EXTENDED-WEAR LENSES

Abstract: Extended-wear lenses formed by polymerizing an organosilicon monomer system, at least a portion of which is a hydroxyorganosilicon monomer, a fluoroorgano monomer, a hydrophilic monomer, and a crosslinking agent. A UV-absorbing agent is optionally present.

Description: EXTENDED- EAR LENSES Cross-Reference to Related Application This application is a continuation-in-part of application Serial No. 722,121, filed April 10, 1985, Background of the Invention The present invention is directed to eye-compatible lenses, particularly hard contact lenses having' excellent oxygen permeability and wettability. Contact lenses presently on the market are classi¬ fied into two large groups: soft contact lenses and hard contact lenses. Hard contact lenses are better able than soft contact lenses to retain visual characteristics, but are less comfortable. The art has sought to increase oxygen permeability of hard contact lenses, to extend the length of time they can be worn without causing corneal damage or discomfort. One proposed solution has been the formation of a copoly er of methyl ethacrylate and a siloxane methacry- late compound. This solution has been less than satis¬ factory, since the lenses offered are not as hard, rigid, nor wettable as lenses formed from poly ethyl methacryl¬ ate. In addition, such lenses are fragile and have poor mechanical processability. The object of the present invention is to' overcome the deficiencies in the state of the art by offering lenses having a high degree of oxygen permeability, excellent wettability, and, if desired, ultraviolet absorption. The primary benefit of UV absorptivity is the resistance to user development of cataracts. Summary of the Invention The present invention is directed to eye-compatible, oxygen-permeable lenses of excellent wettability, formed of copoly ers of an organosilicon monomer system which preferably comprises an organosilane or an organo- siloxane of the general formula: CH? * C - Ri OH I I (i COO-(CH -CH-CH 2 0) a —(CH 2 ) D -X wherein Rj is hydrogen or methyl, a is 0 or 1, b is from 1 to about 4, and X is an organosilicon moiety containing up to about 16 silicon atoms. At least a portion, and as much as 100 percent, of the organosilicon monomer system is a hydroxyorganosilicon monomer which is a monomer having at least one hydroxyl group bonded to silicon. Preferably from 0.1 to about 10 percent by weight of the monomers is a hydroxyorganosilicon monomer. A second component is a fluoroorgano monomer of the formula: CH 2 - C - Hi I (2 COO-(M) a -(CH 2 ) c -y wherein M^ is hydrogen, alkyl, fluoroalkyl, alkyl car¬ boxy, carboxy ester, alkyl carboxy ester, fluorinated carboxy ester, fluorinated alkyl carboxy ester, cyano, or phenyl, M is hydroxy alkyl, alkyl ether, or hydroxy alkyl ether, a is as defined above, c is from 0 to 4, and ϊ is a fluorocarbon group, preferably containing from about 2 to about 21 fluorine atoms. At least one hydrophilic monomer is included, prefer¬ ably an unsaturated carboxylic acid capable of inducing wettability, and is present in an amount sufficient to provide in the resultant polymer a receding contact angle of about 45° or less. Methacrylic acid is preferred. A UV-absorbing agent, if desired, may be included. In this instance, the UV-absorbing agent may be a UV- absorbing monomer, preferably a hydroxybenzophenone or a benzotriazole compound of the formula: wherein R^, a and b are as defined above, d is 1 or 2, and Z is: wherein R is hydrogen, alkyl or hydroxy. Alternately or in addition, the UV-absorbing monomer may be a benzo- triazole of the formula: wherein R and R are as defined above, and R3 is H or alkyl, preferably a C1-C10 alkyl. Alternately, UV- ' absorbing agents may be non-reactive ho opolymers and copolymers preferably containing the UV monomers which are added to the monomer system undergoing reaction, and which become physically entrained in the formed lens. A final component is a crosslinking monomer which is a crosslinking agent, preferably an organosilicon monomer, present in an amount up to about 5, preferably up to about 2, percent by weight based on the total weight of the monomers. It has been found that ' the total organosilicon- monomer content of the polymer may range from about 10 to about 40 percent by weight, preferably from about 15 to about 35 percent by weight based on the total weight of the monomers. The hydrophilic monomer may be present in an amount