Title of Invention	A METHOD OF LOWERING THE YOUNG'S MODULUS AND TAN OF A SILICONE HYDROGEL AND SILICONE HYDROGEL PERSE.
Abstract	A method of lowering the Young's modulus and tan (delta) of a silicone hydrogel comprising the step of incorporating in said hydrogei, a mono-alkyl terminated polydimethylsiloxane monomer having the structure: Where b - 0 to 100; R58 is a monovalent group comprising an ethylenically unsaturated moiety; each R59 is independently a monovalent alkyl, or aryl group, which may be substituted with alcohol, amine, ketone, carboxylic acid or ether groups; and R60 is a monovalent alkyl, or aryl group, which may be substituted with alcohol, amine, ketone, carboxylic acid or ether groups.

Title of Invention

A METHOD OF LOWERING THE YOUNG'S MODULUS AND TAN OF A SILICONE HYDROGEL AND SILICONE HYDROGEL PERSE.

Abstract

A method of lowering the Young's modulus and tan (delta) of a silicone hydrogel comprising the step of incorporating in said hydrogei, a mono-alkyl terminated polydimethylsiloxane monomer having the structure: Where b - 0 to 100; R58 is a monovalent group comprising an ethylenically unsaturated moiety; each R59 is independently a monovalent alkyl, or aryl group, which may be substituted with alcohol, amine, ketone, carboxylic acid or ether groups; and R60 is a monovalent alkyl, or aryl group, which may be substituted with alcohol, amine, ketone, carboxylic acid or ether groups.

