CA2238650A1 - Methods of manufacturing contact lenses - Google Patents

Abstract

A method of forming an ophthalmic lens suited for extended-wear periods without a clinically significant amount of corneal swelling and without substantial wearer discomfort. The lens has a balance of oxygen permeability and ion or water permeability, with the ion or water permeability being sufficient to provide good on-eye movement, such that a good tear exchange occurs between the lens and the eye. The manufacturing method requires the oxygen concentration of the polymerizable material to be low enough to produce a lens having a high ion permeability. A preferred oxygen concentration in the polymerizable material is a concentration below 200 ppm.

Description

CA 022386~0 1998-0~-26 Methods of Manufacturing Contact ~enses BACKGROUND OF THE INVENTION
1. FIELD OF Tl IE INVENTION

This invention reiates broadly to methods of forming polymeric articles (e.g. Ienses) and polymeric materials, especially those useful in optic and ophthalmic arts. In a preferred embodiment, this invention relates to methods of forming polymeric materials useful in the manufacture of contact lenses. In a more preferred embodiment, thls Invention relates to methods of manufacturing contact lenses having a high water, ion and gas permeability which are useful as extended-wear contact lenses.

2. DESCRIPTION OF THE RELATED ART

A wlde variety of research has been conducted in the field of biocompatible polymers. The definition of the term "biocompatible" depends on the particular applicatlon for which the polymer is deslgned. In the field of ophthalmic lenses, and in particular in the field of contact lenses, a biocompatible lens may be generally defined as one which will not substantially damage the surrounding ocular tissue and ocular fluid during the time period of contact. The phrase "ophthalmically compatible" more appropriately describes thebiocompatibility requirements of ophthalmic lenses.

One ophthalmic comrF' ~ ' :y requirement for contact lenses is that the lens must allow oxygen to reach the cornea in an amount which is sufficient for long-term corneal health.
The contact lens must allow oxygen from the surrounding air to reach the cornea because the cornea does not receive oxygen from the blood supply like other tissue. If sufficient oxygen does not reach the cornea, corneal swelling occurs. Extended periods of oxygen deprivation causes the undesirable growth of blood vessels in the cornea. "Soft" contact lenses conform closely to the shape of the eye, so oxygen cannot easily circumvent the lens. Thus, soft contact lenses must allow oxygen to diffuse through the lens to reach the cornea.

CA 022386~0 1998-0~-26 Another ophthalmic compatibility requirement for soft contact lenses is that the lens must not strongly adhere to the eye. Clearly, the consumer must be able to easily remove the lens from the eye for disinfecting, cleaning, or disposal. However, the lens must also be able to move on the eye in order to encourage tear flow between the lens and the eye.
Tear flow between the lens and eye allows for debris, such as foreign partic~ tes or dead epithelial cells, to be swept from beneath the lens and, ultimately, out of the tear fluid.
Thus, a contact lens must not adhere to the eye so strongly that adequate movement of the lens on the eye is inhibited.

While there exist rigid gas permeable ("RGP") contact lenses which have high oxygen permeability and which move on the eye, RGP lenses are typically quite uncomfortable for the consumer. Thus, soft contact lenses are preferred by many consumers because of comfort. Moreover, a contact lens which may be continuously worn for a period of a day or more (including wear during periods of sleeping) requires comfort levels which exclude RGP
lenses as popular extended-wear can~ t~s in order to balance the ophthalmic compaliLIility and consumer comfort requirements in designing a daily wear soft contact lens, polymers and copolymers of 2-hydroxyethyl methacrylate (HEMA) were developed. These hydrophilic polymers move well on the eye and provide sufficient oxygen permeability for daily wear. Certain soft contact lenses have been approved by the FDA for extended wear periods of up to about 6 nights of overnight wear and seven days of daily wear. However, the consumer cannot safely and comfortably wear these poly(HEMA) lenses for extended periods of seven days or more, because the oxygen permeability is insufficient. True extended wear (i.e., seven days or more) of these lenses may result, at a minimum, in corneal ~ 6" ~g and development of surFace blood vessels in the comea.

In order to improve oxygen permeability, polymers containing silicone groups were developed. A variety of siloxane-conl~i"illg polymers have been disclosed as having high oxygen permeability. For example, see U.S. Patent Nos. 3,228,741; 3,341,490; 3,996,187;
and 3,996,189. However, polysiloxanes are typically highly lipophilic. The properties (e.g., lipophil: Ly, glass transition temperature, mechanical properties) of known polysiloxanes has resulted in contact lenses which adhere to the eye, inhibiting the necessary lens movement. In addition, polysiloxane lipophilicity promotes adhesion to the lens of lipids and proteins in the tear fluid, causing a haze which interferes with vision through the lens.

CA 022386~0 1998-0~-26 There have been attempts to blend the desirable hydrophilic properties of hydrophilic polymers, formed from monomers such as HEMA, with the desirable oxygen permeability of polymers formed from siloxane-containing monomers. For example, see U.S. Patent Nos.

3,808,178; 4,136,250; and 5,070,169. However, prior attempts at producing a trueextended wear contact lens have been unsuccessful, either because of the effect of the extended-wear lens on corneal health or because the lens would not move on the eye.
Thus, there remains a need for an ophthalmically compatible, transparent polymeric material which is suited to extended periods of continuous contact with ocular tissue and tear fluid.

Furthermore, there have been efforts directed to improving a variety of aspects of conventional or high volume contact lens manufacturing methods. For example, European Patent Application No. 0 687 550 A2 describes a method of manufacuring contact lenses which requires degassing both concave (front surface) and convex (base curve surface) mold halves. This ~pplic~tion states that the level of oxygen at the reactive monomer/mold interface must be conl,~ d to approximately 300 times less than the concentration of oxygen in air (3x10-3 moles/liter). The reduction of oxygen in the molds is accomplished in order to achieve reduced defects and high speed, high volume manufacturing operations.

Similarly, U.S. Patent No. 5,435,943, issued on Jul. 25, t 995, teaches a process for manufacturing an ophthalmic lens including a step of degassing monomer by drawing and maintaining a subsatmosheric pressure about the exterior of a tube through which the monomer is pumped. The objectives of the process include reducing the amount of nitrogen in the monomer as well as reducing the amount of oxygen in the monomer. The patent states that dissolved gases, such as nitrogen or oxygen, may cause bubbles or interfere with polymeri~,llion.

In addition, PCT Appliç~tion No. WO 96/11782 discloses a method of improving the surface characteristics of cast molded contact lenses. This surface-altering method involves the removal of oxygen from the plastic mold pieces prior to casting the lenses.

OBJECTS AND SUMMARY OF THE INVENTION

An object of this invention is to provide a method of manufacturing a contact lens having good on-eye movement while exhibiting sufficient oxygen permeability for extended wear periods of a week or more.

CA 022386~0 l998-0~-26 WO 97/22019 PCTlIB96/01368 An object of the invention is to provide a method of forming a material having a balance of oxygen permeability, ion permeability, on-eye movement and tear exchange, all of which are sufficient for corneal health and wearer comfort during extended periods of continuous wear.
These and other obiects of the invention are met by the various embodiments described herein.

One embodiment of the invention is a method of producing a contact lens having a balance of high oxygen ll~nsll.issiLilily and good on-eye movement. The method includes the steps of:
(a) providing a polymerizable material coi"~ ri~;l,g:
(i) one or more macromers selected from the group consisli"g of siloxane-containing acrylate macromers and fluorine-conl~i"i, Ig acrylate macromers, and (ii) one or more hydrophilic comonomers selected from the group consisting of acrylamides, methacrylamides, N-vinyl pyrrolidones and mixtures thereof;
(b) removing oxygen from said polymerizable material such that the concenlr~lion of oxygen in said polymerizable material is less than ~00 ppm;
(c) instilling said polymerizable material into a contact lens mold; and (d) polymerizing said polymerizable material to form a contact lens.

Another embodiment is a contact lens formed by the above-described process.

It has been discovered that the presence of oxygen in certain polymerizable ",~l~rials during polymerization will cause the resultant molded artlcle to have a low ion permeability.
Furthermore, it has been found that ion permeability corl~lales well with on-eye movement of contact lenses. Thus, the present invention involves the remarkable discovery that the molding of certain polymerizable mixtures with very low, or negligible, oxygen concentrations produces a contact lens which has good on-eye movement, in addition to high oxygen permeability.

CA 022386~0 1998-0~-26 OUTLINE OF DESCRIPTION OF THE PREFERRED EMBODIMEI~TS

1. DFFINITION OF TERMS

~ Il. CORE POLYMER AND LENS
A. Polymerizable materials B. Weight ratios of polymerizable materials C. Morphology D. Bulk Water Content E. Ion and Water Permeability 1. Ionoflux lon Permeability Measurements 2. Ionoton lon Permeability Measurements 3. Hydrodell Water Permeability Measurements F. Oxygen Permeability and Transmissibility G. Examples of suitable materials 1. Material"A"
2. Material "B"
3. Material"C"

111. OPHTHALMICALLY COMPATIBLE SURFACES

IV. UTILITY
A. Ophthalmic Lenses B. Contact Lenses C. Methods Of Use As Contact Lenses V. METHODS OF LENS MANUFACTURE

DESCRIPTION OF THE PREFERRED EMBODIMENTS

One embodlment of the present invention is a method of forrning an ophthalmically compatible, transparent lens suited to extended periods of continuous contact with ocular tissue and tear fluids. A particularly preferred embodiment of the invention is a method of forming an extended-wear vision correction lens suited for safe and con,fu, lable long term -CA 022386~0 1998-0~-26 wear without removal. In order to properly describe the invention and to delineate the metes and bounds of the claims, a set of basic terms will be defined at the outset.

1. pEFlNlTlON OF TERIUIS

An "ophthalmic lens", as used herein, refers to lenses which are placed in intimate contact with the eye or tear fluid, such as contact lenses for vision correction (e.g., spherical, toric, bifocal), contact lenses for modification of eye color, ophthalmic drug delivery devices, ocular tissue protective devices (e.g., ophthalmic healing promoting lenses~, and the like. A
particularly preferred ophthalmic lens is an extended-wear contact lens, especially extended-wear contact lenses for vision correcffon.

The "ox,vgen transmissibility" of a lens, as used herein, is the rate at which oxygen will pass through a specific ophthalmic lens. Oxygen Ir~lns"lissib.!,ty, Dk/t, is conventionally ek~.ressed in units of barrers/mm, where t is the average thickness of the material [in units of mm] over the area being measured and "barrer" is defined as:
[(cm3 oxygen)(mm) / (cm2)(sec)(mm Hg)~ x 10-9 The "oxygen permeability", Dk, of a lens material does not depend on lens Ihi k"ess.
Oxygen permeability is the rate at which oxygen will pass through a material. Oxygen permeability is conventionally expressed in units of barrers, where "barre~' is defined as:
[(cm3 oxygen)(mm) / (cm2 )(sec)(mm Hg)] x 1 o-10 These are the units commonly used in the art. Thus, in order to be cons;slenl with the use in the art, the unit "barreP will have the meanings as defined above. For example, a lens having a Dk of 90 barrers ("oxygen permeability barrers") and a thickness of 90 microns (0.090 mm) would have a DWt of 100 barrers/mm ("oxygen transmissibility barrers"/mm).

A "macromel", as used herein, refers to a polymeri~ble material which has a molecular weight of at least about 800 grams/mol. The term "macromer", as used herein, also encompasses oligomers.

A "monomeP, as used herein refers to a polymerizable material which has a molecular weight of less than about 800 grams/mol.

A 'phase", as used herein, refers to a region of substantially uniform composition which is a distinct and physically separdLe portion of a heterogeneous polymeric material. However, the term "phase" does not imply that the material described is a chemically pure substance, CA 022386~0 1998-0~-26 but merely that certain bulk properties differ significantly from the properties of another phase within the material. Thus, with respect to the polymeric components of a lens, an ionoperm phase refers to a region composed of essentially only ionoperm polymer (and water, when hydrated), while an oxyperm phase refers to a region composed of essentially only oxyperm polymer.

A "continuous phase", as used herein, refers to a region of substantially uniform composition which forms a continuous pathway from one surface of an article to another surface of an article.

"Co-continuous phases", as used herein, refers to at least two regions, each of substantially uniform composition which differs from the other, and each of which forms a continuous pathway from one surface of an article to another surface of an article. Thus, an ophthalmic lens having co-continuous phases of oxyperm polymer and ionoperm polymer will have two continuous pathways or sets of continuous pathways extending from the inner surface of the lens to the outer surface of the lens.

"Morphology", as used herein, refers to the structure and relationship of the phases of a material.

"Ophthalmically compatible", as used herein, refers to a material or surface of a material which may be in intimate contact with the ocular environment for an extended period of time without significantly damaging the ocular environment and without significant user discomfort. Thus, an ophthalmically compatible contact lens will not produce significant corneal swelling, will adequately move on the eye with blinking to promote adequate tear exchange, will not have substantial amounts of lipid adsorption, and will not cause substantial wearer discomrort during the prescribed period of wear.

"Ocular environment", as used herein, refers to ocular fluids (e.g., tear fluid) and ocular tissue (e.g., the cornea~ which may come into intimate contact with a contact lens used for vision correction, drug delivery, wound healing, eye color modification, or other opl~ll,aln,ic applications.

"Hydlophil.c", as used herein, describes a material or portion thereof which will more readily associate with water than with lipids.

CA 022386~0 l998-0~-26 wo 97/22019 pcTlIss6/ol368 A "hydrophilic surface ", as used herein, refers to a surface which is more hydrophilic and lipophobic than the bulk or core material of an article. Thus, an ophthalmic lens having a hydrophilic surface describes a lens having a core material having a certain hy-l,uphilicity surrounded, at least in part, by a surface which is more h~,d~opllilic than the core.

The "outer surface" of a lens, as used herein, refers to the surface of the lens which faces away from the eye during wear. The outer surface, which is typically substantially convex, may also be referred to as the front curve of the lens. The "inner surface" of a lens, as used herein, refers to the surface of the lens which faces towards the eye during wear. The inner surface, which is typically substantially concave, may also be referred to as the base curve of the lens.

"TRIS", as used herein, refers to 3-methacryloxypropyltris~trimethylsiloxy) silane, which is represented by CAS No. 17096-07-O. The term '~RIS" also includes dimers of 3-methacryloxypropyltris(trimethylsiloxy) silane.

"Molecular weight" of a polymeric material (including monomeric or macromeric materials), as used herein, refers to the number-average molecular weight unless otherwise specifically noted or unless testing conditions indicate otherwise.

"Polymerization", as used herein, refers to both crosslinking and conventional polymerization processes (e.g., free radical polymerization). Polymerization includes all polymerization and/or cr~sslil ,king processes regardless of the means by which the polymerization is initiated or terminated.

A. r~ e M~h,rials It has been surprisingly found that the product from copolymerization of a siloxane- and/or fluorine-containing acrylate macromer with one or more acrylamide or pyrrolidonemonomers can be dramatically changed by the presence of oxygen. While the rate of polymerization of a wide variety of monomeric materials is known to be affected by the presence of oxygen, the present polymerization of the macromeric and monomeric materials in the substantial absence of oxygen yields a material with a remarkably high ion permeability. It has further been found that the measurement of ion permeability through a contact lens correlates well with good movement of the lens on the surface of the eye.
Thus, the removal of oxygen from the process of copolymerizing a siloxane- and/or fluorine--CA 022386~0 1998-05-26 W O 97n2019 PCT~B96/01368 _ g _ containing acrylate macromer with one or more acrylarnide or pyrrolidone monomers results in a contact lens having the extraordinary balance of characteristics necessary for a true extended wear lens, nameiy high oxygen transmissibility and good on-eye movement.

The siloxane- and/or fluorine-containing acrylate macromers include a wide range of materials which may be polymerized to form a polymer displaying a relatively high oxygen diffusion rate therethrough. In addition, these materials must be relatively ophthalmically compatible after polymerization. Macromers having dialkyl siloxane groups, especially dimethyl siloxanes, are particularly preferred. These macromers are broadly referred to as poly~dimethyl siloxanes) (also, PDMS). Examples of suitable siloxane-containing macromers include, without limitation thereto, the Materials A, B, and C as described hereinafter.

The oxygen transmissibility (Dk/t) of the lens is preferably at least 70 barrers/mm, more preferably at least 75 barrers/mm, and most preferably at least 87 barrers/mm. The lens center thickness is typically more than about 30 microns, preferably about 30 to about 200 microns, more preferably about 40 to about 150 microns, even more preferably about 50 to about 120 microns, and most preferably about 60 to about 100 ~ uns.

The oxygen translllissibilily of the extended-wear lens from the outer surface to the inner surface must be sufficient to prevent any substantial corneal swelling during the period of extended wear. It is known that the cornea swells approximately 3% to 4% during overnight periods of sleep when the eyelids are closed, as a result of oxygen deprivation. It is also known that wearing a typical contact lens, such as ACUVUE (Johnson & Johnson), for a period of about 8 hours (overnight wear) causes corneal swelling of about 11%. However, a preferred extended-wear contact lens will produce, after wear of about 24 hours, including normal sleep periods, corneal swelling of less than about 8%, more preferably less than about 6%, and most preferably less than about 4%. A preferred extended-wear contact lens will produce, after wear of about 7 days, including normal sleep periods, corneal swelling of less than about 10%, more preferably less than about 7%, and most preferably less than about 5%. Thus, the extended-wear lens must have oxyperm polymer in anamount sufficient to produce oxygen diffusion pathways from the outer surface to the inner surface of the lens which are sufficient to yield the above properties relating to corneal swelling. Preferably, the extended-wear lens has a continuous phase of oxyperm polymer extending from the outer surface to the inner surface of the lens.

CA 022386~0 1998-0~-26 The acrylamides and pyrrolidones include a wide range of materials which may be copolymerized with the siloxane- and/or fluorine-containing acrylate macromer to form a polymer displaying a relatively high ion diffusion rate therethrough. In addition, these materials must be relatively ophthalmically compatible after polymerization. These materials include, without limitation thereto, acrylamide, methacrylamide, and dimethylacrylamide; N-vinyl pyrrolidones such as N-vinyl-2-pyrrolidone; and the like and mixtures thereof. Other acrylamides and pyrrolidones are disclosed in the specific embodiments of Materials A-C, described below.
B. Weislht F2atiosof PGIV..~ le r~ ~ idls The ratios of siloxane- and/or fluorine-containing acrylate macromers to acrylamide or pyrrolidone monomers may vary substantially, depending on the selected balance of oxygen permeability and ion permeability for the chosen end-use of the molded polymeric article. Preferably, the volumetric ratio of siloxane- and/or fluorine-containing acrylate -macromers to acrylamide or pyrrolidone monomers (including water) in the fully hydrated lens is about 40 to about 60 to about 60 to about 40. However, weight percentages, based on the total weight of the lens, will be defined because weight percentages are more conveniently utilized in lens fabrication. If the extended-wear contact lenses have only siloxane- and/or fluorine-co, llai, l;. I9 acrylate macromers and one or more acrylamide or pyrrolidone monomers, the ratio of macromer to monomer will be about 60 to about 85 weight percent siloxane- and/or fluorine-conl~i,l"lg acrylate macromers and about 15 to about 40 weight percent acrylamide or py, ,ulidone monomers in the prepolymerization mixture, based on total polymerizable material weight. More preferably, the prepolymerization mixture will contain about 70 to about 82 weight percent siloxane- and/or fluorine-conlai. ,i"g acrylate macromers and about 18 to about 30 weight percent acrylamide or pyrrolidone monomers, based on total polymerizable material weight.

A wide variety of additional polymerizable materials may be included in the mixture prior to polymerization. Cross-linking agents, such as ethylene glycol dimethacrylate (EGDMA), may be added to irnprove structural integrity and mechanical strength. Aoli~l.icrobial polymerizable materials such as poly(quaternary ammonium) salts may be added to inhibit microbial growth on the lens material. Also, additional ionoperm monomers or macromers and oxyperm polymerizable materials may be added to adjust the oxygen permeability and ion permeability of the final molded article. An especially advantageous polymerizable CA 022386~0 1998-0~-26 material is TRIS, which may act both to increase oxygen permeability and to improve the modulus of elasticity.
An advantageous polymerizable material comprises:
(i) a siloxane- and/or fluorine-containing acrylate macromer;
(ii) a monomer selected from the group of acrylamides and methacrylamides, preferably dimethylacrylamide; and (iii) a siloxane-conldil lil Ig monomer having a carbon chain length of less than 20 carbon atoms, preferably TRIS.

A preferred polymerizable material comprises:
(i) about 30 to 60 weight percent siloxane- and/or fluorine-containing acrylate macromer;
(ii) about 20 to 40 weight percent monomer selected from the group of acrylamides and methacrylamides, preferably dimethylacrylamide; and (iii~ about 1 to 35 weight percent siloxane-containing monomer having a carbon chain length of less than 20 carbon atoms, preferably TRIS.

A further preferred prepolymerization mixture will include (a) about 30 to 60 weight percent siloxane- and/or fluorine-containing acrylate macromers, (b) about 20 to 40 weight percent acrylamide or py"olidone monomers, and (c) about 1 to 35 weight percent TRIS, based on the total lens weight. More preferably, the amount of TRIS is about 10 to 33 weight percent, based on the total prepolymerization mixture weight.

In a preferred embodiment, the prepolymerization mixture includes less than about 5 weight percent cross-linking agent, based on the total prepolymerization mixture weight. More pr~rdbly, the prepolymerization mixture includes less than about 2 weight percent cross-linking agent, based on the total prepolymerization mixture weight. Even more preferably, the prepolymerization mixture includes substantially no cross-linking agent. In a particularly preferred embodiment, the prepolymt li~alion mixture includes no added cross-linking ~ agent.

~ The previously described ranges for polymerizable materials are offered to enable the reader to better comprehend the invention. However, it should be noted that the specific weight or volume percentages of siloxane~ and/or fluorine-containing acrylate macromers to acrylamide or pyrrolidone monomers are not the most critical factors to consider in CA 022386~0 l998-0~-26 WO 97/2Z019 PCTlIB96/01368 preparing a good extended-wear ophthalmic lens. More importantly, the lens must have sufficient ion permeability for good on-eye movement and sufficient oxygen permeability for good corneal health during the extended wear period.

C. MGr"l-ol~

One requirement olF the lens material is that the lens allow a high visible light transmission from the outer to inner surface of the lens. A lens morphology which includes large phase separated regions will reduce visible light transmission and cause sul~ llial undesirable image distortion, thereby destroying the value of the lens as a vision correction device.
Thus, the lens must have a morphology which allows at least about 80%, more preferably about 90%, visible light transmission and does not produce any significant undesirable image distortion.

In one preferred embodiment, the lens material has at least two phases: the phases including at least one oxyperm phase (i.e. a phase having a high oxygen transl"issil,ilil~) and at least one ionoperm phase (i.e. a phase having a high ion permeability). While there may be two distinct phases, it is believed that there may be a transition phase, or interphase, in which the material composition and the material properties are a blend of those of the oxyperm and ionoperm materials. Thus, there may exist a distinct oxyperm phase or plurality of distinct oxyperm phases, a distinct ionoperm phase or a plurality of distinct ionoperm phases, and an amphipathic phase mixture or blend of oxyperm and ionoperm phases. In one preferred embodiment, the glass transition temperature (Tg) of the oxyperm phase is less than about -115~ Celsius.

The existence of separate oxyperm and ionoperm phases, rather than a complete blend of oxyperm and ionoperm phases, is believed to be advantageous in promoting the diffusion of oxygen and ions. Oxygen will diffuse predominantly through the oxyperm polymer, while the ionoperm polymer provides a higher barrier to oxygen diffusion. Similarly, ions will diffuse well through the ionoperm polymer, but the oxyperrn polymer provides a higher resistance to ion diffusion. Thus, one homogeneous oxyperm/ionoperm phase will provide undesirable resi;jl~nce to both oxygen and ion diffusion, while two separate oxyperm and ionoperm phases will provide low resistance pathways for transmission of both oxygen and ions or water. Thus, the ideal extended-wear lens has a pathway or series of pathways from the outer surface to the inner surface for lldnsmission of oxygen thel~lhluugh, and an analogous continuous pathway or series of pathways for transmission of water or ions CA 022386~0 1998-0~-26 therethrough. In a particularly preferred embodiment, the lens has two co-continuous phases, one an oxyperm phase and the other an ionoperm phase, allowing for permeation of water or ions and oxygen between the front and base curves of the lens.

D. Bulk Water Content The measurement of water content is difficult because the removal of adhered surface droplets, without affecting the bulk lens water content, is difficult. In addition, water may evaporate from the lens surface quickly, thereby lowering the water content from the equilibrium level. Accordingly, a discussion of the bulk water content of a lens warrants a r~icC~ISsjon of the measurement technique used to determine the water content.

The preferred bulk water content of the hydrated lens will be a function of the lens material properties. The material properties are dependent on the prepolymerization macromers and monomers and polymerization conditions. Accordingly, while general ranges for bulk water content are offered for a better understanding of the invention, the invention is not generally limited to specific bulk water cooL~r~

One method of measuring the water content of a lens formed in accordance with the present invention, referred to herein as the " Bulk Technique", is as follows. First the lens is thoroughly hydrated in a physiological saline solution, such that the water in the lens is in equilibrium with the surrounding water. Next the lens is gently blotted between two lint-free blotting cloths to remove surface moisture. The lens is quickly placed on an aluminum weighing pan and the first wet weight, W1, is measured. Next, the aluminum pan with lens is placed in a oven at 36~C for a period of at least 24 hours. After heat treating, the pan with lens is removed, placed in a c!csiGc~tor, and allowed to cool to room temperature (about 22~C). The pan with lens is weighed again to determine the dry weight, Wd. The lens is re-equilibrated in physiological saline solution and a second wet weight W2 is deler, I ~i~ ,ed thereon. The wet weights (W1 and W2) are averaged to yield an average wet weight, Ww~ The bulk water content is determined by the following equation:
~ Percent water content = (Ww - Wd) / Ww X 100 A pr~rer,ed lens bulk water content, determined by the " ~ulk Technique", is less than about 32 weight percent. More preferably, the lens has a water content of about 10 to 30 weight percent, based on the total lens weight. A particularly preferred lens water content is about 15 to about 25 weight percent.

