AU2007234531B2 - Biomedical devices containing internal wetting agents - Google Patents

Description

AUSTRALIA Patents Act 1990 ORIGINAL COMPLETE SPECIFICATION INVENTION TITLE: BIOMEDICAL DEVICES CONTAINING INTERNAL WETTING AGENTS The following statement is a full description of this invention, including the best method of performing it known to us: IS/1 1/07.116949 - cove shect, BIOMEDICAL DEVICES CONTAINING INTERNAL WETTING AGENTS This Application is a divisional of Australian Patent Application No. 2002323661, and the whole contents thereof are included herein by reference. 5 FIELD OF THE INVENTION This invention relates to silicone hydrogels that contain internal wetting agents, as well as methods for their production and use. 10 BACKGROUND OF THE INVENTION Contact lenses have been used commercially to improve vision since at least the 1950s. The first contact lenses were made of hard materials and as such were somewhat uncomfortable to users. Modern lenses have been developed that are made 15 of softer materials, typically hydrogels and particularly silicone hydrogels. Silicone hydrogels are water-swollen polymer networks that have high oxygen permeability and surfaces that are more hydrophobic than hydrophilic. These lenses provide a good level of comfort to many lens wearers, but there are some users who experience discomfort and excessive ocular deposits leading to reduced visual acuity when using 20 these lenses. This discomfort and deposits has been attributed to the hydrophobic character of the surfaces of lenses and the interaction of those surfaces with the protein, lipids and mucin and the hydrophilic surface of the eye. Others have tried to alleviate this problem by coating the surface of 25 silicone hydrogel contact lenses with hydrophilic coatings. For example, it has been 25 disclosed that silicone hydrogel lenses can be made more compatible with ocular surfaces by applying plasma coatings to the lens surface. However, uncoated silicone hydrogel lenses having low incidences of surface deposits have not been disclosed. Incorporating internal hydrophilic agents (or wetting agents) into a macromer containing reaction mixture has been disclosed. However, not all silicone 30 containing macromers display compatibility with hydrophilic polymers. Modifying the surface of a polymeric article by adding polymerizable surfactants to a monomer mix used to form the article has also been la 12/11/07,10 6949.spei,I -2 disclosed. However, lasting in vivo improvements in wettability and reductions in surface deposits are not likely. Polyvinylpyrrolidone (PVP) or poly-2-ethyl-2-oxazoline have been added to a hydrogel composition to form an interpenetrating network which 5 shows a low 5 degree of surface friction, a low dehydration rate and a high degree of biodeposit resistance. However, the hydrogel formulations disclosed are conventional hydrogels and there is no disclosure on how to incorporate hydrophobic components, such as siloxane monomers, without losing monomer compatibility. While it may be possible to incorporate high molecular weight polymers as 10 internal wetting agents into silicone hydrogel lenses, such polymers are difficult to solubilize in reaction mixtures which contain silicones. In order to solubilize these wetting agents, silicone macromers or other prepolymers must be used. These silicone macromers or prepolymers must be prepared in a separate step and then subsequently mixed with the remaining ingredients of the silicone hydrogel 15 formulation. This additional step (or steps) increases the cost and the time it takes to produce these lenses. Therefore it would be advantageous to find a lens formulation that does not require the use of surface treatment to provide on eye wettability and resistance to surface depositions. 20 SUMMARY OF THE INVENTION In one aspect, the present invention provides a method comprising the steps of (a) mixing 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 and (b) curing the product of step 25 (a) to form a biomedical device. In another aspect, the present invention provides a method comprising the steps of (a) mixing reactive components comprising a high molecular weight hydrophilic polymer, at lest one silicone containing macromer and an effective amount of a compatibilizing component and (b) curing the product of step (a) at or 30 above a minimum gel time, to form a wettable biomedical device. In a further aspect, the present invention provides a method for improving the wettability of an ophthalmic device formed from a reaction mixture comprising 17/12/10,dh-16949 - specipg2&3 -rck.doc.2 -3 adding at least one high molecular weight hydrophilic 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. 5 DETAILED DESCRIPTION OF THE INVENTION A biomedical device formed from a reaction mixture comprising, consisting essentially of, or consisting of a silicone containing macromer, at least one high molecular weight hydrophilic polymer and a compatibilizing amount of a 10 compatibilizing component. It has been surprisingly found that biomedical devices, and particularly ophthalmic devices having exceptional in vivo or clinical wettability, without surface modification may be made by including an effective amount of a high molecular weight hydrophilic polymer and a compatibilizing amount of a compatibilizing 15 component in a silicone hydrogel formulation. By exceptional wettability we mean a decrease in advancing dynamic contact angle of at least about 10% and preferably at least about 20% in some embodiments at least about 50% as compared to a similar formulation without any hydrophilic polymer. Prior to the present invention ophthalmic devices formed from silicone hydrogels either had to be surface modified 20 to provide clinical wettability or be formed from at least one silicone containing macromer having hydroxyl functionality. As used herein, a "biomedical device" is any article that is designed to be used while either in or on mammalian tissues or fluid and preferably on or in human tissues or fluid. Examples of these devices include but are not limited to catheters, 25 implants, stents, and ophthalmic devices such as 17/12/10,dh-16949 - specipg2&3 -rck.doc,3 intraocular lenses and contact lenses. The preferred biomedical devices are ophthalmic devices, particularly contact lenses, most particularly contact lenses made from silicone hydrogels. As used herein, the terms "lens" and "opthalmic device" refer to 5 devices that reside in or on the eye. These devices can provide optical correction, wound care, drug delivery, diagnostic functionality or cosmetic enhancement or effect or a combination of these properties. The term lens includes but is not limited to soft contact lenses, hard contact lenses, intraocular lenses, overlay lenses, ocular inserts, and optical inserts. 10 As used herein the term "monomer" is a compound containing at least one polymerizable group and an average molecular weight of about less than 2000 Daltons, as measure via gel permeation chromatography refractive index detection.. Thus, monomers, include dimers and in some cases oligomers, including oligomers made from more than one monomeric unit. 15 As used herein, the phrase "without a surface treatment" means that the exterior surfaces of the devices of the present invention are not separately treated to improve the wettability of the device. Treatments which may be foregone because of the present invention include, plasma treatments, grafting, coating and the like. However, coatings which provide properties 20 other than improved wettability, such as, but not limited to antimicrobial coatings may be applied to devices of the present invention. Various molecular weight ranges are disclosed herein. For compounds having discrete molecular structures, the molecular weights reported herein are calculated based upon the molecular formula and reported in gm/mol. For 25 polymers molecular weights (number average) are measured via gel permeation chromatography refractive index detection and reported in Daltons or are measured via kinematic viscosity measurements, as described in Encyclopedia of Polymer Science and Engineering, N-Vinyl Amide Polymers, Second edition, Vol 17, pgs. 198-257, John Wiley & Sons Inc. and reported in 30 K-values. High Molecular Weight Hydrophilic Polymer As used herein, "high molecular weight hydrophilic polymer" refers to substances having a weight average molecular weight of no less than about 4 100,000 Daltons, wherein said substances upon incorporation to silicone hydrogel formulations, improve the wettability of the cured silicone hydrogels. The preferred weight average molecular weight of these high molecular weight hydrophilic polymers is greater than about 150,000 Daltons; more 5 preferably between about 150,000 to about 2,000,000 Daltons, more preferably still between about 300,000 to about 1,800,000 Daltons, most preferably about 500,000 to about 1,500,000 Daltons (all weight average molecular weight). Alternatively, the molecular weight of hydrophilic polymers of the 10 invention can be also expressed by the K-value, based on kinematic viscosity measurements, as described in Encyclopedia of Polymer Science and Engineering, N-Vinyl Amide Polymers, Second edition, Vol 17, pgs. 198-257, John Wiley & Sons Inc. When expressed in this manner, hydrophilic monomers having K-values of greater than about 46 and preferably between 15 about 46 and about 150. The high molecular weight hydrophilic polymers are present in the formulations of these devices in an amount sufficient to provide contact lenses, which without surface modification remain substantially free from surface depositions during use. Typical use periods include at least about 8 hours, and preferably worn several days in a row, and more 20 preferably for 24 hours or more without removal. Substantially free from surface deposition means that, when viewed with a slit lamp, at least about 80% and preferably at least about 90%, and more preferably about 100% of the lenses worn in the patient population display depositions rated as none or slight, over the wear period. 25 Suitable amounts of high molecular weight hydrophilic polymer include from about 1 to about 15 weight percent, more preferably about 3 to about 15 percent, most preferably about 5 to about 12 percent, all based upon the total weight of all reactive components. Examples of high molecular weight hydrophilic polymers include but 30 are not limited to polyamides, polylactones, polyimides, polylactams and functionalized polyamides, polylactones, polyimides, polylactams, such as DMA functionalized by copolymerizing DMA with a lesser molar amount of a hydroxyl-functional monomer such as HEMA, and then reacting the hydroxyl groups of the resulting copolymer with materials containing radical 5 polymerizable groups, such as isocyanatoethylmethacrylate or methacryloyl chloride. Hydrophilic prepolymers made from DMA or N-vinyl pyrrolidone with glycidyl methacrylate may also be used. The glycidyl methacrylate ring can be opened to give a diol which may be used in conjunction with other 5 hydrophilic prepolymer in a mixed system to increase the compatibility of the high molecular weight hydrophilic polymer, hydroxyl-functionalized silicone containing monomer and any other groups which impart compatibility. The preferred high molecular weight hydrophilic polymers are those that contain a cyclic moiety in their backbone, more preferably, a cyclic amide or cyclic 10 imide. High molecular weight hydrophilic polymers include but are not limited to 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 15 dimethyl-2-pyrrolidone, polyvinylimidazole, poly-N-N-dimethylacrylamide, polyvinyl alcohol, polyacrylic acid, polyethylene oxide, poly 2 ethyl oxazoline, heparin polysaccharides, polysaccharides, mixtures and copolymers (including block or random, branched, multichain, comb-shaped or star shaped) thereof where poly-N-vinylpyrrolidone (PVP) is particularly preferred. 20 Copolymers might also be used such as graft copolymers of PVP. The high molecular weight hydrophilic polymers provide improved wettability, and particularly improved in vivo wettability to the medical devices of the present invention. Without being bound by any theory, it is believed that the high molecular weight hydrophilic polymers are hydrogen bond 25 receivers which in aqueous environments, hydrogen bond to water, thus becoming effectively more hydrophilic. The absence of water facilitates the incorporation of the hydrophilic polymer in the reaction mixture. Aside from the specifically named high molecular weight hydrophilic polymers, it is expected that any high molecular weight polymer will be useful in this 30 invention provided that when said polymer is added to a silicone hydrogel formulation, the hydrophilic polymer (a) does not substantially phase separate from the reaction mixture and (b) imparts wettability to the resulting cured polymer. In some embodiments it is preferred that the high molecular weight hydrophilic polymer be soluble in the diluent at processing temperatures. 6 Manufacturing processes which use water or water soluble diluents may be preferred due to their simplicity and reduced cost. In these embodiments high molecular weight hydrophilic polymers which are water soluble at processing temperatures are preferred. 5 Compatibilizing Component As used herein a "compatibilizing component" is a compound having a number average molecular weight of about less than 5000 Daltons, and preferably less than about 3000 Daltons, and containing at least one 10 polymerizable group, which is capable of solubilizing the selected reactive components. Without a compatibilizing component the high molecular weight hydrophilic polymer and oxygen permeable components are insufficiently miscible, and cannot, with reasonable processing conditions, form an optically transparent ophthalmic device. The compatibilizing component of the present 15 invention solubilizes the oxygen permeable component(s) and high molecular weight hydrophilic polymer via hydrogen bonding, dispersive forces, combinations thereof and the like. Thus any functionality which reacts in any of these ways with the hydrophilic polymer may be used as a compatibilizing component. Macromers (number average molecular weights of between 20 about 5000 and about 15,000 Daltons) may also be used so long as they have the compatibilizing functionality described herein. If a compatibilizing macromer is used it may still be necessary to add an additional compatibilizing component to get the desired level of wettability inthe resulting ophthalmic device. 25 One suitable class of compatibilizing components of the present invention comprise at least one active hydrogen and at least one siloxane group. An active hydrogen has the ability to hydrogen bond with the hydrophilic polymer and any hydrophilic monomers present. Hydroxyl groups readily participate in hydrogen bonding and are therefore a preferred source 30 of active hydrogens. Thus, in one embodiment, the compatibilizing components of the present invention beneficially comprise at least one hydroxyl group and at least one "-Si-O-Si-"group. It is preferred that silicone and its attached oxygen account for more than about 10 weight percent of 7 said compatibilizing component, more preferably more than about 20 weight percent. The ratio of Si to OH in the compatibilizing component is also important to providing a compatibilzing component which will provide the desired degree 5 of compatibilization. If the ratio of hydrophobic portion to OH is too high, the compatibilizing component may be poor at compatibilizing the hydrophilic polymer, resulting in incompatible reaction mixtures. Accordingly, in some embodiments, the Si to OH ratio is less than about 15:1, and preferably between about 1:1 to about 10:1. In some embodiments primary alcohols 10 have provided improved compatibility compared to secondary alcohols. Those of skill in the art will appreciate that the amount and selection of compatibilizing component will depend on how much hydrophilic polymer is needed to achieve the desired wettability and the degree to which the silicone containing monomer is incompatible with the hydrophilic polymer. 15 Examples of compatibilizing components include monomers of Formulae I and Il R1 R2 R R

R

7

-R

6

-C-R

8 -- Si-R 3 20 Ri R2 R 2

R

5

R

7 -Re-C-R -Si-[OSin-R -C-R 6 -R 45 14 R4 4i wherein: 25 n is an integer between 3 and 35, and preferably between 4 and 25; R' is hydrogen, C 1

.

6 alkyl,;

R

2

,R

3 , and R 4 , are independently, C1.

6 alkyl, triC 1

.

6 alkylsiloxy, phenyl, naphthyl, substituted C 1

.

6 alkyl, substituted phenyl, or substituted naphthyl 8 where the alkyl substitutents are selected from one or more members of the group consisting of C 1

.

6 alkoxycarbonyl, C1.6alkyl, C 1 .- alkoxy, amide, halogen, hydroxyl, carboxyl, C1.ealkylcarbonyl and formyl, and where the aromatic substitutents are selected from one or more 5 members of the group consisting of C 1 .ealkoxycarbonyl, C 1 .ealkyl,

C

1 .ealkoxy, amide, halogen, hydroxyl, carboxyl, C 1

.

6 alkylcarbonyl and formyl;

R

5 is hydroxyl, an alkyl group containing one or more hydroxyl groups, or

(CH

2

(CR

9

R'

0 )yO)x)-R" wherein y is 1 to 5, preferably 1 to 3, x is an integer of 10 1 to 100, preferably 2 to 90 and more preferably 10 to 25; R 9 - R" 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; 15 R 6 is a divalent group comprising up to 20 carbon atoms;

R

7 is a monovalent group that can undergo free radical and/or cationic polymerization comprising up to 20 carbon atoms; and

R

8 is a divalent or trivalent group comprising up to 20 carbon atoms. 20 Reaction mixtures of the present invention may include more than one compatibilizing component. For monofunctional compatibilizing components the preferred R' is hydrogen, and the preferred R 2

,R

3 , and R 4 , are C 1

.