Full Text	2 silicone-containing monomer or the hydrophilie monomer may function as a crosslinking agent (a croeslinking agent is a monomer having multiple polymerizable functionalities) or a separate crosslinking agent may be employed. The formation of silicone hydrogels has been disclosed in U.S. Patents Nos. 4,954,587, 5,010,141, 5,079,319, 5,115,056, 5,260,000, 5,336,797, 5,358,995, 5,387,632,5,451,617, 5,486,579 and WO 96/31792. Group Transfer Polymerization techniques for polymerizing acrylic and methacrylic monomers with terminal silyl containing monomers is described in various patents including U.S. Patents Nos. 4,414,372, 4,417,034, 4,508,880, 4,524,196, 4,581,428, 4388,795, 4,598,161, 4,605,716, 4,622,372,4,656,233, 4,659,782, 4,659,783, 4,681,918, 4.695,607, 4,711,942, 4,771,116, 5,019,634 and 5,021,524 each of which is incorporated in its entirety herein by reference. U.S. Patent No. 3,808,178 discloses the formation of copolymers of small silicone-containing monomers and various hydrophilie monomers. U.S. Patent No. 5,034,461 describes silicone hydrogels prepared from various combinations of silicone-polyurethanc macromers and hydrophilie monomers such as HEMA or N,N-dimethyacrylamide ("DMA"). The addition of methacryloxypropyltris-(irimethylsiloxy)silane ("TRIS") reduced the modulus of such hydrogels, but in many examples the modulus was still higher than may be desired. U.S. Patents Nos. 5,358,995 and 5,387,632 describe hydrogels made from various combinations of silicone macromers, TRIS, NVP and DMA. Replacing a substantial portion of the silicone macromer with TRIS reduced the modulus of the resulting hydrogels. Two publications from the same author, "The Role of Bulky Polysiloxanylalkyl Methacryiates in Polyurethane-Polysiloxane Hydrogels", J. Appl. Poly. Sci., Vol. 60,1193-1199 (1996), and "The Role of Bulky Polysiloxanylalkyl Methacryiates in Oxygen-Permeable Hydrogel Materials", J. Appl. Poly. Sci., Vol. 56, 317- 3 324 (199S) also describe experimental results indicating that the modulus of hydrogels made from reaction mixtures of siliconc-macromers and hydrophilic monomers such as DMA decreases with added TRIS. The use of mechacryloxypropylbis(trimethylsiloxy)methylsilane ("MBM") to make hard contact lenses was described in WO 9110155 and in JP 61123609. When relatively high levels of bulky silicone-comaining monomers such as TRIS are incorporated into the hydrogels made from silicone-containing macromers and hydrophilic monomers, the elasticity, or the spe at which the polymer returns to its original shape after stress can be reduce to an extent that is unacceptable to the contact lens wearer. There still remains a need in the an for silicono hydrogels that are s enough to make soft contact lenses, which possess high oxygen penneabili suitable water content, and sufficient elasticity, and are comfortable to the contact lens wearer. Summary of the Invention This invention provides a silicone hydrogel prepared by curing a reaction mixture comprising either or both of the silicone-containing monomers of Structure I and II. Structure I has the following structure: wherein R51 is H or CH3, q is 1 or 2 and for each q, R52, R53 and R54 are independently an alkyl or an aromatic, preferably ethyl, methyl, benzyl, phenyl, or a monovalent siloxanc chain comprising from 1 to 100 repeating Si-O units, p is 1 to 10, r — (3-q), X is O or NR55, where R55 is H or a monovalent alkyl group with 1 to 4 carbons, a is 0 or 1. and L is a divalent 4 linking group which preferably comprises from 2 to 5 carbons, which may also optionally comprise ether or hydroxyi groups, for example, a polyethylene gSyco! chain. Structure II has the following structure: where b = 0 to 100, preferably 8 to 10; R58 is a monovalcnt group containing an ethylcnically unsaturated moiety, preferably a monovalent group containing a styryl, vinyl, or mcthacrylate moiety, more preferably a methacrylate moiety; each R59 is independently a monovalent alkyl, or aryl group, which may be further substituted with alcohol, amine, ketone, carboxylic acid or ether groups, preferably unsubstituted rnonovalent alky! at aryl groups, more preferably methyl; and R«o is a monovalent alkyl, or and group, which maybe further substituted with alcohol, amine, ketone, carboxylic acid or ether groups, preferably unsubstitutcd monovalent alkyl or aryl groups, preferably a C1-10 aliphatic or aromatic group which may include hetero atoms, more preferably C3-6 alkyl groups, most preferably butyl, particularly sec-butyl group. In the preferred embodiment, the silicone hydrogel comprises monomers of both Structure I and n. More preferably, the silicons hydrogel comprises silicone-containing monomer of Structure 1 and H and a hydrophilic monomer. Among the advantages of this invention is that the use of the silicons-containing monomers of either or both Structure I and Structure II in a silicone hydrogel reduces the Young's modulus of the hydrogel especially in hydrogels which comprise these silicone-containing monomers and 5 additional siliconc-containing monomers which act as crosslinkers. The monomers of Structure I and II are more effective at lowering the modulus of the siticone hydrogel than far monomers described in the prior art. Additionally, the tan (delta) of the silicone hydrogels of this invention, may be concurrently preserved. It seems likely that this effect is because the siloxane group is less bulky than that of silicone-containing monomers used in the prior art, such as TRIS. The polymers produced according to this invention can be used to produce soft contact lenses that will provide high oxygen permeability, good elasticity; and can be produced economically and efficiently. The polymer of this invention can be used to make biomedical devices which require biocompatability and high oxygen permeability, preferably contact lenses. Detailed Description of the invention and Preferred Embodiments The term "monomer" used herein refers to low molecular weight compounds (i.e. typically having number average molecular weights less man 700} that can be polymerized, and to medium to high molecular weight compounds or polymers, sometimes referred to as macromonomers, (i.e. typically having number average molecular weights greater than 700) containing functional groups capable of further polymerization. Thus, it is understood that the terms "silicone-containing monomers" and "hydrophilic monomers" include monomers, macromonomers and prepolymers. Prepolyraers are partially polymerized monomers or monomers which are capable of further polymerization. A "silicone-containing monomer" is one that contains at least two [-Si-O-] repeating units in a monomer, macromer or prepolymer. Preferably, the total Si and attached O are present in the silicone-containing monomer in an amount greater than 20 weight percent, and more preferably greater than 30 weight percent of the total molecular weight of the silicone-containing monomer. 6 Examples of the silicone-containing monomers of Structure 1 that can be used to form silicone hydrogels of this invention are, without limitation, methacryloxypropylbis(trimethylsiloxy)methylai]ane, mediacryloxypropylpentarnethyldisiloxane, and (3-methacryloxy-2-hydroxypropyloxy) propylbiB(mmethyisiloxy)methyIsilane. While such silicone monomers may additionally be used, linear mono-alky! terminated polydiniethyisiloxanes ("mPDMS") such as those shown in the following Structure II must be used: where b - 0 to 100, preferably 8 to 10; Rse is a monovaJent group containing a ethylenically unsaturated moiety, preferably a monovalent group containing a styryl, vinyl, or methacrylate moiety, more preferably a methacrylate moiety; each R59 is independently a monovalent alkyl, or aryl group, which may be further substituted with alcohol, amine, kctone, carboxylic acid or ether groups, preferably unsubstituted monovalent alkyl or aryl groups, more preferably methyl; and R«o is a monovalent alkyl, or aryl group, which may be further substituted with alcohol, amine, ketone, carboxylic acid or ether groups, preferably unsubstituted monovalent alkyl or aryl groups, preferably a C1-10 aliphatic or aromatic group which may include hetcro atoms, more preferably C3-8 alkyl groups, most preferably butyl, particularly sec-butyl group. The amount of mPDMS comprising the hydrogel is closely related to the modulus and tan (delta) of the hydrogels made according to this invention. Tan (delta) is defined as the loss modulus of the material divided by its elastic modulus (G"/G'). It is desirable to lower both the modulus and tan (delta) in silicone hydrogel lenses for a number of reasons. First, lower modulus and tan (delta) are manifested as less stiff and after stress quickly 7 return to their original shape. This improves comfort over traditional silicone hydrogel lenses and makes them more aesthetically appealing given their ability to retain their round shape. Further, the incidence of superior epithelial arcurate lesions ("SEALs") is either or both lessened and eliminated by using lenses made from a polymer having a sufficiently low modulus and tan (delta). Thus, replacing lenses made from high modulus, high tan (delta) polymers with those of the instant invention is a means for reducing or eliminating the occurrence of SEALs. This is particularly the case for contact lens wearers that are prone to SEALs. Desirably, silicone hydrogels made according to the invention comprise between about 2 and 70%wt mPDMS based on total weight of reactive monomer components from which the polymer is made. Depending upon the other monomers present, this will generally reduce the modulus of the polymer to between about 20 and 180 psi and a tan (delta) of less than about 0.1 to no more than about 0.3 (measured at a frequency of 1 Hz and a temperature of 25°C, according to the method described in Example 21). Silicone hydrogels made according to the invention and comprising between about 4 and 50 %wt mPDMS (same basis as above) are preferred. These will generally exhibit a modulus between about 30 and 160 psi and a tan (delta) of less than about 0.25 (measured at a frequency of 1 Hz and a temperature of 25C). Silicone hydrogels made according to the invention and comprising between about 8 and 40 %wt mPDMS (same basis as above) are most preferred. These hydrogels will generally exhibit a modulus between about 40 and 130 psi and a tan (delta) of about 0.2 or less (measured at a frequency of I Hz and a temperature of 25°C. Hydrogels having tan (delta) less than about 0.1 can also be made according to this invention as described more fully below. Additional silicone-containing monomers may be combined with the silicone-containing monomers of Stuctures I and II to form the soft contact lenses of the invention. Any known silicone-containmg monomers useful for making silicone hydrogels can be used in combination with the silicone- 8 containing monomer of Structure I and II to form the soft contact lenses of this invention. Many silicone-containing monomers useful for this purpose are disclosed in U.S. Patent No. 6,020,445 incorporated herein in its entirety by reference. Useful additional silicone-containing monomers combined with the silicone-containing monomers of Structure I to form the silicone hydrogels of this invention are the hydroxyalkylamine-functional silicone-containing monomers disclosed in U.S. Patent No. 5,962448 incorporated herein in its entirety by reference. The preferred silicone-containing linear or branched hydroxyalkylamine-functional monomers comprising a block or random monomer of the following structure: Structure III wherein: n is 0 to 500 and m is 0 to 500 and (n + m) = 10 to 500 and more preferably 20 to 250; R2, R4, R5 ,R6 ,and R7 are independently a monovalent allcyl, or aryl group, which may be further substituted with alcohol, ester, amine, ketone, carboxylic acid or ether groups, preferably unsubstituted monovalent alkyl or aryl groups; and R1, R3 and R8 are independently a monovalent alkyl, or aryl group, which may be further substituted with an alcohol, ester, amine, ketone, carboxylic acid or ether group, preferably unsubstituted monovalent alkyl or aryl groups, or are the following nitrogen-containing structure: Structure IV with the proviso that at least one of R1, R3, and R8 are according to Structure 9 IV, wherein R9 is a divalent alkyl group such as -(CH2)s- where s is from ] to 10, preferably 3 to 6 and most preferably 3; R10 and R11 are independently H, a monovalent alkyl or aryl group which may be further substituted with an alcohol, ester, amine. ketone, carboxylic acid or ether group, or has the following structure: Structure V where R14, is H, or a monovalent polymerizable group comprising acryloyl, methacryloyl, styryl, vinyl, allyl or N-viayl lactam, preferably H or methacryloyl; Ri« is either H, a mosovalent alkyl or aryl group which can be further substituted with alcohol, ester, amine, ketone, carboxylic acid or ether groups, or a polymerizable group comprising acrylate, methacrylate, styryl, vinyl, allyl or N-vinyl lactam, preferably alkyl substituted with an alcohol or methacrylatc, R12, R13 and R15 are indepcmdcntly H, a monovalent alkyl or aryl, which can be further substituted wife alcohol, eater, amine, ketone, carboxylic acid or ether groups, or R12 and R13 , or R15 and R13 can be bonded together to form a ring structure, with the proviso that at least some of the Structure IV groups on me monomer comprises polymerizable groups. R12, R 13 and R15 are preferably H. In alternative embodiments, the silicone hydrogcls of this invention, comprising the silicone-contaming monomers of either or both Structure I and Structure II may further comprise hydrophilic monomers. The hydrophilic monomers optionally used to make the hydrogel polymer of this invention can be any of the known hydrophilic monomers disclosed in the prior art to make hydrogels. The preferred hydrophilic monomers used to make the polymer of this invention may be either acrylic- or vinyl-containing. Such hydrophilic monomers may themselves be used as crosslinking agents. The term "vinyl-type" or "vinyl-containing" monomers refer to monomers containing the 10 wnyi grouping (^CH^CHa) and are generally highly reactive. Such lydrophilic vinyl-containing monomers are known to polymerize relatively vastly. type° or "acx^ic^contaiHm^monomers are those monomers ;ontaining the acrylic group; (CHj^CRCOX) wherein R is H or CH3, and X s O or N, which are also known to polymerize! readily, such as N»N-Umethyl aczylamide (DMA), 2-hydroxyethyl melhacryiate (HEMA), glycerol QCthacryiate, 2-hydroxycthyl methacrylaxmde, polyethyieneglycol monoraethacryiate, methacrylic acid and acrylic acid. Hydrophilic vinyl-containing monomers which may be incorporated into the siliconc hydrogels of the present invention include monomers such as N-vinyl lactams (e.g. NVP), N-vinyi-N-methyl acetaraide N-vinyl-N-ethyl acetamide, N-vinyl-N-ethyl formamide, N-vinyl formamidc, with NVP being preferred. Other hydrophilic monomers that can be employed in the invention include polyoxyethylcnc polyols having one or more of the terminal hydroxyl groups replaced with a functional group containing a polymerizablc double bond. Examples include polyethylene glycol, cthoxyiated alky] glucoside, and ethoxylated bxsphenol A reacted with one or more molar equivalents of an end-capping group such as isocyanatoethyl rnethacryiate (*X£MR), methacrylic anhydride, methacryloyt chloride, vinylbcnzoyl chloride, or the like, to prwluce a polyethylene colyol having one or more terminal polymcrizable olefinic groups bonded to the polyethylene polyol through linking moietica such as carbamate or ester groups. Still further examples are the hydrophilic vinyl carbonate or vinyl carbamate monomers disclosed in U.S. Patents No. 5,070,215, and the hydrophilic oxazolone monomers disclosed in U.S. Patents No. 4,910,277. Other suitable hydrophilic monomers will be apparent to one skilled in the art More preferred hydrophilic monomers which may be incorporated into the polymer of the present invention include hydrophilic monomers such 11 as DMA, HEMA, giyeero! methacryiate, 2-hydroxyethyl raethacryiamide, NVP, polyethylcneglycol raonomethacrylate, melhacrylic acid and acrylic acid with DMA being the most preferred. Other monomers that can be present in the reaction mixture used to form the silicone hydrogel of this invention include ultra-violet absorbing monomers, reactive tints and the like. Additional processing aids such as release agents or wetting agents can also be added to the reaction mixture. A polymerization catalyst is preferably included in the reaction mixture. The polymerization catalyst can be a compound such as lauroyl peroxide, benzoyl peroxide, isopropyl percarbonatc, azobisisobutyronitrile, or the like, that generates fixe radicals at moderately elevated temperatures, or the polymerization catalyst can be a photoinitiator system such as an aromatic alpha-hydroxy kctonc or a tertiary smine plus a diketone. Illustrative examples of photoinitiator systems are 2-bydroxy-2-methyl-l -phenyl-propan-1 -one, and a combination of camphoxquinono and ethyl 4-(N,N-dimethylamiiio)benzoat{i. The catalyst is used in the reaction mixture in catalytically effective amounts, e.g., &om about 0.1 to about 2 parts by weight per 100 parts of reactive monomer. Polymerization of the reaction mixture can be initiated using the appropriate choice of heat or visible or ultraviolet light or other means depending on the polymerization initiator used. The preferred initiator is a I; 1 blend of l-bydroxycyclohexyl phenyl ketonc and bis(2, 6-dimcthoxybenzoyl)-2,4,4-trimethylpentyi phosphine oxide and the preferred method of polymerization initiation is UV light. Typically after curing of the reaction mixture of the silicone-containing monomers of either or both Structure I and H and optional hydrophilie monomers and any other optional ingredients such as additional silicone-containing monomers, diluents, crosslinking agents, catalysts, release agents, tints etc. which are blended together prior to polymerization, the resulting polymer is treated with a solvent to remove the diluent (if used) or any traces of unreactcd components, and hydrate the polymer to form the 13 monomers such as 3-(trimethylsiloxy)propyl methacrylate are included in the macromer. Initiators, reaction conditions, monomers, and catalysts that can be used to make GTP polymers are described in "Group-Transfer Polymerization" by O.W. Webster, in Encyclopedia of Polymer Science and Engineering Ed. (John Wiley & Sons) p. 580, 1987. These polymerizations are conducted under anhydrous conditions. Hydroxyl-functional monomers, like HEMA, can be incorporated as their trimethylsiloxy esters, with hydrolysis to form free hydroxyl group alter polymerization. GTP offers the ability to assemble macromers with control over molecular weight distribution and monoroer distribution on the chains. This macromer is then reacted with a reaction mixture comprising predominantly polydimcthylsiloxanc (preferably. Preferred macromer components include mPDMS, TR1S, methyl methacrylate, HEMA, DMA, inethacrylonitrUc, ethyl methacrylate, butyl ntethacrylate, 2-hydroxypropyl-l-methacrylate 2-hydroxyethyI methacrylamidc and methacrylic acid. It is even more preferred that the macromer is made from a reaction mixture comprising HEMA, methyl methacrylate, TRIS, and mPDMS. It is most preferred that macromer is made from a reaction mixture comprising, consisting essentially of, or consisting of about 19,1 moles of HEMA, about 2.8 moles of methyl methacrylate, about 7.9 moles of THIS, and about 3.3 moles of mono* rncthacryloxypropyl terminated mono-butyl terminated polydimcthylsiloxanc, and is completed by reacting the aforementioned material with about 2.0 moles per mole of 3-isoprapenyl-O3,a>-dimethylbenzyI isocyanatc using dibutyltin dilauxate as a catalyst. Silicone hydrogels can be made by reacting blends of macromers, monomers, and other additives such as UV blockers, tints, internal wetting agents, and polymerization initiators. The reactive components of these blends typically comprise a combination of hydrophobic silicone with very 14 hydrophilic components. Since these components are often immiscible because of their differences in polarity, it is particularly advantageous to incorporate & combination of hydrophobia silicone monomers with hydrophilic monomers, especially those with hydroxyi groups* into the macromer. The macromer can then serve to compatibilize the additional silicone and hydrophilic monomers that are incorporated in the final reaction mixture. These blende typically also contain diluents to further compatibilize and solubil&e all components. Preferably, the silicone based hydrogcls are made by reacting the following monomer mix: macromer; an Si?^ monomethacryloxy terminated polydimcthyi siloxane; and hydrophilic monomers together with minor amounts of additives and photoinitiators. It is more preferred that the hydrogels are made by reacting macromer; an Si7.9 monomethacryloxy terminated polydimethyl siloxane; TRIS; DMA; HEMA; and tetraethyleneglycol dimethacrylate ('TEGDMA"). It is most preferred that the hydrogels are made from the reaction of (all amounts are calculated as weight percent of the total weight of the combination) macromer (about 18%); an S17-9 monomethacryloxy terminated polydimethyl siloxane (about 28%); TRIS (about 14%); DMA (about 26%); HEMA (about 5%); TEGDMA (about 1%), polyvinyipyrroHdone (*PVF) (about 5%); with the balance comprising minor amounts of additives and photoinitiators, and that the reaction is conducted in the presence of 20%wt dimethyl-3-octanol diluent. Various processes are known for molding the reaction mixture in the production of contact lenses, including spincasting and static casting. Spincasting methods are disclosed in U.S. Patents Nos. 3,408,429 and 3.660,545, and static casting methods are disclosed in U.S. Patents Nos. 4,113,224 and 4,197,266. The preferred method for producing contact lenses comprising the polymer of this invention is by the direct molding of fee silicone hydrogels, which is economical, and enables precise control over the final shape of the hydrated lens. For this method, the reaction mixture is placed in a, moid having the shape of the final desired silicone hydrogel, i.e. 16 percent of the reactive components Is a hydrophilic monomer, more preferably DMA, about 0.1 to 1.0 percent of the reactive components is a UV or visible light-active photoiuitiator and about 0 to 20 weight percent of the total reaction mixture is a secondary or tertiary alcohol diluent, more preferably a tertiary alcohol. The reaction mixtures of the present invention can be formed by any of the methods known to those skilled in the art, such as shaking or stirring, and used to form polymeric articles or devices by the methods described earlier. For some monomer reaction mixtures it is preferred to polymerize the reaction mixtures at temperatures slightly above room temperature, such as 30-40'C or below room temperature, such as 0-100C, so as to prevent phase separation of the components. Silicone hydrogets of the instant invention have high oxygen permeability. They have O2 Dk values between about 40 and 300 baiter determined by the polarographic method. Polarographic method measurements of oxygen permeability are made as follows. Lenses are positioned on the sensor then covered on the upper side with a mesh support. The oxygen which diffuses through the lens Is measured using a polarographic oxygen sensor consisting of a 4 mm diameter gold cathode and a silver ring anode. The reference values are those measured on commercially available contact lenses using this method. Balafilcon A lenses available from Bausch &. Lamb give a measurement of approximately 79 barrcr. EtafiJcon leases give a measurement of about 20 to 25 barrer. Contact lenses made from the sxlicone hydrogels of the invention may be produced to include a surface layer that is more hydrophilic than the silicone hydzogel. Suitable materials for forming the surface layer are known in the art Preferred materials include poly(acryiic acid), poly(methacrylic acid), poly(maleic acid), poly(itaconic acid), poly(acrylamide), block or random copolymers of (mcth)acryHc acid, acrylic acid, maleic acid, itaconic acid with any reactive vinyl monomer, carboxymethylated polymers, such as carboxymethylccllulose, and the like, and mixtures thereof: Preferably, the 17 carboxyl functional hydraphilic polymer is poly(aerylsc acid), poly(methacrylic acid), poly(meth)aciylamide, or poly(acrylamide). More preferably, poly(acrylic acid) or po!y(acrylamide) is used. Methods for coating contact lenses are disclosed in U.S. patent No. 6,087,415 incorporated herein is its entirely by reference. The non-limiting examples below further describe this invention. In the examples the following abbreviations are used: Examples MBM 3-methacryioxypropylbis(trimcthylsiloxy)methylBilane MPD tncthacryloxypropyipentaraethyJ disiioxanc THIS 3-methacryloxypropyltris (trimethylailoxy) silane DMA N,N-dimethylacrylamide THF tetrahydrofiiran Hv0 dimethyl meta-isopropenyl benzyl isocyanate HEMA 2-hydroxycthy 1 mcthacrylate TEGDMA tetraethyleneglycol dimctbacrylatc EGDMA ethyleneglycol dimethacrylate MMA methyl methactylate TBACB tctrabut>d amm onium-m-chJorobenzoate raPDMS monomcthacryloxypropyl terminated polydiraethylsiloxane PDMS polydimcthylsiloxane 3M3P 3-methyl-3-propanol Norbloc 2-(2-hydroxy-5-methacryiyloxyethylpheiiyl>2H- benzotri azoic CC311850 1:1 (wt) blend of l-hjsJroxycyctohexyl phenyl ketone and bis(2,6-dimcthoxybeii2oyI)-2)4-4-trimethylpentyl phosphine oxide PVP poly(N-vinyl pyrtolidone) IP A isopropyl alcohol 18 DAROCURE 1173 2-hydroxy-2-meihyl-l-phenyI-\|m>pan-i-one D3O 3,7-dimethyl~3-octanol HO Ac acetic acid TAA t-amyl alcohol PREPARATION 1 - Preparation of Polysiloxanc Monomer 500 grams of a,co-bisaminopropyl polydixnethyisiloxane (5000 MW) and 68 grams of glycidyl methacrylate were combined and heated with stirring at 100°C for 10 hours. The product was extracted five times with 1500 mi of acetonitrile to remove residual glycidyl methacrylate to give a clear oU. JR: 3441,2962,1944, 1725,1638,1612,1412 cm"1. This product will be Teferred to as "the reaction product of glycidyl methacrylate and 5000 MW 0,00-bisaminopropyi polydimcthylsiloxane" or alternatively bifi(N,N-bis-2-h>1droxy-3-methacryloxypropyI)aminopropylpolydimethyIsiloxane. Example 1 3S.2 parts by weight of the product of PREPARATION 1 was combined with 2S.8 parts MBM, 33 parts DMA and 1 part DAROCUR 1173 and diluted with 3-methyl-3~peatanol to make a reaction mixture in which the diluent made up 9% of the mass of the complete reaction mixture. The resulting reaction mixture was a clear, homogeneous solution. Polypropylene contact lens molds were filled, closed and irradiated with a total of 3.2 J/cm2 UV light from a fluorescent UV source over a 30-minute period. The molds were opened and the lenses were released into isopropanol and then transferred into deionized water. The lenses were clear and had a tensile modulus of 205 ±12 g/mm2, an elongation at break of 133 ±37 %, and an equilibrium water content of 24.2 ±0.2 %. Tensile properties were determined using an Xnstron™ model 1122 tensile tester. Equilibrium Water Contests (EWC) were determined gravimctrically and are expressed as: 19 %EWC = 100 x (mass of hydratcd lens - mass of dry lens)/mass of hydrated lens Examples 2-16 Reaction mixtures were made using the formulation of Example 1, but with amounts listed in Table 1, All reaction mixtures and lenses were clear. 