Ultraviolet shielding composite fine particles, method for producing the same, and cosmetics

• US 5,902,569 A
• Filed: 08/27/1997
• Issued: 05/11/1999
• Est. Priority Date: 03/10/1995
• Status: Expired due to Fees

• Current Assignee: KAO Corporation
• Original Assignee: KAO Corporation
• Inventors: Nishimura, Toru, Kozaki, Shunji, Miyake, Toshio, Sugawara, Satoshi, Imaizumi, Yoshinobu, Tsuto, Keiichi, Torizuka, Makoto, Oshima, Kentaro
• Primary Examiner(s): Dodson, Shelley A.
• Assistant Examiner(s): Lamm, Marina
• Application Number:
  US08/894,672
• Time in Patent Office: 622 Days
• Field of Search: 424/59, 424/60, 424/400, 424/401, 423/462, 423/592
• US Class Current: 424/59
• CPC Class Codes: A61K 2800/262 Transparent; Translucent
• CPC Class Codes: A61K 2800/413 Nanosized, i.e. having sizes below 100 nm
• CPC Class Codes: A61K 8/0287 the particulate containing a solid-in-solid dispersion
• CPC Class Codes: A61K 8/06 Emulsions
• CPC Class Codes: A61P 17/16 Emollients or protectives, e.g. against radiation
• CPC Class Codes: A61Q 1/02 Preparations containing skin colorants, e.g. pigments preparations in powder form A61Q1/12
• CPC Class Codes: A61Q 1/06 Lipsticks
• CPC Class Codes: A61Q 1/10 for eyes, e.g. eyeliner, mascara
• CPC Class Codes: A61Q 17/04 Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: B82Y 5/00 Nanobiotechnology or nanomedicine, e.g. protein engineering or drug delivery
• CPC Class Codes: C01P 2002/84 by UV- or VIS- data
• CPC Class Codes: C01P 2004/03 obtained by SEM
• CPC Class Codes: C01P 2004/04 obtained by TEM, STEM, STM or AFM
• CPC Class Codes: C01P 2004/10 extending in one dimension, e.g. needle-like
• CPC Class Codes: C01P 2004/20 extending in two dimensions, e.g. plate-like
• CPC Class Codes: C01P 2004/32 Spheres
• CPC Class Codes: C01P 2004/50 Agglomerated particles
• CPC Class Codes: C01P 2004/62 Submicrometer sized, i.e. from 0.1-1 micrometer
• CPC Class Codes: C01P 2004/64 Nanometer sized, i.e. from 1-100 nanometer
• CPC Class Codes: C01P 2004/82 : two phases having the same anion, e.g. both oxidic phases
• CPC Class Codes: C01P 2004/84 : one phase coated with the other
• CPC Class Codes: C01P 2006/60 : Optical properties, e.g. expressed in CIELAB-values
• CPC Class Codes: C01P 2006/80 : Compositional purity
• CPC Class Codes: C01P 2006/90 : Other properties not specified above
• CPC Class Codes: C09C 1/0081 : Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound C09C1/0015, C09C1/0078 take precedence

Abstract

The present invention is directed to ultraviolet shielding composite fine particles having transparency in a visible light region include (a) matrix particles comprising an aggregate of primary particles having an average particle diameter of from 0.001 to 0.3 μm, the aggregate being formed while the primary particles retain their shapes; and (b) daughter particles having an average particle diameter of from 0.001 to 0.1 μm, the daughter particles being dispersed in and supported by the matrix particles. In the composite fine particles, the daughter particles have a smaller band gap energy than the particles constituting the matrix particles and are capable of absorbing ultraviolet light, and the resulting ultraviolet shielding composite fine particles have substantially no catalytic activity.

Claims

1. Ultraviolet shielding composite fine particles having transparency in a visible light region, comprising:

(a) matrix particles comprising an aggregate of primary particles having an average particle diameter of from 0.001 to 0.3 μ

m, said aggregate being formed while the primary particles retain their shapes; and

(b) daughter particles having an average particle diameter of from 0.001 to 0.1 μ

m, said daughter particles being dispersed in and supported by said matrix particles, wherein said daughter particles have a smaller band gap energy than the particles constituting said matrix particles and are capable of absorbing ultraviolet light, and wherein the surface of said ultraviolet shielding composite fine particles is coated with an inorganic material, thereby showing substantially no catalytic activities.