of from about 1 to about 15 percent by weight, preferably from about 2 to about 10 percent by weight based on the total weight of the monomers. The UV- absorbing agent if present, whether mono eric or not, may be present in an amount of from about 0.1 to about 20 percent, preferably from about 2 to about 10 percent by weight based on the total weight of the monomers and/or agent, and the crosslin ing monomer may be present in an amount up to about 2 percent by weight based on the total weight of the monomers. The balance of the monomer system may be solely the fluoroorgano monomers. It is desired -5- that the lens have a Shore D hardness greater than about 78, preferably from about 80 to about 85. There may be desirably included other monomers, such as acrylates, methacrylates, itaconic esters, styrenes, fluorinated styrenes, alkyl styrenes, fluorinated alkyl styrenes, and the like, present in a concentration of up to about 50 percent by weight of the concentration of the fluoro¬ organo monomer, typically up to about 5 percent by weight based on the total weight of the monomers which can effectively be used to modify properties such as hardness, machinability, wettability, oxygen permeability, and the like. It is desired to provide an oxygen permeability at 35°C greater than 50 x 10~ 11 (cm 2 /sec. ) (ml 0 2 /ml x mm Hg). When using low-cost fluoroorgano compounds such as 2,2,2-trifluoroethylmethacrylate, the organosilicon content of the monomer system must be high, typically in the range of from 25 percent to 30 percent or more by weight based on the total weight of the monomers. Organo- silicon monomer content can be advantageously reduced, however, by inclusion of high-performance fluoroorgano- monomers such as hexafluoroisopropyl esters of an unsaturated carboxylic acid containing from 2 to about 6 carbon atoms and 1 or 2 carboxyl groups, preferably hexa- fluoroisopropylmethacrylate. 6/04343 -6- Detailed Description The present invention is directed to eye-compatible, i.e., ocular-compatible, lenses, in particular, hard con- 5 tact lenses formed of an interpolymerized amount of an organosilicon monomer system containing at least one hydroxyorganosilicon monomer, at least one fluoroorgano compound, at least one monomeric unsaturated carboxylic acid hydrophilic monomer, and, if desired, a UV-absorbing 1° agent, which may be a monomer formed of a monomer which is a benzotriazole and/or benzophenone and at least one crosslinking monomer. Other reactive monomers such as acrylates, methacrylates, itaconic esters, styrenes, fluorinated styrenes, alkyl styrenes, fluorinated alkyl ■ 15 styrenes, and the like, may be included as part of the poϊymerizable composition, to achieve a lens of desired hardness for achinability, wettability, oxygen perme¬ ability, and the like, and can be present in an amount of up to about 50 percent by weight of the fluoroorgano 20 monomer content of the polymers. The organosilicon monomers which may be used in accordance with the instant invention include organo¬ silicon monomers which are organosilanes and/or organo- siloxanes of the general formula: 5 CH 2 = C - Ri I (1) COO-(CH 2 -CH0H-CH 2 0) a -(CH ) b -X wherein is hydrogen or methyl, a is 0 or 1, b is from 0 1 to about 4, and X is an organosilicon moiety containing up to about 26 silicon atoms. At least a portion or all of the organosilicon monomer system is a hydroxyorgano¬ silicon monomer, namely, a monomer having at least one hydroxyl group bonded to silicon. 5 Preferred organosilicon compounds are acrylates and methacrylates of the general formula: CH 2 - C - Ri I (2) C00(-CH -CHOH-CH 2 -0-) a -(CH 2 )5-X' R 4 R 6 R 6 wherein X' is -S Ii-(CH 2 ) D -SIi-R7 or -SIi-R7 , I I I R5 R 8 R 8 each of R4 and R5 is independently a C1-C5 alkyl, phenyl, hydroxyl, or -0-Si(CH3)3, and each of RQ , R7 and .Q is independently selected from C1-C5 alkyl; -CH =CH 2 ; phenyl; hydroxyl; -CH 0H; CH 3 CH 3 -0- Ii-0-Si(.CH ) ; -O-Ii-OH 0-Si-[OSi(CH3)3] 3 ; or H 2 -CHOH-CH 2 -0-) a -(CH 2 ) b - wherein Rj, a, and b are as defined above. /04343 -8- 1 The representative monomers included are: * tris(trimethylsiloxy)silylpropylmethacrylate, 1,3-bis(J(-methacryloxypropyl)-l,1,3,3-tetra(trimethyl- siloxy)disiloxane, * vinyl di(trimethylsiloxy)silylpropylmethacrylate, pentamethyldisiloxy-X'-methacryloxypropylsilane, trimethylsilylpropylmethacrylate, methyl di(trimethylsiloxy)silylpropylmethacrylate, and tris(trimethylsiloxy)silylpropylglycerolmethacrylate, and