LENS COMPOSITION, ARTICLES AND METHOD OF MANUFACTURE

Abstract: A copolymer composition, especially suited for fabricating optical lenses comprising a copolymer of copolymerized comonomers which include about one to about forty percent by weight of an acryloxyalkylsilanol; about one to about seventy five percent by weight of a polyacryloxyalkylpolysiloxane; about one to about seventy five percent by weight of an siloxy substituted ester of acrylic or methacrylic acid; and from about one to about 35 percent by weight of an alkyl or cycloalkyl acry­ late or methacrylate having from one to twenty carbon atoms. Contact lenses and contact lens buttons are formed of such copolymer of copolymerized comonomers by convention­ al techniques, by injection molding, and by compression mold­ ing.

Description: DESCRIPTION The present invention relates to new and unique copolymer compositions, methods for handling said copolymers to mold or cast them into optical lenses, especially contact lenses or blanks from which contact lenses may be shaped, and to the buttons and lenses resulting therefrom. More particularly, the present invention relates to novel copolymer compositions having distinctly improved extended wear properties while providing wettability, mechanical stability and optical clarity essential for optical lenses including interoccular and contact lenses, or thef buttons and blanks from which such lenses may be shaped. The buttons or blanks can be formed by either conventional forming techniques, by injection molding or by compression casting. Furthermore, this invention concerns oxygen- permeable copolymers from which contact lenses and the like can be produced which lenses have improved extended wear properties. In addition, these copolymers can be used to manufacture contact lenses by industry-standard manufacturing techniques as well as by inject ion molding or casting which lenses can be cleaned with standard contact lens cleaning solutions without any special surface treatments to impart wettability. For purposes of the following discussion, this invention will be described in terms ol contact lenses although it is readily applicable to various optical lenses and other applications. So-called "hard" contact lenses and compositions for fabricating them are well known in the art. The standard contact lens used for many years was fabricated from polymethyl methacrylate (PMMA) and achieved widespread use throughout the world, despite the tact that a PMMA lens is essentially impermeable to oxygen. The lack of oxygen at the inter face between the contact lens and the cornea will, after even short periodr of time, i.e., less than one day, cause discomfort to the wearer because of edema induced by the lack of oxygen at the surface of the cornea. Consequently, PMMA lenses must be removed at lest daily and prelerrably more often to expose the surface of the cornea to ambient atmospheric oxygen and thereafter replaced, a bothersome procedure. In an attempt to remedy these defects Inherent in standard PiMA contact lenses, the art has devised other copolymer contact lens compositions having improved oxygen-permeability which allow the user to wear the lenses for longer periods of time, sometimes several days, before they must be removed for cleanlng. These oxygen-permeable lenses are of two general types, the so-called "soft" lens formed of the very flexible Hydrogel# material and the so-called "hard permeable lens formed of a solid copolymer of methyl methacrylate with various comonomers. The hard permeable lens avoids certain problems associated with the so-called soft lens, principally in its resistance to contamination and breakage, and provides ease of cleaning and resistance to surface scratching. Although the hard permeable contact lens compositions represented a marked improvement over standard PMMA polymers in terms of oxygen-permeability, they nevertheless suffered certain disadvantages in comparison to standard PMMA lenses in terms of wettability, mechanical stability and chemical stability. Moreover, certain of the present day hard permeable copolymers require special surface pre-treatment to improve wettability and/or special lens treatment solutions which are used throughout the life of the lens to improve or maintain surface properties. Furthermore, the hard permeable copolymers are inherently brittle with the result that they frequently chip at their edges and break. Such chipping obviously creates a potential health hazard to the wearer and imposes a definite economic burden because they must be replaced. This invention will be best understood by reference to the prior art described in Keogh, U.S. 4,259,467, and Ratkowski et al, U.S. 4,419,505, and the several references cited therein. Further background Is available from Gaylord, U.S. 3,808,178; Ellis et al, U.S. 4,168,122; Ellis et al, U.S. 4,152,508; Novieky, U.S. 4,218,303; Novicky, U.S. 4,242,483; Neef, U.S. 4,306,042 and Poley, E.P. 75004. As is apparent from the art, a definite need exists for and it would be highly advantageous to provide a hard oxygen-permeable contact lens composition, lenses manufactured thereof, and methods for manufacturing lenses or lens blanks (buttons) therefrom, all of which could provide contact lenses having at least the oxygen-permeability characteristic exhibited by presently available hard permeable lenses, which would have improved wettability, and which would provide significant production