IMPROVED HYDROGEL CONTACT LENSES

Abstract: A hydrogel contact lens is disclosed which is formed from a hydrated lightly cross-linked copolymer of a monom­ er mixture comprising N-vinyl pyrrolidone (NVP) and a short chain alkyl acrylate or methacrylate in the weight ratio of from about 1.75:1 to 2.25:1, a short chain unsaturated carboxylic acid and a cross-linking monomer, the monomer mixture containing a majority of NVP and alkyl acrylate or methacrylate and having been polymerised using a chemical free radical initiator. The lens produced in accordance with the invention have high water content coupled with good mechanical properties.

Description: IMPROVED HYDROGEL CONTACT LENSES This invention relates to soft contact lenses of a kind which are formed from a hydrated lightly cross-linked copolymer. A large body of prior art exists which relates to the production of copolymer structures suitable for manufacture of contact lenses. For many years the contact lens industry has been striving to produce a contact lens polymer which when hydrated will possess good mechanical strength so that it can be handled normally without risk of damage, good oxygen transmission characteristics and the ability to be accurately machined or moulded into lens forms of desired variety. In practice, improvement in one property has tended to result in deterioration of one of the other properties listed above so that a compromise in these desired properties has had to be accepted. It has now been discovered that when a specially selected monomer mixture is polymerised under definelconditions, a copolymer can be produced which possesses the above properties in a highly desirable combination. According to the present invention, there is provided a soft hydrogel contact lens which is formed from a hydrated lightly cross-linked copolymer of a monomer mixture comprising N-vinyl pyrrolidone (NVP) and a short chain alkyl acrylate or methacrylate in the weight ratio of from about 1.75:1 to 2.25:1, a short chain unsaturated carboxylic acid and a cross-linking monomer, the monomer mixture containing a majority of N-vinyl pyrrolidone and alkyl acrylate or methacrylate and having been polymerised using a chemical, free radical initiator. In general, the short chain carboxylic acid is methacrylic acid (MA) or acrylic acid although other short chain acids containing up to five carbon atoms may be employed. Although the proportion of unsaturated acid which is present in the monomer composition is not critical so far as the upper limit is concerned, we normally prefer to use not more than 10% of the unsaturated acid. The water content of the lens increases with increasing amounts of acid and best results are obtained-when methacrylic or acrylic acid is used in an amount of from about 0.9 to 5% of acid. The main benefits of the present invention are obtained when the resulting copolymer is hydrated or treated prior to use in an alkaline aqueous solution. Preferably, the solution employed is a saline solution having a pH of about 7.4 to 9. Treatment of the copolymers with an aqueous alkaline solution as described in U.K. Patent No. 1,548,158 results in the formation of alkali metal or alkaline earth metal carboxylate groups by reaction with the free carboxylic groups in the copolymer. Preferably, the pH of the saline solution is raised by adding a sodium or potassium carbonate or bicarbonate but other salts which form alkaline solutions may be used as described in the above mentioned British Patent. This treatment results in a marked increase in the water content of the hydrated copolymers and also in their oxygen permeability. Short chain alkyl acrylates or methacrylates having up to about 5 to 6 carbon atars in the alkyl chain may be employed either as single monomers or mixtures of monaners. Preferably, however, either the whole or a substantial proportion of the