Organoantimony compound, process for preparing same, living radical polymerization initiator, process for producing polymer with use of same, and the polymer

Abstract

An organoantimony compound represented by the formula (1), processes for producing polymers with use of the compound, and polymers wherein R 1 and R 2 are C 1 -C 8 alkyl, aryl, substituted aryl or an aromatic heterocyclic group, R 3 and R 4 are each a hydrogen atom or C 1 -C 8 alkyl, and R 5 is aryl, substituted aryl, an aromatic heterocyclic group, oxycarbonyl or cyano.

1 . A living radical polymer which is obtainable by subjecting a vinyl monomer to polymerization with use of a living radical polymerization initiator of the formula (2) 
       
         
           
           
               
               
           
         
       
       wherein R 1  and R 2  are C 1 -C 8  alkyl, aryl, substituted aryl or an aromatic heterocyclic group, R 3  and R 4  are each a hydrogen atom or C 1 -C 8  alkyl, and R 6  is aryl, substituted aryl, an aromatic heterocyclic group, acyl, oxycarbonyl or cyano. 
     
     
         2 . A living radical polymer which is obtainable by subjecting a vinyl monomer to polymerization with use of a living radical polymerization initiator of the formula (2) 
       
         
           
           
               
               
           
         
       
       wherein R 1  and R 2  are C 1 -C 8  alkyl, aryl, substituted aryl or an aromatic heterocyclic group, R 3  and R 4  are each a hydrogen atom or C 1 -C 8  alkyl, and R 6  is aryl, substituted aryl, an aromatic heterocyclic group, acyl, oxycarbonyl or cyano and an azo type polymerization inhibitor. 
     
     
         3 . A random copolymer which is obtainable by subjecting at least two vinyl monomers to polymerization with use of a living radical polymerization initiator of the formula (2) 
       
         
           
           
               
               
           
         
       
       wherein R 1  and R 2  are C 1 -C 8  alkyl, aryl, substituted aryl or an aromatic heterocyclic group, R 3  and R 4  are each a hydrogen atom or C 1 -C 8  alkyl, and R 6  is aryl, substituted aryl, an aromatic heterocyclic group, acyl, oxycarbonyl or cyano. 
     
     
         4 . A random copolymer which is obtainable by subjecting at least two vinyl monomers to polymerization with use of a living radical polymerization initiator of the formula (2) 
       
         
           
           
               
               
           
         
       
       wherein R 1  and R 2  are C 1 -C 8  alkyl, aryl, substituted aryl or an aromatic heterocyclic group, R 3  and R 4  are each a hydrogen atom or C 1 -C 8  alkyl, and R 6  is aryl, substituted aryl, an aromatic heterocyclic group, acyl, oxycarbonyl or cyano and an azo type polymerization inhibitor. 
     
     
         5 . A block copolymer which is obtainable by subjecting a vinyl monomer to polymerization with use of a macro living radical polymerization initiator obtainable by subjecting a vinyl monomer to polymerization with the use of a living radical polymerization initiator of formula (2) 
       
         
           
           
               
               
           
         
       
       wherein R 1  and R 2  are C 1 -C 8  alkyl, aryl, substituted aryl or an aromatic heterocyclic group, R 3  and R 4  are each a hydrogen atom or C 1 -C 8  alkyl, and R 6  is aryl, substituted aryl, an aromatic heterocyclic group, acyl, oxycarbonyl or cyano. 
     
     
         6 . A block copolymer which is obtainable by subjecting a vinyl monomer to polymerization with use of a macro living radical polymerization initiator obtainable by subjecting a vinyl monomer to polymerization with the use of a living radical polymerization initiator of formula (2) 
       
         
           
           
               
               
           
         
       
       wherein R 1  and R 2  are C 1 -C 8  alkyl, aryl, substituted aryl or an aromatic heterocyclic group, R 3  and R 4  are each a hydrogen atom or C 1 -C 8  alkyl, and R 6  is aryl, substituted aryl, an aromatic heterocyclic group, acyl, oxycarbonyl or cyano and azo type polymerization initiator. 
     
     
         7 . A random copolymer which is obtainable by subjecting at least two vinyl monomers to polymerization with use of a mixture of a living radical polymerization initiator of the formula (2) 
       
         
           
           
               
               
           
         
       
       wherein R 1  and R 2  are C 1 -C 8  alkyl, aryl, substituted aryl or an aromatic heterocyclic group, R 3  and R 4  are each a hydrogen atom or C 1 -C 8  alkyl, and R 6  is aryl, substituted aryl, an aromatic heterocyclic group, acyl, oxycarbonyl or cyano and at least one compound selected from ditelluride compound, distibine compound and dibismuthine compound. 
     
