WO2013147012A1 - 凹凸補正効果を有する酸化チタン - Google Patents

凹凸補正効果を有する酸化チタン Download PDF

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WO2013147012A1
WO2013147012A1 PCT/JP2013/059234 JP2013059234W WO2013147012A1 WO 2013147012 A1 WO2013147012 A1 WO 2013147012A1 JP 2013059234 W JP2013059234 W JP 2013059234W WO 2013147012 A1 WO2013147012 A1 WO 2013147012A1
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titanium oxide
acid
coated
iron
water
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PCT/JP2013/059234
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English (en)
French (fr)
Japanese (ja)
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塩　庄一郎
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株式会社 資生堂
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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
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0241—Containing particulates characterized by their shape and/or structure
    • A61K8/0245—Specific shapes or structures not provided for by any of the groups of A61K8/0241
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02—Preparations containing skin colorants, e.g. pigments
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02—Preparations containing skin colorants, e.g. pigments
    • A61Q1/04—Preparations containing skin colorants, e.g. pigments for lips
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02—Preparations containing skin colorants, e.g. pigments
    • A61Q1/10—Preparations containing skin colorants, e.g. pigments for eyes, e.g. eyeliner, mascara
    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • 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
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36—Compounds of titanium
    • C09C1/3607—Titanium dioxide
    • C09C1/3653—Treatment with inorganic compounds
    • C09C1/3661—Coating
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41—Particular ingredients further characterized by their size
    • A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/60—Particulates further characterized by their structure or composition
    • A61K2800/61—Surface treated
    • A61K2800/62—Coated
    • A61K2800/621—Coated by inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/12—Particle morphology extending in one dimension, e.g. needle-like with a cylindrical shape
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/45—Aggregated particles or particles with an intergrown morphology
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer

Definitions

  • the present invention relates to titanium oxide, particularly titanium oxide having a high unevenness correction effect and a method for producing the same.
  • Titanium oxide has been widely used as a pigment in paints, plastics, cosmetics and the like because of its high refractive index and excellent hiding power and coloring power.
  • the particle size of titanium oxide used as such a pigment is usually 0.2 ⁇ m or more.
  • titanium oxide has not been sufficient for correcting the skin unevenness such as pores and wrinkles.
  • Patent Document 1 describes chestnut-shaped titanium oxide having a particle diameter of 0.01 to 100 ⁇ m in which rod-shaped titanium oxide primary particles are aggregated. Since this titanium oxide has protrusions with a length of 0.001 to 0.05 ⁇ m on its surface like a chestnut, the refractive index near the surface is a product of the refractive index of the titanium oxide and the refractive index of the medium. Because of the fact that it has a refractive index of two layers in a pseudo manner, it has the characteristics that the transmittance in the visible region is high and almost constant and the transmittance is reduced in the UV-AB region, and because it is roughly spherical It is described that there is no roughness and it is excellent in usability. However, even such chestnut-shaped titanium oxide has a low correction effect on skin irregularities such as pores and wrinkles.
  • Patent Document 2 describes rutile-type titanium oxide aggregated particles having a particle size of 0.1 to 5 ⁇ m in which fan-shaped particles in which titanium oxide rod-shaped particles are aggregated and / or bonded are further aggregated. It is described that the coefficient (MIU value) is 0.2 to 0.7, and there is no squeaky feeling or rough feeling on the skin, and a natural skin feeling can be produced by an appropriate coloring power and hiding power.
  • the fan-shaped particles have a side size of 0.05 to 0.2 ⁇ m and a thickness of 0.02 to 0.1 ⁇ m.
  • spherical titanium oxide aggregated particles in which such fan-shaped particles are aggregated are obtained. Yes.
  • the titanium oxide aggregated particles of Patent Document 2 also have a low correction effect on skin irregularities such as pores and wrinkles.
  • the present invention has been made in view of the background art described above, and an object thereof is to provide a titanium oxide powder exhibiting an excellent unevenness correcting effect.
  • titanium oxide having a specific shape exhibits a high unevenness correction effect, and has led to the completion of the present invention.
  • the titanium oxide according to the present invention is a titanium oxide particle having a particle diameter of 0.5 to 50 ⁇ m in which rod-shaped titanium oxide primary particles are gathered in a three-dimensional radial pattern, and one ends of the rod-shaped titanium oxide primary particles are aggregated with each other.
  • Titanium oxide characterized in that it forms a core that is the center of titanium oxide particles, the other end forms a three-dimensional radial protrusion from the core, and the protrusion length is 0.05 to 0.5 ⁇ m It is.
  • titanium oxide means titanium dioxide unless otherwise specified.
  • the present invention also provides titanium oxide, characterized in that, in the titanium oxide, the projection diameter is 0.01 to 0.2 ⁇ m and the projection length is equal to or greater than the projection diameter.
  • the present invention provides a titanium oxide characterized in that, in any of the above titanium oxides, the titanium oxide is a rutile type.
  • the titanium oxide of the present invention can have a protrusion diameter of 0.03 to 0.2 ⁇ m and a protrusion length of 0.05 to 0.3 ⁇ m.
  • the shape of the protrusion can be a columnar shape or a prismatic shape.
  • the titanium oxide of the present invention can have a protrusion diameter of 0.01 to 0.05 ⁇ m and a protrusion length of 0.1 to 0.5 ⁇ m. In such a titanium oxide, the tip of the protrusion can become thicker as it approaches the core of the titanium oxide particles.
  • the present invention provides a titanium oxide characterized in that the titanium oxide according to any one of the above is coated with one or more iron oxides selected from iron oxyhydroxide and iron oxide.
  • the titanium oxide according to any one of the above is coated with one or more iron oxides selected from iron oxyhydroxide and iron oxide.
  • the above-mentioned titanium oxide having a protrusion diameter of 0.03 to 0.2 ⁇ m and a protrusion length of 0.05 to 0.3 ⁇ m, and the protrusions are cylindrical or prismatic.
  • titanium oxide in which the titanium oxide is coated with iron oxide are cylindrical or prismatic.
  • the present invention provides a titanium oxide characterized in that the titanium oxide according to any one of the above is coated with silica.
  • a titanium oxide for example, the above-mentioned titanium oxide having a projection diameter of 0.03 to 0.2 ⁇ m and a projection length of 0.05 to 0.3 ⁇ m, and the projections can be cylindrical or prismatic. Examples include titanium oxide in which titanium oxide is coated with silica.
  • the present invention also provides the titanium oxide having a protrusion diameter of 0.03 to 0.2 ⁇ m and a protrusion length of 0.05 to 0.3 ⁇ m, wherein the protrusion can have a columnar or prismatic shape.
  • a titanium oxide characterized by being coated with iron oxide and silica.
  • the cosmetic according to the present invention is a cosmetic characterized by blending any one of the above titanium oxides.
  • the method for producing titanium oxide according to the present invention includes: A heating hydrolysis step in which an aliphatic alcohol and an inorganic acid are added to a titanium salt aqueous solution and heated at 50 to 100 ° C. for hydrolysis; An acid heat treatment step of cooling the reaction solution obtained in the heating hydrolysis step, adding an inorganic acid without solid-liquid separation, and further heating at 50 to 100 ° C .;
  • the reaction solution obtained in the acid heat treatment step is subjected to solid-liquid separation, the obtained solid content is dispersed in water, and the pH of the dispersion is neutralized to 6 to 8 with an alkali;
  • the neutralization liquid obtained in the neutralization step is subjected to solid-liquid separation, and the obtained solid content is dried and / or fired, and a drying / firing step, It is characterized by providing.
