Biomedical devices containing internal wetting agents

Abstract

This invention includes a wettable biomedical device containing a high molecular weight hydrophilic polymer and a hydroxyl-functionalized silicone-containing monomer.

1 . A wettable silicone hydrogel comprising the reaction product of
 at least one siloxane containing macromer;   at least one high molecular weight hydrophilic polymer; and   at least one compatibilizing component.   
   
   
       2 . The hydrogel of  claim 1  wherein said siloxane containing macromer is present in an amount between about 5% to about 50%. 
   
   
       3 . The hydrogel of  claim 1  wherein the siloxane containing macromer or prepolymer is present in an amount between about 10% to about 50%. 
   
   
       4 . The hydrogel of  claim 1  wherein the siloxane containing macromer or prepolymer is present in an amount between about 15% to about 45%. 
   
   
       5 . The hydrogel of  claim 1  wherein said at least on siloxane containing macromer comprises at least one siloxane group, and at least one second group selected from the group consisting of urethane groups, alkylene groups, alkylene oxide groups, polyoxyalkalene groups, arylene groups, alkyl esters, amide groups, carbamate groups, perfluoroalkoxy groups, isocyanate groups, combinations thereof. 
   
   
       6 . The hydrogel of  claim 5  wherein said at least one siloxane containing macromers is formed via polymerizing said siloxane group with at least one acrylic or methacrylic compound. 
   
   
       7 . The hydrogel of  claim 5  wherein said at least one siloxane containing macromer is selected from the group consisting of methacrylate functionalized, silicone-fluoroether urethane macromers, methacrylate functionalized, silicone urethane macromers, styrene functionalized prepolymers of hydroxyl functional methacrylates and silicone methacrylates and vinyl carbamate functionalized polydimethylsiloxane 
   
   
       8 . The hydrogel of  claim 1  comprising about 1% to about 15% high molecular weight hydrophilic polymer. 
   
   
       9 . The hydrogel of  claim 1  comprising about 3% to about 15% high molecular weight hydrophilic polymer. 
   
   
       10 . The hydrogel of  claim 1  comprising about 5% to about 12% high molecular weight hydrophilic polymer. 
   
   
       11 . The silicone hydrogel of  claim 14  wherein said hydrophilic polymer is selected from the group consisting of polyamides, polylactones, polyimides, polylactams, functionalized polyamides, functionalized polylactones, functionalized polyimides, functionalized polylactams, and mixtures thereof. 
   
   
       12 . The silicone hydrogel of  claim 14  wherein said hydrophilic polymer is selected from the group consisting of poly-N-vinyl pyrrolidone, poly-N-vinyl-2-piperidone, poly-N-vinyl-2-caprolactam, poly-N-vinyl-3-methyl-2- caprolactam, poly-N-vinyl-3-methyl-2-piperidone, poly-N-vinyl-4-methyl-2- piperidone, poly-N-vinyl-4-methyl-2-caprolactam, poly-N-vinyl-3-ethyl-2- pyrrolidone, and poly-N-vinyl-4,5-dimethyl-2-pyrrolidone, polyvinylimidazole, poly-N-N-dimethylacrylamide, polyvinyl alcohol, polyacrylic acid, polyethylene oxide, poly 2 ethyl oxazoline, heparin polysaccharides, polysaccharides, mixtures and copolymers thereof 
   
   
       13 . The hydrogel of  claim 1 , wherein the high molecular weight hydrophilic polymer is poly-N-vinylpyrrolidone. 
   
   
       14 . The silicone hydrogel of  claim 1  wherein said compatibilzing component is a compound of Formula I or II 
     
       
         
         
             
             
         
