Coating composition and method for determining the uniformity and thickness of a no-rinse silane pretreatment

Abstract

The invention is directed to a detectable and stable composition comprising an organofunctional silane and/or hydrolyzate and/or partial or complete condensate thereof, a colloidal metal oxide, a water soluble organic dye having a positive charge and a counterion derived from a carboxylic acid of from 1 to 6 carbon atoms, and water. The invention is also directed to a method for determining the uniformity and film thickness of a detectable composition applied to a substrate comprising applying to the surface of the substrate the detectable composition and measuring an optical property of the applied coating, the resulting measurement being related to the uniformity of the applied composition.

1 - 20 . (canceled) 
     
     
         21 . A metal substrate coated with a detectable coating composition comprising:
 a. organofunctional silane or hydrolyzate and/or partial or complete condensate thereof;   b. colloidal metal oxide;   c. water soluble organic dye having a positive charge and a counterion derived from a carboxylic acid containing from 1 to about 6 carbon atoms; and,   d. water,   
       wherein said composition does not contain detrimental amounts of precipitates for a period of at least 48 hours when stored at 2° C. 
     
     
         22 . The metal substrate coated with the detectable coating composition of  claim 21 , wherein the water soluble organic dye (c) has the general formula (IV): 
       
         
           
           
               
               
           
         
         wherein
 G 1  is an organic group having from 1 to about 20 carbon atoms and containing at least one oxygen or nitrogen heteroatom; 
 A is a nitrogen atom or (−) 3 C—R*, where R* is a monovalent group chosen from alkyl, cycloalkyl, alkenyl, aralkyl or aryl group each baying up to about 10 carbon atoms; 
 R 6  is an alkyl, a hydroxylalkyl, alkoxyalkyl, a cycloalkyl, at aralkyl optionally substituted with a halogen or alkoxy group, an aryl optionally substituted with a halogen or alkoxy group, a cyanoalkyl, a carbamatoalkyl or a carboalkoxyalkyl group containing up to about 10 carbon atoms, or hydrogen; 
 R 7  is an alkyl, alkoxy, aryl alkylsulfonyl, or arylsulfonyl group containing up to about 10 carbon atoms or hydrogen; 
 R 8  is an alkyl, alkoxy, aryl alkylsulfonyl, arylsulfonyl, or aminosulfonyl group containing up to about 10 carbon atoms or hydrogen; 
 R 9  is an alkyl, alkoxy, aryl alkylsulfonyl, or arylsulfonyl group containing up to about 10 carbon atoms or hydrogen; 
 R 10  is an alkyl, alkoxy, aryl alkylsulfonyl, or arylsulfonyl group containing up to about 10 carbon atoms or hydrogen; 
 R 11  is an alkyl, a hydroxylalkyl, an alkoxyalkyl, cycloalkyl, an aralkyl optionally substituted with a halogen or alkoxy group, an aryl optionally substituted with a halogen or alkoxy group, a cyanoalkyl, a carbamatoalkyl or an alkoxycarbonylalkyl group containing up to about 10 carbon atoms or hydrogen; 
 R 12  is an alkyl group containing from 1 to about 6 carbon atoms or hydrogen; and 
 
         a is an integer of from 1 to 3, or
 or (VII) 
 
       
       
         
           
           
               
               
           
         
         wherein:
 R 12  is an alkyl group containing from 1 to about 6 carbon atoms or hydrogen; 
 R 23  is hydrogen, an alkyl group of from 1 to about 6 carbon atoms, an aryl group of from 6 to about 10 carbon atoms, an aralkyl group of from 7 to about 12 carbon atoms or an aryl group of from 6 to about 12 carbon atoms substituted with a hydroxycarbonyl group (—C(═O)OH) or substituted with an alkoxycarbonyl group —C(═O)OR 26 , where R 26  is an alkyl group of from 1 to about 4 carbon atoms; 
 R 24  is hydrogen, alkyl group containing 1 to about 6 carbon atoms, hydroxyl or amino having the structure —NR 27 R 28 , where R 27  and R 28  are each independently a hydrogen or alkyl group of from 1 to about 6 carbon atoms; 
 R 25  is hydrogen, an alkyl group containing 1 to about 6 carbon atoms, hydroxyl or amino having the structure —NR 27 R 28 , where R 27  and R 28  are each independently a hydrogen or alkyl group of from 1 to about 6 carbon atoms; and 
 m is an integer from 1 to 3. 
 
