Conductive fluoro-resin compositions

Abstract

A conductive fluoro-resin composition of the addition reaction curing type is provided comprising (A) a reactive fluorinated polyether compound comprising fluorinated polyether units and having at least two aliphatic unsaturated hydrocarbon radicals in a molecule, (B) a compound having at least two hydrogen atoms each directly attached to a silicon atom, (C) a platinum group metal catalyst, and (D) silver particles. The composition cures into rubbery parts having improved heat resistance, weather resistance and solvent resistance and optionally forming firm bonds to various substrates.

1. A conductive fluoro-resin composition comprising
 (A) 100 parts by weight of a reactive fluorinated polyether compound comprising fluorinated polyether units and having at least two aliphatic unsaturated hydrocarbon radicals in a molecule,  
 (B) a compound having at least two hydrogen atoms each directly attached to a silicon atom in a sufficient amount to give 0.4 to 10 equivalents of the silicon atom-attached hydrogen atoms relative to the aliphatic unsaturated hydrocarbon radicals in component (A),  
 (C) a sufficient amount of a platinum group metal catalyst to promote reaction between components (A) and (B), and  
 (D) 50 to 2,000 parts by weight of silver particles wherein the silver particles have a NH 4   +  content of no more than about 10 ppm and a SO 2   2−  content of no more than about 5 ppm.  
 
     
     
       2. The conductive fluoro-resin composition of  claim 1 , wherein the reactive fluorinated polyether compound (A) comprises fluorinated polyether units of the following structural formula (1):
   —(Rf—O) q —  (1)  
 
       wherein Rf is a straight or branched chain perfluoroalkylene radical having 1 to 6 carbon atoms, and q is an integer of 1 to 500. 
     
     
       3. The conductive fluoro-resin composition of  claim 1 , wherein the silver particles (D) contain at least 10% by weight of dendrite or flake shaped silver particles based on the loading of the silver particles. 
     
     
       4. The conductive fluoro-resin composition of  claim 1 , wherein the reactive fluorinated polyether compound is of the formula (2): 
                 
 
       wherein X is independently —CH 2 —, —CH 2 O— or —Y—NR—CO— wherein Y is —CH 2 — or 
                 
 
       inclusive of o, m and p-positions, R is hydrogen, methyl, phenyl or allyl, letter p is independently equal to 0 or 1, l is an integer of 2 to 6, m and n are independently integers of 0 to 200. 
     
     
       5. The conductive fluoro-resin composition of  claim 1 , wherein the reactive fluorinated polyether compound has a number average molecular weight of about 400 to about 100,000. 
     
     
       6. The conductive fluoro-resin composition of  claim 1 , wherein the compound having at least two hydrogen atoms each directly attached to a silicon atom, (B), is a low molecular weight organohydrogenpolysiloxane or cyclic organohydrogenpolycyclosiloxane having 2 to 10 silicon atoms. 
     
     
       7. The conductive fluoro-resin composition of  claim 1 , wherein the compound having at least two hydrogen atoms each directly attached to a silicon atom, (B), is a perfluoropolyether or perfluoropolyalkylene compound having SiH radicals at the ends of the backbones thereof. 
     
     
       8. The conductive fluoro-resin composition of  claim 1 , wherein the silver particles are reduced silver particles, electrolytic silver particles or atomized silver particles. 
     
     
       9. The conductive fluoro-resin composition of  claim 1 , wherein the silver particles have a mean particle size of 0.1 to 10 μm. 
     
     
       10. A conductive fluoro-resin composition comprising
 (A) 100 parts by weight of a reactive fluorinated polyether compound comprising fluorinated polyether units and having at least two aliphatic unsaturated hydrocarbon radicals in a molecule,  
 (B) a compound having at least two hydrogen atoms each directly attached to a silicon atom in a sufficient amount to give 0.4 to 10 equivalents of the silicon atom-attached hydrogen atoms relative to the aliphatic unsaturated hydrocarbon radicals in component (A),  
 (C) a sufficient amount of a platinum group metal catalyst to promote reaction between components (A) and (B), and  
 (D) 50 to 2,000 parts by weight of silver particles;  
 
       wherein the silver particles have been surface treated with an organopolysiloxane or fluorinated polyether compound. 
     
     
       11. The conductive fluoro-resin composition of  claim 10 , wherein said silver particles are surface treated with an organopolysiloxane which is a hydrosilylated organopolysiloxane having at least one hydrogen atom directly attached to a silicon atom. 
     
     
       12. The conductive fluoro-resin composition of  claim 10 , wherein said silver particles are surface treated with an organopolysiloxane which contains up to 500 ppm of non-functional low molecular weight organopolysiloxanes having 3 to 10 silicon atoms. 
     
     
       13. The conductive fluoro-resin composition of  claim 10 , wherein the silver particles are surface treated with a fluorinated polyether compound. 
     