       
     
     wherein:
 n is an integer between 3 and 35 
 R 1  is hydrogen, C 1-6 alkyl, 
 R 2 ,R 3 , and R 4 , are independently, C 1-6 alkyl, triC 1-6 alkylsiloxy, phenyl, naphthyl, substituted C 1-6 alkyl, substituted phenyl, or substituted naphthyl 
 where the alkyl substitutents are selected from one or more members of the group consisting of C 1-6 alkoxycarbonyl, C 1-6 alkyl, C 1-6 alkoxy, amide, halogen, hydroxyl, carboxyl, C 1-6 alkylcarbonyl and formyl, and 
 where the aromatic substitutents are selected from one or more members of the group consisting of C 1-6 alkoxycarbonyl, C 1-6 alkyl, C 1-6 alkoxy, amide, halogen, hydroxyl, carboxyl, C 1-6 alkylcarbonyl and formyl; 
 R 5  is a hydroxyl, an alkyl group containing one or more hydroxyl groups, or (CH 2 (CR 9 R 10 ) y O) x )—R 11  wherein y is 1 to 5, preferably 1 to 3, x is an integer of 1 to 100, preferably 2 to 90 and more preferably 10 to 25; R 9 -R 11  are independently selected from H, alkyl having up to 10 carbon atoms and alkyls having up to 10 carbon atoms substituted with at least one polar functional group; 
 R 6  is a divalent group comprising up to 20 carbon atoms; 
 R 7  is a monovalent group that can undergo free radicals or cationic polymerization, comprising up to 20 carbon atoms, and 
 R8 is is a divalent or trivalent group comprising up to 20 carbon atoms. 
 
   
   
       15 . The silicone hydrogel of  claim 1  wherein said hydroxyl-functionalized silicone-containing monomer is selected from the group consisting of 2-propenoic acid, 2-methyl-2-hydroxy-3-[3-[1,3,3,3-tetramethyl-1-[trimethylsilyl)oxy]disiloxanyl]propoxy]propyl ester, (3-methacryloxy-2-hydroxypropyloxy)propyltris(trimethylsiloxy)silane, (2-methacryloxy-3-hydroxypropyloxy)propylbis(trimethylsiloxy)methylsilane and mixtures thereof. 
   
   
       16 . The hydrogel of  claim 1  wherein said compatibilizing component comprises at least one compound of Formula III:
   IWA-HB-[IWA-HB] x -IWA   Wherein x is 1 to 10;   IWA is a difunctional hydrophilic polymer having a number average molecular weight of between about 1000 and about 50,000 Daltons; and   HB is a difunctional moeity comprising at least one N which is capable of hydrogen bonding.   
   
   
       17 . The hydrogel of  claim 16  wherein said IWA is derived from {acute over (α)},ω-hydroxyl terminated PVP and {acute over (α)},ω-hydroxyl terminated polyoxyalkylene glycols. 
   
   
       18 . The hydrogel of  claim 16  wherein HB is a difunctional group selected from the group consisting of amides, imides, carbamates ureas, and combinations thereof. 
   
   
       19 . The hydrogel of  claim 1  wherein said compatibilizing component is present in an amount between about 5 and about 90 weight %. 
   
   
       20 . The hydrogel of  claim 1  further comprising at least one oxygen permeable component in addition to said siloxane containing macromer or prepolymer. 
   
   
       21 . The hydrogel of  claim 20  wherein said oxygen permeable component is selected from the group consisting of amide analogs of 3-methacryloxypropyltris(trimethylsiloxy)silane; siloxane vinyl carbamate analogs, siloxane vinyl carbonate analogs, and siloxane containing monomers, combinations and oligomers thereof. 
   
   
       22 . The hydrogel  claim 20  wherein said oxygen permeable component is selected from the group consisting of 3-methacryloxypropyltris(trimethylsiloxy)silane, monomethacryloxypropyl terminated polydimethylsiloxanes, polydimethylsiloxanes, 3-methacryloxypropylbis(trimethylsiloxy)methylsilane, methacryloxypropylpentamethyl disiloxane and combinations thereof. 
   
   
       23 . The hydrogel of claim.20 wherein said oxygen permeable component is present in an amount of 0 to about 80 weight %. 
   
   
       24 . The hydrogel of 20 wherein said oxygen permeable component is present in an amount of about 5 to about 60%. 
   
   
       25 . The hydrogel of  claim 20  wherein said oxygen permeable component is present in an amount of about 10 to about 40%. 
   
   
       26 . The hydrogel of  claim 1  further comprising at least one hydrophilic monomer. 
   
   
       27 . The hydrogel  claim 26  wherein said at least one hydrophilic monomer comprises at least one acrylic group, vinyl group or a combination thereof. 
   
   
       28 . The hydrogel of  claim 27  wherein said acrylic group has the formula CH 2 ═CRCOX, where R is hydrogen or C 1-6 alkyl and X is O or N. 
   
