US20020082691A1

US20020082691A1 - Optically clear reinforced silicone elastomers of high optical refractive index and improved mechanical properties for use in intraocular lenses

Info

Publication number: US20020082691A1
Application number: US09/875,410
Authority: US
Inventors: Richard Christ; Brian Nash; Del Petraitis
Original assignee: Allergan Inc
Current assignee: Allergan Inc
Priority date: 1987-02-05
Filing date: 2001-06-05
Publication date: 2002-06-27
Also published as: US5494946A; US5376694A; US5869549A; US5236970A; US6277147B1; US5661195A

Abstract

Optically clear, reinforced cross-linked silicone elastomers of the invention contain 12 to 18 mol percent of aryl substituted siloxane units of the formula R₄,R₅—SiO, end blockers containing silioxane units of the formula R₁R₂R₃—Si—O, and dialkyl siloxane units of the formula R₆R₇—Si—O R₁and R₂are alkyl, aryl or substituted alkyl or substituted aryl groups, and R₃is an alkenyl group. R₄and R₅are phenyl or mono lower alkyl substituted phenyl groups. R₆and R₇are methyl or ethyl groups. The polymer has a degree of polymerization between 100 to 2000, and preferably approximately 250. The polymer also contains trimethyl silyl treated silica as a reinforcer in the weight ratio of approximately 15 to 45 parts of reinforcer to 100 parts of the polymer. After cross-linking, the polymer has properties of an optical refractive index which is at least 1.44, a type A durometer hardness of at least 35, tensile strength of at least 500 psi and tear strength of at least 20 phi. The foregoing properties render the cross-linked polymer especially suitable for forming the bodies of intraocular lenses.

Description

Intraocular lenses made from silicone polymeric materials are usually deformable, so that for implantation a smaller incision needs to be surgically out in the eye than for the implantation of “hard” intraocular lenses. In this respect, the size and mechanical characteristics of the silicone polymeric intraocular lenses play an important role. As it will be well understood by those skilled in the art, for successful implantation the lens rust have sufficent structural integrity, elasticity and small enough size to permit the folding for insertion through a small incision. After insertion, the lens must, of course, regain its original molded shape.

It will be further understood by those skilled in the art that the thinner is the lens, the easier is the surgical insertion procedure. On the other hand, in order to function as an intraocular lens, the lens material must have sufficient optical refractory power. Consequently, the higher is the optical refractive index of the silicone material, the thinner can be the lens to obtain the same optical refractory power.

Some silicone polymeric materials described in the prior art contain a silica reinforcer finely distributed in the polymeric silicone resin. Usually such reinforcement of the silicone polymeric material with silica is necessary for the polymeric material to attain adequate structural strength to be used as a foldable intraocular lens. Such silica reinforced polymeric silicone resins suitable for use as soft contact or intraocular lenses are described in U.S. Pat. Nos. 3,996,187; 4,615,702; 3,996,189. Additional disclosures relating to polymeric silicone materials or silica reinforcers, which comprise the background of the present invention can be found in U.S. Pat. Nos. 3,341,490; 3,284,406; 3,457,214; and in European Patent Application No. 0110537 filed on Oct. 18, 1983.

Additional disclosures relating to intraocular lenses can be found in U.S. Pat. No. 4,573,998, published UK Patent Application GB 2114315, and in co-pending application for U.S. patent Ser. No. 946,703 filed on Dec. 24, 1986 by Reich et. al. The latter U.S. patent application is assigned to one of the co-assignees of the present applications

The prior art intraocular lenses made of silica reinforced silicone copolymers still do not fully satisfy the need for high enough optical refractory power to permit sufficently thin lens size which in turn would make it possible to surgically implant the lens through a desirably small incision in the eye. In other words, there is still need in the art for reinforced silicone polymeric materials which have sufficiently high optical clarity, refractive index, durometer hardness, tensile strength and related mechanical properties to permit construction of thin foldable intraocular lenses. The present invention satisfies this need.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide optically clear reinforced silicone polymeric materials of a refractive index of at least 1.44 coupled with sufficient durometer hardness, tensile strength and other mechanical properties to permit forming of thin intraocular lenses through final cross-linking of the polymeric material into desired lens shapes.

It is another object of the present invention to provide a thin intraocular lens body from a reinforced silicone polymeric material, wherein the lens body has an optical refractive index of at least 1.44 and sufficient mechanical properties to permit implantation through a small incision in the eye.

