Multi-functional material with photocatalytic functions and method of manufacturing same

• US 6,210,779 B1
• Filed: 10/07/1998
• Issued: 04/03/2001
• Est. Priority Date: 12/10/1993
• Status: Expired due to Term

• Current Assignee: Toto Limited
• Original Assignee: Toto Limited
• Inventors: Watanabe, Toshiya, Kitamura, Atsushi, Kojima, Eiichi, Machida, Mitsuyoshi, Nakashima, Yasushi, Chikuni, Makoto, Norimoto, Keiichiro, Kimura, Tamon, Saeki, Yoshimitsu, Hayakawa, Makoto, Kuga, Tatsuhiko
• Primary Examiner(s): Copenheaver, Blaine
• Application Number:
  US09/167,326
• Time in Patent Office: 909 Days
• Field of Search: 156/309.6, 427/125, 427/126.5, 427/126.6, 427/214, 427/217, 428/208, 428/312.8, 428/313.9, 428/317.1, 430/947, 502/439
• US Class Current: 428/208
• CPC Class Codes: B01J 21/063 Titanium; Oxides or hydroxides thereof
• 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 17/007 containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
• CPC Class Codes: C03C 17/3411 with at least two coatings of inorganic materials C03C17/36, C03C17/42 take precedence
• CPC Class Codes: C03C 2217/42 consisting of particles only
• CPC Class Codes: C03C 2217/425 consisting of a porous layer
• CPC Class Codes: C03C 2217/475 Inorganic materials
• CPC Class Codes: C03C 2217/477 Titanium oxide
• CPC Class Codes: C03C 2217/71 Photocatalytic coatings
• CPC Class Codes: C04B 33/00 Clay-wares monolithic refractories or refractory mortars C04B35/66; porous products C04B38/00
• CPC Class Codes: C04B 35/10 based on aluminium oxide
• CPC Class Codes: C04B 41/0045 Irradiation; Radiation, e.g. with UV or IR C04B41/0036 takes precedence
• CPC Class Codes: C04B 41/009 characterised by the material treated
• CPC Class Codes: C04B 41/4535 applied as a solution, emulsion, dispersion or suspension
• CPC Class Codes: C04B 41/4537 by the sol-gel process
• CPC Class Codes: C04B 41/4539 as a emulsion, dispersion or suspension
• CPC Class Codes: C04B 41/455 the coating or impregnating process including a chemical conversion or reaction
• CPC Class Codes: C04B 41/4554 the coating or impregnating material being an organic or organo-metallic precursor of an inorganic material
• CPC Class Codes: C04B 41/4562 : Photographic methods, e.g. making use of photo-sensitive materials
• CPC Class Codes: C04B 41/5022 : with vitreous materials composition of vitreous glazes and enamels C03C; ceramic pigments C09C1/0009
• CPC Class Codes: C04B 41/5041 : Titanium oxide or titanates
• CPC Class Codes: C04B 41/505 : Tin oxide
• CPC Class Codes: C04B 41/51 : Metallising , e.g. infiltration of sintered ceramic preforms with molten metal covering materials with metals in general C23C; ceramic compositions containing free metal bonded to carbides, diamond, oxides, borides, nitrides, silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides or sulfides, other than as macroscopic reinforcing agents C22C; infiltration of preforms containing free metal, e.g. cermets C22C
• CPC Class Codes: C04B 41/5111 : Ag, Au, Pd, Pt or Cu
• CPC Class Codes: C04B 41/52 : Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
• CPC Class Codes: C04B 41/81 : Coating or impregnation
• CPC Class Codes: C04B 41/89 : for obtaining at least two superposed coatings having different compositions
• CPC Class Codes: Y10S 430/148 : Light sensitive titanium compound containing
• CPC Class Codes: Y10T 428/24909 : Free metal or mineral containing
• CPC Class Codes: Y10T 428/24997 : Of metal-containing material
• CPC Class Codes: Y10T 428/249974 : Metal- or silicon-containing element
• CPC Class Codes: Y10T 428/249982 : With component specified as adhesive or bonding agent
• CPC Class Codes: Y10T 428/249985 : Composition of adhesive or bonding component specified

Abstract

Multi-functional materials which have a photocatalytic layer with a photocatalytic function disposed on the surface of a base through an amorphous binder layer 6 interposed therebetween. Photocatalytic particles of the photocatalytic layer are joined together by a surface energy or solid-state sintering. The photocatalytic layer may have a structure in which fine particles fill interstices defined between photocatalytic particles or a structure in which no fine particles fill interstices defined between photocatalytic particles. A metal such as Ag, Pt, or the like may be fixed or not fixed to surfaces of the photocatalytic particles. A lower layer of the photocatalytic layer is embedded in the binder layer such that an intermediate layer is formed between the binder layer and the photocatalytic layer, the intermediate layer including components of the binder and photocatalytic layers in varying concentrations therethrough.

