Coating composition for glass

Abstract

A composition for coating glass by chemical-vapor deposition comprises a mixture of a tin oxide precursor monobutyltin trichloride, a silicon dioxide precursor tetraethylorthosilicate, and an accelerant such as triethyl phosphite; the composition is gaseous below 200° C., and permits coating glass having a temperature from 450° to 650° C. at deposition rates higher than 350 Å/sec. The layer of material deposited can be combined with other layers to produce an article with specific properties such as controlled emissivity, refractive index, abrasion resistance, or appearance.

1. A gaseous composition  process for forming an oxide composition comprising oxidizing a composition which is gaseous at a temperature below about 200° C. at atmospheric pressure, and which is adapted to deposit at least a first layer of tin oxide and silicon oxide onto glass at a rate of deposition greater than about 350 Å/sec. wherein the composition comprises a precursor of tin oxide, a precursor of silicon oxide of formula R m O n Si p , where m is from 3 to 8, n is from 1 to 4, p is from 1 to 4, and R is independently chosen from hydrogen and acyl, straight, cyclic, or branched-chain alkyl and substituted alkyl or alkenyl of from one to about six carbons, and phenyl or substituted phenyl, an accelerant selected from the group consisting of organic phosphites, organic borates and water, and mixtures thereof, and a source of oxygen. 
     
     
       2. The gaseous composition  process of  claim 1 , adapted to deposit at least a first layer comprising tin oxide and silicon oxide onto transparent flat glass at a temperature of from 450° to about 650° C. 
     
     
       3. The gaseous composition  process of  claim 1 , adapted to deposit at least a first layer comprising tin oxide and silicon oxide onto transparent flat glass to produce a glass article having essentially no reflected color in daylight. 
     
     
       4. The gaseous composition  process of  claim 1  adapted to continuously deposit at least a first layer of tin oxide and silicon oxide onto a continuously moving transparent flat glass substrate. 
     
     
       5. The composition  process of  claim 1  where said composition is gaseous at a temperature below about 175° C. 
     
     
       6. The composition  process of  claim 1  wherein the organic phosphite and the organic borate accelerants  have the formula (R″O) 3 P and (R″O) 3 B where R″ is independently chosen from straight, cyclic or branched-chain alkyl or alkenyl of from one to about six carbons; phenyl, substituted phenyl, or R′″ CH 2 CH 2 —, where R′″ is MeO 2 C—, EtO 2 C—, CH 3 CO—, or HOOC—. 
     
     
       7. The composition  process of  claim 1  wherein the precursor of the tin oxide is R n SnX 4−n , where R is a straight, cyclic, or branched-chain alkyl, or alkenyl of from one to about six carbons; phenyl, substituted phenyl, or R′CH 2 CH 2 —, where R′ is MeO 2 C—, EtO 2 C—, CH 3 CO—, or HO 2 C—; X is selected from the group consisting of halogen, acetate, perfluoroacetate, and their mixtures; and where n is 0, 1, or 2. 
     
     
       8. The composition  process of  claim 1  wherein the precursor of the tin oxide is an alkyltin chloride  halide. 
     
     
       9. The composition  process of  claim 1  wherein the precursor of the tin oxide is an alkyltin chloride. 
     
     
       10. The composition  process of  claim 1  wherein the precursor of the tin oxide is chosen from the group consisting of monobutylytin trichloride, dibutylytin dichloride, tributylytin chloride, and tin tetrachloride. 
     
     
       11. The composition  process of  claim 1  wherein the precursor of silicon oxide is selected from the group consisting of tetraethylorthosilicate, diacetoxydi-t-butoxysilane, ethyltriacetoxysilane, methyltriacetoxysilane, methyldiacetoxylsilane, tetramethyldisiloxane, tetraramethylcyclotetrasiloxane, dipinacoloxysilane, 1,1-dimethylsila-2-oxacyclohexane, tetrakis (1-methoxy-2-propoxy) silane, and triethoxysilane. 
     
     
       12. The composition  process of  claim 1  wherein the precursor of silicon oxide is tetraethylorthosilicate. 
     
     
       13. The composition  process of  claim 1  wherein the accelerant comprises triethyl phosphite. 
     
     
       14. The composition  process of  claim 1  wherein the accelerant comprises triethyl phosphite and triethyl borate. 
     
     
       15. The gaseous composition  process of  claim 1  adapted to deposit at least a first layer of tin oxide and silicon oxide onto glass at a rate of deposition greater than about 400 Å/sec. 
     
     
       16. The gaseous composition  process of  claim 1  adapted to deposit at least a first amorphous layer of tin oxide and silicon oxide onto glass. 
     
