Fluoropolymer containing ethylenically unsaturated groups, and curable resin compositions and antireflection coatings, made by using the same

Abstract

An ethylenically unsaturated group-containing fluoropolymer, which is obtained by reacting a compound containing one isocyanate group and at least one ethylenically unsaturated group, and a hydroxyl group-containing fluoropolymer at an isocyanate group/hydroxyl group molar ratio of 1.1 to 1.9. According to the present invention, an ethylenically unsaturated group-containing fluoropolymer having superior antiscratching property, coating property and durability, as well as a curable resin composition and an antireflection film using the same can be provided.

1 - 8 . (canceled)  
     
     
         9 . A curable resin composition, comprising: 
 (a) an ethylenically unsaturated group-containing fluoropolymer, which is obtained by reacting    a compound containing one isocyanate group and at least one ethylenically unsaturated group, and    a hydroxyl group-containing fluoropolymer    at an isocyanate group/hydroxyl group molar ratio of 1.1 to 1.9; and    (b) a polyfunctional (meth)acrylate compound containing at least two (meth)acryloyl groups and/or a fluorine-containing (meth)acrylate compound containing at least one (meth)acryloyl group.    
     
     
         10 . A curable resin composition of  claim 9 , wherein the hydroxyl group containing fluoropolymer contains 20 to 70% by mole of the following structural unit (a), 10 to 70% by mole of the following structural unit (b), 5 to 70% by mole of the following structural unit (c) and 0.1 to 10% by mole of the following structural unit (d) and 
 has a number average molecular weight of 5,000 to 500,000 in terms of polystyrene as measured by gel permeation chromatography:    (a) a structural unit represents by general formula (1);    (b) a structural unit represents by general formula (2);    (c) a structural unit represents by general formula (3);    (d) a structural unit derived from an azo group-containing polysiloxane compound and represented by the following general formula (4);                          wherein, in the general formula (1), R 1  represents a fluorine atom, fluoroalkyl group or group represented as —OR 2  (R 2  represents an alkyl group or fluoroalkyl group);                          wherein, in the general formula (2), R 3  represents a hydrogen atom or methyl group, R 4  represents an alkyl group, group represented as —(CH 2 ) x —OR 5  or —OCOR 5  (R 5  represents an alkyl group or glycidyl group, and x represents a number of 0 or 1), carboxyl group or alkoxycarbonyl group;                          wherein, in the general formula (3), R 6  represents a hydrogen atom or methyl group, R 7  represents a hydrogen atom or hydroxyalkyl group, and v represents a number of 0 or 1;                          wherein, in the general formula (4), R 8  and R 9  may be identical or different and represent a hydrogen atom, alkyl group, halogenated alkyl group or aryl group.    
     
     
         11 . The curable resin composition of  claim 10 , wherein the ethylenically unsaturated group-containing fluoropolymer comprises the structural unit (d) as a part of the following structural unit (e): 
 (e) a structural unit represented by the following general formula (5):                          wherein, in the general formula (5), R 10  to R 13  represent a hydrogen atom, alkyl group or cyano group, R 14  to R 17  represent a hydrogen atom or alkyl group, p and q represent a number of 1 to 6, s and t represent a number of 0 to 6, and y represents a number of 1 to 200.    
     
     
         12 . The curable resin composition of  claim 9 , wherein the ethylenically unsaturated group-containing fluoropolymer further comprises 0.1 to 5% by mole of the following structural unit (f): 
 (f) a structural unit represented by the following general formula (6):                          wherein, in the general formula (6), R 18  represents a group having emulsifying action.    
     
     
         13 . The curable resin composition of  claim 9 , wherein the compound containing one isocyanate group and at least one ethylenically unsaturated group is 2-(meth)acryloyloxyethyl isocyanate.  
     
     
         14 . The ethylenically unsaturated group-containing fluoropolymer according to  claim 9 , wherein the number average molecular weight in terms of polystyrene is 10,000 to 300,000.  
     
     
         15 . The curable resin composition of  claim 9 , wherein the ethylenically unsaturated group-containing fluoropolymer has a number average molecular weight in terms of polystyrene is 10,000 to 100,000.  
     
     
         16 . The curable resin composition of  claim 9 , wherein the isocyanate group/hydroxyl group molar ratio is 1.1 to 1.5.  
     
     
         17 . The curable resin composition of  claim 9 , wherein the isocyanate group/hydroxyl group molar ratio is 1.2 to 1.5.  
     
     
         18 . A method of preparing the curable resin composition of  claim 9 , comprising combining (a) and (b).  
     
     
         19 . A cured resin composition obtained by curing the curable resin composition of  claim 9 .  
     
     
         20 . A method of making a cured resin composition, comprising curing the curable resin composition of  claim 9 .  
     
     
         21 . An antireflection film containing a low refractive index layer comprising a cured product obtained by curing the curable resin composition according to  claim 9 .  
     
     
         22 . A method of preparing the antireflection film of  claim 21 , comprising forming a film comprising the curable resin composition according to  claim 9  and curing the resin composition.