WO2022244741A1 - 酸化チタン粉体及びその製造方法 - Google Patents
酸化チタン粉体及びその製造方法 Download PDFInfo
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- WO2022244741A1 WO2022244741A1 PCT/JP2022/020415 JP2022020415W WO2022244741A1 WO 2022244741 A1 WO2022244741 A1 WO 2022244741A1 JP 2022020415 W JP2022020415 W JP 2022020415W WO 2022244741 A1 WO2022244741 A1 WO 2022244741A1
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- WO
- WIPO (PCT)
- Prior art keywords
- titanium oxide
- oxide powder
- powder according
- value
- firing
- Prior art date
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 249
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 216
- 239000000843 powder Substances 0.000 title claims abstract description 156
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000013078 crystal Substances 0.000 claims abstract description 48
- 238000002835 absorbance Methods 0.000 claims abstract description 32
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 claims abstract description 22
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 17
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims description 69
- 238000010304 firing Methods 0.000 claims description 55
- 239000006185 dispersion Substances 0.000 claims description 37
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 36
- -1 alkali metal titanate Chemical class 0.000 claims description 33
- 239000002537 cosmetic Substances 0.000 claims description 33
- 239000011248 coating agent Substances 0.000 claims description 29
- 238000000576 coating method Methods 0.000 claims description 29
- 238000005259 measurement Methods 0.000 claims description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 19
- 239000003973 paint Substances 0.000 claims description 15
- 150000002484 inorganic compounds Chemical class 0.000 claims description 12
- 229910010272 inorganic material Inorganic materials 0.000 claims description 12
- 150000002894 organic compounds Chemical class 0.000 claims description 12
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- 230000020477 pH reduction Effects 0.000 claims description 10
- 150000004665 fatty acids Chemical class 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 239000002612 dispersion medium Substances 0.000 claims description 7
- 238000005470 impregnation Methods 0.000 claims description 7
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- 239000010936 titanium Substances 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
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- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 3
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- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
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- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
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- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- WTFXARWRTYJXII-UHFFFAOYSA-N iron(2+);iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+2].[Fe+3].[Fe+3] WTFXARWRTYJXII-UHFFFAOYSA-N 0.000 description 1
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical compound O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000000865 liniment Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052627 muscovite Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 229940061571 peg-9 dimethicone Drugs 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 210000003462 vein Anatomy 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- CPYIZQLXMGRKSW-UHFFFAOYSA-N zinc;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+3].[Fe+3].[Zn+2] CPYIZQLXMGRKSW-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
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- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
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- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
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Definitions
- the present invention relates to titanium oxide powder, its uses, and its production method.
- Sunscreen cosmetics are widely used because sunburn caused by ultraviolet rays adversely affects the skin.
- sunscreen cosmetics not only sunscreen cosmetics but also make-up cosmetics are increasingly required to have an ultraviolet shielding effect.
- cosmetics containing inorganic particles such as titanium oxide and zinc oxide, and organic ultraviolet absorbers have been developed.
- titanium oxide is widely used because it has a high ultraviolet shielding effect and does not easily cause skin troubles unlike organic ultraviolet absorbers.
- titanium oxide fine particles having a particle size of several tens of nanometers or less are excellent in visible light transmission because their dimensions are smaller than the wavelength of light. Whitishness is reduced, and transparency is excellent during use (see Patent Documents 1 to 3).
- iron oxide exhibits not only yellow, which is a complementary color of blue, but also red, it is unavoidable that the cosmetic has a dull color, and a better method is desired.
- Patent Document 4 describes a titanium oxide powder containing rutile crystals doped with divalent sulfur atoms (S 2- ), which cancels the bluish color due to Rayleigh scattering and has good transparency. It is said that a cosmetic having good color tone can be obtained. It also describes that the particles contained in the titanium oxide powder have an average minor axis length of 4 to 13 nm and an average aspect ratio of 2 to 7. Thus, by reducing the particle size, the transparency is improved and the UVB (280 to 320 nm) shielding effect is improved, but the UVA (320 to 400 nm) shielding effect is reduced. In order to effectively suppress melanin pigmentation due to sunburn and maintain white skin, an improvement in the UVA shielding effect is required.
- Non-Patent Document 1 describes a photocatalyst composed of nitrogen-doped titanium oxide nanoparticles containing both anatase-type crystals and rutile-type crystals.
- the titanium oxide nanoparticles have been shown to absorb light between 400 and 500 nm (Fig. 4b).
- examples with a ratio of rutile crystals of 18.3%, 20.2% and 36.9% are described, and when 20.2% is the most excellent in photocatalytic activity (see Table 1 and FIG. 5). That is, it is described that photocatalytic activity is high when the content of anatase-type crystals is much larger than that of rutile-type crystals.
- the present invention has been made to solve the above problems, and provides a titanium oxide powder containing rutile crystals as a main component, having excellent UVA shielding effect, high safety to the human body, and good color tone. It is intended to Another object of the present invention is to provide a dispersion, particularly a cosmetic, which has good transparency and good color tone. A further object of the present invention is to provide a suitable method for producing such titanium oxide powder.
- the problem is that the ratio (I A /I R ) of the peak intensity (I A ) of the anatase crystal to the peak intensity (I R ) of the rutile crystal in X-ray diffraction measurement is 0.1 or less,
- the particles contained have an average minor axis length of 10 to 50 nm and an average aspect ratio of 1 to 3,
- the ratio of the absorbance A 450 at a wavelength of 450 nm to the absorbance A 320 at a wavelength of 320 nm (A 450 /A 320 ) is 0.015 to 0.5, and contains nitrogen atoms, and has an ESCA (Electron Spectroscopy for Chemical Analysis)
- the problem is solved by providing a titanium oxide powder in which a peak derived from the nitrogen atom is observed at 395 to 402 eV in measurement.
- the specific surface area is 25-100 m 2 /g. It is also preferred that the absorbance A600 at a wavelength of 600 nm is 0.1 or less. It is also preferable that the L * value is 92 to 99, the a * value is ⁇ 5 to 2, and the b * value is 3 to 30 in the L * a * b * color system.
- the surfaces of particles contained in the powder are coated with a layer of an inorganic compound and/or an organic compound.
- the L * value is 92 to 99
- the a * value is ⁇ 5 to 2
- the b * value is 2 to 30 in the L * a * b * color system.
- a preferred embodiment is a dispersion obtained by dispersing the titanium oxide powder in a dispersion medium.
- Cosmetics, paints, and inks containing the titanium oxide powder are also preferred embodiments.
- a toner containing the titanium oxide powder as an external additive is also a preferred embodiment.
- the above-mentioned problems include an alkalinization step of adding an alkali metal hydroxide to an aqueous dispersion of hydrous titanium oxide to obtain an alkali metal titanate; an acidification step of adding hydrochloric acid to the aqueous dispersion of the alkali metal titanate to obtain titanium oxide containing rutile crystals;
- the problem is also solved by providing a method for producing titanium oxide powder, comprising an impregnation step of impregnating the titanium oxide with a nitrogen-containing compound and a firing step of firing at 200 to 600°C.
- the specific surface area of titanium oxide before firing is preferably 120 to 300 m 2 /g.
- the titanium oxide powder of the present invention is mainly composed of rutile crystals, has excellent UVA shielding effect, is highly safe for the human body, and has a good color tone. As a result, the bluish color due to Rayleigh scattering can be canceled, and a dispersion, particularly a cosmetic, with good transparency and good color tone can be provided. Further, according to the production method of the present invention, such titanium oxide powder can be obtained easily.
- FIG. 1 is a chart of X-ray diffraction measurement of titanium oxide powder (after firing) having a specific surface area of about 80 m 2 /g obtained in Example 1.
- FIG. 1 is a chart of ESCA measurement of titanium oxide powder (after firing) having a specific surface area of about 80 m 2 /g obtained in Example 1.
