Photocatalyst composition

• US 7,211,543 B2
• Filed: 06/03/2002
• Issued: 05/01/2007
• Est. Priority Date: 06/03/2002
• Status: Expired due to Fees

• Current Assignee: Asahi Kasei Kabushiki Kaisha (Asahi Kasei Corporation)
• Original Assignee: Asahi Kasei Kabushiki Kaisha (Asahi Kasei Corporation)
• Inventors: Nakabayashi, Akira, Ota, Kazuya
• Primary Examiner(s): Lorengo; J. A.
• Assistant Examiner(s): FAISON GEE, VERONICA FAYE
• Application Number:
  US10/516,348
• Publication Number:
  US 20050227859A1
• Time in Patent Office: 1,793 Days
• Field of Search: 502/350, 502/150, 502/158
• US Class Current: 502/350
• CPC Class Codes: B01J 21/063 Titanium; Oxides or hydroxides thereof
• CPC Class Codes: B01J 31/0274 containing silicon ligands in coordination complexes B01J31/1608
• CPC Class Codes: B01J 35/39 Photocatalytic properties
• CPC Class Codes: B01J 37/0217 Pretreatment of the substrate before coating
• CPC Class Codes: B01J 37/0219 the coating containing organic compounds
• CPC Class Codes: B01J 37/0225 of metal substrates
• CPC Class Codes: B01J 37/0244 Coatings comprising several layers
• CPC Class Codes: C03C 17/007 containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
• CPC Class Codes: C03C 2217/445 Organic continuous phases
• CPC Class Codes: C03C 2217/477 Titanium oxide
• CPC Class Codes: C03C 2217/71 Photocatalytic coatings
• CPC Class Codes: C08K 3/22 of metals
• CPC Class Codes: C08K 9/06 with silicon-containing compounds
• CPC Class Codes: C09D 5/00 Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced electrically insulating plastics, resins or waxes H01B3/30; Filling pastes
• CPC Class Codes: C09D 7/62 modified by treatment with other compounds
• CPC Class Codes: C09D 7/67 Particle size smaller than 100 nm
• CPC Class Codes: C09D 7/68 Particle size between 100-1000 nm
• CPC Class Codes: Y10S 502/503 Crush strength

Abstract

A photocatalyst composition which comprises (A) modified photocatalyst particles, the modified photocatalyst particles (A) being prepared by subjecting particles of a photocatalyst to a modification treatment with at least one modifier compound selected from the group consisting of different compounds each of which independently comprises at least one structural unit selected from the group consisting of a triorganosilane unit, a monooxydiorganosilane unit and a dioxyorganosilane unit; and (B) a binder component comprising a phenyl group-containing silicone optionally containing an alkyl group. A film formed using the above-mentioned photocatalyst composition, a functional composite comprising a substrate and the above-mentioned film formed on the substrate, and a shaped article produced by shaping the above-mentioned photocatalyst composition.

Claims

1. A photocatalyst composition comprising:

(A) modified photocatalyst particles,

said modified photocatalyst particles (A) being prepared by subjecting particles of a photocatalyst (a) to a modification treatment with at least one modifier compound (b) selected from the group consisting of different compounds each of which independently comprises at least one structural unit selected from the group consisting of a triorganosilane unit represented by formula (1), a monooxydiorganosilane unit represented by formula (2), and a dioxyorganosilane unit represented by formula (3);

R₃Si—

 

 

(1)

wherein each R independently represents a straight chain or branched C₁–

C₃₀ alkyl group, a C₅–

C₂₀ cycloalkyl group, a straight chain or branched C₁–

C₃₀ fluoroalkyl group, a straight chain or branched C₂–

C₃₀ alkenyl group or a C₁–

C₂₀ alkoxy group,

—

(R₂SiO)—

 

 

(2)

wherein each R is as defined for formula (1), and

2. The composition according to claim 1, wherein said phenyl group-containing silicone (BP) is a phenyl group-containing silicone (BP1), containing no alkyl group, represented by formula (5):

R¹_sX_tSiO_(4-s-t)/2 

 

(5)

wherein;

the or each R¹ represents a phenyl group;

the or each X independently represents a hydrogen atom, a hydroxyl group, a C₁–

C₂₀ alkoxy group, a C₁–

C₂₀ acyloxy group, an aminoxy group, a C₁–

C₂₀ oxime group or a halogen atom; and

s and t satisfy the following relationships;

0<

s<

4,

0≦

t<

4, and

0<

(s+t)<

4.

3. The composition according to claim 1 or 3, wherein said binder component (B) further comprises an alkyl group-containing silicone (BA) represented by formula (6):

R²_uX_vSiO_(4-u-v)/2 

 

(6)

wherein;

the or each R² independently represents a straight chain or branched C₁–

C₃₀ alkyl group, a C₅–

C₂₀ cycloalkyl group or a straight chain or branched C₂–

C₃₀ alkenyl group;

the or each X independently represents a hydrogen atom, a hydroxyl group, a C₁–

C₂₀ alkoxy group, a C₁–

C₂₀ acyloxy group, an aminoxy group, a C₁–

C₂₀ oxime group or a halogen atom; and

u and v satisfy the following relationships;

0<

u<

4,

0≦

v<

4, and

0<

(u+v)<

4.