i0 the like. Tris(trimethylsiloxy)-ϊ-methacryloxypropyl- silane is presently preferred. Another important monomer" is 1,3-bis- -methacryloxypropyl)-l,1,3,3-tetra(trimethyl- siloxy)disiloxane, as it serves as a crosslinking agent without sacrificing oxygen permeability. When used for 15 this purpose, concentration may vary from about O.l ' to about 2 parts by weight based on the total weight of the reactants. Representative hydroxyorganosilicon monomers include hydroxy-di(trimethylsiloxy)silylpropyl methacrylate, 2° hydroxy-di(trimethylsiloxy)-y-methacryloxypropyl silane, hydroxy-methyl(trimethylsiloxy)methacryloxymethyl silane, hydroxy-methyK ' trimethylsiloxy)methacryloxyethyl silane, hydroxy-methyl(trimethylsiloxy)methacryloxypropyl silane, hydroxy-di(trimethylsiloxy)-£-methacryloxyethyl silane, 25 hydroxy-di(trimethylsiloxy)-methacryloxy methyl silane, hydroxy-(trimethylsiloxy)-(pentamethyIdisiloxy)-meth- acryloxy-methyl silane, hydroxy-(trimethylsiloxy)- (pentamethyldisiloxy)-y-methacryloxyethyl silane, and the like. Hydroxy-di(trimethylsiloxy)silylpropyl methacrylate 30 is preferred. Other useful organosilicon monomers are disclosed in U.S. Patents 4,152,508 to Ellis; 4,153,641 to Deichert et al; 4,189,546 to Deichert et al; and 4,463,149 to Ellis, each incorporated herein by reference. 35 While total concentrations of organosilicon monomers may range from about 10 to about 40 parts by weight based on the total weight of the monomers, the preferred range is from about 15 to about 35 parts by weight. Oxygen per meability (all other factors being constant) will increas with an increase in organosilicon monomer content. At higher levels, the lens becomes more difficult to machine requiring inclusion of monomers such as acrylates, eth- acrylates and the like, may be employed as part of the monomer system to yield a lens having a Shore D hardness greater than about 78, preferably from about 80 to about 85. Oxygen permeability and wettability of the lens is enhanced by the presence of the hydroxyorganosilicon monomer. Although the presently preferred concentration of the hydroxyorganosilicon monomer is from about 0.1 to about 10 percent by weight of the total monomer, it may be the exclusive organosilicon monomer, except for any multifunctional organosilicon monomer used as a crosslinking monomer. The fluoroorgano monomers utile in the practice of the instant invention are generally compounds of the formula: CH 2 « C - Mi I (3 COO-(M) a -(CH 2 ) c -Y wherein M^ is hydrogen, alkyl, fluoroalkyl, alkyl car¬ boxy, carboxy ester, alkyl carboxy ester, fluorinated carboxy ester, fluorinated alkyl carboxy ester, cyano, or phenyl, M is hydroxy alkyl, alkyl ether, or hydroxy alkyl ether, a is as defined above, c is from 0 to 4, and Y is a fluorocarbon group. Preferably, Y has the general formula: C n F2n+l °r C n F 2n H. High-performance fluorinated compounds are hexafluoroiso- propyl esters of unsaturated carboxylic acids containing from 2 to about 10 carbon atoms and 1 or 2 carboxyl groups. Illustrative of fluoroorgano monomers are: 2,2,2-trifluoroethylmethacrylate, hexafluorobutyl ethacrylate, hexafluoroisopropylmethacrylate, pentafluoro-n-propylmethacrylate, and the like. Hexafluoroisopropylmethacrylate is the preferred monomer for oxygen permeability, with 2,2,2-trifluoroethyl- methacrylate being preferred for cost. Perfluoro or fluorinated styrenes may also be used. Hydrophilic monomers are included in the composition to induce wettability. They preferably comprise an unsat^ urated carboxylic acid, most preferably methacrylic acid, for compatability of monomers and wearer comfort. Acrylic acid is functional but less desirable. Other monomers suc as 2-hydroxyethylmethacrylate, vinyl pyrrolidone, and the like may be used. Concentration may be from about 0.1 to about 15 or more percent by weighty preferably from about to about 10 percent by weight based on the total weight of the monomers. The amount of hydrophilic monomer present depends on whether a UV-absorbing agent, as described below, is employed, as the latter also has the capability of being hydrophilic. If a UV-absorbing agent is employed, whether in onomeric or polymeric form, its concentration may range from about 0.1 to about 20 percent by weight, pre- ferably from about 2 to about 10 percent by weight based on the total weight of the monomers and agent. The UV- absorbing agents used herein cooperate with the hydro¬ philic monomer to