     
       17. The gaseous composition  process of  claim 1  adapted to deposit a plurality of layers comprising tin oxide and silicon oxide onto glass, the outermost layer of which is further adapted for deposited of at least a second layer. 
     
     
       18. The composition  process of  claim 17  adapted to deposit a plurality of layers comprising tin oxide and silicon oxide onto glass, the outermost layer of which is further adapted for deposit of a layer comprising tin oxide. 
     
     
       19. The composition  process of  claim 17  adapted to deposit a plurality of layers comprising tin oxide and silicon oxide onto glass the outermost layer of which is further adapted for deposit of a layer comprising tin oxide and fluorine. 
     
     
       20. The composition  process of  claim 17  wherein the second layer comprises a doped tin oxide. 
     
     
       21. The composition  process of  claim 17  wherein said plurality of layers are deposited from a precursor mixture comprising monobutyltin trichloride, tetraethyl orthosilicate and triethyl phosphite. 
     
     
       22. The composition  process of  claim 1  adapted to deposit at least a first layer comprising tin oxide and silicon oxide onto glass, said first layer having a refractive index which changes continuously between the glass substrate and the top of the layer. 
     
     
       23. A gaseous composition  process for forming an oxide composition comprising oxidizing a composition which is gaseous at a temperature below about 200° C. at atmospheric pressure, adapted to deposit at least a first amphorous layer comprising tin oxide and silicon oxide onto glass at a rate of deposition greater than about 400 Å/sec., the layer having a controlled index of refraction, wherein the composition comprises a tin oxide precursor, a silicon oxide precursor of formula R m O n Si p , where m is from 3 to 8, n is from 1 to 4, p is from 1 to 4, and R is independently chosen from hydrogen and acyl, straight, cyclic, or branched-chain alkyl and substituted alkyl or alkenyl of from one to about six carbons, and phenyl or substituted phenyl, and at least one accelerant chosen from the group consisting of boron and phosphorous esters and water. 
     
     
       24. The gaseous composition  process of  claim 23  adapted to continuously deposit at least a first layer comprising tin oxide and silicon oxide onto a continuously moving flat glass substrate at a temperature of from about 450° to about 650° C., and comprising monobutyltin trichloride, tetraethyl orthosilicate and an accelerant. 
     
     
       25. A gaseous composition  process for forming an oxide composition comprising oxidizing a composition which is gaseous at a temperature below about 200° C. and at atmospheric pressure, and which is adapted to deposit at least a first layer comprising amorphous tin oxide and silicon oxide onto glass at a temperature of front about 450° to 650° C. at a rate of deposition greater than about 350 Å/sec., wherein the composition comprises:
 a tin oxide precursor of formula R n SnX 4−n , where R is a straight, cyclic, or branched-chain alkyl, or alkenyl of from one to about six carbons; phenyl, substituted phenyl, or R′CH 2 CH 2 —, where R′ is MeO 2 C—, EtO 2 C—, CH 3 CO—, or HO 2 C—; X is selected from the group consisting of halogen, acetate;, perfluoroacetate, and their mixtures; and where n is 0, 1, or2;  
 a silicon oxide precursor of formula R m O n Si, where m is from 3 to 8, n is from 1 to 4, p is from 1 to 4, and R is independently chosen from hydrogen and acyl, straight, cyclic, or branched-chain alkyl and substituted alkyl or alkenyl of from one to about six carbons, and phenyl or substituted phenyl;  
 one or more accelerants selected from the group consisting of water and organic phosphites and organic borates of formula (R″O) 3 P and (R″O) 3 B where R″ is independently chosen from straight, cyclic or branched-chain alkyl or alkenyl of from one to about six carbons; phenyl, substituted pheny, or R′″ CH 2 CH 2 —, where R′″ is MeO 2 C—, EtO 2 C—, CH 3 CO—, or HOOC—; and  
 a source of oxygen.  
 
     
     
       26. A composition  process according to  claim 25  in which the precursor of the tin oxide is an alkyltin halide, the precursor of the silicon oxide is tetraethylorthosilicate, diacetoxydi-t-butoxysilane, ethyltriacetoxysilane, methyltriacetoxysilane, methyldiacetoxylsilane, tetramethyldisiloxane, tetramethylcyclotetrasiloxane, dipinacoloxysilane, 1,1-dimethylsila-2-oxacyclohexane, tetrakis (1-methoxy-2-propoxy) silane, or triethoxysilane, and the accelerant comprises one or both of triethyl phosphite and triethyl borate. 
     
     
       27. A composition  process according to  claim 26  in which the tin oxide precursor comprises monobutyltin trichloride, the silicone oxide precursor comprises tetraethyl orthosilicate and the accelerant comprises triethyl phosphite.