   
       29 . The hydrogel of  claim 26  wherein said at least one hydrophilic monomer is selected from the group consisting of N,N-dimethylacrylamide, 2-hydroxyethyl methacrylate, glycerol methacrylate, 2-hydroxyethyl methacrylamide, polyethyleneglycol monomethacrylate, methacrylic acid, acrylic acid, N-vinyl pyrrolidone, N-vinyl-N-methyl acetamide, N-vinyl-N-ethyl acetamide, N-vinyl-N-ethyl formamide, N-vinyl formamide, hydrophilic vinyl carbonate monomers, vinyl carbamate monomers, hydrophilic oxazolone monomers, polydextran and copolymers and combinations thereof. 
   
   
       30 . The hydrogel of  claim 26  wherein said at least one hydrophilic monomer comprises at least one polyoxyethylene polyols having one or more of the terminal hydroxyl groups replaced with a functional group containing a polymerizable double bond. 
   
   
       31 . The hydrogel of  claim 26  wherein said at least one hydrophilic monomer is selected from the group consisting of polyethylene glycol, ethoxylated alkyl glucoside, and polyethylene polyols having one or more terminal polymerizable olefinic groups bonded to the polyethylene polyol. 
   
   
       32 . The hydrogel of  claim 26  wherein said at least one hydrophilic monomer is selected from the group consisting of N,N-dimethylacrylamide, 2-hydroxyethyl methacrylate, glycerol methacrylate, 2-hydroxyethyl methacrylamide, N-vinylpyrrolidone, polyethyleneglycol monomethacrylate, methacrylic acid, acrylic acid and combinations thereof. 
   
   
       33 . The hydrogel of  claim 26  wherein said at least one hydrophilic monomer comprises N,N-dimethylacrylamide. 
   
   
       34 . The hydrogel of  claim 26  wherein said at least one hydrophilic monomer is present in amounts of about 0 to about 70 weight %. 
   
   
       35 . The hydrogel of  claim 26  wherein said at least one hydrophilic monomer is present in amounts of about 5 to about 60 weight %. 
   
   
       36 . The hydrogel of  claim 26  wherein said at least one hydrophilic monomer is present in amounts of about 10 to 50 weight %. 
   
   
       37 . The hydrogel of  claim 1  comprising about 1 to about 15 weight % high molecular weight hydrophilic polymer and about 5 to about 90 weight % hydroxyl-functionalized silicone-containing monomer. 
   
   
       38 . The hydrogel of  claims 1  comprising about 1% to about 15% high molecular weight hydrophilic polymer; about 5 to about 90 weight % compatibilizing component; about 5 to about 50 weight % said siloxane containing macromer, 0 to about 80 weight % siloxane containing monomer and 0 to about 70 weight % hydrophilic monomer. 
   
   
       39 . The hydrogel of  claim 1  comprising about 3% to about 15% high molecular weight hydrophilic polymer; about 10 to about 80 weight % compatibilizing component; about 10 to about 50 weight % said siloxane containing macromer or prepolymer, 5 to about 60 weight % siloxane containing momoner and 5 to about 60 weight % hydrophilic monomer. 
   
   
       40 . The hydrogel of  claim 1  comprising about 5% to about 12% high molecular weight hydrophilic polymer; about 15 to about 55 weight % compatibilizing component; about 15 to about 45 weight % said siloxane containing macromer, 10 to about 40 weight % oxygen permeable component and 10 to about 50 weight % hydrophilic monomer. 
   
   
       41 . A silicone hydrogel contact lens comprising the hydrogel of  claim 1  and wherein said contact lens is not surface modified. 
   
   
       42 . The lens of of  claim 41 , wherein the contact lens is a soft contact lens. 
   
   
       43 . The lens of  claim 41  wherein said lens has an advancing dynamic contact angle of less than about 70°. 
   
   
       44 . The lens of  claim 41  wherein said lens has an advancing dynamic contact angle of less than about 60°. 
   
   
       45 . The lens of  claim 41  wherein said lens, after about one day of wear, has a tear film break up time of at least about 7 seconds. 
   
   
       46 . The lens of  claim 41  wherein said lens further comprises a modulus of less than about 90 psi. 
   