6 alkyl and triC 1

.

6 alkylsiloxy, most preferred methyl and trimethylsiloxy. For multifunctional (difunctional or 25 higher) R 1

-R

4 independently comprise ethylenically unsaturated polymerizable groups and more preferably comprise an acrylate, a styryl, a C 1 .-alkylacrylate, acrylamide, C1.

6 alkylacrylamide, N-vinyllactam, N-vinylamide, , C 2 .1 2 alkenyl,

C

2

.

12 alkenylphenyl, C2-1 2 alkenyinaphthyl, or C2-ealkenylphenylC,-alkyl. The preferred R 5 is hydroxyl , -CH 2 OH or CH 2

CHOHCH

2 OH, with 30 hydroxyl being most preferred.. The preferred R 6 is a divalent C1.ealkyl, C 1

.

6 alkyloxy, C1.

6 alkyloxyC1.

6 alkyl, phenylene, naphthalene, C1-1 2 cycloalkyl,

C

1

.

6 alkoxycarbonyl, amide, carboxy, C 1 .ealkylcarbonyl, carbonyl, C1.

6 alkoxy, substituted C 1 .ealkyl, substituted C1.

6 alkyloxy, substituted C1.6alkyloxyC,.

6 alkyl, 9 substituted phenylene, substituted naphthalene, substituted CI-12cycloalkyl, where the substituents are selected from one or more members of the group consisting of C1.

6 alkoxycarbonyl, CI.alkyl, C 1 .ealkoxy, amide, halogen, hydroxyl, carboxyl, C 1 .ealkylcarbonyl and formyl. The particularly preferred R 6 5 is a divalent methyl (methylene). The preferred R 7 comprises a free radical reactive group, such as an acrylate, a styryl, vinyl, vinyl ether, itaconate group, a C 1 .-alkylacrylate, acrylamide, C 1

.

6 alkylacrylamide, N-vinyllactam, N-vinylamide, C 2

.

1 2 alkenyl,

C

2

-

12 alkenylphenyl, C2-1 2 alkenyinaphthyl, or C2- 6 alkenylphenylC1- 6 alkyl or a 10 cationic reactive group such as vinyl ether or epoxide groups. The particulary preferred R 7 is methacrylate. The preferred R 8 is is a divalent C 1

.

6 alkyl, C 1

.

6 alkyloxy,

C

1 .alkyloxyC 1 .ealkyl, phenylene, naphthalene, C1.12cycloalkyl,

C

1

.

6 alkoxycarbonyl, amide, carboxy, C 1 .ealkylcarbonyl, carbonyl, C 1

.

6 alkoxy, 15 substituted C 1 .ealkyl, substituted C 1 .6alkyloxy, substituted C 1

.

6 alkyloxyC 1 .ealkyl, substituted phenylene, substituted naphthalene, substituted C1.

12 cycloalkyl, where the substituents are selected from one or more members of the group consisting of C 1 .ealkoxycarbonyl, C 1 .-alkyl, C 1 .ealkoxy, amide, halogen, hydroxyl, carboxyl, C1.6alkylcarbonyl and formyl. The particularly preferred Re 20 is C 1 .ealkyloxyC 1 .ealkyl. Examples of compatibilizing component of Formula I that are particularly preferred are 2-propenoic acid, 2-methyl-2-hydroxy-3-[3-[1,3,3,3 tetramethyl-1 -[trimethylsilyl)oxy]disiloxanyl]propoxy]propyl ester (which can also be named (3-methacryloxy-2 25 hydroxypropyloxy)propylbis(trimethylsiloxy)methylsilane. O .. Si(CH 3

)

3 I O O S i-CH3 OH O Si(CH 3

)

3 30 The above compound, (3-methacryloxy-2 hydroxypropyloxy)propylbis(trimethylsiloxy)methylsilane is formed from an 10 epoxide, which produces an 80:20 mixture of the compound shown above and

(

2 -methacryloxy-3-hydroxypropyloxy)propylbis(trimethylsiloxy)methylsilane. In the present invention the 80:20 mixture is preferred over pure (3 methacryloxy-2-hydroxypropyloxy)propylbis(trimethylsiloxy)methylsi lane. In 5 some embodiments of the present invention it is preferred to have some amount of the primary hydroxyl present, preferably greater than about 10 wt% and more preferably at least about 20 wt% Other suitable hydroxyl-functionalized silicone containing monomers include

(

3 -methacryloxy-2-hydroxypropyloxy)propyltris(trimethylsiloxy)silane

S

0 ..S i(CH 3

)

3 O O S'i-0-Si(CH 3

)

3 OH 0 10 Si(CH3)3 111 bis-3-methacryloxy-2-hyd roxypropyloxypropyl polyd imethylsiloxane 0 0 0 0 ,si "* O H '~OH 5 3-methacryloxy-2-(2 hydroxyethoxy)propyloxy)propylbis(trimethylsiloxy)methylsilane 0 s0 00 (l 0-' - - f O 0H I n -i 10 N- 2 -methacryloxyethyI-O-(methyI-bis-trimethylsiloxy-3propy)silyI ca rbamate Me 3 Si SiMe 3 0 0 12 N,N,N',N'-tetrakis(3-methacryloxy-2-hydroxypropyl)-a,w-bis-3-aminopropyl polydimethylsiloxane 5 0 0 HO OH OH HO 0 n = 10-50 The reaction products of glycidyl methacrylate with amino-functional 10 polydimethylsiloxanes may also be used as a compatibilizing components. Other suitable compatibilizing components include those disclosed in columns 6,7 and 8 of US 5,994,488, and monomers disclosed in 4,259,467; 4,260,725; 4,261,875; 4,649,184; 4,139,513, 4,139,692; US 2002/0016383; 4,139,513 and 4,139,692. These and any other patents or applications cited herein are 15 incorporated by reference. Still additional structures which may be suitable compatibilizing components include those similar to the compounds disclosed in Pro. ACS Div. Polym. Mat. Sci. Eng., April 13-17, 1997, p. 42, and having the following structure: 20 OR OR 0 ROH\O R O R RON OR ORO n 0 OR OR 13 where n = 1-50 and R independently comprise H or a polymerizable unsaturated group), with at least one R comprising a polymerizable group, and at least one R, and preferably 3-8 R, comprising H. 5 A second suitable class of compatibilizing components include those having the structure given in Formula IlIl, below: IWA-HB-[lWA-HB],-lWA Wherein x is 1 to 10: 10 IWA is a difunctional hydrophilic polymer as defined below, but 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 with active hydrogens in the hydrophilic polymer and any 15 other component having active hydrogens. Preferred IWA groups may be derived from d,w-hydroxyl terminated PVP and d,w-hydroxyl terminated polyoxyalkylene glycols having number average molecular weights between about 1,000 and about 50,000 Daltons. Preferred HB groups include difunctional amides, imides, carbamates 20 and ureas, combinations thereof and the like. Compatibilizing components of Formula Ill may be made by amine terminated polyoxyalkyleneglycols (Jeffamines) reacted with isocyanates, chloroformates or acyl chlorides or anhydrides. Additional suitable compatibilizing components are disclosed in U.S. 25 Patent 4,235,985 which is hereby incorporated by reference. Suitable compatibilizing components may also comprise silicone containing macromers which have been modified to include compatibilizing functionality as defined above. Such macromers comprise substantial quantities of both Si and HB groups as defined, above, or active hydrogen 30 functionality, such as hydroxyl groups. One class of suitable macromers include hydroxyl functionalized macromers made by Group Transfer Polymerization (GTP), or styrene functionalized prepolymers of hydroxyl functional methacrylates and silicone methacrylates and are disclosed in US6,367,929, which is incorporated herein by reference. In the present 14 ivention, these macromers are preferably used with another compatibilizing component, such as a siloxane containing monomer. Other macromers, such as those made by radical polymerization or condensation reaction may also be used independently or in combination with other compatibilizing 5 components so long as the Si to hydrogen molar ratio (OH) of the macromer is less than about 15:1, and preferably between about 1:1 to about 10:1 or the Si to HB molar ratio is less than about 10:1 and preferably between about 1:1 and about 8:1. However, those of skill in the art will appreciate that including difluoromethylene groups will decrease the molar ratio suitable for providing 10 compatibility. Suitable monofunctional compatibilizing components are commercially available from Gelest, Inc. Morrisville, PA. Suitable multifunctional compatibilizing components are commercially available from Gelest, Inc, Morrisville, PA or may be made using the procedures disclosed in 5,994,488 15 and 5,962,548. Suitable PEG type monofunctional compatibilizing components may be made using the procedures disclosed in PCT/JPO2/02231. Suitable compatibilizing macromers may be made using the general procedure disclosed in US 5,760,100 (material C) or US 6,367,929. 20 While compatibilizing components comprising hydroxyl functionality have been found to be particularly suitable for providing compatible polymers for biomedical devices, and particulaIrly ophthalmic devices, any compatibilizing component which, when polymerized and/or formed into a final article is compatible with the selected hydrophilic components may be used. 25 Compatibilizing components may be selected using the following monomer compatibility test. In this test one gram of each of mono-3-methacryloxypropyl terminated, mono-butyl terminated polydimethylsiloxane (mPDMS MW 800 1000) and a monomer to be tested are mixed together in one gram of 3,7 dimethyl-3-octanol at about 200C. A mixture of 12 weight parts K-90 PVP and 30 60 weight parts DMA is added drop-wise to hydrophobic component solution, with stirring, until the solution remains cloudy after three minutes of stirring. The mass of the added blend of PVP and DMA is determined in grams and recorded as the monomer compatibility index. Any compatibilizing component 15 having a compatibility index of greater than 0.5 grams, more preferably greater than about 1 grams and most preferably greater than about 1.5 grams will be suitable for use in this invention. Those of skill in the art will appreciate that the molecular weight of the active compatibilizing component will effect 5 the results of the above test. Compatibilizing components having molecular weights greater than about 800 daltons may need to mix for longer periods of time to give representative results. An "effective amount" of the compatibilizing component of the invention is the amount needed to compatibilize or dissolve the high molecular weight 10 hydrophilic polymer and the other components of the polymer formulation. Thus, the amount of compatibilizing component will depend in part on the amount of hydrophilic polymer which is used, with more compatibilizing component being needed to compatibilize higher concentrations of high molecular weight hydrophilic polymer. Effective amounts of compatibilizing 15 component in the polymer formulation include about 5% (weight percent, based on the total weight of the reactive components) to about 90 %, preferably about 10% to about 80%, most preferably, about 20% to about 50%. In addition to the high molecular weight hydrophilic polymers and the 20 compatibilizing components of the invention other hydrophilic monomers, oxygen permeability enhancing components, crosslinkers, additives, diluents, polymerization initators may be used to prepare the biomedical devices of the invention. 25 Oxygen Permeable Component The compositions and devices of the present invention may further comprise additional components which provide enhanced oxygen permeability compared to a conventional hydrogel. Suitable oxygen permeable components include siloxane containing monomers, macromers and reactive 30 prepolymers, fluorine containing monomers, macromers and reactive prepolymers and carbon-carbon triple bond containing monomers, macromers and reactive prepolmers and combinations thereof, but exclude the compatibilizing component. For the purposes of this invention, the term macromer will be used to cover both macromers and prepolymers. Preferred 16 oxygen permeable components comprise siloxane containing monomers, macromers, and mixtures thereof Suitable siloxane containing monomers include, amide analogs of TRIS described in U.S. 4,711,943, vinylcarbamate or carbonate analogs decribed in 5 U.S. Pat. 5,070,215, and monomers contained in U.S. Pat. 6,020,445 are useful and these aforementioned patents as well as any other patents mentioned in this specification are hereby incorporated by reference. More specifically, 3-methacryloxypropyltris(trimethylsiloxy)silane (TRIS), monomethacryloxypropyl terminated polydimethylsiloxanes, 10 polydimethylsiloxanes, 3-methacryloxypropylbis(trimethylsiloxy)methylsilane, methacryloxypropylpentamethyl disiloxane and combinations thereof are particularly useful as siloxane containing monomers of the invention. Additional siloxane containing monomers may be present in amounts of about 0 to about 75 wt%, more preferably of about 5 and about 60 and most 15 preferably of about 10 and 40 weight%. Suitable siloxane containing macromers have a number average molecular weight between about 5,000 and about 15,000 Daltons. Siloxane containing macromers include materials comprising at least one siloxane group, and preferably at least one dialkyl siloxane group and more preferably 20 at least one dimethyl siloxane group. The siloxane containing macromers may include other components such as urethane groups, alkylene or alkylene oxide groups, polyoxyalkalene groups, arylene groups, alkyl esters, amide groups, carbamate groups, perfluoroalkoxy groups, isocyanate groups, combinations thereof of and the like. A preferred class of siloxane containing 25 macromers may be formed via the polymerization of one or more siloxanes with one or more acrylic or methacrylic materials. Siloxane containing macromers may be formed via group transfer polymerization ("GTP"), free radical polymerization, condensation reactions and the like. The siloxane containing macromers may be formed in one or a series of steps depending 30 on the components selected and using conditions known in the art. Specific siloxane containing macromers, and methods for their manufucture, include those disclosed in US 5,760,100 as materials A-D (methacrylate functionalized, silicone-fluoroether urethanes and methacrylate functionalized, silicone urethanes), and those disclosed in US 6,367,929 (styrene 17 functionalized prepolymers of hydroxyl functional methacrylates and silicone methacrylates), the disclosures of which are incorporated herein by reference. Suitable siloxane containing reactive prepolymers include vinyl carbamate functionalized polydimethylsiloxane, which is further disclosed in 5 US 5,070215 and urethane based prepolymers comprising alternating "hard" segments formed from the reaction of short chained diols and diisocyantes and "soft" segments formed from a relatively high molecular weight polymer, which is a,w endcapped with two active hydrogens. Specific examples of suitable siloxane containing prepolymers, and methods for their manufacture, 10 are disclosed in US 5,034,461, which is incorporated herein by reference. The hydrogels of the present invention may comprise at least one siloxane containing macromer. The siloxane containing macromer may be present in amounts between about 5 and about 50 weight%, preferably between about 10 and about 50 weight% and more preferably between about 15 15 and about 45 weight%, all based upon the total weight of the reactive components. Suitable fluorine containing monomers include fluorine-containing (meth)acrylates, and more specifically include, for example, fluorine containing C 2

-C

12 alkyl esters of (meth)acrylic acid such as 2,2,2-trifluoroethyl 20 (meth)acrylate, 2,2,2,2',2',2'-hexafluoroisopropyl (meth)acrylate, 2,2,3, 3,4,4,4-heptafluorobutyl (meth)acrylate, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8 pentadecafluorooctyl (meth)acrylate, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9 hexadecafluorononyl (meth)acrylate and the like. Fluorine containing macromers and reactive prepolymers include macromers and prepolymers 25 which include said flurorine containing monomers. It has been found that wettability of macromer containing silicone hydrogels may be improved by including at least one hydrophilic polymer and a compatibilizing component. Improved wettability includes a decrease in advancing dynamic contact angle of at least about 10%, and preferably at 30 least about 20% and in some embodiment a decrease of at least about 50%. In certain embodiments it may be preferred to use mixtures of siloxane containing monomers or mixtures of siloxane containing monomers with siloxane containing macromers or prepolymers. 18 Hydrophilic Monomers Additionally, reactive components of the present invention may also include any hydrophilic monomers used to prepare conventional hydrogels. For example monomers containing acrylic groups (CH 2 =CROX, where R is 5 hydrogen or C1.