The foregoing objects and advantages are attained by an optically clear, reinforced cross-linked silicone elastomer which includes a polymer containing 12 to 18 mol percent of aryl substituted siloxane units of the formula R ₄,R₅—Si—O. In the formula R₄and R₅are identical with one another or are different from one another and represent phenyl, or mono- lower alkyl substituted phenyl groups, or di- lower alkyl substituted phenyl groups. Preferably both R₄and R₅are phenyl.

The polymer has end blockers containing siloxane units of the formula R ₁,R₂,R₃—Si—O wherein R₁and R₂are alkyl, aryl or substituted alkyl or substituted aryl groups, and R₁and R₂may be identical or different from one another. The R₃group of the end blocking siloxane units in an alkenyl group. Preferably, the end blocker is a dimethylvinyl siloxane unit.

The balance of the polymer consists of dialkyl siloxane units of the formula R ₆,R₇—Si—O wherein R₆and R₇are identical with one another or are different from one another and are methyl or ethyl groups, and the polymer has a degree of polymerization approximately between 100 to 2000. Preferably, the R₆and R units are both methyl, and the degree of polymerization is approximately 250.

A trimethyl silyl treated silica reinforcer is finely dispersed in the polymer, in a weight ratio of approximately 15 to 45 parts of the reinforcer to 100 parts of the polymer. Preferably, there is approximately 27 parts of reinforcer to 100 parts of the copolymer.

The polymer when cured by cross-linking in a mold forms the body of an intraocular lens of the invention, and has the properties of an optical refractive index which is at least 1.44, a type A durometer hardness value of at least 35, a tensile strength of at least 500 psi, and a tear strength of at least 20 pli.

Further objects and advantages of the present invention will become readily apparent from the ensuing description wherein the specific embodiments are described as follows.

DESCRIPTION OF THE SPECIFIC EMBODIMENTS

Reinforced elastomeric polysiloxane copolymer compositions are provided in accordance with the present invention, which after appropriate curing by cross-linking, are eminently suitable to serve as the body of foldable “soft” intraocular lenses capable of implantation through a small incision in the eye.

More particularly, the reinforced elastomeric composition of the present invention has the chemical composition of a cross-linked copolymer including approximately 12 to 18 mol per cent of aryl substituted siloxane units of the formula R ₄, R₅—Si—O where the aryl substituents (R₄and R₅groups) can be phenyl groups, mono- lower alkyl substituted phenyl groups, or di- lower alkyl substituted phenyl groups, and can be identical with one another or different from one another. Preferably, both aryl groups are simple phenyl, and the resulting diphenyl siloxane unit is present in the copolymer in a ratio of approximately 14 to 16 mol per cent. In the hereinafter described specific example, the diphenyl siloxane unit content of the copolymer is approximately 15 mol per cent.

It is noted in connection with the diaryl, preferably simple diphenyl substituted siloxane units, that the presence of the aryl groups tends to increase the optical refractive index of the copolymer.

The copolymer is end blocked with trisubstituted (monofunctional) siloxane units, an important feature of which is that at least one substituent of the end blocking group contains an olefenic bond. Thus, the general formula of the end blocking group incorporated in the copolymer of the invention in R ₁,R₂,R₃—Si—O where the nature of the R₁and R₂is not critical, and they may be, for example, alkyl, aryl, or substituted alkyl or substituted aryl groups. R₁and R₂may be identical to one another, and may also be different from one another. The nature of the R₃group is important in that R₃contains an olefenic bond. Thus, R₃is an alkenyl group, preferably a vinyl group. In the preferred embodiment of the invention the end blocking group is a dimethyl, vinyl siloxane unit. The role of the olefenic (vinyl) group, is to enable curing or cross-linking of the polymer an well as covalently linking, in accordance with another feature, certain ultraviolet light absorbing compounds to the cross-linked copolymer matrix of an intraocular lens made in accordance with the invention.

The balance of the siloxane building blocks of the copolymer are dialkyl siloxane units wherein the two alkyl substituents are either ethyl or methyl. In other words, the general formula of the balance of the siloxane building blocks of the copolymer is R ₆,R₇—Si—O where the R₆and R₇groups are methyl or ethyl and the two groups are either identical with one another, or are different from one another. Preferably in the practice of the present invention both R₆and R₇groups are methyl.

In accordance with the present invention the copolymer having the above-described components has a degree of polymerization (dp) of approximately 100 to 2000, although a degree of polymerization of approximately 250 is preferred particularly when the R ₄and R₅groups are phenyl and the R₆and R₇groups are methyl.

Except to the extent that novel features are emphasized below, the preparation of the copolymer having the above described components can be performed in accordance with processes known in the art, from starting materials which are either commercially available or can be made in accordance with well known state-of-the-art processes.