economies, especially it such composition can be used to manufacture contact lenses or buttons therefor, using not only the standard procedures and equipment already known for manufacture of PMMA lenses, but using inject ion molding or casting in such a way that special surface pre-treatments or periodic surface treatments to attain and maintain the desired surface properties are no longer required. Further, if such lens could also have the ability for extended wear, that is, permit the user to keep the lens in place for several weeks, up to a month or more, a major break through would be accomplished. This disclosure is based upon the discovery of lens copolymer compositions, lenses fabricated therefrom, and methods for manufacture ot lenses employing such compositions which achieve the aforedescribed break through in a remarkably unexpected fashion as will be readily discerned from a detailed reading of the following disclosure and examples thereof. Accordingly, a prime object of the present invention is to provide a new and Improved optical lens composition especially useful for the manufacture of contact lenses therefrom having excellent oxygen-permeability, improved wettability, enhanced dimensional stability and extended werability. Another object of the present invention is to provide a new and improved optical lens composition from which lenses can be fabricated using standard production methods as well as by injection molding and casting which require no spec a1 surface treatment to achieve efficacious use. A further object of the present invention is to provide a new and improved composition for the fabrication of optical lens having unexpectedly superior toughness, dimensional stability, clarity, durability, hardness, wettability and high values of oxygen permeability. Still a further object of the present Invention is to provide a new and improved extended wear lens composition which is capable ot producing either hard or soft optical lenses which have and retain optimum physical properties while being readily formed into a variety of optical shapes. These and still further objects as shall hereinafter appear are readily fulfilled by the present invention in a remarkably unexpected manner as will be readily discerned from the following detailed description of an exemplary embodiment thereof. Briefly stated, the composition of the present invention comprise. a copolymer derived from comonomers which include a methycryloxyalkylsilanol; a di(methacryloxyalkyl) polysiloxane; a tris(trialkylsiloxy)methacryloxyalkylsilane and an alkyl methacrylate. The corresponding acrylic acid esters may be used for any of the foregoing components. In the preferred composition, acrylic or methacrylic acid will be used as a wetting agent and, a polyfunctional ester, derived from the reaction of acrylic or methacrylic acid with an aliphatle di- or polyol (e.g. ethylene glycol, tetraethylene glycol, glycerol and the like), will be used as a crosslinker. The invention also provides, as new articles of manufacture, lenses fabricated from these copolymers having extraordinary extended wear which can be produced by injection molding, compression molding or casting either into the desired lens shape or into a lens button or blank from which a lens may be sniped The invention will be best understood by reference to the prior art previously identified, namely, Ratkowski et al, U.S. No. 4,419,505, and Keogh, U. S. No. 4,259,467, (including the several references cited therein). While the copolymers of the present invention bear some similarities to those described by Gaylord, U.S. 3,808,178; Ellis et al, U.S. 4,168,122 and 4,152,508 and Novicky, U.S. patents 4,216,303 and 4,242,483, Neete U.S. 4,306,042 and Foley E.P. 75004 (in that they pre copolymers of alkyl acrylic esters with acrylic so lane esters), they differ significantly, as will hereafter appear, in that the comonomers of the present invention include an acryloxyalkylsilanol or a methacryloxyalkylsilanol, a siloxyalkyl acrylate or methacrylate, a di(acryloryalkyl)polysiloxane or a di(methacryloxyalkyl)- polysiloxane, and a C1-C20 alkyl or cycloalkyl ester of acrylic or methacrylic acid as essential components. Por purposes of this specification It is to be understood that the term "acryloxy" includes methacryloxy and the term acrylic includes methacrylic. The presence of an acryloxymethylsilanol and a dimethaerylpolysiloxane in the comonomer mixture in combination with an siloxyalkyl acrylate or methacrylate, an alkyl or cycloalkyl ester of acrylic or methacrylic acid, methacrylic acid or other wetting agent and a polyol polyacrylate in, carefully selected ratios In the presence of an appropriate catalystlinitiator leads to copolymers which have distinctly improved extended wear properties and which enable one to manufacture contact lenses, or buttons therefor, and other optical lenses by those industry-standard techniques known in connection with the manufacture of PMMA lenses. Further, the mechanical stability ot the copolymer also provides lenses having improved stability of lens curvature which affects focus distance and sharpness. No surface treatment is required to Improve lens wettability and no special cleaning solutions are required to maintain surface properties. In general, the contact lens copolymer compositions (by weight percent) of the present invention are formed by copolymerizing comonomers which Include 1 to 40% of an