Polyoxyalkylene ammonium salts and their use as antistatic agents

Abstract

The present invention provides polyoxyalkylene ammonium imide or methide salts and their use as antistatic agents. Another embodiment provides articles comprising these salts, and processes for making and using these salts.

What is claimed is:  
     
         1 . An antistatic agent consisting of: 
 (a) at least one anion represented by one of the following formulae:                           wherein: 
 each R f  is independently a fluorinated alkyl or aryl group that may be cyclic or acyclic, saturated or unsaturated, and may optionally contain catenated or terminal heteroatoms  
 selected from the group consisting of N, O, and S,  
 Q is independently an SO 2  or a CO linking group, and  
 X is selected from the group consisting of QR f , CN, halogen, H, alkyl, aryl, Q-alkyl, and  
 Q-aryl;  
 where any two contiguous R f  groups may be linked to form a ring; and  
   (b) at least one cation having at least one polyoxyalkylene moiety bonded to at least one cationic nitrogen center.    
     
     
         2 . The antistatic agent according to  claim 1 , wherein in formula (A), X is QR f  and both Qs are SO 2  linking groups.  
     
     
         3 . The antistatic agent according to  claim 1 , wherein the R f  groups are perfluoroalkyl groups.  
     
     
         4 . The antistatic agent according to  claim 1 , wherein formula (A) is a carbonylsulfonyl imide.  
     
     
         5 . The antistatic agent according to  claim 1 , wherein formula (A) is bis(perfluorobutanesulfonyl) imide.  
     
     
         6 . The antistatic agent according to  claim 1 , wherein the anion is selected from the group consisting of:  
       
         
           
           
               
               
           
         
       
     
     
         7 . The antistatic agent according to  claim 1 , wherein in formula (B) X is QR f  and all Q's are SO 2  linking groups.  
     
     
         8 . The antistatic agent according to  claim 1 , wherein formula (B) is a tris(perfluoroalkanesulfonyl) methide.  
     
     
         9 . The antistatic agent according to  claim 1 , wherein said cation is a mono-ammonium, di-ammonium, or tri-ammonium compound.  
     
     
         10 . The antistatic agent according to  claim 1 , wherein said cation is selected from the group consisting of:  
       
         
           
           
               
               
           
         
       
       wherein R is an alkoxy group that may be substituted, R 1  is a hydrogen atom or an alkyl group, n is an integer of 3 to 50, b is an integer of 5 to 150, a and c, the same or different, each is an integer from 0 to 5, such that a+c is an integer from 2 to 5, A is a CH≡, CH 3 C≡, CH 3 CH 2 C≡, or  
       
         
           
           
               
               
           
         
       
       group, x, y and z, equal or different, are integers of 1 to 30 such that the sum of x+y+z≧5, POA is either a homopolymer or a copolymer that is random, blocked, or alternating, and POA comprises 2 to 50 units represented by the formula ((CH 2 ) m CH(R 4 )O) where each unit independently has m and R 4 , 
 where m is an integer from 1 to 4,  
 R 4  is independently hydrogen or a lower alkyl group,  
 R 2  is independently an alkyl, an alicyclic, an aryl, an alkalicyclic, an arylalicyclic, or an alicyclicaryl group that optionally contains one or more heteroatoms,  
 R 3  is independently hydrogen, an alkyl, an alicyclic, an aryl, an alkalicyclic, an arylalicyclic, or an alicyclicaryl group that optionally contains one or more heteroatoms, and d is an integer from 1 to 4.  
 
     
     
         11 . The antistatic agent according to  claim 10 , wherein said R is selected from the group consisting of: methoxy, ethoxy, propoxy, and 2-methoxy-ethoxy.  
     
     
         12 . The antistatic agent according to  claim 1 , wherein said cation is derived from an amine selected from the group consisting of:  
       
         
           
           
               
               
           
         
       
       wherein b is ˜8.5 and a+c is ˜2.5  
       
         
           
           
               
               
           
         
       
       wherein b is ˜15.5 and a+c is ˜2.5  
       
         
           
           
               
               
           
         
       
       wherein x+y+z˜5−6  
       
         
           
           
               
               
           
         
       
       wherein x+y+z˜30 and  
       
         
           
           
               
               
           
         
       
     
     