20 Example 17 21.5% of ?,?-bismethacryloxypropyl polydimethylsiloxane -with an average molecular weight of 5000 g/mol was combined with 42.5% MBM, 35% DMA and 1% DAROCUR 1173 and diluted with 3-methyl-3-penmnol to give a clear solution containing 22 weight % diluent. Lenses were made following the procedure of Example 1. The lens properties are shown is Table 2. Example 18 Lenses were made using the procedure and reaction mixture described in Example 17, but with MPD in place of MBM. The lens properties are shown in Table 2. Comparative Example 1 A reaction mixture was made using the formulation of Example 17, but with TRIE in place of MBM, and with 20% diluent Lenses were made following the procedure of Example 1. The lens properties, shown in Table 2. show that the use of MBM (Example 17) or MPD (Example 18) gave lower moduli when used in place of TRIS. 21 Example 19 29-8% of ?,?-biKnefeaccyloxypropyl polydimethylsiloxane with an average molecular weight of 5000 g/mol was combined with 35% mono-metbacryioxypropyl terminated PDMS (Tl, Structure H, MW = 800 to 1000), 35% DMA and 1% DAROCUH 1173 aad ditoted with 3-methyl-3-peman0l to give a clear solution containing 23.0 weight % diluent Lenses were made following the procedure of Example 1. The lens properties are shown in Table 3. Example 20 29.0% of ?,?-bismcthacryloxypropyl polydimethytsiloxane with an average molecular weight of 5000 g/mol was combined with 35% (3- methacrydoxy-2-hydroxypropyloxy)prapylbis(trimenthythylsiloxy)methylsilane 22 (T2). 35% DMA and 1% DAROCUR1173 and diluted with 3M3P to give a clear solution containing 37.6 weight % diluent. Lenses were made following the procedure of Example 1. The lens properties are shown in Table 3. The Examples show that the contact lenses made using die siticone-conuining monomers of Structure I provide contact lenses which axe clear and have a lower Young's modulus than the contact lenses made according to the Comparative Examples. A low modulus is desirable to provide contact lenses which are comfortable when worn. 23 Example 21 The following compositions were prepared, and cured with UV light into Hat sheets. These sheets were extracted with isopropanol to remove diluent and any unreacted monomer, then equilibrated in isotonic borate buffered saline. 24 1000MW was purchased from Gelest Inc. as "MCR-Mt 1" brand mPDMS. 5000MW was purchased from Gelest Inc. as "MCR-M17' brand mPDMS. (Molecular weights for mPDMS and PDMS shown above are number average molecular weights). The structure of mPDMS used in this example was: For the determination of the properties after hydration, the 25 mm diameter hydrogel disks (each approximately 0.7 mm thick) were held between the 25 mm diameter parallel plates (plated with a crystal clad 80/100 grit coating) of a controlled stress rheometer (ATS Stresstech) with a vertical force of 10 N. The disks were immersed in water during the test to prevent dehydration. A stress sweep from 100 to 10,000 Pa at 1 Hz and 25°C was conducted on a disk of each material, to determine the range of the linear viscoelastic region for each formulation. 25 Once the limit of the linear viscoclastic region had been determined, the rhcomctcr was set in frequency sweep mode using a stress less than the predetermined limit, and G\ G", n. and tan 5 of the 25 mm diameter hydrated disks were measured as a function of frequency from 0.01 - 30 Mz at several temperatures (10,25,40 and 55°C)» all the while maintaining a vertical force of 10 N on the hytirogel disks. The individual frequency scans of C and tan 5 were then combined to foim master curves for each material. Hie data for the shear modulus G* and tan 8 of the hydrogels at a reference temperature of 25°C are shown in tables 4 and 5. The shear modulus of sample A was greater than B is the frequency range in which they were tested (as would be expected since the only difference between them is the molecular weight between crosslinks: 1000 vs. 3000), and their shear moduli gradually increased with increasing frequency. At the high frequency extreme, sample A appeared to be approaching a transition, since the modulus appeared to be approaching a region of more rapid increase. The taxi 5 of samples A and B were below 0.2 for the most pan, with the tan 6 of sample A increasing at the high frequencies in anticipation of a transition at higher frequencies. Similarly, the shear modulus of sample D was greater than £ in the frequency range in which they were tested (the only difference between them is the molecular weight of the dangling chains: 1000 vs. 5000), and their shear moduli gradually increased with increasing frequency. The tan 8 of samples D and £ was below 0.1 for the entire frequency range in which they were tested, with the tan o of sample E (MW 3 000) below that of sample D (MW 5000). The shear modulus of sample C increased rapidly in the frequency range in which it was tested, indicating a transition from a rubbery to a more rigid state. The bulky TRIS moiety reduced the internal molecular mobility of the hydrogel (relative to the PDMS and mPDMS polymers), and caused the "glass" transition to shift to lower frequencies (¦ higher temperatures). 26 The tan 5 of sample C readied a maximum at 100 hz at the reference temperature of 40°C» indicative of the transition. The addition of mono-capped PDMS was more effective than* the addition of di-capped PDMS in reducing the tan 5 of the hydro gel. The elastic properties of a material were controlled by the judicious addition of mPDMS while maintaining the homogeneity of the material. On the other hand, the addition of TRIS increased the tan S of a material. 27 28 29 Example 22- SEALs Study A double masked, contralaieral, randomized, complete block clinical study was conducted to determine the relationship between SEALs and the Young's modulus of contact lenses. Looses were made from two different silicone hydrogel compositions as follows. The silicone-based xnacroraer refers to a prepolyracr in which one mole was made from an average of 19.1 moles of 2-hydroxyetfayl methaerylate, 2.8 moles of methyl methacrylate, 7.9 moles of mcthacryioxypropy]tris(triincthylsiloxy)silane, and 33 moles of mono-methacryloxypropyi terminated mono-butyi terminated polydimcthylailoxane. The macromer was completed by reacting the aforementioned material with 2.0 moles per mole of 3-isopropcnyi-o),t>-dimethylbenzyl isocyanare using dibutyltin dilBurate as a catalyst for the Group Transfer Polymerization used to produce the raacromer product Weight percentages arc computed based on the total weight of all components; the balance of the compositions in Table 5 comprise initiators 30 and additives. The mPDMS was a mono-methacryloxy propyl terminated mPDMS. Lenses were made from these compositions having a nominal base curve of 8.5 mm and a diameter of 14.0 mm at 22°C. They had a nominal center thickness of 0.110 mm and a measured center thickness of 0.119 (Lens A) and O.OSS mm (Lens B). Both lenses were coated with a hydrophilic coating to enhance bio compatibility and wettahility. Lens A had a Young's modulus of 109.4 psi and Lens B had a Young's modulus of 88.5 psi. Subjects participating in the study were given a baseline examination and fined with leases made from the compositions shown in Table 6. They then wore the lenses for one week. Lenses were worn for daily wear. The subjects returned for a clinical evaluation of the presence of SEALs and other clinical data (e.g. visual acuity). Nineteen subjects (38 eyes) completed lite study, eight of whom had a history of SEALs. Ten (10) eyes wearing Lens A exhibited SEALs. No eyes wearing Lens B exhibited SEALs. Example 23 - SEALs Study A study similar to that of Example 22 was conducted using lenses of different center thicknesses. The lenses had the following characteristics and gave the results shown is Table 7. Is Table 7, column 4, E" represents Young's modulus and "CT represents the center thickness. •Refer* to less composition corresponding to Exunple 22. This examples shows the combined effect of lens center thickness and modulus on SEALs. 32 hours. A solution of lO.Og b is (dimethylamino)m ethyls i lane, 154.26 g methyl methaciylate, and 1892.13 g 2-(trimethylsiloxy)ethyl methacrylate was then added and the mixture was again allowed to exotherm. After 2 hours, 2 gallons of anhydrous THF was added, followed by a solution of 439.69 g water, 740.6 g methanol and 8.8 g dichloroacctic acid after the solution was allowed to cool down to 34°C. The mixture was refluxed for 4.5 hours, heating with an oil bath atl 10°C, and volatiles were distilled off at 135°C, with addition of toluene to aid in removal of water, until a vapor temperature of 110°C is reached. The reaction flask was cooled to 110°C, and a solution of 443 g TMI and 5.7 g dibutyltin dilaurate was added. The mixture was reacted for 3.5 hours, then cooled to 30°C. The toluene was evaporated under reduced pressure to yield off-white, anhydrous, waxy, reactive macromer. The theoretical OH content of the macromer is 1.69 mmol/g. Macromer B: The procedure for Macromer A used except that 19.1 mole parts HEMA, 7.8 mole parts MAA, 7.9 mole parts TRIS, 3.3 mole parts TRIS, and 2.0 mole parts TMI were used. Macromer C: The procedure for Macromer A was used except that 19.1 mole parts HEMA, 7.9 mole parts TRIS, 3.3 mole parts TRIS, and 2.0 mole parts TMI were used. Examples 26 - 36 (Lens Formation) Hydrogel were made from the monomer mixtures shown on Table 8. All amounts are calculated as weight percent of the total weight of the combination with the balance of the mixture being minor amounts of additives. Polymerization was conducted in the presence of the diluents listed. 33 Contact lenses were formed by adding about 0.10 g of the monomer mix to che cavity of an eight cavity lens mold of the type described in U.S. Patent 4,640489 and curing for 1200 sec. Polymerization occurred under a nitrogen purge and was photoinitiated with 5 mW cm"2 of UV light generated with an Andover Corp. 420PS10-25 AM39565-02 light filter. After curing, the molds were opened, and the lenses were released into a 1:1 blend of water and ethanoi, then leached in ethanol to remove any residual monomers and diluent. Finally the lenses were equilibrated in physiological boraie-buffcred saline. The lenses had the properties described in Table 8. 34 35 Example 37 To lenses from Example 27 immersed in a solution of 1.0% 250,000 Mw polyacrylic acid in water at 45°C was added 0.1 % 1 -[3-(dimcthyJamino)prDpyl]-3-ctliyIcaibtxiiimide hydrochloride. Alter stirring for 30 minutes the lenses are rinsed in borate-bufFered saline solution. The dynamic contact angles of the resulting poiy(sodmra acrylate)-coated lenses are 44° advancing and 42° receding. Comparative Example 2 Lenses were made by curing a blend of 57.5% TRIS, 40.0 % DMA, 1.5% l,3-bis 36 We claim. I. A method of lowering the Young's modulus and tan (delta) of a silicone hydrogel comprising the step of incorporating in said faydrogel, a mano-alkyi terminated polydimethylsiloxane monomer having the structure: where b = 0 to 100; R58 is a monovalent group comprising an ethyienically unsaturated moiety; each R39 is independently a monovalent alkyj, or aryl group, which may be farther substituted with alcohol, amine, ketonc, carboxylic acid or ether groups; and Ro is a monovalent alkyl, or aryl group, which may be further substituted with alcohol, amine, ketone, carboxylic acid or ether groups. 2. The method of claim 1, wherein b = 8 to 10, R38 is a monovalent group containing a styryl, vinyl, or methacrytate moiety, each R59 is methyl, and Rw is a C34 alky] group. 3. The method of claim 1, wherein b - 8 to 10, R58 is a methacrylate moiety; each R59 is methyl; and R$o is a butyl group. 4. The method of claim 1, wherein about 2-70 % wt» based on the total weight of reactive monomer, of ifee mono-alky! terminated polydimethylsiloxane is incorporated in said silicone hydrogel. 37 5. The method of claim 1, wherein said siiicone hydrogel additionally J> comprises a siliconc-containing monomer other ihan that of claim 1 and having the structure: wherein R3! is H or CH3, q is I or 2 and for each q, R52. R53 and R54 is independently an alkyl group, an aromatic group or a monovalent siloxane chain comprising from I to 100 repeating Si-O units, p is I to 10, r = (3-q)» X is O or NR55, where R55 is H or a monovalent alkyl group with 1 to 4 carbons, a is 0 or 1, and L is a divalent linking group. 6. The method of claim 5, wherein each of R32l R53, and R« is independently ethyl, methyl, benzyl or phenyl. 7. A fiilicone hydrogel having a Young's modulus less than about 180 psi and a Ian (delta) less than about 0.3 at a frequency of I Hz at 2S°C. 8. Use siiicone hydrogel of claim 7, wherein Use Young's modulus is less than about 130 psi 9. The siiicone hydrogel of claim 8, further comprising an Oj Dk greater than about 40 baiter. 38 16. The silicone hydrogel of claim 7, further comprising an O2 DK greater than about 40 barrcr. 11. The silicons hydrogel of claim 7,8,9 or 10,-6mker comprising about 2-70 % wt. based on fee total weight of reactive monomer, of a mono-alkyl terminated polydimethylsiloxane having the structure: where b - 0 to 100; R58 is a monovalent group comprising as ethylenically unsaturated moiety, each R59 is independently a monovalent alkyl. or aryl group, which may be substituted with alcohol, amine, ketone, earboxylic acid or ether groups; and R60 is a monovalent alkyl, or aryl group, which may be substituted with alcohol, amine, ketone, carboxylic acid or ether groups. 12. The method of claim 11, wherein b = 8 to 10, R58 is a monovalent group containing a styryl, vinyl, or methacrylate moiety, each R59 is methyl, andR60 is a C3-8 alkyl group, 13. The method of claim 11, wherein b = 8 to 10, R58 is a methacrylate moiety; each R59 is methyl; and R60 is a butyl group. 39 14. The silicone hydrogel of claim 11, wherein the mono-alkyl terminated polydimethylsiloxane is a monomcthacryloxypropyl terminated polydimethylsiloxane. 15. The siliconc hydrogel of claim 11, having a Young's modulus of about 30-160 psi. 16. The silicone hydrogel of claim 11, having a Young's modulus of about 40-13 psi. 17. A contact lens comprising a silicone hydrogel having a Young's modulus less than about 180 psi and s tan (delta) less than 0.25 at a frequency of 1 Hz at 250C. 18. The contact lens of claim 17, wherein the Young's modulus is less than about 130 psi. 19. The contact lens of claim 18, comprising an O2 Dk greater than about 40 barrcr. 20. The contact lens of claim 17, farther comprising an O2 Dk greater than about 40 barrcr. 21. The contact lens of claim 17, 18, 19 or 20, comprising about 2-70 % wt, based on the total weight of reactive monomer, of a mono-alkyl terminated polydimethylsiloxane having the structure: 40 where b = 0 to 100; R58 is a monovalent group comprising an ethylcnically unsaturated moiety, each R59 is independently a monovalcnt alkyl, or aryl group, which may be substituted with alcohol, amine, ketone, carboxylic acid or ether groups; and R60 is a monovalent alkyl, or aryl group, which may be substituted with alcohol, amine, ketone, carboxyiic acid or ether groups. 22. The method of claim 21, wherein b = 8to 10, R58 is a monovalent group containing a styryl, vinyl, or methacrylate moiety, each R59 is methyl, and R60 is a C3-8 alkyl group. 23. The method of claim 21. wherein b - 8 to 10, R58 is a methacrylate moiety, each R59 is methyl; and R60 is a butyl group. 24. Hie contact lens of claim 21, wherein the monoalkyl terminated polydimethylsiloxane is a rnonomethacryloxypropyl terminated polydimcthylsiloxane. 25. The contact lens of claim 21, wherein said silicone hydrogel has a Young's modulus of about 30-160 psi. 41 26. The contact lens of claim 21, wherein said silicone hydrogel has a Young's modulus of about 40-130 psi. 27. The contact lens of claim 21, comprising a surface layer that is more hydrophilic than said silicone hydrogel. 28. The contact lens of claim 21, Walter-comprising a coating that is more hydrophilic man said silicone hydrogel. 29. The contact lens of claim 27, wherein the surface layer comprises polyfacrylic acid). 30. The contact lens of claim 28, wherein the coating comprises poly(acrylic acid). 31. A silicone hydrogel contact lens comprising a center thickness (CT) of about SO to about 160 ?m and a Young's modulus (E) of about 40 to about 300 psi, wherein (E)(CT2) is less than about 1 psi • mm2. 32. The silicone hydrogel contact lens of claim 31, comprising a tan (delta) less than about 0.3 at a frequency of 1 Hz at 25°C. 33. The silicone hydrogel contact leas of claim 31,comprising an O2Dk greater than about 40 baiter. 34. The silicone hydrogel of claim 32, comprising an O2DK of greater than about 40 barrer. 42 35. The silicone hydrogel contact lens of claim 31, 32, 33, or 34, comprising at least 5% wt of a mono-alkyl terminated polydimethylsiloxane having the structure: where b = 0 to 100; R58 is a monovalent group comprising an ethylenically unsaturated moiety; each R59 is independently a monovalent alky], or aryl group, which may be further substituted with alcohol, amine, ketone, carboxylic acid or ether groups; and R60 is a monovalent alkyl, or aryl group, which may be-farther substituted with alcohol, amine, ketone, carboxylic acid or ether groups. 36. The method of claim 35, wherein b - 8 to 10, R58 is a monovalent group containing a styryl, vinyl, or mcthacrylatc moiety, each RS9 is methyl, andR60 is a C3-8 alkyl group. 37. The method of claim 35, wherein b = 8 to 10, R58 is a methacrylate moiety; each R59 is methyl; and R60 is a butyl group. 38. The silicone hydrogel contact lens of claim 35, wherein the raono- alkyl terminated polydimethylsiloxane is a monomethacryioxypropyl terminated polydimethylsiloxane. 43 39. The contact lens of claim 35, wherein the lens thickness is less than about SS ?m. 40. The contact lens of claim 35, wherein the thickness is less than about 100 pan and the Young's modulus is less than about 100 psi. 41. The contact lens of claim 35, wherein the amount of mono-alkyl terminated polydimcthylsiloxane is about 20 % wt 42. The contact lens of claim 35, wherein the thickness is less than 129 pm and the Young's modulus is less than about 60 psi. 43. The contact lens of claim 32, wherein the amount of mono-alkyl terminated polydimethylsiloxanc is about 30% wt. 44. A method of making a polymer comprising preparing a silicone based macromcr by Group Transfer Polymerization, and reacting said macromex with a polymerizable mixture comprising Si?-9 monomethacryloxy terminated polydimcthyl siloxane, polydimcthylsiloxane other than Si7-» monomethacryloxy terminated polydimethyl siloxane* and a hydrophilic monomer. 45. The method of claim 44, wherein said macromer is the reaction product of a reaction mixture comprising 2-hydroxycthyi rnethacrylate, methyl methacrylate, methacryloxypropyltri3(triincthyisiloxy)sUane, and mono-methacryloxypropyl terminated mono-butyl terminated polydimethylsiloxane. 45 51. The silicone hydrogel of claim 50, wherein the macromer is the Group Transfer Product of a reaction mixture comprising 2-hydroxyethyl methacryiate, methyl methacryiate. mcthacryloxypropyltris(trimethylsiloxy)silane, and mono-mctfaacryloxypmpyl terminated mono-butyl terminated potydimcthylsiloxane. 52. The silicone hydrogel of claim SO, wherein the macromer is the Group Transfer Polymerization product of reaction mixture comprising about 19.1 moles of 2-hydroxyetfay! methacryiate, about 2.8 moles of methyl methacryiate, about 7.9 moles of niediacr5doxy\|m3pyltris(trimetliylsiloxy)silane( and about 33 moles of mono-methacryloxypropyl terminated mono-butyl terminated polydimethylsiloxane 53. The silicone hydrogel of claim SO, 51, or 52 wherein the polymcrizable mixture comprises Si?.« monomethacryloxy terminated poiydimethyi siloxane; methacryioxypropyl tris(trimcthyl siloxy) silane; N,N-dimethyl acrylamide; 2-hydroxy ethyl methacryiate; and tetraethyleneglycol dimethacrylate. 54. The silicone bydrogcl of claim 53, wherein the macromer is present in an amount of about 10 to about 60 wt percent, the Si7.9 monometbacryloxy terminated polydimcthyl siloxane is present In an amount of about 0 to about 45 wt percent; the methacryloxypropyl tris(trimethyl siloxy) silane is present in an amount of about 0 to about 40 wt percent; the N,N-dimethyl acryiamide is present in an amount of about 5 to about 40 wt percent; the 2-hydroxy ethyl methacryiate is present in an amount of about 0 to about 10 wt percent; 46 and the terraethyleneglycol dimethacrylate is present in an amount of about 0 to about 5 wt percent. 55. The silicone hydrogcl of claim 53, wherein the macromer is present in an amount of about 15 to about 25 wt percent, the Si7^ monomethacryioxy terminated polydimethyl siloxane is present in an amount of about 20 to about 30 wt percent; the methacryioxypropyl tris(trimethyl siloxy) silanc is present in an amount of about 15 to about 25 wt percent; the N,N-dimethyI acrylamide is present in an amount of about 20 to about 30 wt percent; the 2- hydroxy ethyl methacrylaie is present 233 an amount of about 2 to about 7 wt percent; and the tetraethyleneglycol dimethacrylsie ts present in an amount of about 0 to about 5 wt percent 56. The silicone hydrogel of claim 53, wherein the polymerizable mixture farther comprises poly(N-vinyl pyrrolidinone). 57. The silicone hydrogel of claim 54, wherein the polymerizable mixture "teller comprises about 0 to about 10 wt percent pory(N-vinyl pyrrolidinone). 58. The silicons hydrogel of claim 55, wherein the polymerizable mixture fisf&el- comprises about 2 to about 7 wt percent poly(N-vinyl pyrrolidinone). 59. A contact lens comprising the reaction product of a silicone based macromer Group Transfer Polymerization product and a polymerizable mixture comprising Si7.9 monomethacryloxy terminated polydimethyl 47 siloxane, polydimeihylsiloxane other than Si7.9 monomethacryloxy terminated potydimethy] siloxane. and a hydrophilic monomer. 60. The contact lens of claim 59, wherein the roacroroer is the Group Transfer Product of a reaction mixture comprising 2-hydroxyethyl methacrytate, methyl roethacrylate, melhacrylox>propyItris(trimcthylsiloxy)Eilanc, and mono-mcthacryloxypropyt terminated mono-butyl terminated polydimdhylsiloxanc. 61. The contact lens of claim 60, wherein the macromcr is the Group Transfer Polymerization product of reaction mixture comprising about 19.1 moles of 2-hydroxyethyl methacrylate, about 2.8 moles of methyl meihacrylatc, about 7.9 moles of raethacryloxypropyltris(triinethyJsiloxy)silanc, and about 3.3 moles of mono-mcthacryloxypropyl terminated mono-butyl terminated polydimethylsiloxane 62. The contact lens of claim 59,60, or 61 wherein the polymerizable mixture comprises Si7-g monomothacryloxy terminated polydimethyl siloxane; mcthacryloxypropyl tris(trimethyl siloxy) silane; N.N-dimethyl acrylamide; 2-hydroxy ethyl methacrylate; and tctraethylenegiycol dimethacrylate. 63. Use contact lens of claim 62, wherein the macromcr is present in an amount of about 10 to about 60 wt percent, the S17.9 monomethacryloxy terminated polydimethyl siloxane is present in an amount of about 0 to about 45 wt percent; the methacryloxypropyl tm(trimethyl siloxy) silane is present in an amount of about 0 to about 40 wt percent; the N,N-dxmethyl acrylamide 48 is present in an. amount of about 5 to about 40 wt percent; the 2-hydroxy ethyl methacryiate is present in an amount of about 0 to about 10 wt percent; and the tetraethyleneglyeol dimethacrylate is present in an amount of about 0 to about 5 wt percent. 64. The contact lens of claim 62, wherein the macromer is present in an amount of about 15 to about 25 wt percent, the Si7-9 monomethacryloxy terminated polydimeihyl siloxane is present in an amount of about 20 to about 30 wt percent; the methacryloxypropyl tris(trimethyl siloxy) silanc is present in an amount of about 15 to about 25 wt percent; the N,N-dimethyI acrylamide is present in an amount of about 20 to about 30 wt percent; the 2-hydroxy cihyl methacrylate is present in an amount of about 2 to about 7 wt percent; and the tetraethyleneglycol dimethacxyiate is present is an amount of about 0 to about 5 wt percent. 65. The contact lens of claim 62, wherein the polymerizable mixture comprises poly(N-vinyi pyrrotidinone). 66. The contact lens of claim 63, wherein the polymerizable mixture comprises about 0 to about 10 wt percent poly(N-vmyl pyrrolidinonc). 67. The contact lens of claim 64, wherein the polymerizable mixture comprises about 2 to about 7 wt percent poly(N-vinyl pyrrolidinone). A method of lowering the Young's modulus and tan (delta) of a silicone hydrogel comprising the step of incorporating in said hydrogei, a mono-alkyl terminated polydimethylsiloxane monomer having the structure: Where b - 0 to 100; R58 is a monovalent group comprising an ethylenically unsaturated moiety; each R59 is independently a monovalent alkyl, or aryl group, which may be substituted with alcohol, amine, ketone, carboxylic acid or ether groups; and R60 is a monovalent alkyl, or aryl group, which may be substituted with alcohol, amine, ketone, carboxylic acid or ether groups.

