WO2021002466A1 - Poudre d'oxyde de titane, et liquide de dispersion et préparation cosmétique l'utilisant - Google Patents

Poudre d'oxyde de titane, et liquide de dispersion et préparation cosmétique l'utilisant Download PDF

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WO2021002466A1
WO2021002466A1 PCT/JP2020/026260 JP2020026260W WO2021002466A1 WO 2021002466 A1 WO2021002466 A1 WO 2021002466A1 JP 2020026260 W JP2020026260 W JP 2020026260W WO 2021002466 A1 WO2021002466 A1 WO 2021002466A1
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Prior art keywords
titanium oxide
oxide powder
particles
titanium
oxide particles
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PCT/JP2020/026260
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English (en)
Japanese (ja)
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鉄平 八久保
伊藤　直子
直 根矢
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住友大阪セメント株式会社
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Publication of WO2021002466A1 publication Critical patent/WO2021002466A1/fr

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/29—Titanium; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/12—Face or body powders for grooming, adorning or absorbing
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36—Compounds of titanium
    • 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
    • C09C3/06—Treatment with inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic 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 titanium oxide powder suitable for cosmetics, and dispersions and cosmetics using the same.
  • the present application claims priority based on Japanese Patent Application No. 2019-124779 filed in Japan on July 3, 2019, the contents of which are incorporated herein by reference.
  • Titanium oxide particles are excellent in light reflection characteristics, ultraviolet shielding characteristics, and hiding power. Therefore, submicron size to micron size titanium oxide particles are used in base makeup cosmetics such as foundations.
  • the titanium oxide particles having excellent hiding power include, for example, octahedral particles in which the average value of the maximum values of the lengths of the line segments connecting the two facing vertices in one particle is 300 nm or more and 1000 nm or less, and the maximum value is described above. It is known that the value obtained by dividing the average value of the values by the average particle size converted from the BET specific surface area (average value of the maximum value / average particle size converted to BET) is 1.0 or more and 2.5 or less. (See, for example, Patent Document 1).
  • the present invention has been made in view of the above circumstances, and is a titanium oxide powder having excellent hiding power when blended in cosmetics and suppressing the phenomenon that the appearance of color differs depending on the viewing angle. , And a dispersion and cosmetics using the same.
  • the titanium oxide powder of the present invention is a titanium oxide powder having a BET specific surface area of 5 m 2 / g or more and 15 m 2 / g or less, and the titanium oxide powder is a polyhedron having eight or more faces. It is characterized by containing titanium oxide particles having a shape and having an L * value of 90 or more in the L * a * b * color space.
  • the dispersion liquid of the present invention is characterized by containing the titanium oxide powder of the present invention and a dispersion medium.
  • the cosmetic of the present invention is characterized by containing the titanium oxide powder of the present invention and a cosmetic base.
  • titanium oxide powder of the present invention and the embodiments of the dispersion liquid and cosmetics using the same will be described. It should be noted that the present embodiment is specifically described in order to better understand the gist of the invention, and is not limited to the present invention unless otherwise specified. For example, unless otherwise specified, conditions such as material, quantity, type, number, size, ratio, time, and temperature may be changed, added, or omitted as necessary.
  • the titanium oxide powder of the present embodiment has a BET specific surface area of 5 m 2 / g or more and 15 m 2 / g or less, contains polyhedral-shaped titanium oxide particles having eight or more faces, and has an L * a * b * color.
  • the L * value in space is 90 or more.
  • the BET specific surface area of the titanium oxide powder of the present embodiment is preferably 5 m 2 / g or more and 15 m 2 / g or less, and preferably 5 m 2 / g or more and 13 m 2 / g or less.
  • the range may be 5 m 2 / g or more and 8 m 2 / g or less, 8 m 2 / g or more and 10 m 2 / g or less, 10 m 2 / g or more and 13 m 2 / g or less.
  • the BET specific surface area of the titanium oxide powder is 5 m 2 / g or more and 15 m 2 / g or less, the paleness peculiar to the titanium oxide particles can be further reduced while having hiding power and transparency. It is advantageous. Further, when the BET specific surface area of the titanium oxide powder is 5 m 2 / g or more, the transparency does not decrease due to light scattering. On the other hand, if the BET specific surface area of the titanium oxide powder does not exceed 15 m 2 / g, the short wavelength light scattering intensity does not increase as compared with the long wavelength light scattering intensity, and the bluish whiteness does not increase.
  • the L * a * b * color space of the titanium oxide powder of this embodiment has an L * value of 90 or more.