acryloxyalkylsilanol; 1 to 75% of a diacrylpolysiloxane; 1 to 75% of a siloxyalkyl ester of acrylic or methacrylic acid; and from 1 to 35% of a C1-C20 alkyl or cycloalkyl ester. of acrylic or methacrylic acid. The acryloxyalkylsilanols which are essential comonomers in forming the copolymer of the present invention are of the general structure: EMI6.1 Wherein: Rt CH3 - - or. H- ; 3 X,Y= C1-C6 alkyl, cyclohexyl, phenyl, or Z; EMI7.1 n = 1-5; m : 1-3; R1 = C1-C6 alkyl, cyclohexyl, or phenyl; R2 = C1-C6 alkyl, cyclohexyl, or phenyl; and R3 = C1 -C6 alkyl, cyclohexyl, or phenyl. Representative acryloxyalkylsilanols of this type include: bis(trimethysiloxy)-&gamma;-methacryloxypropylsilanol; methyl(trimethylsiloxy)-methacryloxymethylsilanol; methyl(trimethylsiloxy)-ss-methacryloxyethylsilanol; methyl(trimethylsiloxy)-&gamma;-metacryloxypropylsilanol; bis(trimethylsiloxy)-ss-methacryloxyethylsilanol; bis(trimethylsiloxy)-methacryloxymethylsilanol; (trimethylsiloxy)-(pentamethyldisiloxanyl) methacryloxymethylsilanol; (trimethylsiloxy)-(pentamethyldisiloxanyl) -ss methacryloxyethylsilanol; (trimethylsiloxy)-(pentamethyldisiloxanyl) -&gamma;- methacryloxypropylsilanol The polysiloxane diacrylates used in this invention+ have the general structure EMI7.2 Where in: R = CH3 - or H m = 0-3 n = 1-5 X = = C1-C6 alkyl, cyclohexyl, phenyl or Z; Y = C1-C6 alkyl, cyclohexyl, phenyl or Z; Z = EMI8.1 R1 = C1-C6 alkyl, cyclohexyl, or phenyl; R2 = = C1-C6 alkyl, cyclohexyl, or phenyl; and R3 t C1-C6 alkyl, cyclohexyl, or phenyl. 1 a Representative polysiloxane dlacrylates are: 1,3-bis(methacryloxypropyl)-1,3,3,terakis(trimethysiloxy) disiloxane; 1,3-bis(acryloxymethyl)-1,1,3,3,tetrakis(trimethylsiloxy) disiloxane; 1,3-bis(methacryloxypropyl)-1,1,3,3,tetrakis(triethylsiloxy) disiloxane; and 1,5-bis(methacryloxymethyl)-1,1,3,3,5,5,hexa(trimethylsiloxy) trisiloxane. The siloxyalkyl acrylates have the general structure: EMI8.2 Wherein R = CH3 - or H- ; X = C1-C6 alkyl, cyclohexyl, phenyl or Z; Y t C1-C6 alkyl, cyclohexyl, phenyl or Z; EMI9.1 R1 X C1-Cs alkyl, cyclohexyl, or phenyl; m = 0-3; R2 = C1-Cs alkyl* cyclohexyl, or phenyl; n = 1-5; R3 = C1-C8 alkyl, cyclohexyl, or phenyl; and R4 3 C1-C6 alkyl. Representative siloxyalkyl acrylates are: &gamma;-methacryloxypropyl-tris(trimethylsiloxy)silane; &gamma;-acryloxypropyl-tris(trimethylsiloxy)silane; and 5-methacryloxypropyl-1,1,1-trimethyl-3,3,5,5,tetrakis(trimethyl siloxy)trisiloxane. The C1-C20 alkyl and cycloalkyl esters of acrylic or methacrylic acid which are useful as comonomers in forming the copolymer of the present invention includes methyl acrylate and methyl methacrylate; ethyl acrylate and ethyl methacrylate; propyl acrylate and propyl methacrylate; isopropyl acrylate and isopropyl methacrylate; butyl acrylate and butyl methacrylate; alkyl acrylate and amyl methacrylate; hexyl acrylate and hexyl methacrylate; heptyl acrylate and heptyl methacrylate; octyl acrylate and octyl methacrylate; 2-ethylhexyl acrylate and 2-ethylhexyl methacrylate; nonyl acrylate and nonyl methacrylate; decyl acrylate and decyl methacrylate; undecyl acrylate and undecyl methacrylate; lauryl acrylate and lauryl methacrylate; cetyl acrylate and cetyl methacrylate; octadecyl acrylate and octadecyl methacrylate; and cyclohexyl methacrylate and cyclohexyl acry late. Other vinyl monomers which readily copolymerize with methylmethacrylate may be used in place of part or all of the preferred acrylates or methacrylates listed In the preceeding paragraph. Suitable replacement vinyl monomers include styrene, &alpha;-methylstyrene, alkylated styrenes, diethyl itaconate, pertluorylethyl vinyl ether, isoprene, isobutylene, 4-methyl-1-pentene and chlorotrifluoro ethylene. Preterrably these monomers have a molecular weight of less than 300. The copolymers of the invention are prepared by mixing comonomers with a catalyst/initiator. My preferred initiator is a free-radical-generating-polymerization-initiator of the type commonly used in polymerizing ethenyl functioning unsatured compounds. Representative free radical polymerization initiators includes acetyl peroxide; lauroyl peroxide; decanoyl peroxide; capryl peroxide; benzoyl peroxide; tertiary-butyl peroxypivalate; ditsopropyl peroxycarbonate; tertiary-butyl peroetoate 2, 2',-azobis(isobutyronitrile); 2, 2',-azobis(2,4dimethyl valeronitrile); methyl ethyl ketone peroxide; di(2-phenoxyethyl)peroxydicarbonate; and di(2-phenoxyethyl)methyl ethyl ketone peroxide. Conventional polymerization techniques are employed to produce the novel copolymers. The comonomer mixture containing between about 0.05-2% by weight of the free radical initiator is heated to a temperature between 30-C-100-C, preferably below 70-C, to initiate and eomplete the polymerization. The polymerization mixture can be heated in a suitable mold or container to form discs, rods or sheets which can then be machined to the desired shape using conventional equipment and procedures employed for fabricating lenses trow polymethyl methacrylate. The temperature is preferably maintained below 70XC in order to minimize the formation of bubbles in the copolymer. Instead of employing the bulk polymerization techniques described above, one can employ solution, emulsion or suspension polymerization to prepare the novel copolymers, using techniques conventionally used in the preparation of polymers from vinyl functioning unsaturated monomers (-CH=CH2), that is, ethenyl-tunctioning monomers. The