   
       47 . The lens of  claims 41  wherein said lens further comprises a water content between about 10 and about 60%. 
   
   
       48 . The hydrogel of  claim 1  wherein said high molecular weight hydrophilic polymer is present in an amount sufficient to provide an article formed from said hydrogel with an advancing dynamic contact angle which is at least about 10% lower than a hydrogel without said hydrophilic polymer. 
   
   
       49 . The hydrogel of  claim 1  wherein said hydrogel is an interpenetrating network or a semi-interpenetrating network. 
   
   
       50 . A method comprising the steps of (a) mixing at least one diluent which is water soluble at processing conditions and reactive components comprising at least one high molecular weight hydrophilic polymer, at least one siloxane containing macromer and an effective amount of at least one compatibilizing component to form a reaction mixture and (b) curing the product of step (a) to form a biomedical device; (c) removing said biomedical device from a mold in which said biomedical device was cured and (d) hydrating said biomedical device, wherein both steps (c) and (d) are performed in aqueous solutions which comprise water as a substantial component. 
   
   
       51 . The method of  claim 50  wherein said biomedical device comprises an ophthalmic device. 
   
   
       52 . The method of  claim 50  wherein said ophthalmic device is a silicone hydrogel contact lens. 
   
   
       53 . (canceled) 
   
   
       54 . The method of  claim 50  wherein said diluent is selected from the group consisting of ethers, esters, alkanes, alkyl halides, silanes, amides, alcohols and mixtures thereof. 
   
   
       55 . The method of  claim 50  wherein said diluent selected from the group consisting amides, alcohols and mixtures thereof. 
   
   
       56 . The method of  claim 50  wherein said diluent selecting the group consisting of tetrahydrofuran, ethyl acetate, methyl lactate, i-propyl lactate, ethylene chloride, octamethylcyclotetrasiloxane, dimethyl formamide, dimethyl acetamide, dimethyl propionamide, N methyl pyrrolidinone mixtures thereof and mixtures of any of the foregoing with at least one alcohol. 
   
   
       57 . The method of  claim 50  wherein said diluent comprises at least one alcohol having at least 4 carbon atoms. 
   
   
       58 . The method of  claim 50  wherein said diluent comprises at least one alcohol having at least 5 carbons atoms. 
   
   
       59 . The method of  claim 50  wherein said diluents are inert and easily displaceable with water. 
   
   
       60 . The method of  claim 50  wherein said diluent comprises at least one alcohol selected from the group consisting of tert-butanol, tert-amyl alcohol, 2-butanol, 2-methyl-2-pentanol, 2,3-dimethyl-2-butanol, 3-methyl-3-pentanol, 3-ethyl-3-pentanol, 3,7-dimethyl-3-octanol and mixtures thereof. 
   
   
       61 . The method of  claim 50  wherein said diluent is selected from the group consisting of hexanol, heptanol, octanol, nonanol, decanol, tert-butyl alcohol, 3-methyl-3-pentanol, isopropanol, t amyl alcohol, ethyl lactate, methyl lactate, i-propyl lactate, 3,7-dimethyl-3-octanol, dimethyl formamide, dimethyl acetamide, dimethyl propionamide, N methyl pyrrolidinone and mixtures thereof. 
   
   
       62 . The method of  claim 50  wherein said diluent is selected from the group consisting of 1-ethoxy-2-propanol, 1-methyl-2-propanol, t-amyl alcohol, tripropylene glycol methyl ether, isopropanol, 1-methyl-2-pyrrolidone, N,N-dimethylpropionamide, ethyl lactate, dipropylene glycol methyl ether and mixtures thereof. 
   
   
       63 . The method of  claim 50  wherein said diluent is present in an amount less than about 40 weight % based upon the reaction mixture. 
   
   
       64 . The method of  claim 50  wherein said diluent is present in an amount between about 10 and about 30 weight % based upon the reaction mixture. 
   
   
       65 . (canceled) 
   
   
       66 . The method of claim  5350  wherein said curing is conducted via heat, exposure to radiation or a combination thereof and said reaction mixture further comprises at least one initiator. 
   
   
       67 . The method of  claim 66  wherein said curing is conducted via irradiation comprises ionizing and/or actinic radiation and said initiator comprises at least one photoinitiator. 
   
