Coating solutions for forming transparent conductive ceramic coatings, substrates coated with transparent conductive ceramic coatings and process for preparing same, and uses of substrates coated with transparent conductive ceramic coatings

• US 5,382,383 A
• Filed: 04/24/1990
• Issued: 01/17/1995
• Est. Priority Date: 08/24/1988
• Status: Expired due to Term

• Current Assignee: AGC Flat Glass Company Limited (AGC, Inc.)
• Original Assignee: AGC Flat Glass Company Limited (AGC, Inc.), Catalysts & Chemicals Industries Co. Ltd. (JGC Holdings Corporation)
• Inventors: Hirai, Toshiharu, Komatsu, Michio, Abe, Yoneji
• Primary Examiner(s): Green, Anthony
• Application Number:
  US07/474,117
• Time in Patent Office: 1,729 Days
• Field of Search: 252/501.1, 252/518, 252/520, 252/500, 252/519, 252/521, 106/287.1, 106/287.16, 106/287.17, 106/287.18, 106/287.19, 106/287.2, 106/287.23, 106/287.29, 556/40
• US Class Current: 252/501.1
• CPC Class Codes: C03C 17/25 by deposition from the liquid phase
• CPC Class Codes: C03C 2217/23 Mixtures
• CPC Class Codes: C03C 2218/11 from solutions or suspensions
• CPC Class Codes: C09D 5/24 Electrically-conducting paints conductive materials H01B1/00
• CPC Class Codes: C23C 18/1208 Oxides, e.g. ceramics
• CPC Class Codes: C23C 18/1245 Inorganic substrates other than metallic
• CPC Class Codes: C23C 18/143 Radiation by light, e.g. photolysis or pyrolysis
• CPC Class Codes: Y10T 428/31504 Composite [nonstructural laminate]

Abstract

In accordance with the present invention, there are provided coating solutions for forming transparent conductive ceramic coatings, said coating solutions being homogeneous solutions or dispersions of acetylacetonate chelate compound, conductive substances and, if necessary, silicon compound and/or alkoxides of metals other than silicon in mixtures of water and organic solvents, and substrates having thereon transparent conductive ceramic coatings formed from said coating solutions and uses thereof.

Claims

1. A coating solution for forming a transparent conductive ceramic coating, said coating solution being a homogeneous solution or dispersion consisting essentially of at least one compound selected from the group consisting of an acetylacetonate chelate compound and condensate thereof, and an inorganic conductive compound in a mixture of water and an organic solvent, wherein the acetylacetonate chelate compound is represented by the following formula:

##STR2## wherein a+b is 2-4, a is 0-3, b is 1-4, R is C_n H_2n+1 -- (n=3 or

     4), X is CH₃ --, CH₃ O--, C₂ H₅ --, or C₂ H₅ O--, and M₁ is an element selected from Groups IB, IIA, IIB, IIIA, IIIB, IVA, IVB, VA, VB, VIA, VIIA, or VIII or vanadyl (VO).

7. The coating solution of claim 1 wherein the inorganic conductive compound is tin oxide, tin oxide doped with antimony, fluorine or phosphorous, indium oxide, or indium oxide doped with tin or fluorine.

8. The coating solution of claim 1, wherein the inorganic conductive compound is dispersed in said coating solution in the form of particles having an average particle diameter of less than 0.4 μ

m.

9. The coating solution of claim 1, wherein the inorganic conductive compound is dispersed in said coating solution in the form of particles having an average particle diameter of 0.01 to 0.1 μ

m.

10. The coating solution of claim 1, wherein a weight ratio of the inorganic conductive compound per the acetylacetonate chelate compound in terms of oxide thereof is from 0.5 to 5, a solids concentration of the inorganic conductive compound and the acetylacetonate chelate compound in terms of oxide thereof is from 0.1% to 15% by weight, and the water concentration in the coating solution is from 0.1 to 50% by weight.