Full Text

2
silicone-containing monomer or the hydrophilie monomer may function as a crosslinking agent (a croeslinking agent is a monomer having multiple polymerizable functionalities) or a separate crosslinking agent may be employed. The formation of silicone hydrogels has been disclosed in U.S. Patents Nos. 4,954,587, 5,010,141, 5,079,319, 5,115,056, 5,260,000, 5,336,797, 5,358,995, 5,387,632,5,451,617, 5,486,579 and WO 96/31792. Group Transfer Polymerization techniques for polymerizing acrylic and methacrylic monomers with terminal silyl containing monomers is described in various patents including U.S. Patents Nos. 4,414,372, 4,417,034, 4,508,880, 4,524,196, 4,581,428, 4388,795, 4,598,161, 4,605,716, 4,622,372,4,656,233, 4,659,782, 4,659,783, 4,681,918, 4.695,607, 4,711,942, 4,771,116, 5,019,634 and 5,021,524 each of which is incorporated in its entirety herein by reference.
U.S. Patent No. 3,808,178 discloses the formation of copolymers of small silicone-containing monomers and various hydrophilie monomers. U.S. Patent No. 5,034,461 describes silicone hydrogels prepared from various combinations of silicone-polyurethanc macromers and hydrophilie monomers such as HEMA or N,N-dimethyacrylamide ("DMA"). The addition of methacryloxypropyltris-(irimethylsiloxy)silane ("TRIS") reduced the modulus of such hydrogels, but in many examples the modulus was still higher than may be desired.
U.S. Patents Nos. 5,358,995 and 5,387,632 describe hydrogels made from various combinations of silicone macromers, TRIS, NVP and DMA. Replacing a substantial portion of the silicone macromer with TRIS reduced the modulus of the resulting hydrogels. Two publications from the same author, "The Role of Bulky Polysiloxanylalkyl Methacryiates in Polyurethane-Polysiloxane Hydrogels", J. Appl. Poly. Sci., Vol. 60,1193-1199 (1996), and "The Role of Bulky Polysiloxanylalkyl Methacryiates in Oxygen-Permeable Hydrogel Materials", J. Appl. Poly. Sci., Vol. 56, 317-

