Soft contact lenses

Abstract

A soft contact lens containing a silicone-hydrogel made by curing a reaction mixture containing a silicone-containing monomer.

We claim:  
     
         1 . A method of lowering the Young's modulus or tan δ of a silicone hydrogel comprising the step of incorporating in said hydrogel, a mono-alkyl terminated polydimethylsiloxane monomer having the structure:  
       
         
           
           
               
               
           
         
       
       where b=0 to 100; R 58  is a monovalent group containing at least one ethylenically unsaturated moiety; R 59  is independently a monovalent alkyl, or aryl group, which may be further substituted with alcohol, amine, ketone, carboxylic acid or ether group; R 60  is a monovalent alkyl, or aryl group, which may be further substituted with alcohol, amine, ketone, carboxylic acid or ether groups; and R 61  is independently alkyl or aromatic, or a monovalent siloxane chain comprising from 1 to 100 repeating Si—O units.  
     
     
         2 . The method of  claim 1 , wherein b is about 4 to about 16, R 58  is a monovalent group containing at least one styryl, vinyl, or methacrylate moiety, R 59  is methyl, R 60  is C 3-8 alkyl group, and R 61  is methyl.  
     
     
         3 . The method of  claim 1 , wherein b is about 8 to about 10, R 58  is a monovalent group containing at least one styryl, vinyl, or methacrylate moiety, R 59  is methyl, R 60  is C 3-8 alkyl group, and R 61  is methyl.  
     
     
         4 . The method of  claim 1 , wherein b is about 4 to about 16, R 58  is a methacrylate moiety; each R 59  is methyl; and R 60  is a butyl group.  
     
     
         5 . The method of  claim 1 , wherein b is about 8 to about 10, R 58  is a methacrylate moiety; each R 59  is methyl, R 60  is a butyl group, and R 61  is methyl.  
     
     
         6 . The method of  claim 1 , wherein about 2 to about 70% wt, based on the total weight of reactive monomer, of the mono-alkyl terminated polydimethylsiloxane is incorporated in said silicone hydrogel.  
     
     
         7 . The method of  claim 1 , wherein about 4 to about 50% wt, based on the total weight of reactive monomer, of the mono-alkyl terminated polydimethylsiloxane is incorporated in said silicone hydrogel.  
     
     
         8 . The method of  claim 1 , wherein about 8 to about 40% wt, based on the total weight of reactive monomer, of the mono-alkyl terminated polydimethylsiloxane is incorporated in said silicone hydrogel.  
     
     
         9 . The method of  claim 1 , wherein said silicone hydrogel additionally comprises a silicone-containing monomer other than that of  claim 1  and having the structure:  
       
         
           
           
               
               
           
         
       
       wherein R 51  is H, C 1-5 alkyl, or an ethylenically unsaturated moiety, q is 1, 2, or 3 and for each q, R 52 , R 53  and R 54  is independently an alkyl group, an aromatic group or a monovalent siloxane chain comprising from 1 to 100 repeating Si—O units, p is 1 to 10, r=(3−q), X is O or NR 55 , where R 55  is H or a monovalent alkyl group with 1 to 4 carbons, a is 0 or 1, and L is a divalent linking group.  
     
     
         10 . The method of  claim 1 , wherein said silicone hydrogel additionally comprises 3-methacryloxypropyltris (trimethylsiloxy) silane.  
     
     
         11 . The method of  claim 9 , wherein each of R 52 , R 53 , and R 54  is independently ethyl, methyl, benzyl or phenyl.  
     
     
         12 . A silicone hydrogel having a Young's modulus of less than about 154 psi and a tan δ of equal to or less than about 0.3 at a frequency of 1 Hz at 25° C.  
     
     
         13 . The silicone hydrogel of  claim 12 , wherein the Young's modulus is less than about 130 psi.  
     
     
         14 . The silicone hydrogel of  claim 12 , wherein the Young's modulus is less than about 100 psi.  
     
     
         15 . The silicone hydrogel of  claim 12 , wherein the Young's modulus is less than about 70 psi.  
     
     
         16 . The silicone hydrogel of  claim 12 , wherein the Young's modulus is less than about 45 psi.  
     
