Method of making coated metal articles

Abstract

A method of making a coated metal article comprises (a) forming a hardcoat layer on at least a portion of a surface of a metal or metalized substrate by physical vapor deposition; (b) forming a tie layer comprising silicon, oxygen, and hydrogen on at least a portion of the surface of the hardcoat layer by plasma deposition; and (c) applying an at least partially fluorinated composition comprising at least one silane group to at least a portion of the surface of the tie layer.

1 . A method of making a coated metal article comprising:
 (a) forming a hardcoat layer on at least a portion of a surface of a metal or metalized substrate by physical vapor deposition;   (b) forming a tie layer comprising silicon, oxygen, and hydrogen on at least a portion of the surface of the hardcoat layer by plasma deposition;   (c) applying an at least partially fluorinated composition comprising at least one silane group to at least a portion of the surface of the tie layer.   
     
     
         2 . The method of  claim 1  wherein the hardcoat layer is formed by cathodic arc, sputtering, thermal evaporation, or e-beam evaporation. 
     
     
         3 . The method of  claim 1  wherein the hardcoat layer comprises a metal nitride or a mixed metal nitride. 
     
     
         4 . The method of  claim 3  wherein the hardcoat layer comprises at least one of titanium nitride, zirconium nitride, aluminum nitride, or titanium aluminum nitride. 
     
     
         5 - 7 . (canceled) 
     
     
         8 . The method of  claim 1  wherein forming the tie layer comprises ionizing a gas comprising at least one of an organosilicon or a silane compound. 
     
     
         9 . The method of  claim 1  wherein the tie layer further comprises at least one of carbon, diamond-like glass, silicon oxycarbide, silicon carbide, silicon oxide, silicon dioxide, silicon nitride, or silicon oxynitride. 
     
     
         10 - 15 . (canceled) 
     
     
         16 . The method of  claim 1  wherein the at least partially fluorinated composition comprising at least one silane group is a quat silane of Formula V: 
       
         
           
           
               
               
           
         
       
       wherein b and c is each independently an integer of 1 to 3; R f  is a perfluorinated ether group; A is a linking group having the formula —C d H 2d ZC g H 2g —, wherein d and g are independently integers from 0 to 10 and Z is selected from the group consisting of a covalent bond, a carbonyl group, a sulfonyl group, a carboxamido group, a sulfonamido group, an iminocarbonyl group, an iminosulfonyl group, an oxycarbonyl group, a urea group, a urethane group, a carbonate group, and a carbonyloxy group; Y is a bridging group having 1 to 10 carbon atoms, a valency of 2 to 6, and comprising at least one of an alkylene group or an arylene group; Q is a connecting group having 1 to 10 carbon atoms, a valency of 2 to 6, and comprising at least one of an alkylene group or an arylene group; R 1  and R 2  are independently selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, and an aralkyl group; each R 3  is independently selected from the group consisting of hydroxy groups, alkoxy groups, acyl groups, acyloxy groups, halo groups, and polyether groups; and X −  is a counter ion selected from the group consisting of inorganic anions, organic anions, and combinations thereof. 
     
     
         17 . The method of  claim 1  wherein the at least partially fluorinated composition comprising at least one silane group is a quat silane of Formula VI: 
       
         
           
           
               
               
           
         
       
       wherein R f  has the structure —CF(CF 3 )(OCF 2 CF(CF 3 )) m OCF 2 CF 2 CF 2 CF 2 O(CF(CF 3 )CF 2 O) n CF(CF 3 )—, wherein m is an integer of 1 to 12 and n is an integer of 2 to 10; c is an integer from about 1 to about 3; A is a linking group having the formula —C d H 2d ZC g H 2g —, wherein d and g are independently integers from about 0 to about 10 and Z is selected from the group consisting of a covalent bond, a carbonyl group, a sulfonyl group, a carboxamido group, a sulfonamido group, an iminocarbonyl group, an iminosulfonyl group, an oxycarbonyl group, a urea group, a urethane group, a carbonate group, and a carbonyloxy group; Y is a bridging group comprising an alkylene group having about 1 to about 6 carbon atoms; Q is a connecting group comprising an alkylene group having about 1 to about 6 carbon atoms; R 1  and R 2  are independently alkyl groups having about 1 to about 4 carbon atoms; each R 3  is independently selected from the group consisting of hydroxy groups, methoxy groups, ethoxy groups, acetoxy groups, chloro groups, and polyether groups; and X −  is a counter ion selected from the group consisting of a halide, sulfate, phosphate, an alkyl sulfonate, an aryl sulfonate, an alkyl phosphonate, an aryl phosphonate, a fluorinated alkyl sulfonate, a fluorinated aryl sulfonate, a fluorinated alkyl sulfonimide, a fluorinated alkyl methide, and combinations thereof. 
     