     
         8 . A random copolymer which is obtainable by subjecting at least two vinyl monomers to polymerization with use of a mixture of a living radical polymerization initiator of the formula (2) 
       
         
           
           
               
               
           
         
       
       wherein R 1  and R 2  are C 1 -C 8  alkyl, aryl, substituted aryl or an aromatic heterocyclic group, R 3  and R 4  are each a hydrogen atom or C 1 -C 8  alkyl, and R 6  is aryl, substituted aryl, an aromatic heterocyclic group, acyl, oxycarbonyl or cyano, an azo type polymerization initiator, and at least one compound selected from ditelluride compound, distibine compound and dibismuthine compound. 
     
     
         9 . A block copolymer which is obtainable by subjecting a vinyl monomer to polymerization with use of a macro living radical polymerization initiator obtainable by subjecting a vinyl monomer to polymerization with use of a mixture of a living radical polymerization initiator of the formula (2) 
       
         
           
           
               
               
           
         
       
       wherein R 1  and R 2  are C 1 -C 8  alkyl, aryl, substituted aryl or an aromatic heterocyclic group, R 3  and R 4  are each a hydrogen atom or C 1 -C 8  alkyl, and R 6  is aryl, substituted aryl, an aromatic heterocyclic group, acyl, oxycarbonyl or cyano, and at least one compound selected from ditelluride compound, distibine compound and dibismuthine compound. 
     
     
         10 . A block copolymer which is obtainable by subjecting a vinyl monomer to polymerization with use of a macro living radical polymerization initiator obtainable by subjecting a vinyl monomer to polymerization with use of a mixture of a living radical polymerization initiator of the formula (2) 
       
         
           
           
               
               
           
         
       
       wherein R 1  and R 2  are C 1 -C 8  alkyl, aryl, substituted aryl or an aromatic heterocyclic group, R 3  and R 4  are each a hydrogen atom or C 1 -C 8  alkyl, and R 6  is aryl, substituted aryl, an aromatic heterocyclic group, acyl, oxycarbonyl or cyano, an azo type polymerization initiator, and at least one compound selected from ditelluride compound, distibine compound and dibismuthine compound. 
     
     
         11 . A resin containing an acid-dissociable group which is obtainable by a process wherein a vinyl monomer is polymerized with use of one of the following (a) to (d),
 (a) a living radical polymerization initiator of the formula (2)   
       
         
           
           
               
               
           
         
       
       wherein R 1  and R 2  are C 1 -C 8  alkyl, aryl, substituted aryl or an aromatic heterocyclic group, R 3  and R 4  are each a hydrogen atom or C 1 -C 8  alkyl, and R 6  is aryl, substituted aryl, an aromatic heterocyclic group, acyl, oxycarbonyl or cyano,
 (b) a mixture of a living radical polymerization initiator of the formula (2), and an azo type polymerization initiator, 
 (c) a mixture of a living radical polymerization initiator of the formula (2), and at least one compound selected from ditelluride compound, distibine compound and dibismuthine compound, and 
 (d) a mixture of a living radical polymerization initiator of the formula (2), an azo type polymerization initiator, and at least one compound selected from ditelluride compound, distibine compound and dibismuthine compound. 
 
     
     
         12 . A radiation-sensitive resin composition comprising a resin containing an acid-dissociable group, and a radiation-sensitive acid producing agent, the resin containing an acid-dissociable group being a resin obtained by subjecting a vinyl monomer to polymerization with use of one of the following (a) to (d),
 (a) a living radical polymerization initiator of the formula (2)   
       
         
           
           
               
               
           
         
       
       wherein R 1  and R 2  are C 1 -C 8  alkyl, aryl, substituted aryl or an aromatic heterocyclic group, R 3  and R 4  are each a hydrogen atom or C 1 -C 8  alkyl, and R 6  is aryl, substituted aryl, an aromatic heterocyclic group, acyl, oxycarbonyl or cyano,
 (b) a mixture of a living radical polymerization initiator of the formula (2), and an azo type polymerization initiator, 
 (c) a mixture of a living radical polymerization initiator of the formula (2), and at least one compound selected from ditelluride compound, distibine compound and dibismuthine compound, and 
 (d) a mixture of a living radical polymerization initiator of the formula (2), an azo type polymerization initiator, and at least one compound selected from ditelluride compound, distibine compound and dibismuthine compound.