  • the heating hydrolysis step can be performed by adding a substance having a carboxyl group or a carbonyl group together with the aliphatic alcohol and the inorganic acid to the titanium salt aqueous solution.
  • the drying / firing step can be performed at 300 to 1,000 ° C., whereby the protrusion diameter is 0.03 to 0.2 ⁇ m and the protrusion length is 0.05 to With the titanium oxide having a thickness of 0.3 ⁇ m, it is possible to obtain the titanium oxide whose protrusions can be columnar or prismatic.
  • a heating hydrolysis step in which an aliphatic alcohol and an inorganic acid are added to an aqueous titanium salt solution and heated at 50 to 100 ° C. for hydrolysis,
  • An acid heat treatment step of cooling the reaction solution obtained in the heating hydrolysis step, adding an inorganic acid without solid-liquid separation, and further heating at 50 to 100 ° C .
  • the reaction solution obtained in the acid heat treatment step is subjected to solid-liquid separation, the obtained solid content is dispersed in water, and the pH of the dispersion is neutralized to 6 to 8 with an alkali;
  • a method for producing titanium oxide characterized by comprising a firing step of firing at 300 to 1,000 ° C.
  • the titanium oxide obtained by solid-liquid separation from the neutralized solution obtained in the neutralization step As a result, the titanium oxide having a protrusion diameter of 0.03 to 0.2 ⁇ m and a protrusion length of 0.05 to 0.3 ⁇ m, and the protrusion having a columnar or prismatic shape can be obtained. it can.
  • the neutralization step solid-liquid separates the reaction solution obtained in the acid heat treatment step, and the obtained solid content is dispersed in water, and an iron source is added to the dispersion.
  • the step of neutralizing the pH of the dispersion to 6 to 8 with an alkali whereby the titanium oxide according to any one of the above is selected from iron oxyhydroxide and iron oxide
  • An iron oxide-coated titanium oxide coated with the iron oxide can be obtained.
  • the protrusion diameter is 0.03 to 0.2 ⁇ m
  • the protrusion length is 0.05 to 0.00.
  • the titanium oxide having a thickness of 3 ⁇ m it is possible to obtain an iron oxide-coated titanium oxide in which the titanium oxide whose projections can be columnar or prismatic are coated with iron oxide.
  • the neutralized solution obtained in the neutralization step is subjected to solid-liquid separation, the obtained solid content is dispersed in water, and a silicon source is added to the dispersion to obtain 80 to 80%.
  • a hydrous silicon oxide coating step for neutralizing the pH of the reaction solution to 6 to 8 with an acid can be performed, followed by a drying / firing step.
  • a silica-coated titanium oxide in which titanium oxide is coated with silica can be obtained.
  • the neutralization step performs solid-liquid separation on the reaction solution obtained in the acid heat treatment step, the obtained solid content is dispersed in water, and after adding an iron source to this dispersion, the pH of the dispersion Is neutralized to 6-8 with alkali, the neutralized solution obtained in this neutralization step is solid-liquid separated, the resulting solid is dispersed in water, and a silicon source is added to this dispersion.
  • a hydrous silicon oxide coating step for neutralizing the pH of the reaction solution to 6 to 8 with an acid can be performed, followed by a firing step.
  • the titanium oxide of the present invention has a specific shape, it can exhibit an excellent unevenness correction effect. Furthermore, the unevenness correction effect can be further enhanced by coating silica.
  • FIG. 6 is a SEM photograph of silica-coated titanium oxide obtained when the firing conditions were changed in Production Example 5.
  • 4 is an SEM photograph of iron oxide-silica-coated titanium oxide (Production Example 8) which is an example of the present invention. Pores coated with silica-coated coral titanium oxide (Production Example 5), coral-like titanium oxide without silica coating (Production Example 4), pigment-grade titanium oxide (Comparative Powder 2), and particulate titanium oxide (Comparative Powder 4), respectively It is a figure which shows the result (b) which carried out the binarization process of the model, the surface photograph (a) of the pore model (control) which has not apply
  • the titanium oxide according to the present invention has a particle size of 0.5 to 50 ⁇ m (typically 0. 5 ⁇ m) formed by three-dimensional radial aggregation of rod-like titanium oxide primary particles. 5-5 ⁇ m) titanium oxide particles.
  • the rod-shaped titanium oxide primary particles have one end closely adhered to each other and agglomerated to form a central portion (core) of the titanium oxide particles, but the other ends exist independently of each other. For this reason, the protrusion which consists of one front-end
  • the protrusion length of the titanium oxide of the present invention is 0.05 to 0.5 ⁇ m.
  • the projection diameter is 0.01 to 0.2 ⁇ m, and the projection length is equal to or greater than the projection diameter.
  • the protrusion diameter may vary depending on the position of the protrusion. In this case, the maximum diameter is adopted as the protrusion diameter.
  • the titanium oxide of the present invention is generally spherical as a whole particle (the ratio of minor axis / major axis is 0.75 or more), but a part thereof may have a crack.
  • a major axis by microscopic observation can be adopted. Other diameters can also be measured by microscopic observation.
  • the titanium oxide of the present invention is similar to the chestnut-shaped titanium oxide of Patent Document 1 in that it has protrusions that protrude radially on the surface of the titanium oxide particles.
  • the protrusions were thin needles, the protrusion diameter was less than 0.01 ⁇ m, typically 0.005 ⁇ m or less, and the protrusion length on the surface of the titanium oxide particles was as short as 0.001 to 0.05 ⁇ m. For this reason, there is almost no unevenness correction effect.
  • the titanium oxide protrusions of the present invention are thicker than the chestnut-shaped titanium oxide of Patent Document 1, and the protrusion diameter is usually 0.01 ⁇ m or more, and in some cases 0.03 ⁇ m or more. Further, the protrusion length is 0.05 ⁇ m or more, typically 0.1 ⁇ m or more, which is longer than the chestnut-shaped titanium oxide of Patent Document 1, and the unevenness correction effect is exhibited by such protrusions.
  • the fan-shaped particles constituting the titanium oxide aggregated particles of Patent Document 2 have almost no protrusions because the rod-shaped primary particles are aggregated in a fan shape, and a part of the rod-shaped primary particles are formed as protrusions at the tips of the fan-shaped particles. Even if it remains, its length is very short, and it is much less than 0.05 ⁇ m from the viewpoint of examples and drawings. Furthermore, in the titanium oxide aggregated particles of Patent Document 2, there is no regularity in the assembly and bonding of the fan-shaped particles constituting the same, and therefore even if the fan-shaped particle tips have protrusions, It is not a protrusion that extends three-dimensionally from the core of the particle center. For this reason, the titanium oxide aggregated particles of Patent Document 2 have almost no unevenness correction effect as in Patent Document 1.
  • the titanium oxide of the present invention may be different from the conventional one.
  • the shape of the protrusion becomes thicker as it approaches the root (the portion near the center of the titanium oxide particle of the protrusion) from the tip of the protrusion, and has a spindle shape or a tongue shape. Some of them have a shape like a dahlia flower as a whole (see FIG. 1).
  • such titanium oxide may be referred to as “dahlia-like titanium oxide” for convenience.
  • Dahlia-like titanium oxide is one of the titanium oxides of the present invention.