- FIG. 1 is a chart of ESCA measurement of titanium oxide powder (after firing) having a specific surface area of about 60 m 2 /g obtained in Example 1.
- FIG. 4 is a chart of ESCA measurement of titanium oxide powder “MT-100Z” used in Comparative Example 3.
- FIG. 1 is a transmission electron microscope (TEM) photograph of titanium oxide powder (after firing) having a specific surface area of about 80 m 2 /g obtained in Example 1.
- FIG. 1 is a transmission electron microscope (TEM) photograph of titanium oxide powder (after firing) having a specific surface area of about 60 m 2 /g obtained in Example 1.
- FIG. 2 is a graph comparing absorbances of titanium oxide powders (after firing) having a specific surface area of about 80 m 2 /g obtained in Example 1 and Comparative Example 2.
- FIG. 1 is a graph comparing the light transmittance of coating films of emulsion formulations having a concentration of 10% by mass obtained in Example 1 and Comparative Example 3.
- the ratio (I A /I R ) of the peak intensity (I A ) of the anatase crystal to the peak intensity (I R ) of the rutile crystal in X-ray diffraction measurement is 0.1 or less.
- the particles contained have an average minor axis length of 10 to 50 nm and an average aspect ratio of 1 to 3,
- the ratio of the absorbance A 450 at a wavelength of 450 nm to the absorbance A 320 at a wavelength of 320 nm is 0.015 to 0.5, and contains nitrogen atoms, and has an ESCA (Electron Spectroscopy for Chemical Analysis) In the measurement, a peak derived from the nitrogen atom is observed at 395-402 eV.
- ESCA Electrode Spectroscopy for Chemical Analysis
- the ratio (I A /I R ) of the peak intensity (I A ) of the anatase-type crystal to the peak intensity (I R ) of the rutile-type crystal in X-ray diffraction measurement is 0.1 or less. is.
- the photocatalytic activity is high, so that when used in applications exposed to ultraviolet rays or visible light, organic substances in contact with the titanium oxide particles are likely to deteriorate.
- titanium oxide is added to cosmetics, it is undesirable because it tends to irritate the skin and cause troubles.
- Each peak appearing in the X-ray diffraction measurement chart does not have to be an independent peak, and the peak of the anatase crystal may be observed as a shoulder peak of the peak of the rutile crystal. Peaks are separated by analysis software attached to the device, and the intensity of each peak is calculated.
- the ratio (I A /I R ) is preferably 0.05 or less, and more preferably no peak of the anatase crystal is observed in the X-ray diffraction measurement.
- no peak of anatase-type crystal is observed means that no peak of anatase-type crystal is detected when measured under the conditions described in the examples of the present application.
- the ratio (I A /I R ) is less than 0.03.
- the particles contained in the titanium oxide powder of the present invention have an average minor axis length of 10 to 50 nm.
- the average minor axis length is 10 nm or more, the UVA (320 to 400 nm) shielding effect is improved. If the average minor axis length is less than 10 nm, the UVB (280 to 320 nm) shielding effect is improved, but the UVA shielding effect is reduced. It is important to block UVB, which can cause skin inflammation, but it is also important to block UVA, which causes melanin pigmentation to darken the skin. Very important.
- the average minor axis length is preferably 12 nm or longer, more preferably 14 nm or longer.
- the average minor axis length is 50 nm or less, the transparency of the coating film containing titanium oxide is improved.
- the average minor axis length is preferably 40 nm or less, more preferably 30 nm or less.
- the average minor axis length and average major axis length are obtained by taking transmission electron microscope (TEM) photographs and image processing the particles.
- the particles contained in the titanium oxide powder of the present invention have an average aspect ratio (average major axis length/average minor axis length) of 1-3.
- average aspect ratio average major axis length/average minor axis length
- needle-like inorganic particles may irritate the lungs and skin, so there are concerns about their safety to the human body. Safety to the human body can be improved by having an average aspect ratio of 3 or less.
- the average aspect ratio is small, the squeaky feeling peculiar to powder when the cosmetic containing titanium oxide is applied to the skin is greatly reduced, so that the feeling of use is excellent.
- the average aspect ratio is more preferably 2.5 or less, even more preferably 2 or less.
- the titanium oxide powder of the present invention has a ratio of absorbance A 450 at a wavelength of 450 nm to absorbance A 320 at a wavelength of 320 nm (A 450 /A 320 ) of 0.015 to 0.5.
- the ratio (A 450 /A 320 ) is 0.015 or more, blue light can be absorbed, and blue light due to Rayleigh scattering can be effectively canceled.
- the color tone is close to the color of the skin, the transparency is improved when applied to the skin.
- the ratio ( A450 / A320 ) is preferably 0.025 or more.
- the ratio (A 450 /A 320 ) exceeds 0.5, the coloring becomes remarkable and it becomes difficult to use in cosmetics.
- the ratio (A 450 /A 320 ) is preferably 0.4 or less, more preferably 0.3 or less.
- the absorbance of the titanium oxide powder is obtained by measuring a molded article obtained by compressing the powder as a sample by a spectrophotometer by the diffuse reflection method.
- the titanium oxide powder of the present invention contains nitrogen atoms, and in ESCA (Electron Spectroscopy for Chemical Analysis) measurement, a peak derived from the nitrogen atoms is observed at 395-402 eV.
- ESCA Electrode Spectroscopy for Chemical Analysis
- the peak of the binding energy of Ti—N appears around 397 eV
- the peak of the binding energies of Ti—N—O and Ti—O—N appears around 400 eV.
- the presence or absence of these peaks is determined by whether or not peaks are observed in the ESCA measurement under the conditions described in the examples of the present application.
- nitrogen atoms are contained by observing any one of these peaks.
- peaks derived from scandium atoms appear as doublet peaks (4.3 eV width) at 406 eV and 401.7 eV.
- the peak at 401.7 eV overlaps with the range of 395 to 402 eV defined in the present invention, but this peak is not considered.
- the titanium oxide powder of the present invention does not normally contain scandium atoms.
- the surface of the particles had a voltage of about 400 eV. There is a peak, and there is a peak around 397 eV inside the particles.
- 400 eV was applied to the particle surface. There is a peak around 397 eV, but there is no peak around 397 eV inside the particle.
- This peak near 400 eV is thought to be due to the bonding of nitrogen atoms derived from nitrogen molecules in the air to the surface of the titanium oxide particles during firing in the air.
- the titanium oxide powder of Comparative Example 2 could not sufficiently absorb the light of 450 nm, and the absorbance A at the wavelength of 450 nm was 450 and the wavelength of 320 nm.
- the ratio (A 450 /A 320 ) to the absorbance A 320 in is 0.015 or less. From the above, even if the Ti—N bond once formed inside the particles disappears by neutralizing with ammonia and then firing at a high temperature, some structure that absorbs light of 450 nm remains. It is estimated to be.
- the titanium oxide powder of the present invention preferably has an absorbance A600 of 0.1 or less at a wavelength of 600 nm.
- absorbance A 600 is 0.1 or less, absorption of red light can be suppressed.
- red light is absorbed in addition to blue light, the color tone becomes dull, which is not preferable when used as a cosmetic.
- the absorbance A600 is more preferably 0.07 or less, even more preferably 0.05 or less.
- the titanium oxide powder of the present invention has an L * value of 92 to 99, an a * value of ⁇ 5 to 2, and a b * value of 3 to 30 in the L * a * b * color system. is preferred.
- the L * value is 92 or more, a highly white powder without dullness can be obtained.
- the L * value is more preferably 93 or higher, and even more preferably 95 or higher.
- redness is suppressed when the a * value is 2 or less.
- the a * value is more preferably 0 or less, and even more preferably -1 or less.
- the b * value of 3 or more can effectively cancel the bluish tint.
- the b * value is more preferably 4 or greater, and even more preferably 5 or greater.
- the yellow color may be too deep.