CA 022386~0 l998-0~-26 E~ lon and Water Pe~ ...eaLJilitY

Unexpectediy, it has been determined that the ion permeability through the lens correlates well with on-eye movement, and furthermore, that the presence of oxygen in polymerization of certain material reduces ion permeability. As ~iscussed earlier, it is known that on-eye movement of the lens is required to ensure good tear exchange, and ultimately, to ensure good corneal health. While the invention is not bound by theory presented herein, it may be useful to discuss some theory for a better understanding of ways to practice the invention.

It is theorized that water permeability is an exceptionally important feature for an extended-wear lens which includes oxyperm polymers such as those disclosed herein. Siloxane-containing oxyperm materials tend to adhere strongly to the eye, thereby stopping on-eye movement. The ability to pass water through the lens is believed to allow a siloxane-containing polymeric lens to move on the eye, where the movement occurs via forces exerted by water being squeezed out of the lens. The water permeability of the lens is also believed important in replenishing lens water content once pressure is removed. Further, the permeability of ions is believed to be directly proportional to the permeability of water.
Thus, ion permeability is a predictor of on-eye movement.

However, regardless of whether the water permeability theory is a correct understanding of the actual on-eye movement phenomenon, it has been unexpectedly found that above a certain threshhold of ion permeability through a lens, from the inner surface of the lens to the outer, or vice versa, the lens will move on the eye, and below the threshhold the lens will adhere to the eye. Thus, the present innovative extended-wear contact lenses provide a balance between the relatively high oxygen permeability (and ~-ssoci~ted high binding capacity) of oxyperm materials with the low binding capacity (high on-eye movement) of ionoperm materials. It is believed that this is accomplished by providing a plurality of continuous ion transl,.i;ision pathways for ion and water movement through the lens.

It should be noted that ions may move through the lens via these ion pathways by a number of means. For example, ions may diffuse through the lens because of concentration differences from one surface to another. Ions may also be forced through the ion pathways by the mechanical action of blinking, with the concomittent compression forces on the lens essentially squeezing water out of the lens. In addition, the charge nature of the surfaces may provide an electromotive force which drives ion permeation through the lens. At times, CA 022386~0 1998-0~-26 WO 97/22019 PCTlIB96/01368 one of these driving forces may be larger than the others, while at other times the relative magnitude may reverse. This discussion is presented to clarify that the invention is not restricted by the method or driving force by which ions move through the lens.

Neither the measurement of water permeability nor ion permeability through an ophthalmic lens is considered a routine matter of testing in the industry. Accordingly, a discussion of the preferred ion or water permeability ranges warrants a discussion of the measurement techniques used to determine the permeability.

The water permeability of a lens may be determined from the rate of water permeation through the lens, from one surface to another surface. The water permeability of a lens may be determined by positioning a lens between two reservoirs holding solutions having known, and different, initial concentrations of radiolabeled water (e.g., tritiated water), and then measuring concentration of radiolabeled water in the "receiving" reservoir (the reservoir towards which the net flow of radiolabeled water is positive) as a function of time.

The relative ion permeability of a lens may be determined from the rate of ion permeation through the lens, from one surface to another surface. The rate of ion permeation may be determined by posiliol,i. ,g a lens between two reservoirs holding solutions having known, and different, initiai ion concentrations, and then measuring conductivity in the "receiving"
reservoir (the reservoir towards which the net flow of ions is positive) as a function of time.
The concentration of ions, such as sodium, can be measured accurately using a pH meter and an ion-selective electrode. Ions are believed to be transmitted through a lens, from inner to outer surfaces and vice versa, primarily by the diffusion of ions through water pathways in the lens. Ion permeability through a lens is believed to be directly proportional to water permeability through a lens.

1. Ionoflux Measurement Technique The following technique, referred to herein as the "lonoflux Technique", is a preferred method for determining the ion permeability of a lens. This technique may be used to - determine the likelihood of adequate on-eye movement.

~ The "lonoflux Technique" involves the use of a conductometer (LF 2000/C, catalog no.
300105, Wissenschaftlich-Technische WerkslaLIen GmbH (WTW), Germany), an electrode equipped with a temperature sensor ~ R 011T, catalog no. 302 520, WTW), a donor CA 022386~0 l998-0~-26 - ~6 -chamber containing a salt solution, a receiving chamber containing about 60 ml of deionized water, a stir bar and a thermostat.

The donor chamber is specially designed for sealing a contact lens thereto, so that the donor solution does not pass around the lens (i.e., ions may only pass through the lens).
The donor chamber is composed of a glass tube which is threaded at the end which is immersed in the receiving solution. The glass tube includes a centrally located hole of about 9 mm in diarneter. A lid, which is threaded to mate with the glass tube, holds a lens-retaining mernber which includes a centrally located hole of about 8 mm in diameter.
The lens-retaining member includes a male portion adapted to mate with and seal the edges of the inner (concave) surface of a lens and a female portion adapted to mate with and seal the edges of ~he outer (convex) surface of a lens.

The lens to be measured is placed in the lens-retaining member, between the male and female portions. The male and female portions include flexible sealing rings which are positioned between the lens and the respective male or female portfon. After positioning the lens in the lens-retaining member, the lens-retaining member is placed in the threaded lid. The lid is screwed onto the glass tube to define the donor chamber. The donor chamber is filled with 16 ml of 0.1 molar NaCI solution. The receiving chamber is filled with 60 ml of deionized water. The leads of the conductivity meter are immersed in the deionized water of the receiving chamber and a stir bar is added to the receiving chamber.
The receiving chamber is placed in a thermostat and the temperature is held at about 35~C.
Finally, the donor chamber is immersed in the receiving chamber.

Measurements of conductivity are taken every 20 minutes for about three hours, starting 10 minutes after immersion of the donor chamber into the receiving chamber. The lonoflux Diffusion Coefficient, D, is determined by applying Fick's law as follows:
D=-n'/(Axdc/dx) where n' = rate of ion transport ~mol/min3 A = area of lens exposed [mm2;
D = lonoflux Diffusion Coefficient[mm2/min3 dc = concentration difference [mol/L]
dx = thickness of lens [mm]

An lonoflux Diffusion Coefficient of greater than about 6.4 x 10~ mm2/min is pre~e" ~d for achieving sufficient on-eye movement. More preferably, the lonoflux Diffusion Coefficient is -CA 022386~0 1998-0~-26 greater than about 2.6 x 10 ~ mm2/min, while most preferably, the lonoflux Diffusion Coefficient is greater than about 1.5 x 10 ~ mm2/min. It must be emphasized that the lonoflux Diffusion Coefficient correlates with ion permeability through the lens, and thereby is a predictor of on-eye movement.

2. Ionoton Measurement Technique The following technique, referred to herein as the "lonoton Technique", is another preferred method for determining the relative ion permeability of a lens. The technique is based on measurement of the diffusion of sodium chloride through a lens.

The "lonoton Technique" involves the use of a pH meter (Beckman, VWR catalog no.BK123142), a VSC-1 Diffusion Celt Drive Console (Crown-Bio, Somerville, NJ), a DCB-100B Diffusion Cell (Crown-Bio), and a 6 cm sodium ion-specific electrode (Microelectronics, Londonderry, NH, catalog no. Ml-414P). The technique is not limited to the aforementioned instruments or materials; equivalent instruments or materials may be used.

First, a contact lens is mounted onto an orifice of the DCB-1 OOB cell chamber, the donor chamber. Next, the connecting cell chamber (receptor chamber) is placed against the cell chamber containing the contact lens and tightly clamped on the clamp holder supplied with the VSC-1 Drive Console. Then, a phosphate-buffered saline (PBS, Mediatech catalog no.
21-031-LV) is placed into the receptor side of the cell chamber. Stir bars are added to each cell chamber. The 6 cm electrode is placed into the PBS saline receptor side. After the electrode has equilibrated in the PBS saline, the pH meter is placed in the mV function to es~tl-:', the 0 mV point. PBS which has been saturated with sodium chloride is added to the donor chamber.

The millivolt signal is recorded at 5, 10, 15, 30, 60, 120, and 180 minute intervals. The millivolt signal is converted to a sodium ion concentration by a standard curve of sodium ion concentration vs. millivolt signal. The lonoton lon Permeability Coefficient, P, is then determined in accordance with the following equation:

In( 1 - 2C(t)/C(0) ) = -2APt / Vd where: C(t) = concentration of sodium ions at time t in the receiving cell C(0) = initial concentration of sodium ions in donor cell A = membrane area, i.e., lens area exposed to cells CA 022386~0 1998-0~-26 V = volume of cell compartment (3.0 ml) d = average lens thickness in the area exposed P = permeability coefficient The average thickness of the lens in the exposed test area may be determined by averaging a number of readings, e.g., 10 readings, with a low-pressure thickness-measuring instrument, such as a Mitotoya micrometer VL-50, or equivalents thereof. The lonoton lon Permeability Coefficient, P, having units of cm2/second, may be determined from the slope of a plot of time (t) v. In( 1 - 2C(t)/C(0) ) x (-2At / Vd~.

An lonoton lon Permeability Coefficient, P, of greater than about 0.2 x 10~ cm2/sec is preferred, while greater than about 0.3 x 10~ cm2/sec is more preferred and greater than about 0.4 x 1 o-6 cm2/sec is most preferred. It must be emphasized that the lonoton lon Permeability Coefficient correlates with ion permeability through the lens, and thereby is a predictor of on-eye movement.

3. Hydrodell Water Permeability Technique The following technique, referred to herein as the "Hydrodell Technique", is a preferred method for determining the water permeability of a lens. This technique may be used to determine the likelihood of adequate on-eye movement.

The Hydrodell Technique involves the measurement of the rate of transfer of the radiolabeled solutes THO (3H-Ho or tritiated water) and l4C-glucose across the contact lens using a two-chamber apparatus. '4C-glucose is used in this measurement technique to reveal any leak in the system during testing. The lens is mounted between chambers, which are stirred at a controllable rate. Chamber I contains a solution with a high concentration of labeled solute. Chamber ll, the "receiving chambeP, contains an identical solution but without the labeled solute. Samples of the solution in chambers I and ll are taken at intervals over the test period. The radioactivity in the samples is measured. The permeability of the lens is calculated from the measured radioactivity, the sample times, the chamber volumes and the lens area exposed to the solutions. A more detailed description of the Hydrodell Technique follows.

a. Solution Preparation Dulbecco's phosplnate buffered saline (DPBS) is prepared by first dissolving, sequentially, about 160 g sodium chloride (NaCI), about 4 grams potassium chloride (KCI), about 23 CA 022386~0 1998-0~-26 grams disodium hydrogen orthophosphate (Na 2HPO4). about 4 grams potassium dihydrogen orthophosphate (KH 2PO4). and about 10 grams sodium azide in a liter of reverse-osmosis (MilliQ) water. Then, the pH is adjusted to about 7.3 by adding appropriate amounts of HCI. Finally, the buffer solution is diluted to 1:20 (50 ml buffer solution with 950 ml reverse-osmosis water). and allowed to degas either in a screw-capped container overnight or under vacuum.

A Cold Glucose buffer solution is prepared by adding about 0.1 grams D-glucose to one liter of DPBS, foliowed by sterilization via filtration through a 0.2 ,ul millipore filter and storage at 4~C until use.

The Chamber I solution is prepared by adding about 6 ,ul THO (TR53, 1.0 mCi/ml activity, available from Amersham Australia, located in North Ryde NSW Australia) and about 16 ~l '4C-glucose (in ethanol, available from Amersham Australia) to about 12 ml of the Cold Glucose buffer solution. Preferably, this solution is used within about 24 hours of preparation. The Chamber ll solution is DPBS.

b. Apparatus Preparation The chambers have a volume sufficient to hold about 12 ml of solution during testing.
While the exact shape of the chambers is not critical, both chambers have rectangular cross-sections for ease of construction. The chambers may be made from a variety of water-proof rigid materials, preferably clear (e.g., acrylic plates, FX Plastics, Marrickville NSW Australia) so that samples may be observed during testing. Each chamber has a circular aperture of about 7 mm diameter appropriate for mounting a lens between the chambers for contact with solutions held within the chambers. Some affixing means, such as a set of mounting bolts, are necessary to securely affix one chamber to the other with the lens mounted in between.

A test contact lens is mounted symmetrically over the aperture of Chamber ll. Folds and wrinkles are manually removed from the lens. Chamber I is positioned adjacent the aperture and mounted lens of Chamber ll, and the chambers are secured to one another using mounting bolts.

About 12 ml (V2) of DPBS is placed in Chamber ll; About 12 ml of the Chamber I labeled solution is placed in Chamber 1, at which point time t=0 is established. Stirrers are added to both chambers and the stirrer speed is set at about 1200 rpm.

CA 022386~0 1998-0~-26 c. Sampling Sampling generally starts at time to = 5 minutes. The final sample time, t" is usualiy at about 50 minutes for high water content lenses and about 120 minutes for low water content lenses, although these times are not critical.

At time to = 5 minutes, two samples of about 0.2 ml volume are pipetted from Chamber 1, and two 0.2 ml aliquots of DPBS are added to Chamber I to restore the volume. These samples are placed into plastic counting tubes with about 4 ml Ultima GoldTM cocktail (available from Packard Instrument Co., Meriden, Connecticut) and about 0.9 ml DPBS.

Also at time to~ one sample of about 1.0 ml volume is pipetted from Chamber ll and one 1.0 ml aliquot of DPBSis added to Chamber ll to restore the volume. The sample is placed into a plastic counting tube with about 4 ml Ultima GoldTM cocktail.

At intermediate times between to and tf (e.g., every 10 minutes), one sample of about 1.0 ml volume is pipetted from Chamber ll and one 1.0 ml aliquot of DPBSis added to Chamber ll to restore the volume. Each sample is placed into a plastic counting tube with about 4 ml Ultima GoldTM cocktail.

At time tf, two samples of about 0.2 ml volume are pipetted from Chamber 1. These samples are placed into plastic counting tubes with about 4 ml Ultima GoldTM cocktail and about 0.9 ml DPBS.

Also at time t~, two samples of about 1.0 ml volume are pipetted from Chamber ll. These samples are placed into plastic counting tubes with about 4 ml Ultima GoldTM cocktail.

d. i\Jleasurements The activity of the samples are measured by liquid scintillation counting, or other appropriate technique. Liquid sc;,llillalion counting may be advantageously accomplished by using protocol number 6 for 3H/14C on a Tri-Carb Liquid Scintillation Analyzer (1 900TR, available from Packard Instrument Co.).

Three standards conlain.ng about 104 to 105 cpm TH0 in reversed-osmosis (MilliQ) water are prepared. Three standards containing about 1 O4 to 1 O5 cpm 14C glucose in reversed-osmosis (MilliQ) water are also prepared. A blank containing MilliQ water is prepared.

CA 022386~0 l998-0~-26 The scintillation analyzer settings are LLA = O KeV and ULA = 12 KeV for 3H ("1") in channel 1 and LLB = 12 KeV and ULB = 156 KeV for 14C ("2") in channel 2. The standards and blank are counted three times during each counting of samples, and the counts are - averaged. The following denote the relevant measured sample activities:
b1 = measured activity of blank sample in channel 1 b2 = measured activity of blank sample in channel 2 S'" = measured activity of standard 3H sample in channet 1 S'~2= measured activity of standard 14C sample in channel 2 S'2t = measured activity of standard 3H sample in channel 1 S'z = measured activity of standard 14C sample in channel 2 y~ = measured activity of test sample (both 3H and 14C) in channel 1 Y2 = measured activity of test sample (both 3H and 14C) in channel 2 e. Water Permeability Calculation In order to calculate the actual activity of a sample, the measured activities of the isotopes, 3H and 14C, must first be corrected to remove the cross-contamination error due to the presence of both isotopes in one sample. Without explaining the mathematical derivations, the following stepwise procedure is offered as an example of one method of determining water permeability from the above measurements:

(1) Calculate S,t, S,2, S21, and S22, from the following equations:
S" = S'" - b1 S,2 = S',2 - b, S2, = S'2, - b2 S22=S'22-b2 (2) Calculate a,2 and a2, from the following equations:
a,2 = S12 / S22 a2, = S2, / S.t (3) C.qlc~ te corrected concentrations of 3H ("1") and 14C ("2") from the following equations:
c, = [(yl- b1) - al2 (Y2- b2)~ / (1- a,2 az1)V
C2 = [(y2- b2) - a21 (y1- b1)] / (1- a,2 a2~)V

CA 022386~0 1998-0~-26 WO 97/22019 PCT/IB96/0~368 where V is the voiume of the test sample.

(4) Calculate water permeability for an interval from t1 to t2 as follows:

P = V~l [c~,(t2)-c~(t1)] / A(cl-cll)(tl-t2) where V~, is the volume of Chamber ll, c"(t2) is the concentration of 3H in Chamber ll at time t2, c~(t~) is the concentration of 3H in Chamber ll at time t1, A is the area of lens exposure, c~ is the average concentration of 3H in Chamber I over the time period t1 to t2 and c~ is the average concentration of 3H in Chamber ll over the time period t1 to t2.

The ophthalmic lenses of one embodiment of the present invention have a Hydrodell Water Permeability Coefficient of greater than about 0.2 x 10~ cm2/sec. The ophthalmic lenses in a preferred embodiment of the invention have Hydrodell Water Permeability Coeflicient of greater than about 0.3 x 10~ cm2/sec. The ophthalmic lenses in a preferred embodiment of the invention have Hydrodell Water Permeability Coefficient of greater than about 0.4 x 10 cm2/sec.

F. Oxvqen Tr~l~sl.,issil~ ilitv and r~r.,-e~Lil:t~

As mentioned earlier, the cornea receives oxygen primarily from the corneal surFace which is exposed to the environment, in cor,lra:jl to other tissues which receives oxygen from blood flow. Thus, an ophthalmic lens which may be worn on the eye for extended periods of time must allow sufficient oxygen to permeate through the lens to the cornea to sustain corneal health. One result of the cornea receiving an inadequate amou~lt of oxygen is that the cornea will swell. In a preferred embodiment, the oxygen l.~nsmissi~,ility of the present ophthalmic lenses is sufficient to prevent any clinically significant amount of corneal swelling from occurring.

A preferred ophthalmic lens material will have an oxygen transmissibility, Dk/t, of at least 70 (cm3 oxygen)(mm)/mm-cm2 x (sec/mm Hg) x 10~~ or [barrers/mml, more preferably at least 75 barrers/mm, and most preferably at least 87 barrers/mm.

The oxygen permeability of a lens and oxygen transmissibility of a lens material may b determined by the following technique. Oxygen fluxes (J) are measured at 34 C in a wet cell (i.e., gas streams are maintained at about 100% relative humidity) using a Dk1000 CA 022386~0 1998-0~-26 instrument (available from Applied Design and Development Co., Norcross, Georgia), or similar analytical instrument. An air stream, having a known percentage of oxygen ~e.g., 21%), is passed across one side of the lens at a rate of about t 0 to 2Q cm3/min., while a nitrogen stream is passed on the opposite side of the lens at a rate of about 10 to 20 cm3/min. The barometric pressure surrounding the system, PmeaSured~ is measured. The thickness (t) of the lens in the area being exposed for testing is determined by measuring about 10 locations with a Mitotoya micrometer VL-50, or similar instrument, and averaging the measurements. The oxygen concentration in the nitrogen stream (i.e., oxygen which diffuses through the lens) is measured using the DK1000 instrument. The oxygen permeability of the lens material, Dk, is determined from the following formula:
Dk = JV(Poxygen) where J = oxygen flux ~microliters 02/cm2-minute]
Poxygen = (Pmeasured - Pwater vapor) x (%~2 in air stream) [mm Hg]
= partial pressure of oxygen in the air stream Pmeasured = barometric pressure ~mm Hg]
Pwater vapor = ~ mm Hg at 34 C (in a dry cell) Imm Hg]
Pwater vapor = 40 mm Hg at 34 C (in a wet cell) [mm Hg]
t = average thickness of the lens over the exposed test area [mm]
where Dk is expressed in units of barrers, i.e., [(cc oxygen)(mm)/cm2] x [sec/mm Hg] x 10 1~.

The oxygen transmissibility (Dk/t) of the material may be calculated by dividing the oxygen permeability ~Dk) by the average thickness (t) of the lens.

G. Ex&l. ' e s o~ Suitable ~' - ials 1. Material "A"
Polysiloxane-comprising perfluoroalkyl etl~ers The Material "A" macromer is defined by formula (I):
P1~(Y)m~(L~X1)p~Q~(X1~L)p~(Y)m~P1 (l) where each P1, independently of the others, is a free-radical-polymerizable group;
each Y, independently of the others, is -CONHCOO-, -CONHCONH-, -OCONHCO-, -NHCONHCO-, -NHCO-, -CONH-, -NHCONH-, -COO-, -OCO-, -NHCOO- or -OCONH-;

CA 022386~0 1998-0~-26 m and p, independently of one another, are 0 or 1;
each 1, independently of the others, is a divalent radical of an organic compound having up to 20 carbon atoms;
each X1, independently of the others, is -NHCO-, -CONH-, -NHCONH-, -COO-, -OCO-,-NHCOO- or -OCONH-; and Q is a bivalent polymer fragment consisting of the segments:

(a) -(E)k-Z-CF2-(OCF2)~f(0CF2CF2)y~0CF2~Z~(E)k~~
where x+y is a number in the range of 10 to 30;
each Z, independently of the others, is a divalent radical having up to 12 carbon atoms or Z
is a bond;
each E, independently of the others, is -(OCH 2CH2)q-, where q has a value of from 0 to 2, and where the link -Z-E- represents the sequence -Z-(OCH 2CH2)q-; and k is 0 or 1 ;

--Alk--Si--O - Si--Alk--b) l I

-- --n where n is an integer from 5 to 100;
Alk is alkylene having up to 20 carbon atoms;
80-100% of the radicals R 1. R2, R3 and R4, independently of one another, are alkyl and 0-20% of the radicals R1, R2, R3 and R4, independently of one another, are alkenyl, aryl or cyanoalkyl; and (c) X2-R-X2, where R is a divalent organic radical having up to 20 carbon atoms, and each X2, independently of the others, is -NHCO-, -CONH-, -NHCONH-, -COO-, -OCO-,-NHCOO- or -OCONH-;
with the provisos that there rr~ust be at least one of each segment (a), (b), and (c) in Q, that each segment (a) or (b) has a segment (c) attached to it, and that each segment (c) has a segment (a) or (b) attached to it.

CA 022386~0 l998-0~-26 The number of segments (b) in the polymer fragment Q is preferably greater than or equal to the number of segments (a). The ratio between the number of segments (a) and (b) in the polymer fragment Q is preferably 3:4, 2:3, 1:2 or 1:1. The molar ratio between the number of segments (a) and (b) in the polymer fragment Q is more preferably 2:3, 1:2 or 1:1.

The mean molecular weight of the polymer fragment Q is in the range of about 10~)0 to about 20000, preferably in the range of about 3000 to about 15000, particularly preferably in the range of about 5000 to about 12000.

The total number of segments (a) and (b) in the polymer fragment Q is preferably in the range of 2 to about 11, particularly preferably in the range of 2 to about 9, and in particular in the range of 2 to about 7. The smallest polymer unit Q is preferably composed of one perfluoro segment (a), one siloxane segment (b) and one segment (c).

In a preferred embodiment of the polymer fragment Q, which preferably has a composition in the abovementioned ratios, the polymer fragment Q is terminated at each end by a siloxane segment (b).

The compositions in a bivalent polymer fragment Q always correspond above and below to a mean statistical composition. This means that, for example, even individual block copolymer radicals containing identical recurring units are included, so long as the final mean statistical composition is as specified.

Xl is preferably -NHCONH-,-NHCOO- or -OCONH-, particularly preferably -NHCOO- or-OCONH-.

The X2-R-X2 segment is preferably a radical derived from a diisocyanate, where each X2, independently of the other, is -NHCONH-,-NHCOO- or -OCONH-, in particular -NHCOO- or -OCONH-.

Z is preferably a bond, lower alkylene or -CONH-arylene, in which the -CO- moiety is linked to a CF2 group. Z is particularly preferably lower alkylene, in particular methylene.

CA 022386~0 l998-0~-26 q is preferably 0, 1, 1.5 or 2, particularly preferably 0 or 1.5.

The perfluoroalkoxy units OCFz and OCF2CF2 with the indices x and y in segment (a) can either have a random distribution or be in the form of blocks in a chain. The sum of the indices x+y is preferably a number in the range of 10 to 2~, particularly preferably of 10 to 15. The ratio x:y is preferably in the range of 0.~ to 1.5, in particular in the range of 0.7 to 1 .1 .