       
     
     
         23 . (canceled) 
     
     
         24 . The metal substrate coated with the detectable coating composition of  claim 21 , wherein the water soluble organic dye (c) is in the amount of from 0.0001 to about 5 weight percent, based upon the total weight of the detectable coating composition. 
     
     
         25 . The metal substrate coated with the detectable coating composition of  claim 22 , wherein the water soluble organic dye (c) has the general formula (IV): 
       
         
           
           
               
               
           
         
         wherein,
 G 1  is an organic group having from 1 to about 20 carbon atoms and containing at least one oxygen or nitrogen heteroatom; 
 A is a nitrogen atom or (−) 3 C—R*, where R* is a monovalent group chosen from alkyl, cycloalkyl, alkenyl, aralkyl or aryl group each having up to about 10 carbon atoms; 
 R 6  is an alkyl, a hydroxylalkyl, an alkoxyalkyl, a cycloalkyl, an aralkyl optionally substituted with a halogen or alkoxy group, an aryl optionally substituted with a halogen or alkoxy group, a cyanoalkyl, a carbamatoalkyl or a carboalkoxyalkyl group containing up to about 10 carbon atoms, or hydrogen; 
 R 7  an alkyl, alkoxy, aryl alkylsulfonyl, or arylsulfonyl group containing up to about 10 carbon atoms or hydrogen; 
 R 8  is an alkyl, alkoxy, aryl alkylsulfonyl, arylsulfonyl, or aminosulfonyl group containing up to about 10 carbon atoms or hydrogen; 
 R 9  is an alkyl, alkoxy, aryl alkylsulfonyl, or arylsulfonyl group containing up to about 10 carbon atoms or hydrogen; 
 R 10  is an alkyl, alkoxy, aryl alkylsulfonyl, or arylsulfonyl group containing up to about 10 carbon atoms or hydrogen; 
 R 11  is an alkyl, a hydroxylalkyl, an alkoxyalkyl, cycloalkyl, an aralkyl optionally substituted with a halogen or alkoxy group, an aryl optionally substituted with a halogen or alkoxy group, a cyanoalkyl, a carbamatoalkyl or an alkoxycarbonylalkyl group containing up to about 10 carbon atoms or hydrogen; 
 R 12  is an alkyl group containing from 1 to about 6 carbon atoms or hydrogen; and 
 n is an integer of from 1 to 3. 
 
       
     
     
         26 . The metal, substrate coated with the detectable coating, composition of  claim 25  wherein G 1  is a monovalent organic group of the general formula (V): 
       
         
           
           
               
               
           
         
         wherein:
 R 13  is an alkyl or alkoxy, group containing from 1 to about 6 carbon atoms, halogen, hydrogen or together with R 14  forms a fused aryl group containing up to about 16 carbon atoms, or a ring containing a —O—CH 2 — group or —O—CH 2 CH 2 —O— group bonded to the aromatic ring of the structure (V) which contains up to about 16 carbon atoms; 
 R 14  is an alkyl or alkoxy group containing 1 to about 6 carbon atoms, hydrogen, halogen, carboxyl, carboalkoxy, aminocarbonyl, carbamato, sulfonyl, aminosulfonyl or together with R 13  or R 15  forms a fused aryl group containing up to about 16 carbon atoms, or a ring containing a —O—CH 2 —O— group or —O—CH 2 CH 2 —O— group bonded to the aromatic ring of the structure (V) which contains up to about 16 carbon atoms; 
 R 15  is an alkyl or alkoxy group of from 1 to about 6 carbon atoms, a halogen or hydrogen or together with R 14  or R 16  forms a fused aryl group of up to about 16 carbon atoms, or together with R 14  or R 16  forms a fused a ring containing, a —O—CH 2 —O— group or —O—CH 2 CH 2 —O— group bonded to the aromatic ring, of the structure (V) which contains up to about 16 carbon atoms, or a monovalent group of from 2 to about 12 carbon atoms derived from 2H-[1,2,3]triazole; 
 R 16  is an alkyl or alkoxy group of from 1 to 6 carbon atoms, halogen or hydrogen or together with R 15  forms a fused aryl group, or a ring containing a —O—CH 2 —O— group or —O—CH 2 CH 2 —O— group bonded to the aromatic ring of the structure (V) which contains up to about 16 carbon atoms; and 
 R 17  is an alkyl group of from 1 to about 6 carbon atoms, hydrogen, or a phenyl group which is optionally substituted with alkyl or alkoxy group. 
 