copolymer thus produced may be pressed or molded into rods, sheets or other convenient shapes which are then cut into buttons and thereafter machined to produce the contact lenses. Alternatively, the copolymer can be directly cast or molded into finished contact lenses or lens blanks with planar, convex or concave surfaces or any desired combination thereof. In a preferred practice owl the present invention, the monomer mixture is thermally polymerized in an appropriate mold or vessel to provide a block, sheet, rod, or plug, each of which may have r radius convex or radius concave or a plano surface, to provide a semitlnished or finished contact lens or other optical lens. The mold and vessel utilized will be formed of polypropylene, polyethylene, nylon, Teflon, glass, or aluminum having its mold surface coated with Teflon As will hereinafter appear, certain applications are well served using glass test tubes or rods as the forming mold. It the wettability of the copolymers described above Is lower than desired, this property can be Improved by the addition to the copolymerizatlon mixture of from about 1-20 parts by weight ot a hydrophilic monomer. Such monomers include hydroxyalkyl acrylates and methacrylates wherein the alkyl group contains about 2 to 5 carbon atoms, acrylic and methacrylic acid, acrylamide, methacrylamide, 2-hydroxyethyl methacrylate, N-methylolacrylamide, N-methylolmethacrylamide, glycidyl acrylate and methacrylate, and N-vinyl-pyrrolldone The hydrophilic monomer content of the copolymerizatlon mixture is preferably about 3 to about 12 percent by weight. The resistance of lenses fabricated from the copolymer of the present Invention to lens flexure and warpage may be increased, if desired, by the Incorporation Into the copolymerization mixture of from about 1 to about 20 percent by weight of an acrylic ester of an alkyl polyol such as, for example, ethylene glycol dimethacrylate, butylene glycol dimethacrylate, neopentyl glycol diacrylate and pentaerythritol triacrylate or tetraacrylate. The alkylpolyol polyacrylate content of the polymerization mixture Is preferrably from about 3 to about 12 percent by weight of the total composition. The principal function of the sllanol molety of the copolymer of the present invention is to improve the mechanical properties of conventional PMMA contact lens polymers. It appears that the Inclusion of the silanol as one of the comonomers in the polymerization mixture chiefly aftects the warpage characteristics of the copolymer which, In turn, as previously noted, determines the stabIlIty of lens curvature which controls focus distance and sharpness. In additon, the silanol moiety of the copolymer Imparts sIgnifIcantly improved oxygen permeability and wettability. Consequently, although the silanol component of the copolymerization mixture may be varied within the 1-40 percent by weight as set forth above, the preferred combination of mechanical and oxygen-permeability properties and wettability is achieved by employing about 1-20 percent by weight of the silanol In the copolymerization mixture. Optimum results are obtained with a silanol concentration of 2-10% by weight In the polymerization mixture. In order to achieve the superior physical properties of the copolymers of the present invention, It is essential to Incorporate from about two to sixty percent by weight of the diacryloxypolysiloxane in the copolymerization mixture. Optimum results have been achieved when from about tour up to about sixty weight percent of a diacryloxy polysiloxane is included in the mixture. This type of comonomer makes possible the introduction of polysiloxane crosslinks as well as pendant groups having acryl and polysiloxane moieties. Such crosslinks and pendant groups enhance such important properties as oxygen permeability and dimensional stability, which provides greater visual acuity and enhanced durabilIty in the final lens. Accordingly, the incorporation of a diacryloxypolysiloxane in the monomer mixture contributes essential properties to the novel lens materials of this Invention The siloxyalkyl acrylates also contribute- to the oxygen permeability of the copolymers of the present invention. Optimum overall properties of the copolymers are obtained when the concentration of the siloxyalkylacrylates in the polymerization mixture Is from about 5% to about 60% by weight. Within the foregoing limitations, the proportion of C1-C20 alkyl or cycloalkyl esters of acrylic of methacrylic acias in the copolymerization mixture is preferably ten to thirty-tive percent by weight. The particular tree radical polymerization initiator employed in accordance with the preferred practice of the Invention Is selected by reference to the required Initiation temperature. Thus, it conventional polymerization techniques are employed to produce cast rods or other shapes which are then machIned to produce the desired lenses, the preferred initiators are 2, 2' -azobis(isobutyronitrile). 