  • the L * value is 90 or more, it is possible to suppress the phenomenon that the appearance of the applied color differs depending on the viewing angle of the skin when the titanium oxide powder is used for the cosmetic.
  • titanium oxide powder having an L * value of less than 75 is blended in the cosmetic, the appearance of the applied color is deteriorated, which is not preferable.
  • titanium oxide powder having an L * value of 75 or more and less than 90 is blended, the appearance of the coating color is improved, but the appearance of the coating color differs depending on the viewing angle of the skin. Therefore, it is not preferable.
  • the upper limit of the L * value is preferably high, but it may be 100, 99, 97, or 95.
  • the present inventors can set the mean square displacement value, which will be described later, to 5.0 ⁇ 10-6 or less as long as the titanium oxide powder has an L * value of 90 or more. Therefore, it has been found that the angle dependence of the color appearance is small and the phenomenon that the color appearance is different is suppressed.
  • the measurement sample 1 has a reflectance of a wavelength of 400 nm to 800 nm (hereinafter, “reflectance (1)”). ”) Is measured. The reflectance is measured every 1 nm.
  • a black spacer having a thickness of 9 mm is provided at a place other than the measurement point (a place where the incident light of the spectrophotometer does not hit) to obtain the measurement sample 2.
  • the reflectance of the measurement sample 2 having a wavelength of 400 nm to 800 nm (hereinafter, referred to as “reflectance (2)”) is measured every 1 nm with an integrating sphere.
  • reflectance (2) since the light scattered at a wide angle is absorbed by the black spacer before reaching the integrating sphere, only the reflectance of the light having a small scattering angle is measured.
  • the high angle scattering reflectance (hereinafter referred to as "reflectance (3)”) is calculated by calculating the reflectance (1) -reflectance (2) for each reflectance at a wavelength of 400 nm to 800 nm.
  • the high-angle scattering reflectance means a reflectance having a large light scattering angle. Then, by dividing each reflectance (3) at the calculated wavelengths of 400 nm to 800 nm by each reflectance (1) (reflectance (3) / reflectance (1)), the high proportion of the reflectance in all directions. Calculate the ratio of angular scattering reflectance.
  • the arithmetic mean value (hereinafter referred to as "arithmetic mean value (4)”) of the ratio of the high-angle scattering reflectance (reflectance (3) / reflectance (1)) at a wavelength of 400 nm to 800 nm is calculated.
  • the ratio of the high-angle scattering reflectance to the omnidirectional reflectance (reflectance (3) / reflectance (1)) is divided by the arithmetic average value (4) ((reflectance (3) / reflectance ().
  • the standard value at each wavelength hereinafter referred to as "standard value (5)" is obtained.
  • the root mean square displacement (6) at a wavelength of 400 nm to 800 nm is arithmetically averaged to calculate the root mean square displacement value (hereinafter, referred to as “mean square displacement value (7)”).
  • mean square displacement value (7) obtained in this way means that the angle dependence of the color appearance of the applied color is small, and the phenomenon that the color appearance differs depending on the skin viewing angle is suppressed. Means.
  • the titanium oxide powder of this embodiment is an aggregate of titanium oxide particles.
  • the shape of the titanium oxide particles of the present embodiment includes a polyhedral shape having eight or more faces. Since the shape of the titanium oxide particles has eight or more surfaces, light can be scattered over a wide range. Therefore, when a cosmetic containing titanium oxide powder is applied to the skin, the transparency and hiding power can be improved.
  • the content of polyhedral titanium oxide particles having eight or more faces in the titanium oxide powder is represented by the number% calculated by the method described later. That is, the content of the polyhedral-shaped titanium oxide particles having eight or more faces in the titanium oxide powder is preferably 50% by number or more, 60% by number or more, or 70% by number or more. There may be.
  • the upper limit of the content of polyhedral titanium oxide particles having eight or more faces in the titanium oxide powder may be 70% by number, 80% by number, or 90% by number. , 100% by number.
  • the content of polyhedron-shaped titanium oxide particles having eight or more faces in the titanium oxide powder is 50% by number or more, excellent hiding power is obtained when a cosmetic containing the titanium oxide powder is applied to the skin. It is preferable in that the paleness peculiar to the titanium oxide particles can be further reduced while having a transparent feeling.
  • the content of the polyhedron-shaped titanium oxide particles having eight or more faces in the titanium oxide powder of the present embodiment, that is, the number%, is determined by, for example, a scanning electron microscope (SEM), the titanium oxide powder. It is a value calculated by observing 50 titanium oxide particles contained in the body and counting the number of polyhedron-shaped titanium oxide particles having eight or more faces contained in the 50 particles.
