Photocatalytic hydrophilic coating compositions

• US 5,755,867 A
• Filed: 12/20/1996
• Issued: 05/26/1998
• Est. Priority Date: 12/22/1995
• Status: Expired due to Term

• Current Assignee: Shin-Etsu Chemical Company Limited, Toto Limited
• Original Assignee: Shin-Etsu Chemical Company Limited, Toto Limited
• Inventors: Chikuni, Makoto, Yamamoto, Akira, Yamaya, Masaaki, Furuya, Masahiro, Hayakawa, Makoto, Watanabe, Toshiya
• Primary Examiner(s): Brunsman, David
• Application Number:
  US08/777,667
• Time in Patent Office: 522 Days
• Field of Search: 106/287.13, 106/287.14, 106/287.16, 106/287.11, 106/287.12, 106/287.15
• US Class Current: 106/287.16
• CPC Class Codes: C08K 3/22 of metals
• CPC Class Codes: C08L 2666/54 Inorganic substances
• CPC Class Codes: C08L 83/04 Polysiloxanes
• CPC Class Codes: C09D 183/04 Polysiloxanes

Abstract

A photocatalytic coating composition comprising (A) a coat-forming element capable of forming a coating of silicone resin when cured and (B) a photocatalyst dispersed therein. The coat-forming element is comprised of an organopolysiloxane having a monovalent organic C₁ -C₁₈ group and a C₁ -C₄ alkoxy group. The coating composition is applied to an article and cured to form a silicone coating thereon. When the coating is exposed to light, typically UV, the photocatalyst is excited to provide photocatalysis permitting organic groups attached to silicon atoms of silicone molecules at the coating surface to be replaced by hydroxyl groups in the presence of water, thereby rendering the coating surface hydrophilic. Thereafter, the coating maintains water affinity semi-eternally and has improved weather resistance.

Claims

1. A photocatalytic hydrophilic coating composition comprising

(A) a coat-forming element comprising an organopolysiloxane of the average compositional formula:

space="preserve" listing-type="equation">R.sup.1.sub.p Si(OR.sup.2).sub.q O.sub.(4-p-q)/2

wherein R¹ is independently a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, R² is independently a hydrogen atom or a monovalent organic group having 1 to 4 carbon atoms, and letters p and q are numbers in the range;

0.7≦

p≦

1.6, 0<

q<

3.3, and 0.7<

p+q<

4, said coat-forming element capable of the forming a coating of silicone resin when cured, and

(B) a particulate photocatalyst dispersed in said coat-forming element which exerts photocatalysis upon photo excitation such that at least some of organic groups attached to silicon atoms of silicone molecules at the surface of said coating are replaced by hydroxyl groups in the presence of water, thereby rendering the coating surface hydrophilic.

2. The photocatalytic hydrophilic coating composition of claim 1 wherein R¹ contains at least one organic group having 3 to 18 carbon atoms.

3. The composition of claim 2, wherein p is from 0.1 to 1.0.

4. The photocatalytic hydrophilic coating composition of claim 1 wherein said organopolysiloxane is obtained by at least partially hydrolyzing a mixture consisting essentially of

(a) 0 to 60 mol % of a silane of the general formula:

R¹₂ SiX₂ wherein R¹ is as defined above and X is chlorine, bromine or an alkoxy group having 1 to 4 carbon atoms,

(b) 10 to 100 mol % of a silane of the general formula;

R¹ SiX₃ wherein R¹ and X are as defined above, and

(c) 0 to 30 mol % of a silane of the general formula;

SiX₄ wherein X is as defined above, followed by polycondensation.

5. The composition of claim 4, wherein the silane (a) is contained in an amount of 1 to 40 mol %, silane (b) is contained in an amount of 30 to 80 mol % and silane (c) is contained in an amount of 0 to 20 mol %.

6. The photocatalytic hydrophilic coating composition of claim 1 which contains 100 parts by weight of the coat-forming element and 10 to 400 parts by weight of the particulate photocatalyst.

7. The photocatalytic hydrophilic coating composition of claim 1 wherein the particulate photocatalyst comprises crystalline titania.

8. The composition of claim 7, wherein the titania has a mean particle size of 0.1 μ

m or less.

9. The photocatalytic hydrophilic coating composition of claim 1 further comprising (C) a metal selected from the group consisting of silver, copper, gold, platinum, palladium, iron, nickel, and zinc or a compound thereof.

10. The photocatalytic hydrophilic coating composition of claim 9 which contains less than 20 parts of the metal or compound thereof per 100 parts by weight of the photocatalyst.