Thus, in accordance with standard practice in the art, readily available cyclic oligomers of the components and suitable state-of-the-art precursors of the end blocking groups are reacted in the presence of a suitable catalyst to achieve polymerization to the desired degree. The cyclic oligomer starting materials are beat exemplified by reference to the specific example of the moat preferred embodiment of the copolymer of the invention. Specifically, a mixture of octophenylcyclo-tetrasiloxane, octanethylcyclo-tetrasiloxane and 1,2 divinyltetramethyldisiloxane are reacted in the presence of a polymerization catalyst to achieve a degree of polymerization which is approximately 250 for the preferred embodiment.

It should be specifically understood in connection with the preparation of the copolymer that after the proper copolymer composition is selected, the selection of suitable starting materials for the polymerization is within the skill of the ordinary artisan. Similarly, the polymerization can be conducted by using state of the art catalyst; the well known N-catalysts and K-catalysts are particularly of choice in this regard. As is known in the art, the K-catalysts used for polysiloxane formation comprise potassium hydroxide, whereas the N-catalysts comprise tetromethylammonium hydroxide.

It is an important aspect of the process for preparing the copolymer of the present invention that the degree of polymerization is monitored by monitoring the viscosity of the reaction mixture. Moreover, the optical refractive index of the reaction mixture is also monitored, and the reaction is not considered completed, nor giving acceptable product unless the reaction mixture has a viscosity within a desired range and an optical refractive index of at least 1.44. The desired viscosity range depends on the nature and composition of the copolymer; for the preferred copolymer having dimethylvinylailoxane end blockers, approximately 15 mol per cent diphenyl siloxane building blocks with the balance being dimethylsiloxane, and a degree of polymerization of approximately 250, the desired viscosity range of the reaction product is approximately 2000 to 2800 centipoise (cp). In this connection it is noted that whereas the aryl content of the copolymer greatly influences the refractive index, the degree of polymerization does not. The degree of polymerization, on the other hand, greatly influences the viscosity of the polymer.

After the desired level of polymerization and refractive index is achieved, the catalyst is inactivated, neutralized, or removed and the reaction product is carefully filtered, for example on a filter press, to remove any unreacted solid starting materials or other solid impurities.

After filtration, volatile materials are carefully removed from the copolymer by repeated exposure to vacuum, preferably while the copolymer is in a thin film form. The careful removal of volatiles, commonly termed “stripping”, is consired important for the purpose of obtaining material suitable for use as intraocular lens. The “stripping” is preferably conducted in a state-of-the-art “wipe film evaporator” using large “wipe films” and the process is monitored by gas column chromatography of the removed volatiles. As it will be readily appreciated by those skilled in the art, the removed “volatiles” are residues of starting materials, cyclic and linear oligosiloxanes and the like.

Moreover, because in virtually every polymerization the molecular weight, or degree of polymerization of the resulting polymeric products follow a substantially bell shaped curve, the crude reaction product copolymer of the present invention also contains products having substantially lesser degree of polymerization, than for example the desired dp of 250 for the preferred embodiment. In this regard it should be understood that a dp of 250 of the preferred embodiment is to be construed as such dp numbers are normally construed in the art of polysiloxane chemistry. A dp of 250 thus means that the average dp of the polymeric product is approximately 250 .

Stripping of the copolymeric product is repeated several times, preferably three times. This process removes a significant amount of the lower dp copolymers; usually approximately 12 percent by weight of the reaction product is removed by “stripping”.

It is considered important in the practice of the present invention to monitor viscosity and refractive index at the end of the process of removing volatiles. The refractive index of the copolymer should be at least 1.44. As it was noted above, the desired viscosity depends on the precise nature of the copolymer, for the preferred embodiment the viscosity of the “stripped” copolymer should be approximately 4100 to 5300 cp.

The elastomeric composition of the present invention contains a trimethylsilyl treated silica reinforcer finely dispersed in the copolymer. Blending trimethylsilyl treated “fume silica” into a polysiloxane copolymer for the purpose of improving the mechanical porperties of the resulting composition per se, is not new in the art. Nevertheless, the composition of the present invention is considered novel and highly unobvious because of the hitherto unattained highly desirable optical and mechanical properties of the reinforced composition.

In accordance with the invention, the fume silica reinforcer is used in a ratio of approximately 15 to 45 parts by weight of the reinforcer to 100 parts of the copolymer. Fume silica itself is commercially available. Processes for trimethylsilylating the surface of fume silica for the purpose of rendering the silica surface hydrophobic and compatible with polysiloxane polymers are also known and within the skill of the ordinary artisan. U.S. Pat. Nos. 3,341,490 and particularly 3,036,985 refer to and describe such processes for trimethylsilylating fume silica, and the specifications of these two patents are expressly incorporated herein by reference.