alkyl acrylate or methacrylate consists of methyl acrylate or methyl methacrylate (MMA), or mixtures with alkyl acrylates and methacrylates in which the alkyl group contains 2 to 4 carbon atoms. For example, methyl acrylate or methacrylate admixed with up to about 30% of butyl acrylate or methacrylate may be advantageously used. Enhanced flexibility is obtained by incorporating a minor proportion, e.g. up to about 5%, of a higher alkyl methacrylate or acrylate, e.g. 2ethylhexyl methacrylate, in the alkyl acrylate or methacrylate compo- nent of the monaner mixture. A chemical polymerisation initiator is added to the monomer mixture to initiate polymerisation Irradiatiqn treatment, e.g. with a gamma ray source, either during or after polymerisation should be avoided since it has been found that such treatment adversely affects the mechanical properties of the final polymer. As initiator AIBN (Azobisisobutyronitrile) is preferred though other chemical free radical initiators may be employed. The proportion of chemical initiator used in the monomer compositions varies according to whether the copolymer is to be used for cast-moulded lenses or for producing larger buttons or work-pieces intended to be machined to finished size. In general, a larger proportion of initiator is necessary when moulding lenses directly from the monomer mixture. We prefer to employ a chemical initiator in an amount of from about .04 gms. of initiator per 100 gms. of monomer to about 1 gm. of initiator per 100 gms. of monomer. The reason for the difference in the amount of initiator employed is not completely understood but one reason maybe that the moulds employed for direct moulding or casting of lenses are commonly made from polypropylene which contains materials which inhibit polymerisation. In producing buttons or cylindrical work-pieces for machining lenses PTFE moulds are commonly employed. The copolymers of the present invention are particularly suitable for casting directly to lenses which then need only edge finishing and hydration to form the finished lens. In casting such lenses, we prefer to maintain the composition while in the polypropylene moulds in a nitrogen purged oven for about 20 to 24 hours at about 400C. thereafter, raising the temperature for about 1 hour to 800C and finally heating the lenses at 1200C in a vacuum oven for about 4 hours. In the case of moulded buttons or work-pieces a preferred polymerisation procedure is to introduce the monomer mixture containing the free radical initiator into suitably sized PTFE moulds and submerging these in a water bath held at about 550C for about 20 hours, followed by raising the temperature to 800C for about 2 hours. Finally, a cure oi about 1 hour at 1200C in a vacuum oven follows this treatment. The following Examples will illustrate the present invention: Example 1 A homogeneous casting mixture was prepared by thoroughly mixing together re-distilled methacrylic acid (3.22 gms.), purified methyl methacrylate (32.18 gms.) and N-vinyl pyrrolidone (64.37 gms.) together with allyl methacrylate (AMA) (.23 gms.). As chemical initiator AIBN was employed at the rate of .05 gms. per 100 gms. of monomer. The resulting mixture was degassed by application of a vacuum and was then added to PTFE moulds, sealed and immersed in a water bath for 20 hours at 55 0C followed by raising the temperature to 800C for 2 hours. The resulting buttons were removed from the mould and then heated for 1 hour at 1200C in a vacuum oven. Lenses were cut by lathing from the resultant buttons and the resulting lenses were hydrated by soaking in a sodium bicarbonatesaline solution at a pH of 7.4. The above procedure was then repeated except that the lenses were directly cast and cured by heating initially for 22 hours at 400C in a nitrogen purged oven followed by 1 hour at 800C in the same oven for 4 hours at 1200C. The