6 alkyl an X is 0 or N) or vinyl groups (-C=CH 2 ) may be used. Examples of additional hydrophilic monomers are N,N-dimethylacrylamide, 2-hydroxyethyl methacrylate, glycerol monomethacrylate, 2-hydroxyethyl methacrylamide, polyethyleneglycol monomethacrylate, methacrylic acid, acrylic acid, N-vinyl pyrrolidone, N-vinyl-N-methyl acetamide, N-vinyl-N-ethyl 10 acetamide, N-vinyl-N-ethyl formamide, N-vinyl formamide and and combinations thereof. Aside the additional hydrophilic monomers mentioned above, polyoxyethylene polyols having one or more of the terminal hydroxyl groups replaced with a functional group containing a polymerizable double bond may 15 be used. Examples include polyethylene glycol, as disclosed in US 5,484,863, ethoxylated alkyl glucoside, as disclosed in US 5,690,953, US 5,304,584, and ethoxylated bisphenol A, as disclosed in US5,565,539, reacted with one or more molar equivalents of an end-capping group such as isocyanatoethyl methacrylate, methacrylic anhydride, methacryloyl chloride, 20 vinylbenzoyl chloride, and the like, produce a polyethylene polyol having one or more terminal polymerizable olefinic groups bonded to the polyethylene polyol through linking moieties such as carbamate, urea or ester groups. Still further examples include the hydrophilic vinyl carbonate or vinyl carbamate monomers disclosed in U.S. Pat. Nos. 5,070,215, the hydrophilic 25 oxazolone monomers disclosed in U.S. Pat. No. 4,910,277, and polydextran. The preferred additional hydrophilic monomers are N,N dimethylacrylamide (DMA), 2-hydroxyethyl methacrylate (HEMA), glycerol methacrylate, 2-hydroxyethyl methacrylamide, N-vinylpyrrolidone (NVP), polyethyleneglycol monomethacrylate, methacrylic acid, acrylic acid and 30 combinations thereof, with hydrophilic monomers comprising DMA being particularly preferred. Additional hydrophilic monomers may be present in amounts of about 0 to about 70 wt%, more preferably of about 5 and about 60 and most preferably of about 10 and 50 weight%, based upon the total weight of the reactive components. 19 Crosslinkers Suitable crosslinkers are compounds with two or more polymerizable functional groups. The crosslinker may be hydrophilic or hydrophobic and in 5 some embodiments of the present invention mixtures of hydrophilic and hydrophobic crosslinkers have been found to provide silicone hydrogels with improved optical clarity (reduced haziness compared to a CSI Thin Lens@). Examples of suitable hydrophilic crosslinkers include compounds having two or more polymerizable functional groups, as well as hydrophilic functional 10 groups such as polyether, amide or hydroxyl groups. Specific examples include TEGDMA (tetraethyleneglycol dimethacrylate), TrEGDMA (triethyleneglycol dimethacrylate), ethyleneglycol dimethacylate (EGDMA), ethylenediamine dimethyacrylamide, glycerol dimethacrylate and combinations thereof Examples of suitable hydrophobic crosslinkers include 15 multifunctional compatibilizing component, multifunctional polyether polydimethylsiloxane block copolymers, combinations thereof and the like. Specific hydrophobic crosslinkers include acryloxypropyl terminated polydimethylsiloxane (n= 10 or 20) (acPDMS), hydroxylacrylate functionalized siloxane macromer, methacryloxypropyl terminated PDMS, butanediol 20 dimethacrylate, divinyl benzene, 1,3-bis(3 methacryloxypropyl)tetrakis(trimethylsiloxy) disiloxane and mixtures thereof. Preferred crosslinkers include TEGDMA, EGDMA, acPDMS and combinations thereof. The amount of hydrophilic crosslinker used is generally about 0 to about 2 weight% and preferably from about 0.5 to about 2 weight % and the 25 amount of hydrophobic crosslinker is about 0 to about 0 to about 5 weight % based upon the total weight of the reactive components, which can alternatively be referred to in mol% of about 0.01 to about 0.2 mmole/gm reactive components, preferably about 0.02 to about 0.1 and more preferably 0.03 to about 0.6 mmole/gm. 30 Increasing the level of crosslinker in the final polymer has been found to reduce the amount of haze. However, as crosslinker concentration increases above about 0.15 mmole/gm reactive components modulus increases above generally desired levels (greater than about 90 psi). Thus, in the present invention the crosslinker composition and amount is selected to 20 provide a crosslinker concentration in the reaction mixture of between about 1 and about 10 mmoles crosslinker per 100 grams of reactive components. Additional components or additives, which are generally known in the art may also be included. Additives include but are not limited to ultra-violet 5 absorbing compounds and monomer, reactive tints, antimicrobial compounds, pigments, photochromic, release agents, combinations thereof and the like. Diluents The reactive components (compatibilizing component, hydrophilic 10 polymer, oxygen permeable components, hydrophilic monomers, crosslinker(s) and other components) are mixed and reacted in the absence of water and optionally, in the presence of at least one diluent to form a reaction mixture. The type and amount of diluent used also effects the properties of the resultant polymer and article. The haze and wettability of the 15 final article may be improved by selecting relatively hydrophobic diluents and/or decreasing the concentration of diluent used. As discussed above, increasing the hydrophobicity of the diluent may also allow poorly compatible components (as measured by the compatibility test) to be processed to form a compatible polymer and article. However, as the diluent becomes more 20 hydrophobic, processing steps necessary to replace the diluent with water will require the use of solvents other than water. This may undesirably increase the complexity and cost of the manufacturing process. Thus, it is important to select a diluent which provides the desired compatibility to the components with the necessary level of processing convenience. Diluents useful in 25 preparing the devices of this invention include ethers, esters, alkanes, alkyl halides, silanes, amides, alcohols and combinations thereof. Amides and alcohols are preferred diluents , and secondary and tertiary alcohols are most preferred alcohol diluents. Examples of ethers useful as diluents for this invention include tetrahydrofuran, tripropylene glycol methyl ether, 30 dipropylene glycol methyl ether, ethylene glycol n-butyl ether, diethylene glycol n-butyl ether, diethylene glycol methyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, tripropylene glycol n-butyl ether, propylene 21 glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n butyl ether, propylene glycol phenyl ether dipropylene glycol dimetyl ether, polyethylene glycols, polypropylene glycols and mixtures thereof. Examples of esters useful for this invention include ethyl acetate, butyl acetate, amyl 5 acetate, methyl lactate, ethyl lactate, i-propyl lactate. Examples of alkyl halides useful as diluents for this invention include methylene chloride. Examples of silanes useful as diluents for this invention include octamethylcyclotetrasiloxane. Examples of alcohols useful as diluents for this invention include those 10 having the formula R'- C- OH R" wherein Where R, R' and R" are independently selected from H, a linear, 15 branched or cyclic monovalent alkyl having 1 to 10 carbons which may optionally be substituted with one or more groups including halogens, ethers, esters, aryls, aminos, amides, alkenes, alkynes, carboxylic acids, alcohols, aldehydes, ketones or the like, or any two or all three of R, R and R" can together bond to form one or more cyclic structures, such as alkyl having 1 20 tol0 carbons which may also be substituted as just described, with the proviso that no more than one of R, R' or R" is H. It is preferred that R, R' and R" are independently selected from H or unsubstituted linear, branched or cyclic alkyl groups having 1 to 7 carbons. It is more preferred that R, R', and R" are independently selected form 25 unsubstituted linear, branched or cyclic alkyl groups having 1 to 7 carbons. In certain embodiments, the preferred diluent has 4 or more, more preferably 5 or more total carbons, because the higher molecular weight diluents have lower volatility, and lower flammability. When one of the R, R' and R" is H, the structure forms a secondary alcohol. When none of the R, R' and R" are H, 22 the structure forms a tertiary alcohol. Tertiary alcohols are more preferred than secondary alcohols. The diluents are preferably inert and easily displaceable by water when the total number of carbons is five or less. Examples of useful secondary alcohols include 2-butanol, 2-propanol, 5 menthol, cyclohexanol, cyclopentanol and exonorborneol, 2-pentanol, 3 pentonal, 2-hexanol, 3-hexanol, 3-methyl-2-butanol, 2-heptanol, 2-octanol, 2 nonanol, 2-decanol, 3-octanol, norborneol, and the like. Examples of useful tertiary alcohols include tert-butanol, tert-amyl, alcohol, 2-methyl-2-pentanol, 2,3-dimethyl-2-butanol, 3-methyl-3-pentanol, 1 10 methylcyclohexanol, 2-methyl-2-hexanol, 3,7-dimethyl-3-octanol, 1-chloro-2 methyl-2-propanol, 2-methyl-2-heptanol, 2-methyl-2-octanol, 2-2methyl-2 nonanol, 2-methyl-2-decanol, 3-methyl-3-hexanol, 3-methyl-3-heptanol, 4 methyl-4-heptanol, 3-methyl-3-octanol, 4-methyl-4-octanol, 3-methyl-3 nonanol, 4-methyl-4-nonanol, 3-methyl-3-octanol, 3-ethyl-3-hexanol, 3-mehtyl 15 3-heptanol, 4-ethyl-4-heptanol, 4-propyl-4-heptanol, 4-isopropyl-4-heptanol, 2,4-dimethyl-2-pentanol, 1-methylcyclopentanol, 1-ethylcyclopentanol, 1 ethylcyclopentanol, 3-hydroxy-3-methyl-1-butene, 4-hydroxy-4-methyl-1 cyclopentanol, 2-phenyl-2-propanol, 2-methoxy-2-methyl-2-propanol 2,3,4 trimethyl-3-pentanol, 3,7-dimethyl-3-octanol, 2-phenyl-2-butanol, 2-methyl-1 20 phenyl-2-propanol and 3-ethyl-3-pentanol, and the like. A single alcohol or mixtures of two or more of the above-listed alcohols or two or more alcohols according to the structure above can be used as the diluent to make the polymer of this invention. In certain embodiments, the preferred alcohol diluents are secondary and 25 tertiary alcohols having at least 4 carbons. The more preferred alcohol diluents include 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. Presently, the most preferred diluents are hexanol, heptanol, octanol, 30 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. Additional diluents useful for this invention 23 are disclosed in US patent 6,020,445, which is incorporated herein by reference. In one embodiment of the present invention the diluent is water soluble at processing conditions and readily washed out of the lens with water in a 5 short period of time. Suitable water soluble diluents include 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, mixtures thereof and the like. The use of a water soluble diluent allows the post molding process to be 10 conducted using water only or aqueous solutions which comprise water as a substantial component. In one embodiment, the amount of diluent is generally less than about 50 weight % of the reaction mixture and preferably less than about 40 weight% and more preferably between about 10 and about 30 weight % 15 based upon the total weight of the components of the reaction mixture. The diluent may also comprise additional components such as release agents. Suitable release agents are water soluble and aid in lens deblocking The polymerization initiators includes compounds such as lauryl peroxide, benzoyl peroxide, isopropyl percarbonate, azobisisobutyronitrile, 20 and the like, that generate free radicals at moderately elevated temperatures, and photoinitiator systems such as aromatic alpha-hydroxy ketones, alkoxyoxybenzoins, acetophenones, acyl phosphine oxides, and a tertiary amine plus a diketone, mixtures thereof and the like. Illustrative examples of photoinitiators are 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1 25 phenyl-propan-1-one, bis(2,6-dimethoxybenzoyl)-2,4-4-trimethylpenty phosphine oxide (DMBAPO), bis(2,4,6-trimethylbenzoyl) phenylphosphineoxide (Irgacure 819), 2,4,6-trimethylbenzyldiphenyl phosphine oxide, 2,4,6-trimethylbenzyoyl diphenylphosphine oxide, benzoin methyl ester,and a combination of camphorquinone and ethyl 4-(N,N 30 dimethylamino)benzoate. Commercially available visible light initiator systems include Irgacure 819, Irgacure 1700, Irgacure 1800, Irgacure 1850 (all from Ciba Specialty Chemicals) and Lucirin TPO initiator (available from BASF). Commercially available UV photoinitiators include Darocur 1173 and Darocur 2959 (Ciba Specialty Chemicals). The initiator is used in the reaction 24 mixture in effective amounts to initiate photopolymerization of the reaction mixture, e.g., from about 0.1 to about 2 parts by weight per 100 parts of reactive monomer. Polymerization of the reaction mixture can be initiated using the appropriate choice of heat or visible or ultraviolet light or other 5 means depending on the polymerization initiator used. Alternatively, initiation can be conducted without a photoinitiator using, for example, e-beam. However, when a photoinitiator is used, the preferred initiator is a combination of 1-hydroxycyclohexyl phenyl ketone and bis(2,6-dimethoxybenzoyl)-2,4-4 trimethylpentyl phosphine oxide (DMBAPO) , and the preferred method of 10 polymerization initiation is visible light. The most preferred is bis(2,4,6 trimethylbenzoyl)-phenylphosphineoxide (Irgacure 819). The preferred range of all silicone containing components (oxygen permeable components and compatibilizing components) is from about 5 to 99 weight percent, more preferably about 15 to 90 weight percent, and most 15 preferably about 25 to about 80 weight percent, based upon the total weight of the reactive components. A preferred range of compatibilizing components is about 5 to about 90 weight percent, preferably about 10 to about 80, and most preferably about 20 to about 50 weight percent. A preferred range of hydrophilic monomer is from about 5 to about 80 weight percent, more 20 preferably about 5 to about 60 weight percent, and most preferably about 10 to about 50 weight percent of the reactive components in the reaction mixture. A preferred range of high molecular weight hydrophilic polymer is about 1 to about 15 weight percent, more preferably about 3 to about 15 weight percent, and most preferably about 5 to about 12 weight percent. A preferred range of 25 macromer is from about 5 to about 50 weight%, preferably from about 10 to about 50 weight % and more preferably from about 15 to about 45 weight %. All of the foregoing ranges are based upon the total weight of all reactive components. A preferred range of diluent is from about 0 to about 70 weight percent, 30 more preferably about 0 to about 50 weight percent, and still more preferably about 0 to about 40 weight percent and in some embodiments, most preferably between about 10 and about 30 weight percent based upon the weight of all components in the total reaction mixture. The amount of diluent 25 required varies depending on the nature and relative amounts of the reactive components. The invention further comprises, consists and consists essentially of a silicone hydrogel, biomedical device, ophthalmic device and contact lenses of 5 the formulations shown below: Wt% components CC HMWHP ASCM SCM HM 5-90 1-15, 3-15 or5-12 0 0 0 10-80 1-15, 3-15 or5-12 0 0 0 15-55 1-15, 3-15 or5-12 0 0 0 5-90 1-15, 3-15 or5-12 5-50 10-80 1-15, 3-15 or5-12 10-50 15-55 1-15, 3-15 or 5-12 15-45 5-90 1-15, 3-15 or 5-12 0-80, 5-60 5-50;10-50; 0-70, 5-60 or 10 or 10-40 15-45 50 10-80 1-15, 3-15 or 5-12 0-80, 5-60 5-50;10-50; 0-70, 5-60 or 10 or 10-40 15-45 50 15-55 1-15, 3-15 or 5-12 0-80, 5-60 5-50;10-50; 0-70, 5-60 or 10 or 10-40 15-45 50 CC is compatibilizing component HMWHP is high molecular weight hydrophilic polymer ASCM is additional siloxane containing monomer 10 HM is hydrophilic monomer SCM is a siloxane containing macromer Thus, the present invention includes silicone hydrogel, biomedical device, ophthalmic device and contact lenses having each of the 15 composition listed in the table, which describes 261 possible compositional ranges. Each of the ranges listed above is prefaced by the word "about". The foregoing range combinations are presented with the proviso that the listed components, and any additional components add up to 100 weight%. In a preferred embodiment, the reactive components comprise about 20 28 wt.