  • SEM scanning electron microscope
  • the maximum value of the length of the line segment connecting the two opposite vertices of the titanium oxide particles is not particularly limited as long as the BET specific surface area of the titanium oxide powder is 5 m 2 / g or more and 15 m 2 / g or less.
  • the maximum value is preferably 100 nm or more and 1000 nm or less, more preferably 150 nm or more and 800 nm or less, and further preferably 200 nm or more and 750 nm or less.
  • the two vertices facing each other are not adjacent vertices. That is, in the two vertices, the line segment connecting the vertices is a line segment that does not pass through the surface of the particle but passes through the inside of the particle. The maximum value is obtained by the combination of vertices located farthest from each other.
  • a polyhedral shape having eight or more faces can be arbitrarily selected.
  • a particle having a polyhedral shape is a particle having a plurality of faces.
  • Examples of the polyhedral shape include octahedron, tetrahedron, dodecahedron, icositetrahedron, and star shape.
  • Each face of the polyhedral shape may have substantially the same shape, or may include a plurality of faces having different shapes such as two types.
  • the polyhedral shape may be a regular polyhedral shape or another polyhedral shape. Specific examples of the polyhedral shape include shapes such as a regular octahedron and a double quadrangular pyramid.
  • the octahedron shape described below is a three-dimensional shape in which the internal space is surrounded by eight triangles as shown in FIG.
  • the eight triangles may all have the same shape, or may include two or more different shapes, including two different shapes.
  • the tips of the vertices of the octahedral titanium oxide particles (points indicated by the symbols A, B, C, D, E, and F in FIG. 1) have a sharp shape, a rounded shape, and a flat shape. It may have a shaped shape. It also includes octahedrons with rounded corners, all or part of which are rounded.
  • the octahedral titanium oxide particles include a shape in which a part of the octahedral particles is damaged. That is, when it has a shape similar to the octahedral particles and it is presumed that this shape is formed from the octahedral particles due to breakage, it is regarded as the octahedral particles. Further, the octahedral titanium oxide particles may be aggregated particles in which octahedral titanium oxide particles are aggregated with each other.
  • the content of octahedral titanium oxide particles (hereinafter, may be abbreviated as "octahedral particles”) is preferably 50% by number or more. It may be 55% or more, or 60% or more.
  • the upper limit of the content of octahedral particles may be 70% by number, 80% by number, 90% by number, 100. The number may be%.
  • octahedral particles in the titanium oxide powder of the present embodiment for example, 50 titanium oxide particles contained in the titanium oxide powder are observed with a scanning electron microscope, and the content of the octahedral particles is included in the 50 particles. It can be calculated by counting the number of octahedral particles.
  • the octahedron shape is a three-dimensional shape in which the space is surrounded by eight triangles, as shown in FIG.
  • the tips of the vertices of the octahedral titanium oxide particles (points indicated by the symbols A, B, C, D, E, and F in FIG. 1) have a sharp shape, a rounded shape, and a flat shape. It may have a shaped shape.
  • the maximum value of the length of the line segment connecting the two opposite vertices of the octahedral particles is that the BET specific surface area of the titanium oxide powder is 5 m 2 / g. As long as it is more than 15 m 2 / g or less, there is no particular limitation.
  • the maximum value is preferably 100 nm or more and 1000 nm or less, more preferably 150 nm or more and 800 nm or less, further preferably 200 nm or more and 700 nm or less, and more preferably 250 nm or more and 600 nm or less. Most preferred.
  • Octahedral particles having a maximum distance between two vertices facing each other of 100 nm or more and 1000 nm or less can scatter visible light in a wider range than spherical and spindle-shaped titanium oxide particles. Therefore, it is presumed that the cosmetic containing the titanium oxide powder containing the octahedral particles can reduce the paleness peculiar to the titanium oxide particles while achieving both hiding power and transparency.
  • the maximum value of the distance between the two vertices facing each other of the octahedral particles is 100 nm or more and 1000 nm or less, when applied to the skin, the paleness peculiar to the titanium oxide particles is further enhanced while having an excellent transparency. It is advantageous in that it can be reduced.
  • X (nm) be the maximum length of the line segment (major axis m of the octahedral particle in FIG. 1) connecting the two opposite vertices (point A and point B in FIG. 1) of the octahedral particle.
  • Two vertices of the octahedral particles facing each other substantially orthogonal to the line segment related to the maximum value (major axis m of the octahedral particles in FIG. 1).
  • the minimum length of the line segment connecting D and the point F) minor axis n, o of the octahedral particle in FIG. 1
  • the ratio of X to Y (X / Y) The average value is preferably 1.5 or more and 3.0 or less, and more preferably 1.5 or more and 2.5 or less.
