Silicone hydrogel materials with chemically bound wetting agents

Abstract

The invention provide a new class of silicone-containing prepolymers containing ethylenically unsaturated groups and latent UV-activated free radical generating moieties. This class of silicone-containing prepolymer is capable of being actinically crosslinked in the presence of one or more hydrophilic vinylic monomers to form a silicone hydrogel material with a hydrophilic surface without post curing surface treatment. The present invention is also related to silicone hydrogel contact lenses made from this class of silicone-containing prepolymers and a vinylic monomer having a latent UV-activated free radical generating moiety.

1 - 13 . (canceled) 
     
     
         14 . An actinically crosslinkable prepolymer, comprises: in the copolymer chain of the prepolymer,
 (1) siloxane units derived from one or more siloxane-containing vinylic monomers and/or one or more siloxane-containing macromers;   (2) hydrophilic units derived from one or more first hydrophilic vinylic monomers and/or one or more hydrophilic macromers;   (3) chain-extending units having latent UV-activated free radical generating moieties; and   (4) ethylenically unsaturated groups,   wherein the prepolymer is capable of being actinically crosslinked, in the presence of one or more second hydrophilic vinylic monomers, to form a silicone hydrogel material including dangling hydrophilic polymer chains each of which is formed from the one or more hydrophilic vinylic monomers and covalently attached to the polymer matrix of the silicone hydrogel material through one chain-extending unit.   
     
     
         15 . The prepolymer of  claim 14 , wherein the prepolymer is obtained from an intermediary copolymer having pendant first functional groups by attaching covalently ethylenically unsaturated groups to the first functional groups, wherein the intermediary copolymer is obtained by thermal copolymerization of a composition comprising:
 (1) at least one siloxane-containing monomer having one ethylenically unsaturated group, at least one siloxane-containing macromer having one ethylenically unsaturated group, at least one siloxane-containing monomer having two or more ethylenically unsaturated groups, at least one siloxane-containing macromer having two or more ethylenically unsaturated groups, or a combination of two or more thereof;   (2) at least one hydrophilic vinylic monomer;   (3) at least one vinylic monomer of formula (II) or (III)   
       
         
           
           
               
               
           
         
         
           in which
 R is H, C 1 -C 12  alkyl, C 1 -C 12  alkoxy, C 1 -C 12  alkyl-NH— or —NR 3 R 4  wherein R 3  and R 4  independent of each other are C 1 -C 8  alkyl, 
 R 1  and R 2  independent of each other are hydrogen, C 1 -C 8  alkyl, C 1 -C 8  cycloalkyl, or C 1 -C 8  aryl, or R 1  and R 2  together are —(CH 2 ) n — where n is an integer from 2 to 6, 
 X is a linkage selected from the group consisting of —O—, —N—, 
 
         
       
       
         
           
           
               
               
           
         
         
           
             where R 5  is H or C 1 -C 8  alkyl, 
             Y is bivalent —NR S — or —O—, 
             L is a divalent radical selected from the group consisting of C 1 -C 12  alkylene radical, C 1 -C 12  substituted alkylene radical, C 1 -C 12  cycloalkylene radical, and C 8 -C 16  arylalkylene radical, and 
             R 6  is H or CH 3 ; and 
           
         
         (4) a thermal initiator, 
         provided that at least one of the polymerizable components contains a first functional group. 
       
     
     
         16 . The prepolymer of  claim 15 , wherein the composition comprises a polysiloxane-containing vinylic monomer or macromer of formula (VII) 
       
         
           
           
               
               
           
         
         in which
 X 1  denotes —COO—, —CONR 18 —, —OCOO—, or —OCONR 18 —, where each R 18  is independently H or C 1 -C 7  alkyl; 
 R 11  denotes a divalent C 1 -C 25  alkylene or C 6 -C 30  arylalkylene radical, which may interrupted by —O—, —COO—, —CONR 18 —, —OCOO— or —OCONR 18 — and may comprise hydroxy group, primary, secondary, or tertiary amine group, carboxy group, or carboxylic acid; 
 R 12  is a monovalent C 1 -C 25  alkyl or C 6 -C 30  aryl radical, which may interrupted by —O—, —COO—, —CONR 14 —, —OCOO— or —OCONR 14 — and may comprise hydroxy group, primary, secondary, or tertiary amine group, carboxy group, or carboxylic acid; 
 R 7 , R 8 , R 9 , R 10 , R 14 , R 15 , R 16 , and R 17 , independently of one another, are C 1 -C 8 -alkyl, C 1 -C 4  alkyl- or C 1 -C 4 — alkoxy-substituted phenyl, fluoro(C 1 -C 18 -alkyl), cyano(C 1 -C 12 -alkyl), hydroxy-C 1 -C 6 -alkyl or amino-C 1 -C 6 -alkyl; 
 m and p independently of each other are an integer of from 5 to 700 and (m+p) is from 5 to 700. 
 