  • the projection diameter (maximum diameter) is usually 0.01 to 0.05 ⁇ m and the projection length is 0.1 to 0.5 ⁇ m.
  • the projection diameter becomes thick (for example, the projection diameter is 0.03 ⁇ m or more, further 0.1 ⁇ m or more), and the projection shape becomes close to a columnar or prismatic shape.
  • the titanium oxide particles as a whole have a shape as if corals are gathered radially (see FIG. 2).
  • such titanium oxide is sometimes referred to as “coral titanium oxide” for convenience.
  • Coral titanium oxide is also one of the titanium oxides of the present invention.
  • the projection diameter is usually 0.03 to 0.2 ⁇ m and the projection length is 0.05 to 0.3 ⁇ m.
  • the titanium oxide of the present invention has an excellent unevenness correcting effect.
  • the reason is that the long projections of the titanium oxide particles are in a state of overlapping in random positional relations with the gaps between them, which may contribute to blurring the irregularities.
  • the irregularity correction effect is very low in the chestnut-shaped titanium oxide of Patent Document 1 and the titanium oxide aggregated particles of Patent Document 2. This is considered to be due to the fact that there is no projection, or even if there is a projection, the projection length is short, so that the region where the projection overlaps with a gap is small.
  • the manufacturing method of the titanium oxide of this invention is not restrict
  • the reaction solution obtained by the acid heat treatment is subjected to solid-liquid separation, the obtained solid content is dispersed in water, and this dispersion is neutralized with an alkali to have a pH of 6-8, preferably 6.5-.
  • the step of 7.5 neutralization step
  • the titanium oxide (dahlia-like titanium oxide) of the present invention is formed.
  • drying usually 120 ° C. or lower
  • drying can be performed to obtain a dry powder of titanium oxide. Yes (drying process).
  • the titanium oxide thus obtained is further baked at 300 to 1,000 ° C. (baking step), whereby the titanium oxide (coral-like) of the present invention in which the protrusions are cylindrical or prismatic. Titanium oxide) can be obtained.
  • Heat hydrolysis step In the heat hydrolysis step, it is necessary to add a fatty alcohol and an inorganic acid to the titanium salt aqueous solution before heat hydrolysis. When no aliphatic alcohol is added, or when no inorganic acid is added, aggregates of fine particles or amorphous particles are formed, and the titanium oxide of the present invention cannot be obtained. Further, in the heat hydrolysis step, when a substance containing a carboxyl group / carbonyl group is further added to the titanium salt aqueous solution and then heat hydrolysis is performed, titanium oxide having relatively uniform protrusion diameters can be obtained. .
  • titanium salt that is hydrolyzed by heating examples include inorganic salts such as titanium sulfate, titanyl sulfate, and titanium tetrachloride.
  • concentration of the aqueous titanium salt solution is not particularly limited, but is usually 0.1 to 5 mol / L.
  • a polyhydric alcohol is preferably used as the aliphatic alcohol added to the titanium salt aqueous solution.
  • the polyhydric alcohol is not particularly limited, but ethylene glycol, propylene glycol, 1,3-butylene glycol, glycerin, erythritol, xylitol, mannitol, sorbitol, maltitol and the like are preferably used. Radiation is formed even when monohydric alcohol is used, but it is difficult to obtain a clean shape compared to polyhydric alcohol.
  • Particularly preferred as the polyhydric alcohol is glycerin.
  • the amount of the aliphatic alcohol added is not particularly limited as long as it does not hinder, but is 0.1 times mol or more, further 0.5 times mol or more, particularly 1 time mol or more with respect to the titanium salt. It is preferable. If the amount added is too small, the titanium oxide of the present invention may not be obtained. On the other hand, since an effect commensurate with it cannot be obtained even if an excessive amount of aliphatic alcohol is added, it is usually 5 times mol or less, preferably 3 times mol or less with respect to the titanium salt.
  • the inorganic acid to be added in the heating hydrolysis step is not particularly limited, and examples thereof include hydrochloric acid, sulfuric acid, nitric acid and the like, preferably hydrochloric acid.
  • the addition amount is not particularly limited as long as there is no problem, but it is preferably 0.1 times mol or more, more preferably 0.5 times mol or more, and particularly preferably 1 time mol or more with respect to the titanium salt. If the amount added is too small, the titanium oxide of the present invention may not be obtained. On the other hand, since the titanium oxide of the present invention may not be obtained even if the addition amount is too large, it is preferably less than 2-fold mol, more preferably 1.5-fold mol or less with respect to the titanium salt.
  • a substance having a carboxyl group or a carbonyl group (hereinafter sometimes referred to as a carboxyl / carbonyl compound) is added in the heating hydrolysis step, such a substance is not limited as long as there is no particular problem.
  • 1 to 22 aliphatic compounds are suitable, and typical examples include aliphatic carboxylic acids or derivatives thereof.
  • Aliphatic carboxylic acids can be monobasic acids such as formic acid, acetic acid, propionic acid, caprylic acid, stearic acid, dibasic acids such as oxalic acid, succinic acid, adipic acid, or more polybasic acids. It is.
  • Derivatives are typically alkali metal salts, alkaline earth metal salts, quaternary ammonium salts and the like, and esters such as methyl esters and ethyl esters, but amino acids and amides are also used as long as there is no particular problem. Is possible.
  • carboxylic acids or derivatives thereof preferred are carboxylic acid, carboxylate and carboxylic acid ester, and particularly preferred is acetic acid.
  • the amount of the carboxyl / carbonyl compound added is not particularly limited as long as it does not hinder, but is preferably 0.1 times mol or more, more preferably 0.5 times mol or more with respect to the titanium salt. If the addition amount is too small, the effect may not be sufficiently exhibited. On the other hand, since an effect commensurate with it cannot be obtained even if it is added in excess, it is preferably 5 times mol or less, more preferably 3 times mol or less with respect to the titanium salt.
  • the heating temperature in the heating hydrolysis step is usually 50 to 100 ° C., preferably 80 to 100 ° C. Below 50 ° C, hydrolysis hardly proceeds.
  • the heating time may be set so that the hydrolysis is sufficiently performed, and is usually 1 to 12 hours although it depends on the heating temperature.
  • the reaction liquid obtained by performing a heating hydrolysis process once cools, and then performs an acid heating process.
  • the reaction solution can be cooled to a temperature not lower than 5 ° C. and lower than 50 ° C. (for example, a temperature of 10 to 45 ° C.). Usually, it may be cooled to around room temperature (about 25 ° C.).
  • the acid heat treatment step it is necessary to add an inorganic acid without solid-liquid separation of the heat-hydrolyzed reaction liquid.
  • the reaction solution hydrolyzed by heating is once cooled and then separated into solid and liquid.
  • the obtained solid content is redispersed with water, and an inorganic acid is added to the dispersion, followed by heat treatment at 50 to 100 ° C. In some cases, titanium oxide particles as in the present invention are hardly obtained.
  • the inorganic acid to be added in the acid heat treatment step examples include those described above, and the amount added is not particularly limited as long as there is no hindrance, but it is 1 mol or more, more preferably 2 with respect to the titanium salt. It is preferable that it is more than double mole, especially 3 times mole or more. When the addition amount is too small, the titanium oxide of the present invention may not be obtained due to the aggregation of fine particles. On the other hand, since an effect commensurate with it cannot be obtained even if it is added excessively, it is preferably 6 times mol or less, more preferably 5 times mol or less with respect to the titanium salt.