     
       14. The conductive fluoro-resin composition of  claim 10 , wherein the silver particles are surface treated with 0.001 to 5% by weight of the organopolysiloxane or fluorinated polyether compound. 
     
     
       15. The conductive fluoro-resin composition of  claim 10 , wherein the reactive fluorinated polyether compound is of the formula (2): 
                 
 
       wherein X is independently —CH 2 —, —CH 2 O— or —Y—NR—CO— wherein Y is —CH 2 — or 
                 
 
       inclusive of o, m and p-positions R is hydrogen, methyl, phenyl or allyl, letter p is independently equal to 0 or 1, l is an integer of 2 to 6, m and n are independently integers of 0 to 200. 
     
     
       16. The conductive fluoro-resin composition of  claim 10 , wherein the reactive fluorinated polyether compound has a number average molecular weight of about 400 to about 100,000. 
     
     
       17. The conductive fluoro-resin composition of  claim 10 , wherein the compound having at least two hydrogen atoms each directly attached to a silicon atom, (B), is a low molecular weight organohydrogenpolysiloxane or cyclic organohydrogenpolycyclosiloxane having 2 to 10 silicon atoms. 
     
     
       18. The conductive fluoro-resin composition of  claim 10 , wherein the compound having at least two hydrogen atoms each directly attached to a silicon atom, (B), is a perfluoropolyether or perfluoropolyalkylene compound having SiH radicals at the ends of the backbones thereof. 
     
     
       19. The conductive fluoro-resin composition of  claim 10 , wherein the silver particles have a NH 4   +  content of no more than about 10 ppm and a SO 2   2−  content of no more than about 5 ppm. 
     
     
       20. The conductive fluoro-resin composition of  claim 10 , wherein the silver particles are reduced silver particles, electrolytic silver particles or atomized silver particles. 
     
     
       21. The conductive fluoro-resin composition of  claim 10 , wherein the silver particles have a mean particle size of 0.1 to 10 μm. 
     
     
       22. A conductive fluoro- resin composition comprising    ( A )    100  parts by weight of a reactive fluorinated polyether compound comprising fluorinated polyether units and having at least two aliphatic unsaturated hydrocarbon radicals in a molecule,      ( B )  a compound having at least two hydrogen atoms each directly attached to a silicon atom in a sufficient amount to give  0 . 4  to  10  equivalents of the silicon atom - attached hydrogen atoms relative to the aliphatic unsaturated hydrocarbon radicals in component  ( A ),    ( C )  a sufficient amount of a platinum group metal catalyst to promote reaction between components  ( A )  and  ( B ) , and      ( D )    50  to  2 , 000  parts by weight of atomized silver particles, wherein the silver particles are not surface treated.     
     
     
       23. The conductive fluoro- resin composition of    claim 22   , wherein the reactive fluorinated polyether compound  ( A )  comprises fluorinated polyether units of the following structural formula  (   1   ):
   —( Rf—O ) q —  (   1   )    
       
         wherein Rf is a straight or branched chain perfluoroalkylene radical having  1  to  6  carbon atoms, and q is an integer of  1  to  500 . 
       
     
     
       24. The conductive fluoro- resin composition of    claim 22   , wherein the silver particles  ( D )  contain at least  10   %  by weight of dendrite or flake shaped silver particles based on the loading of the silver particles.   
     
     
       25. The conductive fluoro- resin composition of    claim 22   , wherein the reactive fluorinated polyether compound is of the formula  (   2   ): 
                   
       
         wherein X is independently —CH 
         2 
         —, —CH 
         2 
         O— or —Y—NR—CO— wherein Y is —CH 
         2 
         — or  
         
           
           
               
               
           
         
       
         inclusive of o, m and p - positions, R is hydrogen, methyl, phenyl or allyl, letter p is independently equal to  0  or  1 , l is an integer of  2  to  6 , and m and n are independently integers of  0  to  200 .   
     
     
       26. The conductive fluoro- resin composition of    claim 22   , wherein the reactive fluorinated polyether compound has a number average molecular weight of about  400  to about  100 , 000 .   
     
     
       27. The conductive fluoro- resin composition of    claim 22   , wherein the compound having at least two hydrogen atoms each directly attached to a silicon atom,  ( B ) , is a low molecular weight organohydrogenpolysiloxane or cyclic organohydrogenpolycyclosiloxane having  2  to  10  silicon atoms.   
     
     
       28. The conductive fluoro- resin composition of    claim 22   , wherein the compound having at least two hydrogen atoms each directly attached to a silicon atom,  ( B ) , is a perfluoro - polyether or perfluoropolyalkylene compound having SiH radicals at the ends of the backbones thereof.   
     
     
       29. The conductive fluoro- resin composition of    claim 22   , wherein the atomized silver particles have a mean particles size of  0 . 1  to  10  μm.   
     
     
       30. The conductive fluoro- resin composition of    claim 22   , wherein the atomized silver particles are prepared by heating silver at or above  1000 ° C. and atomizing the resulting silver melt into water or an inert gas to form the atomized silver particles.