2, 2' -azobis(2, 4-dimethylvaleronitrile), benzoyl peroxide, di(2-phenoxyethyl)peroxydicarbonate, t-butyl peroxyprivalate, and the like On the other hand, it it is desired to produce contact lenses or contact lens blanks by inject ion molding or direct casting, then a polymerizaton initiator having a higher intiation temperature would be employed in order to prevent premature polymerizaton in the injection molding or casting cavities. Such an initiator can be a mixture ot methyl ethyl ketone peroxide and cobalt naphthenate. In one practice of the present Invention, a copolymerization mixture is prepared by mixing the following comonomers, In the relative weight ratios Indicated, in s plastic container equipped with a conventional stirring and blending device. A mixture containing a hydroxysilane acrylate selected from the group consIsting of: bis(trimethylsiloxy)-&gamma;-methacryloxypropylsilanol; methyl(trimethylsiloxy)methacryloxymethylsilanol; methyl(trimethylsiloxy)-ss-methacryloxyethylsilanol; methyl(trimethylsiloxy)-&gamma;-methacryloxypropylsilanol; bis(trimethylsiloxy)-ss-methacryloxyethylsilanol; bis(trimethylsiloxy)-methacryloxymethylsilanol; (trimethylsiloxy)-(pentamethyidisi loxanyl)-methacryloxy- methylsilanol: (trimethylsiloxy)-(pentamethyldisiloxyanyl)methacryloxymethylsilanol, and (trimethylsiloxy) (pentamethyldisiloxyanyl)-&gamma;-methacryloxymethylsilanol; a polysiloxane diacrylate selected from the group consisting ofi 1,3-bis(methacryloxypropyl)-1,1,3,3,tetrakis(trimethylsiloxy) disiloxane; 1,3-bis(acryloxymethyl)-1,1,3,3,tetrakis(trimethylsiloxy) disiloxane; 1,3-bis(methacryloxypropyl)-1,1,3,3,tetrakis(triethylsiloxy) disiloxane; and 1,5-bis(methacryloxymethyl)-1,1,3,3,5,5,hexa(trimethylsiloxy) trisiloxane; an siloxyalkyl acrylate selected from the group consisting of: 2Ç-methneryloxypropyl-tris(trimethylsiloxy)silane; &gamma;-acryloxypropyl-tris(trimethylsiloxy)silane; and 5-methacryloxypropyl-1,1,1-trimethyl-3,3,5,5,tetrakis(trimethyl siloxy)trisiloxane; an alkyl or cycloalkyl ester of acrylic or methacrylic acid in which said alkyl or cyeloalkyl has 1-20 carbon atoms; r wetting agent; a polyol-polyacrylate crosslinker and a catalyst/initiator. The copolymerization mixture will preferably contain from about 2-10 percent by weight of the silanol; from 10-25 percent by weight of C1-C20 alkyl or cycloalkyl ester of acrylic or methacrylic acid; from about 5 to about 60 percent by weight of an siloxyalkyl acrylate; from 4 to about 60 percent by weight of a polysiloxane diacrylate; from about 5 to about 11 percent by weight of a wetting agent; from about S to about 10 percent by weight of a polyol acrylate crosslinker; and about 0.1 to about 1.0 percent by weight of catalyst/ initiator. The mixture, when stirred for about 20 minutes, is readily pourable into a preselected mold which may be constructed of polypropylene, polyethylene, nylon, Teflon#, glass or aluminum having a molding surface coated with Teflon#, The mold when filled with the copolymerization mixture is placed Into a water or silicone bath which in turn is placed into a vacuum oven. Alternatively, the resulting and readily pourable copolymerization mixture can be converted into z solid of the desired shape In a Teflon-coated aluminum tube. In any care, the selected mold will have been thoroughly cleaned, as with a dry brurh and an anti-static air gun, to remove all particulates therefrom. The filled molds are then placed in a water or silicone bath which In turn is placed into the oven. A very alight nitrogen flow is maintained through the oven. The oven, containing the filled molds In the nitrogen environment, is heated to 40* - 50 C to commence polymerization of the copolymer and this temperature ir maintained for r period of from 12 to 48 hours at which time the oven temperature is raised to 60- - 700C for aft additional 18 to 48 hours to complete polymerization. When heating at dO' - 70 C is completed, the oven is cooled to room temperature and the copolymer solids, e.g., rods or blanks are removed from their molds (the polymerization tubes) by gently tapping the bottom of each tube. The copolymer rods or blanks* thus removed from their respective molds, are annealed by placing them upon suitable trays which are then placed In an oven. The oven is then evacuated to approximately 5 mn Hg and heated to a temperature of from 1000 to about 1500 C for a period ot from about 8 to about 36 hours. The duration of the annealing process Is Inversely related to the temperature selected. After heating for the desired time, the oven Is cooled to ambient temperature at which time atmospheric air Is slowly admitted into the oven until the, oven interior reaches atmospheric pressure. When the oven is thus cooled and the pressure balanced, the trays containing the annealed rods or blanks are removed from the oven and the annealed pieces are collected. When contact lenses or blanks are the ultimate objective, the rods wlll be machined to the desired diametrIc dimension, i.e., about 1/2 Inch (13 mn) and then sliced into a plurality of buttons, each having a thickness of approximately 3/16 inch (4 mn). It should be noted that the copolymerization mixture of the present invent Ion can be tinted using any of the physiologically compatible color pigments or dyes currently used In PMWA contact lenses. Other dyes which are characterized as Pood, Drug, and Cosmetic dyes and Drug and Cosmetic dyes' and are physiologically compatible with the optic environment can also be used. Thus lenses having blue, grey, green and brown tints as well as clear lenses can be produced by the present invent ton. To further aid in the understanding of the present invention but not as a limitation thereupon, reference is made to the following Examples. EXAMPLE 1 A copolymerization mixture is prepared by mixing tile following comonomers in the relative weight ratios indicated in a plastic mixing container and stirring