Ultraviolet-screening zinc oxide excellent in transparency and composition containing the same

• US 6,171,580 B1
• Filed: 07/16/1999
• Issued: 01/09/2001
• Est. Priority Date: 11/18/1997
• Status: Expired due to Term

• Current Assignee: Shiseido Company Limited
• Original Assignee: Shiseido Company Limited
• Inventors: Katsuyama, Tomoyuki, Kimura, Asa
• Primary Examiner(s): Dodson, Shelley A.
• Application Number:
  US09/341,145
• Time in Patent Office: 543 Days
• Field of Search: 424/59, 424/60, 424/400, 424/401, 423/622
• 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 8/27 Zinc; Compounds thereof
• 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: C01G 9/02 Oxides; Hydroxides
• CPC Class Codes: C01P 2002/84 by UV- or VIS- data
• CPC Class Codes: C01P 2004/03 obtained by SEM
• CPC Class Codes: C01P 2004/62 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 2006/60 Optical properties, e.g. expressed in CIELAB-values
• CPC Class Codes: C09C 1/043 Zinc oxide

Abstract

The present inventors conducted investigations in order to develop a metal oxide which enables effective UV-screening; i.e. which has excellent screening ability against ultraviolet rays, particularly against long-wavelength ultraviolet rays, as well as excellent visible-light transmission; and to provide a UV-screening composition that contains the metal oxide and can be applied to external use. As a result, the present inventors have found that zinc oxide produced by a particular method has a characteristic form; i.e., primary particles having an average particle diameter of 50-100 nm aggregate in a planer shape, and a ratio represented by lnT_360nm/lnT_400nm (T_xnm: transmittance of transmitted light of X nm) of 10 or more, and exerts excellent screening effect against long-wavelength ultraviolet rays as well as excellent visible-light transmission. The present invention has been accomplished based on this finding. The zinc oxide of the present invention effectively exerts the above-described excellent characteristics; i.e. UV-screening effect and transparency, and can be applied to a composition for external use such as make-up cosmetics or sunscreen cosmetics.

Claims

1. Zinc oxide which is in the form of a plurality of primary particles each having an average particle diameter of 50-100 nm and said plurality of primary particles forming a planar shape, and which has a ratio of the natural logarithm of the transmittance of long-wavelength ultraviolet rays (Γ

=360 nm) to the logarithm of the transmittance of visible light (Γ

=400 nm) is 10 or more.

2. Zinc oxide according to claim 1, wherein:

(a) the zinc oxide has a roughness corresponding to the diameter of one such primary particle;

(b) the longest dimension of the zinc oxide is 0.01-5 μ

m; and

(c) the edge portion of the zinc oxide has indentures having a depth of 10-200 nm, at intervals of 10-200 nm.

3. Zinc oxide aggregate formed from the zinc oxide of claim 1, wherein the zinc oxide aggregates together to resemble a carnation as shown in the photograph, FIG. 1.

4. Zinc oxide aggregate according to claim 3, obtainable by reacting zinc ions (Zn²⁺), carbonate ions (CO₃²⁻

), and hydroxide ions (OH⁻

) in water, while the pH of the aqueous reaction solution is maintained at 7-9 and the mole ratio of hydroxide ion to carbonate ion is fixed to be not greater than 4 (including the case in which the amount of hydroxide ion is

     0), and calcinating basic zinc carbonate formed in the aqueous reaction solution at a temperature of 150-450°

C.

5. Zinc oxide aggregate according to claim 4, wherein the mole ratio of hydroxide ion to carbonate ion is 2.5-3.5.

6. Zinc oxide aggregate according to claim 4, wherein, in the aqueous reaction solution, 1) the zinc ions are provided by zinc chloride, zinc sulfate, or zinc nitrate;

2) the carbonate ions are provided by sodium carbonate or potassium carbonate; and

     3) the hydroxide ions are provided by sodium hydroxide or potassium hydroxide.

7. Zinc oxide aggregate according to claim 4, wherein the temperature of the aqueous reaction solution is 40°

C.-70°

C.