- the b * value is more preferably 20 or less, and even more preferably 15 or less.
- the iron content of the titanium oxide powder of the present invention is preferably 300 ppm or less.
- This iron content (ppm) is the mass of elemental iron relative to the mass of the powder.
- the iron content is more preferably 200 ppm or less, even more preferably 150 ppm or less. If the iron content is too high, the titanium oxide particles may aggregate and the transparency may deteriorate.
- the titanium oxide powders obtained in the present examples and comparative examples do not particularly contain an iron element.
- the titanium oxide powder of the present invention preferably has a specific surface area of 25 to 100 m 2 /g.
- the specific surface area is more preferably 40 m 2 /g or more, still more preferably 50 m 2 /g or more.
- the specific surface area is 100 m 2 /g or less, it is possible to obtain a dispersion, particularly a cosmetic, which can effectively block UVA and suppress the formation of melanin pigments due to sunburn.
- the specific surface area is more preferably 90 m 2 /g or less.
- a suitable production method includes an alkalinization step of adding an alkali metal hydroxide to an aqueous dispersion of hydrous titanium oxide (TiO 2 .nH 2 O) to obtain an alkali metal titanate,
- a method comprising an acidification step of adding hydrochloric acid to the dispersion to obtain titanium oxide (TiO 2 ) containing rutile crystals, an impregnation step of impregnating the titanium oxide with a nitrogen-containing compound, and a firing step of firing at 200 to 600 ° C. is.
- an alkali metal hydroxide is added to an aqueous dispersion of hydrous titanium oxide (titanium dioxide hydrate: TiO 2 ⁇ nH 2 O) to obtain an alkali metal titanate.
- hydrous titanium oxide titanium dioxide hydrate: TiO 2 ⁇ nH 2 O
- the method for producing hydrous titanium oxide used at this time is not particularly limited, but one produced by heating and hydrolyzing an aqueous solution of titanyl sulfate (TiOSO 4 ) can be used.
- TiOSO 4 titanyl sulfate
- the hydrous titanium oxide thus obtained usually contains anatase crystals.
- alkali metal hydroxide to be added to the aqueous dispersion of hydrous titanium oxide examples include sodium hydroxide, potassium hydroxide and lithium hydroxide, with sodium hydroxide and potassium hydroxide being preferred, and sodium hydroxide being particularly preferred.
- the number of moles of alkali metal hydroxide added at this time is preferably 2 to 20 times the number of moles of titanium element in the hydrous titanium oxide.
- the heating temperature at this time is preferably 60 to 120°C. Thereby, an aqueous dispersion of alkali metal titanate is obtained.
- Alkali metal titanates include sodium titanate (Na 2 O 7 Ti 3 ), potassium titanate, and lithium titanate.
- hydrochloric acid is added to the aqueous dispersion of the alkali metal titanate to obtain titanium oxide (TiO 2 ) containing rutile crystals.
- TiO 2 titanium oxide
- hydrochloric acid is added to acidify the aqueous dispersion, an aqueous dispersion in which titanium oxide particles containing rutile crystals are dispersed can be obtained.
- the amount of hydrochloric acid added is an amount that can neutralize excess alkali in the aqueous dispersion and further acidify the aqueous dispersion.
- a suitable aging temperature is 40-110°C.
- Suitable aging times are from 2 minutes to 24 hours. It is more preferably 5 minutes or longer. Moreover, it is more preferably 10 hours or less.
- the obtained titanium oxide is impregnated with a nitrogen-containing compound.
- a nitrogen-containing compound may be added to the aqueous dispersion of titanium oxide obtained in the acidification step, impregnated, and then dried, or the aqueous dispersion may be dried and then impregnated with the nitrogen-containing compound.
- the nitrogen-containing compound used here is not particularly limited, and ammonia, ammonium bicarbonate, amine, urea and the like can be used.
- the impregnation step it is preferable to neutralize the hydrochloric acid remaining after the acidification step with a basic nitrogen-containing compound to impregnate titanium oxide with the nitrogen-containing compound.
- a basic nitrogen-containing compound used at this time, ammonia, ammonium bicarbonate, amine, etc. can be used. Addition of aqueous ammonia is particularly preferred because the operation is simple and inexpensive.
- the titanium oxide particles are heated to remove moisture and dry. A suitable drying temperature is 70°C or more and less than 200°C. After drying, pulverization and sieving can be performed as necessary to obtain titanium oxide powder (before firing).
- the hydrochloric acid remaining after the acidification step can be neutralized with a base other than the nitrogen-containing compound.
- bases include sodium hydroxide, potassium hydroxide and the like.
- the titanium oxide particles are heated to remove moisture and dry. A suitable drying temperature is 70°C or more and less than 200°C. After drying, pulverization and sieving can be performed as necessary to obtain titanium oxide powder (before firing). This titanium oxide powder (before calcination) can be impregnated with a basic nitrogen-containing compound solution, preferably an aqueous solution, and then subjected to a calcination step.
- the titanium oxide powder is fired at 200-600°C.
- the firing temperature is preferably 250° C. or higher, more preferably 300° C. or higher.
- the firing temperature is preferably 550° C. or lower, more preferably 500° C. or lower.
- the atmosphere for firing is not particularly limited, and firing can be performed in an air atmosphere. In this case, nitrogen atoms derived from nitrogen molecules in the atmosphere may bond to the surface of the titanium oxide particles. After sintering, pulverization and sieving can be performed as necessary to obtain titanium oxide powder (after sintering).
- the titanium oxide powder of the present invention can be used for various purposes as it is, but it is preferable to coat the surface. That is, a preferred embodiment of the present invention is a titanium oxide powder obtained by coating the surface of titanium oxide particles contained in the powder with a layer of an inorganic compound and/or an organic compound.
- the inorganic compound coating the titanium oxide particles preferably contains at least one element selected from the group consisting of aluminum, magnesium, calcium, silicon, zinc, titanium, zirconium, iron, cerium and tin.
- An aluminum compound is particularly suitable, and it is preferable to coat in the form of aluminum hydroxide, which improves the dispersion stability and suppresses the photocatalytic activity peculiar to titanium oxide.
- Examples of the method of coating with aluminum hydroxide include a method of adding a salt such as aluminum chloride to a slurry containing titanium oxide particles, hydrolyzing the slurry, and depositing aluminum hydroxide on the surfaces of the titanium oxide particles.
- a preferable content of aluminum in the titanium oxide powder is 2 to 30 parts by mass in terms of Al 2 O 3 with respect to 100 parts by mass of TiO 2 .
- the organic compound that coats the titanium oxide particles includes at least one selected from the group consisting of fatty acids or salts thereof, silicone compounds, coupling agents and fluorine compounds.
- fatty acids or salts thereof are preferred, which can impart lipophilicity to the surface of the titanium oxide particles, facilitating dispersion in the oil phase.
- the cosmetic applied to the skin is less likely to be washed off by sweat or rain, and the durability is improved.
- a higher fatty acid having 12 to 30 carbon atoms is preferably used, and an aluminum salt is preferably used as its salt.
- a fatty acid salt of an alkali metal is added to a slurry containing titanium oxide particles, and then a strong acid such as sulfuric acid is added to precipitate free fatty acids on the surfaces of the titanium oxide particles. and the like.
- a suitable content of the fatty acid or its salt in the titanium oxide powder is 2 to 50 parts by mass with respect to 100 parts by mass of TiO 2 . This content is the amount in terms of free fatty acid.
- the inorganic compound layer that covers the surface of the titanium oxide particles does not need to be a uniform layer, and may partially cover the surface. This point also applies to the organic compound layer.
- the inorganic compound layer and the organic compound layer may be formed as separate layers, or one layer may contain both the inorganic compound portion and the organic compound portion.
- the surface of the titanium oxide particles is covered with a layer containing aluminum hydroxide and a higher fatty acid having 12 to 30 carbon atoms or its aluminum salt.