In accordance with the present invention the fume silica reinforcer used for the composition has a surface area of approximately 100 to 450 meter ²/gram. For the preferred embodiment of the composition the fume silica has a surface area of approximately 200 meter²/gram, is present in a weight ratio of approximately 27 parts to 100 parts of the copolymer, and is preferably trimethylsilylated with hexamethyldisilazone substantially in the same step where the copolymer is intimately mixed with the silica. The intimate mixing is preferably aided by treating the mixture on a roll mill or like device. After intimate mixing, volatiles, such as unreacted silylating agent, gaseous by-products and water are removed from the mixture by heat and vacuum.

The intimate mixture of the trimethylsilylated fume silica with the copolymer is commonly termed “base” in the art. For the purpose of making materials suitable for intraocular lens, the base is dispersed in a suitable inert solvent, such as trichlorotrifluoroethene (FREON) and the dispersion is filtered to remove any solid impurities. Thereafter, the solvent is removed by gentle heat and vacuum.

The resulting, volatile free uncured (not yet cross-linked) and optically clear reinforced silicone elastomer base, has in accordance with the present invention, an optical refractive index of at least 1.44 and a viscosity in such a range which permits intimate mixing of the base with suitable catalyst and cross linking agents, and subsequent manipulation for forming, preferably by molding, into intraocular lenses. The acceptable viscosity range for this purpose is approximately 35,000 to 80,000 cp. For the preferred embodiment of the invention, the refractive index of the uncured base is approximately 1.462±0.003 and the viscosity is in the range of 35,000 to 70,000 cp.

It is an important feature of the present invention that the uncured base has the inherent characteristics of providing, after suitable curing by cross-linking, physical properties which are highly advantageous for a soft intraocular lens. Thus, after the hereinafter described curing or cross-linking steps, the properties of the resulting cross-linked elastomer include in accordance with the present invention the following:

an optical refractive index which is at least 1.44;

a Shore A durometer hardness value of at least 35;

a tensile strength of at least 500 psi;

a 150 percent minimum elongation (without damage), and

a tear strength of at least 20 pounds per lineal inch (pli).

The above listed properties can be measured in accordance with state-of-the-art technology and instruments in accordance with the respective requirements of standard ASTM test methods. More particularly, the durometer test is performed as ASTM D2240, the tensile and elongation tests as ASTM D412 and the tear strength test as ASTM D624 Die B.

Preferably, the optical refractive index of the cross linked elastomer obtainable from the base is approximately 1.462, the durometer hardness is approximately between 38 to 40, the tensile strength is approximately between 700 to 750 psi, and the tear strength is approximately 40 pli. In this regard it is noted that cross-linking tends to slightly increase the optical refractive index as compared to the uncured base.

Preparation of the uncured base for cross-linking is accomplished as follows. The base is filtered once more, preferably through a 325 mesh screen to remove any remaining solid impurities. Thereafter, in accordance with standard practice in the art, the base is divided into two aliquots which preferably are of equal weight. The aliquots are commonly termed “Part A” and “Part B”, or first and second aliquot parts.

As is known in the art, cross-linking is accomplished by utilizing in a platinum catalyzed reaction the terminal silicon bonded olefinic (vinyl) groups of the base, and silicon bonded hydrogen groups. The silicon bonded olefinic (vinyl) groups are present both in the first and second aliquots of the base.

Silicon bonded hydrogen groups are added in the practice of the present invention to the second aliquot (Part B) in the form of suitable cross-linking agents. The cross-linking agents per se are known in the art, and may be made in accordance with the teachings of U.S. Pat. No. 3,436,366 the specification of which is incorporated herein by reference.

Whereas a number of cross-linking agents are suitable for the practice of the invention and can be selected by those skilled in the art, the liquid organohydrogen polysiloxane cross linkers shown in column 2 of the above-noted U.S. Pat. No. 3,436,366 and having the formula (R) _a(H)_bSiO_4-a-b/2wherein R is simple lower alkyl and a ranges from 1.00 to 2.10 and b ranges from 0.1 to 1.0, are eminently suitable. Particularly suitable is the liquid organohydrogen polysiloxane cross-linker of the above-referenced U.S. Pat. No. 3,436,366 having the formula R₂HSiO_½, and the liquid cross linker described in Column 4 lines 3-14 of said patent reference wherein the R groups are primarily or predominantly methyl.

The platinum catalyst can also be selected within the skill of the ordinary artisan, primarily from organo platinum compounds, for example in accordance with the specifications of U.S. Pat. Nos. 2,823,218 and 3,159,601, which are expressly incorporated herein by reference. The platinum catalyst is added to the first aliquot (Part A).