         13 . The antistatic agent according to  claim 1 , wherein said antistatic agent is selected from the group consisting of: 
 C 12 H 25 N + [CH 3 ][(CH 2 CH 2 O) m H][(CH 2 CH 2 O) n H]  − N(SO 2 C 4 F 9 ) 2 ; (m+n=15),    C 18 H 37 N + [CH 3 ][(CH 2 CH 2 O) m H][(CH 2 CH 2 O) n H]  − N(SO 2 C 4 F 9 ) 2 ; (m+n=15), C 12 H 25 N + [CH 3 ][CH 2 CH 2 O) m H][(CH 2 CH 2 O) n H]  − N(SO 2 C 4 F 9 )(SO 2 C 8 H 17 ); (m+n=5),                          where m+n=15                          where m+n=15                          where a+c˜2.5                          where a+c˜2.5                          where a+c2.5                          where x+y+z˜5−6                         where x+y+z5−6                          where x+y+z˜5−6, and                          where x+y+z5−6.    
     
     
         14 . An article comprising an insulating material and the antistatic agent according to  claim 1 .  
     
     
         15 . The article of  claim 14 , wherein said article is photographic film, x-ray film, x-ray screen, fabric, fiber, electronic component, electronic packaging, compact disc, molded object, or blown object.  
     
     
         16 . An article comprising a insulating material coated with an antistatic agent consisting of: 
 (a) at least one anion represented by one of the following formulae:                           wherein: 
 each R f  is independently a fluorinated alkyl or aryl group that may be cyclic or acyclic, saturated or unsaturated, and may optionally contain catenated or terminal heteroatoms selected from the group consisting of N, O, and S,  
 Q is independently an SO 2  or a CO linking group, and  
 X is selected from the group consisting of QR f , CN, halogen, H, alkyl, aryl, Q-alkyl, and  
 Q-aryl;  
 where any two contiguous R f  groups may be linked to form a ring; and  
   (b) at least one cation having at least one polyoxyalkylene moiety bonded to at least one cationic nitrogen center.    
     
     
         17 . The article of  claim 16 , wherein said article is a photographic film, x-ray film, x-ray screen, fabric, fiber, electronic component, electronic packaging, compact disc, molded object, or blown object.  
     
     
         18 . The article of  claim 16 , wherein said insulating material comprises a material that is synthetic.  
     
     
         19 . The article of  claim 18 , wherein said synthetic material is selected from the group consisting of poly(vinyl chloride), polyethylenes (high density, low density, very low density), polypropylene, polybutylene, polystyrene, polyesters, polyamides, polycarbonates, polyoxymethylenes, polyacrylates and polymethacrylates, modified polystyrenes, high-impact polystyrenes, fluoroplastics, poly(phenylene oxide)-polystyrene and polycarbonate-ABS, liquid crystalline polymers (LCPs), polyetherketone (PEK), polysulfones, polyimides, polyetherimides, alkyd resins, phenolic resins, amino resins, epoxy resins, unsaturated polyesters, polyurethanes, allylics, fluoroelastomers, and polyacrylates.  
     
     
         20 . The article of  claim 16 , wherein said insulating material comprises a material that is naturally occurring.  
     
     
         21 . The article of  claim 20 , wherein said naturally occurring material is silk, wool, leather, cellulosic, or proteinaceous.  
     
     
         22 . A light sensitive photographic material comprising: 
 (a) an antistatic agent consisting of: 
 (i) at least one anion represented by one of the following formulae:  
                     
  wherein: 
 each R f  is independently a fluorinated alkyl or aryl group that may be cyclic or acyclic, saturated or unsaturated, and may optionally contain catenated or terminal heteroatoms selected from the group consisting of N, O, and S,  
 Q is independently an SO 2  or a CO linking group, and  
 X is selected from the group consisting of QR f , CN, halogen, H, alkyl, aryl, Q-alkyl, and  
 Q-aryl;  
 where any two contiguous R f  groups may be linked to form a ring; and  
 
 (ii) at least one cation having at least one polyoxyalkylene moiety bonded to at least one cationic nitrogen center.  
   (b) an insulating material;    (c) a silver halide emulsion dispersed in a hydrophilic colloidal binder; and    (d) optionally at least one protective layer for said emulsion.    
     
     
         23 . An antistatic composition comprising 
 (a) at least one antistatic agent consisting of 
 (i) at least one anion represented by one of the following formulae:  
                     
  wherein: 
 each R f  is independently a fluorinated alkyl or aryl group that may be cyclic or acyclic, saturated or unsaturated, and may optionally contain catenated or terminal heteroatoms selected from the group consisting of N, O, and S,  
 Q is independently an SO 2  or a CO linking group, and  
 X is selected from the group consisting of QR f , CN, halogen, H, alkyl, aryl, Q-alkyl, and  
 Q-aryl;  
 where any two contiguous R f  groups may be linked to form a ring; and  
 
 (ii) at least one cation having at least one polyoxyalkylene moiety bonded to at least one cationic nitrogen center; and  
   (b) at least one insulating material.    
     