4. The composition according to claim 1 or 2, wherein said binder component (B) comprises a phenyl group-containing silicone (BP1), containing no alkyl group, represented by formula (5):

R¹_sX_tSiO_(4-s-t)/2 

 

(5)

wherein;

the or each R¹ represents a phenyl group;

the or each X independently represents a hydrogen atom, a hydroxyl group, a C₁–

C₂₀ alkoxy group, a C₁–

C₂₀ acyloxy group, an aminoxy group, a C₁–

C₂₀ oxime group or a halogen atom; and

s and t satisfy the following relationships;

0<

s<

4,

0≦

t<

4, and

0<

(s+t)<

4; and

an alkyl group-containing silicone (BA) represented by formula (6);

R²_uX_vSiO_(4-u-v)/2 

 

(6)

wherein;

the or each R² independently represents a straight chain or branched C₁–

C₃₀ alkyl group, a C₅–

C₂₀ cycloalkyl group or a straight chain or branched C₂–

C₃₀ alkenyl group;

the or each X independently represents a hydrogen atom, a hydroxyl group, a C₁–

C₂₀ alkoxy group, a C₁–

C₂₀ acyloxy group, an aminoxy group, a C₁–

C₂₀ oxime group or a halogen atom; and

u and v satisfy the following relationships;

0<

u<

4,

0≦

v<

4, and

0<

(u+v)<

4.

5. The composition according to claim 3, wherein said alkyl group-containing silicone (BA) comprises a monooxydiorganosilane unit (D) represented by formula (7) and a dioxyorganosilane unit (T) represented by formula (8):

—

(R²₂SiO)—

 

 

(7)

wherein each R² independently represents a straight chain or branched C₁–

C₃₀ alkyl group, a C₅–

C₂₀ cycloalkyl group or a straight chain or branched C₂–

C₃₀ alkenyl group, and

6. The composition according to claim 2, wherein said phenyl group-containing silicone (BP1) has a weight average molecular weight of from 500 to 10,000, as measured by gel permeation chromatography using a calibration curve obtained with respect to standard polystyrenes.

7. The composition according to claim 3, wherein said alkyl group-containing silicone (BA) has a weight average molecular weight of from 500 to 10,000, as measured by gel permeation chromatography using a calibration curve obtained with respect to standard polystyrenes.

8. The composition according to claim 1 or 2, wherein said modified photocatalyst particles (A) have a number average particle diameter of 400 nm or less.

9. The composition according to claim 1 or 2, wherein said photocatalyst particles (a) are titanium oxide particles.

10. The composition according to claim 1 or 2, wherein said modifier compound (b) is an Si—

H group-containing silicon compound (b1) represented by formula (9);

H_xR_ySiO_(4-x-y)/2 

 

(9)

wherein;

the or each R independently represents a straight chain or branched C₁–

C₃₀ alkyl group, a C₅–

C₂₀ cycloalkyl group, a straight chain or branched C₁–

C₃₀ fluoroalkyl group, a straight chain or branched C₂–

C₃₀ alkenyl group, a phenyl group, a C₁–

C₂₀ alkoxy group or a hydroxy group, and

x and y satisfy the following relationships;

0<

x<

4,

0<

y<

4, and

(x+y)≦

4.

11. The composition according to claim 10, wherein said Si—

H group-containing silicon compound (b1) comprises at least one compound selected from the group consisting of;

a mono Si—

H group-containing silicon compound represented by formula (10);

12. The composition according to claim 1 or 2, which further comprises a resin.

13. The composition according to claim 1 or 2, which is a film.

14. The composition according to claim 13, which is anisotropic with respect to the distribution of the modified photocatalyst particles (A), wherein the concentration of the modified photocatalyst particles (A) increases from one surface of the film toward the other surface of the film.

15. The composition according to claim 1 or 2, which is a shaped article.

16. The composition according to claim 15, which is anisotropic with respect to the distribution of the modified photocatalyst particles (A), wherein the concentration of the modified photocatalyst particles (A) increases from the inner portion of the shaped article toward the surface of the shaped article.

17. The composition according to claim 3, which is a film which has a microphase separation structure with respect to said phenyl group-containing silicone (BP) and said alkyl group-containing silicone (BA).

18. The composition according to claim 17, which is anisotropic with respect to the distribution of the modified photocatalyst particles (A), wherein the concentration of the modified photocatalyst particles (A) increases from one surface of the film toward the other surface of the film.

19. The composition according to claim 3, which is a shaped article which has a microphase separation structure with respect to said phenyl group-containing silicone (BP) and said alkyl group-containing silicone (BA).

20. The composition according to claim 19, which is anisotropic with respect to the distribution of the modified photocatalyst particles (A), wherein the concentration of the modified photocatalyst particles (A) increases from the inner portion of the shaped article toward the surface of the shaped article.

21. A functional composite comprising a substrate and a film formed on said substrate, said film comprising the composition of claim 1 or 2.

22. The functional composite according to claim 21, wherein said film is anisotropic with respect to the distribution of the modified photocatalyst particles (A), wherein the concentration of the modified photocatalyst particles (A) increases from a surface of the film which contacts the substrate toward the other, exposed surface of the film.

23. A functional composite comprising a substrate and a film formed on said substrate, said film comprising the composition of claim 3 and having a microphase separation structure with respect to said phenyl group-containing silicone (BP) and said alkyl group-containing silicone (BA).

24. The functional composite according to claim 23, wherein said film is anisotropic with respect to the distribution of the modified photocatalyst particles (A), wherein the concentration of the modified photocatalyst particles (A) increases from a surface of the film which contacts the substrate toward the other, exposed surface of the film.

25. The composition according to claim 1, wherein the or each R of each of formulae (1) to (3) independently represents a straight chain or branched C₁–

C₃₀ alkyl group, a C₅–

C₂₀ cycloalkyl group, a straight chain or branched C₁–

C₃₀ fluoroalkyl group or a straight chain or branched C₂–

C₃₀ alkenyl group.

26. The composition according to claim 1, wherein said modified photocatalyst particles (A) comprise said particles of a photocatalyst (a) and, immobilized thereon, said at least one modifier compound (b).