It is important in accordance with the invention that after mixing of the aliquots (Parts A and Parts B), the cross-linking should not proceed too rapidly at room temperature, thereby allowing at least two, preferably approximately six hours for work time with the mixed aliquots. For this reason, a suitable cross-linking inhibitor, such as 1,2,3,4 tetramethyl-1,2,3,4-tetramethyl cyclotetrasiloxane, is also added to the second aliqout (Part B).

Although the precise amounts can be adjusted within the skill of ordinary artisan, the organo platinum catalyst is added to the first aliquot in 12 part per million (12 ppm) by weight. The cross-linker is added to the second aliquot in the range of approximately 1 to 6 parts per hundred (1-6 pph) by weight. The above specified inhibitor is also added to the second aliquot in the range of 0.01 to 0.2 parts per hundred by weight.

It has been found in accordance with the present invention that best results, in terms of desired curing times, are obtained when the amount of inhibitor used in the second aliquot is adjusted on small samples of each batch. The adjustment within the above-noted ranges serves to provide approximately 6 hours of work time at room temperature. In other words, the material should not cure significantly at room temperature within six hours. Before curing or cross-linking, the first and second aliquots are intimately mixed, preferably in equal amounts.

In addition to the above-described cross-linker and inhibitor, an ultraviolet ray absorbing material is also optionally mixed into the second aliquot in accordance with the teachings of co-pending application for U.S. patent Ser. No. 946,703 filed on Dec. 24, 1986 by Reich et, al, and titled ULTRAVIOLET LIGHT ABSORBING SILICONE COMPOSITIONS.

The ultraviolet ray absorbing material, which in accordance with teachings of the above-noted patent application is a vinyl functional 2-hydroxybenzophenone, or a vinyl functional benzotriazole is covalently linked to the copolymer of the composition during the cross linking step. Preferably, the ultraviolet absorbing material is 2(2′-hydroxy-3′-t-butyl-5′-vinyl-phenyl)-5-chloro-2H-benzotriazole, and is added in an amount of approximately 0.5 weight percent to the second aliquot, Consequently, in the final cured elastomer, the above-named u. v. absorbent is present in approximately 0.25 per cent (by weight).

Although the chemical reactions involved in the crosslinking are well known in the art, they are summarized here for the sake of completeness an involving the formation of ethylenic (CH ₂—CH₂) bridges linking one copolymer chain to a polysiloxane cross linking molecule. The polysiloxane cross linker molecule, in turn, is again linked through an ethylenic bridge to a second copolymer chain. In essence, the chemical reaction involves saturation of a vinyl (or other unsaturated) groups of an end blocker with the hydrogen derived from an at least difunctional organohydrogen polysiloxane and formation of a carbon to silicon bond. This reaction is catalyzed by the platinum catalyst.

The vinyl functional u. v. absorbant reacts with the organohydrogen polysiloxane cross-linking agent in essentially the same way as the vinyl group of the copolymer, and forms a carbon to silicone bond which covalently links the u. v. absorber to the copolymer network.

Formation of intraocular lens bodies from the elastomeric compositions of the present invention may be accomplished by liquid injection molding or by coat or compression molding of the intimately mixed first and second aliquots. Although these processes are well known in the art, they are briefly summarized by description of the following examples.

In the liquid injection molding process the mixed aliquots are injected into a hot mold kept at approximately 120 to 150 C. The cross-linking or curing process is then complete in approximately five minutes.

In the cast or compression molding process, the mixed aliquots are placed into appropriate molds, and the molds are thereafter positioned in an oven heated to approximately 150 C. Under these conditions the cure is complete in approximately 15 to 30 minutes. The cast molding process can also be completed at room temperature in significantly longer time periods.

The intraocular lenses made in accordance with the present invention have the above-described advantagous optical and Mechanical properties. The unusually high optical refractive index of 1.44 or greater, permits the fabrication of lenses which are at their apex only approximately 1.1 to 1.15 mm thick. This is a significant advance over prior art intraocular lenses which, being made of materials having lower refractive indices, at typically are 1.42 mm thick at their apex.

An additional advantage of the intraocular lenses made in accordance with the invention is that they do not absorb energy at 1064 nm, thereby permitting follow-up LASER surgery in the eye after implantation of the lens.

Several modifications of the invention may become readily apparent to those skilled in the art in light of the foregoing disclosure. Therefore the scope of the present invention should be interpreted solely from the following claims. Further particulars of the preferred embodiment of the invention are described in the following description of an example of making the elastomeric compositions of the invention.