% SiGMA; about 31 wt.% 800-1000 MW monomethacryloxypropyl terminated mono-n-butyl terminated polydimethylsiloxane, "mPDMS", about 24 wt.% N,N-dimethylacrylamide, "DMA", about 6 wt.% 2-hydroxyethyl methacryate, "HEMA", about 1.5 wt% tetraethyleneglycoldimethacrylate, "TEGDMA", about 7 wt.% polyvinylpyrrolidone, "K-90 PVP"; with the balance 25 comprising minor amounts of additives and photoinitiators. The polymerization 26 is most preferably conducted in the presence of about 23% (weight % of the combined monomers and diluent blend) 3,7-dimethyl-3-octanol diluent. In a second preferred embodiment the reactive components comprise about 30 wt.% SiGMA, about 23 wt.% mPDMS, about 31 wt% DMA, about 0.5 5 to about 1 wt.% ethyleneglycoldimethacrylate, "EGDMA", about 6 wt.% K-90 PVP; and about 7.5 wt% HEMA, with the balance comprising minor amounts of additives and photoinitiators. The polymerization is most preferably conducted in the presence of tert-amyl-alcohol as a diluent comprising about 29 weight percent of the reaction mixture. The diluent may also comprise 10 about 11 weight % low molecular weight PVP (less than about 5,000 and preferably less than about 3,000 Mn. In a third preferred embodiment, the reactive components comprise about 11-18 wt % macromer (the GTP reaction product of about 24 wt.% HEMA; about 3wt% MMA; about 33wt.% 15 methacryloxypropyltris(trimethylsiloxy)silane and about 32wt.% mono methacryloxypropyl terminated mono-butyl terminated polydimethylsiloxane functionalized with 8 wt % 3-isopropenyl- a,c-dimethylbenzyl isocyanate); about 18-30 wt.% mPDMS, about 2-10 wt% acPDMS, about 27-33 wt.% DMA, about 13-15 wt.% TRIS, about 2-5 wt.% HEMA, and about 5-7 wt.% K 20 90 PVP; with the balance comprising minor amounts of additives and photoinitiators. The polymerization is most preferably conducted in the presence of 25-30% (weight % of the combined monomers and diluent blend) a diluent comprising 3,7-dimethyl-3-octanol. In a fourth preferred embodiment, the reactive components comprise 25 between about 15 to about 40 wt.% macromer (formed from perfluoroether having a mean molecular weight of about 1030 g/mol and a, w-hydroxypropyl terminated polydimethylsiloxane having a mean molecular weight of about 2000 g/mol, isophorone diisocyanate and isocyanatoethyl methacrylate); about 40 to about 52% SiGMA, about 0 to about 5 wt% 3 30 tris(trimethylsiloxy)silylpropy methacrylate, "TRIS", about 22 to about 32 wt.% DMA, about 3 about 8 wt% K-90 PVP with the balance comprising minor amounts of additives and photoinitiators. The polymerization is most preferably conducted in the presence of about 15 to about 40, and preferably 27 between about 20 and about 40% (weight % of the combined monomers and diluent blend), diluent, which may, in some emobodiments preferably be ethanol, 3,7-dimethyl-3-octanol. 5 Processing The biomedical devices of the invention are prepared by mixing the high molecular weight hydrophilic polymer, the compatibilizing component, plus one or more of the following: the oxygen permeability enhancing component, the hydrophilic monomers, the additives ("reactive components"), 10 and the diluents ("reaction mixture"), with a polymerization initator and curing by appropriate conditions to form a product that can be subsequently formed into the appropriate shape by lathing, cutting and the like. Alternatively, the reaction mixture may be placed in a mold and subsequently cured into the appropriate article. 15 Various processes are known for curing the reaction mixture in the production of contact lenses, including spincasting and static casting. Spincasting methods are disclosed in U.S. Pat. Nos. 3,408,429 and 3,660,545, and static casting methods are disclosed in U.S. Pat. Nos. 4,113,224 and 4,197,266. The preferred method for producing contact lenses 20 comprising the polymer of this invention is by the direct molding of the silicone hydrogels, which is economical, and enables precise control over the final shape of the hydrated lens. For this method, the reaction mixture is placed in a mold having the shape of the final desired silicone hydrogel, i.e., water swollen polymer, and the reaction mixture is subjected to conditions whereby 25 the monomers polymerize, to thereby produce a polymer/diluent mixture in the shape of the final desired product. Then, this polymer/diluent mixture is treated with a solvent to remove the diluent and ultimately replace it with water, producing a silicone hydrogel having a final size and shape which are quite similar to the size and shape of the original molded polymer/diluent 30 article. This method can be used to form contact lenses and is further described in U.S. Pat. Nos. 4,495,313; 4,680,336; 4,889,664; and 5,039,459, incorporated herein by reference. 28 Curin Yet another feature of the present invention is a process for curing silicone hydrogel formulations to provide enhanced wettability. It has been found that the gel time for a silicone hydrogel may be used to select cure 5 conditions which provide a wettable ophthalmic device, and specifically a contact lens. The gel time is the time at which a crosslinked polymer network is formed, resulting in the viscosity of the curing reaction mixture approaching infinity and the reaction mixture becoming non-fluid. The gel point occurs at a specific degree of conversion, independent of reaction conditions, and 10 therefore can be used as an indicator of the rate of the reaction. It has been found that, for a given reaction mixture, the gel time may be used to determine cure conditions which impart desirable wettability. Thus, in a process of the present invention, the reaction mixture is cured at or above a gel time that provides improved wettability, or more preferably sufficient 15 wettability for the resulting device to be used without a hydrophilic coating or surface treatment ("minimum gel time"). Preferably improved wettability is a decrease in advancing dynamic contact angle of at least 10% compared to formulation with no high molecular weight polymer. Longer gel times are preferred as they provide improved wettability and increased processing 20 flexibility. Gel times will vary for different silicone hydrogel formulations. Cure conditions also effect gel time. For example the concentration of crosslinker will impact gel time, increasing crosslinker concentrations decreases gel time. Increasing the intensity of the radiation (for photopolymerization) or 25 temperature (for thermal polymerization), the efficiency of initiation (either by selecting a more efficient initiator or irradiation source, or an initiator which absorbs more strongly in the selected irradiation range) will also decrease gel time. Temperature and diluent type and concentration also effect gel time in ways understood by those of skill in the art. 30 The minimum gel time may be determined by selecting a given formulation, varying one of the above factors and measuring the gel time and contact angles. The minimum gel time is the point above which the resulting lens is generally wettable. Below the minimum gel time the lens is generally not wettable. For a contact lens "generally wettable" is a lens which displays 29 an advancing dynamic contact angle of less than about 70 and preferably less than about 60* or a contact lens which displays a tear film break up time equal to or better than an ACUVUEO lens. Thus, those of skill in the art will appreciate that minimum gel point as defined herein may be a range, taking 5 into consideration statistical experimental variability. In certain embodiments using visible light irradiation minimum gel times of at least about 30, preferably greater than about 35, and more preferably greater than about 40 seconds have been found to be advantageous. 10 Curing may be conducted using heat, ionizing or actinic radiation, for example electron beams, Xrays, UV or visible light, ie. electromagnetic radiation or particle radiation having a wavelength in the range of from about 150 to about 800 nm. Preferable radiation sources include UV or visible light having a wavelength of about 250 to about 700 nm. Suitable radiation 15 sources include UV lamps, fluorescent lamps, incandescent lamps, mercury vapor lamps, and sunlight. In embodiments where a UV absorbing compound is included in the reaction mixture (for example, as a UV block or photochromic) curing is conducting by means other than UV irradiation (such as by visible light or heat). In a preferred embodiment the radiation source is 20 selected from UVA (about 315 - about 400 nm), UVB (about 280-about 315) or visible light (about 400 -about 450 nm). In another preferred embodiment, the reaction mixture includes a UV absorbing compound, is cured using visible light. In many embodiments it will be useful to cure the reaction mixture at low intensity to achieve the desired minimum gel time. As used 25 herein the term "low intensity" means those between about 0.1 mW/cm 2 to about 6 mW/cm 2 and preferably between about 1 mW/cm 2 and 3 mW/cm 2 . The cure time is long, generally more than about 1 minute and preferably between about 1 and about 60 minutes and still more preferably between about 1 and about 30 minutes This slow, low intensity cure is one way to 30 provide the desired minimum gel times and produce ophthalmic devices which display good wettability. 30 Initiator concentration also effects gel time. Accordingly, in some embodiments it is preferred to have relatively low amounts of photoinitiator, generally 1% or less and preferably 0.5% or less. The temperature at which the reaction mixture is cured is also 5 important. As the temperature is increased above ambient the haze of the resulting polymer decreases. Temperatures effective to reduce haze include temperatures at which the haze for the resulting lens is decreased by at least about 20% as compared to a lens of the same composition made at 25 0 C. Thus, suitable cure temperatures include those greater than about 25 0 C, 10 preferably those between about 25 0 C and 70 0 C and more preferably those between about 40 0 C and 70 0 C. The precise set of cure conditions (temperature, intensity and time) will depend upon the components of lens material selected and, with reference to the teaching herein, are within the skill of one of ordinary skill in the art to determine. Cure may be conducted in 15 one or a muptiplicity of cure zones. The cure conditions must be sufficient to form a polymer network from the reaction mixture. The resulting polymer network is swollen with the diluent and has the form of the mold cavity. 20 Deblockinq After the lenses have been cured they must be removed from the mold. Unfortunately, the silicone components used in the lens formulation render the finished lenses "sticky" and difficult to release from the lens molds. Lenses can be deblocked (removed from the mold half or tool supporting the lens) 25 using a solvent, such as an organic solvent. However, in one embodiment of the present invention at least one low molecular weight hydrophilic polymer is added to the reaction mixture, the reaction mixture is formed into the desired article, cured and deblocked in water or an aqueous solution comprising, consisting essentially of and consisting of a small amount of surfactant. The 30 low molecular weight hydrophilic polymer can be any polymer having a structure as defined for a high molecular weight polymer, but with a molecular weight such that the low molecular weight hydrophilic polymer extracts or leaches from the lens under deblocking conditions to assist in lens release 31 -32 from the mold. Suitable molecular weights include those less than about 40,000 Daltons and preferably less than about 20,000 Daltons. Those of skill in the art will appreciate that the foregoing molecular weights are averages, and that some amount of material having a molecular weight higher than the given averages may be 5 suitable, so long as the average molecular weight is within the specified range. Preferably the low molecular weight polymer is selected from water soluble polyamides, lactams and polyethylene glycols, and mixtures thereof and more preferably poly-vinylpyrrolidone, polyethylene glycols, poly 2 ethyl-2-oxazoline (available from Plymer Chemistry Innovations, Tuscon, AZ), polymethacrylic acid, 10 poly(l-lactic acid), polycaprolactam, polycaprolactone, polycaprolactone diol, polyvinyl alcohol, polyhema, polyacrylic acid, poly(1-glycerol methacrylate), poly(2-ethyl-2-oxazoline), poly(2-hydroxypropyl methacrylate), poly(2 vinylpyridine N-oxide), polyacrylamide, polymethacrylamide and the like. The low molecular weight hydrophilic polymer may be used in amounts up 15 to about 20 wt.% and preferably in amounts between about 5 and 20 wt.% of the reactive components. Suitable surfactants include non-ionic surfactants including betaines, amine oxides, combinations thereof and the like. Examples of suitable surfactants include polyoxyethylene(20) sorbitan monostearate, sold under the trade name TWEEN@ 20 (ICI), ethoxylated methyl glucoside dioleate, sold under the trade name DOE 120 (Amerchol/Union Carbide) and the like. The surfactants may be used in amounts up to about 10,000 ppm, preferably between about 25 ppm and about 1500 ppm and more preferably between about 100 and about 1200 ppm. Suitable release agents are low molecular weight, and include I -methyl-4 25 piperidone, 3-morpholino-1, 2-propanediol, tetrahydro-2H-pyran-4-ol, glycerol formal, ethyl-4-oxo- I -piperidine carboxylate, 1,3 -dimethyl-3,4,5,6-tetrahydro-2(I H) pyrimidinone and 1 -(2-hydroxyethyl)-2-pyrrolidone. Lenses made from reaction mixtures without low molecular weight hydrophilic polymer may be deblocked in an aqueous solution comprising at least 30 one organic solvent. Suitable organic solvents are hydrophobic, but miscible with water. Alcohols, ethers and the like are suitable, more specifically primary alcohols 03/03/1 Icg 16949 speci pages 32 32a.doc,32 - 32a and more specifically isopropyl alcohol, DPMA, TPM, DPM, methanol, ethanol, propanol and mixtures thereof being suitable examples. 