3
324 (199S) also describe experimental results indicating that the modulus of hydrogels made
from reaction mixtures of siliconc-macromers and hydrophilic monomers such as DMA decreases with added TRIS.
The use of mechacryloxypropylbis(trimethylsiloxy)methylsilane ("MBM") to make hard contact lenses was described in WO 9110155 and in JP 61123609.
When relatively high levels of bulky silicone-comaining monomers such as TRIS are incorporated into the hydrogels made from silicone-containing macromers and hydrophilic monomers, the elasticity, or the spe at which the polymer returns to its original shape after stress can be reduce to an extent that is unacceptable to the contact lens wearer.
There still remains a need in the an for silicono hydrogels that are s enough to make soft contact lenses, which possess high oxygen penneabili suitable water content, and sufficient elasticity, and are comfortable to the contact lens wearer.
Summary of the Invention
This invention provides a silicone hydrogel prepared by curing a reaction mixture comprising either or both of the silicone-containing monomers of Structure I and II. Structure I has the following structure:

wherein R51 is H or CH3, q is 1 or 2 and for each q, R52, R53 and R54 are independently an alkyl or an aromatic, preferably ethyl, methyl, benzyl, phenyl, or a monovalent siloxanc chain comprising from 1 to 100 repeating Si-O units, p is 1 to 10, r — (3-q), X is O or NR55, where R55 is H or a monovalent alkyl group with 1 to 4 carbons, a is 0 or 1. and L is a divalent

4
linking group which preferably comprises from 2 to 5 carbons, which may also optionally comprise ether or hydroxyi groups, for
example, a polyethylene gSyco! chain.
Structure II has the following structure:

where b = 0 to 100, preferably 8 to 10; R58 is a monovalcnt group containing an ethylcnically unsaturated moiety, preferably a monovalent group containing a styryl, vinyl, or mcthacrylate moiety, more preferably a methacrylate moiety; each R59 is independently a monovalent alkyl, or aryl group, which may be further substituted with alcohol, amine, ketone, carboxylic acid or ether groups, preferably unsubstituted rnonovalent alky! at aryl groups, more preferably methyl; and R«o is a monovalent alkyl, or and group, which maybe further substituted with alcohol, amine, ketone, carboxylic acid or ether groups, preferably unsubstitutcd monovalent alkyl or aryl groups, preferably a C1-10 aliphatic or aromatic group which may include hetero atoms, more preferably C3-6 alkyl groups, most preferably butyl, particularly sec-butyl group.
In the preferred embodiment, the silicone hydrogel comprises monomers of both Structure I and n. More preferably, the silicons hydrogel comprises silicone-containing monomer of Structure 1 and H and a hydrophilic monomer.
Among the advantages of this invention is that the use of the silicons-containing monomers of either or both Structure I and Structure II in a silicone hydrogel reduces the Young's modulus of the hydrogel especially in hydrogels which comprise these silicone-containing monomers and

5
additional siliconc-containing monomers which act as crosslinkers. The monomers of Structure I and II are more effective at lowering the modulus of the siticone hydrogel than far monomers described in the prior art. Additionally, the tan (delta) of the silicone hydrogels of this invention, may be concurrently preserved. It seems likely that this effect is because the siloxane group is less bulky than that of silicone-containing monomers used in the prior art, such as TRIS.
The polymers produced according to this invention can be used to produce soft contact lenses that will provide high oxygen permeability, good elasticity; and can be produced economically and efficiently. The polymer of this invention can be used to make biomedical devices which require biocompatability and high oxygen permeability, preferably contact lenses.
Detailed Description of the invention and Preferred Embodiments The term "monomer" used herein refers to low molecular weight compounds (i.e. typically having number average molecular weights less man 700} that can be polymerized, and to medium to high molecular weight compounds or polymers, sometimes referred to as macromonomers, (i.e. typically having number average molecular weights greater than 700) containing functional groups capable of further polymerization. Thus, it is understood that the terms "silicone-containing monomers" and "hydrophilic monomers" include monomers, macromonomers and prepolymers. Prepolyraers are partially polymerized monomers or monomers which are capable of further polymerization.
A "silicone-containing monomer" is one that contains at least two [-Si-O-] repeating units in a monomer, macromer or prepolymer. Preferably, the total Si and attached O are present in the silicone-containing monomer in an amount greater than 20 weight percent, and more preferably greater than 30 weight percent of the total molecular weight of the silicone-containing monomer.

6
Examples of the silicone-containing monomers of Structure 1 that can be used to form silicone hydrogels of this invention are, without limitation, methacryloxypropylbis(trimethylsiloxy)methylai]ane, mediacryloxypropylpentarnethyldisiloxane, and (3-methacryloxy-2-hydroxypropyloxy) propylbiB(mmethyisiloxy)methyIsilane. While such silicone monomers may additionally be used, linear mono-alky! terminated polydiniethyisiloxanes ("mPDMS") such as those shown in the following Structure II must be used:

where b - 0 to 100, preferably 8 to 10; Rse is a monovaJent group containing a ethylenically unsaturated moiety, preferably a monovalent group containing a styryl, vinyl, or methacrylate moiety, more preferably a methacrylate moiety; each R59 is independently a monovalent alkyl, or aryl group, which may be further substituted with alcohol, amine, kctone, carboxylic acid or ether groups, preferably unsubstituted monovalent alkyl or aryl groups, more preferably methyl; and R«o is a monovalent alkyl, or aryl group, which may be further substituted with alcohol, amine, ketone, carboxylic acid or ether groups, preferably unsubstituted monovalent alkyl or aryl groups, preferably a C1-10 aliphatic or aromatic group which may include hetcro atoms, more preferably C3-8 alkyl groups, most preferably butyl, particularly sec-butyl group.
The amount of mPDMS comprising the hydrogel is closely related to the modulus and tan (delta) of the hydrogels made according to this invention. Tan (delta) is defined as the loss modulus of the material divided by its elastic modulus (G"/G'). It is desirable to lower both the modulus and tan (delta) in silicone hydrogel lenses for a number of reasons. First, lower modulus and tan (delta) are manifested as less stiff and after stress quickly

7
return to their original shape. This improves comfort over traditional silicone hydrogel lenses and makes them more aesthetically appealing given their ability to retain their round shape. Further, the incidence of superior epithelial arcurate lesions ("SEALs") is either or both lessened and eliminated by using lenses made from a polymer having a sufficiently low modulus and tan (delta). Thus, replacing lenses made from high modulus, high tan (delta) polymers with those of the instant invention is a means for reducing or eliminating the occurrence of SEALs. This is particularly the case for contact lens wearers that are prone to SEALs.
Desirably, silicone hydrogels made according to the invention comprise between about 2 and 70%wt mPDMS based on total weight of reactive monomer components from which the polymer is made. Depending upon the other monomers present, this will generally reduce the modulus of the polymer to between about 20 and 180 psi and a tan (delta) of less than about 0.1 to no more than about 0.3 (measured at a frequency of 1 Hz and a temperature of 25°C, according to the method described in Example 21). Silicone hydrogels made according to the invention and comprising between about 4 and 50 %wt mPDMS (same basis as above) are preferred. These will generally exhibit a modulus between about 30 and 160 psi and a tan (delta) of less than about 0.25 (measured at a frequency of 1 Hz and a temperature of 25*C). Silicone hydrogels made according to the invention and comprising between about 8 and 40 %wt mPDMS (same basis as above) are most preferred. These hydrogels will generally exhibit a modulus between about 40 and 130 psi and a tan (delta) of about 0.2 or less (measured at a frequency of I Hz and a temperature of 25°C. Hydrogels having tan (delta) less than about 0.1 can also be made according to this invention as described more fully below.
Additional silicone-containing monomers may be combined with the silicone-containing monomers of Stuctures I and II to form the soft contact lenses of the invention. Any known silicone-containmg monomers useful for making silicone hydrogels can be used in combination with the silicone-

8
containing monomer of Structure I and II to form the soft contact lenses of this invention. Many silicone-containing monomers useful for this purpose are disclosed in U.S. Patent No. 6,020,445 incorporated herein in its entirety by reference. Useful additional silicone-containing monomers combined with the silicone-containing monomers of Structure I to form the silicone hydrogels of this invention are the hydroxyalkylamine-functional silicone-containing monomers disclosed in U.S. Patent No. 5,962448 incorporated herein in its entirety by reference. The preferred silicone-containing linear or branched hydroxyalkylamine-functional monomers comprising a block or random monomer of the following structure:

Structure III wherein:
n is 0 to 500 and m is 0 to 500 and (n + m) = 10 to 500 and more preferably 20 to 250; R2, R4, R5 ,R6 ,and R7 are independently a monovalent allcyl, or aryl group, which may be further substituted with alcohol, ester, amine, ketone, carboxylic acid or ether groups, preferably unsubstituted monovalent alkyl or aryl groups; and R1, R3 and R8 are independently a monovalent alkyl, or aryl group, which may be further substituted with an alcohol, ester, amine, ketone, carboxylic acid or ether group, preferably unsubstituted monovalent alkyl or aryl groups, or are the following nitrogen-containing structure:

Structure IV
with the proviso that at least one of R1, R3, and R8 are according to Structure

9
IV, wherein R9 is a divalent alkyl group such as -(CH2)s- where s is from ] to 10, preferably 3 to 6 and most preferably 3;
R10 and R11 are independently H, a monovalent alkyl or aryl group which may be further substituted with an alcohol, ester, amine. ketone, carboxylic acid or ether group, or has the following structure:

Structure V
where R14, is H, or a monovalent polymerizable group comprising acryloyl, methacryloyl, styryl, vinyl, allyl or N-viayl lactam, preferably H or methacryloyl; Ri« is either H, a mosovalent alkyl or aryl group which can be further substituted with alcohol, ester, amine, ketone, carboxylic acid or ether groups, or a polymerizable group comprising acrylate, methacrylate, styryl, vinyl, allyl or N-vinyl lactam, preferably alkyl substituted with an alcohol or methacrylatc, R12, R13 and R15 are
indepcmdcntly H, a monovalent alkyl or aryl, which can be further substituted wife alcohol, eater, amine, ketone, carboxylic acid or ether groups, or R12 and R13 , or R15 and R13 can be bonded together to form a ring structure, with the proviso that at least some of the Structure IV groups on me monomer comprises polymerizable groups. R12, R 13 and R15 are preferably H.
In alternative embodiments, the silicone hydrogcls of this invention, comprising the silicone-contaming monomers of either or both Structure I and Structure II may further comprise hydrophilic monomers. The hydrophilic monomers optionally used to make the hydrogel polymer of this invention can be any of the known hydrophilic monomers disclosed in the prior art to make hydrogels.
The preferred hydrophilic monomers used to make the polymer of this invention may be either acrylic- or vinyl-containing. Such hydrophilic monomers may themselves be used as crosslinking agents. The term "vinyl-type" or "vinyl-containing" monomers refer to monomers containing the

10
wnyi grouping (^CH^CHa) and are generally highly reactive. Such lydrophilic vinyl-containing monomers are known to polymerize relatively vastly.
type° or "acx^ic^contaiHm^monomers are those monomers ;ontaining the acrylic group; (CHj^CRCOX) wherein R is H or CH3, and X s O or N, which are also known to polymerize! readily, such as N»N-Umethyl aczylamide (DMA), 2-hydroxyethyl melhacryiate (HEMA), glycerol QCthacryiate, 2-hydroxycthyl methacrylaxmde, polyethyieneglycol monoraethacryiate, methacrylic acid and acrylic acid.
Hydrophilic vinyl-containing monomers which may be incorporated into the siliconc hydrogels of the present invention include monomers such as N-vinyl lactams (e.g. NVP), N-vinyi-N-methyl acetaraide* N-vinyl-N-ethyl acetamide, N-vinyl-N-ethyl formamide, N-vinyl formamidc, with NVP being preferred.
Other hydrophilic monomers that can be employed in the invention include polyoxyethylcnc polyols having one or more of the terminal hydroxyl groups replaced with a functional group containing a polymerizablc double bond. Examples include polyethylene glycol, cthoxyiated alky] glucoside, and ethoxylated bxsphenol A reacted with one or more molar equivalents of an end-capping group such as isocyanatoethyl rnethacryiate (**X£MR), methacrylic anhydride, methacryloyt chloride, vinylbcnzoyl chloride, or the like, to prwluce a polyethylene colyol having one or more terminal polymcrizable olefinic groups bonded to the polyethylene polyol through linking moietica such as carbamate or ester groups.
Still further examples are the hydrophilic vinyl carbonate or vinyl carbamate monomers disclosed in U.S. Patents No. 5,070,215, and the hydrophilic oxazolone monomers disclosed in U.S. Patents No. 4,910,277. Other suitable hydrophilic monomers will be apparent to one skilled in the art
More preferred hydrophilic monomers which may be incorporated into the polymer of the present invention include hydrophilic monomers such