     
         17 . The silicone hydrogel of  claim 12 , further comprising an O 2  Dk greater than about 40 barrer.  
     
     
         18 . The silicone hydrogel of  claim 12 ,  13 , or  17 , further comprising about 2-70% wt, based on the total weight of reactive monomer, of a mono-alkyl terminated polydimethylsiloxane having the structure:  
       
         
           
           
               
               
           
         
       
       where b=0 to 100, where it is understood that b is a distribution having a mode equal to a stated value, preferably 8 to 10; R 58  is a monovalent group containing at least one ethylenically unsaturated moiety, preferably a monovalent group containing a styryl, vinyl, or methacrylate moiety, more preferably a methacrylate moiety; each R 59  is independently a monovalent alkyl, or aryl group, which may be further substituted with alcohol, amine, ketone, carboxylic acid or ether groups, preferably unsubstituted monovalent alkyl or aryl groups, more preferably methyl; R 60  is a monovalent alkyl, or aryl group, which may be further substituted with alcohol, amine, ketone, carboxylic acid or ether groups, preferably unsubstituted monovalent alkyl or aryl groups, preferably a C 1-10 aliphatic or aromatic group which may include hetero atoms, more preferably C 3-8 alkyl groups, most preferably butyl, and R 61  is independently alkyl or aromatic, preferably ethyl, methyl, benzyl, phenyl, or a monovalent siloxane chain comprising from 1 to 100 repeating Si—O units.  
     
     
         19 . The silicone hydrogel of  claim 18 , wherein b=4 to 16, R 58  is a monovalent group containing at least one styryl, vinyl, or methacrylate moiety, each R 59  is methyl, R 60  is a C 3-8 alkyl group, and R 61  is methyl.  
     
     
         20 . The silicone hydrogel of  claim 18 , wherein b=8 to 10, R 58  is a methacrylate moiety; each R 59  is methyl; R 60  is a butyl group, and R 61  is methyl.  
     
     
         21 . The silicone hydrogel of  claim 18 , wherein the mono-alkyl terminated polydimethylsiloxane is a monomethacryloxypropyl terminated polydimethylsiloxane.  
     
     
         22 . The silicone hydrogel of  claim 18 , having a Young's modulus of about 30-160 psi.  
     
     
         23 . The silicone hydrogel of  claim 18 , having a Young's modulus of about 40-130 psi.  
     
     
         24 . A contact lens comprising a silicone hydrogel having a Young's modulus less than about 180 psi and a tan δ of equal to or less than about 0.25 at a frequency of 1 Hz at 25° C.  
     
     
         25 . The contact lens of  claim 24 , having a Young's modulus of less than about 100 psi.  
     
     
         26 . The contact lens of  claim 24 , further comprising an O 2  Dk greater than about 40 barrer.  
     
     
         27 . The contact lens of  claim 24 ,  25 , or  26 , further comprising about 2-70% wt, based on the total weight of reactive monomer, of a mono-alkyl terminated polydimethylsiloxane having the structure:  
       
         
           
           
               
               
           
         
       
       where b=0 to 100, where it is understood that b is a distribution having a mode equal to a stated value, preferably 8 to 10; R 58  is a monovalent group containing at least one ethylenically unsaturated moiety, preferably a monovalent group containing a styryl, vinyl, or methacrylate moiety, more preferably a methacrylate moiety; each R 59  is independently a monovalent alkyl, or aryl group, which may be further substituted with alcohol, amine, ketone, carboxylic acid or ether groups, preferably unsubstituted monovalent alkyl or aryl groups, more preferably methyl; R 60  is a monovalent alkyl, or aryl group, which may be further substituted with alcohol, amine, ketone, carboxylic acid or ether groups, preferably unsubstituted monovalent alkyl or aryl groups, preferably a C 1-10 aliphatic or aromatic group which may include hetero atoms, more preferably C 3-8 alkyl groups, most preferably butyl, and R 61  is independently alkyl or aromatic, preferably ethyl, methyl, benzyl, phenyl, or a monovalent siloxane chain comprising from 1 to 100 repeating Si—O units.  
     
