Photocatalyst-binder compositions

• US 5,616,532 A
• Filed: 10/21/1994
• Issued: 04/01/1997
• Est. Priority Date: 12/14/1990
• Status: Expired due to Term

• Current Assignee: E. Heller & Company
• Original Assignee: E. Heller & Company
• Inventors: Heller, Ephraim, Heller, Adam, Pishko, Michael V.
• Primary Examiner(s): Pal, Asok
• Application Number:
  US08/327,016
• Time in Patent Office: 893 Days
• Field of Search: 502/242, 502/250, 502/253, 502/248
• US Class Current: 502/242
• CPC Class Codes: B01J 35/30 characterised by their physical properties
• CPC Class Codes: B01J 35/39 Photocatalytic properties
• CPC Class Codes: B01J 37/0215 Coating
• CPC Class Codes: C02F 1/32 with ultraviolet light
• CPC Class Codes: C02F 1/725 by catalytic oxidation
• CPC Class Codes: C02F 2101/32 Hydrocarbons, e.g. oil
• CPC Class Codes: C02F 2305/10 Photocatalysts
• CPC Class Codes: C03C 17/007 containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
• CPC Class Codes: C03C 2217/45 Inorganic continuous phases
• CPC Class Codes: C03C 2217/475 Inorganic materials
• CPC Class Codes: C03C 2217/71 Photocatalytic coatings
• CPC Class Codes: C08G 77/045 containing less than 25 silicon atoms
• CPC Class Codes: C08K 2003/2241 Titanium dioxide
• CPC Class Codes: C09D 183/04 Polysiloxanes

Abstract

A photocatalyst composition containing a substantially non-oxidizable binder which allows large amounts of photocatalytic particles to be adhered to a surface. Upon application to a surface, the composition dries or cures to form an adherent, abrasion-resistant, thermostable, and photocatalytic coating.

Claims

1. A self-cleaning composition comprising:

particles of a photocatalyst responsive to ultraviolet light, said particles having a diameter of about 1-100 nm, said photocatalyst capable of catalyzing oxidation or reduction reactions to degrade organic compounds that contact the composition;

a binder for adhering said particles to a surface, said binder consisting essentially of a substantially non-oxidizable polymer having a backbone sequence of 12 or more atoms, where no more than one in six backbone atoms is carbon, the binder consisting of less than 20 wt % oxidizable carbon and hydrogen atoms;

wherein the particles are dispersed throughout said binder, and wherein the composition forms an abrasion-resistant, thermostable and adherent film when applied to a surface, the binder transmitting a substantial portion of incident ultraviolet light to activate the photocatalyst particles to produce cleaning effects.

2. The composition of claim 1, wherein said binder is a polymer precursor, a non-crosslinked polymer, or a partially crosslinked polymer prior to its curing.

3. The composition of claim 1, wherein said binder cures at a temperature less than approximately 85°

F.

4. The composition of claim 3, wherein said binder cures at ambient temperature.

5. The composition of claim 1, wherein said binder is a silicone.

6. The composition of claim 5, wherein said binder is a cyclomer or a ladder polymer.

7. The composition of claim 5, wherein said binder includes a silicon atom bound to a terminating group comprising H, alkyl group, or aryl group.

8. The composition of claim 1 further comprising a curing agent.

9. The composition of claim 1, wherein said binder, at a thickness of approximately one micron, absorbs less than about 50% of near ultraviolet photons of about 2.5 to about 5.5 eV energy.

10. The composition of claim 9, wherein said binder absorbs less than about 50% of the photons with energy in the range of 2.5-4.0 eV.

11. The composition of claim 10, wherein said binder absorbs less than about 10% of the photons having energies near 3.5 eV.

12. The composition of claim 1, further comprising a cocatalyst doped onto the photocatalyst.

13. The composition of claim 12, wherein said cocatalyst is selected from the group consisting of palladium, platinum, rhodium, ruthenium, tungsten, molybdenum, gold, silver, copper, and oxides or sulfides thereof.

14. The composition of claim 1, wherein said photocatalyst catalyzes oxidation of organic compounds by air or oxygen.

15. The composition of claim 1, wherein said photocatalyst catalyzes dehalogenation in the presence of water.

16. The composition of claim 1, wherein said photocatalyst is selected from the group consisting of TiO₂, ZnO, CaTiO₃, SnO₂, MoO₃, Fe₂ O₃, WO₃, Nb₂ O₅, SiC, and Ti_x (Zr_1-x)O₂, where x has a value between 0 and 1.

17. The composition of claim 1, wherein said photocatalyst is TiO₂, ZnO, SnO₂ or a mixture thereof.

18. The composition of claim 1, wherein said composition, when applied to a surface and dried or cured, transmits no more than about 10% of incident ultraviolet light to the underlying surface.

19. A self-cleaning composition comprising:

particles of a photocatalyst responsive to ultraviolet light, said particles having a diameter of about 1-100 nm, said photocatalyst capable of catalyzing oxidation or reduction reactions to degrade organic compounds that contact the composition;

a binder for adhering said particles to a surface, said binder consisting essentially of hydrated aluminum oxide, hydrated silicon oxide, colloidal tin dioxide, or mixtures thereof,

wherein the particles are dispersed throughout said binder and wherein the composition forms an abrasion-resistant;

thermostable and adherent film when applied to a surface, the binder transmitting a substantial portion incident ultraviolet light to activate the photocatalyst particles to produce cleaning effects.

27. The composite of claim 19, wherein said hydrophobic compound comprises a silicone.

20. A curable self-cleaning composition comprising:

(a) ultraviolet light-absorbing photocatalyst particles having a surface area of at least about 30 m² /g,;

(b) a binder consisting essentially of a substantially non-oxidizable polymer, hydrated aluminum oxide, hydrated silicon oxide, colloidal tin oxide, or mixtures thereof, wherein the particles of the photocatalyst are dispersed in the binder, and wherein the binder transmits a substantial portion of incident ultraviolet light to activate the photocatalyst particles to produce cleaning effects.