SPECIFIC EXAMPLE

Preparation of Crude Copolymer [0060]
In a 50 gallon reactor (Baker Perkins) mix octaphenylcyclotetrasiloxone (phenyl cyclics) (44.550 kg), octaphenylcyclotetrasiloxone (dimethylcyclics) (93.462 kg) and 1,2-divinyltetramethyldisiloxane (1.116 kg) and heat under agitation and a nitrogen gas blanket to 100 C. When the temperature reaches 100 C add 0.18 per cent (by weight) N-catalyst (about 250 g). Continue heating and stirring and monitor viscosity of samples taken from the reaction mixture. If after 45 minutes there is no change in viscosity, add 0.18 per cent more N-Catalyst (about 75 g). After viscosity change has been observed and the phenyl cyclics have dissolved continue heating and stirring for 3 hours. Then neutralize or destroy the catalyst, for example by bubbling CO[0061] ₂into the mixture, or heating to 150 C. Viscosity of the cooled reaction mixture should be between 2000 to 2800 cp, the refractive index should be between 1.459 to 1.465.
Purification of Copolymer [0062]
Filter the cooled reaction mixture on a filter press with a pressure of about 40 psi on five or more filter plates using Zeta Plus filter paper, catalog # A1311-10A. Strip the filtered copolymer at least three times on a “wipe film evaporator”. Monitor the process of stripping by gc, taking samples of 1 g of the volatiles and dissolving the same in 3 g of hexene. Continue stripping until gc indicates adequate devolatilization. Viscosity of stripped copolymer should be between 4100 to 5300 cp, the refractive index should be between 1.459 to 1.465. [0063]
Formulation of Base Including Silica Reinforcer [0064]
In a 50 gallon mixer mix the stripped polymer (75 kg) with hexamethyldisilazane (3.6. kg). Add MS-7 silica (30 kg, surface area 200 m[0065] ²/g) in increments, and with last silica load add distilled water (1.2 kg), mix well. Thereafter mill mixture twice on three roll mill, and return mixture to 50 gallon mixer. Heat mixer to reach internal temperature of 150 to 200 C. After 30 minutes of heating and stirring at above temperature, apply vacuum and continue heating for 2.5 hours while the mixer reactor is under vacuum. Cool mixture under vacuum. After cooling add more stripped polymer (36.11 kg) as a “cut-back” and mix well. Let a small sample of base settle (unstirred) for about 30 minutes and check viscosity at 25 C. of with Brookfield viscometer, viscosity should be between 35,000 to 70,000 cp.
Purification of Base [0066]
Disperse the base in trichlorotrifluoroethane (FREON) in a ratio of about 2 gallons of base to 1 gallon of FREON, and add about 0.5 gallon of dictomaceous earth to the dispersion for each 2 gallons of base. Filter the dispersion on a filter press using Zeta Plus filter paper, catalog # A1311-10A. Pressure during filtration should be kept at about 30 psi and should not exceed that value. Clear filrate is required. Place the collected clear filtrate in a reactor, and agitate under nitrogen purge. Apply vacuum gradually while purging slowly with nitrogen. Heat slowly to 110 C. and continue heating under vacuum. Take samples for weight loss test. Continue heating under vacuum until weight loss on samples taken indicates no more than 0.5 per cent loss. Thereafter cool to obtain stripped base. [0067]
Preparation of Aliquots (Parts A and B) Ready for Cross-Linking. [0068]
Screen stripped base through 325 mesh steel wire screen under pressure. Divide the batch into two equal parts, Part A and Part B. Mix into Part A the organoplatinum catalyst to provide 12 parts per million by weight. Take small samples from Part B and mix in the cross-linker (liquid organohydrogen polysiloxone having the structure R[0069] ₂HSiO_½with the R groups being predominantly methyl). Optimize the cross linker level, so as to obtain a Shore durometer hardness of approximately 35 (ASTM D2240) in the cross-linked product, Thereafter, gradually add increasing amounts of the inhibitor (1,2,3,4 tetramethyl-1,2,3,4-tetravinyl cyclotetrasiloxane) to Part B and test mixed samples of Parts A and B to obtain a working time of about 6 hours at room temperature. Depending on the above-noted sample teat results, the cross linker is added to Part B to provide 1-6 parts per hundred by weight, and the inhibitor is added to Part B to provide 0.01 to 0.2 parts per hundred by weight.
Optionally, intimately mix in the u. v. light absorbent 2(2′-hydroxy-3′-t-butyl-5′-vinyl-phenyl)-5-chloro-2H-benzotriazole in an amount which corresponds to approximately 0.5 per cent by weight in Part B. [0070]

Screen Part A and Part B separately from one another on 325 mesh screen to remove any solid contaminants. For cross-linking or curing to obtain intraocular lenses proceed in accordance with procedures required for liquid infection molding, or cast molding.

