Polymerizable composition comprising perfluoropolyether urethane having ethylene oxide repeat units

Abstract

Presently described are optical substrates having a surface layer and optical displays comprising such optical substrates. The surface layer comprises the reaction product of a polymerizable mixture comprising at least one perfluoropolyether urethane polymeric material comprising at least two free-radically polymerizable groups and greater than 6 ethylene oxide repeat units and at least one non-fluorinated crosslinker comprising at least two free-radically polymerizable groups.

1 . An optical display comprising:
 an optical substrate having a surface layer comprising the reaction product of a polymerizable mixture comprising   at least one perfluoropolyether urethane polymeric material comprising at least two free-radically polymerizable groups and greater than 6 ethylene oxide repeat units;   at least one non-fluorinated crosslinker comprising at least two free-radially polymerizable groups.   
     
     
         2 . The optical display of  claim 1  wherein the perfluoropolyether urethane polymer comprises at least two (meth)acrylate groups. 
     
     
         3 . The optical display of  claim 2  wherein the perfluoropolyether urethane comprises a terminal group having at least two (meth)acrylate groups. 
     
     
         4 . The optical display of  claim 1  wherein the perfluoropolyether urethane comprises a monovalent perfluoropolyether moiety. 
     
     
         5 . The optical display of  claim 1  wherein the perfluoropolyether moiety is F(CF(CF 3 )CF 2 O)aCF(CF 3 )— and a ranges from 4 to 15. 
     
     
         6 . The optical display of  claim 1  wherein the non-fluorinated crosslinker comprise at least three free-radically polymerizable groups. 
     
     
         7 . The optical display of  claim 1  wherein the substrate is selected from polycarbonate, acrylic, cellulose acetate, and cellulose triacetate. 
     
     
         8 . The optical display of  claim 1  wherein the surface layer further comprises inorganic oxide particles. 
     
     
         9 . The optical display of  claim 1  wherein a hardcoat layer comprising inorganic oxide particles is disposed between the substrate and the surface layer. 
     
     
         10 . An optical substrate having a surface layer comprising the reaction product of a polymerizable mixture comprising
 at least one perfluoropolyether urethane polymeric material comprising at least two free-radically polymerizable groups and greater than 6 ethylene oxide repeat units;   at least one non-fluorinated crosslinker comprising at least two free-radially polymerizable groups.   
     
     
         11 . A multifunctional perfluoropolyether urethane composition having the general formula
   Ri-(NHC(O)XQRf), —(NHC(O)OQ(A)p), —(NHC(O)X j (C 2 H 4 O) j R j      wherein Ri is a residue of a multi-isocyanate;   X and X j  are each independently O, S or NR, where R is H or lower alkyl of 1 to 4 carbon atoms;   Q is independently a straight chain, branched chain, or cyclic-containing connecting group having a valency at least 2;   Rf is a monovalent perfluoropolyether moiety composed of groups comprising the formula F(RfcO)xCdF2d-, wherein each Rfc independently represents a fluorinated alkylene group having from 1 to 6 carbon atoms, each x independently represents an integer greater than or equal to 2, and wherein d is an integer from 1 to 6;   A is a (meth)acryl functional group —XC(O)C(R2)=CH2, where R2 is a lower alkyl of 1 to 4 carbon atoms or H or F;   p is 2 to 6;   j ranges from 7 to 40; and   R j  is H, —C(O)C(R 2 )═CH 2 , where R 2  is a lower alkyl of 1 to 4 carbon atoms or H or F, or a group selected from alkyl, aryl, alkaryl, aralkyl, optionally substituted with a heteroatom, heteoratom functional group, or a (meth)acryl functional group.   
     
     
         12 . The composition of  claim 11  with the proviso that when X is O, Q is not methylene. 
     
     
         13 . The composition of  claim 11  wherein Q is selected from an alkylene having at least two carbon atoms, arylene, aralkylene, and alkarylene. 
     
     
         14 . The composition of  claim 13  wherein Q comprises a heteroatom selected from O, N, and S. 
     
     
         15 . The composition of  claim 14  wherein Q comprise a nitrogen containing group. 
     
     
         16 . The composition of  claim 15  wherein Q contains an amide group. 
     
     
         17 . The composition of  claim 16  wherein Q is selected from —C(O)NHCH 2 CH 2 —, —C(O)NH(CH 2 ) 6 —, and —C(O)NH(CH 2 CH 2 O)CH 2 CH 2 —. 
     
     
         18 . A free-radially polymerizable composition comprising a mixture of reaction products of
 i) at least one polyisocyanate;   ii) at least one isocyanate reactive perfluoropolyether compound;   iii) at least one isocyanate reactive compound comprising greater than 6 repeat units of ethylene oxide; and   iv) at least one isocyanate reactive non-fluorinated crosslinker comprising at least two free-radically polymerizable groups.   
     
     
         19 . The composition of  claim 18  dispersed in an alcohol-containing solvent. 
     
     
         20 . The free-radically polymerizable coating of claim  24  wherein ii) and iii) comprise alcohol isocyanate reactive groups.