11
as DMA, HEMA, giyeero! methacryiate, 2-hydroxyethyl raethacryiamide,
NVP,
polyethylcneglycol raonomethacrylate, melhacrylic acid and acrylic acid with
DMA being the most preferred.
Other monomers that can be present in the reaction mixture used to
form the silicone hydrogel of this invention include ultra-violet absorbing
monomers, reactive tints and the like. Additional processing aids such as
release agents or wetting agents can also be added to the reaction mixture. A polymerization catalyst is preferably included in the reaction
mixture. The polymerization catalyst can be a compound such as lauroyl peroxide, benzoyl peroxide, isopropyl percarbonatc, azobisisobutyronitrile, or the like, that generates fixe radicals at moderately elevated temperatures, or the polymerization catalyst can be a photoinitiator system such as an aromatic alpha-hydroxy kctonc or a tertiary smine plus a diketone. Illustrative examples of photoinitiator systems are 2-bydroxy-2-methyl-l -phenyl-propan-1 -one, and a combination of camphoxquinono and ethyl 4-(N,N-dimethylamiiio)benzoat{i. The catalyst is used in the reaction mixture in catalytically effective amounts, e.g., &om about 0.1 to about 2 parts by weight per 100 parts of reactive monomer. Polymerization of the reaction mixture can be initiated using the appropriate choice of heat or visible or ultraviolet light or other means depending on the polymerization initiator used. The preferred initiator is a I; 1 blend of l-bydroxycyclohexyl phenyl ketonc and bis(2, 6-dimcthoxybenzoyl)-2,4,4-trimethylpentyi phosphine oxide and the preferred method of polymerization initiation is UV light.
Typically after curing of the reaction mixture of the silicone-containing monomers of either or both Structure I and H and optional hydrophilie monomers and any other optional ingredients such as additional silicone-containing monomers, diluents, crosslinking agents, catalysts, release agents, tints etc. which are blended together prior to polymerization, the resulting polymer is treated with a solvent to remove the diluent (if used) or any traces of unreactcd components, and hydrate the polymer to form the

13
monomers such as 3-(trimethylsiloxy)propyl methacrylate are included in the macromer. Initiators, reaction conditions, monomers, and catalysts that can be used to
make GTP polymers are described in "Group-Transfer Polymerization" by O.W. Webster, in Encyclopedia of Polymer Science and Engineering Ed. (John Wiley & Sons) p. 580, 1987. These polymerizations are conducted under anhydrous conditions. Hydroxyl-functional monomers, like HEMA, can be incorporated as their trimethylsiloxy esters, with hydrolysis to form free hydroxyl group alter polymerization. GTP offers the ability to assemble macromers with control over molecular weight distribution and monoroer distribution on the chains. This macromer is then reacted with a reaction mixture comprising predominantly polydimcthylsiloxanc (preferably.
Preferred macromer components include mPDMS, TR1S, methyl methacrylate, HEMA, DMA, inethacrylonitrUc, ethyl methacrylate, butyl ntethacrylate, 2-hydroxypropyl-l-methacrylate* 2-hydroxyethyI methacrylamidc and methacrylic acid. It is even more preferred that the macromer is made from a reaction mixture comprising HEMA, methyl methacrylate, TRIS, and mPDMS. It is most preferred that macromer is made from a reaction mixture comprising, consisting essentially of, or consisting of about 19,1 moles of HEMA, about 2.8 moles of methyl methacrylate, about 7.9 moles of THIS, and about 3.3 moles of mono* rncthacryloxypropyl terminated mono-butyl terminated polydimcthylsiloxanc, and is completed by reacting the aforementioned material with about 2.0 moles per mole of 3-isoprapenyl-O3,a>-dimethylbenzyI isocyanatc using dibutyltin dilauxate as a catalyst.
Silicone hydrogels can be made by reacting blends of macromers, monomers, and other additives such as UV blockers, tints, internal wetting agents, and polymerization initiators. The reactive components of these blends typically comprise a combination of hydrophobic silicone with very

14
hydrophilic components. Since these components are often immiscible because of their differences in polarity, it is particularly advantageous to incorporate & combination of hydrophobia silicone monomers with hydrophilic monomers, especially those with hydroxyi groups* into the macromer. The macromer can then serve to compatibilize the additional silicone and hydrophilic monomers that are incorporated in the final reaction mixture. These blende typically also contain diluents to further compatibilize and solubil&e all components. Preferably, the silicone based hydrogcls are made by reacting the following monomer mix: macromer; an Si?^ monomethacryloxy terminated polydimcthyi siloxane; and hydrophilic monomers together with minor amounts of additives and photoinitiators. It is more preferred that the hydrogels are made by reacting macromer; an Si7.9 monomethacryloxy terminated polydimethyl siloxane; TRIS; DMA; HEMA; and tetraethyleneglycol dimethacrylate ('TEGDMA"). It is most preferred that the hydrogels are made from the reaction of (all amounts are calculated as weight percent of the total weight of the combination) macromer (about 18%); an S17-9 monomethacryloxy terminated polydimethyl siloxane (about 28%); TRIS (about 14%); DMA (about 26%); HEMA (about 5%); TEGDMA (about 1%), polyvinyipyrroHdone (**PVF*) (about 5%); with the balance comprising minor amounts of additives and photoinitiators, and that the reaction is conducted in the presence of 20%wt dimethyl-3-octanol diluent.
Various processes are known for molding the reaction mixture in the production of contact lenses, including spincasting and static casting. Spincasting methods are disclosed in U.S. Patents Nos. 3,408,429 and 3.660,545, and static casting methods are disclosed in U.S. Patents Nos. 4,113,224 and 4,197,266. The preferred method for producing contact lenses comprising the polymer of this invention is by the direct molding of fee silicone hydrogels, which is economical, and enables precise control over the final shape of the hydrated lens. For this method, the reaction mixture is placed in a, moid having the shape of the final desired silicone hydrogel, i.e.

16
percent of the reactive components Is a hydrophilic monomer, more preferably DMA, about 0.1 to 1.0 percent of the reactive components is a UV or visible light-active photoiuitiator and about 0 to 20 weight percent of the total reaction mixture is a secondary or tertiary alcohol diluent, more preferably a tertiary alcohol.
The reaction mixtures of the present invention can be formed by any of the methods known to those skilled in the art, such as shaking or stirring, and used to form polymeric articles or devices by the methods described earlier. For some monomer reaction mixtures it is preferred to polymerize the reaction mixtures at temperatures slightly above room temperature, such as 30-40*'C or below room temperature, such as 0-100C, so as to prevent phase separation of the components.
Silicone hydrogets of the instant invention have high oxygen permeability. They have O2 Dk values between about 40 and 300 baiter determined by the polarographic method. Polarographic method measurements of oxygen permeability are made as follows. Lenses are positioned on the sensor then covered on the upper side with a mesh support. The oxygen which diffuses through the lens Is measured using a polarographic oxygen sensor consisting of a 4 mm diameter gold cathode and a silver ring anode. The reference values are those measured on commercially available contact lenses using this method. Balafilcon A lenses available from Bausch &. Lamb give a measurement of approximately 79 barrcr. EtafiJcon leases give a measurement of about 20 to 25 barrer.
Contact lenses made from the sxlicone hydrogels of the invention may be produced to include a surface layer that is more hydrophilic than the silicone hydzogel. Suitable materials for forming the surface layer are known in the art Preferred materials include poly(acryiic acid), poly(methacrylic acid), poly(maleic acid), poly(itaconic acid), poly(acrylamide), block or random copolymers of (mcth)acryHc acid, acrylic acid, maleic acid, itaconic acid with any reactive vinyl monomer, carboxymethylated polymers, such as carboxymethylccllulose, and the like, and mixtures thereof: Preferably, the

17
carboxyl functional hydraphilic polymer is poly(aerylsc acid), poly(methacrylic acid), poly(meth)aciylamide, or poly(acrylamide). More preferably, poly(acrylic acid) or po!y(acrylamide) is used. Methods for coating contact lenses are disclosed in U.S. patent No. 6,087,415 incorporated herein is its entirely by reference.
The non-limiting examples below further describe this invention. In the examples the following abbreviations are used:
Examples
MBM 3-methacryioxypropylbis(trimcthylsiloxy)methylBilane
MPD tncthacryloxypropyipentaraethyJ disiioxanc
THIS 3-methacryloxypropyltris (trimethylailoxy) silane
DMA N,N-dimethylacrylamide
THF tetrahydrofiiran
Hv0 dimethyl meta-isopropenyl benzyl isocyanate
HEMA 2-hydroxycthy 1 mcthacrylate
TEGDMA tetraethyleneglycol dimctbacrylatc
EGDMA ethyleneglycol dimethacrylate
MMA methyl methactylate
TBACB tctrabut>d amm onium-m-chJorobenzoate
raPDMS monomcthacryloxypropyl terminated polydiraethylsiloxane
PDMS polydimcthylsiloxane
3M3P 3-methyl-3-propanol
Norbloc 2-(2*-hydroxy-5-methacryiyloxyethylpheiiyl>2H-
benzotri azoic
CC311850 1:1 (wt) blend of l-hjsJroxycyctohexyl phenyl ketone and
bis(2,6-dimcthoxybeii2oyI)-2)4-4-trimethylpentyl phosphine oxide
PVP poly(N-vinyl pyrtolidone)
IP A isopropyl alcohol

18
DAROCURE 1173 2-hydroxy-2-meihyl-l-phenyI-|m>pan-i-one
D3O 3,7-dimethyl~3-octanol
HO Ac acetic acid
TAA t-amyl alcohol
PREPARATION 1 - Preparation of Polysiloxanc Monomer 500 grams of a,co-bisaminopropyl polydixnethyisiloxane (5000 MW) and 68 grams of glycidyl methacrylate were combined and heated with stirring at 100°C for 10 hours. The product was extracted five times with 1500 mi of acetonitrile to remove residual glycidyl methacrylate to give a clear oU. JR: 3441,2962,1944, 1725,1638,1612,1412 cm"1. This product will be Teferred to as "the reaction product of glycidyl methacrylate and 5000 MW 0,00-bisaminopropyi polydimcthylsiloxane" or alternatively bifi(N,N-bis-2-h>1droxy-3-methacryloxypropyI)aminopropylpolydimethyIsiloxane.
Example 1
3S.2 parts by weight of the product of PREPARATION 1 was combined with 2S.8 parts MBM, 33 parts DMA and 1 part DAROCUR 1173 and diluted with 3-methyl-3~peatanol to make a reaction mixture in which the diluent made up 9% of the mass of the complete reaction mixture. The resulting reaction mixture was a clear, homogeneous solution. Polypropylene contact lens molds were filled, closed and irradiated with a total of 3.2 J/cm2 UV light from a fluorescent UV source over a 30-minute period. The molds were opened and the lenses were released into isopropanol and then transferred into deionized water.
The lenses were clear and had a tensile modulus of 205 ±12 g/mm2, an elongation at break of 133 ±37 %, and an equilibrium water content of 24.2 ±0.2 %. Tensile properties were determined using an Xnstron™ model 1122 tensile tester. Equilibrium Water Contests (EWC) were determined gravimctrically and are expressed as:

19
%EWC = 100 x (mass of hydratcd lens - mass of dry lens)/mass of hydrated lens
Examples 2-16
Reaction mixtures were made using the formulation of Example 1, but with amounts listed in Table 1, All reaction mixtures and lenses were clear.

20
Example 17
21.5% of ?,?-bismethacryloxypropyl polydimethylsiloxane -with an average molecular weight of 5000 g/mol was combined with 42.5% MBM, 35% DMA and 1% DAROCUR 1173 and diluted with 3-methyl-3-penmnol to give a clear solution containing 22 weight % diluent. Lenses were made following the procedure of Example 1. The lens properties are shown is Table 2.
Example 18
Lenses were made using the procedure and reaction mixture described in Example 17, but with MPD in place of MBM. The lens properties are shown in Table 2.
Comparative Example 1
A reaction mixture was made using the formulation of Example 17, but with TRIE in place of MBM, and with 20% diluent Lenses were made following the procedure of Example 1. The lens properties, shown in Table 2. show that the use of MBM (Example 17) or MPD (Example 18) gave lower moduli when used in place of TRIS.

21

Example 19
29-8% of ?,?-biKnefeaccyloxypropyl polydimethylsiloxane with an average molecular weight of 5000 g/mol was combined with 35% mono-metbacryioxypropyl terminated PDMS (Tl, Structure H, MW = 800 to 1000), 35% DMA and 1% DAROCUH 1173 aad ditoted with 3-methyl-3-peman0l to give a clear solution containing 23.0 weight % diluent Lenses were made following the procedure of Example 1. The lens properties are shown in Table 3.
Example 20
29.0% of ?,?-bismcthacryloxypropyl polydimethytsiloxane with an average molecular weight of 5000 g/mol was combined with 35% (3-
methacrydoxy-2-hydroxypropyloxy)prapylbis(trimenthythylsiloxy)methylsilane

22
(T2). 35% DMA and 1% DAROCUR1173 and diluted with 3M3P to give a clear solution containing 37.6 weight % diluent. Lenses were made following the procedure of Example 1. The lens properties are shown in Table 3.