  • the heating conditions in the acid heat treatment step are usually 50 to 100 ° C., preferably 80 to 100 ° C. If it is less than 50 degreeC, the titanium oxide of this invention may not be obtained.
  • the heating time is usually 1 to 12 hours, although it depends on the heating temperature.
  • the reaction solution obtained by carrying out the acid heat treatment step is not affected by the presence or absence of cooling before neutralization, but usually the neutralization step is performed after cooling to near room temperature.
  • the neutralization step the reaction solution obtained by the acid heat treatment is subjected to solid-liquid separation by a known method such as filtration or centrifugation, the solid content is dispersed in water, and the dispersion is neutralized with an alkali. It is necessary.
  • the reaction liquid obtained by the acid heat treatment is neutralized as it is without solid-liquid separation, titanium oxide particles as in the present invention are hardly obtained.
  • the alkali used in the neutralization step is not particularly limited, for example, sodium hydroxide, potassium hydroxide, aqueous ammonia, sodium carbonate and the like are preferably used.
  • the surface of the particles obtained in the neutralization step is further eroded to complete rod-shaped protrusions, and pseudo-spherical particles (generally spherical, minor axis / major axis) in which rod-shaped titanium oxide primary particles gather radially.
  • the titanium oxide (dahlia-like titanium oxide) having a ratio of 0.75 or more is completed.
  • the solid content obtained by solid-liquid separation by a conventional method is washed with water and dried (usually 120 ° C. or lower) to obtain the present invention.
  • a dry powder of titanium oxide (dahlia-like titanium oxide) is obtained. From the SEM observation, the average particle size is in the range of about 0.5 to 50 ⁇ m, typically 1 to 5 ⁇ m. Further, the shape of the protrusion tends to increase as it approaches the root from the tip of the protrusion, the protrusion diameter (maximum diameter) is 0.01 to 0.05 ⁇ m, and the protrusion length is 0.1 to 0.5 ⁇ m.
  • the protrusion length is equal to or more than the protrusion diameter, typically three times or more.
  • the titanium oxide obtained by the above method has a relatively uniform particle size, and for example, a particle size distribution having a mean particle size of ⁇ 50% on the basis of the major axis is obtained.
  • the dahlia-like titanium oxide obtained in this way is baked at a high temperature, titanium oxide (coral titanium oxide) whose protrusions are thickened and changed into a substantially columnar or prismatic shape can be obtained.
  • Such coral-like titanium oxide tends to have a higher unevenness correction effect than dahlia-like titanium oxide.
  • the protrusion length may be slightly shortened by firing, but the particle diameter of the titanium oxide particles themselves hardly changes.
  • the protrusion length is usually equal to or more than the protrusion diameter, typically 1.5 times or more, and sometimes twice or more.
  • the enlargement of the protrusions by firing as described above becomes more prominent as the firing temperature becomes higher.
  • the firing temperature can be higher than the drying temperature, but if it is too low, it takes too much time to obtain coral-like titanium oxide, which is not practical. Therefore, the firing temperature is preferably 300 ° C. or higher, more preferably 700 ° C. or higher. On the other hand, if the firing temperature is too high, the protrusions are excessively enlarged and sintering between the protrusions proceeds, and the unevenness correction effect may be reduced. Therefore, the firing temperature is preferably 1,000 ° C. or lower, more preferably 950 ° C. or lower. Although the firing time depends on the firing temperature, it is usually 30 minutes to 5 hours. In addition, when performing a baking process, a drying process can also be skipped.
  • the above-described radial titanium oxide of the present invention has an iron oxide such as iron oxyhydroxide or iron oxide (Fe 2 O 3 ) in order to adjust its color. Can also be coated. Such iron oxide-coated titanium oxide is also one of the titanium oxides of the present invention.
  • titanium oxide can be coated with a red to brown iron oxide such as iron oxyhydroxide (FeOOH) or iron oxide (Fe 2 O 3 ) to obtain a yellow-red system. Since the coral-like titanium oxide obtained by firing tends to have higher whiteness than the dahlia-like titanium oxide before firing, coating with an iron oxide may be particularly useful.
  • the iron oxide may be coated alone or in the form of a mixture of two or more.
  • iron oxide As a method for coating the iron oxide, a known reaction may be used.
  • an iron salt such as FeCl 2 , FeCl 3 , FeSO 4 , Fe 2 (SO 4 ) 3 , Fe (NO 3 ) 2 , Fe (NO 3 ) 3, etc. in water such as sodium hydroxide, potassium hydroxide, etc.
  • iron oxide (Fe 2 O 3 ) is generated by neutralizing and decomposing with alkali to convert to iron oxyhydroxide (FeOOH), and heating and dehydrating it.
  • iron oxide coating can be performed in the neutralization step.
  • the neutralization step if iron salt or the like is added as an iron source to the aqueous dispersion and then neutralized with an alkali, dahlia-like titanium oxide coated with iron oxyhydroxide can be obtained. it can. Further, when this iron oxyhydroxide-coated dahlia-like titanium oxide is fired at a high temperature as described above, a coral-like titanium oxide coated with Fe 2 O 3 can be obtained. Even if an iron salt is added in the neutralization step, it hardly affects the formation of the characteristic shape of dahlia-like titanium oxide or coral-like titanium oxide by subsequent firing. As long as the object of the present invention can be achieved, other iron oxide coating methods can be employed.
  • Titanium oxide coated with an iron oxide such as iron oxyhydroxide or iron oxide has an unevenness correcting effect equivalent to that of uncoated titanium oxide.
  • titanium oxide coated with iron oxide is smoother in terms of usability. What is necessary is just to adjust the coating amount of an iron oxide suitably according to the target color.
  • the total amount of iron oxide-coated titanium oxide is 0.1 to 10% by mass as Fe. If the amount of the iron source used is equivalent to the above coating amount, almost the entire iron source can be coated.
  • the above-described radial titanium oxide of the present invention further improves the unevenness correction effect by coating silica. This is considered as follows.
  • the long protrusions of the titanium oxide particles are in a state of overlapping a random positional relationship across the voids and / or silica, which contributes to blurring the unevenness. To do.
  • the TiO 2 phase, the (SiO 2 + TiO 2 ) phase, and the (SiO 2 + TiO 2 + air) phase change in order from the particle center to the outer periphery.
  • the phase has changed to the (TiO 2 + air) phase.
  • the silica-coated titanium oxide of the present invention is considered to have a refractive index that decreases from the particle center toward the outer periphery, Such a gradation of refractive index is considered to contribute to the unevenness correction.
  • the reflection intensity at the material interface decreases as the refractive index difference decreases. Since the refractive index of air is about 1, the refractive index difference at the silica-air interface is smaller than the refractive index difference at the titanium oxide-air interface. It is considered that the reflected light intensity is weaker than that of titanium oxide not coated with silica and is less likely to float white, which also contributes to the unevenness correction.
  • the powder gets wet with sebum and the (SiO 2 + TiO 2 + air) phase becomes (SiO 2 + TiO 2 ). Since the refractive index hardly changes even when it becomes a (2+ oil component) phase, the unevenness correction effect is maintained without deteriorating.
  • silica As a method for coating silica, a known reaction can be used. However, as a simple method, the hydrated silicon oxide is coated by coating the hydrated silicon oxide after the neutralization step and then drying and / or firing. By converting to silica, the silica-coated titanium oxide of the present invention can be obtained.