A free-radical-polymerizable group P 1 is, for example, alkenyl, alkenylaryl or alkenylarylenealkyl having up to 20 carbon atoms. Examples of alkenyl are vinyl, allyl, 1-propen-2-yl, 1-buten-2-, -3- and -4-yl, 2-buten-3-yl, and the isomers of pentenyl, hexenyl, octenyl, decenyl and undecenyl. Examples of alkenylaryl are vinylphenyl, vinylnaphthyl or allylphenyl. An example of alkenylarylenealkyl is o-, m-, or p-vinylbenzyl.

P1 is preferably alkenyl or alkenylaryl having up to 12 carbon atoms, particularly preferably alkenyl having up to 8 carbon atoms, in particular alkenyl having up to 4 carbon atoms.

Y is preferably -COO-, -OCO-, -NHCONH-, -NHCOO-, -OCONH-, -NHCO- or-CONH-, parti-cularly preferably -COO-, -OCO-, NHCO- or -CONH-, and in particular, -COO- or -OCO-.

In a preferred embodiment, the indices, m and p, are not simultaneously zero. If p is zero, m is preferably 1.

L is preferably alkylene, arylene, a saturated bivalent cycloaliphatic group having 6 to 20 carbon atoms, arylenealkylene, ~Ikylenearylene, alkylenearylenealkylene or arylenealkylenearylene.

Preferably, L is a diivalent radical having up to 12 carbon atorns, particularly preferably a divalent radical having up to 8 carbon atoms. In a preferred embodiment, L is furthermore alkylene or arylene having up to 12 carbon atoms. A particularly preferred embodiment of L
is lower alkylene, in particular lower alkylene having up to 4 carbon atoms.

CA 022386~0 1998-0~-26 The divalent radical R is, for example, alkylene, arylene, alkylenearylene, arylenealkylene or arylenealkylenearylene having up to 20 carbon atoms, a saturated bivalent cycloaliphatic group having 6 to 20 carbon atoms or cycloalkylenealkylenecycloalkylene having 7 to 20 carbon atoms.

In a preferred embodiment, R is alkylene, arylene, alkylenearylene, arylenealkylene or arylenealkylenearylene having up to 14 carbon atoms or a saturated divalent cycloaliphatic group having 6 to 14 carbon atoms. In a particularly preferred embodiment, R is alkylene or arylene having up to 12 carbon atoms or a saturated bivalent cycloaliphatic group having 6 to 14 carbon atoms.

In a preferred embodiment, R is alkylene or arylene having up to 10 carbon atoms or a saturated bivalent cycloaliphatic group having 6 to 10 carbon atoms.

In a preferred meaning, n is an integer from 5 to 70, particularly preferably 10 to 50, in particular 14 to 28.

In a preferred meaning, 80-100%, preferably 85-100%, in particular 90-100%, of the radicals R1, R2, R3 and R4 are, independently of one another, lower alkyl having up to 8 carbon atoms, particularly preferably lower alkyl having up to 4carbon atoms, especially lower alkyl having up to 2 carbon atoms. A further particularly preferred embodiment of R 1, R2, R3 and R4 is methyl.

In a preferred meaning, 0-20%, preferably 0-15%, in particular 0-10%, of the radicals R 1, R2, R3 and R4 are, independently of one another, lower alkenyl, unsl~hstitllted or lower alkyl- or lower alkoxy-substituted phenyl or cyano(lower alkyl).

Arylene is preferably phenylene or naphthylene, which is un~llhstihlted or substituted by lower alkyl or lower alkoxy, in particular 1,3-phenylene, 1,4-phenylene or methyl-1,4-phenylene, 1,5-naphthylene or 1,8-naphthylene.

Aryl is a carbocyclic aromatic radical which is unsubstituted or substituted preferably by lower alkyl or lower alkoxy. Examples are phenyl, tolyl, xylyl, methoxyphenyl, t-butoxyphenyl, naphthyl and phenanthryl.

CA 022386~0 1998-0~-26 A saturated bivalent cycloaliphatic group is preferably cycloalkylene, for example cyclohexylene or cyclohexylene(lower alkylene), for example cyclohexylenemethylene, which is unsubstituted or substituted by one or more lower alkyl groups, for example methyl groups, for example trimethylcyclohexylenemethylene, for example the bivalent isophorone radical.

For the purposes of the present invention, the term "lower" in connection with radicals and compounds, unless defined otherwise, denotes, in particular, radicals or compounds having up to 8 carbon atoms, preferably having up to 4 carbon atoms.

I ower alkyl has, in particular, up to 8 carbon atoms, preferably up to 4 carbon atoms, and is, for example, methyl, ethyl, propyl, butyl, tert-butyl, pentyl, hexyl or isohexyl.

Alkylene has up to 12 carbon atoms and can be straight-chain or branched. Suitable examples are decylene, octylene, hexylene, pentylene, butylene, propylene, ethylene, methylene, 2-propylene, 2-butylene, 3-pentylene, and the like.

Lower alkylene is alkylene having up to 8 carbon atoms, particularly preferably up to 4 carbon atoms. Particularly pref~rl~d meanings of lower alkylene are propylene, ethylene and methylene.

The arylene unit in alkylenearylene or arylenealkylene is preferably phenylene, un~l Ihstitl Ited or substituted by lower alkyl or lower alkoxy, and the alkylene unit therein is preferably lower alkylene, such as methylene or ethylene, in particular methylene. These radicals are therefore preferably phenylenemethylene or methylenephenylene.

Lower alkoxy has, in particular, up to 8 carbon atoms, preferably up to 4 carbon atoms, and is, for example, methoxy, ethoxy, propoxy, butoxy, tert-butoxy or hexyloxy.

Arylenealkylenearylene is preferably phenylene(lower alkylene)phenylene having up to 8, in particular up to 4, carbon atoms in the alkylene unit, for example phenyleneethylenephenylene or phénylenemethylenephenylene.

.

CA 022386~0 1998-0~-26 The macromers of the formula (I) can be prepared by processes known per se, for example as follows:
In a first step, a perfluoropolyalkyl ether derivative of formula (IV):

X3-(E)k-Z-CF2-(OCF2)x-(OCF2CF2)y~0CF2~Z-(E)k~X3 (IV) in which X3 is -OH, -NH2, -COOH, -COCI, -NCO or -COOR5, where -COOR5 is generally an activated ester in which R5 is alkyl or aryl which is unsubstituted or sl Ihstit(lted by halogen or cyano, and the variables Z, E, k, x and y are as defined above, is preferably reacted with two equivalents of a bifunctional radical of formula (V):

X4-R-X4 (V) in which R is as defined above and X 4 is a functional radical which is coreactive with an X 3 and is preferably -OH-, -NH2, COOH, -COCI, -COOR~ or -NCO; in the presence or absence of a suitable catalyst, where the reaction of X 3 with X4 gives a group X2; after which a reactive derivative of formula (Vl):

X4-R-X2-(E)k-Z-CF2-(OCF2)~n(0CF2CF2)y-OCF2-Z-(E)k-X2-R-X4 (Vl) is obtained which is then preferably reacted with two equivalents of an oc,~-substituted siloxane of formula (Vll):

R1 lR3 X3--Alk--Si O-Si--Alk--X3 (Vll) -- --n where the variables R1, R2, R3, R4, n, X3 and Alk are as defined above, in the presence or absence of a suitable catalyst, giving a compound of formula (Vlll):

X3-Sil-X2-R-X2-PFPE-X2-R-X2-Sil-X3 (Vill) CA 022386~0 l998-0~-26 Wo 97/22019 pcTlIs96lol368 in which PFPE is (E)k-z-cF2-(ocF2)x-(ocF2cF2)y-ocF2-z-(E)k~ Sil is the siloxane radical Alk--S~o-Sj--Alk -- --n and the other variables are as defined above; after which the reactive intermediate of the formula (Vlll) is preferably reacted with two equivalents of a compound of the formula (IXa) or (IXb):

P1-(Y)m-L-X4 (IXa) Pl-Y2 (IXb) in the presence or absence of a catalyst, to give the macromer of the formula (I):

P1~(Y)m~(L-X1)p~Q~(X1~L)p~(Y)m~Pl (I) in which Y2 is a functional radical which is coreactive with X3 and is preferably -OH, -NH2, -COOH, -COCI, -COOR5, -CONCO or-NCO, and the variables are as defined above, and in which X1 is formed from the reaction of X3 with X4 and Y is formed from the reaction of Y2 with X3.

The starting materials of formula (IV) for the preparation of the perfluoroalkyl ethers are known and many are commercially available. For example, U.S. Patent No. 3,810,875 and European Patent No. 0211237 (U.S. Patent No. 4,746,575) describe such compounds.Ausimont, Italy, markets perfluoroalkyl ether dimethanols under the name Fomblin, for example Fomblin ZDOL and Fomblin ZDOL-TX. Further Fomblin derivatives of the formula (IV) are commercially available, including, for example, Fomblin ZDISOC, in which the radical -Z-X3 in the formula (IV) is CONH-C6H3(CH3)-NCO; Fomblin ZDEAL, in which the radical Z-X3 in the formula (IV) is -COOR5; and Fomblin ZDIAC, in which the radical -Z-X3 in the formula (IV) is -COOH.

Bifunctional radicals having a substitution pattern as per formula (V) exist in large numbers and are commercially available. Examples include, without limitation thereto: diisocyanates, CA 022386~0 l998-0~-26 Wo 97/22019 pcT/Is96/ol368 such as isophorone diisocyanate and 2,2,4-trimethylhexane 1,6-diisocyanate; diols, such as glycol and cyclohexane-1,2-diol; dicarboxylic acids, such as adipic acid and maieic acid;
~ diamines, such as ethylenediamine and hexamethylenediamine, diesters, such as diethyl phthalate and dibutyl malonate; derivatives containing various functional groups, such as 2-aminoethanol, monomethyl malonate, glycolic acid, salicylic acid, glycine and glycine methyl ester.

Preference is given to bifunctional derivatives of the formula (V) which have different reactivities irrespective of the nature of their functional radicals X4. In the case of identical radicals X4, this is achieved, for example, through different steric requirements in the direct vicinity of a radical X4. Examples thereof are isophorone diisocyanate, 2,2,4-trimethylhexane 1,6-diisocyanate and toluene 2,4-diisocyanate. The advantage of using bifunctional derivatives of formula (V) of different reactivity is that the chain length of polymer Q (number of segments (a), (b) and (c)) is easily adjustable and controllable.

a,~-substituted siloxanes of formula (Vll) are likewise commercially available, for example a,c3-hydroxypropyl-terminated polydimethylsiloxane KF6001 from Shin-Etsu.

The novel compounds can be prepared in the presence or absence of a solvent. It is advantageous to use a substantially inert solvent, i.e., one which does not participate in the reaction. Suitable examples thereof are ethers, such as tetrahydrofuran (THF), diethyl ether, diethylene glycol dimethyl ether or dioxane, halogenated hydrocarbons, such as chloroform or methylene chloride, bipolar aprotic solvents, such as acetonitrile, acetone, dimethylformamide (DMF) or dimethyl sulfoxide (DMSO), hydrocarbons, such as hexane, petroleum ether, toluene or xylene, and furthermore pyridine or N-methylmorpholine.

In the preparation of novel compounds, the reactants are advantageously employed in stoichiometric amounts. The reaction temperature can be, for example, from -30~C to ~ 1 50~C, preferably from O~ to room temperature. The reaction times are in the range of about 15 minutes to 7 days, preferably about 12 hours. If necessary, the reaction is carried out - under argon or nitrogen as protective gas. In urethane-forming reactions, a suitable catalyst, for example, dibutyltin dilaurate (DBTDL), is advantageously added.

CA 022386~0 1998-0~-26 ~ 32 -The present Material "A" furthermore relates to a polymer comprising a product of the polymerization of at least one compound of formula (I) as defined above and, if desired, at least one vinylic comonomer (a). In a preferred composition of a novel copolymer, the proportion by weight of a compound of forrnula ~I) is in the range of 100 to 0.5%, in particular in the range of 80 to 10%, preferably in the range of 70 to 30%, based on the total polymer.

In a preferred polymer comprising a product of the polymerization of at least one compound of the formula (I), comonomer (a~ is absent and the polymer is a homopolymer.

A comonomer (a) present in the novel polymer can be hydrophilic or hydrophobic or a mixture thereof. ~C l lit~ . comonomers are, in particular, those which are usually used in the production of contact lenses and biomedical materials. A hydrophobic comonomer (a) is taken to mean a monomer which typically gives a homopolymer which is insoluble in water and can absorb less than 10% by weight of water. Analogously, a hyd,o~hilic comonomer (a) is taken to mean a monomer which typically gives a homopolymer which is soluble in water or can absorb at least 10% by weight of water. Suitable hydrophobic comonomers (a) are, without limitation thereto, C 1-Ct8alkyl and C3-C,8cycloalkyl acrylates and methacrylates, C3-Cl8alkylacrylamides and -methacrylamides, acrylonitrile, methacrylonitrile, vinyl Cl-C18alkanoates, C2-C18alkenes, C2-C18haloalkenes, styrene, (lower alkyl)styrene, lower alkyl vinyl ethers, C2-C10perfluoroalkyl acrylates and methacrylates and correspondingly partially fluorinated acrylates and methacrylates, C 3-C12perfluoroalkylethyl-thiocarbonylaminoethyl acrylates and methacrylates, acryloxy- and methacryloxyalkyl-siloxanes, N-vinylcarbazole, C,-C,2alkyl esters of maleic acid, fumaric acid, itaconic acid, mesaconic acid and the like.

Preference is given, for example, to acrylonitrile, C 1-C4alkyl esters of vinylically unsaturated carboxylic acids having 3 to 5 carbon atoms or vinyl esters of carboxylic acids having up to 5 carbon atoms.

Examples of suitable hydrophobic comonomers (a) are methyl acrylate, ethyl acrylate, -propyl acrylate, isopropyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl acrylate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, styrene, chloroprene, vinyl chloride, vinylidene CA 022386~0 l998-0~-26 Wo 97/22019 PCT/IB96/01368 chloride, acrylonitrile, 1-butene, butadiene, methacrylonitrile, vinyltoluene, vinyl ethyl ether, perfluorohexylethylthiocarbonylaminoethyi methacrylate, isobornyl methacrylate, trifluoroethyl methacrylate, hexafluoroisopropyl methacrylate, hexafluorobutyl methacrylate, tristrimethylsilyloxysilylpropyl methacrylate (TRIS), 3-methacryloxy propylpentamethyl-disiloxane and bis(methacryloxypropyl)tetramethyldisiloxane.

Preferred examples of hydrophobic comonomers (a) are methyl methacrylate, TRIS and acrylonitrile.

Suitable hyd, uphilic comonomers (a) are, without this being an exhaustive list, hydroxyl-s~lhstitllted lower alkyl E~crylates and methacrylates, acrylamide, methacrylamide, (lower alkyl)acrylamides and -methacrylamides, ethoxylated acrylates and methacrylates, hydroxyl-substituted (lower alkyl)acrylamides and -methacrylamides, hydroxyl-substituted lower alkyl vinyl ethers, sodium vinylsulfonate, sodium styrenesulfonate, 2-acrylamido-2-methylpropanesulfonic acid, N-vinylpyrrole, N-vinyl-2-pyrrolidone, 2-vinyloxazoline, 2-vinyl-4,4'-dialkyloxazolin-5-one, 2- and 4-vinylpyridine, vinylically unsaturated carboxylic acids having a total of 3 to 5 carbon atoms, amino(lower alkyl)- (where the term "amino" also includes quaternary ammonium), mono(lower alkylamino)(lower alkyl) and di(lower alkylamino)(lower alkyl) acrylates and methacrylates, allyl alcohol and the like. Preference is given, for example, to N-vinyl-2- pyrrolidone, acrylamide, methacrylamide, hydroxyl-sllhstituted lower alkyl acrylates and methacrylates, hydroxy-substituted (loweralkyl)acrylamides and -methacrylamides and vinylically unsaturated carboxylic acids having a total of 3 to 5 carbon atoms.

Fxamples of suitable hydrophilic comonomers ~a) are hydroxyethyl methacrylate (HEMA), hydroxyethyl acryiate, hydroxypropyl acrylate, trimethylammonium 2-hydroxy propylmethacrylate hydrochloride (Blemer~) QA, for example from Nippon Oil), dimethylaminoethyl methacrylate (DMAEMA), dimethylaminoethylmethacrylamide, acrylamide, methacrylamide, N,N-dimethylacrylamide (DMA), allyl alcohol, vinylpyridine, glycerol methacrylate, N-(1,~-dimethyl-3-oxobutyl)acrylamide, N-vinyl-2-pyrrolidone (NVP~, ~ acrylic acid, methacrylic acid and the like.

Preferred hydrophilic comonomers (a) are trimethylammonium 2-hydroxy propylmethacrylate hydrochloride, 2-hydroxyethyl methacrylate, dimethylaminoethyl CA 022386~0 1998-0~-26 methacrylate, trimethylammonium 2-hydroxypropylmethacrylate hydrochlorlde, N,N-dimethylacrylamide and N-vinyl-2-pyrrolidone.

The novel polymers are synthesized in a manner known per se from the corresponding monomers (the term monomer here also including a macromer according to the definition of the formula (I)) by a polymerization reaction customary to the person skilled in the art.
Usually, a mixture of the abovementioned monomers is warmed with addition of a free-radical former. Examples of such free-radical formers are azoisobutyronitrile ~AIBN), potassium peroxodislllfAte, dibenzoyl peroxide, hydrogen peroxide and sodium percarbonate. If, for example, said compounds are warmed, free radicals form with homolysis, and can then initiate, for example, a polymerization.

A polymerization reaction can particularly prefel~bly be carried out using a photoinitiator. In this case, the term photopolymerization is used. In the photopolymerization, it is applopliate to add a photoinitiator which can initiate free-radical polymerization and/or clvssli"king by using light. Examples thereof are customary to the person skilled in the art; suitable photoinitiators are, in particular, benzoin methyl ether, 1-hydroxycyclohexylphenyl ketone, Darocur and Irgacur products, preferably Darocu~3) 1173 and Irgacu~ 2959. Also suitable are reactive photoil ,ilialcjr:i, which can be incorporated, for example, into a macromer, or can be used as a specific comonomer (a). Examples thereof are given in European Patent No. 0632329. The photopolymerization can then be initiated by actinic radiation, for example light, in particular UV light having a suitable wavelength. The spectral requirements can, if necessary, be controlled appropriately by addition of suitable photosensitizers.

A polymerization can be carried out in the presence or absence of a solvent. Suit~hlQ
solvents are in principle all solvents which dissolve the monomers used, for example water, alcohols, such as lower alkanols, for example ethanol or methanol, furthermore carboxamides, such as dimethylformamide, dipolar aprotic solvents, such as dimethyl sulfoxide or methyl ethyl ketone, ketones, for example acetone or cyclohexanone,hydrocarbons, for example toluene, ethers, for example THF, dimethoxyethane or dioxane, halogenated hydrocarbons, for example trichloroethane, and also mixtures of s' lit~hl~
solvents, for example rnixtures of water and an alcohol, for example a water/ethanol or water/methanol mixture.

CA 022386~0 1998-05-26 W O 97/22019 PCT~B96/01368 A polymer network can, if desired, be reinforced by addition of a crosslinking agent, for example a polyunsaturated comonomer (b). In this case, the term crosslinked polymers is used. The invention, therefore, furthermore relates to a crosslinked polymer comprisin~ the product of the polymerization of a macromer of the formula (I), if desired with at least one vinylic comonomer (a) and with at least one comonomer (b).

Examples of typical comonomers (b) are allyl (meth)acrylate, lower alkylene glycol di(meth)acrylate, poly(lower alkyiene) glycol di(meth)acrylate, lower alkylene di(meth)acrylate, divinyl ether, divinyl sulfone, di- and trivinylbenzene, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, bisphenol A di(meth)acrylate, methylenebis(meth)acrylamide, triallyl phthalate and diallyl phthalate.

The amount of comonomer (b) used is expressed in a proportion by weight based on the total polymer and is in the range from 2Q to 0.05%, in particular in the range from 10 to 0.1%, preferably in the range from 2 to 0.1%.

2. Material"B"

Material "B" polymers are formed by polymerizing polymerizable macromers which contain free hydroxyl groups. Macromers which are built up, for example, from an amino-alkylated polysiloxane which is derivatized with at least one polyol component containing an unsaturated polymerizable side chain are disclosed. Polymers can be prepared on the one hand from the macromers according to the invention by homopolymerization. The macromers mentioned furthermore can be mixed and polymerized with one or more hydrophilic and/or hydrophobic comonomers. A special property of the macromers according to the invention is that they function as the element which controls microphase separation between selected hydrophilic and hydrophobic components in a crosslinked end product. The hydrophilic/hydrophobic microphase separation is in the region of less than 300nm. The macromers are preferably crosslinked at the phase boundaries between, for example, an acrylate comonomer on the one hand and an unsaturated polymerizable side chain of polyols bonded to polysiloxane on the other hand, by covalent bonds andadditionally by reversible physical interactions, for example hydrogen bridges. These are formed, for example, by numerous amide or urethane groups. The continuous siloxane CA 022386~0 1998-0~-26 phase which exists in the phase composite has the effect of producing a surprisingly high permeability to oxygen.

The present embodiment of the invention relates to a macromer comprising at least one segment of the formula (I):

--~Z--b--(I) d in which (a) is a polysiloxane segment, (b) is a polyol segrnent which contains at least 4 C atoms, Z is a segment (c) or a group Xl, (c) is defined as X2-R-X2, wherein P~ is a bivalent radical of an organic compound having up to 20 C atoms and each X2 independently of the other is a bivalent radical which contains at least one carbonyl group, X, is defined as X2, and (d) is a radical of the formula (Il):

X3-L-(Y)k-Pl (Il) in which P, is a group which can be polymerized by free r~ c~lc;
Y and X3 independently of one another are a bivalent radical which contairls at least one carbonyl group;
kisOorl; and L is a bond or a divalent radical having up to 20 C atoms of an organic compound.

A polysiioxane segment (a) is derived from a compound of the formula (Ill):

CA 022386~0 1998-0~-26 Wo 97122019 pcT/Is96/ol368 R1 SiO-Si R6 (111) R3Rs -- --n in which n is an integer from 5 to 50Q;
99.8-2~% of the radicals R 11 R2, R3, R4, Rs and R6 independently of one another are alkyl and 0.2-75% of the radicals R 1. R2, R3, R4, Rs and R6 independently of one another are partly fluorinated alkyl, aminoalkyl, alkenyl, aryl, cyanoalkyl, alk-NH-alk-NH 2 or alk-(OCH2)m-(OCH2)p-OR"
R7 is hydrogen or lower alkyl, alk is alkylene, and m and p independently of one another are an integer from 0 to 10, one molecule containing at least one primary amino or hydroxyl group.

The alkylenoxy groups -(OCH2CH2),~, and -(OCH2)p in the siloxane of the formula (111) are either distributed randomly in a ligand alk-(OCH 2CH2)m~(OCH2)p~OR7 or are distributed as blocks in a chain.

A polysiloxane segment (a) is linked a total of 1-50 times, preferabiy 2-30 times, and in particular 4-10 times, via a group Z with a segment (b) or another segment (a), Z in an a-Z-a sequence always being a segment (c). The linkage site in a segment (a) with a group Z is an amino or hydroxyl group reduced by one hydrogen.

In a preferred embodiment, a polysiloxane segment is derived from a compound of the formula (111) in which the radicals R1, R2, R3, R4, Rs and R6 are a total of 1-50 times, more preferably 2-30 times, and in particular 4-10 times, independently either terminally or pendently aminoalkyl or hydroxyalkyl, the other variables being as defined above.

In a pr~er.~d embodiment, a polysiloxane segment is derived from a compound of the formula ~111) in which 95-29% of the radicals R " R2, R3, R4, R5 and R6 independently of one another are alkyl and 5-71% of the radicals R 1, R2, R3, R4, R6 and R6 independently of one another are partly fluorinated alkyl, aminoalkyl, alkenyl, aryl, cyanoalkyl, alk-NH-alk-NH 2 or alk-(OCH2CI 12)m-(OCH2)p-OR7, and in which the variables are as defined above.

CA 022386~0 1998-0~-26 WO 97/:22019 rCTlIB96/01368 In a preferred meaning, n is an integer from 5 to 400, more preferably 10 to 250 and particulariy preferably ~2 to 12~.

In a preferred meaning, the two terminal radicals R1 and R6 are aminoalkyl or hydroxyalkyl, the other variables being as defined above.

In another preferred meaning, the radicals R4 and Rs are 1-50 times, more preferably 2-30 times and in particular 4-10 times pendently aminoalkyl or hydroxyalkyl and the other variables are as defined above.

In another preferred meaning, the radicals R1, R2, R3, R4, R5 and R8 are a total of 1-50 times, more preferably 2-30 times and in particular 4-10 times, independently both terminally and pendently aminoalkyl or hydroxyalkyl and the other variab~es are as defined above.

If Z is X1, X1 is a bivalent group which contains at least one carbonyl group. A carbonyl group mentioned is flanked in any manner, if appropriate, by -O-, -CONH-, -NHCO- or -NH-.
Examples of bivalent groups Z are typically carbonyls, esters, amides, urethanes, ureas or carbonates.

X1 is preferably an ester, amide, urethane or urea group, in particular an ester or amide group.

X2 is defined in the same way as X1 and is preferably an ester, amide, urethane, carbonate or urea group, more preferably an ester, amide, urethane or urea group and in particular an amide, urethane or urea group.