03/03/11 ,cg 16949 speci pages 32 32a.doc,32 Suitable deblocking temperatures range from about ambient to about 100*C, preferably between about 70*C and 95 0 C, with higher temperatures providing quicker deblocking times. Agitation, such as by sonication, may also be used to decrease deblocking times. Other means known in the art, 5 such as vacuum nozzles may also be used to remove the lenses from the molds. Diluent replacement/hydration Typically after curing the reaction mixture, the resulting polymer is 10 treated with a solvent to remove the diluent (if used), unreacted components, byproducts, and the like and hydrate the polymer to form the hydrogel. Alternatively, depending on the solubility characteristics of the hydrogel's components, the solvent initially used can be an organic liquid such as ethanol, methanol, isopropanol, TPM, DPM, PEGs, PPGs, glycerol, mixtures 15 thereof, or a mixture of one or more such organic liquids with water, followed by extraction with pure water (or physiological saline). The organic liquid may also be used as a "pre-soak". After demolding, lenses may be briefly soaked (times up to about 30 minutes, preferably between about 5 and about 30 minutes) in the organic liquid or a mixture of organic liquid and water. After 20 the pre-soak, the lens may be further hydrated using aqueous extraction solvents. In some embodiments, the preferred process uses an extraction solvent that is predominately water, preferably greater than 90% water, more preferably greater than 97% water. Other components may includes salts 25 such as sodium chloride, sodium borate boric acid, DPM, TPM, ethanol or isopropanol. Lenses are generally released from the molds into this extraction solvent, optionally with stirring or a continuous flow of the extraction solvent over the lenses. This process can be conducted at temperatures from 2 to 121 0 C, preferably from 20 to 98*C. The process can be conducted at 30 elevated pressures, particularly when using temperatures in excess of 100C, but is more typically conducted at ambient pressures. It is possible to deblock the lenses into one solution (for example containing some release aid) and then transfer them into another (for example the final packing solution), 33 although it may also be possible to deblock the lenses into the same solution in which they are packaged. The treatment of lenses with this extraction solvent may be conducted for a period of from about 30 seconds to about 3 days, preferably between about 5 and about 30 minutes. The selected 5 hydration solution may additional comprise small amounts of additives such as surfactants and/or release aids. Suitable surfactants include include non ionic surfactants, such as betaines and amine oxides. Specific surfactants include TWEEN 80 (available from Amerchol), DOE 120 (available from Union Carbide), Pluronics, methyl cellulose, mixtures thereof and the like and may 10 be added in amounts between about 0.01 weight% and about 5% based upon total weight of hydration solution used. In one embodiment the lenses may be hydrated using a "step down" method, where the solvent is replaced in steps over the hydration process. Suitable step down processes have at least two, at least three and in some 15 embodiments at least four steps, where a percentage of the solvent is replaced with water. The silicone hydrogels after hydration of the polymers preferably comprise about 10 to about 60 weight percent water, more preferably about 20 to about 55 weight percent water, and most preferably about 25 to about 20 50 weight percent water of the total weight of the silicone hydrogel. Further details on the methods of producing silicone hydrogel contact lenses are disclosed in U.S. Patents 4,495,313; 4,680,336; 4,889,664; and 5,039,459, which are hereby incorporated by reference. The cured biomedical device of the present invention displays excellent 25 resistance to fouling in vivo, even without a coating. When the biomedical device is an ophthalmic device, resistance to biofouling may be measured by measuring the amount of surface deposits on the lens during the wear period, often referred to as "lipid deposits". Lens surface deposits are measured as follows: Lenses were put on 30 human eyes and evaluated after 30 minutes and one week of wear using a slit lamp. During the evaluation the patient is asked to blink several times and the lenses are manually "pushed" in order to differentiate between deposits and back surface trapped debris. Front and back surface deposits are graded as being discrete (i.e. jelly bumps) or filmy. Front surface deposits give a bright 34 reflection while back surface deposits do not. Deposits are differentiated from back surface trapped debris during a blink or a push-up test. The deposits will move while the back surface trapped debris will remain still. The deposits are graded into five categories based upon the percentage of the lens surface 5 which is effected: none (< about 1%), slight (about 1 to about 5%), mild (about 6% to about 15%), moderate (about 16% to about 25%) and severe (greater than about 25%). A 10% difference between the categories is considered clinically significant. The ophthalmic devices of the present invention also display low haze, 10 good wettability and modulus. Haze is measured by placing test lenses in saline in a clear cell above a black background, illuminating from below with a fiber optic lamp at an angle 660 normal to the lens cell, and capturing an image of the lens from above with a video camera. The background-subtracted scattered light image was 15 quantitatively analyzed, by integrating over the central 10 mm of the lens, and then compared to a -1.00 diopter CSI Thin Lens@, which is arbitrarily set at a haze value of 100, with no lens set as a haze value of 0. Wettability is measured by measuring the contact angle or DCA, typically with borate buffered saline, using a Wilhelmy balance at 23 0 C. The 20 wetting force between the lens surface and borate buffered saline is measured using a Wilhelmy microbalance while the sample is being immersed into or pulled out of the saline. The following equation is used F = 2ypcose or 0 = cos 1 (F/2yp) 25 where F is the wetting force, y is the surface tension of the probe liquid, p is the perimeter of the sample at the meniscus and 0 is the contact angle. Typically, two contact angles are obtained from a dynamic wetting experiment - advancing contact angle and receding contact angle. Advancing contact angle is obtained from the portion of the wetting experiment where the sample 30 is being immersed into the probe liquid. At least 4 lenses of each composition are measured and the values reported herein. However, DCA is not always a good predictor of wettability on eye. The pre-lens tear film non-invasive break-up time (PLTF-NIBUT) is one 35 measure of in vivo or "clinical" lens wettability. The PLTF-NIBUT is measured using a slit lamp and a circular fluorescent tearscope for noninvasive viewing of the tearfilm (Keeler Tearscope Plus). The time elapsed between the eye opening after a blink and the appearance of the first dark spot within the tear 5 film on the front surface of a contact lens is recorded as PLTF-NIBUT. The PLTF-NIBUT was measured 30-minutes after the lenses were placed on eye and after one week. Three measurements were taken at each time interval and were averaged into one reading. The PLTF-NIBUT was measured on both eyes, beginning with the right eye and then the left eye. 10 Movement is measured using the "push up" test. The patient's eyes are in the primary gaze position. The push-up test is a gentle digital push of the lens upwards using the lower lid. The resistance of the lens to upward movement is judged and graded according to the following scale: 1 (excessive, unacceptable movement), 2 (moderate, but acceptable 15 movement), 3 (optimal movement), 4 ( minimal, but acceptable movement), 5 (insufficient, unacceptable movement). The lenses of the present invention display moduli of at least about 30 psi, preferably between about 30 and about 90 psi, and more preferably between about 40 and about 70 psi. Modulus is measured by using the 20 crosshead of a constant rate of movement type tensile testing machine equipped with a load cell that is lowered to the initial gauge height. A suitable testing machine includes an Instron model 1122. A dog-bone shaped sample having a 0.522 inch length, 0.276 inch "ear" width and 0.213 inch "neck" width is loaded into the grips and elongated at a constant rate of strain of 2 in/min. 25 until it breaks. The initial gauge length of the sample (Lo) and sample length at break (Lf) are measured. Twelve specimens of each composition are measured and the average is reported. Tensile modulus is measured at the initial linear portion of the stress/strain curve. The contact lenses prepared by this invention have 02 Dk values 30 between about 40 and about 300 barrer, determined by the polarographic method. Lenses are positioned on the sensor then covered on the upper side with a mesh support. The lens is exposed to an atmosphere of humified 2.1% 02. The oxygen that diffuses through the lens is measured using a polarographic oxygen sensor consisting of a 4 mm diameter gold cathode and 36 a silver ring anode. The reference values are those measured on commercially available contact lenses using this method. Balafilcon A lenses available from Bausch & Lomb give a measurement of approx. 79 barrer. Etafilcon lenses give a measurement of 20 to 25 barrer. (1 barrer = 1010 (cm 3 5 of gas x cm 2 )/(cm 3 of polymer x s x cm Hg). Gel time was measured using the following method. The photo polymerization reaction was monitored with an ATS StressTech rheometer equipped with a photo-curing accessory, which consists of a temperature controlled cell with a quartz lower plate and an aluminum upper plate, and a 10 radiation delivery system equipped with a bandpass filter. The radiation, which originates at a Novacure mercury arc lamp equipped with an iris and computer-controlled shutter, was delivered to the quartz plate in the rheometer via a liquid light guide. The filter was a 420 nm (20 nm FWHM) bandpass filter, which simulates the light emitted from a TLO3 bulb. The 15 intensity of the radiation, measured at the surface of the quartz window with an IL1400A radiometer, was controlled to ± 0.02 mW/cm2 with an iris. The temperature was controlled at 45 ± 0.1*C. After approximately 1 mL of the de gassed reactive mixture was placed on the lower plate of the rheometer, the 25 mm diameter upper plate was lowered to 0.500 ± 0.001 mm above the 20 lower plate, where it was held until after the reaction reached the gel point. The sample was allowed to reach thermal equilibrium (-4 minutes, determined by the leveling-off of the steady shear viscosity) before the lamp shutter was opened and the reaction begun. During this time while the sample was reaching thermal equilibrium, the sample chamber was purged with nitrogen 25 gas at a rate of 400 sccm. During the reaction the rheometer continuously monitored the strain resulting from an applied dynamic stress (fast oscillation mode), where time segments of less than a complete cycle were used to calculate the strain at the applied programmable stress. The computer calculated the dynamic shear modulus (G'), loss modulus (G"), and viscosity 30 (v*), as a function of exposure time. As the reaction proceeded the shear modulus increased from <1 Pa to >0.1 MPa, and tan 6 (=G"/G') dropped from near infinity to less than 1. For measurements made herein the gel time is the time at which tan 6 equals 1.(the crossover point when G'=G"). At the time 37 that G' reaches 100 Pa (shortly after the gel point), the restriction on the upper plate was removed so that the gap between the upper and lower plates can change as the reactive monomer mix shrinks during cure. It will be appreciated that all of the tests specified above have a certain 5 amount of inherent test error. Accordingly, results reported herein are not to be taken as absolute numbers, but numerical ranges based upon the precision of the particular test. In order to illustrate the invention the following examples are included. These examples do not limit the invention. They are meant only to suggest a 10 method of practicing the invention. Those knowledgeable in contact lenses as well as other specialties may find other methods of practicing the invention. However, those methods are deemed to be within the scope of this invention. EXAMPLES 15 The following abbreviations are used in the examples below: SiGMA 2-propenoic acid, 2-methyl-2-hydroxy-3-[3-[1,3,3,3-tetramethyl 1-[trimethylsilyl)oxy]disiloxanyl propoxy]propyl ester DMA N,N-dimethylacrylamide HEMA 2-hydroxyethyl methacrylate 20 mPDMS 800-1000 MW (M,) monomethacryloxypropyl terminated mono n-butyl terminated polydimethylsiloxane Norbloc 2-(2'-hydroxy-5-methacrylyloxyethylphenyl)-2H-benzotriazole CGI 1850 1:1 (wgt) blend of 1-hydroxycyclohexyl phenyl ketone and bis(2,6-dimethoxybenzoyl)-2,4-4-trimethylpenty phosphine 25 oxide PVP poly(N-vinyl pyrrolidone) (K value 90) Blue HEMA the reaction product of Reactive Blue 4 and HEMA, as described in Example 4 of U.S. Pat. no. 5,944,853 IPA isopropyl alcohol 30 D30 3,7-dimethyl-3-octanol mPDMS-OH mono-(3-methacryloxy-2-hydroxypropyloxy)propy terminated, mono-butyl terminated polydimethylsiloxane (MW 1100) TEGDMA tetraethyleneglycol dimethacrylate TrEGDMA triethyleneglycol dimethacrylate 38 TRIS 3-methacryloxypropyltris(trimethylsiloxy)silane MPD 3-methacryloxypropyl(pentamethyldisiloxane) MBM 3-methacryloxypropyl bis(trimethylsiloxy)methylsilane AcPDMS bis-3-methacryloxy-2-hydroxypropyloxypropy 5 polydimethylsiloxane TRIS-HEMA 2-trimethylsiloxyethyl methacrylate MMA methyl methacrylate THF tetrahydrofuran TBACB tetrabutylammonium 3-chlorobenzoate 10 TMI 3-isopropenyl- 0.0-dimethylbenzyl isocyanate IPL isopropyl lactate CGI 819 2,4,6-trimethylbenzyldiphenyl phosphine oxide Throughout the Examples intensity is measured using an IL 1400A 15 radiometer, using an XRL 140A sensor. Examples 1-10 The reaction components and diluent (D30) listed in Table 1 were mixed together with stirring or rolling for at least about 3 hours at 23 0 C, until 20 all components were dissolved. The reactive components are reported as weight percent of all reactive components and the diluent is weight percent of reaction mixture. The reaction mixture was placed into thermoplastic contact lens molds (made from Topas@ copolymers of ethylene and norbornene obtained from Ticona Polymers), and irradiated using Philips TL 20W/03T 25 fluorescent bulbs at 45 0 C for about 20 minutes N 2 . The molds were opened and lenses were extracted into a 50:50 (wt) solution of IPA and H 2 0, and soaked in IPA at ambient temperature for about 15 hours to remove residual diluent and monomers, placed into deionized H 2 0 for about 30 minutes, then equilibrated in borate buffered saline for at least about 24 hours and 30 autoclaved at 1220C for 30 minutes. The properties of the resulting lenses are shown in Table 1. 39 Table 1 7 8 9 10 EX.# 1 2 3 4 5 6 Comp. I I SiGMA 28 30 28.6 28 31 32 29 39.4 20 68 PVP (K90) 7 10 7.1 7 7 7 6 6.7 3 7 DMA 23.5 17 24.5 23.5 20 20 24 16.4 37 22 MPDMS 31 32 0 31 31 34 31 29.8 15 0 TRIS 0 0 0 0 0 0 0 0 15 0 HEMA 6 6 6.1 6 6.5 3 5.5 2.9 8 0 Norbloc 2 2 0 2.0 2 2 2 1.9 0 0 CGI 1850 0.98 1 1.02 1 1 1 1 1 1 0 TEGDMA 1.5 2 1.02 1.5 1.5 1 1.5 1.9 0 2 TrEGDMA 0 0 0 0 0 0 0 0 1 0 BlueHEMA 0.02 0 0 0 0 0 0 0 0 0 mPDMS-OH 0 0 31.6 0 0 0 0 0 0 0 Darocur 0 0 0 0 0 0 0 0 0 1 1173 D30 % 23 26 17 23 23 29 32 28 17 27 P operties