for twenty nutes. Commonomers Parts bv weight Bis(trimethylsiloxy) Illthucryloxypropylsilanol 7 1,3-Bis(&gamma;-methacryloxypropyl) l,l,3,3,tetrakis(trimethylsiloxy)- 7 dzslloxane; &gamma;-Methacryloxypropyl-tris- (trimethylsiloxy)silane 48 Methyl Methycrylate 20 Methacrylic Acid 10 Ethylene Glycol Dimethacrylate 8 Initiator 2, 2'-azobis(isobutyronitrile) 0.2 The resulting copolymerization mixture is readily poured into a plurality of thoroughly cleaned tubes, each of which presents a cylindrical mold cavity of approximately 15 mm in diameter and 42 mm in length. The filled tubes are then placed into a water or silicone bath which is, in turn, placed in an oven. A very slight positive nitrogen flow is maintained through the oven. The oven containing the molds in the nitrogen s.iivironment is then heated to 40 - 50 C for 24 - 48 hours and thereafter the temperature is increased to 60 - 700C for an additional 18-36 hours to complete polymerization. The oven I thereafter cooled to room temperature and the copolymer rods are removed from the molds. The copolymer rods are annealed by placing them flat In trays which are placed Into the vacuum oven. The oven is then evacuated to approximately 5 mm Hg and the oven is heated to 100-1500C for 8-36 hours according to Table A below. S S 0 0 TABLE A Temperature( C) Duration (hours) 100 36.0 105 33.2 110 30.4 115 27.6 120 24.8 125 22.0 130 19.2 135 16.4 140 13.6 145 10.8 150 8.0 * * * * * The oven is then cooled to ambient temperature at which time atmosphere air is slowly admitted into the oven until the oven interior reaches atmospheric pressure. The trays containing the annealed rods are then removed from the oven and the rods are collected. Each rod is then machined to the desired diametric dimension, about 13 mm, and thereafter sliced into a plurality of buttons (lens blanks), each being approximately 4 mn thick. EXAMPLE 2 Standard Method for Determining Wetting Angle Ten contact lens buttons (approximately 13 mm in diameter and 4 mm thick) are prepared by slicing one of the copolymer rods produced according to Example 1, "facing" one flat surface of each button with a diamond turning tool and polishing the faced surface to the degree normally acceptable by contact lens standards. After immersing the buttons in a contact lens soaking solution such as benzalkonium chloride (available as SOCLENS@ from Alcon) or the like for 24 hours, each button is thoroughly washed with distilled water, blotted dry, and then thoroughly dried under vacuum in a 40- C oven for one week. After this preparation, the buttons are subjected to wetting angle determinations as described in the "Standard Method for Determining Wetting Angle" issued by the Contact Lens Manufacturers Association, Chicago, Illinois, dated April 10, 1978. Note that the smaller the "wetting angle" (in degrees), the better the tear pump exchange. The results obtained for the ten buttons of this example gave an average wetting angle of 26.0 with a standard deviation of# 1.50. S 0 * * * EXAMPLE 3 Por comparison, the wetting angles of other commercially available contact lens polymers and copolymers were determined utilizing the same procedure as described in Example 2. The results are reported in Table 8, below: TABLE B Standard Wetting Angle Deviation Polymer Degrees (I Degrees) PARAGON 18- (Paragon) 18.3 0.49 PMMA &num;2 (Glassflex") 25.6 1.77 PMMA &num; ;4 (Glassflex") 24.3 3.8 Polycone (Gaylord-Syntex) 30.4 .77 -Sil-O2-Flex# (Novicky) 25.4 - Boston (Ellis)(Polymer Tech) 33.3 - PARAGON 95 20.4 - PARAPERM@ O2 (Paragon) 23.1 1.63 * * * * * EXAMPLE 4 The contact lens copolymers of Examples 2 and 3 were tested for oxygen-permeability with a Schema-Versatac polarographic amplifier using the polarographic current. Permeability is expressed as the Dk unit with "D" being the diffusion coetticlent and "k" being a solubility constant. Dk = (y) 10-11 (cmê/sec) (ml O2 x ml x mm Hg) The contact lens is measured by 35 to 37 In an atmospherically controlled chamber. The schema versatae accuracy for low permeable materials, i.e., under Dk 30, is #1x10-11 and for high permeable materials, i.e., over Dk 30, is #3x10-11. The results are reported in Table C, below: TABLE C O Permeability Polymer ê(Dk x 10-11)* PARAGON 95 (Paragon) < 1 PARAGON 18- (Paragon) < 1 PMMA &num; (Glassflex") < 1 PM &num;4 (Glassflex") < 1 Polycon@ (Gaylord-Syntex) 3.8 Polycon@ II (Syntex) 9.9 Sil-O2-Flex@ (Novicky) 7.5 Boston (Ellis) (Polymer Tech) 11.1 Boston II (Polymer Tech) 14.6 Boston IV (Polymer Tech) 26.0 PARAPERM@ 2 (Paragon) 15.6 PARAPERM@ O22 PLUS (Paragon) 39.0 Example 1 56 (cmê/sec) (ml O2/ml x mm Hg) * * * * * EXAMPLE 5-25 Following the general procedure as described in Example 1, copolymers are prepared for use in fabricating contact lenses which, depending on the specitic application, have a desired combination of mechanical strength, dimensional stability, optical clarity, oxygen permeability, wettability, and extended wear. These copolymers are Identified in Tables D-l, D-2, and D-3, below. TABLE D-1 Como nome r Parts by weight in copolymerization mixture Example 5 6 7 8 9 10 11 Bis(trimethylsiloxy) -&gamma;-methacryloxypropyl- silanol 7 6.5 6 5.5 5 4.5 4 &gamma;-Methacryloxypropyl -tr;-'-(trimethylsiloxy)- silane 70 65 60 55 50 47.9 44.8 1,3-Bis(&gamma;-methacryloxypropyl )-1,1 ,3,3,tetrakis- (trimethylsiloxy)disiloxane; 5.6 5.2 4.8 4.4 4 3.6 3.2 Methyl Methacrylate 10 15 10 20 23 25 27 Methacrylic Acid 1 3 4.2 5 12 