  • the obtained neutralized solution is subjected to solid-liquid separation, and the obtained solid content is dispersed in water, and a silicon source such as sodium silicate or potassium silicate is added to the dispersion.
  • a water-soluble salt of silicon such as is added and heated at 80 to 100 ° C.
  • the silicon oxide particles are precipitated on the surface of the titanium oxide particles by neutralizing to pH 6 to 8 (preferably 6.5 to 7.5) with an inorganic acid such as hydrochloric acid.
  • the solid content obtained by solid-liquid separation is washed with water, dried and / or calcined, whereby the silica-coated titanium oxide of the present invention can be obtained.
  • the baking is performed at a high temperature.
  • the silica-coated titanium oxide particles themselves have a coral shape.
  • the firing temperature for silica coating is preferably 300 ° C. or higher, more preferably 750 ° C. or higher, and particularly preferably 800 ° C. or higher. If the temperature is too high, the particles may be sintered with each other. Therefore, the temperature is preferably 1,000 ° C. or lower, and more preferably 950 ° C. or lower.
  • the firing time depends on the temperature, it is usually 30 minutes to 5 hours.
  • the amount of the silicon source to be used is not particularly limited, but usually an amount that makes Si 0.1 to 0.5 times mol with respect to Ti is used. If the amount is too small, the silica coating amount is small, so that the effect of improving the unevenness correction effect is lowered. Even if blended in excess, only silica particles increase in the reaction solution, and no more silica coverage can be obtained. If it is the said range, almost the whole quantity of a silicon source will be coat
  • the heating time after addition of the silicon source is usually 10 minutes to 12 hours, although it depends on the heating temperature and the like.
  • the solid content of the neutralized solution obtained in the neutralization step is washed with water and then dried at 100 to 120 ° C. or calcined at a temperature higher than that to dry the dahlia-like titanium oxide or coral-like titanium oxide.
  • silica coating by adding the silicon source to the dispersion obtained by re-dispersing the dry powder in water as described above. May be difficult to adsorb on the titanium oxide surface.
  • the coating order is not particularly limited, as one suitable method, after the neutralization step is performed in the presence of an iron source, the resulting neutralized solution is coated with hydrous silicon oxide and then calcined.
  • the method of performing is mentioned.
  • the neutralization step after adding an iron source to the aqueous dispersion and neutralizing with an alkali, the obtained neutralized solution was subjected to solid-liquid separation, and the obtained solid content was dispersed in water.
  • the silicon source was added to the dispersion, heated at 80 to 100 ° C., neutralized with acid, and solid-liquid separation was performed in this order, and the resulting solid content was washed with water and then fired to obtain iron oxide and silica.
  • Coral titanium oxide coated with can be obtained.
  • the titanium oxide of the present invention is excellent in the unevenness correction effect, makeup, especially makeup bases, foundations, funny, eye shadows, blushers, lipsticks, etc. for the purpose of unevenness correction effect. It can mix
  • the titanium oxide of the present invention may be used after being subjected to a surface treatment by a known method. Examples thereof include, but are not limited to, a hydrophobic treatment such as an aluminum treatment, a silicone treatment, a fatty acid soap treatment, a dextrin fatty acid ester treatment, and a fluorine treatment.
  • cosmetics containing the titanium oxide of the present invention oil, water, powder, surfactant, lower alcohol, polyhydric alcohol, moisturizer, whitening agent, UV protection agent, preservative, Components that are usually blended in cosmetics such as molecules, antioxidants, fragrances, and various drugs can be blended as needed.
  • the form of the cosmetic is not particularly limited, and any form such as powder, cream, emulsion, solid, semi-solid, stick, mousse or gel can be adopted.
  • the obtained titanium oxide powder is composed of particles in which rod-shaped titanium oxide primary particles are gathered radially, and the surface has protrusions extending three-dimensionally from the center of the particle. It became a spindle-like or tongue-like shape that became thicker as it approached the center, and it was a particle like a dahlia flower.
  • the particle diameter was in the range of about 0.5-3 ⁇ m
  • the protrusion length was about 0.1-0.5 ⁇ m
  • the protrusion diameter was in the range of about 0.01-0.05 ⁇ m
  • the protrusion length was larger than the protrusion diameter. .
  • Production Example 2 Production of Coral Titanium Oxide
  • the dried dahlia-like titanium oxide obtained in Production Example 1 was fired at 900 ° C. for 3 hours to obtain a rutile-type titanium oxide powder.
  • An SEM photograph of the obtained powder is shown in FIG.
  • the protrusions were thickened by firing to be generally cylindrical or prismatic, and coral titanium oxide was obtained.
  • the particle diameter is in the range of about 0.5-3 ⁇ m
  • the protrusion length is about 0.05-0.3 ⁇ m
  • the diameter of the protrusion tip is in the range of about 0.03-0.2 ⁇ m
  • the protrusion length is from the protrusion diameter.
  • Production Example 3 Production of Iron Oxide-Coated Titanium Oxide Titanium oxide obtained in the same manner as in Production Example 1 (3) except that the iron salt was added to the aqueous dispersion and then neutralized with an alkali. Firing in the same manner as in No. 2 to obtain titanium oxide powder. Specifically, the reaction liquid obtained by acid heat treatment in (2) of Production Example 1 was cooled to room temperature and filtered, and the obtained solid content was redispersed in water to 1000 mL. 0.025 mol of FeCl 3 ⁇ 6H 2 O was added to the obtained aqueous dispersion, and then the pH was adjusted to about 7 with 10 M NaOH, followed by filtration.
  • the obtained solid was washed with water and dried (105 ° C., 12 hours) to obtain a titanium oxide powder coated with iron oxyhydroxide.
  • the resulting titanium oxide powder particles had the same shape as the dahlia-like titanium oxide obtained in Production Example 1. Further, this dried product of iron oxyhydroxide-coated dahlia-like titanium oxide was fired at 900 ° C. for 3 hours in the same manner as in Production Example 2 to obtain titanium oxide powder coated with iron oxide. As shown in FIG. 3, the obtained powder particles had the same shape as the coral-like titanium oxide obtained in Production Example 2.
  • Test Example 1 Irregularity Correction Effect The unevenness correction effect was examined using a pore model.
  • the test method is as follows. An appropriate amount of the test powder was applied to the surface of a pseudo pore urethane model (skin model No. 10A (40's) #Biocolor, manufactured by Beaulux Co., Ltd.) with a makeup brush, and the coated surface was photographed. After binarizing the photograph, a correction factor was calculated from the detection area obtained using image analysis software (LIA32, free software, recognition pixel size condition: ⁇ 1 to 50 pixels) by the following formula. A higher correction rate means a higher correction effect.
  • image analysis software LIA32, free software, recognition pixel size condition: ⁇ 1 to 50 pixels
  • Comparative powder 1 spherical calcium carbonate (Karumaru, Sakai Chemical Industry Co., Ltd., average particle size 5 ⁇ m, refractive index 1.6)
  • Comparative powder 2 Pigment grade titanium oxide (RKB-2, Bayer AG, average particle size 200 nm, refractive index 2.7),
  • Comparative powder 3 chestnut-like titanium oxide (manufactured according to Patent Document 1 Example 2, average particle diameter of about 2 ⁇ m, protrusion length of 0.01 ⁇ m)
  • the titanium oxide according to the present invention has a very high unevenness correction effect equivalent to or better than spherical calcium carbonate (comparative powder 1), which is a commercially available powder having a soft focus effect.
  • the chestnut-shaped titanium oxide of Patent Document 1 has almost no unevenness correction effect.