%EWC

1 36 33 39 40 36 37 39 25 48 29 Modulus 68 78 112 61 67 50 66 92 43 173 (psi) % Elongation 301 250 147 294 281 308 245 258 364 283 DCA 62 55 58 64 72 65 61 55 92 72 (advancing)II Dk' 103 111 101 131 110 132 106 140 64 76 (edge corrected) 1. Equilibrium water content 2. Dynamic contact angle, measured with physiological borate-buffered saline using a Wilhelmy balance. 5 3. Oxygen permeability, edge corrected, in Barrers. The results of Examples 1-10 show that the reaction mixture components and their amounts may be varied substantially, while still providing uncoated lenses having an excellent balance of mechanical 10 properties and wettability. The contact angle (DCA) of Example 9 may be too high to form a lens that would be clinically wettable, and the modulus may be lower than desired to provide a mechanically robust lens. Example 9 contained the lowest concentration of SiGMA (20%). Because the SiGMA 40 had been reduced, less PVP could be added to the formulation and still provide a compatible reaction mixture. Thus, these examples show that SiGMA is effective in compatibilizing PVP and that when sufficient SiGMA and PVP are present lenses with desirable wettability and other mechanical 5 properties can be made without any form of surface modification. Example 11 Lenses having the formulation of Example 1 were remade, without controlling cure intensity. The mechanical properties are reported in Table 2, 10 below. These lenses were clinically evaluated using ACUVUE@ 2 lenses as controls. The test lenses were worn in one eye and an ACUVUE*2 lens was worn on the contralateral eye. The lenses were worn by 6 patients in a daily wear mode (nightly removal) for a period of one week. At one week the PLTF-NIBUT was 3.6 (±3.0) seconds compared to 5.8 (±2.5) seconds for 15 ACUVUE@ 2 lenses. The front surface deposition was graded none to slight for 50% of the test lenses and 100% for the control lenses. The movement was acceptable for both test and control lenses. Example 12 20 Example 11 was repeated except that the cure intensity was reduced to 1.0 mW/cm 2 . The mechanical properties are reported in Table 2, below. These lenses were clinically evaluated using ACUVUE@ 2 lenses as controls. The test lenses were worn by 15 patients in a daily wear mode (nightly removal), in one eye for a period of one week and an ACUVUE* 2 lens was 25 worn in the contralateral eye. At one week the PLTF-NIBUT was 8.2 (±1.7) seconds compared to 6.9 (±1.5) seconds for ACUVUE@ 2 lenses. The front surface deposition was graded none to slight for all of the patients for both test and control lenses. The movement was acceptable for both test and control lenses. 30 Table 2 Ex.# 1 11 12 %EWC 36 36 36 Modulus (psi) 68 74 87 41 Elongation 301 315 223 DCA 62 77 56 Dk 103 127 102 Generally the mechanical properties for Examples 1, 11 and 12 are consistent results for multiple runs of the same material. However, the clinical results for Examples 11 (uncontrolled cure intensity) and 12 (low, controlled 5 cure intensity) are substantially different. The on eye wettability after one week of wear for Example 11 (measured by PLTF-NIBUT) was worse that the ACUVUE* 2 lenses (3.6 v. 5.8) and half the lenses had more than slight surface depositions. The Example 12 lenses (controlled, low intensity cure) displayed significantly improved on-eye wettability, which was measurably 10 better than ACUVUE* 2 lenses (8.2 v. 6.9) and no surface depositions. Thus, using a low, controlled cure provides an uncoated lens having on-eye wettability which is as good as, and in some cases better than conventional hydrogel lenses. 15 Examples 13-17 Reaction mixtures described in Table 3 and containing low or no compatibilizing component (in these Examples SiGMA) were mixed with constant stirring at room temperature for 16 hours. Even after 16 hours each of the reaction mixtures remained cloudy and some contained precipitates. 20 Accordingly, these reaction mixtures could not be used to produce lenses. Table 3 Ex.# 13 14 15 16 17 Composition SiGMA 0 0 0 10 20 PVP (K90) 12 12 10 8.0 8.0 DMA 10 10 8.3 19 19 MPDMS 37 37 30.8 35 28 TRIS 14 14 11.7 17 14 HEMA 25 25 37.5 8.0 8.0 Norbloc 0 0 0 0 0 CGI 1850 0 0 0 0 0 TEGDMA 1.0 1.0 0.83 2.0 2.0 TrEGDMA 0 0 0 0 0 Blue HEMA 0 0 0 0 0 42 mPDMS-OH 0 0 0 0 0 Darocur 1173 1.0 1.0 0.83 1.0 1.0 D30 % 23 31 31 27 27 Examples 13 through 15 show that reaction mixtures without any compatibilizing component (SiGMA or mPDMS-OH) are incompatible, and not suitable for making contact lenses. Examples 16 and 17 show that 5 concentrations of compatibilizing component less than about 20 weight% are insufficient to compatibilize signifincant amounts of high molecular weight PVP. However, comparing Example 17 to Example 9, lesser amounts of high molecular weight PVP (3 weight %) can be included agd still form a compatible reaction mixture. 10 Examples 18-26 A solution of 1.00 gram of D30, 1.00 gram of mPDMS and 1.00 gram of TRIS was placed in a glass vial (Ex. 18). As the blend was rapidly stirred at about 20 to 23 0C with a magnetic stir bar, a solution of 12 parts (wt) PVP 15 (K90) and 60 parts DMA was added dropwise until the solution remained cloudy after 3 minutes of stirring. The mass of the added DMA/PVP blend was determined in grams and reported as the "monomer compatibility index". This test was repeated using SiGMA (Ex. 19), MBM (Ex. 20), MPD (Ex. 21), acPDMS, where n=10 (Ex. 22), acPDMS where n=20'(Ex. 23), iSiGMA-3Me 20 (Ex. 24) and TRIS2-HOEOP2 (Ex. 25) as test silicone monomers in place of TRIS. Table 4 Ex. # Test silicone- Monomer Si:OH containing monomer compatibility index 18 SiGMA 1.8 3:1 19 TRIS 0.07 4:0 20 MBM 0.09 3:0 21 MPD 0.05 2:0 22 1.9 11:2 acPDMS (n=10)* 43 23 1 21:2 acPDMS (n=20)* 24 0.15 4:0 ISiMAA-3Me 25 0.11 3:2 TRIS2-HOEOP2 26 0.64 -11:2 MPDMS-OH Doug - should we try mPDMS-OH and see what that number is? Structures for acPDMS, iSiGMA-3Me and TRIS2-HOEOP2 are shown below. 5 acPDMS (n averages 10 or 20): o 0 O O- S O , S O O OH OH TRIS2-HOEOP2 10 0 O H O - Si O S , O, OH ) iSiMAA3-Me OMe O O S(OSiMe 3

)