If Z in formula (I) is X1, a polyol segment b is preferably understood as meaning a polyol derived from a carbohydrate, carbohydrate monolactone or carbohydrate dilactone. A
carbohydrate is understood as meaning a mono-, di-, tri-, tetra-, oligo- or polysaccharide. A
carbohydrate lactone is understood as meaning the lactone of an aldonic or uronic acid. An aldonic or uronic acid is, for example, a carboxylic acid formed by oxidation of a mono-, di-, tri-, tetra-, oligo- or polyssccharide. Examples of aldonic acid lactones are gluconolactone, galactonolactone, lactobionolactone or maltoheptaonolactone; examples of uronic acid -CA 022386~0 1998-0~-26 lactones are glucuronic acid lactone, mannuronic acid tactone or iduronic acid lactone. An example of a carbohydrate dilactone is D-glucaro-1,4:6,3-dilactone.

A carbohydrate lactone reacts, for example, with a primary amino group or a hydroxyl group of segment (a) to form a covalent amide or ester bond of the type X ,. Such linkages are the constituent of a further preferred embodiment of macromers according to the invention.
Such macromers have an alternating distribution of segments of type (a) and (b) which are interrupted by X1.

This embodiment of the invention preferably relates to a macromer of the formula (IV):

a--X1 b (IV) d in which the variables are as defined above.

An embodiment of the invention furthermore preferably relates to a macromer according to formula (V):

~EX1 bl ~ (V) (d)X

in which the polysiloxane segment (a) contains q pendent ligands, xisO, 1 or2, q has an average numerical value of 1-20, preferably 1-10, and in particular 1-5, and the segments (b) in a macromer according to the formula (V) are linked in total (per molecule) with up to 20, preferably with up to 15, and in particular with up to polymerizable segments (d~.

An embodiment of the invention furthermore preferably relates to a macromer according to formula (Vl):

CA 022386~0 1998-0~-26 ~X~ ~ (Vl) (d3x in which a linear sequence is present, xisO, 1 or2, q has an average numerical value of 1-20, preferably 1-10, and in particular 1-5, and the segments (b) in a macromer according to the formula (Vl) are linked in total ~per molecule) with up to 20, preferably with up to 1 ~i, and in particular with up to 6 polymerizable segments (d).

An embodiment of the invention furthermore very preferably relates to a macromeraccording to formula (Vll):

(d)x (d)x ~X1 ~ X1 1 (Vll) (d) (d)x inwhichxisO, 1 or2,and the average number of segments (d) per molecule of the formula (Vll) is preferably in the range from 2 to 5, and very preferably is in the range from 3 to 4.

A polyol segment (b) is derived from a polyol which carries no lactone group if the group Z
is a segment (c). Examples of such polyols are a 1 ,2-polyol, for ex~ le the reduced monosaccharides, for example mannitol, glucitol, sorbitol or iditol, a 1,3-polyol, for example polyvinyl alcohol (PVA), which is derived from partly or completely hydrolysed polyvinyl acetate, and furthermore amino-terrninal PVA telomers, aminopolyols, aminocyclodextrins, aminomono-, -di-, -tri-, -oligo- or -polysaccharides or cyclodextrin derivatives, for example hydroxypropylcyclodextrin. An abovementioned carbohydrate dilactone can be reacted, for example, with plefelably 2 equivaients of an amino-terminal PVA telomer to give a polyol macromer which carries, in the central part, the carbohydrate compound derived from the dilactone. Such polyols of this composition are likewise understood to be a suitable polyol.

CA 022386~0 1998-0~-26 As illustrated in formula (I), a segment (b) carries at least one vinylic polymerizable segment (d), a linkage of a segment (d) via the bivalent radical X 3 thereof to an amino or hydroxyl group, of a segment (b), reduced by a hydrogen atom being intended.

vinylic polymerizable segment (d) is incorporated either terminally or pendently preferably -20 times, more preferably 2-15 times, and in particular 2-6 times, per macromer molecule according to the invention.

A vinylic polymerizable segment (d) is incorporated terminally and also pendently as desired (as a terminal/pendent mixture) preferably 1-20 times, more preferably 2-15 times and in particular 2-6 times, per macromer molecule according to the invention.

A group P 1 which can be polymerized by free radicals is, for example, alkenyl, alkenylaryl or alkenylarylenealkyl having up to 20 C atoms. Examples of alkenyl are vinyl, allyl, 1-propen-2-yl, 1-buten-2- or -3- or -4-yl, 2-buten-3-yl and the isomers of pentenyl, hexenyl, octenyl, decenyl or undecenyl. Examples of alkenylaryl are vinylphenyl, vinylnaphthyl or allylphenyl.
An example of alkenylarylenealkyl is vinylbenzyl.

P1 is preferably alkenyl or alkenylaryl having up to 12 C atoms, more preferably alkenyl having up to 8C atoms and in particular alkenyl having up to 4 C atoms.

L is preferably alkylene, arylene, a saturated bivalent cycloaliphatic group having 6 to 20 carbon atoms, arylenealkylene, alkylenearylene, alkylenearylenealkylene or arylenealkylenearylene. In a preferred meaning, L furthermore is preferably a bond.

In a preferred meaning, L is a divalent radical having up to 12 C atoms, and more preferably a divalent radical having up to 8 C atoms. In a preferred meaning, L furthermore is alkylene or arylene having up to 12 C atoms. A very preferred meaning of L is lower alkylene, in particular lower alkylene having up to 4C atoms.

Y is prererdbly a carbonyl, ester, amide or urethane group, in particular a carbonyl, ester or amide group, and very preferably a carbonyl group.

CA 022386~0 l998-0~-26 Wo 97/22019 pcT/Is96/~l368 In another preferred meaning, Y is absent, i.e., k is O.

In a preferred meaning, X3 iS a urethane, urea, ester, amide or carbonate group, more preferably a urethane, urea, ester or amide group, and in particular a urethane or urea group.
A vinylic poiymerizable segment (d) is derived, for example, from acrylic acid, methacrylic acid, methacryloyl chloride, 2-isocyanatoethyl methacrylate (IEM), allyl isocyanate, vinyl isocyanate, the isomeric vinylbenzyl isocyanates or ~d~llcts of hydroxyethyl methacrylate (HEMA) and 2,4-tolylene diisocyanate (T~:)l) or isophorone diisocyanate (IPDI), in particular the 1:1 adduct.
The invention furthermore preferably relates to a macromer in which a segment (d) is incorporated either terminally or pendently or as a terminal/pendent mixture 5 times.
The invention furthermore preferably relates to a macromer in which a segment (d) is incorporated ten,.inally ~i times.

The diradical R is, for example, alkylene, arylene, alkylenearylene, arylenealkylene or arylenealkylenearylene having up to 20 carbon atoms, a saturated bivalent cycloaliphatic group having 6 to 20 car~on atoms or cycloalkylenealkylenecycloalkylene having 7 to 20 carbon atoms.

In a preferred meaning, R is alkylene, arylene, alkylenearylene, arylenealkylene or arylenealkylenearylene having up to 14 carbon atoms or a saturated bivalent cycloaliphatic group having 6 to 14 carbon atoms.

In a preferred meaning, R is alkylene, arylene, alkylenearylene or arylenealkylene having up to 14 carbon atoms, or a saturated bivalent cycloaliphatic group having 6 to 14 carbon atoms.
In a preferred meaning, R is alkylene or arylene having up to 12 carbon atoms, or a saturated bivalent cycloaliphatic group having 6 to 14 carbon atoms.

In a pr~l~r,~:d meaning, R is alkylene or arylene having up to 10 carbon atoms, or is a saturated bivalent cycloaliphatic group having 6 to10 carbon atoms.

CA 022386~0 1998-0~-26 In a very preferred meaning, a segment (c) is derived from a diisocyanate, for example from hexane 1,6-diisocyanate, 2,2,4-trimethylhexane 1,6-diisocyanate, tetramethylene diisocyanate, phenylene 1,4-diisocyanate, toluene 2,4-diisocyanate, toluene 2,6-diisocyanate, m- or p-tetramethylxylene diisocyanate, isophorone diisocyanate orcyclohexane 1,4-diisocyanate.

A preferred embodiment of segment (c) is furthermore derived from a diisocyanate in which the isocyanate groups have different reactivities. The different reactivity is influenced, in particular, by the spatial requirements and/or electron density in the neighbourhood of an isocyanate group.

The average molecular weight of a macromer according to the invention is preferably in the range from about 300 to about 30,000, very preferably in the range from about 500 to about 20,000, more preferably in the range from about 800 to about 12,000, and particularly preferably in the range from about 1000 to about 10,000.

A preferred embodiment of the macromer has a segment sequence of the formula (Vlll):

b-Z-a-{c-a}r(Z-b)t ~Vlll) in which r is an integer from 1 to 10, preferably from 1 to 7, and in particular from 1 to 3;
t is 0 or 1, and prefelably 1;
a linear (c-a) chain which may or may not be terminated by a segment (b) is present (t=1 );
and the above preferences apply to the total number of segments (d), which are preferably bonded to a segment (b).

A pl~felled embodiment of the macromer has a segment sequence of formula (IX):

b-Z-a-{c-a-(Z-b).}r (IX) in which the sequence (c-a)-(Z-b)t hangs pendently r times on the segment (a) and may or may not be terminated by a segment (b);

CA 022386~0 1998-0~-26 r is an integer from 1 to 10, preferably from 1 to 7, and in particular from 1 to 3;
t is O or 1, and is preferably 1;
Z is a segment (c) or a group X 1; and the above preferences apply to the total number of segments (d), which are preferably bonded to a segment (b).

Another preferred embodiment of the macromer has a segment sequence of formula (X):

b-c-{a-c}s-B (X) in which s is an integer from 1 to 10, preferably from 1 to 7, and in particular from 1 to 3;
B is a segment (a) or (b); and the above preferences apply to the number of segments (d), which are bonded to asegment (b).

Another preferred embodiment of the macromer has a segment sequence of the formula (Xl):
B-(c-b)5-Z-a-(b), (Xl) in which the structures are linear, s is an integer from 1 to 10, preferably from 1 to 7, and in particular from 1 to 3;
B is a segment ~a) or (b);
tisOor1,and the above preferences apply to the number of segments (d), which are bonded to asegment (b).

The ratio of the number of segments (a) and (b) in a macromer according to the Material 'IBn embodiment of the invention is preferably in a range of (a):(b)=3:4, 2:3, 1:2, 1:1, 1:3 or 1:4.
The total sum of segments (a) and (b) or, where apprupliale, (a) and (b) and (c) is in a range from 2 to 50, preferably 3 to 30, and in particular in the range from 3 to 12.

Alkyl has up to 20 carbon atoms and can be straight-chain or branched. Suitable examples include dodecyl, octyl, hexyl, pentyl, butyl, propyl, ethyl, methyl, 2-propyl, 2-butyl or 3-pentyl.

CA 022386~0 1998-0~-26 Arylene is preferably phenylene or naphthylene, which is unsubstituted or substituted by lower alkyl or lower alkoxy, in particular 1 ,3-phenylene, 1 ,4-phenylene or methyl-1,4-phenylene; or 1,5-naphthylene or 1,8-naphthyiene.

Aryl is a carbocyclic aromatic radical, which is unsubstituted or sl Ihstituted by preferably lower alkyl or lower alkoxy. Examples are phenyl, toluyl, xylyl, methoxyphenyl, t-butoxyphenyl, naphthyl or phenanthryl.

A saturated bivalent cycloaliphatic group is preferably cycloalkylene, for example cyclohexylene or cyclohexylene-lower alkylene, for example cyclohexylenemethylene, which is unsubstituted or substituted by one or more lower alkyl groups, for example methyl groups, for example trimethylcyclohexylenemethylene, for example the bivalent isophorone radical. The term "lower" in the context of this invention in connection with radicals and compounds, unless defined otherwise, means, in particular, radicals or compounds having up to 8 carbon atoms, preferably having up to 4 carbon atoms.

Lower alkyl has, in particular, up to 8 carbon atoms, preferably up to 4 carbon atoms, and is, for example, methyl, ethyl, propyl, butyl, tert-butyl, pentyl, hexyl or isohexyl.

Alkylene has up to 12 carbon atoms and can be straight-chain or branched. Suitable examples include decylene, octylene, hexylene, pentylene, butylene, propylene, ethylene, methylene, 2-propylene, 2-butylene or 3-pentylene.

Lower alkylene is alkylene having up to 8, and particularly preferably having up to 4 carbon atoms. Particularly preferred examples of lower alkylenes are propylene, ethylene and methylene.

~he arylene unit of alkylenearylene or arylenealkylene is preferably phenylene, which is unsl ~hstitl Ited or sl Ihstituted by lower alkyl or lower alkoxy, and the alkylene unit of this is preferably lower alkylene, such as methylene or ethylene, in particular methylene. Such radicals are therefore preferably phenylenemethylene or methylenephenylene.

Lower alkoxy has, in particular, up to 8 carbon atoms, preferably up to 4 carbon atoms, and is, for example, methoxy, ethoxy, propoxy, butoxy, tert-butoxy or hexyloxy.

CA 022386~0 1998-0~-26 Partly fluorinated alkyl is understood as meaning alkyl in which up to 90%, preferably up to 70%, and in particular up to 50%, of the hydrogens are replaced by fluorine.

Arylenealkylenearylene is preferably phenylene-lower alkylene-phenylene having up to 8, and in particular having up to 4 carbon atoms in the alkylene unit, for example phenylenethylenephenylene or phenylenemethylenephenylene.

A monosaccharide In the context of the present invention is understood as meaning an aldopentose, aldohexose, aldol~l~ose, ketopentose or ketohexose.

Examples of an aldopentose are D-ribose, D-arabinose, D-xylose or D-lyose; examples of an aldohexose are D-allose, D-altrose, D-glucose, D-mannose, D-gulose, D-idose, D-g~l~ctose, D-talose, L-fucose or L-rhamnose; examples of a ketopentose are D-ribulose or D-xylulose; examples of a tetrose are D-erythrose or threose; and examples of a ketohexose are D-psicose, D-fructose, D-sorbose or D-t~g~tc~se. Examples of a disaccharide are trehalose, maltose, somaltose, cellobiose, gentiobiose, saccharose, lactose, chitobiose, N,N-diacetylchitobiose, palatinose or sucrose. Raffinose, panose or maltotriose may be mentioned as an example of a trisaccharide. Examples of an oligosaccharide are maltotetraose, maltohexaose, chitoheptaose and furthermore cyclic oligosaccharides, such as cyclodextrins.

Cyclodextrins contain 6 to 8 identical units of a-1,4-glucose. Some examples are a-, ~-and ~-cyclodextrin, derivatives of such cyclodextrins, for example hydroxypropylcyclodextrins, and branched cyclodextrins.

The macromers according to this embodiment of invention can be prepared by processes known per se, for example as follows.

In a first step, a polysiloxane co~ g at least one primary amino- or hydroxyalkyl group is reacted with a carbohydrate lactone, an amide or ester bond being formed and a compound of the formula (Xlla) or ~Xllb) being formed:
(a-Z-b)q (Xlla) CA 022386~0 1998-0~-26 a-tZ-b)q (Xllb) in which the variables are as defined above and Z is a group X "
after which the compound (Xll) is reacted with an unsaturated polymerizable compound of the formula (Xlll):
X4-L-(Y)k-P1 (Xlll) in which X4 is a group which is coreactive with a hydroxyl or amino group of segment (b), an X3 group of a segment (d) according to formula (Il) being formed from such a reaction, where X4 is preferably -COOH, -COOR1o, -COCI or -NCO, in which R~o is alkyl, or is aryl which is unsubstituted or substituted by lower alkyl or lower alkoxy, and the other variables are as defined above, after which a macromer according to the formula (IV) or (V) is formed * X1 b d (IV) ~EX1 b] (V) (d)X
in which the segments (d) are incorporated terminally or pendently.

Another process starts from a polysiloxane (a) which contains terminal primary amino- or hydroxya!kyl groups and is reacted with a carbohydrate dilactone to form linear structures of the formula (XIV):

~X1 1~ (XIV) q in which the variables are as defined and preferred above, after which a compound of the formula ~XIV3 is reacted with a compound of the formula (Xlll) analogously to the above process to give a macromer of the formula (Vl):

~X1 ~3 (Vl) - (d)X

in which the variables are as defined and preferred above.

CA 022386~0 1998-0~-26 Wo 97/22019 PCT/IB96101368 Another process starts from a polysiloxane (a) which contains terminal primary amino- or hydroxyalkyl groups and is initially reacted with a bifunctional compound of the formula (XV):
X4-R-X4 (XV) in which X4 is a group which is coreactive with a hydroxyl or amino group of segment (a), an X2 group of a segment (c) being formed from such a reaction, where X4 is preferably -COOH, -COOR1o, -COCI or -NCO, in which R10 is alkyl, or aryl which is unsubstituted or substituted by lower alkyl or lower alkoxy, and R is as defined above, after which this intermediate is reacted with a polyol which carries no lactone group to give a compound of the formula (XVI):

b-c-~a-c}S-b (XVI) in which the variables are as defined and preferred above, after which the compound of the formula (XVI) is reacted with a compound of the formula (Xlll) to give a macromer of the formula (X):

b-c-{a-c}8-B (X) in which s is an integer from 1 to 10, preferably from 1 to 7, and in particular from 1 to 3;
B is a segment (a) or (b); and the above preferences apply to the number of segments (d) which are bonded to a segment (b).

Another process starts from a bifunctional compound of the formula (XV):

X4-R-X4 (XV) which is reacted wilth an excess of polysiloxane (a) to give an -a-(c-a)r- sequence, in which the above meanings apply, after which, in a second step, the intermediate is reacted with a polyol which carries no lactone to give a compound of the formula (XVII):

b-Z-a-{c-a}r-Z-b (XVII) CA 022386~0 1998-0~-26 after which the compound (XVII) is reacted with the compound (Xlll) to give a macromer of the formula (Vlll):

b-Z-a-{c-a}~(Z-b)t (Vlll) in which r is an integer from 1 to 10, preferably from 1 to 7, and in particular from 1 to 3; t is O or 1, and is preferably 1; in which a linear (c-a) chain, which may or may not be terminated by a segment (b), is present (t=1 ); and the above preferences apply to the total number of segments (d), which are preferably bonded to a segment (b).

Another process starts from a carbohydrate lactone which is reacted in a first step with a compound of the formula (Xlll), the lactone function being retained, after which the intermediate is reacted with a polysiloxane containing at least one amino or hydroxyl group to give a compound of the formula (IV) or (V):

* X1 b d (IV) a EX1 bl (V) (d)X
in which q is typically 1 or 2, and in which the above meanings and preferences otherwise apply, and the segments (d) are incorporated terminally or pendently.

The present embodiment of the invention furthermore relates to the intermediates which are novel and which occur during synthesis of the macromers according to the invention.

The invention therefore furthermore relates to a compound of the formula (Xlla):
(a-Z-b)q (Xlla) in which q is greater than 1, (a) is derived from a polysiloxane as defined by formula (I) above and (b) is derived from a carbohydrate dilactone.

CA 022386~0 1998-0~-26 An embodiment of the invention furthermore relates to a compound of the formula (Xllb):
a-~Z-b)q (Xllb) in which Z, (b) and q are as defined and preferred above, but with the proviso that a segment (a) is derived from a compound of the formula (Ill):

Rl Si O-Si--R6 (111) -- --n in which n is an integer from 5 to 500;
g9.8 - 25% of the radicals R 1. Rz, R3, R4, R5 and R6 independently of one another are alkyl and 0.2 - 75 % of the radicals R 1, R2, R3, R4, P~5 and R6 independently of one another are partly fluorinated alkyl, aminoalkyl, alkenyl, aryl, cyanoalkyl, alk-NH-Alk-NH 2 or alk-(OC~12CH2)m-~OCHz)p-OR7 in which R, is hydrogen or lower alkyl, alk is alkylene and m and p independently of one another are an integer from 0 to 10, one molecule containing at least one primary amino or hydroxyl group and at least one partly fluorinated alkyl group.
The invention furthermore relates to a compound of the formula (XVI):
b-c-{a-c}8-b (XVI) in which a segment (b) is derived from a polyol which carries no lactone and the other variables are as defined and preferred above.

An embodiment of the invention furthermore relates to a compound of the formula (XVII):
b-Z-a-{c-a}r-Z-b (XVII) in which a segment (b) is derived from a polyol which carries no lactone and the other variables are as defined and preferred above.

A sitoxane (a) containing at least one primary amino or hydroxyl group is, for example, commercially obtainable. Examples are KF-6002, KF-8003, X-22-161 C (Shin Etsu) or GP4 (Genesee). Other siloxanes can be synthesized with the aid of published processes.

A polyol (b) required for the synthesis is as a rule commercially obtainable. Examples are ~31uconolactone or lactobionolactone. Otherwise, they can be synthesized with the aid of a published process.

CA 022386~0 1998-0~-26 The compounds according to the invention can be prepared in the presence or absence of a solvent. A solvent which is largely inert, i.e., does not participate in the reaction, is advantageously used. Suitable examples of these are ethers, such as tetrahydrofuran (THF), 1,2-dimethoxyethane, diethylene glycol dimethyl ether or dioxane, halogenated hydrocarbons, such as chloroform or methylene chloride, bipolar aprotic solvents, such as acetonil,i!c, acetone, dimethylformamide (DMF) or dimethyl sulfoxide (DMSO), hydrocarbons, such as toluene or xylene, and furthermore pyridine or N-methylmorpholine.

The reactants are advantageously employed in stoichiometric amounts for the preparation of the compounds according to the invention. The reaction temperature can be, for example, from -30~C to 1 50~C. The range from O~C to 40~C is a preferred temperature range. The reaction times here are in the range from about 15 minutes to 7 days,prefeltlbly in the region of about 12 hours. If necessary, the reaction is carried out under argon or nitrogen as an inert gas. A sll t~~le catalyst is advantageously added for urethane-forming reactions, for example dibutyltin dilaurate (DBTDL).

The present invention furthermore relates to a polymer con lpl i:,;. lg a polymerization product of at least one macromer according to the invention as defined above and, if approplia~e, at least one vinylic comonomer (a).

The preferred composition of a polymer accordi. Ig to the invention comprises a weight content, with respect to the total polymer, of a macromer according to the invention in the range from 100 to 0.5%, in particular in the range from 80 to 10%, and prefeldbly in the range from 70 to 30%.

In a plt:~el,~ad polymer cornpri~ g a polymerization product of at least one macromer according to the invention, comonomer (a) is absent and the polymer is preferably a homopolymer.

A comonomer (a) which is contained in a polymer according to the invention can be hydrophilic or hydrophobic or a mixture of both. Suitable comonomers include, in particular, those which are usually used for the preparation of contact lenses and biomedical materials.

CA 022386~0 1998-0~-26 - ~2 -A hydrophobic comonomer (a) is understood as meaning monomers which typically give, as a homopolymer, polymers which are water-insoluble and can absorb less than 10% by weight of water.

Analogously, a hydrophilic comonomer (a) is understood as meanin~ a monomer which typically gives, as a homopolymer, a polymer which is water-soluble or can absorb at least 10% by weight of water.

Suitable hydrophobic comonomers (a) include, without this list being exhaustive, C 1-C,8alkyl and C3-C18cycloalkyl acrylates and methacrylates, C3-C18alkylacrylamides and -methacrylamides, acrylonitrile, methacrylonitrile, vinyl C,-C18alkanoates, C2-C,8alkenes, C2-~,8haloalkenes, styrene, lower alkyl styrene, lower alkyl vinyl ethers, C 2-C10perfluoroalkyl acrylates and methacrylates or correspondingly partly fluorinated acrylates and methacrylates, C3-C12perfluoroalkyl-ethyl-thiocarbonylaminoethyl acrylates and methacrylates, acryloxy- and methacryloxy-alkylsiloxanes, N-vinylcarbazole and C 1-Cl2alkyl esters of maleic acid, fumaric acid, itaconic acid, mesaconic acid and the like. Preferred comonomers are, for example, acrylonitrile, C 1-C4alkyl esters of vinylically unsaturated carboxylic acids having 3 to 5 carbon atoms, or vinyl esters of carboxylic acids having up to 5 carbon atoms.

Examples of suitable hydrophobic comonomers (a) include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, isobutyl acrylate (IBA), isooctyl acrylate (OA), isodecyl acrylate (DA), cyclohexyl acrylate, 2-ethylhexyl acrylate (EHA), methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl acrylate, vinyl acetate, vinyl propionale, vinyl butyrate, vinyl valerate, styrene, chlo,~prene, vinyl chloride, vinylidene chloride, acrylonitrile, 1-butene, butadiene, methacrylonitrile, vinyl toluene, vinyl ethyl ether, perfluorohexylethylthiocarbonylaminoethyl methacrylate, isobornyl methacrylate, trifluoroethyl methacrylate, hexafluoroisopropyl methacrylate, hexafluorobutyl (meth)acrylate (HFBMA and HFBA), tris-trimethylsilyloxy-silyl-propyl methacrylate (TRIS), 3-methacryloxy-propylpentamethyl~ neand bis(methacryloxypropyl) lelr~ elhyldl loy~rle~
Preferred examples of hydrophobic comonomers (a) are methyl methacrylate, IBA, HFBA, HFBMA, OA, EHA, ~A, TRIS and acrylonitrile.