- the L * value in the L * a * b * color system is from 92 to 99, and a It is preferred that the * value is from -5 to 2 and the b * value is from 2 to 30. Since coating the surface reduces the b * value compared to the uncoated one, the preferred lower limit of the b * value was lowered to 2 for the coated titanium oxide powder. More preferable ranges of L * value, a * value and b * value are the same as those of the uncoated titanium oxide powder.
- a preferred embodiment is a dispersion obtained by dispersing the titanium oxide powder of the present invention thus obtained in a dispersion medium.
- the dispersion medium at this time may be water or an organic solvent.
- a mixed solvent of water and an organic solvent may be used, or an emulsion formed from water and an organic solvent may be used.
- Suitable applications include cosmetics, paints, inks, toners, etc. containing the titanium oxide powder of the present invention.
- a particularly suitable use is cosmetics, and it is suitably used as a cosmetic having an ultraviolet shielding effect, particularly a cosmetic capable of suppressing the deposition of melanin pigment.
- Inorganic pigments and organic pigments other than the titanium oxide powder of the present invention can be blended into the cosmetic of the present invention.
- Inorganic pigments that can be used include titanium oxide, zinc oxide, red iron oxide, yellow iron oxide, black iron oxide, ultramarine blue, Prussian blue, cerium oxide, talc, muscovite, synthetic mica, phlogopite, biotite, synthetic fluorine phlogopite, and mica.
- Magnesium, boron nitride, bismuth oxychloride, alumina, zirconium oxide, magnesium oxide, chromium oxide, calamine, carbon black, hydroxyapatite and composites thereof can be used.
- Organic pigments that can be used include silicone powder, polyurethane powder, cellulose powder, nylon powder, silk powder, polymethyl methacrylate (PMMA) powder, starch, polyethylene powder, polystyrene powder, tar pigments, natural pigments, and their pigments. Composites and the like can be used.
- the cosmetic of the present invention can contain other ingredients depending on the purpose.
- pH adjusters, humectants, thickeners, surfactants, dispersion stabilizers, preservatives, antioxidants, sequestering agents, astringents, antiphlogistic agents, UV absorbers, perfumes, etc. may be added as appropriate. can.
- Forms of the cosmetic of the present invention include milky lotions, lotions, oils, creams, pastes, and the like. Specific uses include sunscreen cosmetics, makeup bases, foundations, concealers, control colors, lipsticks, lip balms, eye shadows, eyeliners, mascara, cheek colors, makeup cosmetics such as nail polish, and skin care. Cosmetics and hair care cosmetics are exemplified.
- the titanium oxide particles When the titanium oxide powder of the present invention is used for paint or ink, the titanium oxide particles may be dispersed in a solution in which the base polymer is dissolved, or the titanium oxide particles may be dispersed in an aqueous emulsion in which the base polymer particles are dispersed. The particles may be dispersed.
- additives that are commonly added to paints and inks such as pigments, matting agents, surfactants, dispersion stabilizers, leveling agents, thickeners, antioxidants, and UV absorbers, can be added.
- Some paints containing fine particles of titanium oxide exhibit a so-called “flip-flop” effect, in which the color tone changes depending on the viewing angle. A "flop" coating can be formed.
- the titanium oxide powder of the present invention When used as an external additive for toner, it is used by being mixed with toner particles containing a pigment. By using fine particles of titanium oxide, it is possible to provide a toner with excellent charging performance stability under various environments. At this time, the toner may contain various additives that are usually added.
- the peak intensity (I R ) of rutile-type titanium oxide (110 plane) near 2 ⁇ 27.5° and the peak intensity (I A ) were measured and their ratio (I A /I R ) was calculated.
- the peak search was performed under the following conditions.
- the ratio (I A /I R ) at the detection limit of the peak of the anatase crystal is 0.03. Therefore, the ratio (I A /I R ) is less than 0.03 when the anatase crystal peak is not detected.
- ESCA Electrode Spectroscopy for Chemical Analysis
- ESCA3400 X-ray photoelectron spectrometer
- the powder of the sample was compacted into a thin film, fixed with a carbon tape, and then measured.
- the distribution of nitrogen atoms with respect to the depth direction of the sample was measured by repeatedly etching the surface by argon sputtering for 15 seconds. Correction was made with the C1s binding energy of 284.6 eV. Measurement conditions and etching conditions are as follows.
- the specific surface area was measured by the BET method using a fully automatic specific surface area measuring device (“Macsorb HM model-1208” manufactured by Mountec Co., Ltd.). Measurement was performed after deaeration at 150° C. for 20 minutes in a nitrogen gas atmosphere.
- Macsorb HM model-1208 manufactured by Mountec Co., Ltd.
- Powder color An aluminum ring (43 ⁇ ) for powder samples (manufactured by Rigaku Co., Ltd., dimensions: outer diameter 43mm, inner diameter 40mm, height 5mm) was set on the medicine packaging paper, and the ring was filled with titanium oxide powder. It is flattened with a tablet press ("BRE-32" manufactured by Mayekawa Test Machine Co., Ltd.), and pressed at 15 MPa for 30 seconds to form a thickness of 2.5 to 3.0 mm. A tablet was obtained and used as a sample for measurement. The color of the sample thus obtained was measured using a color difference meter "CR-400" manufactured by Konica Minolta, Inc. After performing white calibration of the colorimeter, the L * value, a * value and b * value in the L * a * b * color system were measured.
- CR-400 color difference meter
- L * 1 , a * 1 and b * 1 are the L * , a * and b* values of the blank, L * 2 , a * 2 and b * 2 are the L * and a of the coated portion. * values and b * values.
- Example 1 An aqueous solution of titanyl sulfate (TiOSO 4 ) was heated to 100° C. for hydrolysis to precipitate hydrous titanium oxide (titanium dioxide hydrate) (TiO 2 ⁇ nH 2 O) to obtain a slurry.
- the cake obtained by filtering this slurry was washed with water to obtain 35 kg of hydrous titanium oxide cake (10 kg in terms of TiO 2 ).
- the obtained hydrous titanium oxide contains anatase type crystals.
- 70 kg of a 48% by mass sodium hydroxide aqueous solution was added with stirring, then heated and stirred at a temperature range of 95 to 105° C. for 2 hours to obtain a slurry of sodium titanate (Na 2 O 7 Ti 3 ).
- the cake was dried at 110° C., pulverized with an impact pulverizer, and passed through a 0.3 mm sieve to obtain titanium oxide powder (before firing).
- This titanium oxide powder had an average minor axis length of 6 nm and an average aspect ratio of 3.5.
- the specific surface area measured by the BET method was 204 m 2 /g, and the L * value measured with a colorimeter was 97.99, the a * value was ⁇ 0.53, and the b * value was 2.41. .
- Table 1 The above evaluation results are summarized in Table 1.
- the obtained titanium oxide powder (before firing) was placed in a crucible with a lid that does not shut off the air, and a box-type electric furnace ("KBF828N1" manufactured by Koyo Thermo Systems Co., Ltd.) was used in an air atmosphere to determine the specific surface area. It was calcined at 380° C. for 120 minutes so that the density was about 80 m 2 /g.
- the resulting fired product was pulverized with an impact pulverizer and passed through a 0.3 mm sieve to obtain titanium oxide powder (after firing) having a specific surface area of 82.0 m 2 /g. Further, in the same operation, by changing the firing temperature to 480° C. so that the specific surface area is about 60 m 2 /g, titanium oxide powder (after firing) with a specific surface area of 60.3 m 2 /g was also obtained. Obtained.
- FIG. 1 shows a chart of X-ray diffraction measurement of titanium oxide powder (after firing) having a specific surface area of about 80 m 2 /g.
- No peak of the anatase-type crystal was detected, and the ratio (I A /I R ) of the peak intensity (I A ) of the anatase-type crystal to the peak intensity (I R ) of the rutile-type crystal was less than 0.03.