induce wettability and antisepticability i.e., self-sterilizable, in consequence of hydroxy-substi- tuted benzene moieties. In the polymerized state, the UV-absorbing agents absorb in the range of from about 300nm to about 450nm, preferably with no less than about 70% UV radiation at 370nm. Preferred UV-absorbing agents are, or are formed of, monomers of the formula: wherein R is hydrogen or methyl, a is 0 or 1, b is from about 1 to about 3, d is 1 or 2, and Z is; wherein R 2 is hydrogen; an alkyl, preferably a Cχ-Cs alkyl or hydroxyl, and c is 1 or 2. In the alternative or in addition, there may be employed a phenyl benzotriazole of the formula: wherein Rx and R are as defined above, preferably a Cχ~ Cχo alkyl, and R3 is H, alkyl, preferably a Cχ-Cχo alkyl, or hydroxyl. Preferred UV-absorbing monomers for forming agents include: 2-hydroxy-4-(2-methacryloyloxyethoxy)benzophenone, 2-hydroxy-4-(2-acryloyloxyethoxy)benzophenone, 2-hydroxy-4-(2-hydroxy-3-methacryloxypropyl)benzophenone, 2-(2-hydroxy-5-vinylphenyl)-2H-benzotriazole, and the like. They may be added to the monomer system and interpolymerized therewith, or added as part of the non-reactive homopolymers and copolymers which are added to the monomer system and are physically entrained in the final polymer formed. The hard contact lenses of the instant invention are formulated to have high oxygen permeability (Dk) of at least about 15 and preferably greater than 50, as expressed in units of 10 — ■ 1 L -1 L (cm Λ /sec. ) (ml 0 2 /ml x mm Hg) and as determined at 35°C. Values are achieved using high concentrations of the organosilicon monomer and/or selection of the fluoroorgano monomer. With compositions of high organosilicon-monomer content there are displayed increased brittleness and a reduction in capability to undergo machining. At least one crosslinking agent, such as a multi-functional organosilicon monomer, a fluoro¬ organo monomer, an acrylate and/or a methacrylate, is employed in an amount sufficient to control hardness of the lens in the range of Shore D hardness of from about 80 to about 85. A highly multi-functional organosilicon monomer is preferred, as it does not interfere with oxygen permeability. Other crosslinking agents which may be used include ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol- dimethacrylate, diethylene glycol diacrylate, and the like. Lens formation is by free radical polymerization such as azobisisobutyronitrile (AIBN) and peroxide catalysts under conditions set forth in U.S. Patent -13- 3,808,179, incorporated herein by reference. Colorants and the like may be added prior to monomer polymerization. It is preferred to form the lens base in sheet form between layers of a non-adherent surface. The sheet is cut into smaller lense precursors from which the lens is ground to user specifications. Spin-casting, as described for instance in U.S. Patent 3,408,429, incorporated herein by reference, may also be used. Without limiting, the following Examples are illus- trative.of the instant invention. With reference to the Examples, properties Of the contact lenses were measured according to the following methods. Oxygen permeability values were determined using a test method developed by Dr. Irving Fatt of Berkeley, California, and disclosed in the paper, entitled: "Oxygen Transmissibility and Permeability of Gas Permeable Hard Contact Lenses and Materials" by Irving Fatt, Ph.D., International Contact Lens Clinic, Vol. II, No. 3, March 1984. The instrument was a polarographic cell with a curved surface for finished lenses, polarographic amplifier, recorder and a constant temperature chamber equipped with a temperature control unit. The measure¬ ments were made at 35°C and the units of oxygen permea- bility (Dk) are (cm /sec. ) (ml 02/ml x mm Hg). The water wettability of the contact lense material was determined by the sesile drop method using a Rame- Hart goniometer with an environmental chamber. Both the advancing and the receding contact an._es were determined. The hardness was measured as Shore D at 22°C using a hardness tester, and percent light transmission was measured using a recording spectrophotometer. The absorption spectra of the copolymer were determined on a "Perkin Elmer" UV-Vis spectrophotometer. using 0.1-0.15mm-thin optically polished discs. The amount of materials extractable from the lenses were evaluated by first storing them in a saline solution for 10 days at 35°C. The lenses were then rinsed