  • the cosmetic containing titanium oxide powder containing octahedral particles has an octahedral shape when applied to the skin. It is advantageous in that the light scattering effect of the particles can be obtained more effectively and the transparency can be further improved.
  • the octahedron shape is a double quadrangular pyramid in which two quadrangular pyramids share the bottom surface of the quadrangle.
  • the octahedral shape in the present embodiment is preferably a shape in which two congruent quadrangular pyramids share a square bottom surface.
  • the side surface shape of the quadrangular pyramid is an isosceles triangle, not an equilateral triangle.
  • the maximum value (X) of the distance between the two vertices facing each other of the octahedral particles is the length of the line segment that gives the distance between the two vertices existing in the direction orthogonal to the bottom surface of the square pyramid. means.
  • the minimum value (Y) of the distance between two vertices facing each other of the octahedral particles means the length of the shorter diagonal line of the two diagonal lines on the bottom surfaces of the two square pyramids.
  • FIG. 1 is a schematic view showing an example of octahedral titanium oxide particles in the titanium oxide particles of the present embodiment.
  • the distance between the two apex of the octahedral particle is the distance a between the point A and the point C, the distance b between the point A and the point D, the distance c between the point A and the point E, and the point A in FIG.
  • the maximum value of the distance between the two vertices of the octahedral particle facing each other is the distance m, which corresponds to the maximum value (X) of the distance between the two vertices of the octahedral particle facing each other.
  • the line segments connecting the two opposite vertices of the octahedral particles, which are substantially orthogonal to the line segment related to the maximum value X are the distance n and the distance o. Of the distance n and the distance o, the shorter one corresponds to the minimum value (Y) of the distance between the two vertices facing each other of the octahedral particles.
  • the maximum value (X) (nm) of the distance between two vertices facing each other of the octahedral particle and the minimum value (Y) (nm) of the distance between the two vertices facing each other of the octahedral particle are, for example, scanning type. It can be measured by observing the octahedral particles using a scanning electron microscope (SEM). If a part of the octahedral particles is damaged and the shape before the damage can be inferred, the shape of the octahedral particles before the damage is the above maximum value (X) (nm) and the above. The minimum value (Y) (nm) is measured.
  • the above ratio (X / Y) is calculated by observing titanium oxide particles using a scanning electron microscope (SEM) and measuring the above maximum value (X) and the above minimum value (Y).
  • the fact that the titanium oxide powder is anatase type can be confirmed by, for example, an X-ray diffractometer, for example, an X-ray diffractometer (trade name: X'Pert PRO, manufactured by Spectris). If the measurement result by the X-ray diffractometer is anatase single phase, the titanium oxide powder is anatase type.
  • an X-ray diffractometer for example, an X-ray diffractometer (trade name: X'Pert PRO, manufactured by Spectris). If the measurement result by the X-ray diffractometer is anatase single phase, the titanium oxide powder is anatase type.
  • D50 is obtained by the following procedure.
  • the maximum value of the distance between two vertices facing each other of a polyhedral particle having 50 or more faces is measured.
  • the measured maximum value is cubed and multiplied by a constant to obtain a volume.
  • the constant may be appropriately determined according to the shape of the titanium oxide particles.
  • the constant for a polyhedral shape having eight or more faces is 0.145
  • the constant for a spherical shape is 4.19 (4 ⁇ / 3).
  • the volume particle size distribution of the maximum value is calculated by using the measured maximum value and the volume value obtained by calculation.
  • d50 means the maximum value when the cumulative value is 50%.
  • the titanium oxide powder of the present embodiment preferably has a crystallinity of 0.95 or more, more preferably 0.96 or more, further preferably 0.97 or more, and 0.98 or more. Is most preferable.
  • the upper limit of the crystallinity of the titanium oxide powder of this embodiment is 1.0.
  • the degree of crystallization is 0.95 or more, the refractive index of the titanium oxide particles is high, the light scattering intensity is increased, and light can be scattered with a small amount of addition. Therefore, when blended in cosmetics, it has a hiding property. And the transparency is excellent.
  • the crystallinity of the titanium oxide powder can be measured by X-ray diffraction (XRD). Specifically, for example, first, an X-ray diffractometer, preferably an X-ray diffractometer (trade name: X'Pert PRO MPS, manufactured by PANalytical Co., Ltd.) is used, CuK ⁇ ray is used as an X-ray source, and an output is 45 kV. , 40 mA, and the diffraction angle 2 ⁇ is in the range of 20 ° to 30 °, and the X-ray intensity is measured.