- no peak of anatase-type crystal was detected in the X-ray diffraction measurement of the titanium oxide powder (after firing) having a specific surface area of about 60 m 2 /g.
- no peak of anatase-type crystals was detected.
- FIG. 2 shows a chart of ESCA measurement of titanium oxide powder (after firing) having a specific surface area of about 80 m 2 /g.
- a peak was observed near the binding energy of 400 eV, and after etching for 15 seconds and 30 seconds (Ar-15 seconds, Ar-30 seconds), a large peak near the binding energy of 397 eV was observed. and a small peak near 400 eV were observed. All peaks were peaks derived from nitrogen atoms.
- FIG. 3 shows a chart of ESCA measurement of titanium oxide powder (after firing) having a specific surface area of about 60 m 2 /g.
- FIG. 5 shows a transmission electron microscope (TEM) photograph of titanium oxide powder (after firing) having a specific surface area of about 80 m 2 /g.
- the average minor axis length calculated by image processing based on the TEM photograph was 12.7 nm, and the average aspect ratio was 1.60.
- FIG. 6 shows a transmission electron microscope (TEM) photograph of a titanium oxide powder (after firing) having a specific surface area of about 60 m 2 /g.
- the average short axis length calculated by image processing based on the TEM photograph was 22.4 nm, and the average aspect ratio was 1.54.
- the graph of the absorbance of the titanium oxide powder (after firing) having a specific surface area of about 80 m 2 /g measured with a spectrophotometer was compared with the titanium oxide powder having a specific surface area of about 80 m 2 /g obtained in Comparative Example 2. It is shown in FIG. 7 together with the absorbance of the powder (after firing).
- the titanium oxide powder of Example 1 has a characteristic absorption around 450 nm, but Comparative Example 2, which was not neutralized with ammonia, did not have an absorption around 450 nm.
- the titanium oxide powder (after firing) having a specific surface area of about 80 m 2 /g had an absorbance of 1.041 at 320 nm, an absorbance of 0.088 at 450 nm, and an absorbance of 0.014 at 600 nm. Therefore, the ratio ( A450 / A320 ) was 0.085.
- the titanium oxide powder (after firing) having a specific surface area of about 60 m 2 /g had an absorbance of 1.034 at 320 nm, an absorbance of 0.081 at 450 nm, and an absorbance of 0.007 at 600 nm. rice field. Therefore, the ratio ( A450 / A320 ) was 0.078.
- the titanium oxide powder having a specific surface area of about 80 m 2 /g (after firing) is shown in Table 2
- the titanium oxide powder having a specific surface area of about 60 m 2 /g (after firing) is shown in Table 3. Shown together.
- lacquer varnish 3500 g of lacquer varnish was prepared by uniformly mixing the following materials.
- the solid content concentration of nitrocellulose (NC) at this time was 10% by mass.
- ⁇ n-butyl acetate 1050 g
- Ethyl acetate 700 g
- Ethylene glycol mono-n-butyl ether 350 g
- Toluene 900 g
- the paint thus obtained is applied onto a PET film (manufactured by Panac: Lumirror 100T60) using an automatic bar coater equipped with a wire bar (No. 22) and dried at room temperature for 24 hours to form a coating film. did.
- the color difference ⁇ E between the formed coating film and BIOSKIN was evaluated according to the above method. As a result, ⁇ E was 9.6. Further, when a paint and a coating film were prepared in the same manner using titanium oxide powder having a specific surface area of about 60 m 2 /g and evaluated, ⁇ E was 10.2.
- titanium oxide powder (after firing) having a specific surface area of about 80 m 2 /g or about 60 m 2 /g to obtain a titanium oxide slurry of 70 g/L in terms of TiO 2 .
- This titanium oxide slurry was heated to 85° C., added with a 10 mass % aqueous solution of polyaluminum chloride (PAC: [Al 3 (OH) n Cl 6-n ] m ), and aged for 10 minutes.
- PAC polyaluminum chloride
- the amount of PAC added is 6 parts by mass as Al 2 O 3 for 100 parts by mass of titanium oxide powder having a specific surface area of about 80 m 2 /g, and 6 parts by mass as Al 2 O 3 for 100 parts by mass of titanium oxide powder having a specific surface area of about 60 m 2 /g. On the other hand, the amount was 4 parts by mass as Al 2 O 3 . After adjusting the pH to 6.0 using a 48% by mass sodium hydroxide aqueous solution, the mixture was aged for 30 minutes, and sodium stearate was added.
- the amount of sodium stearate to be added is 7 parts by mass with respect to 100 parts by mass of titanium oxide powder with a specific surface area of about 80 m 2 /g, and is 7 parts by mass with respect to 100 parts by mass of titanium oxide powder with a specific surface area of about 60 m 2 /g.
- the amount was 5 parts by mass.
- the cake was dried at 110° C., pulverized with an impact pulverizer, and passed through a 0.3 mm sieve to obtain surface-coated titanium oxide powder.
- the titanium oxide particles in the resulting powder were coated with a layer of aluminum hydroxide and stearic acid (or aluminum stearate).
- the average short axis length and average aspect ratio of the particles contained in the titanium oxide powder surface-treated in this manner were almost the same as those of the titanium oxide powder before surface treatment.
- an emulsified preparation having a titanium oxide concentration of 25% by mass was prepared.
- an emulsified formulation having a titanium oxide concentration of 10% by mass was prepared using a surface-coated titanium oxide powder having a specific surface area of about 60 m 2 /g. All emulsified formulations are intended for cosmetics.
- the thus-obtained emulsified formulation having a concentration of 25% by mass was applied onto a PET film (manufactured by Panac: Lumirror 100T60) using an automatic bar coater equipped with a wire bar (No. 6), and allowed to stand still at room temperature for 24 hours. It was left to dry to form a coating film.
- the color difference ⁇ E between the formed coating film and BIOSKIN was evaluated according to the above method. As a result, ⁇ E was 4.8.
- a surface-coated titanium oxide powder having a specific surface area of about 60 m 2 /g was used to prepare an emulsified formulation having a concentration of 25% by mass and evaluated in the same manner, and ⁇ E was 6.4.
- the 10% by mass emulsified preparation thus obtained was applied to a PET film (manufactured by Panac: Lumirror 100T60) using an automatic bar coater equipped with a wire bar (No. 6) to form a coating film.
- a PET film manufactured by Panac: Lumirror 100T60
- BIOSKIN an automatic bar coater equipped with a wire bar (No. 6)
- the color difference ⁇ E between this coating film and BIOSKIN immediately after application was measured according to the above method, it was 6.4. became.
- the color difference ⁇ E immediately after application was 6.4, the same as the emulsified preparation of this example, but the color difference ⁇ E after drying was the same as that of the emulsified preparation of this example. It was 4.4, which is greater than the emulsified formulation of the example. From this, it was found that the emulsified formulation of the present example has improved transparency after drying compared to the conventional product.
- this emulsified preparation was applied to a polypropylene film (manufactured by Mitsui Chemicals Tohcello Co., Ltd.: plain OPP sheet #40) using an automatic bar coater equipped with a wire bar (No. 6) to form a coating film.
- the light transmittance of this coating film was measured using a spectrophotometer (“U-4100” manufactured by Hitachi High-Technologies Corporation, using an integrating sphere) under the following conditions.
- a graph plotting the transmittance against wavelength is shown in FIG. 8 together with the transmittance of the emulsion preparation of Comparative Example 3. It can be seen that the effect of shielding UVA (320 to 400 nm) is greater than in Comparative Example 3 using commercially available titanium oxide powder.
- the transmittance at 400 nm was 66.0%
- the transmittance at 450 nm was 78.9%
- the wavelength at which the transmittance was 50% was 374 nm.
- the feeling of use, whiteness, bluishness and transparency of the obtained emulsified preparation were evaluated according to the above methods. voted which one is better.