2. The ultraviolet shielding composite fine particles according to claim 1, wherein said particles constituting the matrix particles have a band gap energy of from 3 to 9 eV.

3. The ultraviolet shielding composite fine particles according to claim 1, wherein the difference between the band gap energies of the daughter particles and the particles constituting the matrix particles is not less than 0.2 eV.

4. The ultraviolet shielding composite fine particles according to claim 1, wherein said daughter particles are dispersed in and supported by said matrix particles in an amount of from 0.1 to 85% by volume.

5. The ultraviolet shielding composite fine particles according to claim 1, wherein the average particle diameter of the ultraviolet shielding composite fine particles is not more than 0.5 μ

m.

6. The ultraviolet shielding composite fine particles according to claim 1, wherein the average refractive index of the ultraviolet shielding composite fine particles is from 1.3 to 2.5.

7. The ultraviolet shielding composite fine particles according to claim 1, wherein said particles constituting the matrix particles are selected from the group consisting of metal oxides, fluorine compounds, and mixtures thereof.

8. The ultraviolet shielding composite fine particles according to claim 7, wherein said metal oxide is selected from the group consisting of SiO₂, Al₂ O₃, and a mixture thereof.

9. The ultraviolet shielding composite fine particles according to claim 1, wherein said daughter particles are selected from the group consisting of TiO₂, ZnO, CeO₂, SiC, SnO₂, WO₃, BaTiO₃, CaTiO₃, SrTiO₃, and mixtures thereof.

10. The ultraviolet shielding composite fine particles according to claim 1, wherein the inorganic material is a metal oxide.

11. The ultraviolet shielding composite fine particles according to claim 10, wherein the metal oxide used for the inorganic material is selected from the group consisting of SiO₂, Al₂ O₃, and a mixture thereof.

12. The ultraviolet shielding composite fine particles according to claim 1, wherein the surface of sa id composite fine particles is further treated by a water-repellant.

13. The ultraviolet shielding composite fine particles according to claim 1, wherein said ultraviolet shielding composite fine particles have a light transmittance of not less than 80% at a wavelength of 800 nm, a light transmittance of not less than 20% at a wavelength of 400 nm, and a light transmittance of not more than 5% at least at one wavelength within the range from 380 nm to 300 nm, the light transmittance being determined by suspending said composite fine particles in a medium having substantially the same refractive index level as the composite fine particles, and measuring with an ultraviolet-visible light spectrophotometer using an optical cell having an optical path length of 1 mm.

14. The ultraviolet shielding composite fine particles according to claim 1, obtained by the steps of:

(a) preparing a liquid mixture comprising;

(i) starting materials for matrix particles which are present in one or more forms selected from the group consisting of sols containing particles constituting matrix particles and powders of the matrix particles, the matrix particles having a primary particle with an average particle diameter of from 0.001 to 0.3 μ

m; and

(ii) starting materials for daughter particles which are present in one or more forms selected from the group consisting of sols containing daughter particles and powders of the daughter particles, the daughter particles having a primary particle with an average particle diameter of from 0.001 to 0.1 μ

m, and treating the liquid mixture in a mill and/or an apparatus for high-pressure dispersion, to thereby produce composite fine particles wherein the daughter particles and the matrix particles are aggregated;

(b) coating the composite fine particles obtained in step (a) with an inorganic material;

(c) subjecting the composite fine particles coated with the inorganic material obtained in step (b) to a water-repellent treatment; and

(d) drying and/or pulverizing the composite fine particles subjected to the water-repellent treatment obtained in step (c).