  • XRD X-ray diffraction
  • the titanium oxide powder of the present embodiment may have either an inorganic compound or an organic compound on the surface.
  • Examples of the method of adhering either the inorganic compound or the organic compound to the surface of the titanium oxide particles include a method of surface treatment using a surface treatment agent.
  • the surface treatment agent is not particularly limited as long as it can be used in cosmetics, and can be appropriately selected depending on the intended purpose.
  • Examples of the surface treatment agent include an inorganic component and an organic component.
  • inorganic component examples include inorganic oxides.
  • silica, alumina and the like can be mentioned.
  • silicone compound examples include silicone oils such as methylhydrogenpolysiloxane, dimethylpolysiloxane, and methylphenylpolysiloxane; alkylsilanes such as methyltrimethoxysilane, ethyltrimethoxysilane, hexyltrimethoxysilane, and octyltrimethoxysilane; Fluoroalkylsilanes such as trifluoromethylethyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane; methicone, hydrogendimethicone, triethoxysilylethylpolydimethylsiloxyethyldimethicone, triethoxysilylethylpolydimethylsiloxyethylhexyldimethicone, (Acrylate / acrylic) Examples thereof include tridecyl acid acid / triethoxysily
  • fatty acids examples include palmitic acid, isostearic acid, stearic acid, lauric acid, myristic acid, behenic acid, oleic acid, logonic acid, 12-hydroxystearic acid, ricinoleic acid and the like.
  • fatty acid ester examples include dextrin fatty acid ester, cholesterol fatty acid ester, sucrose fatty acid ester, starch fatty acid ester and the like.
  • organic titanate compound examples include isopropyltriisostearoyl titanate, isopropyldimethacrylic isostearoyl titanate, isopropyltri (dodecyl) benzenesulfonyl titanate, neopentyl (diallyl) oxy-tri (dioctyl) phosphate titanate, and neopentyl (diallyl) oxy-.
  • examples include trineododecanoyl titanate.
  • the titanium oxide powder of the present embodiment when a cosmetic containing the titanium oxide powder is applied to the skin, it has excellent hiding power and suppresses the phenomenon that the appearance of color differs depending on the viewing angle. .. Further, according to the titanium oxide powder of the present embodiment, when a cosmetic containing the titanium oxide powder is applied to the skin, it has excellent transparency in addition to hiding power, and has a paleness peculiar to titanium oxide particles. It is possible to obtain a natural finish with reduced.
  • a reaction solution is prepared by mixing a hydrolysis product of titanium alkoxide or a hydrolysis product of a titanium metal salt with a compound having a five-membered ring containing nitrogen. It has a first step of producing titanium oxide particles by hydrolyzing this reaction solution. Further, the method for producing the titanium oxide powder of the present embodiment includes, if necessary, a reaction solution containing titanium oxide particles after hydrothermal synthesis obtained in the first step and a first step before hydrothermal synthesis. It has a second step of mixing the same reaction solution and hydrothermal synthesis.
  • the reaction solution obtained in the first step or the second step is washed and calcined at 650 ° C. or higher and 850 ° C. or lower to remove organic substances. It has 3 steps. Each step will be described below.
  • the first step is a step of producing titanium oxide particles.
  • a reaction solution is prepared by mixing a hydrolysis product of titanium alkoxide or a hydrolysis product of a titanium metal salt with a compound having a five-membered ring containing nitrogen, and this reaction solution is hydrothermally synthesized. This is a step of producing titanium oxide particles.
  • the materials used in the first step will be described below.
  • the hydrolysis product of titanium alkoxide or the hydrolysis product of the titanium metal salt is obtained by hydrolyzing the titanium alkoxide or the titanium metal salt.
  • the hydrolysis product of titanium alkoxide or the hydrolysis product of titanium metal salt is, for example, a cake-like solid which is a white solid, and is titanium hydroxide containing metatitanium acid or orthotitanium acid.
  • titanium metal salt examples include titanium tetrachloride and titanium sulfate.
  • One of these titanium metal salts may be used alone, or two or more thereof may be used in combination.
  • Hydrolysis products of titanium alkoxides or hydrolysis products of titanium metal salts include by-products such as alcohols, hydrochloric acid and sulfuric acid. Since the by-product inhibits the nucleation and crystal growth of titanium oxide particles, it is preferable to pre-wash the hydrolysis product of titanium alkoxide or the hydrolysis product of titanium metal salt with pure water. Examples of the method for cleaning the hydrolysis product of titanium alkoxide or the hydrolysis product of titanium metal salt include decantation, Nutche method, ultrafiltration method and the like.