- the emulsified formulation of this example has a lower viscosity than the emulsified formulation of Comparative Example 3, and the emulsified formulation spreads easily immediately after being dropped on the skin, and the squeaky feeling peculiar to powder is greatly reduced. Therefore, all 10 panelists judged that the feeling of use was good.
- the whiteness, bluishness and transparency after spreading and drying all 10 panelists said that the emulsified formulation using the titanium oxide powder of this example had less whiteness and bluishness. , judged to be transparent.
- an emulsified formulation with a concentration of 10% by mass was produced in the same manner as above except that the oil phase raw material was changed as shown below.
- the viscosity after adjustment was measured using a Brookfield viscometer. It was 1278 mPa ⁇ s when measured under the conditions of 3 rotors, 25° C. and 60 rpm. (Oil phase raw material) ⁇ Dimethicone 28.33 g: “KF-96L-1.5cs” manufactured by Shin-Etsu Chemical Co., Ltd.
- Liquid paraffin 4.375 g “Moresco White P-70” manufactured by MORESCO Co., Ltd. ⁇ PEG-9 polydimethylsiloxyethyl dimethicone 4.375 g: “KF-6028P” manufactured by Shin-Etsu Chemical Co., Ltd. ⁇ 1.42 g of aluminum stearate
- the emulsified formulation after viscosity adjustment was evenly applied on a PMMA plate in an amount of 1.3 mg/cm 2 , dried naturally at room temperature for 30 minutes, and SPF and SPF were measured using an SPF analyzer (Optometrics, Labsphere UV-2000S). UVAPF was measured. As a result, SPF was found to be 12.6, effectively blocking UVB. Moreover, UVAPF was 4.7, and it turned out that UVA is also shielded effectively. Table 4 summarizes the above evaluation results.
- Example 2 Titanium oxide powder was produced, analyzed and evaluated in the same manner as in Example 1, except that the slurry after adding hydrochloric acid was aged in the range of 100 to 105° C. for 30 minutes. The evaluation results are summarized in Tables 1 to 3.
- Example 3 Titanium oxide powder was produced, analyzed and evaluated in the same manner as in Example 1, except that the slurry after the addition of hydrochloric acid was aged at 50° C. for 20 minutes. The evaluation results are summarized in Tables 1 to 3. For the titanium oxide powder (after firing) having a specific surface area of about 60 m 2 /g, only the specific surface area was measured.
- Comparative example 1 Titanium oxide powder was produced in the same manner as in Example 1, except that 10.0 kg of 35% by mass hydrochloric acid was added to the slurry containing sodium titanate, heated, and aged in the range of 100 to 105° C. for 5 hours. , analyzed and evaluated. The evaluation results are summarized in Tables 1 to 3.
- Comparative example 2 This is an example in which the nitrogen-containing compound was not impregnated. 14.0 kg of 35% by mass hydrochloric acid was added to the slurry containing sodium titanate, heated, and aged at 80° C. for 10 minutes. The aged slurry was diluted with water to obtain a slurry containing 70 g/L of titanium oxide in terms of TiO 2 . The obtained titanium oxide contains rutile type crystals. This titanium oxide slurry was heated to 80° C., adjusted to pH 6.4 with a 24 mass % sodium hydroxide aqueous solution, and aged for 30 minutes.
- Example 4 This is an example in which ammonia water is sprayed immediately before firing. Oxidation was carried out in the same manner as in Comparative Example 2, except that 10 parts by mass of 24% by mass ammonia water was sprayed on 100 parts by mass of the dried titanium oxide powder (before firing) obtained in the same manner as in Comparative Example 2. Titanium powder (after firing) was produced, analyzed and evaluated. The evaluation results are summarized in Tables 1 to 3.
- Comparative example 3 In the emulsified formulation with a concentration of 10% by mass produced in Example 1, instead of the surface-coated titanium oxide powder used, a commercially available titanium oxide powder (manufactured by Tayka Co., Ltd.: "MT-100Z”) was used to prepare the paint. An emulsified formulation was prepared under the same conditions except that the dispersion time with the conditioner was changed to 2 hours. "MT-100Z” is a titanium oxide powder containing spindle-shaped particles, having an average minor axis length of 7.9 nm and an average aspect ratio of 4.0. Surface treated with polyaluminum chloride and sodium stearate. A chart of ESCA measurement of this powder is shown in FIG.