2. A coating solution for forming a transparent conductive ceramic coating, said coating solution being a homogeneous solution or dispersion consisting essentially of:

at least one compound selected from the group consisting of an acetylacetonate chelate compound and condensates thereof wherein said acetylacetonate chelate compound excludes dialkoxybisacetylacetonatozirconium;

an inorganic conductive compound; and

a hydrolyzable silicon compound;

in a mixture of water and an organic solvent,

wherein the acetylacetonate compound is represented by the following formula;

##STR3## wherein a+b is 2-4, a is 0-3, b is 1-4, R is C_n H_2n+1 -- (n=3 or

     4), X is CH₃ --, CH₃ O--, C₂ H₅ --, or C₂ H₅ O--, and M₁ is an element selected from Groups IB, IIA, IIB, IIIA, IIIB, IVA, IVB, VA, VB, VIA, VIIA, or VIII or vanadyl (VO).

5. The coating solution of claim 2 or 4 wherein said hydrolyzable silicon compound is at least one of the compounds selected from the group consisting of a hydrolyzable silicon compound represented by the following formula (II):

space="preserve" listing-type="equation">R.sub.a --Si(OR'"'"').sub.4-a (II)

wherein R is C_n H_2n+1 -- (n=1-4), hydrogen or halogen atom, R'"'"' is C_n H2n+1-- (n=1-4), hydrogen atom or C_n H_2n+1 OC₂ H₄ -- (n=1-4), and a is 0-3; and

condensate thereof.

11. The coating solution as claimed in claim 2, 3 or 4, wherein a weight ratio of the acetylacetonate chelate compound per the inorganic conductive compound in terms of oxide thereof is from 0.001 to 1 and the water concentration in the coating solution is from 0.1 to 50% by weight.

12. The coating solution of claim 2, wherein a weight ratio of the acetylacetonate chelate compound per the hydrolyzable silicon compound in terms of oxide thereof is from 0.001 to 10, a weight ratio of the inorganic conductive compound per total amount of the acetylacetonate chelate compound and the hydrolyzable silicon compound in terms of oxide thereof is from 0.5 to 5 and a solids concentration of the inorganic conductive compound, the acetylacetonate chelate compound and the hydrolyzable silicon compound in terms of oxide thereof is from 0.1% to 15% by weight.

3. A coating solution for forming a transparent conductive ceramic coating, said coating solution being a homogeneous solution or dispersion consisting essentially of:

at least one compound selected from the group consisting of an acetylacetonate chelate compound and condensates thereof;

an inorganic conductive compound; and

an alkoxide of metal other than silicon;

in a mixture of water and an organic solvent,

wherein the acetylacetonate compound is represented by the following formula;

##STR4## wherein a+b is 2-4, a is 0-3, b is 1-4, R is C_n H_2n+1 -- (n=3 or

     4), X is CH₃ --, CH₃ O--, C₂ H₅ --, or C₂ H₅ O--, and M₁ is an element selected from Groups IB, IIA, IIB, IIIA, IIIB, IVA, IVB, VA, VB, VIA, VIIA, or VIII or vanadyl (VO).

6. The coating solution of claim 3 or 4 wherein said alkoxide of metal other than silicon is at least one of the compounds selected from the group consisting of an alkoxide of metal other than silicon represented by the following formula (III):

space="preserve" listing-type="equation">M.sub.2 (OR).sub.n (III)

wherein n is an integer equal to a valency of M₂, R is alkyl or C_n H_2n O-- (n=3-10), and M₂ is a metal other than silicon; and

condensate thereof.

13. The coating solution of claim 3, wherein a weight ratio of the acetylacetonate chelate compound per the alkoxide of metal other than silicon in terms of oxide thereof is from 0.001 to 10, a weight ratio of the inorganic conductive compound per total amount of the acetylacetonate chelate compound and the alkoxide of metal other than silicon in terms of oxide thereof is from 0.5 to 5 and a solids concentration of the inorganic conductive compound, the acetylacetonate chelate compound and the alkoxide of metal other than silicon in terms of oxide thereof is from 0.1% to 15% by weight.