  • a compound having a five-membered ring containing nitrogen is included in the reaction solution because of its function as a pH adjuster for the reaction solution and as a catalyst for hydrothermal synthesis.
  • the nitrogen-containing compound having a five-membered ring include pyrrole, imidazole, indole, purine, pyrrolidine, pyrazole, triazole, tetrazole, isothiazole, isoxazole, frazan, carbazole, 1,5-diazabicyclo- [4.3 .0] -5-Nonen and the like.
  • These nitrogen-containing five-membered ring compounds may be used alone or in combination of two or more.
  • the compound having a five-membered ring containing nitrogen is a compound containing one nitrogen atom from the viewpoint that the particle size distribution of the titanium oxide powder can be narrowed and the crystallinity can be further improved.
  • pyrrole, indole, pyrrolidine, isothiazole, isoxazole, frazan, carbazole, and 1,5-diazabicyclo- [4.3.0] -5-nonene are preferred.
  • the compound having a five-membered ring containing nitrogen contains one nitrogen atom and has a five-membered ring because the particle size distribution of the titanium oxide powder can be narrowed and the crystallinity can be further improved. Is more preferably a compound having a saturated heterocyclic structure.
  • pyrrolidine, 1,5-diazabicyclo- [4.3.0] -5-nonene is more preferable.
  • reaction solution The method for preparing the reaction solution is not particularly limited, and can be appropriately selected depending on the intended purpose.
  • Examples of the method for preparing the reaction solution include a method of mixing using a stirrer, a bead mill, a ball mill, an attritor, a dissolver and the like.
  • water may be added to the reaction solution to adjust the concentration of the reaction solution.
  • water added to the reaction solution include deionized water, distilled water, pure water and the like.
  • the pH of the reaction solution is preferably 9 or more and 13 or less, and 11 or more and 13 or less, from the viewpoint that the catalytic action of the compound having a five-membered ring containing nitrogen functions appropriately and the nucleation rate becomes appropriate. Is more preferable.
  • the pH of the reaction solution is in the range of 9 or more and 13 or less, the efficiency of producing titanium oxide particles and crystal growth is improved.
  • the pH of the reaction solution can be adjusted by controlling the content of the compound having a five-membered ring containing nitrogen.
  • the titanium atom concentration in the reaction solution can be appropriately selected depending on the size of the target titanium oxide particles, but is preferably 0.05 mol / L or more and 3.0 mol / L or less, and is 0. More preferably, it is 5.5 mol / L or more and 2.5 mol / L or less.
  • titanium atom concentration in the reaction solution is 0.05 mol / L or more and 3.0 mol / L or less, titanium oxide powder having the same particle size can be obtained, which is preferable.
  • the titanium atom concentration in the reaction solution can be adjusted by controlling the content of the hydrolysis product of titanium alkoxide or the hydrolysis product of titanium metal salt.
  • the first heating holding temperature in hydrothermal synthesis can be arbitrarily selected, but is preferably 100 ° C. or higher and 200 ° C. or lower, and more preferably 120 ° C. or higher and 180 ° C. or lower.
  • the generation and growth reaction of particles can be separated, and particles having a desired size can be obtained. That is, in the one-step heating, the temperature continues to rise, so that it is considered that new fine particles are generated in parallel with the growth of the generated fine particles, and coalescence of the fine particles that have not sufficiently grown occurs.
  • the first heating holding temperature in hydrothermal synthesis is within the above range, it is possible to prevent the titanium oxide fine particles from being excessively produced.
  • the obtained solid matter is calcined at 650 ° C. or higher and 850 ° C. or lower.
  • organic substances are removed while maintaining the shape of the titanium oxide particles, and the titanium oxide powder of the present embodiment having an L * value of 90 or more can be obtained.
  • the obtained titanium oxide powder can be stored by a preferred method selected if necessary.
  • ester oil examples include isopropyl myristate, cetyl isooctanoate, glyceryl trioctanoate and the like.
  • the content of the cosmetic base in the cosmetics is not particularly limited and can be appropriately selected according to the purpose.
  • the cosmetic of the present embodiment may contain other components as long as the effects of the present embodiment are not impaired.
  • ingredients can be appropriately selected from those usually used in cosmetics.
  • examples of other components include solvents, oils, surfactants, moisturizers, organic ultraviolet absorbers, antioxidants, thickeners, fragrances, colorants, bioactive components, antibacterial agents and the like.
  • One of these components may be used alone, or two or more thereof may be used in combination.
  • the content of other ingredients in the cosmetics is not particularly limited and can be appropriately selected depending on the intended purpose.
  • Examples of the cosmetics of the present embodiment include base make-up, manicure, lipstick and the like. Of these, base makeup is preferable.