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Abstract
Description
含まれる粒子の、平均短軸長さが10~50nmであり、平均アスペクト比が1~3であり、
450nmの波長における吸光度A450と320nmの波長における吸光度A320との比(A450/A320)が0.015~0.5であり、かつ
窒素原子を含み、ESCA(Electron Spectroscopy for Chemical Analysis)測定において、該窒素原子に由来するピークが395~402eVに観察される、酸化チタン粉体を提供することによって解決される。
該アルカリ金属チタン酸塩の水分散液に塩酸を加えてルチル型結晶を含む酸化チタンを得る酸性化工程、
該酸化チタンに含窒素化合物を含浸させる含浸工程、及び
200~600℃で焼成する焼成工程を有する、酸化チタン粉体の製造方法を提供することによっても解決される。
含まれる粒子の、平均短軸長さが10~50nmであり、平均アスペクト比が1~3であり、
450nmの波長における吸光度A450と320nmの波長における吸光度A320との比(A450/A320)が0.015~0.5であり、かつ
窒素原子を含み、ESCA(Electron Spectroscopy for Chemical Analysis)測定において、該窒素原子に由来するピークが395~402eVに観察されるものである。このような酸化チタン粉体は、本発明者らが鋭意検討することによって初めて製造することができたものである。以下、詳細に説明する。
ガラス板で試料ホルダーに平面状に押し付けられた酸化チタン粉体をX線回折装置(フィリップス社製)で測定した。測定条件は以下の通りである。
・Diffractometer system:XPERT-PRO
・線源:CuKα
・走査サイズ:2θ=0.008°
・電圧:45kV
・電流:20mA
・測定範囲:2θ=5~100°
・解析用付属ソフトウェア:HighScore Plus
・最小有意度:0.50
・最小ピークチップ:0.10°
・最大ピークチップ:1.00°
・ピークベース幅:2.00°
・方法:2次微分の最小値
ESCA(Electron Spectroscopy for Chemical Analysis)測定は、X線光電子分光分析装置(株式会社島津製作所製「ESCA3400」)を用いて行った。試料の粉体を薄膜状に押し固めてからカーボンテープで固定して測定した。15秒間のアルゴンスパッタリングによる表面のエッチングを繰り返し行うことによって試料の深さ方向に対する窒素原子の分布を測定した。C1sの結合エネルギー284.6eVで補正した。測定条件及びエッチング条件は以下の通りである。
・X線源:Mg-Kα線
・フィラメント電圧-電流:12kV-15mA
・真空度:1.0×10-6Pa未満
・測定範囲:385~415eV
・測定ステップ:0.1eV
・積算回数:30回
(アルゴンエッチング条件)
・フィラメント電圧-電流:2kV-20mA
・イオン源:アルゴンガス
・アルゴンエッチング中の真空度:1.0×10-4Pa
・エッチング時間:15秒/回
透過型電子顕微鏡(TEM)写真を撮影し、粒子を画像処理することによって、それぞれの粒子の長軸長さ(nm)と短軸長さ(nm)を求めた。アスペクト比は(長軸長さ/短軸長さ)で求められる値である。粒子を200個以上計測し、平均短軸長さ(nm)と平均アスペクト比を求めた。
全自動比表面積測定装置(株式会社マウンテック製「Macsorb HM model-1208」)を用いて、BET法によって比表面積を測定した。測定に際しては、窒素ガス雰囲気下、150℃で20分間脱気してから測定した。
薬包紙上に粉体試料用アルミリング(43φ)(株式会社リガク製 寸法:外径43mm、内径40mm、高さ5mm)をセットし、リング内に酸化チタン粉体を充填して平らにならし、錠剤成型圧縮機(株式会社前川試験機製作所社製「BRE-32」)を用いて、15MPaで30秒間加圧、成型し、厚さが2.5~3.0mmの錠剤を得て、測定用試料とした。こうして得られた試料の色を、コニカミノルタ株式会社製色彩色差計「CR-400」を用いて測定した。色彩色差計の白色校正を行ってから、L*a*b*表色系におけるL*値、a*値及びb*値を測定した。
上記「(5)粉体色」と同様にして得られた錠剤を試料として、積分球付き分光光度計(株式会社日立ハイテクノロジーズ製「U-4100」)を用いて拡散反射法によって吸光度を得た。測定条件は以下の通りである。測定は、硫酸バリウム標準白色板を用いて標準補正してから行った。
・スキャンスピード:300nm/分
・サンプリング間隔:2nm
・測定波長:250~700nm
450nmの波長における吸光度A450と320nmの波長における吸光度A320から、吸光度比(A450/A320)を算出した。
表面の一部に塗膜が形成されたPETフィルムを、肌色の標準色であるバイオスキン(株式会社ビューラックス、♯バイオカラー BSC)上に置き、当該塗膜側から、色彩色差計(コニカミノルタ株式会社製「CR-400」)を用いて色差を測定した。色彩色差計の白色校正を行ってから、PETフィルム上の未塗布部分(ブランク)と、塗布部分のそれぞれについて、L*a*b*表色系におけるL*値、a*値及びb*値を測定した。塗布部分を2回測定した平均値を用い、以下の計算式からブランクと塗布部分の色差ΔEを算出した。ΔEの値が小さいほど、肌の色からの乖離が少なく、肌なじみが良いことを表す。
10人のパネラーが、日光の下で乳化製剤を前腕部の肌に塗布し、使用感を評価すると共に、見る角度を変えながら目視で白さ、青み及び透明感を評価した。青みの評価については、特に、静脈が青く透けて見える部分での青みを観察した。
硫酸チタニル(TiOSO4)の水溶液を100℃に加熱して加水分解し、含水酸化チタン(二酸化チタン水和物)(TiO2・nH2O)を析出させてスラリーを得た。このスラリーをろ過して得られたケーキを水で洗浄して、含水酸化チタンのケーキ35kg(TiO2換算で10kg)を得た。得られた含水酸化チタンは、アナタース型結晶を含むものである。このケーキに、48質量%水酸化ナトリウム水溶液70kgを撹拌しながら加えた後に加熱し、95~105℃の温度範囲で2時間撹拌してチタン酸ナトリウム(Na2O7Ti3)のスラリーを得た。このスラリーをろ過して得られたケーキを十分に水で洗浄し、チタン酸ナトリウムのケーキを得た。得られたケーキに水を加えて、TiO2換算で170g/Lのチタン酸ナトリウムを含むスラリーを得た。
以下の材料を均一に混合し、ラッカーワニス3500gを作製した。このときのニトロセルロース(NC)の固形分濃度は10質量%であった。
・ニトロセルロース(H1/2):500g
(キシダ化学株式会社製 固形分濃度約70質量%)
・酢酸n-ブチル:1050g
・酢酸エチル:700g
・エチレングリコールモノ-n-ブチルエーテル:350g
・トルエン:900g
こうして得られたラッカーワニス40g、比表面積が約80m2/gの酸化チタン粉体(焼成後)1.714g及び分散メディアとしてのφ0.5mmジルコニアビーズ(株式会社シンマルエンタープライゼス製)130gを100mLのボトル(ニッコーハンセン株式会社製:Jボトル丸形広口)に入れ、ペイントコンディショナー(RED DEVIL社製「1400-OH」)で90分間分散したのち、ジルコニアビーズを分離し、塗料を作製した。得られた塗料では、固形分全体に対して酸化チタンが30質量%含まれていた。
こうして得られた塗料を、ワイヤーバー(No.22)が装着された自動バーコーターを用いてPETフィルム(パナック社製:ルミラー100T60)上に塗布し、室温で24時間乾燥させ、塗膜を形成した。形成した塗膜の、バイオスキンとの色差ΔEを、上記方法に従って評価した。その結果、ΔEは9.6であった。また、比表面積が約60m2/gの酸化チタン粉体を用いて同様に塗料および塗膜を作製して評価したところ、ΔEは10.2であった。
比表面積が約80m2/g又は比表面積が約60m2/gの酸化チタン粉体(焼成後)に水を加え、TiO2換算で70g/Lの酸化チタンスラリーを得た。この酸化チタンスラリーを85℃まで昇温し、ポリ塩化アルミニウム(PAC:[Al3(OH)nCl6-n]m)の10質量%水溶液を添加してから10分間熟成した。PACの添加量は、比表面積約80m2/gの酸化チタン粉体100質量部に対してはAl2O3として6質量部、比表面積約60m2/gの酸化チタン粉体100質量部に対してはAl2O3として4質量部となる量であった。48質量%水酸化ナトリウム水溶液を用いてpHを6.0に調整してから30分間熟成し、ステアリン酸ナトリウムを添加した。ステアリン酸ナトリウムの添加量は、比表面積約80m2/gの酸化チタン粉体100質量部に対して7質量部となる量、比表面積約60m2/gの酸化チタン粉体100質量部に対して5質量部となる量であった。ステアリン酸ナトリウムを添加して60分間熟成した後50質量%硫酸でpHを6.0に調整し、さらに30分間熟成して得られたスラリーを濾過し、水で洗浄して、水酸化アルミニウムとステアリン酸(又はステアリン酸アルミニウム)の層で被覆された酸化チタンのケーキを得た。このケーキを110℃で乾燥してから、衝撃式粉砕機で粉砕し、0.3mmのふるいを通して、表面が被覆された酸化チタン粉体を得た。得られた粉体中の酸化チタン粒子は、水酸化アルミニウムとステアリン酸(又はステアリン酸アルミニウム)の層で被覆されたものであった。このようにして表面処理された酸化チタン粉体に含まれる粒子の平均短軸長さ及び平均アスペクト比は、表面処理される前の酸化チタン粉体とほとんど同じであった。