Claims

1. A multi-functional material with a photocatalytic function, comprising:

a base;

a photocatalytic layer having a photocatalytic function and disposed on a surface of said base, said photocatalytic layer including at least a surface layer exposed outwardly, said surface layer being composed of fine photocatalytic particles joined together with interstices defined therebetween at a predetermined porosity and electron-capturing particles fixed to surfaces of the photocatalytic particles;

an amorphous binder layer interposed between the surface of the base and the photocatalytic layer;

said photocatalytic layer further including a lower layer embedded in said binder layer; and

an intermediate layer interposed between the binder layer and said photocatalytic layer, said intermediate layer including components of said photocatalytic layer and said binder layer, and concentrations of said components varying continuously in said intermediate layer.

2. A multi-functional material according to claim 1, wherein said intermediate layer has a thickness which is at least ⅓

of the thickness of said photocatalytic layer.

3. A multi-functional material according to claim 1, wherein said electron-capturing particles are made of at least one of Cu, Ag, Zn, Fe, Co, Ni, Pd, Cu₂O, and Pt.

4. A multi-functional material according to claim 1, wherein said binder layer is made of glaze, inorganic glass, thermoplastic resin, or thermoplastic material of solder.

5. A multi-functional material according to claim 1, further including small particles filled in said interstices between said photocatalytic particles.

6. A multi-functional material according to claim 5, wherein said particles filled in the interstices between said photocatalytic particles have a diameter of less than 0.01 μ

m.

7. A multi-functional material according to claim 5, wherein said particles filled in the interstices defined between said photocatalytic particles include at least one of Ag, Ag₂O, Cu, Cu₂O, Zn, Fe, Pt, Co, Pd, and Ni.

8. A multi-functional material according to claim 5, wherein said particles filled in the interstices defined between said photocatalytic particles have a photocatalytic activity.

9. A multi-functional material according to claim 5, wherein said small particles are filled in said interstices by coating at least one of a metal alkoxide and an organic metal salt on said surface layer, and then drying and heating same.

10. A multi-functional material according to claim 5, wherein said small particles are filled in said interstices by coating a Ti alkoxide on said surface layer in an amount ranging from 10 g/cm² to 100 g/cm² in terms of the amount of TiO₂.

11. A multi-functional material according to claim 5, wherein said small particles are filled in said interstices by coating a solution containing Ti alkoxide on said surface layer, said solution also contains hydrochloric acid in an amount ranging from 1-10 weight % with respect to the amount of TiO₂.

12. A method of manufacturing a multi-functional material with a photocatalytic function of claim 1, comprising the steps of:

forming a binder layer on a surface of a base by coating a solution containing photocatalytic particles onto said binder layer, and firing the solution and the binder layer at an elevated temperature such that the binder layer is softened and the lower surface of the photocatalytic layer becomes embedded in said binder layer forming an intermediate layer between the photocatalytic layer and the binder layer;

forming a photocatalytic layer having a surface layer exposed from said binder layer and a lower layer embedded in said binder layer;

thereafter coating an aqueous solution of metal ions of at least one of Ni, Pd, and Pt, and photoreducing the coated solution to separate out and fix metal particles to surfaces of said photocatalytic particles.

13. A method according to claim 12, wherein said binder layer is made of glaze, inorganic glass, thermoplastic resin, or thermoplastic material of solder.

14. A method according to claim 12, wherein said intermediate layer has a thickness which is at least ⅓

of the thickness of said photocatalytic layer.

15. A method according to claim 12, further including the steps of coating a metal alkoxide or an organic metal salt on a surface of said photocatalytic layer, then drying and heating the coated metal alkoxide or organic metal salt to fill interstices defined between photocatalytic particles with particles smaller than the interstices.

16. A method according to claim 15, wherein said metal alkoxide coated on the surface of said photocatalytic layer comprises a Ti alkoxide, said Ti alkoxide being coated in an amount of 10 g/cm² or greater and 100 g/cm² or smaller in terms of the amount of TiO₂.

17. A method according to claim 15, wherein said metal alkoxide coated on the surface of said photocatalytic layer comprises a Ti alkoxide, said Ti alkoxide being heated at a temperature of 400°

C. or higher and 800°

C. or lower.

18. A method according to claim 15, wherein said metal alkoxide coated on the surface of said photocatalytic layer comprises a Ti alkoxide, said Ti alkoxide being contained in a coating solution which also contains hydrochloric acid in an amount of 1 weight % or more and 10 weight % or less with respect to the Ti alkoxide.

19. A method according to claim 12, wherein said step of forming the photocatalytic layer occurs after the step of forming the binder layer on the surface of the base.