       
     
     
         27 . The metal substrate coated with the detectable coating composition of  claim 25  wherein G 1  is a monovalent organic group of the general formula (VI): 
       
         
           
           
               
               
           
         
         wherein:
 each R 18 , R 19 , R 20 , R 21  and R 22  is independently an alkyl group of from 1 to about 6 carbon atoms or hydrogen. 
 
       
     
     
         28 . The metal substrate coated with the detectable coating composition of  claim 25  wherein A is equal to —CR* where R* is a monovalent group selected from alkyl, cycloalkyl, alkenyl, aralkyl or aryl group having up to about 10 carbon atoms and G 1  is the group of the formula (VI) 
       
         
           
           
               
               
           
         
         wherein:
 each R 18 , R 19 , R 20 , R 21  and R 22  is independently an alkyl group of from 1 to about 6 carbon atoms or hydrogen. 
 
       
     
     
         29 . The metal substrate coated with the detectable coating composition of  claim 28 , wherein R 18 , R 19  and R 20  are each methyl and R 21  and R 22  are each hydrogen. 
     
     
         30 . The metal substrate coated with the detectable coating composition of  claim 25 , wherein A is a nitrogen atom and G 1  is the group of the formula (V) 
       
         
           
           
               
               
           
         
         wherein:
 R 13  is an, alkyl or alkoxy group containing from 1 to about 6 carbon atoms, halogen, hydrogen or together with R forms a fused aryl group containing up to about 16 carbon atoms, or a ring containing a —O—CH 2 —O— group or —O—CH 2 CH 2 —O— group bonded to the aromatic ring of the structure (V) which contains up to about 16 carbon atoms; 
 R 14  is an alkyl or alkoxy group containing 1 to 6 carbon atoms, hydrogen, halogen, carboxyl, carboalkoxy, aminocarbonyl, carbamato, sulfonyl, alkylsulfonyl, aminosulfonyl or together with R 13  or R 15  forms a fused aryl group containing up to about 16 carbon atoms, or a ring containing a —O—CH 2 —O— group or —O—CH 2 CH 2 —O— group bonded to the aromatic ring of the structure (V) which contains up to about 16 carbon atoms; 
 R 15  is an alkyl or alkoxy group of from 1 to about 6 carbon atoms, a halogen or hydrogen or together with R 14  or R 16  forms a fused aryl group of up to about 16 carbon atoms, or together with R 14  or R 16  forms a fused a ring containing a —O—CH 2 —O— group or —O—CH 2 CH 2 *—O— group bonded to the aromatic ring of the structure (V) which contains up to about 16 carbon atoms, or a monovalent group of from 2 to about 12 carbon atoms derived from 2H-[1,2,3]triazole; 
 R 16  an alkyl or alkoxy group of from 1 to about 6 carbon atoms, halogen or hydrogen or together with forms a fused aryl group, or a ring containing a —O—CH 2 —O— group or —O—CH 2 CH 2 —O— group bonded to the aromatic ring of the structure (V) which contains up to about 6 carbon atoms; and 
 R 17  is an alkyl group of from 1 to about 6 carbon atoms, hydrogen, or a phenyl, group which is optionally substituted with alkyl or alkoxy group. 
 