with -14- distilled water, dried, weighed, and placed in stoppered, 25cc volumetric flasks, again containing saline as the extracting medium. The saline was analyzed daily for its extracted ultraviolet absorber by placing 4cc of the extract in a spectrophotometer cell and determining the absorption at 320nm. The absorption values were compared against the calibration curve made for the pure ultravio¬ let absorber. Extractables can also be determined by the Soxhlet extraction * method, using water as the solvent. The amount of extractables was determined only for a few of the materials in the Examples. Based on 0.04 gr average lens weight, extractables were found, on the average, to be less than 1 x 10~4 mc grams/lens/day. For a few selected copolymer materials, the leacha- bility-diffusibility was evaluated by cytotoxicity assay- agar overlay method. The assay is based on the method described by Guess, W.L., Rosenbluth, S.A., Schmidt, B. , and Autian, J. , in "Agar Diffusion Method for Toxicity Screening of Plastics on Cultured Cell Monolayers" , J. Pharm. Sci. 54:1545-1547, 1965, incorporated herein by reference, and is designed to detect the response of a mammalian monolayer cell culture to readily diffusible components from materials or test solutions applied to the surface of an agar layer overlaying the monolayer. The response of the cell monolayer is evaluated, with respect to the discoloration of the red-stained mono¬ layer, under and around the sample when the petri dish is viewed against a white background. Loss of color of the stained cells is considered to be a physiologically sig¬ nificant reaction of the cells. The extent of discolora¬ tion is confirmed by examination of the monolayer on an inverted microscope,- and the extent of lysis of the cells within the discoloration zone is estimated. Typically, discoloration of cells precedes lysis, as manifested by a region and a region showing lysis. A sample-~ιs reported as "cytotoxic" only if lysis is observed. Examples 1-11 and Controls A-F Candidate lens compositions were formulated as shown in Table I. The mixture was homogenized, degassed and placed in a polymerization cell made of two glass plates separated by a seal and held together by spring clamps. After filling, the cell was purged with nitrogen, sealed and placed in a circulating water bath at 60 β C for 10 hours. After the initial polymerization period, the cell was heated at 80 β C for 3 hours, 100 β C for one hour, and then allowed to cool to room temperature. The clamps wer then removed and the transparent sheet heated for 2 hours at 100 β C. The plastic sheet, about 1/4-inch in thickness was cut into squares, then formed to discs which were used to prepare corneal contact lenses using conventional hard-contact-lens-making equipment. The properties of the lens materials are also shown in Table I. Of the controls. Control A was too brittle to be used as a functional lens, and brittleness was attributed to excessive organosilicon-monomer content. The brittle¬ ness of the remaining control was attributed to the level of silicon monomer employed and an excessive amount of a crosslinking and/or wetting monomer. Controls G-U Following the procedure of Examples 1-11, there were prepared a number of polymers of the formulations shown in Table II. Polymers of Controls G-0 and U failed because they could not retain their radius of curvature. Failure was attributed to too high an organosilicon- monomer content. Controls P-I were too brittle to be machinable. They shattered in the lathe. to to Oi OI o o Oi TABLE I Examples 1-11 and Controls A-F Examples 1-11 (parts hy weight) Reactant 10 11 Tris(Trimethylsiloxy)silylprcpylmethacrylate 26 9.5 19 29 17 17 17 19 19 17 17 l,3-bis(J-methacryloxypr pyl)-l,l,3,3-t tra(- .04 0.1 0.1 0.1 0.3 0.3 0.3 0.1 0.1 0.3 0.3 trimethylsiloxyldisiloxane Vinyl di(tr_jrnethyldiloxy)silylprrpylmBthacrylate • Pentamethyldisiloxy-y-methacryloxypropylsilane Hydroxy-<1i(trijτ>ethylsiloxy)silylproρylιw.thacrylate 3.6 0.4 0.9 0.9 2.7 2.7 2.7 0.9 0.9 2.7 2.7 2,2,2-trifluoroethylmethacrylate 85 75 65 73 73 73 75.5 75 Hexafluorobutylmethacrylate 75 Hexafluσroisopropyljnethacrylate 75 Meth lmethacryla e 55 I n-Butylmethacrylate H Cyclohexylmethacrylate 10 2 2-Bthylhexylmethacrylate 2 Methacrylic Acid 5 5 5 5 5 5 5 5 5 2 5 2-Hydroxyeth lmethacrylate 2 E hy1eneglycoldi ethacry1ate 0.5 AIBN 02 .02 .02 .02 .02 .02 .02 .02 .02 .02 .02 Properties Oxygen Permeability* 12 15 28 92 