Ionic silicone hydrogels comprising pharmaceutical and/or nutriceutical components and having improved hydrolytic stability

Abstract

The present invention relates to ionic silicone hydrogel polymers displaying improved thermal stability. More specifically, the present invention relates to a polymer formed from reactive components comprising at least one silicone component and at least one ionic component comprising at least one anionic group. The polymers of the present invention display good thermal stability and desirable protein uptake.

We claim: 
     
         1 . A polymer formed from reactive components comprising about 10 to about 20 mmol/100 gm reactive mixture of at least one anionic component and at least one silicone component selected from the group consisting of reactive polydialkylsiloxane selected from compounds of Formula I: 
       
         
           
           
               
               
           
         
         where b=2 to 20; terminal R 1  are independently selected from monovalent groups comprising at least one ethylenically unsaturated moiety, monovalent alkyl group having 2 to 16 carbon atoms, provided that one terminal R 1  comprises an ethylenically unsaturated moiety, and the remaining R 1  are selected from monovalent alkyl groups having 1 to 16 carbon atoms, wherein said reactive components comprise less than 5 wt % TRIS, are free of linear polysiloxane crosslinkers and wherein said contact lens further comprises at least one pharmaceutical or neutraceutical component. 
       
     
     
         2 . The contact lens of  claim 1  wherein said reactive components are free of TRIS. 
     
     
         3 . The contact lens of  claim 2  wherein said ionic component comprises at least one polymerizable group and three to ten carbon atoms. 
     
     
         4 . The contact lens of  claim 2  where said ionic component comprises three to eight carbon atoms. 
     
     
         5 . The contact lens of  claim 1  wherein said ionic component is a carboxylic acid containing component selected from the group consisting of free radical reactive carboxylic acids comprising 1-8 carbon atoms. 
     
     
         6 . The contact lens of  claim 1  wherein said ionic component comprises at least one carboxylic acid group. 
     
     
         7 . The contact lens of  claim 1  wherein said carboxylic acid-containing component is selected from the group consisting of (meth)acrylic acid, acrylic acid, itaconic acid, crotonic acid, cinnamic acid, vinylbenzoic acid, fumaric acid, maleic acid, N-vinyloxycarbonyl alanine, 3-acrylamidopropionic acid, 4-acrylamidobutanoic acid, 5-acrylamidopentanoic acid, N-vinyloxycarbonyl-α-alanine, N-vinyloxycarbonyl-β-alanine (VINAL), 2-vinyl-4,4-dimethyl-2-oxazolin-5-one (VDMO), reactive sulphonate salts, including sodium-2-(acrylamido)-2-methylpropane sulphonate, 3-sulphopropyl(meth)acrylate potassium salt, 3-sulphopropyl(meth)acrylate sodium salt, b is 3-sulphopropyl itaconate di sodium, bis 3-sulphopropyl itaconate di potassium, vinyl sulphonate sodium salt, vinyl sulphonate salt, styrene sulphonate, 2-sulphoethyl methacrylate and mixtures thereof. 
     
     
         8 . The contact lens of  claim 1  wherein said carboxylic acid-containing component comprises methacrylic acid, 3-acrylamidopropionic acid, 4-acrylamidobutanoic acid, 5-acrylamidopentanoic acid, N-vinyloxycarbonyl-α-alanine, N-vinyloxycarbonyl-β-alanine (VINAL), and mixtures thereof. 
     
     
         9 . The contact lens of  claim 8  wherein said carboxylic acid-containing component comprises methacrylic acid. 
     
     
         10 . The contact lens of  claim 1  wherein said at least one silicone component is selected from the group consisting of mono(meth)acryloxypropyl terminated mono-n-C 1-4 -alkyl terminated polydialkylsiloxane, (meth)acryloxypropyl-terminated polydialkylsiloxane, mono-(3-methacryloxy-2-hydroxypropyloxy)propyl terminated, mono-C 1-4 alkyl alkyl terminated polydialkylsiloxane and combinations thereof. 
     
     
         11 . The contact lens of  claim 1  wherein said at least one silicone component is selected from mono(meth)acryloxypropyl terminated mono-n-butyl terminated polydimethylsiloxane, mono(meth)acryloxypropyl terminated polydimethylsiloxane, mono-(3-methacryloxy-2-hydroxypropyloxy)propyl terminated, mono-butyl terminated polydialkylsiloxane mono-(3-methacryloxy-2-hydroxypropyloxy)propyl terminated, mono-methyl terminated polydialkylsiloxane combinations thereof and the like. 
     
     
         12 . The contact lens of  claim 1  wherein said at least one silicone component is selected from monomethacryloxypropyl-terminated mono-n-butyl terminated polydimethysiloxane, methacryloxypropyl-terminated polydimethylsiloxane and mono-(3-methacryloxy-2-hydroxypropyloxy)propyl terminated, mono-butyl terminated polydimethylsiloxane and mixtures thereof. 
     