properties including the water content refractive index and swell factors of the resulting lenses are shown in the following Table 1. In this Table "Dia" means Lens Diameter and "BC" means Base Curve, PROPERTIES OF CONTACT OF NEW POLYMERIC MATERIALS MADE FROM, NVP, MMA AND MA CROSSLINKED WITH 0.23% w/AMA ON MONOMERS (wt. Ratio NVP : MMA = 2:1). TABLE 1 EMI7.1 Polymer <SEP> MA <SEP> content <SEP> of <SEP> Swell <SEP> Factor <SEP> (21 C) <SEP> Refractive <SEP> index <SEP> Refractive <SEP> index <SEP> Water <SEP> content <SEP> (% <SEP> w/w <tb> <SEP> Lathed <SEP> lens <SEP> Moulded <SEP> lens <SEP> hydrated <SEP> (21 C) <SEP> dry, <SEP> &commat; <SEP> 25 C) <tb> Code <SEP> monomer <SEP> mixture <SEP> Lathed <SEP> Moulded <SEP> Lathed <SEP> Moulded <SEP> Lathed <SEP> Moulded <tb> <SEP> (% <SEP> w/w) <SEP> Dia. <SEP> BC <SEP> Lens <SEP> Lens <SEP> Lens <SEP> Lens <SEP> Lens <SEP> Lens <tb> EXAMPLE <SEP> 0.92 <SEP> 1.52 <SEP> 1.52 <SEP> 69.8 <tb> <SEP> 2 <tb> EXAMPLE <SEP> 1.04 <SEP> 1.53 <SEP> 1.52 <SEP> 70.2 <tb> <SEP> 3 <tb> EXAMPLE <SEP> 1.31 <SEP> 1.55 <SEP> 1.51 <SEP> 70.0 <SEP> 71.2 <tb> <SEP> 4 <tb> EXAMPLE <SEP> 2.27 <SEP> 1.56 <SEP> 1.62 <SEP> 1.60 <SEP> 1.381 <SEP> 1.379 <SEP> 1.520 <SEP> 70.9 <SEP> 74.6 <tb> <SEP> 5 <tb> EXAMPLE <SEP> 2.91 <SEP> 1.59 <SEP> 1.67 <SEP> 1.63 <SEP> 1.378 <SEP> 1.374 <SEP> 1.517 <SEP> 72.5 <SEP> 76.4 <tb> <SEP> 6 <tb> EXAMPLE <SEP> 3.22 <SEP> 1.61 <SEP> 1.68 <SEP> 1.65 <SEP> 1.376 <SEP> 1.374 <SEP> 1.519 <SEP> 73.4 <SEP> 76.7 <tb> <SEP> 1 <tb> The above procedure was repeated using the same relative proportions of NVP to MMA but varying the amount of methacrylic acid in the monomer mixture. The precise proportions are shown in the attached Table 2. Again, lenses were made by direct moulding and by lathing and the properties of these lenses are shown in Table 1. Water content is related to the oxygen permeability of the hydrogel polymers and in general the higher the water content, the greater the oxygen permeability. This is, however, not the only factor and two polymer hydrogels having the same water content may have different oxygen permeabilities. Table 3 shows in graphical form the relationship between the amount of methacrylic acid in the monomer mixture against the water content and the linear swell factor of the resulting hydrogels. As can be seen from this graph water contents in the range of 70 to 76% are obtained using methacrylic acid in amounts of about 1 to 3.5% of acid. MONOMER COMPOSITIONS (PARTS BY WEIGHT) TABLE 2 Example 2 Example 3 Example 4 Example 5 Example 6 Example 1 NVP 65.90 65.82 65.63 65.00 64.57 64.37 MMA 32.95 32.91 32.82 32.50 32.29 32.18 MA 0.92 1.04 1.31 2.27 2.91 3.22 AMA 0.23 0.23 0.24 0.23 0.23 0.23 100.00 100.00 100.00 100.00 100.00 100.00 TABLE 3 WATER CONTENT IN NaCl-NaHCO3 (ph 7.4) at 21 C (% w/w) RELATION OF MA MONOMER MIXTURE AND WATER CONTENT # AND SWELL # EMI10.1 MA in Monomers (% w/w) LINEAR SWELL FACTOR (21 C) The oxygen transmission characteristic of the polymers produced in Example 1 have been directly tested in the form of a contact lens having a centre thickness from about .06 to .3 mm. Such thicknesses cover a wide range of conventional thicknesses for contact lenses. The results of these tests, which were carried out using the procedure described by Hill and Fatt, indicate that the polymers of the present invention when formed into contact lenses exhibit a oxygen transmission rate which is exceptionally high and which when tested on a 0.06 mm. central thickness contact lens, was not significantly different from the situation where no lens was used. Such a result indicates that lenses made in accordance with the present invention could be safely worn for an extended period e.g. several months without removal. A graphical indication of the results of the oxygen transmission rate of the lens is shown in the attached Table 4 which is a graphical