24 .24 24 42 234 24 24 Contact Angle, receding 28 23 25 28 25 25 25 26 28 22 Light Transmission T T T T T T T T T T Hardness 87 87 84 80 80 84 80 78 79 84 85 Others Cytotoxicity Assay N N N N N N T = transparent R = brittle N = negative * x I0 "1 1 (cm 2 /sec . ) (ml 0 inl x nm Hg) TABLE I (continued) Examples 1-11 and Controls A-F Controls A-F (parts by weight) Reactant Tris(Tri e hyIsiloxy)silylpropylmethacr late 44 19 8 29 l,3-bis(J"-methacryloxypropyl)-l,l,3,3-tetra(- 0.6 0.1 0.2 0.1 trimethylsiloxy)disiloxane Vinyl di(trime_hyldiloxy)silylpropylmethacrylate 30 Penta ethyIdisiloxy-Jf-methacryloxypropylsilane 30 10 Hydroxy-di( rimethylsiloxy)silylpropylmethacrylate 5.4 0.9 1.8 0.9 2,2,2-trifluoroethylmethacrylate 70 58 70 60 65 Hexaflπorobυtylmethacrylate I Hexafluor isopropylmethacrylate Methylmethacrylate 35 n-Rutylmethacrylate Cyclohexylmethacrylate 10 5 5 2-Ethylhexylme hacrylate Methacrylic Acid 5 5 5 8 2-Hydroxyethylmethacr late 5 5 5 Ethyleneglycoldimethacrylate 2 2 AIBN .02 .02 .02 .02 .02 .02 Properties Oxygen Permeability* 28 25 37 24 39 93 Contact Angle, receding 25 15 28 28 25 26 Light Transmission T T T T T T Hardness 82 83 82 84 82 85 Others B B B B B B Cytotoxicity Assay N N N T = transparent B = brittle TABLE II Controls G-U Controls G-M (parts by weight) Monomers H M Properties Oxygen Permeability* 50 110 65 80 92 45 67 Hardness 84 80 82 78 79 80 78 TABLE II (continued) Controls G-U Controls N-U (parts by weight) Monomers N U Tris(TrimethyIsiloxy)silylpropylme hacrylate 44.5 44.5 44.5 44.5 34.6 44.5 34.6 39.5 1,3 bis(2f-methacryloxypropyl)-l,l,3,3-tetra 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.4 ( rimethylsiloxy)disiloxane Hydroxy-di(trimethylsiloxyJsilylpropylmethacrylate 0.4 0.4 0.4 0.4 0.3 0.4 0.3 0.1 2,2,2-trifluoroethylmethacrylate 20 20 30 35 45 35 45 20 Ethylmethacrylate 25 25 Isopropylmethacrylate 1 n-Butylmethacrylate 10 Cyclohexylmethacrylate 1 t-Butylmethacrylate 25 Methacrylic Acid 5 5 15 15 15 2-Hydrσxyethylmethacrylate 10 15 15 10 Ethyleneglycoldimethacrylate 5 5 5 5 5 5 5 5 AIBN .02 .02 .02 .02 .02 .02 .02 .02 Properties Oxygen Permeability* 92 66 92 85 Hardness 80 79 74 78 -20- Example 12 Following the procedure of Examples 1-11, an oxygen- permeable copolymer was prepared from a mixture of 22 parts by weight tris(trimethylsiloxy)-3'-methacryloxy- propylsilane, 2.7 parts by weight hydroxy-di(trimethyl- siloxy)silylpropylmethacrylate, 0.3 parts by weight 1,3 bis(y-methacryloxypropyl)-1,1,'3,3-tetra(trimethyl- siloxy)disiloxane, 65 parts by weight trifluoroethyl- methacrylate, 5 parts by weight 2-hydroxy-4-(2-acrylσxy- ethoxy)benzophenone, 5 parts by weight methacrylic acid, and 0.02 parts by weight AIBN. The properties of this lens material are shown in Table III. TABLE III * Oxygen Permeability 54 Contact Angle 20 Light Transmission Transparent Hardness 84 Cytotoxicity Assay Negative Example 13 The procedure of Examples 1-11 was repeated, except that the formulation contained 28.5 parts by weight tris(trimethylsiloxy)- -methacryloxypropylsilane, 1.3 parts by weight hydroxy-di(trimethylsiloxyJsilylpropyl¬ methacrylate, 0.2 parts by weight 1,3 bis(2f-methacryloxy- propyl)-1,1,3,3-tetra(trimethylsiloxy)disiloxane, 65 parts by weight hexafluoroethylmethacrylate, 5 parts by weight methacrylic acid, and 0.2 parts by weight AIBN. Average oxygen permeability was 398 x 10~H(cm^/sec. ) (ml 0 2 /ml x mm Hg).

Claims: -21- WHAT IS CLAIMED IS: 1. An oxygen-permeable lens comprising an interpolymerized amount of: a) an organosilicon monomer system present in an amount of from about 10 to about 40 percent by weight based on the total weight of the monomers and in which at least a portion of the organosilicon monomer system is at 0 least one hydroxyorganosilicon monomer having at least one hydroxyl group attached to silicon-of the organosilicon moiety; b) at least one hydrophilic monomer present in an amount sufficient to provide in the resultant polymer 5 a contact angle of less than about 45°; " c) at least one crosslinking monomer, the total of crosslinking monomer being present in an amount up to about 5 percent by weight based on the total weight of the monomers; and 0 d) the balance of the monomers comprising at least one fluoroorgano monomer of the formula: 5 wherein Mx is hydrogen, alkyl, fluoroalkyl, alkyl carboxy, carboxy ester, alkyl carboxy ester, fluorinated carboxy ester, cyano, or phenyl, M is hydroxy alkyl, alkyl ether, or hydroxy alkyl ether, U a is as defined above, c is from 0 to 4, and Y is a fluorocarbon group preferably containing from about 2 to about 21 fluorine atoms. 