     
         28 . The contact lens of  claim 27 , wherein b=4 to 16, R 58  is a monovalent group containing at least one styryl, vinyl, or methacrylate moiety, each R 59  is methyl, R 60  is C 3-8 alkyl group, and R 61  is methyl.  
     
     
         29 . The contact lens of  claim 27 , wherein b=8 to 10, R 58  is a methacrylate moiety; each R 59  is methyl, R 60  is a butyl group, and R 61  is methyl.  
     
     
         30 . The contact lens of  claim 27 , wherein the mono-alkyl terminated polydimethylsiloxane is a monomethacryloxypropyl terminated polydimethylsiloxane.  
     
     
         31 . The contact lens of  claim 27 , wherein said silicone hydrogel has a Young's modulus of about 30-160 psi.  
     
     
         32 . The contact lens of  claim 27 , wherein said silicone hydrogel has a Young's modulus of about 40-130 psi.  
     
     
         33 . The contact lens of  claim 27 , further comprising a surface layer that is more hydrophilic than said silicone hydrogel.  
     
     
         34 . The contact lens of  claim 33 , further comprising a coating that is more hydrophilic than said silicone hydrogel.  
     
     
         35 . The contact lens of  claim 33 , wherein the surface layer comprises poly(acrylic acid).  
     
     
         36 . A silicone hydrogel contact lens comprising a (CT) of about 50 to about 160 μm and a Young's modulus (E) of about 40 to about 300 pSi, wherein (E)(CT) 2  is less than about 1 psi·mm 2 .  
     
     
         37 . The silicone hydrogel contact lens of  claim 36 , further comprising a tan δ of equal to or less than about 0.3 at a frequency of 1 Hz at 25° C.  
     
     
         38 . The silicone hydrogel contact lens of  claim 36 , further comprising a O 2 Dk greater than about 40 barrer.  
     
     
         39 . The silicone hydrogel contact lens of  claim 36 ,  37 , or  38 , further comprising at least 5% wt of a mono-alkyl terminated polydimethylsiloxane having the structure:  
       
         
           
           
               
               
           
         
       
       where b=0 to 100; R 58  is a monovalent group comprising at least one ethylenically unsaturated moiety; each R 59  is independently a monovalent alkyl, or aryl group, which may be further substituted with alcohol, amine, ketone, carboxylic acid or ether groups; R 60  is a monovalent alkyl, or aryl group, which may be further substituted with alcohol, amine, ketone, carboxylic acid or ether groups, and R 61  is independently alkyl or aromatic, or a monovalent siloxane chain comprising from 1 to 100 repeating Si—O units.  
     
     
         40 . The silicone hydrogel contact lens of  claim 39 , wherein b=4 to 16, R 58  is a monovalent group containing at least one styryl, vinyl, or methacrylate moiety, each R 59  is methyl, and R 60  is C 3-8 alkyl group.  
     
     
         41 . The silicone hydrogel contact lens of  claim 39 , wherein b=8 to 10, R 58  is a methacrylate moiety; each R 59  is methyl; R 60  is a butyl group, and R 61  is methyl.  
     
     
         42 . The silicone hydrogel contact lens of  claim 39 , wherein the mono-alkyl terminated polydimethylsiloxane is a monomethacryloxypropyl terminated polydimethylsiloxane.  
     
     
         43 . The silicone hydrogel contact lens of  claim 39 , wherein the center thickness is less than about 85 μm.  
     
     
         44 . The silicone hydrogel contact lens of  claim 39  wherein the thickness is less than about 100 μm and the Young's modulus is less than about 100 psi.  
     
     
         45 . The silicone hydrogel contact lens of  claim 39 , wherein the amount of mono-alkyl terminated polydimethylsiloxane is about 20% wt.  
     
     
         46 . The silicone hydrogel contact lens of  claim 39 , wherein the center thickness is less than 129 μm and the Young's modulus is less than about 60 psi.  
     
     
         47 . The silicone hydrogel contact lens of  claim 39 , wherein the amount of mono-alkyl terminated polydimethylsiloxane is about 30% wt.  
     