   
       68 . The method of  claim 67  wherein said radiation comprises light having a wavelength of about 150 to about 800 nm and said initiator is selected from the group consisting of aromatic alpha-hydroxy ketones, alkoxydoxybenzoins, acetophenones, acyl phosphine oxides, mixtures of tertiary amines and diketones, and mixtures thereof. 
   
   
       69 . The method of  claim 67  wherein said initiator is selected from the group consisting of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, bis(2,6-dimethoxybenzoyl)-2,4-4-trimethylpentyl phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide, 2,4,6-trimethylbenzyldiphenyl phosphine oxide and 2,4,6-trimethylbenzyoyl diphenylphosphine oxide, benzoin methyl ester, combinations of camphorquinone and ethyl 4-(N,N-dimethylamino)benzoate and mixtures thereof. 
   
   
       70 . The method of  claim 67  wherein said initiator is present in the reaction mixture in amounts from about 0.1 to about 2 weight percent based upon said reactive components. 
   
   
       71 . The method of  claim 67  wherein said curing is conducted via visible light irradiation. 
   
   
       72 . The method of  claim 71  wherein said initiator comprises 1-hydroxycyclohexyl phenyl ketone, bis(2,6-dimethoxybenzoyl)-2,4-4-trimethylpentyl phosphine oxide and mixtures thereof. 
   
   
       73 . The method of  claim 71  wherein said initiator comprises bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide. 
   
   
       74 . The method of  claims 67  wherein said reactive components further comprises at least one UV absorbing compound. 
   
   
       75 . The method of  claim 71  wherein said curing step is conducted at a cure intensity between about 0.1 and about 6 mW/cm 2 . 
   
   
       76 . The method of  claim 71  wherein said curing step is conducted at a cure intensity of between about. 0.2 mW/cm 2  to about 3 mW/cm 2 . 
   
   
       77 . The method of  claims 75  wherein said curing step further comprises a cure time of at least about 1 minute. 
   
   
       78 . The method of  claims 75  wherein said curing step further comprises a cure time of between about 1 and about 60 minutes. 
   
   
       79 . The method of  claim 75  wherein said curing step further comprises a cure time of between about 1 and about 30 minutes. 
   
   
       80 . The method of  claim 75  wherein said curing step is conducted at a temperature greater than about 25° C. 
   
   
       81 . The method of  claim 75  wherein said curing step is conducted at a temperature between about 25° C. and 70° C. 
   
   
       82 . The method of  claim 75  wherein said curing step is conduct at a temperature between about 40° C. and 70° C. 
   
   
       83 . The method of claim  5350  wherein said reaction mixture is cured in a mold and said method further comprises the step deblocking said ophthalmic device from said mold. 
   
   
       84 . The method of  claim 83  wherein said reaction mixture further comprises at least one low molecular weight hydrophilic polymer. 
   
   
       85 . The method of  claim 84  wherein said low molecular weight hydrophilic polymer has a number average molecular weight of less than about 40,000 Daltons. 
   
   
       86 . The method of  claim 84  wherein said low molecular weight hydrophilic polymer has a number average molecular weight of less than about 20,000 Daltons. 
   
   
       87 . The method of  claim 84  wherein the low molecular weight polymer is selected from the group consisting of water soluble polyamides, lactams and polyethylene glycols, and mixtures thereof. 
   
   
       88 . The method of  claim 84  wherein the low molecular weight polymer is selected from the group consisting poly-vinylpyrrolidone, polyethylene glycols, poly 2 ethyl-2-oxazoline and mixtures thereof. 
   
   
       89 . The method of  claim 84  wherein the low molecular weight hydrophilic polymer is present in amounts up to about 20 weight % based upon the reaction mixture. 
   
   
       90 . The method of  claim 84  wherein the low molecular weight hydrophilic polymer is present in amounts between about 5 and about 20 weight % based upon the reaction mixture. 
   
   
       91 . The method of  claim 84  wherein said deblocking is conducted using an aqueous solution. 
   
   
       92 . The method of  claim 84  wherein said aqueous solution further comprises at least one surfactant. 
   
   
       93 . The method of  claim 92  wherein said surfactant comprises at least one non-ionic surfactant. 
   
   
       94 . The method of  claim 92  wherein said surfactant comprises TWEEN®, or DOE120. 
   