plot showing the percentage oxygen equivalent against centre thickness of the lens. It will be appreciated that 21% represents a condition where no lens is worn at all. TABLE 4 EQUIVALENT OXYGEN % EMI12.1 CENTRE THICKNESS (mm) Despite the very high oxygen permeability characteristics of the polymers in accordance with this invention they do show improved tensile strength as compared with conventional lenses. Thus, for example, the polymer produced in accordance with Example 4 of the present invention is compared in Table 5 below with a copolymer of methyl methacrylate and NVP cross-linked with the same amount of allyl methacrylate but containing no methacrylic acid. TABLE 5 MECHANICAL PROPERTIES (CAST SHEETS) Tear Strength Water Tensile (kg f cm-I Content Strength (InitiationI Sample ( w) (kg f cm 2) Propagation 1. Example 4 70 8.5 0.43/0.26 2. Copolymer of MMA and NVP (MMA/NVP 9 1:2.865 wt. ratio) cross-linked with 0.23% AMA on monomers 71 4.0 0.19/0.13 3. Polyhema cross linked with 0.5% EGDM 38 9.4 0.36/0.22 Material Samples 2 and 3 are polymers not in accordance with the invention and are for comparison. The improved mechanical properties of Sample 1 .(in accordance with the invention) over Sample 2 (no acid and larger proportion of NVP) are believed to be a consequence of the presence in Sample 1 of a higher concentration of reinforcing hydrophobic (MMA) domains. This comparative copolymer when hydrated under the same conditions contained 71% of water. As will be seen, the tensile strength of the Example 4 copolymer was over twice that of the comparative hydrated copolymer and there is a similar improvement in the tear strength of the material.

Claims: CLAIMS: 1. A soft hydrogel contact lens which is formed from a., hydrated lightly cross-linked copolymer of a monomer mixture comprising N-vinyl pyrrolidone (NVP) and a short chain alkyl acrylate or methacrylate in the weight ratio of from about 1.75 : 1 to 2.25 : 1, a short chain unsaturated carboxylic acid and a cross-linking monomer, the monomer mixture containing a majority of NVP and alkyl acrylate or methacrylate and having been polymerised using a chemical free radical initiator. 2. A lens according to claim 1 wherein the unsaturated carboxylic acid comprises from about 0.9 to 5% by weight of the monomer mixture. 3. A lens according to claim 2 wherein the acid is methacrylic or acrylic acid. 4. A lens according to claim 3 wherein the chemical initiator is employed in an amount of from about 0.04 to 1 gram per 100 grams of monomer. 5. A lens according to claim 1 wherein the crosslinking agent is present in the monomer mixture in an amount of up to 1% by weight. 6. A lens according to claim 5 wherein the crosslinking agent is allyl methacrylate. 7. A lens according to claim 1 wherein the copolymer contains alkali metal or alkaline earth metal carboxylate groups resulting from treating the copolymer with an aqueous solution having a pH greater than 7 and containing alkali metal or alkaline earth metal cations. 8. A lens according to claim 1 which has a water content of from 70 to 80%. 9. A method of producing a soft hydrogel contact lens which comprises preparing a polymerisation mixture comprising NVP and an alkyl acrylate or methacrylate, wherein the alkyl group contains from 1 to 4 carbon atoms, in the weight ratio of from about 1.75:1 to 2.25:1, 0.9 to 10% of an unsaturated carboxylic acid and up to 5% of a cross-linking monomer, inducing polymerisation of said mixture solely by means of a chemical free radical initiator and treating the resulting lens with an aqueous solution having a pH greater than 7 to convert free carboxylic acid groups to carboxylate groups.

Inventors: ATKINSON, IVOR B., HOLDSTOCK, BARRY C., KNOWLTON, JOHN L.
Applicants: COOPERVISION OPTICS LIMITED
Application year: 1983
Main classification: C08F226
IPC codes: C08F20, G02C7, C08F226, G02B1