Polyorganosilsesquioxane, hard coat film, adhesive sheet, and laminate

Abstract

Provided is a polyorganosilsesquioxane capable of forming, when cured, a cured product that offers high surface hardness and good heat resistance, is highly flexible, and has excellent processability. The present invention relates to a polyorganosilsesquioxane including a constitutional unit represented by Formula (1). The polyorganosilsesquioxane includes a constitutional unit represented by Formula (I) and a constitutional unit represented by Formula (II) in a mole ratio of the constitutional unit represented by Formula (I) to the constitutional unit represented by Formula (II) of 5 or more. The polyorganosilsesquioxane has a total proportion of the constitutional unit represented by Formula (1) and a constitutional unit represented by Formula (4) of 55% to 100% by mole based on the total amount (100% by mole) of all siloxane constitutional units. The polyorganosilsesquioxane has a number-average molecular weight of 1000 to 3000 and a molecular-weight dispersity (weight-average molecular weight to number-average molecular weight ratio) of 1.0 to 3.0. [R 1 SiO 3/2 ]  (1) [Chem. 2] [R a SiO 3/2 ]  (I) [Chem. 3] [R b SiO(OR c )]  (II) [Chem. 4] [R 1 SiO(OR c )]  (4)

1 - 20 . (canceled) 
     
     
         21 . A polyorganosilsesquioxane comprising:
 a constitutional unit represented by Formula (I); and   a constitutional unit represented by Formula (II),   
       in a mole ratio of the constitutional unit represented by Formula (I) to the constitutional unit represented by Formula (II) of from 5 to 18,
 the polyorganosilsesquioxane comprising
 a constitutional unit represented by Formula (1), 
 
 the polyorganosilsesquioxane having a total proportion of the constitutional unit represented by Formula (1) and a constitutional unit represented by Formula (4) of 55% to 100% by mole based on a total amount (100% by mole) of all siloxane constitutional units, 
 the polyorganosilsesquioxane having a number-average molecular weight of 1000 to 3000 and a molecular-weight dispersity (weight-average molecular weight to number-average molecular weight ratio) of 1.0 to 3.0, 
 
       Formulae (1), (I), (II), and (4) expressed as follows:
   [Chem. 1] 
   [R 1 SiO 3/2 ]  (1)
 
 
       wherein R 1  represents an epoxy-containing group,
   [Chem. 2] 
   [R a SiO 3/2 ]  (I)
 
 
       wherein R a  is selected from an epoxy-containing group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, and a hydrogen atom,
   [Chem. 3] 
   [R b SiO(OR c )]  (II)
 
 
       wherein R b  is selected from an epoxy-containing group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, and a hydrogen atom; and R c  is selected from a hydrogen atom and a C 1 -C 4  alkyl group, and
   [Chem. 4] 
   [R 1 SiO(OR c )]  (4)
 
 
       wherein R 1  is as defined in Formula (1); and R c  is as defined in Formula (II). 
     
     
         22 . The polyorganosilsesquioxane according to  claim 21 , further comprising
 a constitutional unit represented by Formula (2):
   [Chem. 5] 
   [R 2 SiO 3/2 ]  (2)
 
   
       wherein R 2  is selected from a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted alkenyl group. 
     
     
         23 . The polyorganosilsesquioxane according to  claim 21 ,
 wherein R 1  is selected from:
 a group represented by Formula (1a); 
 a group represented by Formula (1b); 
 a group represented by Formula (1c); and 
 a group represented by Formula (1d), 
   Formulae (1a), (1b), (1c), and (1d) expressed as follows:   
       
         
           
           
               
               
           
         
         wherein R 1a  represents a straight or branched chain alkylene group, 
       
       
         
           
           
               
               
           
         
         wherein R 1b  represents a straight or branched chain alkylene group, 
       
       
         
           
           
               
               
           
         
         wherein R 1c  represents a straight or branched chain alkylene group, 
       
       
         
           
           
               
               
           
         
         wherein R 1d  represents a straight or branched chain alkylene group. 
       
     
     
         24 . The polyorganosilsesquioxane according to  claim 22 ,
 wherein R 2  is a substituted or unsubstituted aryl group.   
     
     
         25 . A curable composition comprising:
 the polyorganosilsesquioxane according to  claim 21 .   
     
     
         26 . The curable composition according to  claim 25 , further comprising
 a curing catalyst.   
     
     
         27 . The curable composition according to  claim 26 ,
 wherein the curing catalyst comprises a cationic photoinitiator.   
     
     
         28 . The curable composition according to  claim 26 ,
 wherein the curing catalyst comprises a cationic thermal initiator.   
     
     
         29 . The curable composition according to  claim 25 , further comprising
 a vinyl ether compound.   
     
     
         30 . The curable composition according to  claim 25 , further comprising
 a vinyl ether compound containing a hydroxy group in molecule.   
     
     
         31 . The curable composition according to  claim 25 , as a curable composition for formation of a hard coat layer. 
     
     
         32 . The curable composition according to  claim 25 , as an adhesive composition. 
     
     
         33 . A cured product of the curable composition according to  claim 25 . 
     
     
         34 . A hard coat film comprising:
 a substrate; and   a hard coat layer disposed on or over at least one side of the substrate,   the hard coat layer being a layer of a cured product of the curable composition according to  claim 31 .   
     
     
         35 . The hard coat film according to  claim 34 ,
 wherein the hard coat layer has a thickness of 1 to 200 μm.   
     
     
         36 . The hard coat film according to  claim 34 ,
 wherein the hard coat film is producible by a roll-to-roll process.   
     
     
         37 . The hard coat film according to  claim 34 , further comprising
 a surface-protecting film on or over the hard coat layer.   
     
     
         38 . A method for producing a hard coat film, the method comprising the steps of:
 (A) unwinding a wound, rolled substrate;   (B) applying the curable composition according to  claim 31  to at least one side of the unwound substrate, and curing the applied curable composition to form a hard coat layer on the substrate to thereby give a hard coat film; and   (C) rewinding the hard coat film into a roll,   the steps (A), (B), and (C) being performed successively.   
     
     
         39 . An adhesive sheet comprising:
 a substrate; and   an adhesive layer disposed on or over the substrate,   the adhesive layer being a layer of the curable composition according to  claim 32 .   
     
     
         40 . A laminate comprising
 three or more layers,   the three or more layers comprising:
 two adherend layers; and 
 an adhesive layer disposed between the two adherend layers, the adhesive layer being a layer of a cured product of the curable composition according to  claim 32 .