3 15 The results, shown in Table 4, show that SiGMA, acPDMS (where n= 10 and 20) and mPDMS-OH more readily incorporate into a blend of a diluent, another silicone containing monomer, a hydrophilic monomer, and an high 20 molecular weight polymer (PVP) than alternative silicone-containing monomers. Thus, compatibilizing silicone containing monomers having a compatibility index of greater than about 0.5 are useful for compatibilizing high molecular weight hydrophilic polymers like PVP. 44 Example 27 -35 Lenses were made using the reaction mixture formulation of Example 1. The plastic contact lens molds (made from Topas@ copolymers of ethylene and norbornene obtained from Ticona Polymers) were stored overnight in 5 nitrogen (<0.5% 02) before use. Each mold was dosed with 75 p1l reaction mixture. Molds were closed and lenses photocured using the times and cure intensities indicated in Table 5. Lenses were formed by irradiation of the monomer mix using visible light fluorescent bulbs, curing at 45 0 C. The intensity was varied by using a variable balast or light filters, in two steps of 10 varied intensity and cure time. The step 2 time was selected to provide the same total irradiation energy (about 830 mJ/cm 2 ) for each sample. The finished lenses were demolded use a 60:40 mixture of isopropyl alcohol/DI water. The lenses were transferred to a jar containing 300 g 100% isopropyl alcohol (IPA). The IPA was replaced every 2 hours for 10 hours. At 15 the end of about 10 hours, 50% of the IPA was removed and replaced with DI water and the jar was rolled for 20 minutes. After 20 minutes, 50% of the IPA was removed and replaced with DI water and the jar was rolled for another 20 minutes. The lenses were transferred to packing solution, rolled for 20 minutes and then tested. 20 Table 5 Ex.# Step 1 Step I Step 2 Step 2 Advancing intensity time intensity time Contact (mW/cm 2 ) (min:sec) (mW/cm 2 ) (min:sec) Angle 27 1.1 6:55 5.5 1:28 51 ± 1 28 1.1 2:46 5.5 2:21 55 ± 2 29 1.1 11:03 5.5 0:35 55± 1 30 1.7 6:30 5.5 0:35 50 ± 1 31 1.7 1:37 5.5 2:21 55 ± 1 32 1.7 4:04 5.5 1:28 54± 2 33 2.4 2:52 5.5 1:28 62 ± 6 34 2.4 4:36 5.5 0:35 76 ± 9 35 2.4 1:09 5.5 0:35 78 ± 6 The contact angles for Examples 27 through 232 are not significantly 25 different, indicating that step 1 cure intensities of less than about about 2 mW/cm 2 provide improved wettability for this lens formulation regardless of 45 the step 1 cure time. However, those of skill in the art will appreciate that shorter step 1 cure times (such as those used in Examples 28 and 31) allow for shorter overall cure cycles. Moreover, it should be noted that even though the contact angles for Examples 33 through 35 are measurably higher than 5 those of Examples 27-32, the lenses of Examples 33-35 may still provide desirable on eye wettability. Examples 36 - 41 The reaction components of Example 1, were blended with either 25% 10 or 40% D30 as diluent in accordance with the procedure of Example 1. The resultant reaction mixtures were charged into plastic contact lens molds (made from Topas@ copolymers of ethylene and norbornene obtained from Ticona Polymers) and cured in a glove box under a nitrogen atmosphere, at about 2.5 mW/cm 2 intensity, about 30 minutes and the temperatures shown in 15 Table 6, below. The lenses were removed from the molds, hydrated and autoclaved as describe in Example 1. After hydration the haze values of the lenses were determined. The results shown in Table 6 show that the degree of haziness was reduced at the higher temperatures. The results also show that as the concentration of diluent decreases the haze also decreases. 20 Table 6 Ex. # %D30 Temp. (*C) % haze DCA(*) 36 25 25 30 (6) .99 37 25 50-55 12(2) :100 38 25 60-65 14 (0.2) 59 39 40 25 50(10) 68 40 40 50-55 40 (9) 72 41 40 60-65 32(1) 66 Haze (std. dev.) 25 The results in Table 6 show that haze may be reduced by about 20% (Example 41 v. Example 39) and up to as much as about 65% (Example 37 v. Example 36) by increasing the cure temperature. Decreasing diluent concentration from 40 to 25% decrease haze by between about 40 and 75%. 30 46 Examples 42-47 Lenses were made from the formulations shown in Table 8 using the procedure of Example 1, with a 30 minute cure time at 25 0 C and an intensity of about 2.5 mW/cm 2 . Percent haze was measured and is reported in Table 5 7. Table 7 Ex.# 42 43 44 45 46 47 SiGMA 28.0 28.0 28.0 28.0 28.0 28.0 mPDMS 31.0 31.0 28.0 28.0 28.0 28.0 acPDMS 0.0 0.0 4.0 4.0 4.0 4.0 (n=10) DMA 23.5 23.5 23.5 23.5 24.0 24.0 H EMA 6.0 6.0 5.0 5.0 6.0 6.0 TEGDMA 1.5 1.5 1.5 1.5 0.0 0.0 Norbloc 2.0 2.0 2.0 2.0 2.0 2.0 PVP (K- 7.0 7.0 7.0 7.0 7.0 7.0 90) CGI 1850 1.0 1.0 1.0 1.0 1.0 1.0 D30 25.0 40 25.0 40.0 25.0 40.0 Properties Haze 30 50 7.3 14 26 25 Modulus 74 56 148 104 74 NT (psi) Elongation 326 395 188 251 312 NT (%) EWC(%) 38 41 33 35 38 39 10 A comparision of the results for formulations having the same amount of diluent and either TEGDMA or acPDMS (Examples 42 and 46 and Examples 43 and 47) shows that acPDMS is an effective crosslinker and provides lenses with properties which are comparable to those where TEGDMA is used as a crosslinker. Examples 44 and 45 contain both 15 crosslinkers. Haze for these Examples decreased substantially compared to the lenses made from either crosslinker alone. However, modulus and elongation were negatively impacted (likely because the amount of crosslinker was too great). 47 Examples 48-52 Reaction mixtures were made using the formulations shown in Table 8 with a mixture of 72.5% t-amyl alcohol and 27.5% PVP (Mw = 2500) as the diluent. The reaction mixtures were placed into thermoplastic contact lens 5 molds, and irradiated using Philips TL 20W/03T fluorescent bulbs at 450C, 0.8 mW/cm 2 for about 32 minutes. The molds were opened and lenses were released into deionized water at 950C over a period of 20 minutes. The lenses were then placed into borate buffered saline solution for 60 minutes and autoclaved at 122 0 C and 30 minutes. The properties of the resulting 10 lenses are shown in Table 9. Table 8 Ex. # 48 49 50 51 52 53 54 Components SiGMA 30 30 30 33 34 25 20 PVP 6 6 6 6 7 6 6 DMA 31 31 31 30 30 31 31 MPDMS 19 22 23.5 16.5 19 25 28 AcPDMS 2 0 0 3 0 0 0 (n=10) I I HEMA 9.85 8.5 6.95 9 6 10.5 12.5 Norbloc 1.5 1.5 1.5 2 1.5 1.5 1.5 CGI 819 0.23 0.23 0.25 0.48 0 0.23 0.23 CG11850 0 0 0 0 1 0 0 EGDMA 0.4 0.75 0.8 0 0 0.75 0.75 TEGDMA 0 0 0 0 1.5 0 0 Blue HEMA 0.02 0.02 0 0 0 0.02 0.02 % Diluent' 40.0 40.0 27.3 39.4 25.9 40 40 Diluent comp A A B C D A A Properties EWC (%) 45 45 47 49 47. 49 50 DCA 52(2) 51(7) 74(10) 108 75(6) 47(2) 56(11) (advancing) Modulus (psi) 91 77 69 55 49 63 67 Elongation NT 232 167 275 254 110 124 (%) I Dk (barrers) 54 60 78 44 87 59 60 Diluents (weight parts): A = 72.5% t-amyl alcohol and 27.5 PVP (Mw = 2500) 48 B = t-amyl alcohol C = 15/38/38% TMP/2M2P/ PVP (Mw = 2500) D= 57/43 2M2P/TMP 5 NT - not tested Thus, Examples 48, 51 show that formulations comprising both hydrophilic (EGDMA or TEGDMA) and hydrophobic crosslinkers (acPDMS) provide silicone hydrogel compositions which display an excellent balance of 10 properties including good water content, moderate Dk, wettabiltiy, modulus and elongation. Example 55 The lenses of Example 48 were clinically evaluated. The lenses were 15 worn by 18 patients in a daily wear mode (nightly removal) for a period of one week. At one week the PLTF-NIBUT was 8.4 (±2.9) seconds compared to 7.0 (±1.3) seconds for ACUVUE@ 2 lenses., The front surface discrete deposition was graded none to slight for 97% of the patients with the test lenses, compared with 89% in control lenses. The movement was acceptable for 20 both test and control lenses. Example 56 The lenses of Example 49 were clinically evaluated. The lenses were worn by 18 patients in a daily wear mode (nightly removal) for a period of one 25 week. At one week the PLTF-NIBUT was 8.4 (±2.9) seconds compared to 7 (±1.3) seconds for ACUVUE@ 2 lenses. The front surface discrete deposition was graded none to slight for 95% of the patients with the test lenses, compared with 89% in control lenses. The movement was acceptable for both test and control lenses. 30 Example 57 The lenses of Example 51 were clinically evaluated. The lenses were wom by 13 patients in a daily wear mode (nightly removal) for a period of one week. At one week the PLTF-NIBUT was 4.3 (±1.9) seconds compared to 9.6 35 (±2.1) seconds for ACUVUE@2 lenses. The front surface discrete deposition was graded none to slight for 70% of the patients with the test lenses, compared with 92% in control lenses. The movement was acceptable for 49 both test and control lenses. Thus, there is some correlation between contact angle measurements (1080 for Example 51 versus 520 for Example 48) and clinical wettability as measure by PLTF-NIBUT (4.3 seconds for Example 51 versus 8.4 seconds for Example 48). 5 Examples 58-68 Silicone hydrogel lenses were made using the components listed in Table 9 and the following procedure: 10 The components were mixed together in a jar to for a reaction mixture. The jar containing the reaction mixture was placed on a jar mill roller and rolled overnight. The reaction mixture was placed in a vacuum desiccator and the oxygen removed by applying vacuum for 40 minutes. The desiccator was 15 back filled with nitrogen. Contact lenses were formed by adding approximately 0.10 g of the degassed lens material to the concave front curve side of TOPAS@ mold cavities in a glove box with nitrogen purge. The molds were closed with polypropylene convex base curve mold halves. Polymerization was carried out under a nitrogen purge and was photoinitiated 20 with 5 mW cm 2 of visible light generated using 20W fluorescent lights with a TL-03 phosphor. After curing for 25 minutes at 45*C, the molds were opened. The concave front curve portion of the lens mold was placed into a sonication bath (Aquasonic model 75D) containing deionized water under the conditions (temperature and amount of Tween) shown in Table 10. The lens deblock 25 time is shown in Table 10. The lenses were clear and of the proper shape to be contact lenses. Table 9 Ex. 58 Ex. 59 Ex. 60 Ex. 61 3.05 3.2 3.2 3.0 SiGMA MPDMS 1.7 1.7 1.7 1.7 DMA 3.2 3.0 3.1 3.2 PVP 0.6 0.6 0.6 0.6 HEMA 1.0 0.8 0.8 1.0 TEGDMA 0.2 0.4 0.3 0.2 Norblock 0.15 0.2 0.2 0.2 50 1850 0.1 0.1 0.3 0.3 Triglide 1.5 1.5 1.5 2M2P 2.5 2.5 2.5 2.5 PVP low 0.5 1.5 1.5 0.5 Table 10 Ex. # Form. [Tween] (ppm) Temp (*C) Deblock time Ex. # (mn.) 62 58 850 75 10 63 58 10,000 70 10-15 64 58 0 75 20-22 65 58 850 22 10-15 66 59 850 85 3 67 60 850 85 6 68 61 850 75 18 5 Example 69 The lenses of Example 59 which were deblocked in Example 66, were further hydrated in deionized water at 65*C for 20 minutes. The lenses were then transferred into borate buffered saline solution and allowed to equilibrate for at least about 24 hours. The lenses were clear and of the proper shape to 10 be contact lenses. The lenses had a water content of 43%, a modulus of 87 psi, an elongation of 175%, and a Dk of 61 barriers. The lenses were found to have an advancing contact angle of 57 degrees. This indicates the lenses were substantially free of hydrophobic material. 15 Example 70 The concave front curve portion of the lens mold from Example 61 was placed into a sonication bath (Aquasonic model 75D) containing about 5% DOE-120 in deionized water at about 750C. The lenses deblocked from the frame in 18 minutes. 20 Example 71 (use of an organic solvent) The concave front curve portion of the lens mold from example 61 was placed into a sonication bath (Aquasonic 75D) containing about 10% of 2 propanol an organic solvent in deionized water at 75*C. The lenses 25 deblocked form the frame in 15 minutes. When Tween was used as the additive (Example 68) the deblock time was 18 minutes. Thus, the present 51 example shows that organic solvents may also be used to deblock lenses comprising low molecular weight hydrophilic polymers. EXAMPLE 72 (contains no low molecular weight PVP) 5 Silicone hydrogel lenses wee made using the formulation and procedure of Example 58, but without any low molecular weight PVP. The following procedure was used to deblock the lenses. The concave front curve portion of the lens mold was placed into a sonication bath (Aquasonic model 75D) containing about 850ppm of Tween in 10 deionized water at about 65*C. The lenses did not release from the mold. The deblock time for the formulation which contained low molecular weight hydrophilic polymer (Example 58 formuation) under similar deblock conditions (Example 62 - 850 ppm Tween and 75 0 C) was 10 minutes. Thus, the present Example shows that deblocking cannot be accomplished in water only, in this 15 formulation without including low molecular weight hydrophilic polymer in the formulation. Example 73 The concave front curve portion of the lens mold from example 72 was 20 placed into a sonication bath (Aquasonic 75D) containing about 10% of 2 propanol an organic solvent in deionized water at 75 0 C. The lenses deblocked form the frame in 20 to 25 minutes. Thus, lenses of the present invention which do not contain low molecular weight hydrophilic polymer may be deblocked using an aqueous solution comprising an organic solvent. 25 Examples 74-76 Formulations were made according to Example 49, but with varying amounts of photoinitiator (0.23, 0.38 or 0.5 wt.%), curing at 45*C with Philips TL 20W/03T fluorescent bulbs (which closely match the spectral output of the 30 visible light used to measure gel time) irradiating the molds at 2.0 mW/cm 2 . The advancing contact angles of the resulting lenses are shown in Table 11. Table 11 Ex. # Wt% | Advancing DCA Gel time (sec 52 74 0.23 59 (4) 65 75 0.38 62 (6) 57 76 0.5 80(7) 51 Examples 77-79 Gel times were measured for the formulation of Example 1 at 45 0 C at 5 1.0, 2.5 and 5.0 mW/cm 2 . The results are shown in Table 12. Table 12 Ex. # Intensity gel time (sec) (mW/cm 2 77 1 52 78 2.5 38 79 5 34 10 The results of Examples 74 through 76 and 77 through 79 compared with Examples 27-35, show that as gel times increase, wettability improves. Thus, gel points can be used, in coordination with contact angle measurements, to determine suitable cure conditions for a given polymer formulation and photoinitiator system. 15 Example 80 (Macromer Preparation) To a dry container, which was housed in a dry box under nitrogen at ambient temperature was added 30.0 g (0.277 mol) of 20 bis(dimethylamino)methylsilane (a water scavenger) , a solution of 13.75 ml of a 1 M solution of TBACB (386.0 g TBACB in 1000 ml dry THF), 61.39 g (0.578 mol) of p-xylene, 154.28 g (1.541 mol) methyl methacrylate (1.4 equivalents relative to initiator), 1892.13 (9.352 mol) 2-(trimethylsiloxy)ethyl methacrylate (8.5 equivalents relative to initiator) and 4399.78 g (61.01 mol) of THF. This 25 mixture was charged to a dry, three-necked, round-bottomed flask equipped with a thermocouple and condenser, all connected to a nitrogen source. The initial mixture was cooled to 15 *C while stirring and purging with nitrogen. After the solution reached 15 *C, 191.75 g (1.100 mol) of 1 trimethylsiloxy-1-methoxy-2-methylpropene (1 equivalent) was injected into 30 the reaction vessel. The reaction was allowed to exotherm to approximately 62 *C and then 30 ml of a 0.40 M solution of 154.4 g TBACB in 11 ml of dry 53 THF was metered in throughout the remainder of the reaction. After the temperature of reaction reached 30 *C and the metering began, a solution of 467.56 g (2.311 mol) 2-(trimethylsiloxy)ethyl methacrylate (2.1 equivalents relative to the initiator), 3636.6. g (3.463 mol) n-butyl 5 monomethacryloxypropyl-polydimethylsiloxane (3.2 equivalents relative to the initiator), 3673.84 g (8.689 mol) TRIS (7.9 equivalents relative to the initiator) and 20.0 g bis(dimethylamino)methylsilane was added. This mixture was allowed to exotherm to approximately 38-42 0C and then allowed to cool to 30 *C. At that time, a solution of 10.0 g (0.076 mol) 10 bis(dimethylamino)methylsilane, 154.26 g (1.541 mol) methyl methacrylate (1.4 equivalents relative to the initiator) and 1892.13 g (9.352 mol) 2 trimethylsiloxy)ethyl methacrylate (8.5 equivalents relative to the initiator) was added and the mixture again allowed to exotherm to approximately 40 *C. The reaction temperature dropped to approximately 30 OC and 2 gallons of 15 THF were added to decrease the viscosity. A solution of 439.69 g water, 740.6 g methanol and 8.8 g (0.068 mol) dichloroacetic acid was added and the mixture refluxed for 4.5 hours to remove the trimethylsiloxy protecting groups on the HEMA. Volatiles were then removed and toluene added to aid in removal of the water until a vapor temperature of 110 0C was reached. 20 The reaction flask was maintained at approximately 110 0C and a solution of 443 g (2.201 mol) TMI and 5.7 g (0.010 mol) dibutyltin dilaurate were added. The mixture was reacted until the isocyanate peak was gone by IR. The toluene was evaporated under reduced pressure to yield an off-white, anhydrous, waxy reactive macromer. The macromer was placed into acetone 25 at a weight basis of approximately 2:1 acetone to macromer. After 24 hrs, water was added to precipitate out the macromer and the macromer was filtered and dried using a vacuum oven between 45 and 60 0C for 20-30 hrs. Examples 81- 881 30 Reaction mixtures were made in a nitrogen-filled glove box using the formulations shown in Table 12 with a D30 and/or IPL as the diluent. The reaction mixtures were placed into thermoplastic contact lens molds, and irradiated using Philips TL 20W/03T fluorescent bulbs at 50*C, for about 60 minutes. The molds were opened and lenses were released IPA, leached 54 and transferred into borate buffered saline. The properties of the resulting lenses are shown in Table 13. Table 13 Example 81 82 83 84 85 '86 87 88 Component Macromer 18 18 13 13 13 13 13 11 MPDMS 23 18 29 28 28 28 26 28 AcPDMS 5 10 3 3 3 5 5 5 (n=10) I I TRIS 14 14 15 15 15 14 13 14 DMA 27 27 28 29 30 30 33 32 HEMA 5 5 2 2 2 2 2 2 Norbloc 2 2 2 2 2 i2 2 2 PVPK-90 5 5 7 6 5 15 5 5 Blue HEMA 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 CG11850 1 1 1 1 1 1 1 1 %Diluent 20 20 30 30 30 30 30 30 % D30 in dil. 60 60 100 100 100 60 100 100 % IPL in dil. 40 40 0 0 0 40 0 0 EWC(%) 36 32 40 40 39 37 40 38 OCA 48 46 45 50 57 (advancing) Modulus (psi) 149 268 85 90 91 107 134 129 Elongation 216 149 294 300 290 251 176 209 (%) I I Dk (barrers) 89 76 114 100 116 117 5 Example 89 The lenses of Example 83 were clinically evaluated. The lenses were worn by 10 patients in a daily wear mode (nightly removal) for a period of 30 10 minutes. For each patient, the test lens was worn in one eye and an Bauch & Lomb Purevision lens was worn in the contralateral eye. At thirty minutes the PLTF-NIBUT was 7.5 (±1.6) seconds compared to 8.6 (+1.6) seconds for the Bausch & Lomb Purevision lens. . The front surface discrete deposition was graded none to slight for 100% of the patients with the test lenses, compared 15 with 100% in control lenses. The movement was acceptable for both test and control lenses. The lenses of the present invention are comparable in performance to the B&L lens, which has a plasma coating. Thus, the present 55 Example shows that lenses formed from a polymer network comprising a siloxane containing macromer, high molecular weight hydrophilic polymer and a compatibilizing component display good wettability and deposition resistance without a coating. 5 Example 90 Trifluoromethane sulfonic acid (2.3 ml) was added to 27.8 g 1,3 bis(hydroxybutyl)tetramethyldisiloxane and 204.4 g octamethylcyclotetrasiloxane. The resulting solution was stirred overnight. 10 17.0 g Na 2

CO

3 were added and the mixture was stirred for one hour. About 50 ml hexane was added and the mixture was stirred for about one hour, then filtered. The hexane was evaporated under reduced pressure and cyclics were removed by heating to 11 0*C at < 1 mBar for about one hour to produce hydroxybutyl terminated polydimethylsiloxane. 15 In a separate flask 12.2 g CH 2 OH terminated Fluorolink@ Polymer Modifier D10 with an average equivalent weight of 500 (Ausimont USA, equivalent to Fomblin@ ZDOL) was combined with 11.8 mg dibutyltin dilaurate. The resulting solution was evacuated to about 20 mBar twice, each time refilling with dry N 2 . 5.0 ml isophorone diisocyanate was added and the 20 mixture was stirred overnight under N 2 to produce a clear viscous product. 47.7 g of the hydroxybutyl terminated polydimethylsiloxane from above was combined with 41.3 grams anhydrous toluene. This solution was combined with the Fluorolink@-Isophorone diisocyanate product and the resulting mixture was stirred under nitrogen overnight. The toluene was 25 evaporated from the product over about 5 hours at < 1 mBar. 3.6 g 2 isocyanatoethyl methacrylate was added and the resulting mixture was stirred under N 2 for four days to produce a slightly opaque viscous liquid fluorosilicone macromer. 30 Example 91 2.60 g of the fluorosilicone macromer made in Example 90 was combined with 1.12 g ethanol, 1.04 g TRIS, 1.56 g DMA, 32 mg Darocur 1173 to produce a slightly hazy blend containing 18% diluent (ethanol). Contact lenses were made from this blend in plastic molds (Topas) curing 30 minutes 35 under fluorescent UV lamps at room temperature in a N 2 atmosphere. The 56 molds were opened, and the lenses released (deblocked) into ethanol. The lenses were leached with CH 2

