８０ｃｍ－１、および９５０ｃｍ－１であることを特徴とする請求項５または６に記載の表面処理金属酸化物粒子の製造方法。 The peak derived from the alkoxy group, 1170cm -1, 1100cm -1, 1080cm -1, and a method for producing a surface-treated metal oxide particles according to claim 5 or 6, characterized in that 950cm -1.
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