The Examples show that the contact lenses made using die siticone-conuining monomers of Structure I provide contact lenses which axe clear and have a lower Young's modulus than the contact lenses made according to the Comparative Examples. A low modulus is desirable to provide contact lenses which are comfortable when worn.

23
Example 21
The following compositions were prepared, and cured with UV light into Hat sheets. These sheets were extracted with isopropanol to remove diluent and any unreacted monomer, then equilibrated in isotonic borate buffered saline.

24

1000MW was purchased from Gelest Inc. as "MCR-Mt 1" brand mPDMS.
5000MW was purchased from Gelest Inc. as "MCR-M17*' brand mPDMS.
(Molecular weights for mPDMS and PDMS shown above are number average molecular weights). The structure of mPDMS used in this example was:

For the determination of the properties after hydration, the 25 mm diameter hydrogel disks (each approximately 0.7 mm thick) were held between the 25 mm diameter parallel plates (plated with a crystal clad 80/100 grit coating) of a controlled stress rheometer (ATS Stresstech) with a vertical force of 10 N. The disks were immersed in water during the test to prevent dehydration. A stress sweep from 100 to 10,000 Pa at 1 Hz and 25°C was conducted on a disk of each material, to determine the range of the linear viscoelastic region for each formulation.

25
Once the limit of the linear viscoclastic region had been determined, the rhcomctcr was set in frequency sweep mode using a stress less than the predetermined limit, and G\ G", n*. and tan 5 of the 25 mm diameter hydrated disks were measured as a function of frequency from 0.01 - 30 Mz at several temperatures (10,25,40 and 55°C)» all the while maintaining a vertical force of 10 N on the hytirogel disks. The individual frequency scans of C and tan 5 were then combined to foim master curves for each material. Hie data for the shear modulus G* and tan 8 of the hydrogels at a reference temperature of 25°C are shown in tables 4 and 5.
The shear modulus of sample A was greater than B is the frequency range in which they were tested (as would be expected since the only difference between them is the molecular weight between crosslinks: 1000 vs. 3000), and their shear moduli gradually increased with increasing frequency. At the high frequency extreme, sample A appeared to be approaching a transition, since the modulus appeared to be approaching a region of more rapid increase.
The taxi 5 of samples A and B were below 0.2 for the most pan, with the tan 6 of sample A increasing at the high frequencies in anticipation of a transition at higher frequencies.
Similarly, the shear modulus of sample D was greater than £ in the frequency range in which they were tested (the only difference between them is the molecular weight of the dangling chains: 1000 vs. 5000), and their shear moduli gradually increased with increasing frequency.
The tan 8 of samples D and £ was below 0.1 for the entire frequency range in which they were tested, with the tan o of sample E (MW 3 000) below that of sample D (MW 5000).
The shear modulus of sample C increased rapidly in the frequency range in which it was tested, indicating a transition from a rubbery to a more rigid state. The bulky TRIS moiety reduced the internal molecular mobility of the hydrogel (relative to the PDMS and mPDMS polymers), and caused the "glass" transition to shift to lower frequencies (¦ higher temperatures).

26
The tan 5 of sample C readied a maximum at 100 hz at the reference temperature of 40°C» indicative of the transition.
The addition of mono-capped PDMS was more effective than* the addition of di-capped PDMS in reducing the tan 5 of the hydro gel. The elastic properties of a material were controlled by the judicious addition of mPDMS while maintaining the homogeneity of the material. On the other hand, the addition of TRIS increased the tan S of a material.

27

28

29
Example 22- SEALs Study
A double masked, contralaieral, randomized, complete block clinical study was conducted to determine the relationship between SEALs and the Young's modulus of contact lenses. Looses were made from two different silicone hydrogel compositions as follows.

The silicone-based xnacroraer refers to a prepolyracr in which one mole was made from an average of 19.1 moles of 2-hydroxyetfayl methaerylate, 2.8 moles of methyl methacrylate, 7.9 moles of mcthacryioxypropy]tris(triincthylsiloxy)silane, and 33 moles of mono-methacryloxypropyi terminated mono-butyi terminated polydimcthylailoxane. The macromer was completed by reacting the aforementioned material with 2.0 moles per mole of 3-isopropcnyi-o),t>-dimethylbenzyl isocyanare using dibutyltin dilBurate as a catalyst for the Group Transfer Polymerization used to produce the raacromer product
Weight percentages arc computed based on the total weight of all components; the balance of the compositions in Table 5 comprise initiators

30
and additives. The mPDMS was a mono-methacryloxy propyl terminated mPDMS.
Lenses were made from these compositions having a nominal base curve of 8.5 mm and a diameter of 14.0 mm at 22°C. They had a nominal center thickness of 0.110 mm and a measured center thickness of 0.119 (Lens A) and O.OSS mm (Lens B). Both lenses were coated with a hydrophilic coating to enhance bio compatibility and wettahility. Lens A had a Young's modulus of 109.4 psi and Lens B had a Young's modulus of 88.5 psi.
Subjects participating in the study were given a baseline examination and fined with leases made from the compositions shown in Table 6. They then wore the lenses for one week. Lenses were worn for daily wear. The subjects returned for a clinical evaluation of the presence of SEALs and other clinical data (e.g. visual acuity). Nineteen subjects (38 eyes) completed lite study, eight of whom had a history of SEALs. Ten (10) eyes wearing Lens A exhibited SEALs. No eyes wearing Lens B exhibited SEALs.
Example 23 - SEALs Study
A study similar to that of Example 22 was conducted using lenses of different center thicknesses. The lenses had the following characteristics and gave the results shown is Table 7. Is Table 7, column 4, **E" represents Young's modulus and "CT** represents the center thickness.

•Refer* to less composition corresponding to Exunple 22.
This examples shows the combined effect of lens center thickness and
modulus on SEALs.

32
hours. A solution of lO.Og b is (dimethylamino)m ethyls i lane, 154.26 g methyl methaciylate, and 1892.13 g 2-(trimethylsiloxy)ethyl methacrylate was then added and the mixture was again allowed to exotherm. After 2 hours, 2 gallons of anhydrous THF was added, followed by a solution of 439.69 g water, 740.6 g methanol and 8.8 g dichloroacctic acid after the solution was allowed to cool down to 34°C. The mixture was refluxed for 4.5 hours, heating with an oil bath atl 10°C, and volatiles were distilled off at 135°C, with addition of toluene to aid in removal of water, until a vapor temperature of 110°C is reached.
The reaction flask was cooled to 110°C, and a solution of 443 g TMI and 5.7 g dibutyltin dilaurate was added. The mixture was reacted for 3.5
hours, then cooled to 30°C. The toluene was evaporated under reduced
pressure to yield off-white, anhydrous, waxy, reactive macromer. The
theoretical OH content of the macromer is 1.69 mmol/g.
Macromer B:
The procedure for Macromer A used except that 19.1 mole parts
HEMA, 7.8 mole parts MAA, 7.9 mole parts TRIS, 3.3 mole parts TRIS, and
2.0 mole parts TMI were used.
Macromer C:
The procedure for Macromer A was used except that 19.1 mole parts HEMA, 7.9 mole parts TRIS, 3.3 mole parts TRIS, and 2.0 mole parts TMI were used.
Examples 26 - 36 (Lens Formation)
Hydrogel were made from the monomer mixtures shown on Table 8. All amounts are calculated as weight percent of the total weight of the combination with the balance of the mixture being minor amounts of additives. Polymerization was conducted in the presence of the diluents listed.

33
Contact lenses were formed by adding about 0.10 g of the monomer mix to che cavity of an eight cavity lens mold of the type described in U.S. Patent 4,640*489 and curing for 1200 sec. Polymerization occurred under a nitrogen purge and was photoinitiated with 5 mW cm"2 of UV light generated with an Andover Corp. 420PS10-25 AM39565-02 light filter. After curing, the molds were opened, and the lenses were released into a 1:1 blend of water and ethanoi, then leached in ethanol to remove any residual monomers and diluent. Finally the lenses were equilibrated in physiological boraie-buffcred saline. The lenses had the properties described in Table 8.

34

35
Example 37
To lenses from Example 27 immersed in a solution of 1.0% 250,000 Mw polyacrylic acid in water at 45°C was added 0.1 % 1 -[3-(dimcthyJamino)prDpyl]-3-ctliyIcaibtxiiimide hydrochloride. Alter stirring for 30 minutes the lenses are rinsed in borate-bufFered saline solution. The dynamic contact angles of the resulting poiy(sodmra acrylate)-coated lenses are 44° advancing and 42° receding.
Comparative Example 2
Lenses were made by curing a blend of 57.5% TRIS, 40.0 % DMA, 1.5% l,3-bis

36
We claim.
I. A method of lowering the Young's modulus and tan (delta) of a silicone hydrogel comprising the step of incorporating in said faydrogel, a mano-alkyi terminated polydimethylsiloxane monomer having the structure:

where b = 0 to 100; R58 is a monovalent group comprising an ethyienically unsaturated moiety; each R39 is independently a monovalent alkyj, or aryl group, which may be farther substituted with alcohol, amine, ketonc, carboxylic acid or ether groups; and R*o is a monovalent alkyl, or aryl group, which may be further substituted with alcohol, amine, ketone, carboxylic acid or ether groups.
2. The method of claim 1, wherein b = 8 to 10, R38 is a monovalent
group containing a styryl, vinyl, or methacrytate moiety, each R59 is methyl,
and Rw is a C34 alky] group.
3. The method of claim 1, wherein b - 8 to 10, R58 is a methacrylate
moiety; each R59 is methyl; and R$o is a butyl group.
4. The method of claim 1, wherein about 2-70 % wt» based on the total
weight of reactive monomer, of ifee mono-alky! terminated
polydimethylsiloxane is incorporated in said silicone hydrogel.

37
5. The method of claim 1, wherein said siiicone hydrogel additionally J> comprises a siliconc-containing monomer other ihan that of claim 1 and having the structure:

wherein R3! is H or CH3, q is I or 2 and for each q, R52. R53 and R54 is independently an alkyl group, an aromatic group or a monovalent siloxane chain comprising from I to 100 repeating Si-O units, p is I to 10, r = (3-q)» X is O or NR55, where R55 is H or a monovalent alkyl group with 1 to 4 carbons, a is 0 or 1, and L is a divalent linking group.
6. The method of claim 5, wherein each of R32l R53, and R« is
independently ethyl, methyl, benzyl or phenyl.
7. A fiilicone hydrogel having a Young's modulus less than about 180
psi and a Ian (delta) less than about 0.3 at a frequency of I Hz at 2S°C.
8. Use siiicone hydrogel of claim 7, wherein Use Young's modulus is
less than about 130 psi
9. The siiicone hydrogel of claim 8, further comprising an Oj Dk greater
than about 40 baiter.

38
16. The silicone hydrogel of claim 7, further comprising an O2 DK greater
than about 40 barrcr.
11. The silicons hydrogel of claim 7,8,9 or 10,-6mker comprising about 2-70 % wt. based on fee total weight of reactive monomer, of a mono-alkyl terminated polydimethylsiloxane having the structure:

where b - 0 to 100; R58 is a monovalent group comprising as ethylenically unsaturated moiety, each R59 is independently a monovalent alkyl. or aryl group, which may be substituted with alcohol, amine, ketone, earboxylic acid or ether groups; and R60 is a monovalent alkyl, or aryl group, which may be substituted with alcohol, amine, ketone, carboxylic acid or ether groups.
12. The method of claim 11, wherein b = 8 to 10, R58 is a monovalent
group containing a styryl, vinyl, or methacrylate moiety, each R59 is methyl,
andR60 is a C3-8 alkyl group,
13. The method of claim 11, wherein b = 8 to 10, R58 is a methacrylate
moiety; each R59 is methyl; and R60 is a butyl group.

39
14. The silicone hydrogel of claim 11, wherein the mono-alkyl terminated
polydimethylsiloxane is a monomcthacryloxypropyl terminated polydimethylsiloxane.
15. The siliconc hydrogel of claim 11, having a Young's modulus of
about 30-160 psi.
16. The silicone hydrogel of claim 11, having a Young's modulus of
about 40-13 psi.
17. A contact lens comprising a silicone hydrogel having a Young's
modulus less than about 180 psi and s tan (delta) less than 0.25 at a
frequency of 1 Hz at 250C.
18. The contact lens of claim 17, wherein the Young's modulus is less
than about 130 psi.
19. The contact lens of claim 18, comprising an O2 Dk greater
than about 40 barrcr.