       
     
     
         17 . The prepolymer of  claim 15 , wherein the composition comprises 3-methacryloxy propylpentamethyldisiloxane, bis(methacryloxypropyl)tetramethyl-disiloxane, N-[tris(trimethylsiloxy)silylpropyl]acrylamide, N-[tris(trimethylsiloxy)silylpropyl]methacrylamide, tristrimethylsilyloxysilylpropyl methacrylate (TRIS), N-[tris(trimethylsiloxy)silylpropyl]methacrylamide (“TSMAA”), N-[tris(trimethylsiloxy)-silylpropyl]acrylamide (“TSAA”), (3-methacryloxy-2-hydroxypropyloxy)propylbis(trimethylsiloxy)methylsilane), (3-methacryloxy-2-hydroxypropyloxy)propyltris(trimethylsiloxy)silane, 3-methacryloxy-2-(2-hydroxyethoxy)propyloxy)propylbis(trimethylsiloxy)methylsilane, N-2-methacryloxyethyl-O-(methyl-bis-trimethylsiloxy-3-propyl)silyl carbamate, 1,3-bis[4-vinyloxycarbonyloxy)but-1-yl]tetramethyl-disiloxane, 3-(trimethylsilyl)propyl vinyl carbonate, 3-(vinyloxycarbonylthio)propyl-[tris(trimethylsiloxy)silane], 3-[tris(trimethylsiloxy)silyl]propylvinyl carbamate, 3-[tris(trimethylsiloxy)silyl]propyl allyl carbamate, 3-[tris(trimethylsiloxy)silyl]propyl vinyl carbonate, t-butyldimethylsiloxyethyl vinyl carbonate, trimethylsilylethyl vinyl carbonate, trimethylsilylmethyl vinyl carbonate, or a mixture thereof. 
     
     
         18 . The prepolymer of  claim 15 , wherein the composition comprises N,N-dimethylacrylamide (DMA), 2-hydroxyethylmethacrylate (HEMA), 2-hydroxyethyl acrylate (HEA), hydroxypropyl acrylate, hydroxypropyl methacrylate (HPMA), trimethylammonium 2-hydroxy propylmethacrylate hydrochloride, aminopropyl methacrylate hydrochloride, dimethylaminoethyl methacrylate (DMAEMA), glycerol methacrylate (GMA), N-vinyl-2-pyrrolidone (NVP), dimethylaminoethylmethacrylamide, acrylamide, methacrylamide, allyl alcohol, vinylpyridine, N-(1,1-dimethyl-3-oxobutyl)acrylamide, acrylic acid, a C 1 -C 4 -alkoxy polyethylene glycol(meth)acrylate having a weight average molecular weight of from 200 to 1500, methacrylic acid, N-vinyl formamide, N-vinyl acetamide, N-vinyl isopropylamide, N-vinyl-N-methyl acetamide, allyl alcohol, N-vinyl caprolactam, or a mixture thereof. 
     
     
         19 . The prepolymer of  claim 15 , wherein the first functional groups are amine, hydroxyl, carboxyl, isocyanate, or epoxy groups, wherein ethylenically functionalizing of the intermediary copolymer is carried out by reacting a vinylic monomer having a hydroxy, amino, carboxyl, epoxy, acid-chloride, isocyanate group, which is coreactive with the first functional groups of the intermediary copolymer in the absence or presence of a coupling agent. 
     
     
         20 . A vinylic monomer, having a structure formula of (II) or (III) 
       
         
           
           
               
               
           
         
         in which
 R is H, C 1 -C 12  alkyl, C 1 -C 12  alkoxy, C 1 -C 12  alkyl-NH— or —NR 3 R 4  wherein R 3  and R 4  independent of each other are C 1 -C 8  alkyl; 
 R 1  and R 2  independent of each other are hydrogen, C 1 -C 8  alkyl, C 1 -C 8  cycloalkyl, or C 1 -C 8  aryl, or R 1  and R 2  together are —(CH 2 ) n — where n is an integer from 2 to 6; 
 X is a linkage selected from the group consisting of —O—, —N—, 
 
       
       
         
           
           
               
               
           
         
         
           where R 5  is H or C 1 -C 8  alkyl; 
           Y is bivalent —NR S — or —O—; 
           L is a divalent radical selected from the group consisting of C 1 -C 12  alkylene radical, C 1 -C 12  substituted alkylene radical, C 1 -C 12  cycloalkylene radical, and C 8 -C 16  arylalkylene radical; and 
           R 6  is H or CH 3 .