以下に示す油相原料30.87g、表面が被覆された比表面積約80m2/gの酸化チタン粉体22.05g及び分散メディアとしてのφ0.5mmジルコニアビーズ(株式会社シンマルエンタープライゼス製)130gを100mLのボトル(ニッコーハンセン株式会社製:Jボトル丸形広口)に入れ、ペイントコンディショナー(RED DEVIL社製、1400-OH)で5時間分散したのち、ジルコニアビーズを分離し、油相分散体を作製した。この油相分散体37.80gを100mLのポリプロピレン製カップに入れ、高速乳化・分散機(プライミクス株式会社製「T.K.ロボミックス」)を用いて、撹拌速度3000rpmで撹拌しながら、以下に示す水相原料の混合物25.2gを加え、3000rpmのままで5分間撹拌して、乳化製剤を作製した。
(油相原料)
・シクロペンタシロキサン21.07g:信越化学工業株式会社製「KF-995」
・流動パラフィン4.9g:株式会社MORESCO製「モレスコホワイト P-70」
・PEG-9ジメチコン4.9g:信越化学工業株式会社製「KF-6019」
(水相原料)
・イオン交換水17.53g
・1,3-ブチレングリコール7.67g
以下に示す油相原料38.50g、表面が被覆された比表面積約60m2/gの酸化チタン粉体8.75g及び分散メディアとしてのφ0.5mmジルコニアビーズ(株式会社シンマルエンタープライゼス製)130gを100mLのボトル(ニッコーハンセン株式会社製:Jボトル丸形広口)に入れ、ペイントコンディショナー(RED DEVIL社製、1400-OH)で5時間分散したのち、ジルコニアビーズを分離し、油相分散体を作製した。この油相分散体37.80gを100mLのポリプロピレン製カップに入れ、高速乳化・分散機(プライミクス株式会社製「T.K.ロボミックス」)を用いて、撹拌速度3000rpmで撹拌しながら、以下に示す水相原料の混合物32.2gを加え、3000rpmのままで5分間撹拌して、乳化製剤を作製した。この乳化製剤の粘度を、B型粘度計を用いて、No.2ローター、25℃、60rpmの条件において測定したところ、72mPa・sであった。
(油相原料)
・ジメチコン29.75g:信越化学工業株式会社製「KF-96L-1.5cs」
・流動パラフィン4.375g:株式会社MORESCO製「モレスコホワイト P-70」
・PEG-9ポリジメチルシロキシエチルジメチコン4.375g:信越化学工業株式会社製「KF-6028P」
(水相原料)
・イオン交換水22.4g
・1,3-ブチレングリコール9.8g
・スキャンスピード:300nm/分
・サンプリング間隔:2nm
・測定波長:250~700nm
(油相原料)
・ジメチコン28.33g:信越化学工業株式会社製「KF-96L-1.5cs」
・流動パラフィン4.375g:株式会社MORESCO製「モレスコホワイト P-70」
・PEG-9ポリジメチルシロキシエチルジメチコン4.375g:信越化学工業株式会社製「KF-6028P」
・ステアリン酸アルミニウム1.42g
塩酸を加えた後のスラリーを、100~105℃の範囲で30分間熟成した以外は実施例1と同様にして、酸化チタン粉体を製造し、分析及び評価した。評価結果をまとめて表1~3に示す。
塩酸を加えた後のスラリーを、50℃で20分間熟成した以外は実施例1と同様にして、酸化チタン粉体を製造し、分析及び評価した。評価結果をまとめて表1~3に示す。比表面積が約60m2/gの酸化チタン粉体(焼成後)については、比表面積のみを測定した。
前記チタン酸ナトリウムを含むスラリーに、35質量%塩酸10.0kgを加えて加熱し、100~105℃の範囲で5時間熟成した以外は実施例1と同様にして、酸化チタン粉体を製造し、分析及び評価した。評価結果をまとめて表1~3に示す。
含窒素化合物を含浸させなかった例である。前記チタン酸ナトリウムを含むスラリーに、35質量%塩酸14.0kgを加えて加熱し、80℃で10分間熟成した。熟成後のスラリーを水で希釈して、TiO2換算で70g/Lの酸化チタンを含むスラリーを得た。得られた酸化チタンは、ルチル型結晶を含むものである。この酸化チタンスラリーを80℃に昇温し、24質量%水酸化ナトリウム水溶液でpH6.4に調整してから、30分間熟成した。熟成完了後、24質量%水酸化ナトリウム水溶液又は塩酸でpH6.4に再調整したスラリーをろ過、洗浄して、酸化チタンのケーキを得た。このケーキを実施例1と同様にして、乾燥、粉砕、ふるい分けを行って、酸化チタン粉体(焼成前)を得た。以降の工程は実施例1と同様にして、酸化チタン粉体(焼成後)を製造し、分析及び評価した。評価結果をまとめて表1~3に示す。
焼成の直前にアンモニア水を噴霧した例である。比較例2と同様にして得られた乾燥後の酸化チタン粉体(焼成前)100質量部に対し、10質量部の24質量%アンモニア水を噴霧した以外は比較例2と同様にして、酸化チタン粉体(焼成後)を製造し、分析及び評価した。評価結果をまとめて表1~3に示す。
実施例1で製造した濃度10質量%の乳化製剤において、用いた表面被覆酸化チタン粉体の代わりに、市販の酸化チタン粉体(テイカ株式会社製:「MT-100Z」)を用いて、ペイントコンディショナーでの分散時間を2時間とした以外は同様の条件で乳化製剤を作製した。「MT-100Z」は、紡錘形状の粒子を含む酸化チタン粉体であり、その平均短軸長さが7.9nm、平均アスペクト比が4.0のものであり、実施例1と同様に、ポリ塩化アルミニウムとステアリン酸ナトリウムで表面処理をしたものである。この粉体のESCA測定のチャートを図4に示す。395~402eVにピークが観察されないことがわかる。ここで、分散時間を短縮した理由は、分散中に粘度が上昇したためであり、また、塗布直後の塗膜のバイオスキンとの色差ΔEが本発明品と同等(6.4)となったためである。この乳化製剤の粘度を、B型粘度計を用いて、No.3ローター、25℃、60rpmの条件において測定したところ、1492mPa・sであった。得られた乳化製剤を実施例1と同様に評価した結果を表4にまとめて示す。
Claims (17)
- X線回折測定におけるルチル型結晶のピーク強度(IR)に対するアナタース型結晶のピーク強度(IA)の比(IA/IR)が0.1以下であり、
含まれる粒子の、平均短軸長さが10~50nmであり、平均アスペクト比が1~3であり、
450nmの波長における吸光度A450と320nmの波長における吸光度A320との比(A450/A320)が0.015~0.5であり、かつ
窒素原子を含み、ESCA(Electron Spectroscopy for Chemical Analysis)測定において、該窒素原子に由来するピークが395~402eVに観察される、酸化チタン粉体。 - 前記X線回折測定においてアナタース型結晶のピークが観察されない、請求項1に記載の酸化チタン粉体。
- 比表面積が25~100m2/gである、請求項1又は2に記載の酸化チタン粉体。
- 600nmの波長における吸光度A600が0.1以下である、請求項1~3のいずれかに記載の酸化チタン粉体。
- L*a*b*表色系における、L*値が92~99であり、a*値が-5~2であり、b*値が3~30である、請求項1~4のいずれかに記載の酸化チタン粉体。
- 前記粉体に含まれる粒子の表面を、無機化合物及び/又は有機化合物の層で被覆してなる、請求項1~4のいずれかに記載の酸化チタン粉体。
- 前記粒子の表面を無機化合物の層で被覆してなる酸化チタン粉体であって、該無機化合物が、アルミニウム、マグネシウム、カルシウム、ケイ素、亜鉛、チタニウム、ジルコニウム、鉄、セリウム及び錫からなる群から選択される少なくとも一種の元素を含む、請求項6に記載の酸化チタン粉体。
- 前記粒子の表面を有機化合物の層で被覆してなる酸化チタン粉体であって、該有機化合物が、脂肪酸又はその塩、シリコーン系化合物、カップリング剤及びフッ素化合物からなる群から選択される少なくとも一種である、請求項6又は7に記載の酸化チタン粉体。
- L*a*b*表色系における、L*値が92~99であり、a*値が-5~2であり、b*値が2~30である、請求項6~8のいずれかに記載の酸化チタン粉体。
- 請求項1~9に記載の酸化チタン粉体を分散媒に分散させてなる分散体。
- 請求項1~9に記載の酸化チタン粉体を含有する化粧料。
- 請求項1~9に記載の酸化チタン粉体を含有する塗料。
- 請求項1~9に記載の酸化チタン粉体を含有するインキ。
- 請求項1~9に記載の酸化チタン粉体を外添剤として含有するトナー。
- 含水酸化チタンの水分散液にアルカリ金属水酸化物を加えて、アルカリ金属チタン酸塩を得るアルカリ化工程、
該アルカリ金属チタン酸塩の水分散液に塩酸を加えてルチル型結晶を含む酸化チタンを得る酸性化工程、
該酸化チタンに含窒素化合物を含浸させる含浸工程、及び
200~600℃で焼成する焼成工程を有する、酸化チタン粉体の製造方法。 - 焼成する前の酸化チタンの比表面積が120~300m2/gである、請求項15に記載の酸化チタン粉体の製造方法。
- 含浸工程において、酸性化工程後に残存する塩酸を塩基性含窒素化合物で中和して、酸化チタンに含窒素化合物を含浸させる、請求項15又は16に記載の酸化チタン粉体の製造方法。
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