CA 022386~0 1998-0~-26 ~ 53 -Suitabie hydrophilic comonomers (a) include, without this list being conclusive, hydroxyl-substituted lower alkyl acrylates and methacrylates, acrylamide, methacrylamide, lower alkylacrylamides and -methacrylamides, ethoxylated acrylates and methacrylates, hydroxyl-substituted lower alkylacrylamides and -methacrylamides, hydroxyl-sllhstituted lower alkyl vinyl ethers, sodium vinylsulfonate, sodium styrenesulfonate, 2-acrylamido-2-methylpropanesulfonic acid, N-vinylpyrrole, N-vinyl-2-pyrrolidone, 2-vinyloxazoline, 2-vinyl-4,4'-dialkyloxazolin-5-one, 2- and 4-vinylpyridine, vinylically unsaturated carboxylic acids having a total of 3 to 5 carbon atoms, amino-lower alkyl (where the term "amino" also includes quaternary ammonium), mono-lower alkylamino-lower alkyl and di-lower alkylamino-lower alkyl acrylates and methacrylates, allyl alcohol and the like. Preferred comonomers are, for example, N-vinyl-2-p~"~lidone, acrylamide, methacrylamide, hydroxyl-substituted lower alkyl acrylates and methacrylates, hydroxyl-substituted lower alkylacrylamides and -methacrylamides and vinylically unsaturated carboxylic acids having a total of 3 to 5 carbon atoms.

Examples of suitable hy.J,opl1 ' ~ comonomers (a) include hydroxyethyl methacrylate (HEMA), hydroxyethyl acrylate, hydroxypropyl acrylate, trimethylammonium-2-hydroxypropyl methacrylate hydrochloride (Blemer(!~QA, for example from Nippon Oil), dimethylaminoethyl meth acrylate (DMA~MA), dimethylaminoethyl methacrylamide, acrylamide, methacrylamide, N,N-dimethylacrylamide (DMA), allyl alcohol, vinylpyridine, glycerol methacrylate, N-(1,1-dimethyl-3-oxobutyl)acrylamide, N-vinyl-2-pyrrolidone (NVP), acrylic acid, methacrylic acid and the like.

Preferred hydrophilic comonomers (a) are 2-hydroxyethyl methacrylate, dimethylaminoethyl methacrylate, trimethylammonium-2-hydroxypropyl methacrylate hydrochloride, N,N-dimethylacrylamide and N-vinyl-2-p~ 'one.

The polymers according to the invention are built up in a manner known per se from the corresponding monomers (the term monomers here also including a macromer according to the invention) by a polymerization reaction with which the expert is familiar. Usually, a mixture of the abovementioned monomers is heated, with the addition of an agent which forms free r~-~ic~s Such an agent which forms free radicals is, for example, a~oisobutyronitrile (AIBN), potassium peroxo~isl~ te, dibenzoyl peroxide, hydrogen peroxide or sodium percarbonate. If the compounds mentioned are heated, for example, CA 022386~0 1998-0~-26 free radicals are then formed, by homolysis, and can then, for example, initiate a polymerization .

A polymerization reaction can particularly preferably be carried out using a photr.. Iilialor.
Photopolymerization is the term used in this case. For photopolymerization, a photoinitiator which can initiate free radical polymerization and/or crosslinking by the use of light is suitably added. Examples of this are familiar to the expert, and specifically, 5llit~hlE
photoi,liliators are benzoin methyl ether, 1-hydroxycyclohexyl phenyl ketone and Darocur and Irgacur types, preferably Darocur 1 1 73(g~ and Darocur 2959(i~) . Reactive ph~luil ,iliators which can be incorporated, for example, into a macromer or can be used as a special comonomer (a) are also sllit~hlc. Examples of these are to be found in EP 632 329. The photopolymerization can then be triggered off by actinic radiation, for example light, in particular UV light of a suitable wavelength. The spectral requirements can be controlled accordingly, if appropriate, by addition of suitable photosensili~ers.

Polymerization can be carried out in the presence or absence of a solvent. .c uit~hlc solvents are in principle all solvents which dissolve the monomers used, for example water, alcohols, such as lower alkanols, for example ethanol or methanol, and furthermore carboxylic acid amides, such as dimethyl~or"~a",i~'c, dipolar aprotic solvents, such as dimethyl sulfoxide or methyl ethyl ketone, ketones, for example actone or cyclohexanone, hydrocarbons, for example toluene, ethers, for example THF, dimethoxyethane or dioxane, and halogenated hydrocarbons, for example trichloroethane, and also mixtures of suitable solvents, for example mixtures of water with an alcohol, for example a water/ethanol or a water/methanol mixture.

If applc,p,i~le, a polymer network can be intensified by addition of a so-cailed cro~C" .ki"g agent, for example a polyunsaturated comonomer (b). The invention furthermore relates to a polymer con"~ g the polymerization product of a macromer according to the invention with, if appropriate, at least one vinylic comonomer (a) and with at least one comonomer (b).

Examples of typical comonomers (b) are, for example, allyl(meth)acrylate, lower alkylene glycol di(meth)acrylate, poly lower alkylene glycol di(meth)acrylate, lower alkylene di(meth)acrylate, divinyl ether, divinyl sulfone, di- or trivinylbenzene, trimethylolpropane CA 022386~0 l998-0~-26 tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, bisphenol A di(meth)acrylate, methylenebis(meth)acrylamide, triallyl phthalate or diallyl phthalate.

The amount of comonomer (b) used is expressed in the weight content with respect to the total polymer and is in the range from 20 to 0.05 %, in particular in the range from 10 to 0.1%, and preferably in the range from 2 to 0.1%.

3. "Material C"

Another advantageous embodiment of the present invention relates to the use of asiloxane-containing macromer which is formed from a poly(dialkylsiloxane) dialkoxyalkanol having the following structure:

H~R1OR2--li O~i R30R4--OH
R6 ~8 where n is an integer from about 5 to about 500, preferably about 20 to 200, more preferably about 20 to 100;
the radicals R" R2, R3, and R4, independently of one another, are lower alkylene, preferably C1-C6 alkylene, more preferably C t-C3 alkylene, wherein in a preferred embodiment, the total number of carbon atoms in R 1 and R2 or in R3 and R4 is greater than 4; and R5, R6, R7, and R8, independently of one another, are lower alkyl, preferably C 1-C6 alkyl, more preferably C1-C3 alkyl.

The general structure of the Material "C" macromer follows:

ACRYLATE - LINK - ALK - O - ALK - PDAS - ALK - O - ALK - LINK - ACRYLATE

where the ACRYLATE is selected from acrylates and methacrylates; LINK is selected from urethanes and diurethane linkages, ALK - O - ALK is as defined above (R 1-O-R2 or R3-O-R4), and PDAS is a poly(dialkylsiloxane).

CA 022386~0 1998-0~-26 WO 97/22019 PCTlIB96/01368 For example, a Material "C" macromer may be prepared by reacting isophorone diisocyanate, 2-hydroxyethyl (meth)acrylate and a poly(dialkylsiloxane) dialkoxyalkanol in the presence of a catalyst.

A preferred Material "C" macromer may be prepared by reacting a slight excess ofisocyanatoalkyl methacrylate, especially isocyanatoethyl methacrylate (IEM), with a poly(dialkylsiloxane) dialkoxyalkanol"~re~e~bly poly(dimethylsiloxane) dipropoxyethanol, in the presence of a catalyst, especially an organotin catalyst such as dibutyltin dilaurate (DBTL). The primary resulting structure is as follows:

o f--R2 ~i _o i R3 O o H2C= I--CO--R9 NHIlO--R1 R6 R8 R4 OCNH--R11 OC--C=CH2 R10 ~ ~ l2 where R9 and R1, are alkylene; preferably C 14 alkylene, more preferably ethylene;
Rlo and R12 are methyl or hydrogen.

The Material "C" prepolymer mixture may be formed by mixing the aforementioned siloxane-containing macromer with one or more hydrophilic monomers and a thermoi. ,iliator or a photoinitiator such as Darocur~g) 1173. A solvent, such as hexanol, is preferably added to homogenize the mixture. r,~terdbly, an appropriate amount of TRIS is added to lower the modulus of elasticity to a desired level. The ionoperm monomer or monomers may be selected from any of the aforementioned ionoperm or hyd,vpl,ilic monomers. Preferably, the ionoperm monomer is selected from the group consisili"g of acrylates, methacrylates, acrylamides, methacrylamides and mixtures thereof. More preferably, the ionopermmonomers are selected from dimethylacrylamide (DMA) and methacrylic acid (MAA).

A preferred Material "C" prepolymer mixture, in weight percentages based on total mixture weight, includes about 35 to 60% Material "C" macromer; about 6 to 25% TRIS; about 15 to 35% ionoperm monomer; about 0.1 to 1% photoi"ilialol, and about 10 to 20% solvent. A
more preferred Material ac" prepolymer mixture, in weight percentages based on total mixture weight, includes the following: about 40 to 55% Material D macromer; about 8 to CA 022386~0 1998-0~-26 16% TRIS; about 20 to 30% dimethylacrylamide; about 0.2 to 2% methacrylic acid; about 0.1 to 1% photoinitiator; and about 10 to 20% solvent. A particularly preferred Material "C"
prepolymer mixture, in weight percentages based on total mixture weight, includes the following: about 44 to 50% Material "C" macromer; about 10 to 12% TRIS; about 22 to 26%
dimethylacrylamide; about 0 to 1% methacrylic acid; about 0.2 to 0.6% photc-. ,iliator; and about 10 to 20% solvent.

The prepolymer mixture may be formed into lenses and other ophthalmic devices by any of a number of techniques known in the art and disclosed herein. Preferably, the prepolymer mixture is conveyed into a concave half of a lens mold, the convex mold half is mated with the concave mold half, and an appropriate amount of radiation is applied to initiate polymerization. While ultraviolet (UV) radiation is preferred, a number of other energy sources known in the art and disclosed herein may also be used.

The Material "C" ophthalmic lens is preferably a polymerization product of the following macromeric and monomeric components, based on total weight of polymerizable material:
(a~ about 45 to about 65 percent Material "C" macromer;
(b) about 5 to about 25 percent TRIS; and (c) about 20 to about 40 percent ionoperm monomer.

The Material "C"ophthalmic lens is more preferably a polymerization product of the following macromeric and monomeric components, based on total weight of polymerizable material:
(a) about 50 to about 60 percent Material "Cn macromer;
(b) about 10 to about 2Q percent TRIS; and (c) about 25 to about 35 percent ionoperm monomer.

In a preferred embodiment, the Material "C" ophthalmic lens is a polymerization product of the following macromeric and monomeric components, based on total weight of polymerizable material:
(a) about 50 to about 60 percent Material "C" macromer;
~ (b) about 10 to about 20 percent TRIS;
(c) about 25 to about 35 percent DMA; and (d) up to about 2 percent MAA.

CA 022386~0 1998-0~-26 In another preferred embodiment, about 0.2 to 1.0 weight percent MAA is used, together with the components (a), (b), and (c) in the above-cited amounts.

Those formula numbers and variables that appear more than once in the above chapter G, may have a separate meaning in each of the Materials "A", "B" and "C".
Ill. OPHTHALMICALLY COMPATIBLE SURFACFS

The ophlllal,llic lenses of the present invention have a surface which is biocompatible with ocular tissue and ocular fluids during the desired extended period of contact. In one prt~ r,ad embodiment, the ophthalmic lenses of the present invention include a core material, as defined above, surrounded, at least in part, by a surface which is more hydrophilic and lipophobic than the core material. A h~/dluphilic surface is desirable in order to enhance the co,l~pz~libilily of the lens with the ocular tissues and tear fluids. As surface hydrophilicity increases, undesirable attraction and adherence of lipids and proteinaceous matter typically decreases. There are factors other than surface hydrophilicity, such as immunological response, which may contribute to deposit accumulation on the lens.
Deposition of lipids and proteinaceous matter causes haze on the lens, thereby reducing visual clarity. Proteinaceous deposits may also cause other problems, such as irritation to the eye. After extended periods of continuous or intermittent wear, the lens must be removed from the eye for cleaning, i.e., deposit removal. Therefore, increased surface hydrophilicity, and concomittent reductions in deposits of bioiogical matter, allows increased wear time.

"Surface treatment procecses", as used herein, refers to processes to render a surface more ophthalmically compatible, in which, by means of contact with a vapor or liquid, and/or by means of ~pplic~tion of an energy source ~1 ) a coating is applied to the surface of an article, (2) chemical species are adsorbed onto the surface of an article, (3) the chemical nature ~e.g., ele.;l,u~ lic charge) of chemical groups on the surface of an article are altered, or ~4) the surface properties of an article are otherwise modified.

There are a variety of methods ~lisclosed in the art for rendering a surface of a material hydrophilic. For example, the lens may be coated with a layer of a hydrophilic polymeric CA 022386~0 1998-0~-26 Wo 97/22019 pcT/ls96lol368 material. Alternatively, hycllophilic groups may be grafted onto the surface of the lens, thereby producing a monolayer of hydrophilic material. These coating or grafting processes may be effected by a number of processes, including without limitation thereto, exposing the lens to plasma gas or immersing the lens in a monomeric solution under approp,iate conditions.

Another set of methods of altering the surface properties of a lens involves treatment prior to polymerization to form the lens. For example, the moid may be treated with a plasma (i.e., an ionized gas), a static electrical charge, irradiation, or other energy source, thereby causing the prepolymerzation mixture immediately adjacent the mold surface to differ in composition from the core of the prepolymerization mixture.

A preferred class of surface treatment processes are plasma processes, in which an ionized gas is applied to the surface of an article. Plasma gases and processing conditions are described more fully in U.S. Patent Nos. 4,312,575 and 4,632,844, which are incorporated herein by reference. The plasma gas is preferably a mixture of lower alkanes and nitrogen, oxygen or an inert gas.

In a pl~lened embodiment, the lens is plasma treated in the presence of a mixture of (a) a C1~ alkane and (b) a gas selected from the group consisting of nitrogen, argon, oxygen, and mixtures thereof. in a more preferred embodiment, the lens is plasma treated in the presence of a mixture of methane and air.

IV~ UTILITY

A. O~ l.all. _ Lenses i_xamples of ophthalmic moldings, in addition to contact lenses, include without limitation thereto, contact lenses for vision correction, contact lenses for eye color modification, opl~ al"lic drug delivery devices, ophthalmic wound healing devices, and the like.

CA 022386~0 1998-0~-26 WO 97/22019 PCTtIB96/01368 B. Contact Lenses A specific embodiment of the invention is directed to contact lenses which comprise a novel polymer or polyrneric network formed by a novel polymerization process. Such contact lenses have a range of unusual and extremely advantageous properties. Amongst these properties are, for example, their excellent com~aliL,ility with the human cornea (if necessary after suitable surface treatment (coating)) and with tear fluid, which is based on a balanced ratio between ion or water permeability, oxygen transl";ssil..' ~y and mechanical and adsorptive properties. This balance of desirable properties results in high comfort and the absence of irritation and allergenic effects. Owing to their favorable permeability properties with respect to various salts, nutrients, water and diverse other components of tear fluid and gases (CO2 and ~2). the novel contact lenses have no effect, or virtually no effect, on the natural metabolic plocesses in the cornea. In contrast to many other siloxane-containing contact lenses, the present innovative extended-wear lenses have chemical and mechanical properties and ion permeability sufficient to avoid the undesired binding effect.
Furthermore, the novel contact lenses have high dimensional stability and shelf life.

It must be emphasized that this balance of properties, especially the high ion permeability in combination with the high oxygen permeability, is key to producing a true extended-wear contact lens. The high oxygen permeability is required to prevent corneal swelling, thereby reducing the likelihood of ocular damage and wearer di ~col"rort during periods of extended wear. The high ion permeability enables the lens to move on the eye such that corneal health is not substantially altered and wearer co~ u, l is acceptable during a period of extended, continuous contact with ocular tissue and ocular fluids.

The preferred extended-wear contact lenses of the present invention are those which are com~orLable over the period of extended wear. If the lens diameter is too small, the eyelids will not cover any portion of the lens when the eye is open. Thus, the eyelids will contact the edge of the lens each time the eyelid is closed. This repeated eyelid-lens interaction typically causes i.liL~Iion, wearer discomfort, and lens dislodgement. Accordingly, the p~ ~erl ed contact lens diameters are those which are sufficiently large to ~ e eyelid-lens interaction and the ~ssoci~ted irritation. Preferably, the contact lens has a diameter of about 12 to about 16 millimeters, more preferably about 13 to 15 mm, and most preferably about 13.5 to 14.8 mm.

CA 022386~0 1998-0~-26 C. Methods of Use as a Contact Lens The above-described ophthalmic lenses have special utility as extended-wear contact lenses. Contact lenses having sufficient oxygen and water transmission rates from inner (base curve) to outer ffront curve) surface may be continuously worn for long periods of time without substantial corneal swelling or wearer discomfort. The method of wear includes (a) applying the lens to the eye and (b) allowing the lens to remain in i~llir~lale contact with the eye and tear fluids for a period of at least 24 hours without substantial adverse impact on corneal health or wearer comfort.

A preferred method includes additional steps of (c) removing the lens from the ocular environment; (d) treating the lens (i.e., disinfecting or cleaning the lens); (e) re-applying the lens to the eye; and (f) allowing the lens to remain in intimate contact with the eye and tear fluids for a period of at least an additional 24 hours without substantial adverse impact on corneal health or wearer comt~,, l.

In a preferred embodiment, the lens is worn for a continuous period of at least four (4) days without substantial corneai swelling or wearer discorl Itort. In another preferred embodiment, the lens is worn for a continuous period of at least seven (7) days without substantial corneal swelling or wearer discolllrul l. In another preferred embodiment, the lens is worn for a continuous period of at least 14 days without substantial comeal swelling or wearer discomfort. In yet another preferred embodiment, the lens is worn for a continuous period of at least 30 days without substantial corneal swelling or wearer discomfort.

~. M~:THODS OF MANUFACTURE

The remarkable balance of high ion permeability with high oxygen permeability, in the polymeri~lion of the aforementioned specific polymerizable materials, requires the strict removal of oxygen from certain aspects of the lens forming process. In a preferred embodiment, oxygen is rigorously removed from the polymerizable material, rigorously removed from the mold halves used to shape the lens, and rigorously removed from the casting environment.

CA 022386~0 1998-0~-26 However, one or more of these steps may be omitted, or a rigorous removai of oxygen may not be required. For example, it may be determined that, for a particular siloxane- and/or fluorine-containing acrylate macromer and acrylamide monomer mixture, degassing of the mold halves does not substantially increase the ion permeability (and, hence, on-eye movement) of the resultant contact lens. In particular, if molds having a relatively low oxygen permeability are used (e.g., polypropylene molds), the rigorous removal of oxygen may not be required.

In general, the ophthalmic lens may be manufactured by thoroughly mixing the siloxane-and/or fluorine-containing acrylate macromer and acrylamide or pyrrolidone monomer, degassing the mixture, applying an approplit te amount of the mixture to a lens mold cavity, sealing the mold and initiating polymerization. However, alternatively, the siloxane- and/or fluorine-conl~i"i. ,g acrylate macromer and acrylamide or pyrrolidone monomer may be degassed separately, and subsequently mixed in an atmosphere which is oxygen-free or substantially oxygen-free.

Pho' liliatol~, such as those commercially available pho- ~-nilialor~ srlosed above, may be added to the prepolymerization mixture to aid in initiating polymerization. Polymerization may be initiated by a number of well known techniques, which, depending on the polymerizable material, may include applicalion of radiation such as microwave, thermal, e-beam and ultraviolet. A preferred method of initiating polymerization is by application of ultraviolet radiation.

Suitable gases in which the polymerization may be conducted and which are readily commercially available include, without limitation thereto, nitrogen and carbon dioxide.
Thus, the polymerizable materials are copolymerized advantageously in an atmosphere having less than about 500 ppm oxygen. More preferably, the atmosphere surrounding the polymerizable material contains less than about 200 ppm oxygen. Even more preferably, the surrounding atmosphere contains less than about 100 ppm oxygen or particularly less than about 50 ppm oxygen, while the most pre~el,ed oxygen content is less than about 20 Ppm.

CA 022386~0 1998-0~-26 In the aforementioned embodiment, the prepolymer mixture must be rigorously degassed prior to polymerization. The degassing may be accomplished by a number of techniques known in the art. One technique for degassing the prepolymer mixture involves the use of a series of freezing and thawing steps which are repeated until the appropriate gas concentration level is achieved in the prepolymer mixture. This freeze/thaw method involves cooling the prepolymer mixture until the mixture solidifies, applying a vacuum to the solidified prepolymer mixture, discontinuing the vacuum, and thawing the prepolymer mixture until the mixture is again in liquid form. While this degassing technique is advantageous in a laboratory setting, other degassing techniques known in the art may be more advantageous for commercial lens manufacturing processes.

Another means of degassing polymerizable material is to pass an inert gas through the polymerizable material, thereby replacing dissolved oxygen with the inert gas. Yet another means is to merely apply a vacuum to the polymerizabie material, in order to cause the dissolved oxygen to convert to a gaseous phase because of reduced pressure. Similarly, oxygen may be removed from the polymerizable material by placing the polymerizable material in a chamber adjacent to an evacuated chamber, the chambers being separated from each other by a semipermeable membrane. The aforementioned processes may beoperated in batch, semi-batch or continuous manners, and a variety of commercialequipment available for degassing of solutions and solvents may be easiiy applied to the present application by a person having ordinary skill in the art.

An exemplary means for degassing polymerizable material is to pass the polymerizable mixture through a gas-permeable, liquid-impermeable membrane or tube while reducing the pressure outside the membrane or tube, e.g., to a subatmospheric pressure, such that the presssure differential between the inside and outside of the membrane or tube drives dissolved oxy3en oui of ~he polymerizabl~: material. Suiiabie s3as-permeabie membranes and tubes are well known in the art. For example, European Patent ApFli- ~n 376 638 and U.S. Patent No. 5,123,937 issued to Shibata, et al., teach methods for degassing ~arious solvents using gas-permeable tubes.

The concentration of oxygen d.ssolved in the polymerizable mixture is preferably less than about ~00 ppm. More preferably, the free oxygen concentration in the polymerizable mixture is less than about 200 ppm. Even more preferably, the free oxygen concentration CA 022386~0 1998-0~-26 WO 97122019 PCTlIB96/01368 in the polymerizable mixture is less than about 100 ppm, while a most preferred level is below 20 ppm.

In order to degas the iens molds, a preferred technique is to merely store the lens molds in an environment having no oxygen, or substantialiy no oxygen, for a sufficient period of time to achieve substantial equilibration. Preferably the lens molds are stored in an inert substantially oxygen-free atmosphere, e.g., nitrogen or carbon dioxide, prior to use. A
preferred method of degassing molds is to subject the mold halves to an inert atmosphere having an oxygen concentration of less than 100 ppm for a period of at least 4 hours. A
more preferred method involves exposing the molds halves to an inert atmosphere having an oxygen concentration of less than ~;0 ppm for a period of at least 6 hours. In an even more prefer, ed method, the lens mold halves are exposed to an inert atmosphere having an oxygen concentration of less than 20 ppm for a period of at least 8 hours.

Thus, in a preferred embodiment of dollhle sided molding, the lens is formed by the following steps: (1) the polymerizable mixture is degassed, (2) oxygen is rigorously removed ~rom the lens mold halves, (3) a lens mold half is filled with the prepolymer mixture, ~4) the mold halves are affixed to one another in an environment subsl~l ,lially free of oxygen, and (5) the polymerization is initiated in an environment substantially free of oxygen to form the lens, where the lens mold halves are formed from a material having a low oxygen permeability. However, it is conceivable that steps (4)-(5) may occur in the presence of oxygen.

An essential feature of the manufacturing methods of the present innovative lenses is that a balance of high oxygen perrneability and high ion permeability is achieved. Manufacturing techniques and conditions which result in lowering either the oxygen permeability or the ion permeability below levels sufficient to ~I~ai~ good corneal health and on-eye movement during periods of extended wear are unacceptable to produce the innovative extended-wear contact lenses of the present invention.

Preferably, the manufacturing method produces a contact lens having a DWt of at least 70 barrers/mm and a lonoton lon Permeability Coefficient of at least 0.2 x 10~ cm2/sec. More preferably, the manufacturing method produces a contact lens having a DWt of at least 75 barrers/mm and a lonoton lon Permeability Coefficient of at least 0.3 x 10~ cm2/sec. The -CA 022386~0 1998-0~-26 manufacturing method preferably provides a contact lens having a Dklt of at least 87 barrerslmm and a lonoton !on Permeability Coefficient of at least 0.4 x 1 o-6 cm2/sec.

A preferred process for the manufacture of a contact lens comprises:
~ (a) providing a polymerizable material comprising:
(i) about 30 to 60 weight percent siloxane- and/or fluorine-containing acrylate macromer, (ii) about 20 to 40 weight percent monomer selected from the group of acrylamides and methacrylamides, and ~iii) about 1 to 35 weight percent siloxane-containing monomer having a carbon chain length of less than 20 carbon atoms;
(b) removing oxygen from said polymerizable material such that the concentration of oxygen in said polymerizable material is less than 200 ppm;
(c) providing a contact lens mold comprising a base curve mold half and a front curve mold half ~d) subjecting the mold halves to an inert atmosphere having an oxygen concentration of less than 100 ppm for a period of at least 4 hours;
(e) instilling said polymerizable material into said front curve mold half;
(f) mating said base curve mold half to said front curve mold half; and (g~ polymerizing said polymerizable material to form a contact lens having an lonoflux Diffusiont Coefficient of at least 1.5 x 10~ mmZ/min. and an oxygen transmissibility of at least about 75 barrers/mm.

The previous disclosure will enable one having ordinary skill in the art to practice the invention. In order to better enable the reader to understand specific embodiments and the advantages thereof, reference to the following examples is suggested. However, the following examples should not be read to limit the scope of the invention.

Examples A-C are arranged in accordance with the materials defined above. Thus, Examples A-1, A-2, etc. relate to Material "A" as defined above, Examples B-1, B-2, etc.
relate to Material "B" as defined above, and Examples C-1, C-2, etc. relate to Material "C".
Temperatures are stated in degrees Celsius unless otherwise specified.