       
     
     
         31 . The metal substrate coated with the detectable coating composition of  claim 22 , wherein the water soluble organic dye (c) has the general formulae (VII): 
       
         
           
           
               
               
           
         
         wherein:
 R 12  is an alkyl group containing from 1 to about 6 carbon atoms or hydrogen; 
 R 23  is hydrogen, an alkyl group of from 1 to about 6 carbon atoms, an aryl group of from 6 to about 10 carbon atoms, an aralkyl group of from 7 to about 12 carbon atoms or an aryl group of from 6 to about 12 carbon atoms substituted with a hydroxycarbonyl group (—C(═O)OH) substituted with an alkoxycarbonyl group —C(═O)OR 26 , where R 26  is an alkyl group of from 1 to about 4 carbon atoms; 
 R 24  is hydrogen, an alkyl group containing 1 to about 6 carbon atoms, hydroxyl or amino having the structure —NR 27 R 28 , where R 27  and R 28  are each independently a hydrogen or alkyl group of from 1 to about 6 carbon atoms; 
 R 25  is hydrogen, an alkyl, group containing 1 to about 6 carbon atoms, hydroxyl or amino having the structure —NR 22 R 28 , where R 27  and R 28  are each independently a hydrogen or alkyl group of from 1 to about 6 carbon atoms; and 
 m is an integer from 1 to 3. 
 
       
     
     
         32 . The metal substrate coated with the detectable coating, composition of  claim 31 , wherein R 24  and R 25  are each an —NR 27 R 28  group, where R 27  and R 28  are each independently a hydrogen or an alkyl, group of from 1 to about 3 carbon atoms and R 23  is C 6 H 4 —CO 2 H. 
     
     
         33 . The metal substrate coated with the detectable coating composition of  claim 21 , wherein the silicon-containing compound (a) selected from the group consisting of organofunctional silane, a hydrolyzate of said organofunctional silane, a condensate of the said organofunctional silane and mixtures thereof, wherein the organofunctional silane (a) is of the general formula (I): 
       
         
           
           
               
               
           
         
         wherein X is an organofunctional group of valence r, including mono-, di-, or polyvalent groups; 
         each occurrence of R 1  is independently a linear, branched or cyclic divalent organic group containing up to about 12 carbon atoms, and optionally containing one or more heteroatoms, with the proviso that X and the silicon atom of the silyl group are bonded to the R 1  group through a covalent bond to a carbon atom of R 1 , thereby forming a bridge between organofunctional group X and the silyl group; 
         each occurrence of R 2  independently is alkyl, alt oxy-substituted alkyl, aryl, or aralkyl, all containing up to about 16 carbon atoms, each R 3  independently is acetyl, alkyl, or alkoxy-substituted alkyl, all containing up to about 16 carbon atoms, or hydrogen; 
         X is an organofunctional group of valence r, including mono-, di- or polyvalent functional groups; 
         r is an integer of from 1 to 4; and 
         a is 0, 1 or 2. 
       
     
     
         34 . The metal substrate coated with the detectable coating composition of  claim 33 , wherein the organofunctional silane (a) is selected from the group consisting of vinylmethyldiethoxysilane, vinyltrimethoxysilane, vinyldimethylethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyl-tris(2-methoxyethoxysilane, styrylethyltrimethoxysilane, gamma-acryloxypropyltrimethoxysilane, gamma-acryloxypropyl)methyldimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-methacryloxypropyltriethoxysilane, gamma-methacryloxypropylmethyldimethoxysilane, gamma-methacryloxypropylmethyldiethoxysilane, gamma-methacryloxypropyl-tris-(2-methoxyethoxy)silane, beta-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, beta-(3,4-epoxycyclohexyl)ethyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma-glycidoxypropylmethyldiethoxysilane, gamma-glycidoxypropylmethyldimethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, gamma-thiooctanoylpropyltrimethoxysilane, gamma-thiooctanoylpropyltriethoxysilane, bis-(trimethoxysilylpropyl)tetrasulfane, bis-(triethoxysilylpropyl)disulfane, gamma-ureidopropyltrimethoxysilane, gamma-ureidopropyltriethoxysilane, gamma-ureidopropyldimethoxyethoxysilane, gamma-ureidopropylmethoxydiethoxysilane, gamma-ureidopropylmethyldimethoxysilane, gamma-ureidopropylmethyldiethoxysilane, gamma-ureidopropylmethylmethoxyethoxysilane, gamma-carbamatopropyltrimethoxysilane, gamma-carbamatopropyltriethoxysilane, isocyanurate propyltrimethoxysilane, bis-(trimethoxysilylpropyl)urea, bis-(triethoxysilylpropyl)urea, 2-cyanoethyltrimethoxysilane, 2-cyanoethyltriethoxysilane and combinations thereof. 
     