  • base makeup for example, it is used as a makeup base mainly used for reducing unevenness of the skin, a foundation mainly used for adjusting the color of the skin, and mainly for improving the fixation of the foundation on the skin. Examples include face powder and the like.
  • the cosmetic of the present embodiment when applied to the skin, it has excellent hiding power and suppresses the phenomenon that the appearance of color differs depending on the viewing angle. Further, according to the cosmetic of the present embodiment, it is possible to reduce the paleness peculiar to titanium oxide particles while having a transparent feeling.
  • Example 1 (Preparation of titanium oxide powder) Put 1 L of pure water in a glass container with a capacity of 2 L, add 2 mol of tetraisopropoxytitanium (trade name: A-1, manufactured by Nippon Soda Co., Ltd.) while stirring, and add white suspension, which is a hydrolysis product of titanium alkoxide. Obtained liquid. Next, the white suspension was solid-liquid separated to obtain a white cake (2 mol (160 g) in terms of titanium oxide) which is a solid portion of the hydrolysis product of titanium alkoxide.
  • tetraisopropoxytitanium trade name: A-1, manufactured by Nippon Soda Co., Ltd.
  • reaction solution (B1) 35% hydrochloric acid (manufactured by Kanto Chemical Co., Inc., special grade reagent) was added dropwise to the obtained reaction solution (B1) until the pH reached 7. Then, the reaction solution was filtered, and washing with pure water was repeated until the conductivity of the filtrate became 100 ⁇ S / cm or less. Next, the solid matter on the filter paper was recovered, dried at 200 ° C., and then calcined at 700 ° C. to obtain the titanium oxide powder of Example 1.
  • hydrochloric acid manufactured by Kanto Chemical Co., Inc., special grade reagent
  • Example 1 The liquid foundation of Example 1 was applied to a glass substrate by screen printing to a thickness of about 20 ⁇ m. The sample was allowed to stand for 3 minutes and dried on a hot plate at 200 ° C. for 5 minutes to prepare a measurement sample 1 having a thickness of about 10 ⁇ m.
  • the reflectance (reflectance (1)) of the measurement sample 1 having a wavelength of 400 nm to 800 nm was measured with an integrating sphere using a spectrophotometer (trade name: V-700, manufactured by JASCO Corporation).
  • a black spacer having a thickness of 9 mm was provided in addition to the measurement location to prepare the measurement sample 2.
  • the reflectance (reflectance (2)) of the measurement sample 2 having a wavelength of 400 to 800 nm was measured with an integrating sphere.
  • the reflectance (1) -reflectance (2) was calculated, and the high angular reflectance (reflectance (3)) was calculated.
  • the reflectance (3) ⁇ reflectance (1) is calculated at a wavelength of 400 nm to 800 nm, and the ratio of the high-angle scattering reflectance to the reflectance in all directions (reflectance (3) / reflectance (1)).
  • the arithmetic mean value (arithmetic mean value (4)) of the ratio of the high-angle scattering reflectance (reflectance (3) / reflectance (1)) at a wavelength of 400 nm to 800 nm was calculated.
  • the ratio of the high-angle scattering reflectance to the omnidirectional reflectance is divided by the arithmetic mean value (4) ((reflectance (3) / reflectance).
  • the standard value (standard value (5)) was obtained by (1) / arithmetic mean value (4)).
  • (standard value (5) -1) 2 was calculated, and the square displacement (square displacement (6)) at each wavelength was calculated.
  • the root mean square displacement (6) at a wavelength of 400 nm to 800 nm was arithmetically averaged to calculate the root mean square displacement value (mean square displacement value (7)). The results are shown in Table 1.
  • Example 2 Titanium oxide powder of Example 2 was obtained in the same manner as in Example 1 except that it was fired at 800 ° C. instead of firing at 700 ° C. in Example 1. Table 1 shows the evaluation results in the same manner as in Example 1. Moreover, as a result of calculating (X / Y) in the same manner as in Example 1, it was 2.0.
  • Comparative Example 2 Titanium oxide powder of Comparative Example 2 was obtained in the same manner as in Example 1 except that it was fired at 900 ° C. instead of firing at 700 ° C. in Example 1.
  • the content of the octahedral particles was measured in the same manner as in Example 1, the particle shape was spherical, and the content of the octahedral particles was 0%.
  • Comparative Example 3 instead of washing until the conductivity of the filtrate becomes 100 ⁇ S / cm or less, the titanium oxide powder of Comparative Example 3 was washed in the same manner as in Example 1 except that it was washed until it became 1000 ⁇ S / cm or less and 990 ⁇ S / cm. I got a body. Table 1 shows the results of measurement in the same manner as in Example 1.