11 9 Ethylene Glycol Dimethacrylate 6.4 5 15 10 5 9 12 Initiator 2, 2' azobis(lsobutyronitrile) - 0.2 - 0.4 0.4 0.2 Benzoyl Peroxide 0.3 - 0.1 - - - 0.2 TABLE D-2 Comonomer Parts by weight in copolymerlzation mixture Example 12 13 14 15 16 17 18 Bis( trimethylslloxy) -3-methacryloxypropyl- silanol 3.5 3 5 1 1.3 20 7.0 &gamma;-Methacryloxypropyl -tris-(trimethylsiloxy)- silane 47.7 35 50 42.2 56.2 30 57.4 1,3-Bis(&gamma;-methacryloxy- propyl)-1,1,3,3,tetrakis (trimethylsiloxy)disiloxane; 2.8 9.4 15 11.8 1 2.4 11.6 Methyl Methacrylate 29 35 21 30 25 27.6 10 Methacrylic Acid 10 10 8 8 5.5 8 7 Ethylene Glycol Dimethacrylate 8 7.6 1 7 11 8 8 Initiator 2, 2' azobis(isobutyronitrile) 0.2 0.2 0.2 - - 0.2 Benzoyl Peroxide - - - 0.3 0.3 0.3 * * * * * TABLE D-3 Comonomer Parts by weight in eopolymerization copolymerizat ion mixture Example 19 20 21 22 23 24 25 His(trimethylsiloxy) -y-methacryloxypropyl- silanol 5.4 5.8 5.9 6.1 5.8 1 4.3 &gamma;-Methacryloxypropyl -trls-(trimethylsiloxy)- silane 44.3 47.6 48.4 50 47.6 8.2 35 1,3-Bis(&gamma;-methacryloxy- propyl)-1,1,3,3,tetrakis (trimethylsiloxy)disiloxane; 14.3 14.6 10.7 4.9 4.6 60 30 Methyl Methacrylate 25 15 20 25 20 22.8 20.7 Methacrylic Acid 5 11 11 6 10 7 7 Ethylene Glycol Dimethacrylate 6 6 4 8 5 i 3 Initiator 2, 2' azobis(isobutyronitrile) 0.2 0.2 - - 0.2 0.2 0.2 Benzoyl Peroxide - - 0.3 0.3 - - * * * * * Following the general procedures of Example 1, copolymers are prepared of other comonomers, whIch, depending on the specitic desired balance of properties of mechanical strength, dimensional stability, resistance to warpage, optical characteristics, oxygen permeability and wettability, are suitable for use in fabricating contact lenses according to the present invention Referring to Table D, the following substitutions can be made for all or part of the indicated monomers without departing from the present invention Bis(trimethylsiloxy)-methacryloxymethylsilanol or methyl- (trimethylsiloxy)-&gamma;-methacryloxypropylsilanol for bis-ttrimethylslloxy)-?r-methacryloxypropylsilanol; methacryloxymethyl-tris-(trimethylsiloxy)silane or &gamma;-acryloxymethyl-tris-(triethylsiloxy)silane for &gamma;-methacryloxypropyl-tris-(trimethylsiloxy)silane; 1,3-bis(methacryloxymethyl)-1,1,3,3,tetrakis(trimethylsiloxy) disiloxane or 1, 3-bis-( &gamma;-methacryloxypropyl-1, 1-dimethyl-3, 3-bis-trimethylsiloxy-disiloxane for 1,3-bis(&gamma;-methacryloxy- propyl)-1,1,3,3,tetrakis(trimethylsiloxy)disiloxane; methyl acrylate, ethyl methacrylate or 2-ethoxyethyl methacrylate ior methyl methacrylate; acrylic acid, acrylamide or 2-hydroxyethyl methacrylate for methacrylic acid; and 1,3-propylene diacrylate or tetraethylene glycol dimethacrylate for ethylene glycol dimethacrylate. Various acceptable alternative initiators have been disclosed earlier with preferred initiators being shown at the bottom of Tables D-1, D-2, and D-3. S S * * * EXAMPLE 26 Representative lenses produced according to the present invention were subjected to microbiological testing for toxicity and physiological biocompatibility as recommended in the FDA Cuidelines for "Toxicological Testing of New Contact Lenses and Soaking/Wetting Solutions Used With New Contact Lenses". The specimens met the FDA guidelines. * * * * * EXAMPLE 27 Copolymer formulations of the present invention were subjected to physical and chemical testing. The formulations were found to be chemically stable and provided the following typical physical characteristics. TABLE E Properties Specification Test Results hardiness ANSI/ASTM D2240-75 D79 - D85 Scratch resistance ANSI Z80.6; 4.2 2 < x < 3 Absorption (normal saline) ANSI Z80 6; 4.6.1 < 2% Absorption (distilled water) ANSI Z80.6; 4.6.2 < z% Wetting angle CLMA procedure 20 -30 Gas permeability Schema Versatae Dk=30-100x10-11 Dk=(y)x10-11 cmê/ml O2/sec-ml-mmHg at 37-C by polarography Shelf life ANSI Z80.6 4.4 Unlimited Luminous transmittance (colorless lenses) (370-740 nm) ANSI Z80.6; ; 4.5 > 90% Heat distorsion ANSI/ASTM D648 > 60 C Dimensional stability ANSI/ASTM D756 < 1% Refractive Index ANSI/ASTM D542 1.40-1.50 (Nd at 25 C) S Tensile strength ANSI/ASTM D638 1-3x10 psi Flexural strength ANSI/ASTM D79U 2-6x10 psi EXAMPLE 28 Contact lenses formulated from the copolymer formulations of the present invention were shaped to provide spherical, toric, biotoric and asperic characteristics. The lenses provided base curves of 6.5 to 9.0 mn, diameters of 7 to 10.5 mm and thicknesses of 0.05 to 0.70 mn to provide custom corneal fittings. These lenses are found to conform to ANSI Z80.2 prescription requirements for first quality contact lenses and are capable of providing correction of refractive error in patients with non-therapeutic eyes having ametropias, including myopia, hyperopia and those with astigmatism. S S Prom the foregoing, it becomes apparent that a new and useful copolymer composition, method for handling said copolymers to mold or cast them into optical lenses or blanks from which contact lenses may be shaped, and the buttons and lenses resulting therefrom have been herein described and illustrated which fulfill all of the aforesaid objectives in a remarkably unexpected fashion, it being understood that such modifications, alterations and adaptations as may readily occur to an artisan having the ordinary skills to which this invention pertains are intended within the spirit of the present invention which is limited only by the scope of the claims appended hereto.