  • FIG. 4 shows a control pore model and a surface photograph (binarized) of a pore model coated with the powder of Production Example 1 or Comparative Powder 1. Also from FIG. 4, it is understood that the titanium oxide of the present invention has a very high unevenness correction effect comparable to that of the comparative powder 1.
  • FIG. 5 is a surface photograph of the control pore model and the pore model coated with the powders of Production Examples 1 to 3.
  • the coral-like titanium oxide of Production Example 2 has a whiter coating film than the dahlia-like titanium oxide of Production Example 1, but the coral-like titanium oxide coated with iron oxide as in Production Example 3 Such whiteness was suppressed, and a coating film having a natural color similar to that of Production Example 1 was obtained.
  • Test Example 2 The effect of the inorganic acid in the aqueous solution of titanium salt that was hydrolyzed by heating with the inorganic acid in the heating hydrolysis step was changed to examine the influence. Specifically, titanium oxide was produced in the same manner as in Production Example 1 except that the amount of hydrochloric acid in Production Example 1 (1) was changed. As a result, as shown in Table 2, when hydrochloric acid was not added to the titanium salt aqueous solution, agglomerates of fine particles were formed, and dahlia-like titanium oxide was not obtained. When hydrochloric acid was added, dahlia-like titanium oxide was obtained, and when the obtained dahlia-like titanium oxide was baked in the same manner as in Production Example 2, coral-like titanium oxide was obtained. However, when hydrochloric acid is added excessively with respect to the titanium salt, amorphous titanium oxide may be formed and dahlia-like titanium oxide may not be obtained.
  • Test Example 3 The case where no aliphatic alcohol was added to the aqueous solution of titanium salt that was hydrolyzed with aliphatic alcohol in the heating hydrolysis step was examined. Specifically, titanium oxide was produced in the same manner as in Production Example 1 except that glycerin was not added in (1) of Production Example 1. The obtained titanium oxide was indefinite, and the dahlia-like titanium oxide as in Production Example 1 was not obtained.
  • Test Example 4 Acid Heat Treatment A case where acid heat treatment was not performed was examined. Specifically, the reaction liquid obtained by heating and hydrolysis as in (1) of Production Example 1 was cooled to room temperature and filtered, and the obtained solid content was redispersed in water to 1000 mL. . The pH of the obtained aqueous dispersion was adjusted to about 7 with 10M NaOH and then filtered. The obtained solid content was washed with water and then dried (105 ° C., 12 hours) to produce titanium oxide. Most of the obtained titanium oxide was simply an aggregate of titanium oxide fine particles. Only a part of the particles were observed to have protrusions, but the particle shape was very uneven, the protrusion length was short, and the dahlia-like titanium oxide particles of the present invention were not recognized.
  • Test Example 6 Cooling of reaction liquid before acid heat treatment The reaction liquid obtained in the heating and hydrolysis step was examined for the case where acid was added and heating continued without cooling. Specifically, 4 mol of hydrochloric acid was added to the reaction solution obtained by heating and hydrolysis in the same manner as in (1) of Production Example 1 while maintaining the temperature at 90 ° C, and the temperature was maintained at 90 ° C for 3 hours. did. The obtained reaction liquid was cooled to room temperature and filtered, and the obtained solid content was redispersed in water to 1000 mL. The pH of the obtained aqueous dispersion was adjusted to about 7 with 10M NaOH. The obtained neutralized solution was filtered, and the obtained solid content was washed with water and then dried (105 ° C., 12 hours) to produce titanium oxide. The obtained titanium oxide was an amorphous particle in which fine particles were aggregated as shown in FIG. 6, and the dahlia-like titanium oxide as in Production Example 1 was not obtained.
  • Test Example 7 The case where the acid heat treatment was performed after solid-liquid separation of the reaction solution obtained by solid-liquid separation and heating hydrolysis before the acid heat treatment was examined. Specifically, in (2) of Production Example 1, the reaction liquid obtained by hydrolysis under heating was cooled to room temperature, filtered, and the obtained solid content was redispersed in water to 1000 mL. Titanium oxide was produced in the same manner as in Production Example 1 except that 4 mol of hydrochloric acid was added to the aqueous dispersion and heat-treated at 90 ° C. for 3 hours. As for the obtained titanium oxide, most of the particles had no protrusions on the surface, and some of the particles had protrusions, but the dahlia-like titanium oxide as in Production Example 1 was obtained. I could't.
  • Test Example 8 The case where the neutralizing step was performed without solid-liquid separation of the reaction liquid obtained by the solid-liquid separation acid heat treatment before neutralization was examined. Specifically, in Production Example 1 (3), the reaction liquid obtained by acid heat treatment was cooled to room temperature, and after adjusting the pH of the reaction liquid to about 7 with 10M NaOH without solid-liquid separation, Titanium oxide was produced in the same manner as in Production Example 1 except that filtration, washing of the obtained solid with water, and drying (105 ° C., 12 hours) were performed. As for the obtained titanium oxide, most of the particles had no protrusions on the surface, and some of the particles had protrusions, but the dahlia-like titanium oxide as in Production Example 1 was obtained. I could't.
  • Test Example 9 A case where a carboxyl / carbonyl compound was not added to a titanium salt aqueous solution which was hydrolyzed by heating with a carboxyl / carbonyl compound was examined. Specifically, titanium oxide was produced in the same manner as in Production Example 1 except that the amount of acetic acid added was 0, 1, and 3 mol in (1) of Production Example 1. As a result, in any case, dahlia-like titanium oxide was obtained, and when calcined in the same manner as in Production Example 2, coral-like titanium oxide was obtained. However, as the amount of acetic acid added decreased, the protrusion length tended to be shortened, and the diameter at the protrusion tip portion tended to be uneven.
  • Production Example 1 (1) when 1 mol of acetic acid and 1 mol of sodium acetate were used instead of 3 mol of acetic acid, the same dahlia-like titanium oxide as in Production Example 1 was obtained, and this was calcined at 900 ° C. for 3 hours. Then, the same coral-like titanium oxide as in Production Example 2 was obtained.
  • Test Example 10 Firing temperature
  • titanium oxide was produced in the same manner except that the firing temperature was changed (firing time 3 hours).
  • the firing temperature was changed (firing time 3 hours).
  • the protrusions become thicker as the firing temperature increases. Such a change becomes remarkable at 300 ° C. or higher, and the projection diameter becomes very uniform at 700 ° C. or higher.
  • the firing temperature is preferably 1000 ° C. or lower, and more preferably 950 ° C. or lower.
  • Production Example 4 Production of coral-like titanium oxide (1) Heat hydrolysis: 1 mol of titanium tetrachloride, 1 mol of hydrochloric acid, 1 mol of glycerin, and 3 mol of acetic acid were mixed, the total amount was adjusted to 1000 mL with ion-exchanged water, and the mixture was stirred at room temperature for 30 minutes. Heating of the aqueous titanium salt solution was started, and after reaching 90 ° C., 90 ° C. was maintained for 5 hours. (2) Acid heat treatment: After cooling the reaction solution obtained by hydrolysis with heating to room temperature, 4 mol of hydrochloric acid was added. Heating was started again, and after reaching 90 ° C., 90 ° C. was maintained for 3 hours.
  • the particle diameter is in the range of about 0.5 to 3 ⁇ m
  • the protrusion length is about 0.05 to 0.3 ⁇ m
  • the protrusion diameter is in the range of about 0.03 to 0.2 ⁇ m
  • the protrusion length is equal to or greater than the protrusion diameter.
