Curable fluorine-containing polymer, curable resin composition prepared from same and antireflection film

Abstract

A curable fluorine-containing polymer having a number average molecular weight of from 500 to 1,000,000 and is represented by the formula (1): -(A)-(M)- in which the structural unit M is a structural unit derived from a fluorine-containing ethylenic monomer and represented by the formula (M): [—(CX 1 X 2 —CX 3 )—]—(CX 4 CX 5 ) a —(C═O) b (O) c —Rf, wherein X 1 and X 2 are the same or different and each is H or F; X 3 is H, F, CH 3 or CF 3 ; X 4 and X 5 are the same or different and each is H, F or CF 3 ; Rf is an organic group as defined herein; a is 0 or an integer of from 1 to 3; b and c are the same or different and each is 0 or 1, and the structural unit A is derived from a monomer copolymerizable with the fluorine-containing ethylenic monomer from which M is derived.

1 . A curable fluorine-containing polymer which has a number average molecular weight of from 500 to 1,000,000 and is represented by the formula (1):
   MA  (1)   in which the structural unit M is a structural unit derived from fluorine-containing ethylenic monomer and represented by the formula (M):   
     
       
         
         
             
             
         
       
       wherein X 1  and X 2  are the same or different and each is H or F; X 3  is H, F, CH 3  or CF 3 ; X 4  and X 5  are the same or different and each is H, F or CF 3 ; Rf is an organic group in which 1 to 3 of Y 1  (Y 1  is a monovalent organic group having 2 to 10 carbon atoms and an ethylenic carbon-carbon double bond at its end) are bonded to a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having 2 to 100 carbon atoms and ether bond; a is 0 or an integer of from 1 to 3; b and c are the same or different and each is 0 or 1, 
       the structural unit A is a structural unit derived from monomer copolymerizable with the fluorine-containing ethylenic monomer represented by the formula (M), 
       said polymer comprises from 0.1 to 100% by mole of the structural unit M and from 0 to 99.9% by mole of the structural unit A. 
     
   
   
       2 . A curable fluorine-containing polymer which has a number average molecular weight of from 500 to 1,000,000 and is represented by the formula (1-1):
   MA1A2  (1-1)   in which the structural unit M is the same structural unit as said formula (M),   the structural unit A1 is a structural unit represented by the formula (A1):   
     
       
         
         
             
             
         
       
       wherein X 11 , X 12  and X 13  are the same or different and each is H or F; X 14  is H, F or CF 3 ; h is 0, 1 or 2; i is 0 or 1; Rf 4  is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and ether bond; Z 1  is selected from —OH, —CH 2 OH, —COOH, carboxylic acid derivative, —SO 3 H, sulfonic acid derivative, epoxy group and cyano group, 
       the structural unit A2 is a structural unit represented by the formula (A2): 
     
     
       
         
         
             
             
         
       
       wherein X 15 , X 16  and X 18  are H or F; X 17  is H, F or CF 3 ; h1, i1 and j are 0 or 1; Z 2  is H, F or Cl; Rf 5  is a fluorine-containing alkylene group having 1 to 20 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and ether bond, 
       said polymer comprises from 0.1 to 90% by mole of the structural unit M, from 0 to 99.9% by mole of the structural unit A1 and from 0 to 99.9% by mole of the structural unit A2 and contains from 10 to 99.9% by mole of A1+A2. 
     
   
   
       3 . The curable fluorine-containing polymer of  claim 1 , wherein at least one Y 1  is bonded to an end of Rf. 
   
   
       4 . The curable fluorine-containing polymer of  claim 1 , wherein in the formula (1) or (1-1), the structural unit M is a structural unit M1 derived from fluorine-containing ethylenic monomer and represented by the formula (M1): 
     
       
         
         
             
             
         
       
       wherein X 1  and X 2  are the same or different and each is H or F; X 3  is H, F, CH 3  or CF 3 ; X 4  and X 5  are the same or different and each is H, F or CF 3 ; Rf is an organic group in which 1 to 3 of Y 1  (Y 1  is a monovalent organic group having 2 to 10 carbon atoms and an ethylenic carbon-carbon double bond at its end) are bonded to a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having 2 to 100 carbon atoms and ether bond; a is 0 or an integer of from 1 to 3; c is 0 or 1. 
     
   
   
       5 . The curable fluorine-containing polymer of  claim 1 , wherein in the formula (1) or (1-1), the structural unit M is a structural unit M2 derived from fluorine-containing ethylenic monomer and represented by the formula (M2): 
     
       
         
         
             
             
         
       
       wherein Rf is an organic group in which 1 to 3 of Y 1  (Y′ is a monovalent organic group having 2 to 10 carbon atoms and an ethylenic carbon-carbon double bond at its end) are bonded to a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having 2 to 100 carbon atoms and ether bond. 
     
   
   
       6 . The curable fluorine-containing polymer of  claim 1 , wherein in the formula (1) or (1-1), the structural unit M is a structural unit M3 derived from fluorine-containing ethylenic monomer and represented by the formula (M3): 
     
       
         
         
             
             
         
       
       wherein Rf is an organic group in which 1 to 3 of Y 1  (Y 1  is a monovalent organic group having 2 to 10 carbon atoms and an ethylenic carbon-carbon double bond at its end) are bonded to a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having 2 to 100 carbon atoms and ether bond. 
     
   
   
       7 . The curable fluorine-containing polymer of  claim 1 , wherein Y 1  is an organic group represented by the formula:
   O d C═O) e —Y 2      wherein Y 2  is an alkenyl group or fluorine-containing alkenyl group having 2 to 5 carbon atoms and an ethylenic carbon-carbon double bond at an end thereof; d and e are the same or different and each is 0 or 1.   
   
   
       8 . The curable fluorine-containing polymer of  claim 1 , wherein Y 1  is represented by the formula:
   —O(C═O)CX 6 ═CX 7 X 8      wherein X 6  is H, F, CH 3  or CF 3 ; X 7  and X 8  are the same or different and each is H or F.   
   
   
       9 . The curable fluorine-containing polymer of  claim 2 , wherein in the formula (1-1), the structural unit (A1) is represented by the formula (A1-1): 
     
       
         
         
             
             
         
       
       wherein Rf 4  and Z 1  are as defined in the formula (A1). 
     
   
   
       10 . The curable fluorine-containing polymer of  claim 2 , wherein in the formula (1-1), the structural unit (A1) is represented by the formula (A1-2): 
     
       
         
         
             
             
         
       
       wherein Rf 4  and Z 1  are as defined in the formula (A1). 
     
   
   
       11 . The curable fluorine-containing polymer of  claim 2 , wherein in the formula (1-1), the structural unit (A2) is a structural unit derived from at least one monomer selected from tetrafluoroethylene, vinylidene fluoride, chlorotrifluoroethylene and hexafluoropropylene. 
   
   
       12 . The curable fluorine-containing polymer of  claim 2 , wherein the polymer of the formula (1-1) comprises from 10 to 80% by mole of the structural unit M, from 1 to 60% by mole of the structural unit A1 and from 20 to 85% by mole of the structural unit A2 and contains from 20 to 90% by mole of A1+A2. 
   
   
       13 . The curable fluorine-containing polymer of  claim 1 , which has a refractive index of not more than 1.40. 
   
   
       14 . The curable fluorine-containing polymer of  claim 1 , which is soluble in at least one solvent selected from the group consisting of ketone solvents, acetic acid ester solvents, alcohol solvents and aromatic hydrocarbon solvents. 
   
   
       15 - 49 . (canceled)