     
         13 . The contact lens of  claim 1  wherein said at least one pharmaceutical pharmaceutical or neutraceutical component is cationic. 
     
     
         14 . The contact lens of  claim 1  wherein said at least one pharmaceutical pharmaceutical or neutraceutical component is selected from the group consisting of atropine, pirenzepine, doxycycline, brimonidine, brinzolamide, dorzolamide, betaxolol, apraclonidine, ccr2 antagonist, olopatadine, alcaftadine, betaxolol, bupivacaine, carbachol, carteolol, chlortetracycline, cyclopentolate, dibutoline, dipivefrin, ephedrine, erythromycin, gentamycin, gramicidin, homatropine ketotifen, levobunolol, levocabastine, lidocaine, lignocaine, lomefloxacin, mepivacaine, naphazoline, neomycin, ofloxacin, oxybuprocaine, pheniramine, physostigmine, pilocarpine, polymyxin B, proparacaine, pyrilamine, tetracaine, tetracycline, tetrahydrozoline, timolol, tropicamide, vidarabine, pharmaceutically acceptable salts thereof and combinations thereof and the like. 
     
     
         15 . The contact lens of  claim 1  wherein said at least one pharmaceutical pharmaceutical or neutraceutical component is selected from the group consisting of atropine, pirenzepine, doxycycline, brimonidine, brinzolamide, dorzolamide, betaxolol, apraclonidine, ccr2 antagonist, olopatadine, alcaftadine, betaxolol, bupivacaine, carbachol, carteolol, chlortetracycline, cyclopentolate, dibutoline, dipivefrin, erythromycin, gentamycin, gramicidin, homatropine ketotifen, levobunolol, levocabastine, lidocaine, lignocaine, lomefloxacin, mepivacaine, naphazoline, ofloxacin, pheniramine, physostigmine, pilocarpine, polymyxin B, proparacaine, pyrilamine, tetracaine, tetrahydrozoline, timolol, tropicamide pharmaceutically acceptable salts thereof and combinations thereof and the like. 
     
     
         16 . The contact lens of  claim 1  wherein said at least one pharmaceutical pharmaceutical or neutraceutical component is selected from the group consisting of atropine, ketotifen, olopatadine, alcaftadine, levocabastine, pirenzepine, doxycycline, brimonidine, brinzolamide, dorzolamide, betaxolol, apraclonidine, ccr2 antagonist, olopatadine pharmaceutically acceptable salts thereof and combinations thereof and the like. 
     
     
         17 . The contact lens of  claim 1 ,  14 ,  15  or  16 , wherein said at least one pharmaceutical or neutraceutical component in a symptom mitigating effective amount. 
     
     
         18 . The contact lens of  claims 17  wherein said symptom mitigating effective amount is between about 5 μg and about less than 200 μg. 
     
     
         19 . The contact lens of  claims 17  wherein said symptom mitigating effective amount is between about 9 μg and about 100 μg. 
     
     
         20 . The contact lens of  claims 17  wherein said symptom mitigating effective amount alleviates symptoms for between about 5 minutes, and about 12 hours from insertion of said contact lens on a human's eye. 
     
     
         21 . The contact lens of  claim 1  wherein said contact lens absorbs at least about 50 μg lysozyme. 
     
     
         22 . The contact lens of  claim 1  wherein said contact lens absorbs at least about 100 μg lysozyme. 
     
     
         23 . The contact lens of  claim 1  wherein said contact lens absorbs at least about 200 μg lysozyme. 
     
     
         24 . The contact lens of  claim 1  wherein said contact lens absorbs about 3 μg or less lipocalin. 
     
     
         25 . The contact lens of  claim 1  wherein at least about 60% of all proteins absorbed in or on said contact lens are in native form. 
     
     
         26 . The contact lens of  claim 1  wherein at least about 75% of all proteins absorbed in or on said contact lens are in native form. 
     
     
         27 . The contact lens of  claim 1  further comprising a water content of at least about 15%. 
     
     
         28 . The contact lens of  claim 1  further comprising a Dk of at least about 50. 
     
     
         29 . The contact lens of  claim 28  wherein at least about 75% of all proteins absorbed in or on said contact lens are in native form. 
     
     
         30 . A contact lens formed by polymerizing components comprising at least one silicone component and at least one ionic component comprising at least one carboxylic acid group in molar concentrations up to about 9.3 mmol/100 gm and wherein said contact lens absorbs at least about 10 μg lysozyme, less than about 5 μg lipocalin and wherein at least about 50% of proteins absorbed in or on said contact lens are in native form.