     
         35 . The metal substrate coated with the detectable coating composition of  claim 21 , wherein the silicon-containing compound (a) in the amount of 0.01 to 80 weight percent, based upon the total weight of the detectable coating composition. 
     
     
         36 . The metal substrate coated with the detectable coating composition of  claim 21 , wherein the colloidal metal oxide (b) is cerium oxide particles in the amount of from about 0.001 to about 36 weight percent, based upon the total weight of the detectable coating composition. 
     
     
         37 . The metal substrate coated with the detectable coating composition of  claim 21 , wherein the composition consists essentially of:
 a. at least one ureido silane having the structure:   
       
         
           
           
               
               
           
         
         
           wherein R is independently hydrogen or alkyl of from 1 to about 4 carbon atoms, or condensate compounds therefrom in the amount of from about 0.01 to about 80 weight percent; 
         
         b. cerium oxide particles in the amount of from about 0.001 to about 36 weight percent; 
         c. water soluble organic dye in an amount of from about 0.001 to about 2 weight percent and having the general formula (IV): 
       
       
         
           
           
               
               
           
         
       
       wherein:
 G 1  is an organic group having from 1 to about 20 carbon atoms and containing at least one oxygen, or nitrogen heteroatom; 
 A is a nitrogen atom or (−) 3 C—R*, where R* is a monovalent group chosen from alkyl, cycloalkyl, alkenyl, aralkyl or aryl group each having up to about 10 carbon atoms; 
 R 6  is an alkyl, a hydroxylalkyl, an alkoxyalkyl, a cycloalkyl, ala aralkyl optionally substituted with a halogen or alkoxy group, an aryl optionally substituted with a halogen or alkoxy group, a cyanoalkyl, a carbamatoalkyl or a carboalkoxyalkyl group containing up to about 10 carbon atoms, or hydrogen; 
 R 7  is an alkoxy, aryl alkylsulfonyl or arylsulfonyl group containing up to about 10 carbon atoms or hydrogen; 
 R 8  is an alkyl, alkoxy, aryl alkylsulfonyl, arylsulfonyl, or aminosulfonyl group containing up to about 10 carbon atoms or hydrogen; 
 R 9  is an alkyl, alkoxy, alkylsulfonyl, or arylsulfonyl group containing up to about 10 carbon atoms or hydrogen; 
 R 10  is an alkyl, alkoxy, aryl alkylsulfonyl, or arylsulfonyl group containing up to about 10 carbon atoms or hydrogen; 
 R 11  is an alkyl, a hydroxylalkyl, a s alkoxyalkyl, cycloalkyl, an aralkyl optionally substituted with a halogen or alkoxy group, an aryl optionally substituted with a halogen or alkoxy group, a cyanoalkyl, a carbamatoalkyl or an alkoxycarbonylalkyl group containing up to about 10 carbon atoms or hydrogen; 
 R 12  is an alkyl group containing from 1 to about 6 carbon atoms or hydrogen; and 
 n is an integer of from 1 to 3; and 
 d. water in an amount of the remainder of the weight of the coating composition 
 wherein the weight of the ureido silane is the sum of the weights of each ureido silane component and the weight percent are based upon the total weight of the coating composition. 
 