CA 022386~0 1998-0~-26 Examples E, F and G are directed to demonstrating a correlation between on-eye movement and the lonoton lon Permeability Coefficient, the lonoflux lon Permeability Coefficient, and the Hydrodell Water Permeability Coefficient, respectively.

Examples I and J are directed to showing the correlation of oxygen content in the polymerlzable material andtor molds with ion permeability.

Macromer synthesis 51.5g ~50 mmol) of the perfluoropolyether Fomblin(g) ZDOL (from Ausimont S.p.A, Milan) having a mean molecular weight of 1030 g/mol and containing 1.96meq/g of hydroxyl groups according to end-group titration is introduced into a three-neck flask together with 50mg of dibutyltin dilaurate. The flask conle~ are evacuated to about 20 mbar with stirring and subsequently decompressed with argon. This operation is repeated twice. 22.2g (0.1 mol) of freshly distilled isophorone diisocyanate kept under argon are subsequently added in a counterstream of argon. The temperature in the flask is kept below 30~C by cooling with a waterbath. After stirring overnight at room temperature, the reaction is complete. Isocyanate titration gives an NCO content of 1.40 meq/g (theory: 1.35 meq/g).

202g of the a,~-hydroxypropyl-terrninated polydimethylsiloxane KF-6001 from Shin-Etsu having a mean molecular weight of 2000g/mol (1.OOmeq/g of hydroxyl groups according to titration) are introduced into a flask. The flask contents are ev~u-?~ted to approx. 0.1 mbar and decompressed with argon. This operation is repeated twice. The degassed siloxane is dissolved in 202ml of freshly distilled toluene kept under argon, and 100mg of dibutyltin dilaurate (DBT~:)L) are added. After co~.~pleIe homogeni~dlion of the solution, all the per~luoropolyether reacted with isophorone diisocyanate (IPDI~ is added under argon. After stirring ove,l,igl~l at room temperature, the reaction is col"plet~. The solvent is stripped off under a high vacuum at room temperature. Micl~lilrdlion shows 0.36meq/g of hydroxyl groups (theory 0.37meq/g).

13.78g (88.9mmol) of 2-isocyanatoethyl methacrylate (IEM) are added under argon to 247g of the a,~3-hydroxypropyl-terminated polysiloxane-perfluoropolyether-polysiloxane three-block copolymer (a three-block copolymer on stoichiometric average, but other block CA 022386~0 1998-0~-26 lengths are also present). The mixture is stirred at room temperature for three days.
Mic,.~lil,~lion then no longer shows any isocyanate groups (detection limit 0.01meq/g).
~ 0.34meq/g of methacryl groups are found (theory 0.34meq/g).
The macromer prepared in this way is completely colourless and clear. It can be stored in air at room temperature for several months in the absence of light without any change in molecular weight.

Macromer synthesis The first step of the macromer synthesis described under Example A-1 is repeated. An isocyanate titration of the perfluoropolyether reacted with IPDI gives a content of 1.33meq/g of NCO (theory 1.35meq/g).

in a second step, 87.1g of the oc,~o-hydroxypropyl-terminated polydimethylsiloxane TegomerH-Si2111 (Th. Golds~;hil,idt AG, Essen) having a mean molec~ r weight of 890g/mol (2.25meqlg of hydroxyl groups according to titration) are dissolved In 87ml of toluene. After the reaction has been carried out as indicated under A-1 and the solvent has been removed, a hydroxyl group content of 0.66meq/g is determined by microlil~lion (theory 0.60meq/g). The resultant intermediate is in turn reacted with a stoichiometric amount of isocyanatoethyl methacrylate. Mi~:otil~lion then no longer shows any isocyanate groups (detection limit 0.01 meq/g). 0.56meq/g of methacryl groups are found (theory 0.53meq/g). The macromer prepared in this way is completely colourless and clear and has a long shelf life.

Macromer synthesis The first step of the macromer synthesis described under Example A-1 is repeated, but using a different perfluoropolyether: Fomblin~g) ZDOLTX (from Ausimont S.p.A., Milan). This material is terminated by O~CF2~CH2~(0CH2CH2)n~0H (where n = 0,1 or 2). The material used has a mean molecular weight of 1146g/mol, and contains 1.72meq/g of hydroxyl groups according to end-group analysis. An isocyanate titration of the perfluoropolyether reacted with IPDI shows a content of 1.23meq/g of NCO (theory1.25meq/g).

CA 022386~0 1998-0~-26 In the second step, a stoichiometric amount of Tegomer Hi-Si2111 and toluene are again added. After the reaction has been carried out as indicated under Example A-1 and the solvent has been removed, a hydroxyl group content of 0.63meq/g is determined bymicrotitration (theory 0.58meq/g). The resultant intermediate is in turn reacted with a stoichiometric amount of isocyanatoethyl methacrylate. Mi~;rolil,dlion then no longer shows any isocyanate groups (detection limit 0.01 meq/g). 0.55meq/g of methacryl groups are found (theory 0.61 meq/g). The macromer prepared in this way is completely colourless and clear and has a long shelf life.

EXAMPLE A~
Macromer synthesis The first step of the macromer synthesis described under Fxample A-1 is repeated, but 5.0 g of Fomblin/ZDOL and 2.18 g of IPDI are employed. When the reaction is complete, mi.;rolil,;~lion shows an isocyanate group content of 1.31 meq/g of hydroxyl groups (theory 1.36 meq/g).

The second step of the synthesis described under Example A-1 is likewise carried out analogously, the stoichiometric ratio between isocyanate-terminated perfluoropolyether and hydroxypropyl-terminated polysiloxane being 2:3. After the reaction has been completed and the solvent has been removed",.icroLill~tion shows a content of 0.2mecl/g of hydroxyl groups (theory 0.18meq/g).

The third step of the synthesis described under Example A-1 is likewise carried out analogously, IEM being employed in a precisely stoichiometric ratio. After the reaction, free isocyanate groups can no longer be detected (detection limit 0.01meq/g). 0.19meq/g of methacryl groups are found (theory 0.1 gmeq/g).

Production of contact lenses 1 3.0g of macromer from Example A-1 are dissolved in 5.6g of ethanol (Fluka, puriss. p.a.) (70% by weight solution). After complete homogeni~ation of the solution, 5.2g of 3-tris(l,i",~ll"/lsiloxy)silylpropyl methacrylate ~TRIS from Shin-Etsu, product No. KF-2801), 7.8g of freshly distilled dimethylacrylamide (DMA) and 1 60mg of photoinitiator Darocur~) CA 022386~0 1998-0~-26 1173 (Ciba) are added. This solution is filtered through a Teflon membrane having a pore width of 0.45mm under an argon pressure of from 1 to 2 atm. The filtered solution is frozen ~ in a flask in liquid nitrogen, the flask is evacuated under a high vacuum, and the solution is returned to room temperature with the flask sealed. This degassing operation is repeated twice. The flask containing the macromer/comonomer solution is then transferred into a glove box with an inert-gas atmosphere, where the solution is pipetted into dust-free contact-lens moulds made from polypropylene. The moulds are closed, and the polymerization reaction is effected by UV irradiation (15mW/cm2, 5min.), with simultaneous crosslinking. The moulds are then opened and placed in ethanol, causing the resultant lenses to swell out of the moulds. The lenses are extracted for 24 hours with constantly replenished distilled dichloromethane and subsequently dried in a high vacuum. The dried lenses are equilibrated in phosphate-buffered physiological saline solution in autoclave-resistant vials and then autoclaved at 120~C for 30minutes. All physical data measurements are carried out on autoclaved lenses.

The lenses produced in this way are characterized by the following values: oxygen permeability (Dk) 77 barrer ~determined by the "wet" method described below), water content of the equilibrated lenses 32 percent by weight, elongation at break at 35~C 360%, modulus of elasticity 30~C 0.5MPa ~measured using a Minimat from Polymer Laboratories, UK)-"\/Vet" measurement of the oxvqen permeabilitv:The oxygen permeability of a material is cleler",i,.ed by the coulometric method. To this end, pre-autoclaved lenses are clamped in a holder and then covered on the upper side with a 2cm layer of water. A gas mixture comprising 21% of oxygen and 79% of nitrogen is passed continuously through the water layer with swirling. The oxygen which diffuses through the lens is measured using a coulometric detector. The reference values are those measured on commercially available contact lenses using this method. Cibasoft~/ ~CIBA-Vision, llEMA lens) gives a measurement of approx. 7-10 barrer, and Excelens~/ ~CIBA-Vision, PVA lens) gives a measurement of approx. 22 barrer.

CA 022386~0 1998-0~-26 Unfortunately, the oxygen permeability of, for example, contact lenses is frequently given in the literature as a straight Dk value without further definition and frequently without giving any reference materlal. These are usually values determined on dry material (drymeasurement).
A comparative measurement of the oxygen permeabiiity of polymer A-5 shows the differences:
a) "wet" measurement: 77 barrer b) dry measurement: 158 barrer The process described under Example A-5 for the production of contact lenses is repeated, but the mixture of comonomers has the following composition (in per cent by weight):
55 % of macromer from Example A-1 22 % of TRIS
22.5 % of DMA
0.5 % of Bleme~ QA

The process described under Example A-5 for the production of contact lenses is repeated, but the mixture of comonomers has the following composition (in percent by weight):
55 % of macromer from Example A-1 22 % of TRIS
23 % of DMA

Analogously to EXAMPLE A-5 (in weight percent):
40 % of macromer from Example A-1 30 % of TRIS
30 % of DMA

The process described under A-5 for the production of contact lenses is repeated, but a 70% by weight solution of the macromer in toluene is used instead of the 75% by weight CA 022386~0 1998-0~-26 solution in ethanol described above. The mixture of comonomers has the followingcomposition (in per cent by weight):
55 % of macromer from Example A-1 22%ofTRlS
23 % of DMA

The process described under A-5 for the production of contact lenses is repeated, but a 70% by weight solution of the macromer in octamethylcyclotet~ x~ne is used instead of the 75% by weight solution in ethanol described above. The mixture of comonomers has the following composition (in per cent by weight):
55 % of macromer from Example A-1 22 % of TRIS
23 % of DMA

Physical measurement data for the contact-lens materials from Examples A-5 to A-10 (O 2 Dk value, wet method) are presented in TABLE A-l:

TABLE A-l ExampleWater ContentDkModulus of ElasticityElongation atBreak ~%] [barrer] [MPa] [%]
A-5 32 77 0.5 360 A-6 23.8 110 t.1 160 A-7 19.5 110 0.6 130 A-8 30.9 81 0.3 300 About 10.0 grams of macromer from Example A-1 are dissolved in 3.3 grams of ethanol ~Fluka, puriss. p.a.). After complete homogenization of the solution, about 4.0 grams of 3-tris(trimethylsiloxy)silylpropyl methacrylate (TRIS, from Shin-Etsu, product no. KF-2801), CA 022386~0 1998-0~-26 about 5.9 9. freshly distilled dimethylacryiamide (DMA), about 0.1 9. Blemer~) QA (a methacrylate having quaternary ammonium sllhstitlJents, Linz Chemie) and about 100 mg of photoinitiator Darocu~ 1173 (Ciba) are added. The solution is filtered through a TEFLON membrane having a pore width of 0.45 mm under an argon pressure of from about 1 to2atm.

The filtered solution is frozen in a flask in liquid nitrogen, the flask is ev~ul~t~d under a high vacuum, and the solution is returned to room temperature with the flask sealed. This degassing operation is repeated twice. The flask containing the macromer/comonomer solution is then transferred into a glove box with an inert gas atmosphere, where the solution is pipetted into dust-free, polypropylene contact lens molds. The molds are closed, and the polymerization reaction is effected by UV irradiation, with simultaneous c~ossli"king.
The molds are then opened and placed in isopr~pyl alcohol, causing the resultant lenses to swell out of the molds. The lenses are extracted for about 24 hours with nearly continuous replenishing of isopropyl alcohol. Sl Ihse~uently, the lenses are dried under high vacuum.

The dried contact lenses are equilibrated in autoclave-resistant vials in phosphate-buffered physiological saline solution, and then autoclaved for 30 minutes at about t20 ~C. Physical measurement data for the autoclaved lens is presented below:

Dk ~barrer]: 93 water content [%~: 20.3%
modulus of elasticity [Mpa]: 0.96 Lenses are prepared in accordance with the procedures described in Example A-11, but are subsequent surface treated as follows. The dried lenses are transferred into a plasma coating apparatus wherein they are surface treated in a methaner'airr' mixture ("air', as used here, denotes 79% nitrogen and 2t % oxygen) for a period of about 5 minutes. Theapparatus and plasma treatment process have been disclosed by H. Yasuda in "Plasma Polyrnerizationn, Academic Press, Orlando, Florida ~1985~, pages 319 forward.

The plasma-treated contact lenses are e~ d in autoclave-resistant vials in phosphate-buffered physiological saline solution, and then autoclaved for 30 minutes at CA 022386~0 1998-0~-26 about 120~C. Physical measurement data for the plasma-coated autoclaved lens is presented below:
Dk [barrer]: 88 water content [%]: 21.8%
modulus of elasticity [Mpa]: 1.03 Lenses are prepared in accordance with the procedures described in Example A-5, but the mixture of comonomers has the following composition, in weight percentages:
Macromer of Example A-1: 60%
TRIS: 25%
DMA: 15%

Lenses are prepared in accordance with the procedures described in Example A-6, with the same comonomer composition, but the comonomers are dispensed into dust-free contact lens molds in ambient air atmosphere.

EXAMPL~ B-1 Reaction of o~,a)-bis-aminopropyl-dimethylpo!ysiloxane with D(+)gluconic acid d-lactone:

Before the reaction, the amino-functionalized polydimethylsiloxane employed for the synthesis (X-22-161-C, Shin Etsu, JP) was finely dispersed in acelor,il-i!c, extracted and then subjected to molecular di~lillalion.

The following reactions take place with exclusion of H20. 200g of purified amino-functionalized polydimethylsiloxane (0.375meq of NH2/g; Mn(VPO) 3400-3900 (VPO, Vapour Pressure Osmometry)), dissolved in 200 ml of absolute THF, are slowly added dropwise to a suspension of 13.35g (75 mmoJ) of D(~)gluconic acid d-lactone in 50ml of absolute THF and the mixture is stirred at 40~C for about 24 hours until the lactone has reacted completely. (Monitoring of the reaction by thin layer chromatography ~TLC): silica gel; i-propanol/H20/ethyl acetate 6:3:1; staining with Ce(lV) sulfate/phosphoromolybdic acid CA 022386~0 1998-0~-26 solution (CPS reagent)). After the reaction, the reaction solution is concentrated to dryness and the residue is dried under 3 Pa ~0.03 mbar) for 48 hours. 213.3 g of a,c3-bis(3-gluconamidopropyl)-poly-dimethylsiloxane are obtained. Titration of the amino groups with perchloric acid shows a conversion of the amino groups of more than 99.8%.

Reaction of oc,~-bis-3-~luconamidopro~yl-dimethylpolysiloxane with IEM:
The product obtained above (213.3 g) is dissolved in 800 ml of absolute THF and the solution is heated to 40~C with the addition of catalytic amounts of dibutyltin dilaurate (DBTDL).14 g (90 mmol) of IEM in 20 ml of absolute THF are added dropwise to this solution over a period of about 4 hours. This corresponds to a concentration of 1.2 equivalents of IEM per gluconamide unit. The reaction is carried out in the course of 48 hours (monitoring of the reaction by IR spectroscopy detection of the NCO ties). The reaction solution is concentrated and the product is dried in a brown glass flask under 3 Pa (0.03mbar) for 24 hours, while cooling with ice. 227.2 g of a colourless rubber-elastic product of high optical transparency remain.

EXAMPLE B-2 to B-7 Further amino propyl-dimethylpolysiloxanes (PDMS) are reacted with a different amount of gluconolactone and concenl-~tions of IEM analogously to Example B-1. The examples are summarized in Table B-l TABLE B-l Poly(dimethyl siloxane) [PDMS] Amount of batch ExampleName TypeMn NH2* PDMS Glu IEM
g(mmol g (mmol)g (mmol) of NH2) B-1 X-22-161-C term. 3400 2 200 13.4 14.0 (90.0) (75) (75) B-2 X-22-161 -C term. 3400 2 200 13.4 25.7 (74) (75) (165.0) B-3 X-22-161 -C term. 3400 2 200 13.4 29.2 (75) (75) (187.5) B-4 PS 813 pen.1200 CA 022386~0 1998-0~-26 B-5 GP 4 pen. 3150 2.6 B-6 GP 6 pen. 5960 3 B-7 KF 8003 pen. 9700 4.7 20017.5 18.2 ~98) ~98) (11 7.4) Leqend:

X-22-161-C and KF 8003 are products from Shin Etsu (Japan), PS813 is a product from Petrarch-H Is, GP4 and GP6 are products from Genesee.
* Amino groups per macromer chain Glu:D(~) gluconic acid d-lactone term: terminal pen: pendent The reaction is carried out in accordance with Example B-1, but instead of D(+)gluconic acid d-lactone, 75mmol of lactobionic acid 1,5-lactone, suspended in 50 ml of absolute Tl IF, are added dropwise to a solution of amino-functionalized polydimethylsiloxane (X-22-1 61-C) in 180 ml of absolute THF and 20 ml of DMSO (pure, 99%). Titration of the amino groups with perchloric acid indicates a reaction conversion of 99% (c0.01 meq of NH 2/g). Here also, a colourless optically clear macromer is obtained.

EXAMPLE B-9 and B-10 The reactions are carried out analogously to Example B-1. However, the catalyst necessary for addition of the isocyanate onto the hydroxyl groups is varied. Instead of DBTDL, catalytic amounts of 1,4-diazabicyclo[2.2.23cctane (DABCO) or 4-dimethylamino-pyridine (DMAP) are added and the reaction is continued as described under Example B-1. In both cases, an optically clear, colourless rubber-elastic macromer results in a manner corresponding to Example B-1.

The reaction is carried out analogously to Example B-1. In a manner corresponding to Example B-8, 0.1 mol of lactobionic acid 1 ,5-lactone is suspended in ~0 ml of absolute THF

CA 022386~0 1998-0~-26 and the suspension is added dropwise to a solution of amino-functionalized polydimethylsiloxane (KF-8003) in 180 ml of absolute THF and 20 ml of DMSO (pure, 99%).
The reaction time is increased to about 48 hours. A residual content of 0.07meq of NH 2/g can be detected, and is reacted completely by addition of the corresponding molar amount of D(~)gluconic acid d-lactone to the reaction solution. The colourless highly transparent product has a residual content of amino groups of c0.01 meq/g.

62.09 g (9.78 mmol) of purified amino-functionalized polydimethylsiloxane (X-22-161-C, Shin Etsu JP), dissolved in 110 ml of absolute THF, are initially introduced into the reaction vessel under an inert gas atmosphere, and 1.14g (6.52 mmol) of D-glucaro-1,4:6,3-dilactone, dissolved in 20 ml of ~hSolute THF, are added. The reaction solution is stirred at room temperature for 15 hours and then worked up in a manner correspondZng to Example B-1. The amine content is 0.134meq/g. The terminal amino groups of the resulting penta-block macromer are reacted with gluconolactone in the following reaction step. 41.84 g (5.146 meq of NH2) of the above macromer and 0.917g (5.15 mmol) of D(~)gluconic acid d-lactone are suspended in 300ml of absolute THF and the suspension is stirred under nitrogen at 40~C for 18 hours. The filtered solution is then concentrated and the residue is dried under 3 Pa (0.03mbar) for 48 hours. A highly viscous optically clear substance having a residual content of amino groups of 0.013 meq/g results.

Preparation of an amino- and perfluoroalkyl-functionalized polydimethylsiloxane:3.0 ml of absolute toluene are added to 15 g of poly(dimethylsiloxane-co-methylhydrosiloxane) [Bayer Silopren U-230; 10,000 g/mol; 2.3mmol of Si-H/g], and 1.72 g (9.2mmol) of allylphthalimide ~CAS Reg. No. 5428-09-1] are then added. The mixture is frozen several times and the flask ev~cu;~ted and then brought to room temperature again.
The flask is then let down with argon. 0.7ml of a 0.005 molar solution of Lamoreaux catalyst (prepared in accordance with US 3,220,972, General Electric) in ~hsolute toluene (lOOppm of Pt~mol of Si-H~ is added and the mixture is heated to 80~C. After a reaction time of half an hour, a colourless, clear to slightly cloudy solution, the 1H-NMR spectrum of which no longer shows resonances of allylic hydrogen atoms, is obtained.

CA 022386~0 1998-0~-26 Thereafter, 6.2 g (15.3 mmol) of degassed allyl 1H,1H,2H,2H-perfluorooctyl ether are slowly added and the mixture is stirred at 80~C for 2 hours. A tH-NMR spectrum now shows a severely weakened resonance of the Si-H function at 4.6ppm and an intense resonance at 0.5 ppm, which originates from Si-CH 2 hydrogen atoms.

3.0 ml of 1-hexene are then added in order to react the remaining excess of Si-H groups, which could otherwise cause crosslinking of the polymer when air later has ~ccess. The mixture is further stirred at 80~C for another half an hour. The reaction mixture is then left to stand overnight. The product is purified over a silica gel column with hexane/ethyl acetate (3:2), the solvent is stripped off and the macromer is dried under a high vacuum. A
colourless, clear, viscous product is obtained. The macromer purified in this way is taken up in 20 ml of hexane, 20 ml of methylamine [33% in ethanol] are added and the mixture is heated to 40~C. After 10-15 minutes, a white voluminous precipitate separates out. After 30 minutes, the suspension is cooled and filtered and the precipitate is washed with a little hexane. The filtrate is evaporated and the residue is then dried under a high vacuum.
Thereafter, the content of amino groups is determined by titrimetry (perchloric acid).

The resulting macromer is clear and viscous. The amino group content is 78.6% of theory.
The total yield of macromer after the chromatographic purification is 75%.

Preparation of a gluconamide:
17.3 g (corresponding to an amine content of 5.4 meq) of this aminoalkyl-sl~hstitllted product are dissolved in 20 ml of dried THF. The solution is repeatedly frozen, degassed and let down with argon. All the following operations are carried out in an argon atmosphere. 712 mg of D(+)-gluconic acid d-lactone (4mmol) are then added. Because of the low solubility of the lactone, a suspension is initially obtained. After stirring overnight at 50~C, the solution is clear and the lactone has been used completely. The stoichiometric remaining amount of D(~)-gluconic acid d-lactone (260mg, 1.46mmol) is then added and the ~ mixture is stirred again at 50~C overnight. A trace of unreacted lactone is observed.
Completion of the reaction is monitored by means of thin layer chromatography on silica gel plates with the mobile phase 1-propanol/ethyl acetate/water (6:1:3). The silica gel plates are developed by means of Ce(lV) sulfate/phosphoromolybdic acid solution. S-lhsequent titration on amino groups yields a residual amino content of < 0.1%. After filtration and "

CA 022386~0 1998-0~-26 removal of the solvent by distillation, a highly viscous clear macromer with 0.295 mequivalent of gluconamide per gram of macromer is obtained.

Before the polymerization, the acrylates employed, isobutyl acrylate (IBA), N,N-dimethylacrylamide (DMA) and 3-methacryloyloxypropyl-tris(trimethylsilyloxy)silane (TRIS) are each freed from inhibitors by distillation. 0.32g (2.76mmol) of IBA, 0.80g (8.1 mmol) of DMA and 1.44g (3.4mmol) of TRIS are weighed into a 50ml round-bottomed flask and the flask is flushed with N2 for half an hour, while cooling with ice.1.44g of macromer from Example B-1 are transferred to a round-bottomed flask with a nitrogen attachment, degassed under 3 Pa (0.03mbar) for 24 hours and then dissolved in 2.7 g of ethanol which has been flushed with N2 for half an hour beforehand. The subsequent preparation of samples and the polymerization are carried out inside a glove box with exclusion of oxygen.
The above monomer mixture and the macromer solution from Example B-1 are mixed, with the addition of 0.012g (0.21 mmol) of Darocur~ 1173 and the mixture is subjected to micr~filL~lion (0.45 mm filter).180,ul of this mixture are introduced into a polypropylene mould, which is then closed with an appropriate lid of polypropylene. The mixture is then irradiated with a UV-A mercury high pressure lamp in a nitrogen atmosphere in a UV oven equipped for this for 5 minutes. The lamps (5 each of the brand TLK40W/lOR, Philips) are above and below the holder inserted. The irradiation intensity is 14.5mWlcm2.

The polypropylene mould is opened and the finished discs or lenses are removed by soaking by means of a solvent mixture of methylene chloride and ethanol (2:3). The lenses and discs are extracted in ethanol at room temperature in special polypropylene cages for 48 hours and then dried at 40~C under 10Pa (O.lmbar) for 24 hours (autoclaving at 120~C, 30 minutes). The discs show an E modulus of 1.1 MPa, a permeability to oxygen of 183 barrier and a hardness (Shore A) of 53.

EXAMPLE B-15 to B-19 Further polymers are prepared in a manner corresponding to Example B-14 (composition in percentages by weight). Table B-ll shows examples B-1 ~i to B-19 and the propertles of the resulting materials measured on discs.