5 2. An oxygen-permeable lens as claimed in claim 1 which the organosilicon monomer system includes monomers of the formula CH 2 * C - Ri OH COO-(CH 2 -CH-CH 2 0) a -(CH 2 ) b -X wherein Rx is hydrogen or methyl, a is 0 or 1, b is from 1 to about 4, and X is an organosilicon moiety containing up to about 16 silicon atoms. 3. An oxygen-permeable lens as claimed in claim 1 in which at least one UV-absorbing agent is present in an amount of from about 0.1 to about 20 percent by weight based on the weight of the UV-absorbing agent and the monomers. * 4. An oxygen-permeable lens as claimed in claim 2 in which at least one UV-absorbing agent is present in an amount of from about 0.1 to about 20 percent by weight based on the weight of the UV-absorbing agent and the monomers. 5. An oxygen-permeable lens as claimed in claim 4 in which the UV-absorbing agent comprises a polymerized amount of at least one monomer selected from the group consisting of a hydroxybenzophenone or benzotriazole of the formula: Claim 5, continued. . . wherein Rx , a is 0 or 1, b is from 1 to about 4, d is 1 or 2, and Z is: wherein R 2 is hydrogen, alkyl or hydroxy and a phenyl benzotriazole of the formula: wherein Rx and R are as defined above, and R3 is H; alkyl, preferably a Cχ-Cχ alkyl, or hydroxyl. 6. An oxygen-permeable lens as claimed in claim 1 in which the organosilicon monomer is present in a concentration of from about 15 to about 30 percent by weight based on the total weight of interpolymerized monomers. 7. An oxygen-permeable lens as claimed in claim 2 in which the organosilicon monomer is present., in a concentration of from about 15 to about 30 percent by weight based on the total weight of interpolymerized monomers. 8. An oxygen-permeable lens as claimed in claim 1 in which the hydroxyorganosilicon monomer is present in an amount of from about 0.1 to about 10 percent by weight of the total weight of the interpolymerized monomers. 9. An oxygen-permeable lens as claimed in claim 2 in which the hydroxyorganosilicon monomer is present in an amount of from about 0.1 to about 10 percent by weight of the total weight of the interpolymerized monomers. 10. An oxygen-permeable lens as claimed in claim 5 in which the hydroxyorganosilicon monomer is present in an amount of from about 0.1 to about 10 percent by weight of the total weight of the interpolymerized monomers. 11. An oxygen-permeable lens as claimed in any one of the previous claims in which the oxygen permeability is at least about 15 x lO ' ^fcm^/sec. ) (ml 0 2 /ml x mm Hg). 12. An oxygen-permeable lens as claimed in any one of claims 1 to 10 in which the oxygen permeability is at least about 50 x lO-* 1 (cm /sec. ) (ml 02/ml x mm Hg) and a Shore hardness greater than about 78. 13. An oxygen-permeable lens as claimed in claim 2 in which the organosilicon monomers are selected from compounds of the formula: H 2 -CH0H-CH 2 -0-) a -(CH 2 ) b -X' Clai 13, continued. . . wherein X' is -R wherein each of R4 and R5 is independently a C -Cs alkyl, phenyl, hydroxyl, or -0-Si(CH3)3, and e * ch of R 6» R 7 and Re is independently selected from C -Cs; -CH =CH 2 ; phenyl; hydroxyl; -CH 2 OH; CH3 CH 3 -0-S Ii-0-Si(CH3)3 ; -O-SIi-OH ; I I CH3 CH3 ; 0-Si-[OSi(CH3)3Ϊ3 ; or CH 2 - C-Rχ COO-(CH 2 -CHOH-CH 2 -0-) a -(CH 2 ) b - wherein Rx is hydrogen or methyl, a is 0 or 1, and b is from 1 to about 4. 14. An oxygen-permeable lens as claimed in claim 1 in which the organosilicon monomer is selected from tris(trimethylsiloxyJ-ϊ'-methacryloxypropylsilane, 1 ,3-bis-(y-methacryloxypropyl-)l ,1,3,3-tetra(trimethyl- siloxy)disiloxane and mixtures thereof, and in which the hydroxyorganosilicon monomer is hydroxy-di-(trimethyl¬ siloxy)silylpropylmethacrylate. 04343 -26- 15. An oxygen-permeable lens as claimed in claim 10 in which the organosilicon monomer is selected from tris(trimethylsiloxyJ-T-methacryloxypropylsilane, 1,3-bis-(y-methacryloxypropyl-)l,1,3,3-tetra(trimethyl- siloxy)disiloxane and mixtures thereof, and in which the hydroxyorganosilicon monomer is hydroxy-di-(trimethyl- βiloxy)silylpropylmethacrylate. 10 16. An oxygen-permeable lens as claimed in claim 1 in which the fluoroorgano monomer is 2,2,2-trifluoro¬ ethylmethacrylate, hexafluorobutylmethacrylate, hexafluoroisopropylmethacrylate and mixtures thereof. * 5 17. An oxygen-permeable lens as claimed in claim 2 in which the fluoroorgano monomer is 2,2,2-trifluoro¬ ethylmethacrylate, hexafluorobutylmethacrylate, hexafluoroisopropylmethacrylate and mixtures thereof. 