     
         18 . The method of  claim 1  wherein the at least partially fluorinated composition comprising at least one silane group comprises hexafluoropropyleneoxide. 
     
     
         19 . The method of  claim 1  wherein the at least partially fluorinated composition comprising at least one silane group comprises a composition comprising:
 (a) a first polyfluoropolyether silane of the Formula VIIa:
   CF 3 CF 2 CF 2 O(CF(CF 3 )CF 2 O) p CF(CF 3 )—C(O)NH(CH 2 ) 3 Si(Y) 3   VIIa
 
 
 
       wherein each Y is independently a hydrolyzable group and wherein p is 3 to 50; and
 (b) a second polyfluoropolyether silane of the Formula IIXa:
   (Y′) 3 Si(CH 2 ) 3 NHC(O)—CF 2 O(CF 2 O) m (C 2 F 4 O) q CF 2 —C(O)NH(CH 2 ) 3 Si(Y′) 3   IIXa
 
 
 
       wherein each Y′ is independently a hydrolyzable group and wherein m is 1 to 50 and q is 3 to 40. 
     
     
         20 . The method of  claim 1  wherein the at least partially fluorinated composition comprising at least one silane group comprises a composition comprising:
 (a) a first polyfluoropolyether silane entity of the Formula VIIb:
   CF 3 CF 2 CF 2 O(CF(CF 3 )CF 2 O) p CF(CF 3 )—C(O)NH(CH 2 ) 3 Si(O—) 3   VIIb
 
 
 
       wherein p is 3 to 50; and
 (b) a second polyfluoropolyether silane entity of the Formula IIXb:
   (—O) 3 Si(CH 2 ) 3 NHC(O)—CF 2 O(CF 2 O) m (C 2 F 4 O) q CF 2 —C(O)NH(CH 2 ) 3 Si(O—) 3   IIXb
 
 
 
       wherein m is 1 to 50 and q is 3 to 40. 
     
     
         21 . The method of  claim 1  wherein the hardcoat layer is formed using cathodic arc deposition, the tie layer is formed using ion-assisted plasma deposition, and the at least partially fluorinated composition is applied by thermal evaporation and condensation of the composition. 
     
     
         22 . The method of  claim 21  wherein the hardcoat layer is formed, the tie layer is formed, and the at least partially fluorinated composition is applied within a single deposition chamber. 
     
     
         23 . The method of  claim 1  wherein the metal or metalized substrate comprises stainless steel. 
     
     
         24 . A coated metal article comprising:
 (a) a metal or metalized substrate;   (b) a physical vapor deposited hardcoat layer disposed on at least a portion of the metal or metalized substrate;   (c) a plasma deposited tie layer comprising silicon, oxygen, and hydrogen disposed on at least a portion of the surface of the hardcoat layer; and   (d) an at least partially fluorinated composition comprising at least one silane group disposed on at least a portion of the surface of the tie layer.   
     
     
         25 . The coated metal article of  claim 24  wherein the article is a cutting tool or element. 
     
     
         26 . The coated metal article of  claim 24  wherein the article is a kitchen or bathroom fixture or appliance. 
     
     
         27 . The coated metal article of  claim 24  wherein the hardcoat layer comprises a metal nitride or a mixed metal nitride. 
     
     
         28 . The coated metal article of  claim 24  wherein the tie layer further comprises carbon. 
     
     
         29 . The coated metal article of  claim 24  wherein the at least partially fluorinated composition comprising at least one silane group comprises hexafluoropropyleneoxide.