     
         48 . A method of making a polymer comprising preparing a silicone based macromer by Group Transfer Polymerization and reacting said macromer with a polymerization mixture comprising a mono-alkyl terminated polydimethylsiloxane monomer having the structure:  
       
         
           
           
               
               
           
         
       
       where b=0 to 100; R 58  is a monovalent group containing at least one ethylenically unsaturated moiety; R 59  is independently a monovalent alkyl, or aryl group, which may be further substituted with alcohol, amine, ketone, carboxylic acid or ether group; R 60  is a monovalent alkyl, or aryl group, which may be further substituted with alcohol, amine, ketone, carboxylic acid or ether groups; and R 61  is independently alkyl or aromatic, or a monovalent siloxane chain comprising from 1 to 100 repeating Si—O units.  
     
     
         49 . The method of  claim 48  wherein said silicone based macromer comprises a mono-alkyl terminated polydimethylsiloxane monomer having the structure:  
       
         
           
           
               
               
           
         
       
       where b=0 to 100; R 58  is a monovalent group containing at least one ethylenically unsaturated moiety; R 59  is independently a monovalent alkyl, or aryl group, which may be further substituted with alcohol, amine, ketone, carboxylic acid or ether group; R 60  is a monovalent alkyl, or aryl group, which may be further substituted with alcohol, amine, ketone, carboxylic acid or ether groups; and R 61  is independently alkyl or aromatic, or a monovalent siloxane chain comprising from 1 to 100 repeating Si—O units.  
     
     
         50 . The method of  claim 48  wherein said polymerizable mixture comprises Si 8-10  monomethacryloxy terminated polydimethyl siloxane, a polydimethylsiloxane other than Si 8-10  monomethacryloxy terminated polydimethyl siloxane, and a hydrophilic monomer.  
     
     
         51 . The method of  claim 48 , wherein said macromer is the reaction product of a reaction mixture comprising 2-(trimethylsiloxy)ethyl methacrylate, methyl methacrylate, methacryloxypropyltris(trimethylsiloxy)silane, and mono-methacryloxypropyl terminated mono-butyl terminated polydimethylsiloxane.  
     
     
         52 . The method of  claim 48 , wherein the macromer is functionalized with a free radical polymerizable group.  
     
     
         53 . The method of  claim 48 , wherein the reaction mixture of  claim 48  is treated with a catalyst and a molecule containing both an isocyanate group and a free radical polymerizable group.  
     
     
         54 . The method of  claim 53  wherein said catalyst comprises, tin, bismuth or a tertiary amine and said molecule containing both an isocyanate group and said free radical polymerizable group is dimethyl meta-isopropenyl benzyl isocyanate.  
     
     
         55 . A macromer useful for making silicone hydrogels comprising a Group Transfer Polymerization product of a reaction mixture comprising 2-(trimethylsiloxy)ethyl methacrylate, methyl methacrylate, methacryloxypropyltris(trimethylsiloxy)silane, and mono-methacryloxypropyl terminated mono-butyl terminated polydimethylsiloxane.  
     
     
         56 . The macromer of  claim 55 , wherein the Group Transfer Polymerization product reaction mixture comprises about 19.1 moles of 2-(trimethylsiloxy)ethyl methacrylate, about 2.8 moles of methyl methacrylate, about 7.9 moles of methacryloxypropyltris(trimethylsiloxy)silane, and about 3.3 moles of mono-methacryloxypropyl terminated mono-butyl terminated polydimethylsiloxane.  
     
     
         57 . A silicone hydrogel comprising the reaction product of a silicone based macromer Group Transfer Polymerization product and a polymerizable mixture comprising Si 8-10  monomethacryloxy terminated polydimethyl siloxane, a polydimethylsiloxane other than Si 8-10  monomethacryloxy terminated polydimethyl siloxane, and a hydrophilic monomer.  
     
     
         58 . The silicone hydrogel of  claim 57 , wherein the macromer is the Group Transfer Product of a reaction mixture 2-(trimethylsiloxy)ethyl methacrylate, methyl methacrylate, methacryloxypropyltris(trimethylsiloxy)silane, and mono-methacryloxypropyl terminated mono-butyl terminated polydimethylsiloxane.  
     