  • Production Example 5 Production of Silica-Coated Titanium Oxide A hydrous silicon oxide step was carried out after the (3) neutralization step in Production Example 4. Specifically, it is as follows. (1) Heat hydrolysis: 1 mol of titanium tetrachloride, 1 mol of hydrochloric acid, 1 mol of glycerin, and 3 mol of acetic acid were mixed, the total amount was adjusted to 1000 mL with ion-exchanged water, and the mixture was stirred at room temperature for 30 minutes. Heating of the aqueous titanium salt solution was started, and after reaching 90 ° C., 90 ° C. was maintained for 5 hours. (2) Acid heat treatment: After cooling the reaction solution obtained by hydrolysis with heating to room temperature, 4 mol of hydrochloric acid was added.
  • Production Example 6 Production of Silica-Coated Titanium Oxide Silica-coated rutile coral titanium oxide powder was obtained in the same manner as in Production Example 5 except that the amount of sodium silicate added was 0.3 mol (particle size was About 0.5 to 3 ⁇ m). An SEM photograph of the obtained powder is shown in FIG.
  • Production Example 7 Production of Silica-Coated Titanium Oxide Silica-coated rutile titanium oxide was produced in the same manner as in Production Example 5 except that the calcination temperature was changed (calcination time was 1 hour). An SEM photograph of the obtained powder is shown in FIG. Moreover, the SEM photograph of the powder of titanium oxide (without silica coating) obtained in the same manner except that the firing temperature was changed in Production Example 4 is also shown (the firing time is 1 hour). The particle size of the powder in FIG. 11 was in the range of about 0.5 to 3 ⁇ m. From FIG.
  • the silica-coated titanium oxide of the present invention has dahlia- or coral-like titanium oxide particles as core particles, the core particle surface is coated with silica, and at least a part of the gap between the projections of the core particles is coated with silica. It is thought that it was done.
  • FIG. 12 shows silica-coated rutile titanium oxide obtained in the same manner as in Production Example 5 except that calcination was performed at 900 ° C. for 2 hours or 800 ° C. for 3 hours (particle diameter was about 0.5 to 3 ⁇ m) SEM photograph. 11 to 12, when silica is coated, it is less affected by firing than when silica is not coated, and the silica-coated titanium oxide particles themselves have a coral shape, which is higher than when silica is not coated. It was suggested that firing at temperature was necessary.
  • Production Example 8 Production of iron oxide-silica-coated titanium oxide
  • a neutralization step was performed in the presence of an iron source, and a hydrous silicon oxide step was further performed between the neutralization step and the drying / calcination step.
  • it is as follows. (1) Heat hydrolysis: 1 mol of titanium tetrachloride, 1 mol of hydrochloric acid, 1 mol of glycerin, and 3 mol of acetic acid were mixed, the total amount was adjusted to 1000 mL with ion-exchanged water, and the mixture was stirred at room temperature for 30 minutes. Heating of the aqueous titanium salt solution was started, and after reaching 90 ° C., 90 ° C. was maintained for 5 hours.
  • Test Example 11 Irregularity Correction Effect The unevenness correction effect of silica-coated titanium oxide was examined using a pore model.
  • the test method is as follows. An appropriate amount of the test powder was applied to the surface of a pseudo pore urethane model (skin model No. 10A (40's) #Biocolor, manufactured by Beaulux Co., Ltd.) with a makeup brush, and the coated surface was photographed. After binarizing the photo, the ratio of white area to the total area (%) obtained using image analysis software (LIA32, free software, recognition pixel size condition: -1 to 50 pixels) The correction rate was calculated by the formula. A higher correction rate means a higher correction effect.
  • Correction rate (%) (White area% at powder application-control white area%) / control white area% ⁇ 100
  • Comparative powder 2 Pigment grade titanium oxide (RKB-2, Bayer AG, average particle size 200 nm, refractive index 2.7), Comparative powder 4: Fine particle titanium oxide (MT-700B, Teika Co., Ltd., titanium stearate-treated titanium oxide, average particle size 80 nm)
  • FIG. 14A is a surface photograph of each pore model
  • FIG. 14B is a result of binarizing the surface photograph
  • Table 4 shows correction factors.
  • titanium oxide conventionally used in cosmetics such as pigment grade titanium oxide (comparative powder 2) and fine particle titanium oxide (comparative powder 4) has no unevenness correction effect.
  • the coral-like titanium oxide of the present invention (Production Example 4) and the silica-coated titanium product (Production Example 5) have a high unevenness correction effect, particularly when silica is not coated. A very high effect was obtained even compared to.
  • the silica-coated titanium oxide of the present invention has lower whiteness than the pigment grade titanium oxide (comparative powder 2) and fine particle titanium oxide (comparative powder 4), and almost no pore removal phenomenon. I understand that there is no.
  • the present invention is not limited to these.
  • Dahlia-like titanium oxide, coral-like titanium oxide, and iron oxide-coated coral-like titanium oxide were produced according to Production Examples 1 to 3, respectively, and those subjected to a known surface treatment as needed were used. .
  • Formulation example 4 Liquid foundation Decamethylcyclopentasiloxane 30% by mass Dimethylpolysiloxane 5 Polyether-modified silicone 3 Organically modified bentonite 1.5 Polymethylmethacrylate spherical powder 5 Hydrophobized yellow iron oxide 2 Hydrophobized red iron oxide 1 Hydrophobized black iron oxide 0.2 Hydrophobized iron oxide coated coral titanium oxide 8 Ion exchange water to100 Glycerin 2 1,3-butylene glycol 5 Preservative appropriate amount
  • Formulation Example 8 O / W type liquid foundation Talc 3% by mass Coral titanium oxide 15 Red iron oxide 0.5 Yellow iron oxide 1.4 Black iron oxide 0.1 Bentonite 0.5 POE sorbitan monostearate 0.9 Triethanolamine 1 Propylene glycol 10 Ion exchange water to100 Stearic acid 2.2 Isohexadecyl alcohol 7 Glycerol monostearate 2 Liquid lanolin 2 Liquid paraffin 2 Preservative Appropriate amount Fragrance Appropriate amount
  • Formulation Example 9 W / O type foundation Hydrophobized talc 7% by mass Hydrophobic treated dahlia titanium oxide 12 Silicic anhydride 2 Nylon powder 4 Color pigment 2 Octamethylcyclotetrasiloxane 10 Rosin acid pentaerythritz 1.5 Diisooctanoic acid neopentyl glycol 5 Squalane 2.5 Triisooctanoic acid glycerin 2 Polyoxyethylene-modified dimethylpolysiloxane 1.5 Ion exchange water to100 1,3-butylene glycol 4 Ethanol 7 Preservative Appropriate amount Fragrance Appropriate amount
  • Formulation Example 11 Lipstick 8% by mass of polyethylene wax Deodorized polybutene 15 Polyglyceryl triisostearate 10 N-lauroyl-L-glutamic acid di (phytostearyl, 2-octyldodecyl) ester 10 Methylphenylpolysiloxane to100 Diisostearyl malate 23 Di-2-hebutylundecanoic acid glycerin 2 Dipentaerythrityl hexahydroxystearate 5 Tetra (behenic acid / benzoic acid / ethylhexanoic acid) Pentaerythrityl 5 Hydrophobized coral-like titanium oxide 1 Hydrophobized titanium oxide 1.3 Hydrophobized iron oxide yellow 0.6 Hydrophobized iron oxide red 1.4 Resol Rubin BCA (Ba 2 SO 4 ) 0.5 Antioxidant appropriate amount
  • the cosmetics of the above formulation examples 1 to 11 were prepared by a conventional method. None of the cosmetics had problems with the appearance or stability of the product. And when apply
  • silica-coated titanium oxide or iron oxide-silica-coated titanium oxide of the present invention are examples of cosmetics containing the silica-coated titanium oxide or iron oxide-silica-coated titanium oxide of the present invention.