  • reaction solution (B2) containing titanium oxide particles.
  • Example 1 and Example 2 and the foundation of Comparative Example 4 were applied to the face, respectively, and the difference in the applied colors when observed from the front and when observed from an angle of 45 degrees was visually evaluated. ..
  • the foundations of Example 1 and Example 2 seemed to have the same coating color regardless of whether they were observed from the front or at an angle of 45 degrees.
  • the foundation of Comparative Example 4 had a bluish coating color and a poor complexion when observed from an oblique angle of 45 degrees as compared with the case of observing from the front.
  • Example 1 By comparing Example 1 and Example 2 with Comparative Examples 1 to 4, the cosmetic containing titanium oxide powder having an L * value of 90 or more has a small average square displacement value and a color appearance. It was confirmed that the angle dependence of the one was small.
  • the present invention is a titanium oxide powder that has excellent hiding power and suppresses the phenomenon that the appearance of color differs depending on the viewing angle when blended in cosmetics, and dispersions and cosmetics using the same. I will provide a.
  • the titanium oxide powder of the present invention contains polyhedral-shaped titanium oxide particles having a BET specific surface area of 5 m 2 / g or more, 15 m 2 / g or less, and eight or more faces, and is in the L * a * b * color space. Since the L * value is 90 or more, when applied to the skin, the hiding power and the applied color are excellent, and the phenomenon that the appearance of the color differs depending on the viewing angle is suppressed.
  • the titanium oxide powder of the present invention can be suitably used for base makeup cosmetics such as foundations. Further, since the titanium oxide powder of the present invention is also excellent in performance as a white pigment, it can be used for industrial applications such as white ink, and its industrial value is great.

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Abstract

Une poudre d'oxyde de titane selon la présente invention contient des particules d'oxyde de titane, dont chacune présente une surface spécifique BET comprise entre 5 m2/g et 15 m2/g et une forme polyédrique ayant huit surfaces ou plus ; et la valeur L * de cette poudre d'oxyde de titane dans un espace de couleur L * a * b * est de 90 ou plus.
PCT/JP2020/026260 2019-07-03 2020-07-03 Poudre d'oxyde de titane, et liquide de dispersion et préparation cosmétique l'utilisant WO2021002466A1 (fr)

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Citations (4)

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Publication number Priority date Publication date Assignee Title
CN102849793A (zh) * 2011-06-29 2013-01-02 财团法人交大思源基金会 二氧化钛纳米粉末及其制造方法
WO2016052561A1 (fr) * 2014-09-30 2016-04-07 住友大阪セメント株式会社 Procédé de production de particules d'oxyde de titane, particules d'oxyde de titane, solution de dispersion de particules d'oxyde de titane, pâte d'oxyde de titane, film d'oxyde de titane et cellule solaire sensibilisée par colorant
WO2018003851A1 (fr) * 2016-06-29 2018-01-04 住友大阪セメント株式会社 Particules d'oxyde de titane, dispersion de particules d'oxyde de titane et produits cosmétiques les utilisant
WO2019131833A1 (fr) * 2017-12-28 2019-07-04 住友大阪セメント株式会社 Poudre d'oxyde de titane, et dispersion et produit cosmétique l'utilisant

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Publication number Priority date Publication date Assignee Title
CN102849793A (zh) * 2011-06-29 2013-01-02 财团法人交大思源基金会 二氧化钛纳米粉末及其制造方法
WO2016052561A1 (fr) * 2014-09-30 2016-04-07 住友大阪セメント株式会社 Procédé de production de particules d'oxyde de titane, particules d'oxyde de titane, solution de dispersion de particules d'oxyde de titane, pâte d'oxyde de titane, film d'oxyde de titane et cellule solaire sensibilisée par colorant
WO2018003851A1 (fr) * 2016-06-29 2018-01-04 住友大阪セメント株式会社 Particules d'oxyde de titane, dispersion de particules d'oxyde de titane et produits cosmétiques les utilisant
WO2019131833A1 (fr) * 2017-12-28 2019-07-04 住友大阪セメント株式会社 Poudre d'oxyde de titane, et dispersion et produit cosmétique l'utilisant

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MATSUKURA AKI, ONODA HIROAKI: "Influences of additives on phosphoric acid treatment of titanium dioxide as a novel white pigment", JOURNAL OF ADVANCED CERAMICS, vol. 4, no. 3, 2015, pages 211 - 216, XP055783969, DOI: 10.1007/s40145-015-0151-3 *

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