21. The composition of claim 20, wherein the surface area is at least about 100 m² /g.

22. The composition of claim 20, wherein the composition is curable upon drying at ambient temperature or by the application of heat, radiation, or curing agent.

23. The composition of claim 22, wherein the composition is curable at ambient temperature.

24. A self-cleaning composition comprising:

particles of a photocatalyst responsive to ultraviolet light, said particles having a diameter of about 1-100 nm, said photocatalyst capable of catalyzing oxidation or reduction reactions to degrade organic compounds that contact the composition;

a binder for adhering said particles to a surface, said binder consisting essentially of a substantially non-oxidizable polymer having a backbone sequence of 12 or more atoms, where no more than one in six backbone atoms is carbon, the binder consisting of less than 20 wt % oxidizable carbon and hydrogen atoms;

wherein the particles are dispersed throughout said binder; and

a film-forming hydrophobic composition permeable to organic molecules and to molecular oxygen,

wherein the composition dries to form an abrasion-resistant, thermostable and adherent film when applied to a surface, the binder transmitting a substantial portion of incident ultraviolet light to activate the photocatalyst particles to produce cleaning effects.

25. The composition of claim 24, wherein the hydrophobic composition comprises a silicone.

26. A composite adhered to a surface, the composite comprising:

a first layer consisting essentially of particles of a photocatalyst responsive to ultraviolet light dispersed in a substantially non-oxidizable binder, said particles having a diameter of about 1-100 nm, said photocatalyst capable of catalyzing oxidation or reduction reactions to degrade organic compounds, said binder consisting essentially of a substantially non-oxidizable polymer having a backbone sequence of 12 or more atoms, where no more than one in six backbone atoms is carbon, the binder consisting of less than 20 wt % oxidizable carbon and hydrogen atoms; and

a second, hydrophobic layer permeable to organic molecules and to molecular oxygen.

28. A self-cleaning composition comprising:

particles of a photocatalyst responsive to ultraviolet light, said particles having a diameter of about 1-100 nm and a surface area at least about 30 m² /g; and

a substantially non-oxidizable binder for adhering particles to a surface, said binder consisting essentially of an inorganic colloid or a polymer having a backbone sequence of 12 or more atoms where no more than one in six backbone atoms is carbon, the binder having fewer than 20% by weight oxidizable carbon and hydrogen atoms,

wherein the particles are dispersed in the binder and the composition forms an abrasion-resistant, thermostable and adherent film, the binder transmitting a substantial portion of incident ultraviolet light to activate the photocatalyst particles to produce cleaning effects.

29. The composition of claim 28, wherein said binder is selected from the group consisting of hydrated aluminum oxide, hydrated silicon oxide, colloidal tin oxide, and mixtures thereof.

30. The composition of claim 28, wherein said binder is a silicone polymer.

31. The composition of claim 28, further comprising pigment particles forming a self-cleaning paint.

32. A self-cleaning composition comprising:

particles of a photocatalyst responsive to ultraviolet light, said particles having a diameter of about 1-100 nm and a surface area at least about 30 m² /g; and

a substantially non-oxidizable binder for adhering said particles to a surface,

wherein the particles are dispersed in the binder in the absence of photoactivity-masking agents, and wherein the composition forms an abrasion-resistant, thermostable and adherent film when applied to a surface, the binder transmitting a substantial portion of incident ultraviolet light to activate the photocatalyst particles to produce cleaning effects.

33. The composition of claim 32, wherein said binder cures at a temperature less than approximately 85°

F.

34. The composition of claim 32, wherein said binder cures at ambient temperature.

35. The composition of claim 32, wherein said binder is a silicone.

36. The composition of claim 35, wherein said binder is a cyclomer or a ladder polymer.

37. The composition of claim 35, wherein said binder includes a silicon atom bound to a terminating group comprising H, alkyl group, or aryl group.

38. The composition of claim 32, further comprising a curing agent.

39. The composition of claim 32, wherein said binder, at a thickness of approximately one micron, absorbs less than about 50% of near ultraviolet photons of about 2.5 to about 5.5 eV energy.

40. The composition of claim 39, wherein said binder absorbs less than about 50% of the photons with energy in the range of 2.5-4.0 eV.

41. The composition of claim 40, wherein said binder absorbs less than about 10% of the photons having energies near 3.5 eV.

42. The composition of claim 32, further comprising a cocatalyst doped onto the photocatalyst.

43. The composition of claim 42, wherein said cocatalyst is selected from the group consisting of palladium, platinum, rhodium, ruthenium, tungsten, molybdenum, gold, silver, copper, and oxides or sulfides thereof.

44. The composition of claim 32, wherein said photocatalyst catalyzes oxidation of organic compounds by air or oxygen.

45. The composition of claim 32, wherein said photocatalyst catalyzes dehalogenation in the presence of water.

46. The composition of claim 32, wherein said photocatalyst is selected from the group consisting of TiO₂, ZnO, CaTiO³, SnO₂, MoO₃, Fe₂ O₃, WO₃, Nb₂ O₅, SiC, and Ti_x (Zr_1-x) O₂, where x has a value between 0 and 1.

47. The composition of claim 46, wherein said photocatalyst is TiO₂, ZnO, SnO₂ or a mixture thereof.

48. The composition of claim 32, wherein said composition, when applied to a surface and dried or cured, transmits no more than about 10% of incident ultraviolet light to the underlying surface.

49. The composition of claim 32, further comprising pigment particles forming a self-cleaning paint.