8. Zinc oxide, obtained by crushing the zinc oxide aggregate as described in claim 3.

9. A UV-screening composition containing the zinc oxide as described in claim 1.

10. A UV-screening composition according to claim 9, which is a composition for external use.

11. A UV-screening composition according to claim 10, wherein the composition for external use is make-up cosmetics.

12. A UV-screening composition according to claim 10, wherein the composition for external use is sunscreen cosmetics.

13. An external-use composition comprising the zinc oxide aggregate as described in claim 3.

14. An external-use composition according to claim 13, which is make-up cosmetics.

15. An external-use composition according to claim 13, which is sunscreen cosmetics.

16. A method for use of an external-use composition as described in claim 13, which comprises applying to skin the external-use composition to generate a frictional force;

allowing the frictional force to crush the zinc oxide aggregate on the skin; and

developing, on the skin, transparency and UV-screening ability of the zinc oxide expressed by the ratio of the natural logarithm of the transmittance of long-wavelength ultraviolet rays (Γ

=360 nm) to the natural logarithm of the transmittance of visible light (Γ

=400 nm) of 10 or more.

17. Zinc oxide aggregate wherein the zinc oxide as described in claim 2 aggregates together.

18. Zinc oxide aggregate according to claim 5, wherein, in the aqueous reaction solution, 1) the zinc ions are provided by zinc chloride, zinc sulfate, or zinc nitrate;

2) the carbonate ions are provided by sodium carbonate or potassium carbonate; and

     3) the hydroxide ions are provided by sodium hydroxide or potassium hydroxide.

19. Zinc oxide aggregate according to claim 5, wherein the temperature of the aqueous reaction solution is 40°

C.-70°

C.

20. Zinc oxide aggregate according to claim 6, wherein the temperature of the aqueous reaction solution is 40°

C.-70°

C.

21. Zinc oxide, obtained by crushing the zinc oxide aggregate as described in claim 3.

22. Zinc oxide, obtained by crushing the zinc oxide aggregate as described in claim 4.

23. Zinc oxide obtained by crushing the zinc oxide aggregate as described in claim 5.

24. Zinc oxide obtained by crushing the zinc oxide aggregate as described in claim 6.

25. Zinc oxide obtained by crushing a zinc oxide aggregate as described in claim 17.

26. Zinc oxide obtained by crushing a zinc oxide aggregate as described in claim 17 which is formed by causing a reaction between zinc ions (Zn²⁺), carbonate ions (CO₃²⁻

), and hydroxide ions (OH⁻

) in water, while the pH of the aqueous reaction solution is maintained at 7-9 and the mole ratio of hydroxide ion to carbonate ion is fixed to be not greater than 4 (including the case in which the amount of hydroxide ion is

     0), and calcinating basic zinc carbonate formed in the aqueous reaction solution.

27. Zinc oxide according to claim 26 wherein said reaction is carried out with a mole ratio of hydroxide ion to carbonate ion of 2.5-3.5.

28. Zinc oxide according to claim 27 wherein in the aqueous reaction solution, 1) the zinc ions are provided by zinc chloride, zinc sulfate, or zinc nitrate;

2) the carbonate ions are provided by sodium carbonate or potassium carbonate; and

     3) the hydroxide ions are provided by sodium hydroxide or potassium hydroxide.

29. Zinc oxide according to claim 28 wherein the temperature of the aqueous reaction solution is 40°

C-70°

C.

30. An external-use composition comprising the zinc oxide aggregate as described in claim 4.

31. An external-use composition comprising the zinc oxide aggregate as described in claim 5.

32. An external-use composition comprising the zinc oxide aggregate as described in claim 6.

33. An external-use composition comprising the zinc oxide aggregate as described in claim 7.

34. A v-screening composition containing the zinc oxide as described in claim 1.

35. A UV-screening composition according to claim 11, wherein the composition for external use is sunscreen cosmetics.

36. An external-use composition according to claim 14, which is a sunscreen cosmetic.

37. The method for use of an external-use composition according to claim 16, wherein said external-use composition is a make-up cosmetic.

38. The method for use of an external-use composition according to claim 16, wherein said external-use composition is a Sunscreen cosmetic.