CA 022386~0 1998-0~-26 TABLE B-ll Ex.Water Macro- Macro- DMA DMEA TRIS E Dk Content mer from mer weight weight weightmodulus~barrer]
[%] Example weight percentpercent percent [Mpa]
percent B-15not mea- B-3 32.8 - 30 37.2 sured B-1619.9 B-3 32.9 34.3 - 32.7 0.7 84 B-1725.1 B-3 39.3 34.3 - 36.4 0.9 72 B-1817.5 B-3 35.7 34.3 - 30.0 0.7 100 B-1923.4 B-3 33.3 33.3 - 33.4 0.7 96 Legend:
DMA: N,N-Dimethylacrylamide TRIS: 3-Methacryloyloxypropyl-tris(trimethylsilyloxy)silane DMEA: 2-Dimethylaminoethyl acrylate Uncoated contact lens A contact lens is prepared in a manner corresponding to Example B-14, using the Example B-3 macromer, with the following composition in percentages by weight:

Macromer: 33.3 DMA: 33 3 TRIS: 33.4 The lens has a Dk of about 94 and a water content of about 20.0 weight percent. The results are presented in TABLE B-lll for comparision with coated lens properties.

CA 022386~0 1998-0~-26 WO 97n~019PCT/IB96/01368 Piasma-treated contact lens Dried lenses prepared in accordance with the procedures described in Example B-20 are transferred into a plasma coating apparatus where the lenses are surface treated in a methaner'air" mixture ~"air", as used here, denotes 79% nitrogen and 21% oxygen). The apparatus and plasma treatment process have been disclosed by H. Yasuda in "Plasma Polymerization", Academic Press, Orlando, Florida (t985), pages 319 forward.

The dried plasma-treated contact lenses are e~uilibrated in autoclave-resistant vials in phosphate-buffered physiological saline solution, and then autoclaved for 30 minutes at about 120~C. The plasma-treated autoclaved lens has a Dk [barrer3 of 90 and a water content of 21.5%. The results are presented in TABLE B-lll for comparision with coated lens properties.

TABLE B-lll Example Surface type Dk [barrer]Water content [%]
B-20 untreated 94 20.0 ~3-21 plasma-treated 90 21.5 The synthesis of this polymer corresponds to Example B-1~ with the following comonomer composition: Example B-3 macromerfrFslS/DMA: 32.8%/32.6~/~134.2% (in percentages by weight) and an addition of 0.4% by weight of trimethylammonium-2-hydroxypropyl methacrylate hydrochloride (Blemer~) QA, Nippon Oil Corp.). The polymer has a modulus of 0.9MPa and a permeability to oxygen of 82 barrer. The water content is 25.1% (after 30 minutes' autoclaving at 1 20~C). For comparison, Example B-16 has a water content of 20%
with a very similar comonomer composition (no addition of Bleme~ QA).

The polymer is prepared analogously to Example B-14, but the polymerization is carried out in bulk, which means without addition of ethanol. The composition of the comonomers and the material properties of the polymer synthesized, measured on discs is given below.

CA 022386~i0 1998-0~i-26 Example B-7 macromer: 41 %
IBA: 23%
1 -vinyl-2-pyrrolidone (NVP): 24%
acrylonitrile (AN): 12%

Hardness (shore A): 68 The polymerization is carried out in accordance with Example B-14 but with the following changed comonomer composition:
macromer of Example B-7/lBA/TRlS 20~Joll 9%/60% and 1 % (in percentages by weight) of bis(3-methacryloyloxypropyl)tetra methyldisiloxane.

An optically clear polymer with an E modulus of 0.4MPa, a permeability to oxygen of 241 barrer and a hardness (Shore A) of 42 is obtained.

EXAMPLES B-25 through B-27 Contact lenses are prepared in acco.l~ance with the procedure described in Example B-14.
The compositions in weight percentages are as follows:

ExampleMacromerMacromerIBA weight DMA TRIS HFBA
weight percent weight weight weight percent percent percentpercent B-25 B-3 36.0 8.0 20.0 36.0 B-26 B-2 35.0 5.0 20.0 35.0 5.0 B-27 B-3 32.8 - 30.0 37.2 where IBA is isobutylacrylate, DMA is N,N-Dimethylacrylamide TRIS is 3-methacryloyloxypropyl-tris(trimethylsiloxy) silane HFBA is 2,2-3,4,4,4-hexafluorbutylester CA 022386~0 1998-0~-26 The polymerization is carried out in accordance with Example B-14 but with the following changed comonomer composition: macromer of Example B-1/DMA/TRIS 33.3% / 33.3% /
33.3%. An optically clear polymer is obtained.

Macromer Synthesis In a dry box under nitrogen atmosphere, about 200 grams of dry PDMS dipropoxyethanol (Shin-Etsu) is added to a container. Isocyanatoethyl methacrylate (IEM) in an amount equal to about 2 moles per mole PDMS dialkanol is added to the container. About 0.1 weight percent dibutyltin dilaurate (DBTL) catalyst, based on PDMS dialkanol weight, is added to the container along with a stir bar. The container is immersed in an oil bath atop a stir plate, and secured in place with a clamp. A stream of UPC air at about 2 psig is passed over the mixture. The mixture is agitated at room temperature (about 22~C) for about 24 hours. An iterative procedure follows in which the mixture is analyzed for isocyanate content and IEM
is added if the PDMS dialkoxyalkanol has not been completely reacted. The mixture is stirred about 24 hours more. The macromer produced is a siloxane-containing macromer.

Lens fabrication A prepolymerization mixture is prepared by mixing about 56 grams of the macromer from Example C-1, about 14 grams of TRIS, about 29 grams N,N-dimethylacrylamide (DMA), about 1 gram methacrylic acid, about 0.5 grams Darocu~) 1173 photoinitiator, and about 20 grams hexanol. The mixture is ~git?~te~ for about 20 minutes at room temperature.

Next, the mixture is degassed via a series of freezing and thawing steps. The container is placed in a liquid nitrogen bath until the mixture solidifies. A vacuum is applied to the container at a pressure of about 200 millitorr or less for about 5 minutes. Then, the container is placed in a bath of room temperature water until the mixture is liquld again.
This process is performed a total of three times.

The mixture is then polymerized to form contact lenses. The prepolymerization mixture is poured into polypropylene contact lens molds in a nitrogen atmosphere. The polymerization is effected by applying UV radiation (about 4-6 mW/cm2) for a period of about 15 minutes.

CA 022386~0 l998-0~-26 wo 97/22019 PCTIIB96/01368 The resulting fully hydrated contact lens has a water content of about 23%. The lens has a Dk of about 115 barrers and a modulus of elasticity of about 2 MPa.

Lens fabrication A contact lens is prepared in accordance with the procedure described in Example C-2, with the difference being that the composition is about 50% macromer of Example C-1, about 20% TRIS and about 30% DMA.

The resulting fully hydrated contact lens has a water content of about 20%. The lens has a Dk of about 118 barrers and a modulus of elasticity of about 1.8 Mpa.

Material A
A contact lens is prepared substantially in accordance with the procedure described in Example A-10. Prior to polymerization, nitrogen gas is bubbled through the prepolymer mixture in order to remove oxygen from the prepolymer mixture.

The prepolymer mixture is cured in a nitrogen atmosphere to form the contact lens. The cured lens has an equilibrium water content of about 26 weight percent. No coating is applied to the surface.

The lonoton lon Permeability Coefficient of the lens is - 0.063 x 10 3 cm21sec. Clinical examination shows that the lens does not move on the human eye. See Table E for a summary of the results.

Material A
A contact lens is prepared substantially in accordance with the procedure described in Example A-12. Prior to polymeri~tll;on, the prepolymerization mixture is degassed by cooling the prepolymer mixture with liquid nitrogen until the mixture solidifies and is near liquid nitrogen temperature, then applying a vacuum (about 0.1 mm Hg) to the solidified prepolymer mixture, disconLil1uing the vacuum, and thawing the prepolymer mixture until the CA 022386~0 l998-0~-26 mixture is again in liquid form. This degassing procedure is performed a total of three times on the prepolymerization mixture.

The prepolymer mixture is cured in a nitrogen atmosphere to form the contact lens. The cured lens has an equilibrium water content of about 30 weight percent. Subsequent to curing, the lens is plasma treated for about 3 minutes in an atmosphere of methane and air at a 2:1 CH4:air volume:volume ratio. The working pressure of the gas is about 50 millitorr.
The plasma treatment is accomplished in a Plasma Polymerization Apparatus LCVD-20-400A ~Plasmacarb, Bedford, Massachusetts~.

The lonoton lon Permeability Coefficient of the lens is 0.50 x 1 O-3 cm2/sec. Clinical examination shows that the lens moves on the human eye. See Table E for a summary of the results.

Material A
A contact lens is prepared substantially in accordance with the procedure described in Example A-12. Prior to polymerization, the prepolymeri~alion mixture is degassed by the repeated freeze/thaw procedure of Example E-2.

The prepolymer mixture is cured in a nitrogen atmosphere to form the contact lens. The cured lens has an equilibrium water content of about 30 weight percent. Subsequent to curing, the lens is plasma treated for about !~ minutes in an atmosphere of methane and air at a 2 1 CH4:air volume ratio.

The lonoton lon Permeability Coefficient of the lens is 0.47 x 10 3 cm2/sec. Clinical examination shows that the lens moves on the human eye. See Table E for a summary of the results.

EXAMP~ E E-4 Material A
A contact lens is prepared substantially in accordance with the procedure described in Example A-12. Prior to polymerization, the prepolymerization mixture is degassed by the repeated freeze/thaw procedure of Example E-2.

CA 022386~0 1998-0~-26 The prepolymer mixture is cured in a nitrogen atmosphere to form the contact lens. The cured iens has an equilibrium water content of about 30 weight percent. Subsequent to curing, the lens is plasma treated for about 7.5 minutes in an atmosphere of methane and air at a 2:1 CH4:air volume ratio.

The lonoton lon Permeability Coefficient of the lens is 0.35 x 10-3 cm2/sec. Clinical examination shows that the lens moves on the human eye. See Table E for a summary of the results.

Material A
A contact lens is prepared substantially in accordance with the procedure described in Example A-11. Prior to polymerization, the prepolymerization mixture is degassed by the repeated freeze/thaw procedure of Example E-2.

The prepolymer mixture is cured in a nitrogen atmosphere to form the contact lens. The cured lens has an equilibrium water content of about 30 weight percent. The lens is not subsequently coated.

The lonoton lon Permeability Coefficient of the lens is 1.1 x 10-3 cm2/sec. Clinical examination shows that the lens moves on the human eye. See Table E for a summary of the results.

Material B
A contact lens is prepared substantially in accordance with the procedure described in Example B-21. Prior to polymerization, the prepolymerization mixture is degassed by the repeated freeze/thaw procedure of Example E-2.

The prepolymer mixture is cured in a nitrogen atmosphere to form the contact lens.
Subsequent to curing, the lens is plasma treated for about 5 minutes in an atmosphere of methane and air at a 2:1 CH4:air volume ratio.

CA 022386~0 l998-0~-26 Wo 97/22019 pcTlIs96/ol368 The lonoton lon Permeability Coefficient of the lens is 2.9 x 10-3 cm2/sec. Clinical examination shows that the lens moves on the human eye. See Table E for a summary of the results.

Material B
A contact lens is prepared substantially in accordance with the procedure described in Example B-21. Prior to polymerization, the prepolymerization mixture is degassed by the repeated freeze/thaw procedure of Example E-2.

The prepolymer mixture is cured in a nitrogen atmosphere to form the contact lens.
Subsequent to curing, the lens is plasma treated for about 7.5 minutes in an atmosphere of methane and air at a 2:1 CH4:air volume ratio.

The lonoton lon ~ermeability Coefficient of the lens is 0.25 x 10-3 cm2/sec. Clinical examination shows that the lens moves on the human eye. See Table E for a summary of the results.

Material B
A contact lens is prepared substantially in accordance with the procedure described in Example B-20. Prior to polymerization, the prepolymerization mixture is degassed by the repeated freeze/thaw procedure of Example E-2.

The prepolymer mixture is cured in an air atmosphere to form the contact lens. Subse~uent to curing, the lens is not surface treated.

The lonoton lon Permeability Coefficient of the lens is 0.008 x 10-3 cm2/sec. Clinical examination shows that the lens does not move on the human eye. See Table E for a summary of the results.

CA 022386~0 l998-0~-26 WO 97/22~19 PCT/IB96/01368 Material C

A contact lens is prepared substantially in accordance with the procedure described in Example C-2. Prior to polymerization, the prepolymerization mixture is degassed by the repeated freeze/thaw procedure of Example E-2. The prepolymer mixture is cured in a nitrogen atmosphere to form the contact lens. Subsequent to curing, the lens is not surface treated.

The lonoton lon Permeability Coefficient of the lens is 1.4 X 10-3 cm2/sec. Clinical examination shows that the lens moves on the human eye. See Table E for a summary of the results.

Material C

A contact lens is prepared substantially in accordance with the procedure described in Example C-2. Prior to polymerization, the prepolymerization mixture is degassed by the repeated freeze/thaw procedure of Example E-2. The prepolymer mixture is cured in a nitrogen atmosphere to form the contact lens. Subsequent to curing, the lens is plasma treated for about 7.5 minutes in an atmosphere of methane and air at a 2:1 CH4:air volume ratio.

The lonoton lon Permeability Coefficient of the lens is 0.61 X 1t)-3 cm2/sec. Clinical examination shows that the lens moves on the human eye. See Table E for a summary of the results.

Material C

A contact lens is prepared substantially in accordance with the procedure described in Example C-2. Prior to polymerization, the prepolymerization mixture is degassed by the repeated freeze/thaw procedure of Example E-2.

CA 022386~0 1998-0~-26 WO 97/22019 PCT/IE~96/01368 The prepolymer mixture is cured in a nitrogen atmosphere to form the contact lens.
Subsequent to curing, the lens is plasma treated for about 5 minutes in an atmosphere of methane and air at a 2:1 CH4:air volume ratio.

The lonoton lon Permeability Coefficient of the lens is 1.5 x 10-3 cm2/sec. Clinical examination shows that the iens moves on the human eye. See Table E for a summary of the results.

Material C

A contact lens is prepared substantially in accordance with the procedure described in Example C-2. Prior to polymerization, the prepolymerization mixture is degassed by the repeated freeze/thaw procedure of Example E-2. The prepolymer mixture is cured in an air atmosphere to form the contact lens. Subsequent to curing, the lens is not surface treated.

The lonoton lon Permeability Coefficient of the lens is -0.001 x 10 3 cm2/sec. Clinical examination shows that the lens does not move on the human eye. See Table E for a summary of the results.

TABLE E
Ex. Mate- Degassing Curing Surface lonoton lon On-eye rial atmos- treatment Permeability Movement phere CH4:airCoefficient plasma[10 3 cmZ/sec]
~minutes]
E-1 Anitrogen nitrogen no plasma -0.063 NO
bubble E-2 A 3-cycle nitrogen 3 0.50 YES
freeze/thaw E-3 A 3-cycle nitrogen 5 0.47 YES
freeze/thaw CA 022386~0 1998-0~-26 E-4 A 3-cycle nitrogen 7.5 0.35 YES
freeze/thaw E-5 A3-cycle nitrogenno plasma 1.1 YES
freeze/thaw E-6 B3-cycle nitrogen 5 2.9 YES
freeze/thaw E-7 B3-cycle nitrogen 7.5 0.25 YES
freeze/thaw E-8 B3-cycle air no plasma 0.008 NO
freeze/thaw E-9 C3-cycle nitrogenno plasma 1.4 YES
freeze/thaw E-l 0 C3-cycle nitrogen 7.5 0.~1 YES
freeze/thaw E-11 C3-cycle nitrogen 5 1.5 YES
freezelthaw E-12 C3-cycle air no plasma -0.001 NO
freezelthaw Considering Examples E-l through E-12 of Table E, the lowest value of lonoton lon Permeability Coefficient for which a lens moves on the eye is 0.25 x 10-3 cm2/sec. The highest value of lonoton lon Permeability Coefficient for a lens which bound on the eye is 0.008 x 10 3 cm2/sec. Thus, a contact lens preferably has an lonoton lon Permeability Coefficient greater than about 0.008 x 10-3 cm2/sec., more preferably greater than about 0.25 x 10-3 cm2/sec.

Material B
~ A contact iens is prepared suL,~l~nlially in accordance with the procedure described in Example B-25. Prior to surface treatment, the lonoflux lon Permeability Coefficient is determined to be about 0 mm 2/min.

.
CA 022386~0 l99X-0~-26 Subse~uent to ion permeability measurements, the lens surface is coated with polyvinylpyrrolidone (PVP) in accordance with the following procedure, using a glass plasma reactor equipped with an external ring electrode and a 27.13 MHz radio frequency (RF) generator for the generation of an inductively-coupled, cold glow discharge plasma.
Highly purified argon is used as a plasma gas and as a carrier gas for N-vinylpyrrolidone (NVP) monomer feed. The NVP feed line is located about 10 cm below the glow zone.

The contact lens is placed in the 20 cm diameter plasma reactor at a position about 15 cm below the plasma glow zone. The reactor is then evacuated for about 30 minutes to about 0.009 mbar. Subquent to evacuation, the plasma gas flow is set to 20 sccm (standard cubic centimeters), the glow discharge is started at a pressure of about 0.15 mbar and maintained for about one minute at a power of about 170 Watts (in order to clean and activate the lens surface). ~fter reduction of argon plasma gas flow to about 10 sccm, the argon carrier gas flow for the NVP monomer is also set to 10 sccm. The temperature of the NVP source (with the carrier gas bubbling through the liquid NVP) is held at about 40~C. The lenses are treated for about 10 minutes with a pulsing glow discharge plasma (1 ,usec. on, 3 ,usec. off) at about 0.35 mbar pressure and about 150 Watts power.

After interrupting the glow discharge and the carrier gas flow, the reactor is continuously purged with a 20 sccm argon stream at a pressure of about 0.009 mbar for about 30 minutes, in order to remove residual monomer and activated species. The PVP coated contact lenses thus produced are highly wettable and show the following dynamic contact angles, measured with a KRUESS (Hamburg, Germany) K-12 instrument:

Untreated Treated - Advancing 102 38 Receding 48 23 Hysteresis 53 15 Clinical tests show that the lens does not move on the eye. See Table F for a summary of the results.

CA 022386~0 1998-0~-26 WO g7/22019 PCTIIB96/01368 Material B
A contact lens is prepared substantially in accordance with the procedure described in Example B-26. Prior to surface treatment, the lonoflux lon Permeability Coefficient is determined to be about 2.8 x 10-' mm2/min. Subsequent to ion permeability measurements, the lens surface is coated with polyvinylpyrrolidone as in Example F-1. Clinical tests show that the lens does not move on the eye. See Table F for a summary of the results.

EXAI~APLE F-3 Material B
A contact lens is prepared substantially in accordance with the procedure described in Example B-27. Prior to surface treatment, the lonoflux lon Permeability Coefficient is determined to be about 9.3 x 10 7 mm2/min. Subsequent to ion permeability measurements, the lens surface is coated with polyvinylpy".li:'one as in Example F-1. Clinical tests show that the lens does not move on the eye. See Table F for a summary of the results.

Material B
A contact lens is prepared substantially in accordance with the procedure described in Example B-18. Prior to surface treatment, the lonoflux lon Permeability Coefficient is determined to be about 2.6 x 10 4 mm2/min.

Subsequent to ion permeability measurements, the lens surface is coated with polyvinylpy"c'i :'ane as in Example F-1. Clinical tests show that the lens moves on the eye.
See Table F for a summary of the results.

Material B
A contact lens is prepared substantially in accordance with the procedure described in Example B-16. Prior to surface treatment, the lonoflux lon Permeability Coefficient is del,a,l" ned to be about 1.3 x 10-5 mm2/min. Subsequent to ion permeability measurements, the lens surface is coated with polyvinylpyrrolidone as in Example F-1. Clinical tests show that the lens moves on the eye. See Table F for a summary of the results.

WO 97/~2019 PCT/IB96/~11368 Material B
A contact lens is prepared substantially in accordance with the procedure described in Example B-19. Prior to surface treatment, the lonoflux lon Permeability Coe~Ficient is determined to be about 2.7 x 10 5 mm2fmin. Subsequent to ion permeability measurements, the lens surface is coated with polyvinylpyrrolidone as in Example F-1. Clinical tests show that the lens moves on the eye. See Table F for a summary of the results.

~XAMPLE F-7 Material B
A contact lens is prepared substantially in accordance with the procedure described in Example B-17. Prior to surface treatment, the lonoflux lon Permeability Coefficient is deterrnined to be about 7.8 x 10 ~ mm2/min. Subsequent to ion permeability measurements, the lens surface is coated with polyvinylpyrrolidone as in Example F-1. Clinical tests show that the lens moves on the eye. See Table F for a summary of the results.

Material A
A contact lens is prepared s~b:,la~,liatly in accordance with the procedure described in Example A-13. Prior to surface treatment, the lonoflux lon Permeability Coefficient is determined to be about 1.5 x 10 ~ mm2/min.

Subsequent to ion permeability measurements, the lens surface is coated with polyvinylpyrrolidone as in Example F-1. Clinical tests show that the lens does not move on the eye. See Table F for a summary of the results.

Material A
A contact lens is prepared substantially in accordance with the procedure described in Example A-14. Prior to surface treatment, the lonoflux lon Permeability Coefficient is determined to be about 1.1 x 10 ~ mm2/min. ~S~ Ihse-luent to ion permeability measurements, the lens surFace is coated with polyvinylpyrrolidone as in Example F-1. Clinical tests show that the lens does not move on the eye. See Table F for a summary of the results.

CA 022386~0 1998-0~-26 Material A
A contact lens is prepared substantially in accordance with the procedure described in Example A-7. Prior to surface treatment, the lonoflux lon Permeability Coefficient is ~ determined to be about 3.8 x 10-6 mm2/min. Subsequent to ion permeability measurements, the lens surface is coated with polyvinylpyrrolidone as in Example F-1. Clinical tests show that the lens moves on the eye. See Table F for a summary of the results.

Material A
A contact lens is prepared substantially in accordance with the procedure described in Example A-6. Prior to surface treatment, the lonoflux lon Permeability Coefficient is determined to be about 8.5 x 10-6 mm2/min. Subsequent to ion permeability measurements, the lens surface is coated with polyvinylpyrrolidone as in Example F-1. Clinical tests show that the lens moves on the eye. See Table F for a summary of the results.

Material A
A contact lens is prepared substantially in accordance with the procedure described in Example A-~. Prior to surface treatment, the lonoflux lon Permeability Coefficient is determined to be about 7.1 x 10 ~~ mm2/min.

Subsequent to ion permeability measurements, the lens surface is coated with polyvinylpyrrolidone as in Example F-1. Clinical tests show that the lens moves on the eye.
See Table F for a summary of the results.

TABLE F
EXAMPLE MATERIAL IONOFLUX ION ON-EYE
(Example reference PERMEABILITY MOVEMENT-number) COEFFICIENT~ CLINICAL
[mm2/minl DETERMINATION

F-2 B-26 0.28 x 10~ NO

CA 022386~0 l998-0~-26 WO 97/22~19 PCT/IB96/01368 F-3 B-27 0.93x 10~ NO
F~ B-18 2.6 x 10 B YES
F-5 B-16 13.0 x 10~ YES
F-6 B-19 27.0 x 10~ YES
F-7 B-17 7.8 x 10~ YES
F-8 A-13 1.5 x 10~ NO
F-9 A-14 1.1 x 1O6 NO
F-10 A-7 3.8 x 10~ YES
F-11 A-6 8.5 x 10~ YES
F-12 A-5 71.0 x 10~ YES
* All lonoflux lon Permeability Coefficients were determined on uncoated lenses.
Considering only Examples F-1 through F-12 of Table F, the lowest value of lonoflux lon Permeability Coefficient for which a lens moves on the eye is 2.6 x 10~ mm2/min. The highest value of lonoflux lon Permeability Coefficient for a lens which binds on the eye is 1.5 x 1 o~6 mm2/min. Thus, a contact lens preferably has an lonoflux lon Permeability Coefficient greater than about 1.5 x 10~ mm2/min., more preferably greater than about 2.6 x 10~ mm2/min.

A contact lens is prepared substantially in accordance with the procedure described in Example A-5. The Hydrodell Water Permeability Coefficient is determined to be about 1.09 x 10~ cm2/second. Clinical tests show that the lens moves on the eye. See Table G for a summary of the results.

A contact lens is prepared substantially in accordance with the procedure described in Example A-6. The lens is surFace treated in a plasma gas in accordance with the procedure described in Example F-1. The Hydrodell Water Permeability Coefficient is determined to be about 0.27 x 10~ cm2/second. Clinical tests show that the lens moves on the eye. See Table G for a summary of the results.
;

CA 022386~0 1998-0~-26 A contact lens is prepared suLwlallLially in accordance with the procedure described in Example B-19. The lens is surface treated in a plasma gas in accordance with theprocedure described in Example F-1. The Hydrodell Water Permeability Coefficient is determined to be about 0.37 x 10~ cm2/second. Clinical tests show that the lens moves on the eye. See Table G for a summary of the results.

A contact lens is prepared substantially in accordance with the procedure described in Example C-2. The Hydrodell Water Permeability Coefficient is determined to be about 1.26 x 1 o~6 cm2/second. Clinical tests show that the lens moves on the eye. See Table G for a summary of the results.

A contact lens is prepared substantially in accordance with the procedure described in Example B-14. The Hydrodell Water Permeability Coefficient is determined to be about 0.08 x 10 6 cm2/second. Clinical tests show that the lens does not move on the eye. See Table G for a summary of the results.