     
         24 . The antistatic composition according to  claim 23 , wherein said composition is prepared by forming a blend of components (a) and (b).  
     
     
         25 . The antistatic composition according to  claim 24 , wherein said blend is a melt blend.  
     
     
         26 . The antistatic composition according to  claim 23 , wherein said insulating materials is selected from the group consisting of thermoplastic polymers and thermoset polymers.  
     
     
         27 . The antistatic composition according to  claim 26 , wherein said insulating material is a thermoplastic polymer.  
     
     
         28 . A fiber comprising the antistatic agent of  claim 1 .  
     
     
         29 . A fabric comprising the antistatic agent of  claim 1 .  
     
     
         30 . A film comprising the antistatic agent of  claim 1 .  
     
     
         31 . A molded or blown object comprising the antistatic agent of  claim 1 .  
     
     
         32 . A coating comprising the antistatic agent of  claim 1 .  
     
     
         33 . A process for preparing an antistatic composition comprising the steps of: 
 (a) combining 
 (i) at least one antistatic agent consisting of 
 (I) at least one anion represented by one of the following formulae:  
                     
  wherein: 
 each R f  is independently a fluorinated alkyl or aryl group that may be cyclic or acyclic, saturated or unsaturated, and may optionally contain catenated or terminal heteroatoms selected from the group consisting of N, O, and S,  
 Q is independently an SO 2  or a CO linking group, and  
 X is selected from the group consisting of QR f , CN, halogen, H, alkyl, aryl, Q-alkyl, and  
 Q-aryl;  
 where any two contiguous R f  groups may be linked to form a ring; and  
 
 (II) at least one cation having at least one polyoxyalkylene moiety bonded to at least one cationic nitrogen center; and  
 
 (ii) at least one insulating material; and  
   (b) melt processing the resulting combination.    
     
     
         34 . A process for preparing an antistatic composition comprising the steps of 
 (a) combining 
 (i) at least one antistatic agent consisting of 
 (I) at least one anion represented by one of the following formulae:  
                     
  wherein: 
 each R f  is independently a fluorinated alkyl or aryl group that may be cyclic or acyclic, saturated or unsaturated, and may optionally contain catenated or terminal heteroatoms selected from the group consisting of N, O, and S,  
 Q is independently an SO 2  or a CO linking group, and  
 X is selected from the group consisting of QR f , CN, halogen, H, alkyl, aryl, Q-alkyl, and  
 Q-aryl;  
 where any two contiguous R f  groups may be linked to form a ring; and  
 
 (II) at least one cation having at least one polyoxyalkylene moiety bonded to at least one cationic nitrogen center;  
 
 (ii) at least one insulating material, and  
 (iii) at least one thermosetting polymer, ceramer, or the reactive precursors of said polymer or ceramer; and  
   (b) allowing the resulting combination to cure.    
     
     
         35 . A process for preparing an antistatic composition comprising the step of applying a topical treatment composition to at least a portion of at least one surface of at least one insulating material, said topical treatment composition comprising at least one antistatic agent consisting of 
 (a) at least one anion represented by one of the following formulae:                           wherein: 
 each R f  is independently a fluorinated alkyl or aryl group that may be cyclic or acyclic, saturated or unsaturated, and may optionally contain catenated or terminal heteroatoms selected from the group consisting of N, O, and S,  
 Q is independently an SO 2  or a CO linking group, and  
 X is selected from the group consisting of QR f , CN, halogen, H, alkyl, aryl, Q-alkyl, and  
 Q-aryl;  
 where any two contiguous R f  groups may be linked to form a ring; and  
   (b) at least one cation having at least one polyoxyalkylene moiety bonded to at least one cationic nitrogen center.    
     
     
         36 . A process for preparing an antistatic composition comprising the steps of 
 (a) dissolving 
 (i) at least one antistatic agent of  claim 1 , and  
 (ii) at least one insulating material in at least one solvent;  
   (b) casting or coating the resulting solution on at least one substrate; and    (c) allowing evaporation of said solvent.    
     
     
         37 . A process for preparing an antistatic composition comprising the steps of 
 (a) combining 
 (i) at least one antistatic agent of  claim 1 , and  
 (ii) at least one monomer; and  
   (b) allowing polymerization of the monomer to occur.