   
       95 . The method of  claim 92  wherein said surfactant is present in amounts up to about 10,000 ppm. 
   
   
       96 . The method of  claim 92  wherein said surfactant is present in amounts between about 100 and about 1200 ppm. 
   
   
       97 . The method of  claim 83  wherein said aqueous solution comprises at least one organic solvent. 
   
   
       98 . The method of  claim 83  wherein said deblocking is conducted at a temperature between about ambient and about 100° C. 
   
   
       99 . The method of  claim 83  wherein said deblocking is conducted at a temperature between about 70° C. and about 95° C. 
   
   
       100 . The method of  claim 83  wherein said deblocking is conducted using agitation. 
   
   
       101 . The method of  claim 83  wherein said agitation comprises sonication. 
   
   
       102 . A method comprising the steps of (a) mixing reactive components comprising a high molecular weight hydrophilic polymer and an effective amount of a compatibilizing component and (b) curing the product of step (a) at or above a minimum gel time, to form a wettable biomedical device. 
   
   
       103 . The method of  claim 102  wherein said device is a ophthalmic lens. 
   
   
       104 . The method of  claim 103  wherein said device is a contact lens. 
   
   
       105 . The method of  claim 103  wherein said lens comprises an advancing dynamic contact angle of about 80° or less. 
   
   
       106 . The method of  claim 103  wherein said lens comprises an advancing dynamic contact angle of about 70° or less. 
   
   
       107 . The method of  claim 103  wherein said lens comprises a tear film break up time of at least about 7 seconds. 
   
   
       108 . The method of  claim 103  wherein said reactive components further comprises at least one initiator 
   
   
       109 . The method of  claim 108  wherein said cure is conducted via irradiation and said conditions comprise an initiator concentration and cure intensity effective to provide said minimum gel time. 
   
   
       110 . The method of  claim 109  wherein said initiator is present in an amount up to about 1% based upon all reactive components. 
   
   
       111 . The method of  claim 109  wherein said initiator is present in an amount less than about 0.5% based upon all reactive components. 
   
   
       112 . The method of  claim 109  wherein said cure is conducted via irradiation at an intensity of less than about 5 mW/cm 2 . 
   
   
       113 . The method of  claim 109  wherein said gel time is at least about 30 seconds. 
   
   
       114 . The method of  claim 109  wherein said gel time is at least about 35 seconds. 
   
   
       115 . The method of  claim 102  wherein said compatibilizing component is not a hydroxyl functionalized macromer made by group transfer polymerization. 
   
   
       116 . The method of  claim 102  wherein said reactive components further comprise at least one macromer. 
   
   
       117 . The method of  claim 50  wherein said compatibilizing component is not a hydroxyl functionalized macromer made by group transfer polymerization. 
   
   
       118 . A method for improving the wettability of an ophthalmic device formed from a reaction mixture comprising adding at least one high molecular hydrophilic weight polymer and a compatibilizing effective amount of at least one compatibilizing component to said reaction mixture, wherein said compatibilizing component is not a styrene functionalized prepolymer made from hydroxyl functional methacrylates. 
   
   
       119 . The method of  claim 118  wherein said compatibilizing component has a compatibility index of greater than about 0.5. 
   
   
       120 . The method of  claim 118  wherein said compatibilizing component has a compatibility index of greater than about 1. 
   
   
       121 . The method of  claim 118  wherein said compatibilizing component comprises at least one siloxane group. 
   
   
       122 . The method of  claim 121  wherein said compatibilizing component further comprises hydroxyl functionality and has a Si to OH ratio of less than about 15:1. 
   
   
       123 . The method of  claim 121  wherein said compatibilizing component has a Si to OH ratio of between about 1:1 to about 10:1. 
   
   
       124 . An ophthalmic lens comprising a silicone hydrogel which has, without surface treatment, a tear film break up time of at least about 7 seconds 
   
   
       125 . A silicone hydrogel contact lens comprising at least one oxygen permeable component, at least one compatibilizing component and an amount of high molecular weight hydrophilic polymer sufficient to provide said device, without a surface treatment, with tear film break up time after about one day of wear of at least about 7 seconds. 
   
   
       126 . A device comprising a silicone hydrogel contact lens which is substantially free from surface deposition without surface modification.