     
         59 . The silicone hydrogel of  claim 57 , wherein the macromer is the Group Transfer Polymerization product of reaction mixture comprising about 19.1 moles of 2-(trimethylsiloxy)ethyl methacrylate, about 2.8 moles of methyl methacrylate, about 7.9 moles of methacryloxypropyltris(trimethylsiloxy)silane, and about 3.3 moles of mono-methacryloxypropyl terminated mono-butyl terminated polydimethylsiloxane  
     
     
         60 . The silicone hydrogel of  claim 57 ,  58 , or  59  wherein the polymerizable mixture comprises Si 8-10  monomethacryloxy terminated polydimethyl siloxane; methacryloxypropyl tris(trimethyl siloxy) silane; N,N-dimethyl acrylamide; 2-(trimethylsiloxy)ethyl methacrylate; and tetraethyleneglycol dimethacrylate.  
     
     
         61 . The silicone hydrogel of  claim 60 , wherein the macromer is present in an amount of about 10 to about 60 wt percent, the Si 8-10  monomethacryloxy terminated polydimethyl siloxane is present in an amount of about 0 to about 45 wt percent; the methacryloxypropyl tris(trimethyl siloxy) silane is present in an amount of about 0 to about 40 wt percent; the N,N-dimethyl acrylamide is present in an amount of about 5 to about 40 wt percent; the 2-hydroxy ethyl methacrylate is present in an amount of about 0 to about 10 wt percent; and the tetraethyleneglycol dimethacrylate is present in an amount of about 0 to about 5 wt percent.  
     
     
         62 . The silicone hydrogel of  claim 60 , wherein the macromer is present in an amount of about 15 to about 25 wt percent, the Si 8-10  monomethacryloxy terminated polydimethyl siloxane is present in an amount of about 20 to about 30 wt percent; the methacryloxypropyl tris(trimethyl siloxy) silane is present in an amount of about 15 to about 25 wt percent; the N,N-dimethyl acrylamide is present in an amount of about 20 to about 30 wt percent; the 2-hydroxy ethyl methacrylate is present in an amount of about 2 to about 7 wt percent; and the tetraethyleneglycol dimethacrylate is present in an amount of about 0 to about 5 wt percent.  
     
     
         63 . The silicone hydrogel of  claim 60 ,  61 , or  62  wherein the polymerizable mixture further comprises poly(N-vinyl pyrrolidinone).  
     
     
         64 . The silicone hydrogel of  claim 61 , wherein the polymerizable mixture further comprises about 0 to about 10 wt percent poly(N-vinyl pyrrolidinone).  
     
     
         65 . The silicone hydrogel of  claim 62 , wherein the polymerizable mixture further comprises about 2 to about 7 wt percent poly(N-vinyl pyrrolidinone).  
     
     
         66 . A contact lens comprising the reaction product of a silicone based macromer Group Transfer Polymerization product and a polymerizable mixture comprising Si 8-10  monomethacryloxy terminated polydimethyl siloxane, a polydimethylsiloxane other than Si 8-10  monomethacryloxy terminated polydimethyl siloxane, and a hydrophilic monomer.  
     
     
         67 . The contact lens of  claim 66 , wherein the macromer is the Group Transfer Product of a reaction mixture, comprising 2-(trimethylsiloxy)ethyl methacrylate, methyl methacrylate, methacryloxypropyltris(trimethylsiloxy)silane, and mono-methacryloxypropyl terminated mono-butyl terminated polydimethylsiloxane.  
     
     
         68 . The contact lens of  claim 66 , wherein the macromer is the Group Transfer Polymerization product of reaction mixture comprising about 19.1 moles of 2-(trimethylsiloxy)ethyl methacrylate, about 2.8 moles of methyl methacrylate, about 7.9 moles of methacryloxypropyltris(trimethylsiloxy)silane, and about 3.3 moles of mono-methacryloxypropyl terminated mono-butyl terminated polydimethylsiloxane  
     
     
         69 . The contact lens of  claim 66 ,  67 , or  68  wherein the polymerizable mixture comprises Si 8-10  monomethacryloxy terminated polydimethyl siloxane; methacryloxypropyl tris(trimethyl siloxy) silane; N,N-dimethyl acrylamide; 2-hydroxy ethyl methacrylate; and tetraethyleneglycol dimethacrylate.  
     
