Method and apparatus for producing a photocatalytic material

• US 6,368,668 B1
• Filed: 03/03/2000
• Issued: 04/09/2002
• Est. Priority Date: 07/30/1998
• Status: Expired due to Term

• Current Assignee: Toto Limited
• Original Assignee: Toto Limited
• Inventors: Tanaka, Shinji, Mayumi, Yoshitaka, Kobayashi, Hideki, Nakashima, Yasushi, Saeki, Yoshimitsu
• Primary Examiner(s): Zimmerman, John J.
• Application Number:
  US09/518,909
• Time in Patent Office: 767 Days
• Field of Search: 428/701, 428/702, 427/376.2, 427/376.3, 427/380, 427/419.3, 427/419.4, 432/128, 432/207
• US Class Current: 427/376.2
• 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: C03C 17/23 Oxides C03C17/02 takes precedence
• CPC Class Codes: C03C 2217/212 TiO2
• CPC Class Codes: C03C 2217/229 Non-specific enumeration
• CPC Class Codes: C03C 2217/71 Photocatalytic coatings
• CPC Class Codes: C03C 2218/32 After-treatment
• CPC Class Codes: C04B 2103/0015 Noble metal or copper compounds
• CPC Class Codes: C04B 2103/0016 Cu
• CPC Class Codes: C04B 2111/2061 Materials containing photocatalysts, e.g. TiO2, for avoiding staining by air pollutants or the like
• CPC Class Codes: C04B 33/00 Clay-wares monolithic refractories or refractory mortars C04B35/66; porous products C04B38/00
• CPC Class Codes: C04B 41/0072 Heat treatment
• CPC Class Codes: C04B 41/009 characterised by the material treated
• CPC Class Codes: C04B 41/4543 by spraying, e.g. by atomising
• CPC Class Codes: C04B 41/5041 Titanium oxide or titanates
• CPC Class Codes: C04B 41/5089 Silica sols, alkyl, ammonium or alkali metal silicate cements
• CPC Class Codes: C04B 41/87 Ceramics
• CPC Class Codes: C23C 30/00 Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process C23C26/00, C23C28/00 take precedence

Abstract

Disclosed is a method and an apparatus are provided which can efficiently produce a functional material having a satisfactory level of photocatalytic activity. A photocatalyst coating composition comprising a photocatalytic metal oxide and/or a precursor of the photocatalytic metal oxide is coated on the surface of a substrate. The surface of the coated substrate is rapidly heated to fix the photocatalytic metal oxide onto the surface of the substrate. This rapid heating can realize the production of a functional material having a satisfactory level of photocatalytic activity in an efficient manner. The apparatus, which can continuously carry out the rapid heating immediately after the production of the substrate, can produce the functional material having photocatalytic activity in an efficient manner.

Claims

1. A process for producing a functional material having photocatalytic activity, comprising the steps of:

coating a photocatalyst coating composition comprising a photocatalytic metal oxide and/or a precursor of the photocatalytic metal oxide onto the surface of a substrate; and

rapidly heating the surface of the coated substrate to fix the photocatalytic metal oxide onto the surface of the substrate, characterized in that;

the rapid heating is carried out by a heating means provided with a heating element having a heating value per unit area of not less than 120 MJ/m²hr, and the distance between the heating element and the surface of the substrate is 5 to 300 mm, and the rapid heating is carried out for 2 to 60 seconds.

2. The process according to claim 1, wherein the rapid heating is carried out by heating the surface of the substrate to 100 to 800°

C.

3. The process according to claim 2, wherein the rapid heating is carried out by heating the surface of the substrate to 150 to 600°

C.

4. The process according to claim 3, wherein, during the rapid heating, the substrate is placed in an atmosphere of 100 to 1000°

C.

5. The process according to claim 1, wherein during the rapid heating, the heating temperature is kept substantially constant.

6. The process according to claim 1, wherein the surface of the substrate is preheated before coating of the photocatalyst coating composition.

7. The process according to claim 6, wherein the preheating is carried out by heating the surface of the substrate to 20 to 400°

C.

8. The process according to claim 1, wherein the rapid heating is carried out by intensively supplying heat energy only to the surface of the substrate.

9. The process according to claim 1, wherein the substrate coated with the photocatalyst coating composition is dried before the rapid heating.

10. The process according to claim 1, wherein the surface of the rapidly heated substrate is then rapidly cooled.

11. The process according to claim 1, wherein the photocatalytic metal oxide is selected from the group consisting of TiO₂, ZnO, SnO₂, SrTiO₂, WO₃, Bi₂O₃, Fe₂O₃, and V₂O₅.

12. The process according to claim 1, wherein the precursor of the photocatalytic metal oxide is a compound which contains at least one metal selected from the group consisting of titanium, zinc, tin, strontium, tungsten, bismuth, iron, and vanadium and, upon the rapid heating, is converted to the photocatalytic metal oxide.

13. The process according to claim 1, wherein the photocatalyst coating composition further comprises a binder.

14. The process according to claim 13, wherein the binder comprises:

at least one member selected from the group consisting of inorganic oxide particles, silicone resin film precursors capable of forming silicone resin films, and silica film precursors capable of forming silica films; and

a solvent.

