Film-forming material containing phosphorous

Abstract

Film-forming materials include resins and/or crosslinkers having a covalently bonded phosphorous atom, the phosphorous atom having at least one covalently bonded oxygen atom. Film-forming resins containing phosphorous can include epoxy, acrylic, polyurethane, polycarbonate, polysiloxane, polyvinyl, polyether, aminoplast, and polyester resins. A process to produce a film-forming resin includes reacting various polymers to incorporate a pendent group comprising a covalently bonded phosphorous atom. Film-forming resins can be used in methods of producing coating compositions. Coating compositions can be used to coat a substrate, such as a metal substrate, by electrodeposition. Applied coatings containing the film-forming resins can be cured to form crosslinked films on substrates.

1 . A film-forming material comprising:
 a resin, wherein the resin includes
 at least one pendent group comprising a phosphorous atom covalently linked by a carbon-phosphorous bond or a by a phosphoester bond, said phosphorous atom having at least one covalently bonded oxygen atom; and 
 at least one crosslinkable group. 
   
   
   
       2 . A film-forming material of  claim 1 , wherein the resin is an epoxy, acrylic, polyurethane, polycarbonate, polysiloxane, polyvinyl, polyether, aminoplast, or polyester resin. 
   
   
       3 . A film-forming material of  claim 1 , wherein the crosslinkable group is a group reactive with a crosslinker, a self-condensing group, an addition polymerizable group, or a group curable with actinic radiation. 
   
   
       4 . A film-forming material of  claim 1 , wherein the crosslinkable group is an epoxide, hydroxyl, carboxyl, carbamate, or amine group. 
   
   
       5 . A film-forming material of  claim 1 , wherein the pendent group comprises a phosphate, an organophosphate, a phosphonate, an organophosphonate, a phosphinate, or an organophosphinate. 
   
   
       6 . A film-forming material of  claim 1 , wherein the pendent group comprises an organophosphate, an organophosphonate, or an organophosphinate wherein one or two oxygen atoms covalently bonded to the phosphorous atom form ester linkages to alkyl or aryl groups, wherein alkyl groups include from 1 to about 12 carbon atoms and aryl groups include substituted and unsubstituted phenyl and benzyl groups. 
   
   
       7 . A film-forming material of  claim 1 , wherein the pendent group is bonded to the resin via an ester, amine, urethane, or ether linkage. 
   
   
       8 . A film-forming material of  claim 1 , wherein the pendent group further comprises a carboxylic acid group. 
   
   
       9 . A film-forming material of  claim 1 , further comprising a metal or metal compound coordinated by the film-forming material. 
   
   
       10 . A film-forming material of  claim 9 , wherein the metal or metal compound is selected from a group consisting of M, MO, M 2 O 3 , M(OH) n , R x MO, and combinations thereof; wherein, M is a metal selected from the group consisting of Al, Au, Bi, Ce, Cu, Fe, Pb, Sn, Sb, Ti, Y, Zn, and Zr; n is an integer satisfying the valency of M; R is an alkyl or aromatic group; and x is an integer from 1 to 6. 
   
   
       11 . A film-forming material of  claim 9 , wherein the metal or metal compound comprises a metal catalyst selected from a group consisting of dibutyltin oxide, dibutyltin dilaurate, zinc oxide, bismuth oxide, tin oxide, yttrium oxide, copper oxide, and combinations thereof. 
   
   
       12 . A film-forming material of  claim 1 , wherein the resin comprises a structure: 
     
       
         
         
             
             
         
       
       wherein,
 X 1  and X 2  are independently hydrogen, hydroxyl, epoxide, or amine functional monovalent radicals; 
 each R 1 , R 2 , and R 3  is independently an organic divalent radical; 
 each Y 1  is independently an organic trivalent radical having from 1 carbon atom to about 36 carbon atoms; 
 each Z 1  is independently a phosphate, organophosphate, phosphonate, organophosphonate, phosphinate, or organophosphinate monovalent radical; 
 n is an integer from 1 to about 12; 
 m is an integer from 0 to about 12; and 
 p is an integer from 1 to about 12. 
 
     
   
   
       13 . A film-forming material of  claim 12 , wherein each Z 1  is independently an organophosphate, organophosphonate, or organophosphinate monovalent radical, wherein one or two oxygen atoms covalently bonded to the phosphorous atom form ester linkages to alkyl or aryl groups, wherein the alkyl groups include from 1 to about 12 carbons and the aryl groups include substituted and unsubstituted phenyl and benzyl groups. 
   
   
       14 . A film-forming material of  claim 12 , wherein R 1 , R 2 , and R 3  are 2,2-diphenylpropane divalent radicals. 
   
   
       15 . A film-forming material of  claim 12 , wherein the film-forming material is capped with an aminoorganophosphate or aminoorganophosphonate when at least one of X 1  and X 2  is a hydroxyl or epoxide monovalent radical. 
   
   
       16 . A film-forming material comprising a structure: 
     
       
         
         
             
             
         
       
       wherein,
 R 4  is a monovalent radical of a resin having from 2 to 12 monomer units or a monovalent radical comprising the film-forming resin of  claim 1 ; 
 R 5  is a monovalent radical of hydrogen, a resin having from 2 to 12 monomer units, or a radical comprising the film-forming resin of  claim 1 ; and 
 Z 2  is a monovalent radical comprising a covalently bonded phosphorous atom covalently linked by a carbon-phosphorous bond or a by a phosphoester bond, said phosphorous atom having at least one covalently bonded oxygen atom. 
 
     
   
   
       17 . A film-forming material of  claim 16 , wherein Z 2  is a monovalent radical comprising a phosphate, organophosphate, phosphonate, organophosphonate, phosphinate, or organophosphinate. 
   
   
       18 . A film-forming material of  claim 16 , wherein Z 2  is a monovalent radical comprising: 
     
       
         
         
             
             
         
       
       wherein R 6  and R 7  are independently hydrogen, an alkyl group including from 1 to about 12 carbons, or an aryl group including substituted and unsubstituted phenyl and benzyl groups; and n is an integer from 1 to about 12. 
     
   
   
       19 . A film-forming material of  claim 16 , wherein Z 2  is a monovalent radical comprising an organophosphate, organophosphonate, or organophosphinate wherein one or two oxygen atoms covalently bonded to the phosphorous atom form ester linkages to alkyl or aryl groups, wherein alkyl groups include from 1 to about 12 carbons and aryl groups include substituted and unsubstituted phenyl and benzyl groups.