15. A dispersion oil agent of the ultraviolet shielding composite fine particles as defined in claim 1, obtained by the steps of:

(a) preparing a liquid mixture comprising;

(i) starting materials for matrix particles which are present in one or more forms selected from the group consisting of sols containing particles constituting matrix particles and powders of the matrix particles, the matrix particles having a primary particle with an average particle diameter of from 0.001 to 0.3 μ

m; and

(ii) starting materials for daughter particles which are present in one or more forms selected from the group consisting of sols containing daughter particles and powders of the daughter particles, the daughter particles having a primary particle with an average particle diameter of from 0.001 to 0.1 μ

m, and treating the liquid mixture in a mill and/or an apparatus for high-pressure dispersion, to thereby produce composite fine particles wherein the daughter particles and the matrix particles are aggregated;

(b) coating the composite fine particles obtained in step (a) with an inorganic material;

(c) subjecting the composite fine particles coated with the inorganic material obtained in step (b) to a water-repellent treatment; and

(d'"'"') dispersing in an oil agent the composite fine particles subjected to the water-repellent treatment obtained in step (c).

20. Cosmetics comprising ultraviolet shielding composite fine particles as defined in claim 1.

21. Cosmetics comprising the dispersion oil agent of the ultraviolet shielding composite fine particles as defined in claim 15.

22. The cosmetics according to claim 20, wherein an amount of said ultraviolet shielding composite fine particles is from 0.01 to 50% by weight.

23. The cosmetics according to claim 20, further containing an ultraviolet protecting agent.

24. The cosmetics according to claim 20, wherein SPF measured by using an analyser "SPF-290," manufactured by The Optometrics Group is not less than 8, and wherein Δ

E*ab before and after skin application is not more than 3 as defined according to JIS Z8729-1980.

25. A method of shielding skin from ultraviolet light which comprises applying to said skin, a cosmetic composition comprising ultraviolet shielding composite particles according to claim 1.

16. A method for producing the ultraviolet shielding composite fine particles comprising daughter particles being dispersed in and supported by said matrix particles, the ultraviolet shielding composite fine particles having substantially no catalytic activities and having transparency in a visible light region, obtained by the steps of:

(a) preparing a liquid mixture comprising (i) starting materials for matrix particles which are present in one or more forms selected from the group consisting of sols containing particles constituting matrix particles and powders of the matrix particles, the matrix particles having a primary particle with an average particle diameter of from 0.001 to 0.3 μ

m; and

(ii) starting materials for daughter particles which are present in one or more forms selected from the group consisting of sols containing daughter particles and powders of the daughter particles, the daughter particles having a primary particle with an average particle diameter of from 0.001 to 0.1 μ

m, and treating the liquid mixture in a mill and/or an apparatus for high-pressure dispersion, to thereby produce composite fine particles wherein the daughter particles and the matrix particles are aggregated; and

(b) coating the composite fine particles obtained in step (a) with-an inorganic material.

17. The method according to claim 16, further comprising, subsequent to said step (b):

(c) subjecting the composite fine particles coated with the inorganic material obtained in step (b) to a water-repellent treatment.

18. The method according to claim 17, further comprising, subsequent to said step (c):

(d) drying and/or pulverizing the composite fine particles subjected to the water-repellent treatment obtained in step (c).

19. A method for producing a dispersion oil agent of the ultraviolet shielding composite fine particles comprising daughter particles being dispersed in and supported by said matrix particles, the ultraviolet shielding composite fine particles having substantially no catalytic activities and having transparency in a visible light region, obtained by the steps of:

(a) preparing a liquid mixture comprising (i) starting materials for matrix particles which are present in one or more forms selected from the group consisting of sols containing particles constituting matrix particles and powders of the matrix particles, the matrix particles having a primary particle with an average particle diameter of from 0.001 to 0.3 μ

m; and

(ii) starting materials for daughter particles which are present in one or more forms selected from the group consisting of sols containing daughter particles and powders of the daughter particles, the daughter particles having a primary particle with an average particle diameter of from 0.001 to 0.1 μ

m, and treating the liquid mixture in a mill and/or an apparatus for high-pressure dispersion, to thereby produce composite fine particles wherein the daughter particles and the matrix particles are aggregated;

(b) coating the composite fine particles obtained in step (a) with an inorganic material;

(c) subjecting the composite fine particles coated with the inorganic material obtained in step (b) to a water-repellent treatment; and

(d'"'"') dispersing in an oil agent the composite fine particles subjected to the water-repellent treatment obtained in step (c).