15. The process according to claim 13, wherein the binder comprises:

a member selected from the group consisting of silicon, aluminum, potassium, lithium, sodium, cesium, calcium, magnesium, titanium, phosphorus, boron, zirconium, rubidium, francium, yttrium, hafnium, lanthanides, and compounds of said elements; and

an alkali silicate represented by formula Me₂O nSiO₂ wherein Me represents an alkali metal.

16. The process according to claim 1, wherein an identical photocatalyst coating composition is coated a plurality of times on the surface of the substrate to form a stacked or multi-layered coating, or alternatively, a plurality of different photocatalyst coating compositions are provided followed by successive coating of the plurality of photocatalytic coating compositions onto the surface of the substrate to form a stacked or multi-layered coating.

17. The process according to claim 1, which comprises the steps of:

providing at least one coating composition comprising a binder and substantially free from the photocatalytic metal oxide and the precursor of the photocatalytic metal oxide and a photocatalyst coating composition comprising the photocatalytic metal oxide and/or the precursor of the photocatalytic metal oxide or a photocatalyst coating composition comprising the photocatalytic metal oxide and/or the precursor of the photocatalytic metal oxide and the binder;

coating them onto the surface of the substrate to form a multi-layered coating; and

then rapidly heating the assembly.

18. The process according to claim 1, wherein the photocatalyst coating composition further comprises a metal and/or a metal oxide selected from silver, copper, zinc, metals of the platinum group, and oxides of said metals.

19. The process according to claim 18, wherein the metal and the metal oxide are present, in a supported state, on the surface of the photocatalytic metal oxide.

20. The process according to claim 19, wherein the metal and the metal oxide have been supported on the surface of the photocatalytic metal oxide by photoreduction fixation using ultraviolet light irradiation.

21. The process according to claim 1, wherein the concentration of the photocatalytic metal oxide and/or the precursor of the photocatalytic metal oxide in the photocatalyst coating composition is 0.001 to 35% by weight on a solid basis.

22. The process according to claim 1, wherein the photocatalyst coating composition contains a binder in an amount of 0.001 to 100 parts by weight based on one part by weight of the photocatalytic metal oxide and the precursor of the photocatalyst metal oxide.

23. The process according to claim 22, wherein the photocatalyst coating composition contains the binder in an amount of 0.1 to 5 parts by weight based on one part by weight of the photocatalytic metal oxide and the precursor of the photocatalytic metal oxide.

24. The process according to claim 1, wherein the substrate is made of a metal, an inorganic material, an organic material, or a composite material thereof.

25. The process according to claim 1, wherein the functional material having photocatalytic activity is an interior or exterior material.

26. The process according to claim 1, wherein the functional material having photocatalytic activity is a tile, a sanitary ware, a table ware, a calcium silicate board, a building material, a ceramic substrate, a semiconductor material, an insulator, a glass, or a mirror.

28. The apparatus according to claim 27, which carries out the method according to claim 1.

41. A functional material having photocatalytic activity, produced by the method according to claim 1 or the apparatus according to claim 27.

27. An apparatus for producing a functional material having photocatalytic activity, said apparatus comprising

at least a rapid heating means for rapidly heating the surface of a substrate coated with a photocatalyst coating composition comprising a photocatalytic metal oxide and/or a precursor of the photocatalytic metal oxide to fix the photocatalytic metal oxide onto the surface of the substrate, characterized in that:

the rapid heating means comprises at least;

a heating element of which the heating value per unit area is not less than 120 MJ/m²hr and which is provided so that the distance between the heating element and the surface of the substrate is 5 to 300 mm with the distance being fixed or variable;

a heat-resistant material which covers the heating element while forming a given heating space;

a holding means for holding the substrate within the heating space for 2 to 60 seconds;

a carry-in port for carrying the substrate into the heating space; and

a carry-out port for carrying out the substrate from the heating space.

29. The apparatus according to claim 27 wherein the heating means can maintain the heating temperature at a substantially constant value.

30. The apparatus according to claim 27, wherein the heating means maintains the heating temperature at a substantially constant value over a zone length of 5 cm to 30 m.

31. The apparatus according to claim 27, which further comprises preheating means for preheating the surface of the substrate before coating the photocatalyst coating composition.

32. The apparatus according to claim 27, which further comprises drying means for drying the substrate coated with the photocatalyst coating composition.

33. The apparatus according to claim 27, which further comprises cooling means for rapidly cooling the surface of the substrate heated by the heating means.

34. The apparatus according to claim 27, which comprises carrying means for continuously moving and carrying the substrate within the apparatus.

35. The apparatus according to claim 27, wherein the heating means is disposed immediately downstream of the coating means.

36. The apparatus according to claim 27, which is disposed immediately downstream of an apparatus for producing the substrate.

37. The apparatus according to claim 34, wherein the carrying means is a belt conveyor or a roller conveyor.

38. The apparatus according to claim 37, wherein the carrying means is a belt conveyor of a heat-resistant belt having a percentage surface opening of not less than 20% or a roller conveyor of a group of rollers.

39. The apparatus according to claim 37, wherein the belt conveyor comprises a heat-resistant net having a mesh size up to 50 mm×

50 mm.

40. The apparatus according to claim 37, wherein the roller conveyor comprises continuous heat-resistant rollers having a pitch of 1 to 300 mm.

42. The apparatus according to claim 27, which further comprises a coating means for coating said photocatalyst coating composition onto the surface of the substrate.