11. The composition of claim 1, wherein in the organopolysiloxane,

the R¹ groups are independently hydrogen or an alkyl, cycloalkyl, alkenyl, aryl or aralkyl group optionally substituted by halogen atoms, epoxy-containing groups, (meth)acryloxy groups, amino groups or mercapto groups, and

the R² groups are independently hydrogen or an alkyl group.

12. The composition of claim 1, wherein the photocatalyst exerts photocatalysis by photo excitation from sunlight.

13. The composition of claim 1, wherein the particulate photocatalyst is titanium dioxide, tin oxide, zinc oxide, ferric oxide, tungsten trioxide, dibismuth trioxide or strontium titanate.

14. A photocatalytic hydrophilic coating composition comprising

(a) 0 to 60 mol % of a silane of the general formula:

R¹₂ SiX₂ wherein R¹ is independently a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms and X is chlorine, bromine or an alkoxy group having 1 to 4 carbon atoms,

(b) 10 to 100 mol % of a silane of the general formula;

R¹ SiX₃ wherein R¹ and X are as defined above,

(c) 0 to 30 mol % of a silane of the general formula;

SiX₄ wherein X is as defined above, and

(d) a particulate photocatalyst, wherein said composition, when applied to a substrate, forms a coating of silicone resin through hydrolysis of the silanes in the presence of water and dehydrating polycondensation, and

said photocatalyst exerts photocatalysis upon photo excitation such that at least some of the organic groups attached to silicon atoms of silicone molecules at the surface of said coating are replaced by hydroxyl groups in the presence of water, thereby rendering the coating surface hydrophilic.

15. The composition of claim 14, wherein the R¹ groups are independently hydrogen or an alkyl, cycloalkyl, alkenyl, aryl or aralkyl group optionally substituted by halogen atoms, epoxy-containing groups, (meth)acryloxy groups, amino groups or mercapto groups.

16. A photocatalytic hydrophilic coating composition of the two part type comprising

(A) a first liquid part having dispersed in a dispersing medium an organopolysiloxane of the average compositional formula:

space="preserve" listing-type="equation">R.sup.1.sub.p Si(OR.sup.2).sub.q O.sub.(4-p-q)/2

wherein R¹ is independently a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, R² is independently a hydrogen atom or a monovalent organic group having 1 to 4 carbon atoms, and letters p and q are numbers in the range;

0.7≦

p≦

1.6, 0<

q<

3.3, and 0.7<

p+q<

4, said first liquid part capable of forming a coating of silicone resin when cured in the presence of water, and

(B) a second liquid part having dispersed in an aqueous dispersing medium a particulate photocatalyst which exerts photocatalysis upon photo excitation such that at least some of the organic groups attached to silicon atoms of silicone molecules at the surface of said coating are replaced by hydroxyl groups in the presence of water, thereby rendering the coating surface hydrophilic.

17. The composition of claim 16, wherein in the organopolysiloxane,

the R¹ groups are independently hydrogen or an alkyl, cycloalkyl, alkenyl, aryl or aralkyl group optionally substituted by halogen atoms, epoxy-containing groups, (meth)acryloxy groups, amino groups or mercapto groups, and

the R² groups are independently hydrogen or an alkyl group.

18. A photocatalytic hydrophilic coating composition of the two part type comprising

(A) a first liquid part having dispersed in a non-aqueous dispersing medium

(a) 0 to 60 mol % of a silane of the general formula:

R¹₂ SiX₂ wherein R¹ is independently a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms and X is chlorine, bromine or an alkoxy group having 1 to 4 carbon atoms,

(b) 10 to 100 mol % of a silane of the general formula;

R¹ SiX₃ wherein R¹ and X are as defined above, and

(c) 0 to 30 mol % of a silane of the general formula;

SiX₄ wherein X is as defined above,

said first liquid part capable of forming a coating of silicone resin when cured in the presence of water, and

(B) a second liquid part having dispersed in an aqueous dispersing medium a particulate photocatalyst which exerts photocatalysis upon photo excitation such that at least some of the organic groups attached to silicon atoms of silicone molecules at the surface of said coating are replaced by hydroxyl groups in the presence of water, thereby rendering the coating surface hydrophilic.

19. The composition of claim 18, wherein the R¹ groups are independently hydrogen or an alkyl, cycloalkyl, alkenyl, aryl or aralkyl group optionally substituted by halogen atoms, epoxy-containing groups, (meth)acryloxy groups, amino groups or mercapto groups.