  • the present invention is not limited to these.
  • Silica-coated titanium oxide and iron oxide-silica-coated titanium oxide were produced by methods according to Production Example 5 and Production Example 8, respectively, and those subjected to a known surface treatment as needed were used.
  • Formulation example 12 Powdery foundation Hydrophobized talc 30% by mass Mica to100 Zinc oxide 3 Fine particle titanium oxide 1 Silica-coated titanium oxide 11 Hydrophobized yellow iron oxide 2.7 Hydrophobized red iron oxide 1 Hydrophobized black iron oxide 0.25 Barium sulfate 6 Cross-linked dimethicone copolymer 8 Isooctyl methoxycinnamate 1 Hydrogenated olefin oligomer 2.5 Methylphenyl polysiloxane 2 Diisostearyl malate 3 Sorbitan sesquiisostearate 1.5 Preservative appropriate amount
  • Formulation Example 14 Face powder Hydrophobized talc 49% by mass Talc to100 Mica 3 Silica-coated titanium oxide 1 Zinc oxide 1 Mica titanium 13 Yellow iron oxide 0.5 Red iron oxide 0.07 Black iron oxide 0.01 Polymethyl methacrylate 1 Vaseline 1 Synthetic hydrocarbon wax 2 Triisooctanoic acid glyceride 5 Preservative appropriate amount
  • Formulation example 15 Liquid foundation Decamethylcyclopentasiloxane 30% by mass Dimethylpolysiloxane 5 Polyether-modified silicone 3 Organically modified bentonite 1.5 Polymethylmethacrylate spherical powder 5 Hydrophobized yellow iron oxide 2 Hydrophobized red iron oxide 1 Hydrophobized black iron oxide 0.2 Hydrophobized silica-coated titanium oxide 8 Ion exchange water to100 Glycerin 2 1,3-butylene glycol 5 Preservative appropriate amount
  • Formulation Example 16 Base for cosmetics Decamethylcyclopentasiloxane 30% by mass Dimethylpolysiloxane 5 Polyether-modified silicone 3 Organically modified bentonite 1.5 Polymethylmethacrylate spherical powder 4 Silicone-treated silica-coated titanium oxide 5 Organopolysiloxane elastomer spherical powder 5 Hydrophobized black iron oxide 0.2 Hydrophobic talc 5 Ion exchange water to100 Glycerin 2 1,3-butylene glycol 5 Preservative appropriate amount
  • Formulation Example 18 Sunscreen oil Hydrophobized zinc oxide 10% by mass Hydrophobized silica-coated titanium oxide 3 Liquid paraffin to100 Isopropyl myristate 10 Silicone oil 30 Silicone resin 2 Antioxidant Appropriate amount Perfume Appropriate amount
  • Formulation Example 19 O / W liquid foundation Talc 3% by mass Silica-coated titanium oxide 15 Red iron oxide 0.5 Yellow iron oxide 1.4 Black iron oxide 0.1 Bentonite 0.5 POE sorbitan monostearate 0.9 Triethanolamine 1 Propylene glycol 10 Ion exchange water to100 Stearic acid 2.2 Isohexadecyl alcohol 7 Glycerol monostearate 2 Liquid lanolin 2 Liquid paraffin 2 Preservative Appropriate amount Fragrance Appropriate amount
  • Formulation Example 20 W / O type foundation Hydrophobized talc 7% by mass Hydrophobized silica-coated titanium oxide 12 Silicic anhydride 2 Nylon powder 4 Color pigment 2 Octamethylcyclotetrasiloxane 10 Rosin acid pentaerythritz 1.5 Diisooctanoic acid neopentyl glycol 5 Squalane 2.5 Triisooctanoic acid glycerin 2 Polyoxyethylene-modified dimethylpolysiloxane 1.5 Ion exchange water to100 1,3-butylene glycol 4 Ethanol 7 Preservative Appropriate amount Fragrance Appropriate amount
  • Formulation Example 22 Lipstick 8% by mass of polyethylene wax Deodorized polybutene 15 Polyglyceryl triisostearate 10 N-lauroyl-L-glutamic acid di (phytostearyl, 2-octyldodecyl) ester 10 Methylphenylpolysiloxane to100 Diisostearyl malate 23 Di-2-hebutylundecanoic acid glycerin 2 Dipentaerythrityl hexahydroxystearate 5 Tetra (behenic acid / benzoic acid / ethylhexanoic acid) Pentaerythrityl 5 Hydrophobized silica-coated titanium oxide 1 Hydrophobized titanium oxide 1.3 Hydrophobized iron oxide yellow 0.6 Hydrophobized iron oxide red 1.4 Resol Rubin BCA (Ba 2 SO 4 ) 0.5 Antioxidant appropriate amount
  • the cosmetics of the above formulation examples 12 to 22 were prepared by a conventional method. None of the cosmetics had problems with the appearance or stability of the product. When applied to the skin, it does not whiten and exhibits a high unevenness correction effect as compared with cosmetics not containing the silica-coated titanium oxide or iron oxide-silica-coated titanium oxide of the present invention. It was. In addition, when cosmetics were applied to the face of female panels in their 40s and 50s, no pore removal was observed. In contrast, pore removal was observed in the cosmetics containing pigment grade titanium oxide (Comparative Powder 2) instead of silica-coated titanium oxide or iron oxide-silica-coated titanium oxide of the present invention.
  • Comparative Powder 2 pigment grade titanium oxide

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JP6245832B2 (ja) * 2013-04-01 2017-12-13 大阪瓦斯株式会社 チタニアナノ粒子及びチタニア分散液の製造方法
JP6309858B2 (ja) * 2014-08-07 2018-04-11 花王株式会社 粉末化粧料
JP2017002019A (ja) * 2015-06-08 2017-01-05 株式会社ピカソ美化学研究所 メイクアップ化粧料
JP6630508B2 (ja) * 2015-07-28 2020-01-15 花王株式会社 乳化化粧料
JP6920806B2 (ja) * 2016-10-27 2021-08-18 花王株式会社 水中油型乳化組成物
JP7084112B2 (ja) * 2017-06-26 2022-06-14 株式会社 資生堂 二酸化チタン粉体およびそれを配合した粉末化粧料
JP7017326B2 (ja) * 2017-06-26 2022-02-08 株式会社 資生堂 二酸化チタン粉体を配合した化粧料
JP7017325B2 (ja) 2017-06-26 2022-02-08 株式会社 資生堂 二酸化チタン粉体を配合した乳化化粧料
WO2019225491A1 (ja) * 2018-05-23 2019-11-28 株式会社コーセー 新規酸化チタン粉体及びそれを配合する化粧料
JP7490348B2 (ja) * 2018-10-26 2024-05-27 株式会社コーセー 粉末化粧料

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CN110769802B (zh) * 2017-06-26 2023-11-07 株式会社资生堂 固体粉末化妆品

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