TABLE G
EXAMPLE MATERIAL SURFACE HYDRODELL ON-EYE
(Example TREATMENT WATER MOVEMENT-reference PERMEABILITY CLINICAL
number) COEFFICIENT DETERMINATION
[cm2/sec.]
G-1 A-5 none 1.09 x 10-6 YES
G-2 A-6 PVP 0.27 x 10~ YES
G-3 B-19 PVP 0.37 x 1 o~6 YES
G-4 C-2 none 1.26 x 10~ YES
G-5 B-14 none 0.08 x 10-6 NO
.

Considering only Examples G-1 through G-~ of Table G, the lowest value of Hydrodell Water Permeability Coefficient for which a lens moves on the eye is 0.27 x 10-6 cm2/sec.

CA 022386~0 1998-0~-26 The highest value of Hydrodell Water Permeability CoeKicient for a lens which binds on the eye is 0.08 x 10 6 cm2/sec. Thus, a contact lens preferably has a Hydrodell Water Permeability Coefficient greater than about 0.08 x 10~ cm2/sec., more preferably greater than 0.27 X10~ cm2/sec.

EXAMPLE l-1 A polymerizable mixture containing about 25 weight percent Material B macromerl about 25% TRIS and about 25% dimethylacrylamide (DMA) is prepared with about 25% ethanol solvent and Darocur 1173 photoinitiator.

The polymerizable mixture is subjected to a freeze-thaw process in order to remove oxygen before polymerization. The freeze-thaw process is accomplished by (a) cooling the prepolymer mixture in a container by applying liquid nitrogen until the mixture solidifies, (b) applying a vacuum (about 0.1 mm Hg) to the solidified polymerizable material, (c) d;sconli"uing the vacuum, (d) sealing the container, and (e) thawing the prepolymer mixture until the mixture is again in liquid form. This cycle is performed a total of three times on the polymerizable material.

Before the polymerizable material is introduced into the double-sided polypropylene mold, a glove box is prepared by evacuating and then filling with nitrogen. The degassedpolymerizable mixture is then introduced into the front curve mold half in a glove box. Next, the base curve mold half is mated with the front curve mold half. The polymerizable mixture is cured in a glove box by applying 15 mW ultraviolet light for a period of about 5 minutes.

This process yields a contact lens having an oxygen trans~" s ~ "~y of 87 barrers/mm and an lonoflux Diffusion Coefficient of 3.5 x 10 4 mm2/min. See Table I for comparative results.

E~(AMPLE 1-2 A polymerizable mixture is prepared as in Example l-1. The mixture is subjected to a freeze-thaw degassing process as in Example 1-1. The degassed mixture is cast into a contact lens in accordance with the glove box procedure of Example 1-1 by applying 8 mW
ultraviolet light for a period of about 20 minutes. This process yields a contact lens having CA 022386~0 l998-0~-26 an oxygen transmissibility of 104 barrers/mm and an lonoflux Diffusion Coefficient of 3.5 x 104 mm2/min. See Table I for comparative results.

A polymerizable mixture is prepared as in Example 1-1. The mixture is subjected to a freeze-thaw degassing process as in Example 1-1. The degassed mixture is cast into a contact lens in accordance with the glove box procedure of Example 1-1 by applying 8 mW
ultraviolet light for a period of about 10 minutes. This process yields a contact lens having an oxygen transmissibility of 95 barrers/mm and an lonoflux Diffusion Coefficient of 4.1 X 104 mm2/min. See Table I for comparative results.

A polymerizable mixture is prepared as in Example 1-1. The mixture is subjected to a freeze-thaw degassing process as in Example l-1. The degassed mixture is cast into a contact lens in ambient atmosphere by applying 8 mW ultraviolet light for a period of about 15 minutes. This process yields a contact lens having an oxygen trans",issibility of 97 barrers/mm and an lonoflux Diffusion Coefficient of 2.0 x 10~ mm2/min. See Table I for comparative results.

A polymerizable mixture is prepared as in Example l-1. The mixture is subjected to a freeze-thaw degassing process as in Example l-1. The degassed mixture is cast into a contact lens in ambient atmosphere by applying 8 mW ultraviolet light for a period of about 30 minutes. This process yields a contact lens having an oxygen transmissibility of 85 barrers/mm and an lonoflux Diffusion Coefficient of 2.2 x 10~ mm2/min. See Table I for comparative results.

EXAMPLE l-6 A polymerizable mixture is prepared as in Example 1-1. The mixture is subjected to a freeze-thaw degassing process as in Example l-1. The degassed mixture is cast into a contact lens in ambient atmosphere by applying 15 mW ultraviolet light for a period of about 5 minutes. This process yields a contact lens having an oxygen trans",.ssiL,ility of 93 barrers/mm and an lonoflux Diffusion Coefficient of 1.9 x 1 O4 mm2/min. See Table I for comparative results.

CA 022386~0 1998-0~-26 A polymerizable rnixture is prepared as in Example 1-1. The mixture is subJected to a freeze-thaw degassing process as in Example 1-1. The degassed mixture is cast into a contact lens in ambient atmosphere by applying 15 mW ultraviolet light for a period of about 10 minutes. This process yields a contact lens having an oxygen transmissibility of 96 barrers/mm and an lonoflux Diffusion Coefficient of 1.6 x 1 O4 mm2/min. See Table I for comparative resullts.

A polymerizable rrlixture is prepared as in Example 1-1. The mixture is degassed by applying a vacuum via the conventional laboratory technique of tap water aspiration for a period of about 20 minutes. The degassed mixture is cast into a contact lens in ambient atmosphere by applying 8 mW ultraviolet light for a period of about 15 minutes.

This process yields a contact lens having an oxygen transmissibility of 94 barrers/mm and an lonoflux Diffusion Coefficient of 1.6 x 1oJ' mm2/min. See Table I for comparative results.

A polymerizable mixture is prepared as in Example 1-1. The mixture is degassed by applying a vacuum via the conventional laboratory technique of tap water aspiration for a period of about 20 minutes. The degassed mixture is cast into a contact lens in ambient atmosphere by applying 8 mW ultraviolet light for a period of about 30 minutes. This process yields a contact lens having an oxygen transmissibility of 94 barrers/mm and an lonoflux Diffusion Coefficient of 1.3 x 104 mmZ/min. See Table I for comparative results.

A polymerizable mixture is prepared as in Example 1-1. The mixture is degassed by applying a vacuum via the conventional laboratory technique of tap water aspiration for a period of about 20 minutes. The degassed mixture is cast into a contact lens in ambient atmosphere by applying 8 mW ultraviolet light for a period of about 60 minutes. This process yields a contact lens having an oxygen transmissibility of 96 barrers~mm and an lonoflux Diffusion Coefficient of 0.9 x 10~ mm2/min. See Table I for comparative results.

CA 022386~0 l998-0~-26 _ 99 _ EXAMPLE l-1 1 A polymerizable mixture is prepared as in Example 1-1. The mixture is degassed by bubbling nitrogen through the mixture for a period of about 30 minutes. The degassed mixture is cast into a contact lens in ambient atmosphere by applying 8 mW ultraviolet light for a period of about 15 minutes. This process yields a contact lens having an oxygen transmissibility of 91 barrers/mm and an lonoflux Diffusion Coefficient of 1.6 x lQ~
mm2/min. See Table I for comparative results.

EXAMPLE l-1 2 A polymerizable mixture is prepared as in Example 1-1. The mixture is degassed by bubbling nitrogen through the mixture for a period of about 30 minutes. The degassed mixture is cast into a contact lens in ambient atmosphere by applying 8 mW ultraviolet light for a period of about 30 minutes. This process yields a contact lens having an oxygen transmissibility of 94 barrers/mm and an lonoflux Diffusion Coefficient of 1.1 x 10 mm2/min. See Table I for comparative results.

TABLE I
Ex. Material Casting UV Cure Oxygen Degas/ lonoflux Diff.
Degass,. ,9 Conditionsintensity Time Trans. Cast Coeff.
Method lmW3 [min.] [bar.t:r/u.. n] Category [x 10 ' mm2/min.]

freeze-thaw glove box 15 5 87 1 3.5 2freeze-thaw glove box 8 20 104 1 3.5 3freeze-thaw glove box 8 10 95 1 4.1 4freeze-thaw .~.. o~ hel~ 8 15 97 2 2.0 5freeze-thaw ~I"-ospha~e 8 30 85 2 2.2 6freeze-thaw ~ . .o:.~,l .e. ~, 15 5 93 2 1.9 7freeze-thaw at.-,o:,l,hur~ 15 10 96 2 1.6 < 8aspirator ~ll.. los,ul,e,~: 8 15 94 3 1.6 9~ ,llor ~ ~ ,.osphe,e 8 30 94 3 1.3 10~ - ~lor ~I."oipl-a,e 8 60 96 3 0.9 11bubble N2 t.l",os,~l)elt 8 15 91 4 1.6 12bubble N2 ~ u~ullt:-~ 8 30 94 4 1.1 CA 022386~0 1998-0~-26 Table I shows that a freeze-thaw degassing procedure produces a higher lonoflux Diffusion Coefficient than the aspirator or nitrogen purge techniques. The freeze-thaw technique is more rigorous, and produces a mixture having a lower oxygen concentration. Accordingly, lower oxygen concentrations in the polymerizable mixture result in higher ion permeability in the cured contact lens. Furthermore, the correlation between ion permeability and on-eye movement was established in prior Examples. Thus, a lower oxygen concentration in the polymerizable mixture produces a contact lens having a better on-eye movement.

Similarly, the glove box curing technique produced a high ion permeability, and hence better on-eye movement, than the atmosphere curing techni~ues. Accordingly, in order toproduce a lens having a balance of high oxygen permeability and good on-eye movement, it is highly preferred to polymerize a siloxane-containing methacrylate macromer with an --acrylamide monomer in the absence or substantial absence of oxygen.

A polymerizable mixture conlai"ing about 50 weight percent Material A macromer, about 20% TRIS, about 25.5% dimethylacrylamide (DMA), and about Q.5% BLEMER QA, is prepared, with all percentages based on total polymerizable mixture weight. Ethanol is added as a solvent at about 22.4% and about 0.5% Darocur 1173 is added as a photoinitiator, with percentages based on total mixture weight.

The mixture is subjected to a freeze-thaw degassing process as described in Example 1-1.
The degassed mix~ure is cast into a contact lens in accordance with the glove box procedure of Example 1-1 by applying 15 mW ultraviolet light for a period of about 5 minutes.

This freeze-thaw/glove box process yields a contact lens having an oxygen transmissibility of 96 barrers/mm and an lonoflux Diffusion Coefficient of 3.5 x 10~ mm2/min. See Table J
for comparative results.

A polymerizable mixture is prepared as in Example J-1. The mixture is subjected to a freeze-thaw degassing process as described in Example 1-1. The degassed mixture is cast into a contact lens in accordance with the glove box procedure of Example l-1 by applying 8 . .

CA 022386~0 1998-0~-26 mW ultraviolet light for a period of about 20 minutes. This freeze-thaw/glove box process yields a contact lens having an oxygen transmissibility of 116 barrers/mm and an lonoflux Diffusion Coefficient of 4.1 x 104 mm2/min. See Table J for comparative results.

A polymerizable mixture is prepared as in Example J-1. The mixture is subjected to a freeze-thaw degassing process as described in Example 1-1. The degassed mixture is cast into a contact lens in accordance with the glove box procedure of Example 1-1 by applying 8 mW ultraviolet light for a period of about 10 minutes.

This freeze-thaw/glove box process yields a contact lens having an oxygen transmissibility of 118 barrers/mm and an lonoflux Diffusion Coefficient of 3.8 x 104 mm2/min. See Table J
for comparative results.

A polymerizable mixture is prepared as in Example J-l. The mixture is subjected to a freeze-thaw degassing process as described in Example 1-1. The degassed mixture is cast into a contact lens in an ambient atmosphere by applying 8 mW ultraviolet light for a period of about 15 minutes. This process yields a contact lens having an oxygen ll~nsl".ssiL,ilily of 111 barrers/mm and an lonoflux Diffusion Coefficient of 0.06 x 104 mm2/min. See Table J
for comparative results.

A polymerizable mixture is prepared as in Example J-~. The mixture is subjected to a freeze-thaw degassing process as described in Example 1-1. The degassed mixture is cast into a contact lens in an ambient atmosphere by applying 8 mW ultraviolet light for a period of about 30 minutes. This process yields a contact lens having an oxygen trans",issibility of 114 barrers/mm and an lonoflux Diffusion Coefficient of 0.09 x 104 mm2/min. See Table J
for comparative results.

A polymerizable mixture is prepared as in Example J-1. The mixture is subjected to a freeze-thaw degassing process as described in Example 1-1. The degassed mixture is cast into a contact lens in an ambient atmosphere by applying 15 mW ultraviolet light for a CA 022386~0 1998-0~-26 period of about 5 minutes. This process yields a contact lens having an lonoflux Diffusion Coefficient of 0.25 x 10~ mm2/min. See Table J for comparative results.

r A polymerizable mixture is prepared as in Example J-1. The mixture is subjected to a freeze-thaw degassing process as described in Example 1-1. The degassed mixture is cast into a contact lens in an ambient atmosphere by applying 15 mW ultraviolet light for a period of about 10 minutes.

This process yields a contact lens having an oxygen transl"issiL,iiiLy of 90 barrers/mm and an lonoflux Diffusion Coefficient of 0.47 x 10~ mm2/min. See Table J for comparative results.

A polymerizable mixture is prepared as in Example J-1. The mixture is subjected to an aspirator degassing process as described in Example l-8. The degassed mixture is cast Into a contact lens in an ambient atmosphere by applying 8 mW ultraviolet light for a period of about 15 minutes. This process yields a contact lens having an oxygen liilnsmissil,ility of 98 barrers/mm and an lonoflux Diffusion Coefficient of 0~31 x 10~ mm2/min. See Table J
for comparative results.

A polymerizable mixture is prepared as in Example J-1. The mixture is subjected to an aspirator degassing process as described in Example 1-8. The degassed mixture is cast into a contact lens in an ambient atmosphere by applying 8 mW ultraviolet light for a period of about 30 minutes.
This process yields a contact lens having an oxygen trans,l,issil,ilil~ of 93 barrers/mm and an lonoflux Diffusion Coefficient of 0.31 x 10~ mm2/min. See Table J for comparative results.

A polymerizable mixture is prepared as in Example J-1. The mixture is subjected to an aspirator degassing process as described in Example 1-8. The degassed mixture is cast into a contact lens in an ambient atmosphere by applying 8 mW ultraviolet light for a period CA 022386~0 l998-0~-26 Wo 97/22019 PCT/IB96/~1368 of about 60 minutes. This process yields a contact lens having an oxygen transmissibility of 9~ barrers/mm and an lonoflux Diffusion Coefficient of 0.19 x 10~ mm2/min. See Table J
for comparative results.
.

EXAM~L~ J-1 1 A polymerizable mixture is prepared as in ~xample J-1. The mixture is subjected to a nitrogen bubbling degassing process as described in Example l-8. The degassed mixture is cast into a contact lens in an ambient atmosphere by applying 8 mW ultraviolet light for a period of about 1~ minutes.

This process yields a contact lens having an oxygen trans",issiL.ilily of 119 barrers/mm and an lonoflux Diffusion Coefficient of O.O9 x 10~ mm2/min. See Table J for comparative results.

A polymerizaible mixture is prepared as in Example J-1. The mixture is subjected to a nitrogen bubbling degassing process as described in Example l-8. The degassed mixture is cast into a contact lens in an ambient atmosphere by applying 8 mW ultraviolet light for a period of about 30 minutes. This process yields a contact lens having an oxygen transmissibility of 1 18 barrers/mm and an lonoflux Diffusion Coefficient of 0.16 x 10 4 mm2/min. See Table J for comparative results.

TABLE J
Ex.MaterialCasting UV Cure Oxygen Degas/lonoflux Diff.
Deg~ss;. ,gConditions intensity Time Trans. Cast Coeff.
Method ~mW] lmin.][bar,~ "1"3Category[x 10~
mm2/min.]

freeze-thawglove box 15 5 96 1 1.6 . 2freeze-thawglove box 8 20 116 1 4.1 3freeze-thawglove box 8 10 118 1 3.8 4freeze-thaw~t,.-o:,~uh~nd 8 15 111 2 0.06 5freeze-thaw~ l ,e, t, 8 30 114 2 0.09 6freeze-thaw,ox~-here 15 5 2 0.25 7freeze-thawllt.l.os,~he,t:15 10 90 2 0.47 .

CA 022386~0 l998-0~-26 WO 97/22019 PCTtIB96/01368 8 aspirator atmosphere 8 15 98 3 0.~1 9 aspirator atmosphere 8 30 93 3 0.31 10 aspirator atmosphere 8 60 95 3 0.19 11 bubble N2 atmosphere 8 15 119 4 o.09 12 bubble N2 ~l-"~s,~ el~ 8 30 118 4 0.16 Table J shows that a freeze-thaw degassing procedure produces a higher lonoflux Diffusion Coefflcient than the aspirator or nitrogen purge techniques. As with Table 1, this data further illustrates that a lower oxygen concentration in the polymerizable mixture produces a contact lens having a better on-eye movement.

A similar conclusion may be drawn from a comparison of the glove box curing technique to the atmosphere curing technique. Accordingly, in order to produce a lens having a balance of high oxygen permeability and good on-eye movement, it is highly preferred to polymerize a siloxane-containing methacrylate macromer with an acrylamide monomer in the absence or substantial absence of oxygen.

The invention has been described in detail, with reference to certain preferred embodiments, in order to enable the reader to practice the invention without undue experimentation. Theories of operation have been offered to better enable the reader to understand the invention, but such theories do not limit the scope of the invention. In addition, a person having ordinary skill in the art will readily recognize that many of the previous components, compositions, and parameters may be varied or modified to areasonable extent without departing from the scope and spirit of the invention.
Furthermore, tities, headings, example materials or the like are provided to enhance the reader's comprehension of this document, and should not be read as limiting the scope of the present invention. Accordingly, the intellectual property rights to the invention are defined by the following claims, reasonable extensions and equivalents thereof, as interpreted in view of the disclosure herein.

Claims (20)

What is claimed is:

1. A process for the manufacture of a contact lens, comprising:
(a) providing a polymerizable material comprising:
(i) one or more macromers selected from the group consisting of siloxane-containing acrylate macromers and fluorine-containing acrylate macromers, and (ii) one or more hydrophilic comonomers selected from the group consisting of acrylamides, methacrylamides, N-vinyl pyrrolidones and mixtures thereof;
(b) removing oxygen from said polymerizable material such that the concentration of oxygen in said polymerizable material is less than 500 ppm;
(c) instilling said polymerizable material into a contact lens mold; and (d) polymerizing said polymerizable material to form a contact lens.

2. A process of claim 1, wherein the concentration of oxygen in said polymerizable material is less than about 200 ppm.

3. A process of claim 2, wherein the concentration of oxygen in said polymerizable material is less than about 50 ppm.

4. A process of claim 3, wherein the concentration of oxygen in said polymerizable material is less than about 20 ppm.

5. A process of claim 1, wherein the contact lens has an lonoton lon Permeability Coefficient of at least 0.2 x 10-6 cm2/sec.

6. A process of claim 5, wherein the contact lens has an lonoflux Diffusiont Coefficient of at least 1.5 x 10-6 mm2/min.

7. A process of claim 6, wherein the contact lens has a Hydrodell Water Permeability Coefficient of at least 0.2 x 10-6 cm2/sec.

8. A process of claim 1, wherein said macromer has a structure of formula (I):

P1-(Y)m-(L-X1)p-Q-(X1-L)p-(Y)m-P1 (I) where each P1, independently of the others, is a free-radical-polymerizable group;
each Y, independently of the others, is -CONHCOO-, -CONHCONH-, -OCONHCO-, -NHCONHCO-, -NHCO-, -CONH-, -NHCONH-, -COO-, -OCO-, -NHCOO- or -OCONH-;
m and p, independently of one another, are 0 or 1;
each L, independently of the others, is a divalent radical of an organic compound having up to 20 carbon atoms;
each X1, independently of the others, is -NHCO-, -CONH-, -NHCONH-, -COO-, -OCO-,-NHCOO- or -OCONH-; and Q is a bivalent polymer fragment consisting of the segments:

(a) -(E)k-Z-CF2-(OCF2)x-(OCF2CF2)y-OCF2-Z-(E)k-, where x+y is a number in the range of from 10 to 30;
each Z, independently of the others, is a divalent radical having up to 12 carbon atoms or Z
is a bond;
each E, independently of the others, is -(OCH2CH2)q-, where q has a value of from 0 to 2, and where the link -Z-E- represents the sequence -Z-(OCH2CH2)q-; and k is 0 or 1;

where n is an integer from 5 to 100;
Alk is alkylene having up to 20 carbon atoms;
80-100% of the radicals R1, R2, R3 and R4, independently of one another, are alkyl and 0-20%
of the radicals R1, R2, R3 and R4, independently of one another, are alkenyl, aryl or cyanoalkyl; and (c) X2-R-X2, where R is a divalent organic radical having up to 20 carbon atoms, and each X2, independently of the others, is -NHCO-, -CONH-, -NHCONH-, -COO-, -OCO-,-NHCOO- or -OCONH-;
with the provisos that there must be at least one of each segment (a), (b), and (c) in Q, that each segment (a) or (b) has a segment (c) attached to it, and that each segment (c) has a segment (a) or (b) attached to it.

9. A process of claim 1, wherein said macromer has a structure comprising at least one segment of formula (I):

in which (a) is a polysiloxane segment, (b) is a polyol segment which contains at least 4 C atoms, Z is a segment (c) or a group X1, (c) is defined as X2-R-X2, wherein R is a bivalent radical of an organic compound having up to 20 C atoms and each X2 independently of the other is a bivalent radical which contains at least one carbonyl group, X1 is defined as X2, and (d) is a radical of the formula (II):

X3-L-(Y)k-P1 (II) in which P1 is a group which can be polymerized by free radicals;
Y and X3 independently of one another are a bivalent radical which contains at least one carbonyl group;
k is O or 1; and L is a bond or a divalent radical having up to 20 C atoms of an organic compound.

10. A process of claim 1, wherein said macromer has the structure:

where n is an integer from about 5 to about 500, R1, R2, R3, and R4, independently of one another, are lower alkylene, R5, R6, R7, and R8, independently of one another, are alkyl, R9 and R11 are alkylene, and R10 and R12 are methyl or hydrogen.

11. A process of claim 1, wherein said contact lens mold comprises a base curve mold half and a front curve mold half, and wherein the process further comprises the step of subjecting the mold halves to an inert atmosphere having an oxygen concentration of less than 100 ppm for a period of at least 4 hours.

12. A process of claim 11, wherein said contact lens mold comprises a base curve mold half and a front curve mold half, and wherein the process further comprises the step of subjecting the mold halves to an inert atmosphere having an oxygen concentration of less than 50 ppm for a period of at least 6 hours.

13. A process of claim 12, wherein said contact lens mold comprises a base curve mold half and a front curve mold half, and wherein the process further comprises the step of subjecting the mold halves to an inert atmosphere having an oxygen concentration of less than 20 ppm for a period of at least 8 hours.

14. A process of claim 1, wherein said polymerizable material comprises:
(i) a siloxane- and/or fluorine-containing acrylate macromer;
(ii) a monomer selected from the group of acrylamides and methacrylamides; and (iii) a siloxane-containing monomer having a carbon chain length of less than 20 carbon atoms.

15. A process of claim 14, wherein said acrylamide is dimethylacrylamide.

16. A process of claim 14, wherein said siloxane-containing monomer is TRIS.

17. A process of claim 13, wherein said polymerizable material comprises:
(i) about 30 to 60 weight percent siloxane- and/or fluorine-containing acrylate macromer;
(ii) about 20 to 40 weight percent monomer selected from the group of acrylamides and methacrylamides; and (iii) about 1 to 35 weight percent siloxane-containing monomer having a carbon chain length of less than 20 carbon atoms.

18. A process of claim 1, wherein the contact lens has an oxygen transmissibility of at least about 75 barrers/mm.

19. A process for the manufacture of a contact lens, comprising:
(a) providing a polymerizable material comprising:
(i) about 30 to 60 weight percent siloxane- and/or fluorine-containing acrylate macromer, (ii) about 20 to 40 weight percent monomer selected from the group of acrylamides and methacrylamides, and (iii) about 1 to 35 weight percent siloxane-containing monomer having a carbon chain length of less than 20 carbon atoms;
(b) removing oxygen from said polymerizable material such that the concentration of oxygen in said polymerizable material is less than 200 ppm;
(c) providing a contact lens mold comprising a base curve mold half and a front curve mold half (d) subjecting the mold halves to an inert atmosphere having an oxygen concentration of less than 100 ppm for a period of at least 4 hours;
(e) instilling said polymerizable material into said front curve mold half;
(f) mating said base curve mold half to said front curve mold half; and (g) polymerizing said polymerizable material to form a contact lens having an lonoflux Diffusiont Coefficient of at least 1.5 x 10-6 mm2/min. and an oxygen transmissibility of at least about 75 barrers/mm.

20. A contact lens formed by a process comprising the steps of:
(a) providing a polymerizable material comprising:
(i) a siloxane- and/or fluorine-containing acrylate macromer, and (ii) one or more hydrophilic comonomers selected from the group consisting of acrylamides, methacrylamide, N-vinyl pyrrolidones and mixtures thereof;
(b) removing oxygen from said polymerizable material such that the concentration of oxygen in said polymerizable material is less than 500 ppm;
(c) instilling said polymerizable material into a contact lens mold; and (d) polymerizing said polymerizable material to form a contact lens.