Claims: CLAIMS 1. A copolymer composition, especially suited for fabricating optical lenses, comprising a copolymer of copolymerized comonomers containing: a) about one to about forty percent by weight of an acryloxyalkylsllanol having the structure EMI27.1 wherein R = CH3 - - or H-; X, Y = C -c alkyl; phenyl or Z 16 EMI27.2 n = 1-5 m : 1-3 R1 = C -c alkyl, cyclohexyl, or phenyl R2 = C11-C66 alkyl, cyclohexyl, or phenyl R3 = C1-C6 alkyl, cyclohexyl, or phenyl b) about one to about seventy five percent by weight of a polyacryloxyalkylpolysiloxane having the structure EMI27.3 Wherein R 2 CII - or H-; 3 m = 0-3 n = 1-5 X = C1-C6 alkyl, cyclohexyl, phenyl or Z Y = C1-C6 alkyl, cyclohexyl, phenyl or Z EMI28.1 c) about one to about.seventy five percent by weight of a siloxy substituted ester of acrylic or methacrylic acid having the structure: : EMI28.2 Wherein R = CH3 - or H-; X = C1-C6 alkyl, cyclohexyl, phenyl or Z Y = C1-C6 alkyl, cyclohexyl, phenyl or Z EMI28.3 R1 = C1-C6 alkyl, cyclohexyl, or phenyl m = 0-3 R2 = C1-C6 alkyl, cyclohexyl, or phenyl n = 1-5 R3 = C1-C6 alkyl, cyclohexyl, or phenyl R4 = C1-C6 alkyl or cyclohexyl; and d) about one to about thirty-five percent by weight of an alkyl or cycloalkyl acrylate or methacrylate having from one to 20 carbon atoms. '2. A composition according to Claim 1 in which said copolymer of copolymerized comonomers includes as a comonomer an additional crosslinking monomer, and preferably said crosslinking monomer is present in an amount equal to about one percent to about twenty percent by weight of said copolymer. 3. A composition according to Claim 2 in which said additional crosslinking monomer is a polyol acrylate 4. A composition according to Claim 2 in which said crosslinking monomer is selected from the group consisting of ethylene glycol-dimethacrylate and butylene glycol-dimethacrylate. 5. A composition according to Claim 1 or 2 in which said copolymer of comonomers includes as a comonomer a wetting monomer, and preferably said wetting comonomer is present in an amount equal to about one per cent to about twenty percent by weight of said copolymer. 6. A composition according to Claim 5 in which said wetting monomer is selected from the group consisting of methacrylic acid, acrylic acid, acrylamide, and 2-hydroxyethyl methacrylate. 7. A composition according to Claim 1 or 2 in which said comonomer mixture includes, prior to polymerization, a catalyst/initiator, and said catalyst/initiator is present in an amount equal to about 0.1 to about 1.0 percent by weight of said comonomer mixture. 8. A composition according to Claim 7 in which said catalyst/initiator is selected from the group consisting of benzoyl peroxide, t-butyl peroxypivalate, 2, 2'-azobis(isobutyronitrile), and 2, 2'-azobis(2,4dimethylvaleronitrile). 9. A composition according to Claim 1 containing from about 3 to about 12 percent by weight of a wetting agent selected from the group consisting of methacrylic acid, acrylic acid, acrylamide, and 2-hydroxyethyl methacrylate; from about 3 to about 12 percent by weight of a crosslinker selected from the group consisting of ethylene glycol dimethacrylate and butylene glycol dimethacrylate; and from 0.1 to about 0.5 percent by weight of a catalyst/initiator selected from the group consisting of benzoyl peroxide, t-butyl peroxypivalate, 2,2'-azobis (isobutyronitrile), and 2'-azobis(2,4-dimethylvaleronitrile). 10. A composition according to Claim 9 containing from about three to about twenty percent by weight of said acryloxyalkylsilanol, from three to about sixty percent by weight of said polyacryloxyalkylpolysiloxane; from about five to about sixty percent by weight of said siloxy substituted ester of acrylic or methacrylic acid; and from about five to about thirty percent by weight of said alkyl or cycloalkyl acrylate or methacrylate having from one to twenty carbon atoms. 11. As a new article of manufacture, an optical lens fabricated from the copolymer of copolymerized comonomers according to any preceding claim. 12. An article of manufacture according to Claim 11 comprising a contact lens. 13. As a new article of manufacture, a contact lens button fabricated from the copolymer of copolymerized comonomers according to any preceding claim. 14. As a new article of manufacture, a contact lens formed from the button according to Claim 13.

Inventors: RATKOWSKI, DONALD J.
Applicants: PARAGON OPTICAL INC
Application year: 1985
Main classification: C08F230
IPC codes: C08F30, C08F230, G02B1