4. A coating solution for forming a transparent conductive ceramic coating, said coating solution being a homogeneous solution or dispersion consisting essentially of:

at least one compound selected from the group consisting of an acetylacetonate chelate compound and condensates thereof;

an inorganic conductive compound;

a hydrolyzable silicon compound; and

;

an alkoxide of metal other than silicon;

in a mixture of water and an organic solvent,

wherein the acetylacetonate compound is represented by the following formula;

##STR5## wherein a+b is 2-4, a is 0-3, b is 1-4, R is C_n H_2n+1 -- (n=3 or

     4), X is CH₃ --, CH₃ O--, C₂ H₅ --, or C₂ H₅ O--, and M₁ is an element selected from Groups IB, IIA, IIB, IIIA, IIIB, IVA, IVB, VA, VB, VIA, VIIA, or VIII or vanadyl (VO).

14. The coating solution of claim 4, wherein a weight ratio of the acetylacetonate chelate compound per total amount of the hydrolyzable silicon compound and the alkoxide of metal other than silicon in terms of oxide thereof is from 0.001 to 10, a weight ratio of the inorganic conductive compound per total amount of the acetylacetonate chelate compound, the hydrolyzable silicon compound and the alkoxide of metal other than silicon in terms of oxide thereof is from 0.5 to 5, a weight ratio of the alkoxide of metal other than silicon per total amount of the hydrolyzable silicon compound and the alkoxide of metal other than silicon in terms of oxide thereof is from 0.001 to 0.99 and a solids concentration of the inorganic conductive compound, the acetylacetonate chelate compound, the hydrolyzable silicon compound and the alkoxide of metal other than silicon in terms of oxide thereof is from 0.1% to 15% by weight.

15. A coating solution for forming a transparent conductive ceramic coating, said coating solution being a homogeneous solution or dispersion comprising:

at least one compound selected from the group consisting of an acetylacetonate chelate compound and condensates thereof;

an inorganic conductive compound;

in a mixture of water and an organic solvent,

wherein the acetylacetonate compound is represented by the following formula;

##STR6## wherein a+b is 2-4, a is 0-3, b is 1-4, R is C_n H_2n+1 -- (n=3 or

     4), X is CH₃ --, CH₃ O, C₂ H₅ --, or C₂ H₅ O--, and M₁ is an element selected from Groups IB, IIA, IIB, IIIA, IIIB, IVA, IVB, VA, VB, VIA, VIIA, or VIII or vanadyl (VO).

16. The coating solution of claim 15 wherein said acetylacetonate chelate compound excludes dialkoxybisacetylacetonatozirconium, and wherein said coating solution further comprises a hydrolyzable silicon compound.

17. The coating solution of claim 15 further comprising an alkoxide of metal other than silicon.

18. The coating solution of claim 15 further comprising a hydrolyzable silicon compound and an alkoxide of metal other than silicon.

19. The coating solution of claim 16 or 18 wherein said hydrolyzable silicon compound is at least one of the compounds selected from the group consisting of a hydrolyzable silicon compound represented by the following formula (II):

space="preserve" listing-type="equation">R.sub.a --Si(OR'"'"').sub.4-a (II)

wherein R is C_n H_2n+1 -- (n=l-4), hydrogen or halogen atom, R'"'"' is C_n H_2n+1 -- (n=1-4), hydrogen atom or C_n H_2n+1 OC₂ H₄ -- (n=1-4), and a is 0-3; and

condensate thereof.

20. The coating solution of claim 17 or 18 wherein said alkoxide of metal other than silicon is at least one of the compounds selected from the group consisting of an alkoxide of metal other than silicon represented by the following formula (III):

space="preserve" listing-type="equation">M.sub.2 (OR).sub.n (III)

wherein n is an integer equal to a valency of M₂, R is alkyl or C_n H_2n O-- (n=3-10), and M₂ is a metal other than silicon; and

condensate thereof.

21. The coating solution of claim 15 wherein the inorganic conductive compound is tin oxide, tin oxide doped with antimony, fluorine or phosphorous, indium oxide, or indium oxide doped with tin or fluorine.