     
     
         38 . The metal substrate coated with the detectable coating composition of  claim 21  wherein said composition consists essentially of
 a. at least one ureido silane having the structure: 
 
       
         
           
           
               
               
           
         
         
           wherein R is independently hydrogen or an, alkyl of from 1 to about 4 carbon atoms, or condensate compounds therefrom in the amount of from about 0.01 to about 80 weight percent; 
         
         b. cerium oxide particles in the amount of from about 0.001 to about 36 weight percent; 
         c. water soluble organic dye in an amount of from 0.001 to about 1 weight percent and having the structure of formula (IV): 
       
       
         
           
           
               
               
           
         
       
       wherein:
 G 1  is an organic group having from 1 to about 20 carbon atoms and containing at least one oxygen or nitrogen heteroatom; 
 A is a nitrogen atom or (−) 3 C—R*, where R* is a monovalent group chosen from alkyl, cycloalkyl, alkenyl, aralkyl or aryl group each having up to about 10 carbon atoms; 
 R 6  is an alkyl, a hydroxylalkyl, an alkoxyalkyl, cycloalkyl, aralkyl optionally substituted with a halogen or, alkoxy group, an aryl optionally substituted with a halogen or alkoxy group, a cyanoalkyl, a carbamatoalkyl or a carboalkoxyalkyl group containing up to about 10 carbon atoms, or hydrogen; 
 R 7  is an alkyl, alkoxy, aryl alkylsulfonyl, or arylsulfonyl group containing up to about 10 carbon atoms or hydrogen; 
 R 8  is an alkyl, alkoxy, aryl alkylsulfonyl, arylsulfonyl, or aminosulfonyl group containing up to about 10 carbon atoms or hydrogen; 
 R 9  is an alkyl, alkoxy, aryl alkylsulfonyl, or arylsulfonyl group containing up to about 10 carbon atoms or hydrogen; 
 R 10  is an alkyl, alkoxy, aryl alkylsulfonyl, or arylsulfonyl group containing up to about 10 carbon atoms or hydrogen; 
 R 11  is an alkyl, a hydroxylalkyl, an alkoxyalkyl, cycloalkyl, air aralkyl optionally substituted with a halogen or alkoxy group, an aryl optionally substituted with a halogen or alkoxy group, a cyanoalkyl, a carbamatoalkyl or an alkoxycarbonylalkyl group containing tap to about 10 carbon atoms or hydrogen, 
 R 12  is an alkyl, group containing from 1 to about 6 carbon atoms or hydrogen; and 
 as is a integer of from 1 to 3; 
 or (VII) 
 
       
         
           
           
               
               
           
         
         wherein:
 R 12  is an alkyl group containing from 1 to about 6 carbon atoms or hydrogen; 
 R 23  is hydrogen, an alkyl group of from 1 to about 6 carbon atoms, an aryl group of from 6 to about 10 carbon atoms, an aralkyl group of from 7 to about 12 carbon atoms or an aryl group of from 6 to about 12 carbon atoms substituted with a hydroxycarbonyl group (—C(═O)OH) or substituted with an alkoxycarbonyl group —C(═O)OR 26 , where R 26  is an alkyl group of from 1 to about 4 carbon atoms; 
 R 24  is hydrogen, an alkyl group containing 1 to about 6 carbon atoms, hydroxyl or amino having the structure —NR 27 R 28 , where R 27  and R 28  are each independently a hydrogen or alkyl group of from 1 to about 6 carbon atoms; 
 R 25  is hydrogen, an alkyl group containing 1 to about 6 carbon atoms, hydroxyl or amino having the structure —NR 27 R 28 , where R 27  and R 28  are each independently a hydrogen or alkyl group of from 1 to about 6 carbon atoms; and 
 m is an integer from 1 to 3; 
 
         d. water in an amount of the remainder of the weight of the composition; and fun er consisting essentially of 
         e. stabilizing agent in the amount of about 1 to about 20 weight percent, wherein the weight of the ureido silane is the sum of the weights of each ureido silane component and the percents by weight are based upon the total weight of the composition. 
       
     
     
         39 . The metal substrate coated with the detectable coating composition of  claim 38 , wherein the stabilizing agents is selected from the group consisting, of alcohols, glycols, triols, polyols, glycol ethers, esters, ketones, pyrrolidones, or polyethersilanes and combinations thereof. 
     
     
         40 . The metal substrate coated with the detectable coating composition of  claim 21 , wherein said detectable coating is dried.