20. The contact lens of claim 17, farther comprising an O2 Dk greater
than about 40 barrcr.
21. The contact lens of claim 17, 18, 19 or 20, comprising about
2-70 % wt, based on the total weight of reactive monomer, of a mono-alkyl
terminated polydimethylsiloxane having the structure:

40

where b = 0 to 100; R58 is a monovalent group comprising an ethylcnically unsaturated moiety, each R59 is independently a monovalcnt alkyl, or aryl group, which may be substituted with alcohol, amine, ketone, carboxylic acid or ether groups; and R60 is a monovalent alkyl, or aryl group, which may be substituted with alcohol, amine, ketone, carboxyiic acid or ether groups.
22. The method of claim 21, wherein b = 8to 10, R58 is a monovalent
group containing a styryl, vinyl, or methacrylate moiety, each R59 is methyl,
and R60 is a C3-8 alkyl group.
23. The method of claim 21. wherein b - 8 to 10, R58 is a methacrylate
moiety, each R59 is methyl; and R60 is a butyl group.
24. Hie contact lens of claim 21, wherein the monoalkyl terminated
polydimethylsiloxane is a rnonomethacryloxypropyl terminated
polydimcthylsiloxane.
25. The contact lens of claim 21, wherein said silicone hydrogel has a
Young's modulus of about 30-160 psi.

41
26. The contact lens of claim 21, wherein said silicone hydrogel has a
Young's modulus of about 40-130 psi.
27. The contact lens of claim 21, comprising a surface layer that is
more hydrophilic than said silicone hydrogel.
28. The contact lens of claim 21, Walter-comprising a coating that is
more hydrophilic man said silicone hydrogel.
29. The contact lens of claim 27, wherein the surface layer comprises
polyfacrylic acid).
30. The contact lens of claim 28, wherein the coating comprises
poly(acrylic acid).
31. A silicone hydrogel contact lens comprising a center thickness (CT)
of about SO to about 160 ?m and a Young's modulus (E) of about 40 to
about 300 psi, wherein (E)(CT2) is less than about 1 psi • mm2.
32. The silicone hydrogel contact lens of claim 31, comprising a
tan (delta) less than about 0.3 at a frequency of 1 Hz at 25°C.
33. The silicone hydrogel contact leas of claim 31,comprising
an O2Dk greater than about 40 baiter.
34. The silicone hydrogel of claim 32, comprising an O2DK of
greater than about 40 barrer.

42
35. The silicone hydrogel contact lens of claim 31, 32, 33, or 34, comprising at least 5% wt of a mono-alkyl terminated polydimethylsiloxane having the structure:

where b = 0 to 100; R58 is a monovalent group comprising an ethylenically unsaturated moiety; each R59 is independently a monovalent alky], or aryl group, which may be further substituted with alcohol, amine, ketone, carboxylic acid or ether groups; and R60 is a monovalent alkyl, or aryl group, which may be-farther substituted with alcohol, amine, ketone, carboxylic acid or ether groups.
36. The method of claim 35, wherein b - 8 to 10, R58 is a monovalent
group containing a styryl, vinyl, or mcthacrylatc moiety, each RS9 is methyl,
andR60 is a C3-8 alkyl group.
37. The method of claim 35, wherein b = 8 to 10, R58 is a methacrylate
moiety; each R59 is methyl; and R60 is a butyl group.
38. The silicone hydrogel contact lens of claim 35, wherein the raono-
alkyl terminated polydimethylsiloxane is a monomethacryioxypropyl
terminated polydimethylsiloxane.

43
39. The contact lens of claim 35, wherein the lens thickness is less than
about SS ?m.
40. The contact lens of claim 35, wherein the thickness is less than about
100 pan and the Young's modulus is less than about 100 psi.
41. The contact lens of claim 35, wherein the amount of mono-alkyl
terminated polydimcthylsiloxane is about 20 % wt
42. The contact lens of claim 35, wherein the thickness is less than 129
pm and the Young's modulus is less than about 60 psi.
43. The contact lens of claim 32, wherein the amount of mono-alkyl
terminated polydimethylsiloxanc is about 30% wt.
44. A method of making a polymer comprising preparing a silicone based
macromcr by Group Transfer Polymerization, and reacting said macromex
with a polymerizable mixture comprising Si?-9 monomethacryloxy terminated
polydimcthyl siloxane, polydimcthylsiloxane other than Si7-»
monomethacryloxy terminated polydimethyl siloxane* and a hydrophilic
monomer.
45. The method of claim 44, wherein said macromer is the reaction
product of a reaction mixture comprising 2-hydroxycthyi rnethacrylate,
methyl methacrylate, methacryloxypropyltri3(triincthyisiloxy)sUane, and
mono-methacryloxypropyl terminated mono-butyl terminated
polydimethylsiloxane.

45
51. The silicone hydrogel of claim 50, wherein the macromer is the
Group Transfer Product of a reaction mixture comprising 2-hydroxyethyl methacryiate, methyl methacryiate.
mcthacryloxypropyltris(trimethylsiloxy)silane, and mono-mctfaacryloxypmpyl terminated mono-butyl terminated potydimcthylsiloxane.
52. The silicone hydrogel of claim SO, wherein the macromer is the
Group Transfer Polymerization product of reaction mixture comprising about
19.1 moles of 2-hydroxyetfay! methacryiate, about 2.8 moles of methyl
methacryiate, about 7.9 moles of
niediacr5doxy|m3pyltris(trimetliylsiloxy)silane( and about 33 moles of mono-methacryloxypropyl terminated mono-butyl terminated polydimethylsiloxane
53. The silicone hydrogel of claim SO, 51, or 52 wherein the
polymcrizable mixture comprises Si?.« monomethacryloxy terminated
poiydimethyi siloxane; methacryioxypropyl tris(trimcthyl siloxy) silane;
N,N-dimethyl acrylamide; 2-hydroxy ethyl methacryiate; and
tetraethyleneglycol dimethacrylate.
54. The silicone bydrogcl of claim 53, wherein the macromer is present in
an amount of about 10 to about 60 wt percent, the Si7.9 monometbacryloxy
terminated polydimcthyl siloxane is present In an amount of about 0 to about
45 wt percent; the methacryloxypropyl tris(trimethyl siloxy) silane is present
in an amount of about 0 to about 40 wt percent; the N,N-dimethyl acryiamide
is present in an amount of about 5 to about 40 wt percent; the 2-hydroxy
ethyl methacryiate is present in an amount of about 0 to about 10 wt percent;

46 and the terraethyleneglycol dimethacrylate is present in an amount of about 0
to about 5 wt percent.
55. The silicone hydrogcl of claim 53, wherein the macromer is present in
an amount of about 15 to about 25 wt percent, the Si7^ monomethacryioxy
terminated polydimethyl siloxane is present in an amount of about 20 to
about 30 wt percent; the methacryioxypropyl tris(trimethyl siloxy) silanc is
present in an amount of about 15 to about 25 wt percent; the N,N-dimethyI
acrylamide is present in an amount of about 20 to about 30 wt percent; the 2-
hydroxy ethyl methacrylaie is present 233 an amount of about 2 to about 7 wt
percent; and the tetraethyleneglycol dimethacrylsie ts present in an amount of
about 0 to about 5 wt percent
56. The silicone hydrogel of claim 53, wherein the polymerizable mixture
farther comprises poly(N-vinyl pyrrolidinone).
57. The silicone hydrogel of claim 54, wherein the polymerizable mixture
"teller comprises about 0 to about 10 wt percent pory(N-vinyl
pyrrolidinone).
58. The silicons hydrogel of claim 55, wherein the polymerizable mixture
fisf&el- comprises about 2 to about 7 wt percent poly(N-vinyl pyrrolidinone).
59. A contact lens comprising the reaction product of a silicone based
macromer Group Transfer Polymerization product and a polymerizable
mixture comprising Si7.9 monomethacryloxy terminated polydimethyl

47
siloxane, polydimeihylsiloxane other than Si7.9 monomethacryloxy
terminated potydimethy] siloxane. and a hydrophilic monomer.
60. The contact lens of claim 59, wherein the roacroroer is the Group Transfer Product of a reaction mixture comprising 2-hydroxyethyl methacrytate, methyl roethacrylate,
melhacrylox>propyItris(trimcthylsiloxy)Eilanc, and mono-mcthacryloxypropyt terminated mono-butyl terminated
polydimdhylsiloxanc.
61. The contact lens of claim 60, wherein the macromcr is the Group
Transfer Polymerization product of reaction mixture comprising about 19.1
moles of 2-hydroxyethyl methacrylate, about 2.8 moles of methyl
meihacrylatc, about 7.9 moles of
raethacryloxypropyltris(triinethyJsiloxy)silanc, and about 3.3 moles of mono-mcthacryloxypropyl terminated mono-butyl terminated polydimethylsiloxane
62. The contact lens of claim 59,60, or 61 wherein the polymerizable
mixture comprises Si7-g monomothacryloxy terminated polydimethyl
siloxane; mcthacryloxypropyl tris(trimethyl siloxy) silane; N.N-dimethyl
acrylamide; 2-hydroxy ethyl methacrylate; and tctraethylenegiycol
dimethacrylate.
63. Use contact lens of claim 62, wherein the macromcr is present in an
amount of about 10 to about 60 wt percent, the S17.9 monomethacryloxy
terminated polydimethyl siloxane is present in an amount of about 0 to about
45 wt percent; the methacryloxypropyl tm(trimethyl siloxy) silane is present
in an amount of about 0 to about 40 wt percent; the N,N-dxmethyl acrylamide

48
is present in an. amount of about 5 to about 40 wt percent; the 2-hydroxy
ethyl methacryiate is present in an amount of about 0 to about 10 wt percent; and the tetraethyleneglyeol dimethacrylate is present in an amount of about 0 to about 5 wt percent.
64. The contact lens of claim 62, wherein the macromer is present in an
amount of about 15 to about 25 wt percent, the Si7-9 monomethacryloxy
terminated polydimeihyl siloxane is present in an amount of about 20 to
about
30 wt percent; the methacryloxypropyl tris(trimethyl siloxy) silanc is present in an amount of about 15 to about 25 wt percent; the N,N-dimethyI acrylamide is present in an amount of about 20 to about 30 wt percent; the 2-hydroxy cihyl methacrylate is present in an amount of about 2 to about 7 wt percent; and the tetraethyleneglycol dimethacxyiate is present is an amount of about 0 to about 5 wt percent.
65. The contact lens of claim 62, wherein the polymerizable mixture
comprises poly(N-vinyi pyrrotidinone).
66. The contact lens of claim 63, wherein the polymerizable mixture
comprises about 0 to about 10 wt percent poly(N-vmyl
pyrrolidinonc).
67. The contact lens of claim 64, wherein the polymerizable mixture
comprises about 2 to about 7 wt percent poly(N-vinyl pyrrolidinone).
A method of lowering the Young's modulus and tan (delta) of a silicone hydrogel comprising the step of incorporating in said hydrogei, a mono-alkyl terminated polydimethylsiloxane monomer having the structure:
Where b - 0 to 100; R58 is a monovalent group comprising an ethylenically unsaturated moiety; each R59 is independently a monovalent alkyl, or aryl group, which may be substituted with alcohol, amine, ketone, carboxylic acid or ether groups; and R60 is a monovalent alkyl, or aryl group, which may be substituted with alcohol, amine, ketone, carboxylic acid or ether groups.

Documents:

« Previous Patent

Next Patent »

Patent Number

210019

Indian Patent Application Number

IN/PCT/2002/00432/KOL

PG Journal Number

37/2007

Publication Date

14-Sep-2007

Grant Date

13-Sep-2007

Date of Filing

04-Apr-2002

Name of Patentee

JOHNSON & JOHNSON VISION CARE. INC..

Applicant Address

7500 CENTURION PARKWAY, SUITE 100, JACKSONVILLE, FLORIDA 32256,

Inventors:

#	Inventor's Name	Inventor's Address
1	DOUGLAS G. VANDERLAAN	8114 PARKRIDGE CIRCLE SOUTH, JACKSONVILLE, FL 32211,
2	DAVID C. TURNER,	12159 TRAVERTIINE TRAIL, JACKSONVILLE, FL 32223; UNITED STATES OF AMERICA
3	MARCIE V. HARGISS	12472 ALLPORT ROAD, JACKSONVILLE, FL 32258; UNITED STATES OF AMERICA
4	ANNIE C. MAIDEN,	1558 HOPE VALLEY DRIVE, JACKSONVILLE, FL 32221; UNITED STATES OF AMERICA
5	ROBERT N. LOVE,	1748 EL CAMINO ROAD, APARTMENT 3, JACKSONVILLE, FL 32216; UNITED STATES OF AMERICA
6	JAMES D. FORD,	515 NASSAU COURT, ORANGE PARK, FL 32073; UNITED STATES OF AMERICA.
7	ROBERT B. STEFFEN.	1158 BLUE HERON LANE WEST, JACKSONVILLE BEACH, FL 32250; UNITED STATES OF AMERICA
8	GREGORY A. HILL,	1918 HICKORY LANE, ATLANTIC BEACH, FL 32223; UNITED STATES OF AMERICA
9	AZAAM ALLI	7816 SOUTHSIDE BOULEVARD, APARTMENT 221, JACKSONVILLE, FL 32256; UNITED STATES OF AMERICA
10	JOHN B. ENNS,	9251 JAYBIRD CIRCLE EAST, JACKSONVILLE, FL 32257; UNITED STATES OF AMERICA
11	KEVEN P. MCCABE,	10550-205 BAYMEADOWS ROAD, JACKSONVILLE, FL 32256; UNITED STATES OF AMERICA
12	FRANK F. MOLOCK,	1543 WILDFERN DRIVE, ORANGE PARK FL 32073; UNITED STATES OF AMERICA

PCT International Classification Number

C08F 230/08

PCT International Application Number

PCT/US00/24856

PCT International Filing date

2000-09-11

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	09/652,817	2000-08-30	U.S.A.
2	09/414,365	1999-10-07	U.S.A.
3	09/532,943	2000-03-22	U.S.A.