     
         70 . The contact lens of  claim 69 , wherein the macromer is present in an amount of about 10 to about 60 wt percent, the Si 5-10 monomethacryloxy terminated polydimethyl siloxane is present in an amount of about 0 to about 45 wt percent; the methacryloxypropyl tris(trimethyl siloxy) silane is present in an amount of about 0 to about 40 wt percent; the N,N-dimethyl acrylamide is present in an amount of about 5 to about 40 wt percent; the 2-hydroxy ethyl methacrylate is present in an amount of about 0 to about 10 wt percent; and the tetraethyleneglycol dimethacrylate is present in an amount of about 0 to about 5 wt percent.  
     
     
         71 . The contact lens of  claim 69 , wherein the macromer is present in an amount of about 15 to about 25 wt percent, the Si 8-10  monomethacryloxy terminated polydimethyl siloxane is present in an amount of about 20 to about 30 wt percent; the methacryloxypropyl tris(trimethyl siloxy) silane is present in an amount of about 15 to about 25 wt percent; the N,N-dimethyl acrylamide is present in an amount of about 20 to about 30 wt percent; the 2-hydroxy ethyl methacrylate is present in an amount of about 2 to about 7 wt percent; and the tetraethyleneglycol dimethacrylate is present in an amount of about 0 to about 5 wt percent.  
     
     
         72 . The contact lens of  claim 69 , wherein the polymerizable mixture further comprises poly(N-vinyl pyrrolidinone).  
     
     
         73 . The contact lens of  claim 70 , wherein the polymerizable mixture further comprises about 0 to about 10 wt percent poly(N-vinyl pyrrolidinone).  
     
     
         74 . The contact lens of  claim 71 , wherein the polymerizable mixture further comprises about 2 to about 7 wt percent poly(N-vinyl pyrrolidinone).  
     
     
         75 . A method of lowering the Young's modulus and tan δ of a silicone hydrogel comprising the step of incorporating in said hydrogel, a mono-alkyl terminated polydimethylsiloxane monomer having the structure:  
       
         
           
           
               
               
           
         
       
       where b=0 to 100; R 58  is a monovalent group containing at least one ethylenically unsaturated moiety; R 59  is independently a monovalent alkyl, or aryl group, which may be further substituted with alcohol, amine, ketone, carboxylic acid or ether group; R 60  is a monovalent alkyl, or aryl group, which may be further substituted with alcohol, amine, ketone, carboxylic acid or ether groups; and R 61  is independently alkyl or aromatic, or a monovalent siloxane chain comprising from 1 to 100 repeating Si—O units.  
     
     
         76 . The method of  claim 75 , wherein said silicone hydrogel additionally comprises a silicone-containing monomer other than that of  claim 1  and having the structure:  
       
         
           
           
               
               
           
         
       
       wherein R 51  is H, C 1-5 alkyl, or an ethylenically unsaturated moiety, q is 1, 2, or 3 and for each q, R 52 , R 53  and R 54  is independently an alkyl group, an aromatic group or a monovalent siloxane chain comprising from 1 to 100 repeating Si—O units, p is 1 to 10, r=(3−q), X is O or NR 55 , where R 55  is H or a monovalent alkyl group with 1 to 4 carbons, a is 0 or 1, and L is a divalent linking group.  
     
     
         77 . The method of  claim 75 , wherein said silicone hydrogel additionally comprises 3-methacryloxypropyltris (trimethylsiloxy) silane.  
     
     
         78 . The method of  claim 76 , wherein each of R 52 , R 53 , and R 54  is independently ethyl, methyl, benzyl or phenyl.  
     
     
         79 . The method of  claim 75  wherein Young's modulus is lowered to less than about 100 psi and tan δ of equal to or less than about 0.25 at a frequency of 1 Hz at 25° C.  
     
     
         80 . The method of  claim 75  wherein Young's modulus is lowered to less than about 80 psi and tan δ of equal to or less than about 0.25 at a frequency of 1 Hz at 25° C.