0 18. An oxygen-permeable lens as claimed in claim 1 in which the hydrophilic monomer is methacrylic acid. 19. An oxygen-permeable lens as claimed in claim 2 in which the hydrophilic monomer is methacrylic acid. 25 20. An oxygen-permeable lens as claimed in claim 14 in which the hydrophilic monomer is methacrylic acid. 21. An oxygen-permeable lens as claimed in claim 3 0 in which the UV-absorbing monomer is selected from the group consisting of 2-hydroxy-4-(2-methacryloyloxyethoxy)benzophenone, 2-hydroxy-4-(2-acryloyloxyethoxy)benzophenone, 2-hydroxy-4-{2-hydroxy-3-methacryloxypropy1)benzophenone, 35 2-(2-hydroxy-5-vinylphenyl)-2H-benzotriazole, and mixtures thereof. 22. An oxygen-permeable lens comprising an interpolymerized amount of: a) an organosilicon monomer system including the formula: CH 0) a -(CH 2 ) b -X wherein R is hydrogen or methyl, a is 0 or 1, b is from 1 to about 4, and X is an organosilicon moiety containing up to about 16 silicon atoms, the total organosilicon monomer being present in an amount of from about 10 to about 35 percent by weight based on the total weight of the monomers and in which from about 0.1 to about 10 percent by weight of the total monomers is an hydroxy oragnosilicon monomer having at least one hydroxyl group attached to a silicon of the organosilicon moiety; b) a UV-absorbing agent containing an interpolymerized amount of at least one monomer selected from the group consisting of a hydroxybenzophenone or benzotriazole of the formula: H -CH0H-CH 2 0) a -(CH 2 ) b - wherein Rχ» a and b are as defined above, d is 1 or 2, and Z is: Claim 22, continued. wherein R is hydrogen, alkyl or hydroxy and a phenyl benzotriazole of the formula: wherein Rx and R 2 are as defined above, and R3 is H; alkyl, preferably a Cχ-Cχo alkyl, or hydroxyl, said UV-absorbing agent being present in an amount of from about 0 to about 10 percent by weight based on the total weight of the agent and the monomers; c) methacrylic acid in an amount sufficient to provide in the resultant polymer a contact angle of less than about 45°; d) at least one crosslinking monomer, the total of crosslinking monomers being present in a concentration of from about 0.1 to about 2 percent by weight based on the total weight of the monomers; and e) the balance of the monomers comprising at least one fluoroorgano monomer of the formula: ) a -(CH 2 ) c -Y -29- Claim 22, continued. . . wherein Mx is hydrogen, alkyl, fluoroalkyl, alkyl car¬ boxy, carboxy ester, alkyl carboxy ester, fluorinated carboxy ester, cyano, or phenyl, M is hydroxy alkyl, alkyl ether, or hydroxy alkyl ether, a is as defined above, c is from 0 to 4, and Y is a fluorocarbon group preferably containing from about 2 to about 21 fluorine atoms, said lens having a Shore D hardness from about 80 to about 85 and containing sufficient organosilicon monomer to provide an oxygen permeability of at least 50 x 10 ""1:l (cm 2 /sec. ) (ml 0 2 /ml x mm Hg). 23. An oxygen-permeable lens as claimed in claim 22 in which the organosilicon monomer is present in a concentration of from about 15 to about 35 percent by weight based on the total weight of interpolymerized monomers. 24. An oxygen-permeable lens as claimed in claim 22 in which the organosilicon monomer is selected from the group consisting of tris(trimethylsiloxy)-y~methacryloxy- propylsilane, 1,3-bis-( -me hacryloxypropyl)1,1,3,3- tetra(-trimethylsiloxy)disiloxane and mixtures thereof, and in which the hydroxyorganosilicon monomer is hydroxy-di(trimethylsiloxy)silylpropylmethacrylate. 25. An oxygen-permeable lens as claimed in claim 22 in which the fluoroorgano monomer is selected from the group consisting of 2, 2 ,2-trifluoroethylmethacrylate, hexafluorobutylmethacrylate, hexafluoroisopropyl- methacrylate and mixtures thereof. 26, An oxygen-permeable lens as claimed in claim 25 in which the UV-absorbing monomer is selected from the group consisting of 2-hydroxy-4-(2-methacryloyloxyethoxy)benzophenone , 2-hydroxy-4-(2-acryloyloxyethoxy)benzophenone, 2-hydroxy-4-(2-hydroxy-3-methacryloxypropyl)benzophenone, 2-(2-hydroxy-5-vinylpheny1)-2H-benzotriazole, and mixtures thereof.

Inventors: STOYAN NICK, STOYAN, NICK
Applicants: BAUSCH & LOMB, BAUSCH AND LOMB INCORPORATED
Application year: 1986
Main classification: C08F230
IPC codes: C08F220, C08F230, G02B1