CI

2 and then IPA for about 30 minutes each at room temperature, then placed into borate buffered saline for about 2 hours and then autoclave at 121*C for 30 minutes. The resulting lenses were tacky 5 to the touch and had a tendency to stick to each other. The advancing DCA of these lenses was measured and is shown in Table 14. Example 92-88 Reaction mixtures were made using the reactive components (amounts 10 based upon reactive components) shown in Table 14 and D30 as a diluent. The amount of D30 is based upon the total amount of reactive components and diluent. The reaction mixture and lenses were made using procedure of Example 91. The resulting lenses were slippery to the touch and did not stick to each other. 15 The advancing DCA of these lenses was measured and is shown in Table 14, below. Table 14 Example 92 93 94 Component (wt %) Fluorosilicone macromer 49.7 28.5 19 TRIS 19.9 0 0 DMA 29.8 24.8 24.7 PVP (K90) 0 5 4.9 SiGMA 0 40.7 50.1 EGDMA 0 0.4 0.6 Darocur 1173 0.6 0.6 0.6 Diluent Ethanol D30 D30 % Diluent in final blend 18 18 18 Advancing DCA 132 (8) 69(7) 59 (9) 20 Examples 92 through 94 clearly show that hydrophilic polymer may be used to improve wettability. In these Examples contact angles are reduced by up to about 50% (Example 93) and up to about 60% (Example 94). Compositons comprising higher amounts of fluorosilicone macromer and hydrophilic polymer can also be made by functionalizing the fluorosilicone 25 macromer to include active hydrogens. 57 Examples 95-95 Reaction mixtures were made using reactive components shown in Table 15 and 29% (based upon all reactive components and diluent) t-amyl alcohol as a diluent and 11% PVP 2,500 (based upon reactive components). 5 Amounts indicated are based upon 100% reactive components. The reaction mixtures were placed into thermoplastic contact lens molds, and irradiated using Philips TL 20W/03T fluorescent bulb at 60*C, 0.8 mW/cm 2 for about 30 minutes under nitrogen. The molds were opened and lenses were released into deionized water at 95 0 C over a period of 15 minutes. The lenses were 10 then placed into borate buffered saline solution for 60 minutes and autoclaved at 1220 C for 30 min. The properties of the resulting lenses are shown in Table 15. Table 15 Ex.# 95 96 97 98 99 Components SiGMA 30 30 30 30 30 PVP 0 1 3 6 8 DMA 37 36 34 31 29 MPDMS 22 22 22 22 22 HEMA 8.5 8.5 8.5 8.5 8.5 Norbloc 1.5 1.5 1.5 1.5 1.5 CGI 819 0.25 0.25 0.25 0.25 0.25 EGDMA 0.75 0.75 0.75 0.75 0.75 Properties DCA 122(8) 112(6) 66(13) 58(8) 54(3) (advancing) Haze 18(4) 1(1l) 13(1) 14(2) 12(1) 15 Table 15 shows that the addition of PVP dramatically decreases contact angle. As little as 1% decreases the dynamic contact angle by about 10% and as little as 3% decreases dynamic contact angle by about 50%. These improvements are consistent with those observed for macromer based 20 polymers, such as those in Examples 92-94. Example 100 Preparation of mPDMS-OH (used in Examples 3) 58 96 g of Gelest MCR-E1 1 (mono-(2,3-epoxypropyl)-propyl ether terminated polydimethylsiloxane(1000 MW)), 11.6 g methacrylic acid, 0.10 g triethylamine and 0.02 g hydroquinone monomethylether were combined and heated to 140*C with an air bubbler and with stirring for 2.5 hours. The product was extracted with saturated 5 aqueous NaHCO 3 and CH 2

CI

2 . The CH 2

CI

2 layer was dried over Na 2

SO

4 and evaporated to give 94 g of product. HPLC/MS was consistent with desired structure: 0 10 o o-sr(O S, OSiCAH OH /\ /\10-15 15 Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", and variations such as "comprises" and "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps. 20 The reference to any prior art in this specification is not, and should not be taken as, an acknowledgment or any form or suggestion that the prior art forms part of the common general knowledge in Australia. 59 EDITORIAL NOTE APPLICATION NUMBER - 2007234531 Description has page 1 a occurring both at the beginning and at the end.

BIOMEDICAL DEVICES CONTAINING INTERNAL WETTING AGENTS This Application is a divisional of Australian Patent Application No. 2002323661, and the whole contents thereof are included herein by reference. 5 FIELD OF THE INVENTION This invention relates to silicone hydrogels that contain internal wetting agents, as well as methods for their production and use. 10 BACKGROUND OF THE INVENTION Contact lenses have been used commercially to improve vision since at least the 1950s. The first contact lenses were made of hard materials and as such were somewhat uncomfortable to users. Modern lenses have been developed that are made 15 of softer materials, typically hydrogels and particularly silicone hydrogels. Silicone hydrogels are water-swollen polymer networks that have high oxygen permeability and surfaces that are more hydrophobic than hydrophilic. These lenses provide a good level of comfort to many lens wearers, but there are some users who experience discomfort and excessive ocular deposits leading to reduced visual acuity when using 20 these lenses. This discomfort and deposits has been attributed to the hydrophobic character of the surfaces of lenses and the interaction of those surfaces with the protein, lipids and mucin and the hydrophilic surface of the eye. Others have tried to alleviate this problem by coating the surface of 25 silicone hydrogel contact lenses with hydrophilic coatings. For example, it has been 25 disclosed that silicone hydrogel lenses can be made more compatible with ocular surfaces by applying plasma coatings to the lens surface. However, uncoated silicone hydrogel lenses having low incidences of surface deposits have not been disclosed. Incorporating internal hydrophilic agents (or wetting agents) into a macromer containing reaction mixture has been disclosed. However, not all silicone 30 containing macromers display compatibility with hydrophilic polymers. Modifying the surface of a polymeric article by adding polymerizable surfactants to a monomer mix used to form the article has also been la 16/I I/07,16949.speci.j

Claims (69)

1. A method comprising the steps of (a) mixing 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 5 compatibilizing component and (b) curing the product of step (a) to form a biomedical device.

2. A method according to claim 1, wherein said reactive components are mixed in the presence of a diluent to form a reaction mixture.

3. A method according to claim 2, wherein said diluent is selected from the 10 group consisting of ethers, esters, alkanes, alkyl halides, silanes, amides, alcohols and mixtures thereof.

4. A method according to claim 2, wherein said diluent is selected from the group consisting of tetrahydrofuran, ethyl acetate, methyl lactate, i-propyl lactate, ethylene chloride, octamethylcyclotetrasiloxane, dimethyl formamide, dimethyl 15 acetamide, dimethyl propionamide, N methyl pyrrolidmnone mixtures thereof and mixtures of any of the foregoing with at least one alcohol.

5. A method according to claim 2, wherein said diluent comprises at least one alcohol having at least 4 carbon atoms.

6. A method according to claim 2, wherein said diluent comprises at least 20 one alcohol having at least 5 carbons atoms.

7. A method according to any one of claims 2 to 6, wherein said diluent is inert and easily displaceable with water.

8. A method according to claim 2, wherein said diluent comprises at least one alcohol selected from the group consisting of tert-butanol, tert-amyl alcohol, 2 25 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.

9. A method according to claim 2, 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 30 propyl lactate, 3,7-dimethyl-3-octanol, dimethyl formamide, dimethyl acetamide, dimethyl propionamide, N methyl pyrrolidinone and mixtures thereof. 17/12/10,dh-16949 - claimsclean - rck.doc,60 -61

10. A method according to claim 2, wherein said diluent is selected from the group consisting of I-ethoxy-2-propanol, I-methyl-2-propanol, t-amyl alcohol, tripropylene glycol methyl ether, isopropanol, l-methyl-2-pyrrolidone, N,N imethylpropionamide, ethyl lactate, dipropylene glycol methyl ether and mixtures 5 thereof.

11. A method according to any one of claims 2 to 10, wherein said diluent is present in an amount less than about 40 weight% based upon the reaction mixture.

12. A method according to claim t1, wherein said diluent is present in an amount between 10 and 30 weight% based upon the reaction mixture. 10

13. A method according to any one of claims 2 to 12, wherein said diluent is water soluble at processing conditions and said process further comprises (c) removing said lens from a mold in which said lens was cured and (d) hydrating said lens, wherein both steps (c) and (d) are performed in aqueous solutions which comprise water as a substantial component. 15

14. A method according to any one of claims 1 to 13, wherein said curing is conducted via heat, exposure to radiation or a combination thereof and said reaction mixture further comprises at least one initiator.

15. A method according to claim 14, wherein said curing conducted via irradiation comprises ionizing and/or actinic radiation and said initiator comprises at 20 least one photoinitiator.

16. A method according to claim 15, wherein said radiation comprises light having a wavelength of from 150 to 800nm 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, 25 and mixtures thereof.

17. A method according to claim 16, wherein said initiator is selected from the group consisting of I -hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-i phenyl-propan-I -one, bis(2,6-dimethoxybenzoyl)-2,4-4-trimethylpentyl phosphine oxide, bis(2,4 ,6-trimethylbenzoyl)-phenylphosphineoxide, 2,4,6 30 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. 17/12/ 10.dh-16949 - claimsclean - rck.doc,61 - 62

18. A method according to any one of claims 17 to 20, wherein said initiator is present in the reaction mixture in amounts of from 0.1 to 2 weight percent based upon said reactive components.

19. A method according to any one of claims 15 to 18, wherein said curing is 5 conducted via visible light irradiation.

20. A method according to claim 19, wherein said initiator comprises I hydroxycyclohexyl phenyl ketone, bis(2 ,6-di methoxybenzoyl)-2 ,4-4 trimethylpentyl phosphine oxide and mixtures thereof.

21. A method according to claim 19, wherein said initiator comprises 10 bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide.

22. A method according to any one of claims 15 to 21, wherein said reactive components further comprise at least one UV absorbing compound.

23. A method according to any one of claims 19 to 22, wherein said curing step is conducted at a cure intensity of between 0.1 and 6 mW/cm2. 15

24. A method according to claim 23, wherein said curing step is conducted at a cure intensity of between 0.2 mW/cm2 to 3 mW/cm2.

25. A method according to any one of claims I to 24, wherein said curing step further comprises a cure time of at least about 1 minute.

26. A method according to claim 25, wherein said curing step further 20 comprises a cure time of between 1 and 60 minutes.

27. A method according to claim 26, wherein said curing step further comprises a cure time of between I and 30 minutes.

28. A method according to any one of claims I to 27, wherein said curing step is conducted at a temperature greater than about 25 0 C. 25

29. A method according to claim 28, wherein said curing step is conducted at a temperature of between 25 0 C and 70 0 C.

30. A method according to claim 29, wherein said curing step is conducted at a temperature of between 40*C and 70*C.

31. A method according to any one of claims 2 to 30, wherein said reaction 30 mixture is cured in a mold and said method further comprises the step of deblocking said ophthalmic device from said mold. 17/12/10,dh-16949 - claimsclean - rck.doc,62 -63

32. A method according to claim 31, wherein said reaction mixture further comprises at least one low molecular weight hydrophilic polymer.

33. A method according to claim 32, wherein said low molecular weight hydrophilic polymer has a number average molecular weight of less than about 5 40,000 Daltons.

34. A method according to claim 33, wherein said low molecular weight hydrophilic polymer has a number average molecular weight of less than about 20,000 Daltons.

35. A method according to any one of claims 32 to 34, wherein the low 10 molecular weight polymer is selected from the group consisting of water soluble polyamides, lactams and polyethylene glycols, and mixtures thereof.

36. A method according to any one of claims 32 to 34, wherein the low molecular weight polymer is selected from the group consisting of poly vinylpyrrolidone, polyethylene glycols, poly 2 ethyl-2-oxazoline and mixtures 15 thereof.

37. A method according to any one of claims 32 to 36, wherein the low molecular weight hydrophilic polymer is present in amounts up to about 20 weight% based upon the reaction mixture.

38. A method according to claim 37, wherein the low molecular weight 20 hydrophilic polymer is present in amounts of between 5 and 20 weight% based upon the reaction mixture.

39. A method according to any one of claims 31 to 38, wherein said deblocking is conducted using an aqueous solution.

40. A method according to claim 39, wherein said aqueous solution further 25 comprises at least one surfactant.

41. A method of claim 40, wherein said surfactant comprises at least one non-ionic surfactant.

42. A method according to claim 40, wherein said surfactant comprises polyoxyethylene(20) sorbitan monostearate or ethoxylated methylglucoside dioleate. 30

43. A method according to any one of claims 40 to 42, wherein said surfactant is present in amounts up to about 10,000 ppm. 03/03/1 I,cg 16949 claimsclean - pcs.doc,63 -64

44. A method according to claim 43, wherein said surfactant is present in amounts between 100 and 1200 ppm.

45. A method according to any one of claims 39 to 44, wherein said aqueous solution comprises at least one organic solvent. 5

46. A method according to any one of claims 31 to 45, wherein said deblocking is conducted at a temperature between ambient and I 00*C.

47. A method according to claim 46, wherein said deblocking is conducted at a temperature between 70'C and 95'C.

48. A method according to any one of claims 31 to 47, wherein said 10 deblocking is conducted using agitation.

49. A method according to claim 48, wherein said agitation comprises sonication.

50. A method comprising the steps of (a) mixing reactive components comprising a high molecular weight hydrophilic polymer, at lest one silicone 15 containing macromer 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.

51. A method according to either claim I or claim 50, wherein said device is an ophthalmic lens. 20

52. A method according to any one of claims 1, 50 or 51, wherein said device is a contact lens.

53. A method according to either claim 51 or claim 52, wherein said lens comprises an advancing dynamic contact angle of about 800 or less.

54. A method according to claim 53, wherein said lens comprises an 25 advancing dynamic contact angle of about 700 or less.

55. A method according to any one of claims 50 to 54, wherein said lens comprises a tear film break up time of at least about 7 seconds.

56. A method according to any one of claims 50 to 55, wherein said reactive components further comprise at least one initiator. 30 17/12/10.dh-16949 - claimsclean - rck.doc,64 -65

57. A method according to claim 56, wherein said curing is conducted via irradiation and said conditions comprise an initiator concentration and cure intensity effective to provide said minimum gel time.

58. A method according to claim 57, wherein said initiator is present in an 5 amount up to about 1% based upon all reactive components.

59. A method according to claim 58, wherein said initiator is present in an amount less than about 0.5% based upon all reactive components.

60. A method according to any one of claims 50 to 59, wherein said curing is conducted via irradiation at an intensity of less than about 5 mW/cm2. 10

61. A method according to any one of claims 50 to 60, wherein said gel time is at least about 30 seconds.

62. A method according to claim 61, wherein said gel time is at least about 35 seconds.

63. A method for improving the wettability of an ophthalmic device formed 15 from a reaction mixture comprising adding at least one high molecular weight hydrophilic 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. 20

64. A method according to claim 63, wherein said compatibilizing component has a compatibility index of greater than about 0.5.

65. A method according to claim 64, wherein said compatibilizing component has a compatibility index of greater than about 1.

66. A method according to any one of claims 63 to 65, wherein said 25 compatibilizing component comprises at least one siloxane group.

67. A method according to claim 66, wherein said compatibilizing component further comprises hydroxyl functionality and has a Si to OH ratio of less than about 15:1.

68. A method according to claim 67, wherein said compatibilizing 30 component has a Si to OH ratio of between 1:1 to 10:1.

69. A method according to any one of claims 1, 50 or 63, substantially as hereinbefore described with reference to any one of the examples. 17/12/10,dh-16949 - claimsclcan - rck.doc,65