	APPENDIX A


	DOCKET NO.	PATENT #

	14101	3,873,696
	14104CIP	4,029,817
	14106	4,127,674
	14108CIP-2	4,395,346
	14109	4,230,724
	14111	4,244,948
	14144	3,888,782
	14145	3,822,780
	14146	3,954,965
	14147	3,966,924
	14149	4,197,301
	14150	4,255,419
	14152	3,749,776
	14153	3,733,178
	14167	D279,357
	14192	4,524,063
	14204	4,743,588
	16502	4,670,178
	16502Reissue	RE32,672
	16505	4,786,651
	16518	4,725,620
	16519	4,739,098
	16534CIP-1	4,763,651
	16540DIV-1	4,786,445
	16542FWC	4,759,761
	16543	4,704,122
	16544	4,834,751
	16544DIV1	4,894,062
	16544RE-DIV	RE34,448
	16546	4,790,846
	16546DIV-1	4,888,013
	16546DIV-2	4,880,426
	16546DIV-3	4,938,767
	16546DIV-4-CIP-1	5,133,746
	16546DIV-4	4,978,354
	16546DIV-4-CON-1	5,171,268
	16547	4,684,014
	16548FWC	4,838,682
	16549	4,842,782
	16549-CIP-2	5,053,171
	16549-CIP-2-DIV1	5,179,262
	16549DIV-FWC	5,061,840
	16550	4,932,970
	16552	4,576,798
	16553DIV-1	4,927,947
	16553DIV-2	4,980,484
	16553FWC	4,923,884
	16554	4,597,649
	16556FWC-2	5,236,970
	16556-FWC-2-DIV-1	5,376,694
	16557DIV-1	4,983,580
	16557DIV-2	4,981,841
	16559CIP	4,868,251
	16560	5,149,705
	16560DIV	5,246,962
	16560DIV-2	5,354,776
	16560DIV-3	5,466,690
	16561CIP-1	5,089,509
	16561CIP-2	5,264,578
	16561CIP-DIV	5,234,926
	16561CIP-DIV-4	5,380,877
	16561CIP-DIV-3	5,348,972
	16561DIV-CIP-2	5,468,879
	16561CON-DIV-2-CIP	5,354,752
	16562	4,810,804
	16564CIP&16653CIP	5,134,128
	16568	4,759,359
	16569	4,834,748
	16571	4,817,789
	16571DIV	4,928,815
	16575	4,208,365
	16578	4,452,925
	16578REISSUE	RE33,997
	16580	4,388,428
	16582	5,030,231
	16582DIV-1	5,088,809
	16582CIP-DIV-1	5,196,028
	16584	4,517,138
	16588	4,551,086
	16590	4,468,184
	16591	4,647,261
	16592	4,681,295
	16594DIV-1	4,584,148
	16594	4,534,723
	16597	4,492,854
	16607	DE256,049
	16608	DE256,391
	16609	DE256,392
	16610	DE257,174
	16611	DE257,486
	16612	DE257,789
	16613	DE264,377
	16614	DE267,652
	16615	DE276,367
	16616	3,925,825
	16617	3,996,627
	16618	3,975,779
	16619	3,971,073
	16620CIP-1	3,996,626
	16620	4,150,471
	16621	4,012,823
	16622	4,015,965
	16623	4,028,082
	16624DIV-1	4,071,343
	16624	4,025,965
	16625	4,014,049
	16626	4,139,915
	16628	4,079,470
	16632	4,838,413
	16636	4,845,180
	16638FWC-2	5,192,316
	16639CON-DIV-1	5,231,113
	16639CONT	5,130,335
	16640	4,895,868
	16640CIP	5,015,658
	16642	4,897,079
	16643	4,842,602
	16643DIV-1	4,888,014
	16644FWC	5,300,262
	16644	5,076,683
	16645	4,935,530
	16646	4,860,885
	16647CIP-1	5,089,485
	16648CIP-1	5,059,611
	16649CIP-1	4,957,917
	16651CIP	5,424,078
	16652CIP-1	5,045,564
	16652CIP-2	5,376,676
	16654FWC-2-CIP	5,399,573
	16655	5,044,743
	16657DIV-1	4,328,148
	16657DIV-2	4,465,794
	16657	4,275,183
	16660	4,469,646
	16661	4,517,140
	16662	4,516,924
	16663	4,645,811
	16664	4,568,501
	16665	4,534,916
	16669	4,445,362
	16670	4,583,830
	16680	4,438,100
	16687FWC-DIV-2	5,166,711
	16687FWC-DIV-1-CIP	5,225,858
	16687FWC-DIV-3	5,270,744
	16693	3,739,455
	16694	3,829,536
	16695	3,827,798
	16697	3,751,138
	16715	4,983,901
	16740	DE315,164
	16744-CIP	5,180,721
	16744DIV-CIP	5,281,591
	16748	4,889,421
	16752	5,310,571
	16752DIV	5,475,450
	16753	4,666,446
	16754	5,078,908
	16754DIV-2	5,306,440
	16754DIV-FWC	5,246,662
	16755FWC	5,028,624
	16756FWC	5,446,041
	16757	4,992,468
	16757DIV-1	5,068,252
	16758FWC	5,034,413
	16760	5,034,406
	16761CIP-1	5,112,822
	16761CIP-2	5,231,096
	16761CIP-2-DIV	5,326,763
	16761CIP-2-DIV-2	5,373,010
	16761CIP-2-DIV-3	5,418,234
	16761DIV-1	5,204,347
	16761DIV-2	5,300,504
	16761DIV-CIP	5,198,442
	16761	5,077,292
	16763	5,093.329
	16764	5,045,551
	16764DIV	5,183,827
	16764DIV-2	5,272,156
	16764DIV-3	5,407,937
	16765	4,980,369
	16765CIP-DIV	5,162,546
	16765CIP-DIV-2	5,278,318
	16766	5,023,341
	16766DIV	5,053,523
	16766DIV-3	5,248,777
	16767	5,279,673
	16767DIV-1	5,152,912
	16768CIP	5,262,097
	16768CIP-DIV	5,344,449
	16768	5,147,397
	16769CIP	5,135,623
	16769	4,997,626
	16769DIV	5,320,806
	16771	5,171,526
	16772	5,145,643
	16772CIP	5,277,901
	16772CIP-2	5,451,398
	16773	4,955,889
	16774	5,098,439
	16774DIV-FWC	5,222,972
	16775DIV	5,194,449
	16775	5,011,856
	16777CON-DIV	5,258,400
	16777CON	5,112,853
	16778	5,019,097
	16779	5,021,416
	16784CON	5,198,545
	16784	5,055,467
	16785DIV-2-CIP	5,453,434
	16785	5,264,449
	16786	4,615,702
	16787	4,702,865
	16788	4,878,910
	16796	5,013,744
	16796DIV	5,175,185
	16796DIV-2	5,264,456
	16796DIV-3	5,414,007
	16797	5,006,550
	16798CIP	5,215,991
	16800	4,757,089
	16801	5,130,441
	16801DIV	5,237,072
	16802	5,129,999
	16804	5,281,353
	16804DIV-1	5,330,752
	16805DIV-1	5,312,588
	16807	5,111,029
	16808	5,202,471
	16808CON	5,349,105
	16809	5,066,664
	16812	5,151,440
	16812DIV	5,252,595
	16813CIP	5,441,732
	16813	5,252,318
	16814	5,081,147
	16814DIV	5,212,172
	16815	5,081,261
	16816CIP	5,376,737
	16816CIP-2	5,352,753
	16816CIP-2-DIV	5,466,768
	16816CIP-3	5,397,848
	16816	5,164,462
	16818CIP	5,395,621
	16818FWC	5,362,444
	16819	5,013,850
	16820CIP	5,474,780
	16822	5,238,961
	16823	5,037,811
	16824	5,043,457
	16826	5,173,298
	16827	5,100,431
	16829	5,139,491
	16831	5,323,775
	16834	5,296,228
	16835	5,275,820
	16836	5,276,044
	16838	5,091,528
	16841	5,270,049
	16845	5,183,906
	16846	5,225,571
	16847	5,169,963
	16848	5,171,864
	16851CIP	5,262,437
	16854	5,312,832
	16855	5,288,754
	16856CON	5,346,915
	16857CON	5,270,002
	16860	5,145,644
	16864CIP	5,082,954
	16864DIV	5,171,863
	16864DIV-2	5,322,953
	16864DIV-3	5,298,633
	16868	5,292,517
	16870	5,356,555
	16871	5,143,104
	16872FWC	5,209,783
	16873	5,455,265
	16877	5,134,159
	16877DIV	5,324,744
	16877DIV-2	5,348,975
	16878CIP	5,338,480
	16878CIP-2	5,324,447
	16878CIP-3	5,336,434
	16879CON	5,346,895
	16881	5,391,590
	16883CIP	5,242,449
	16883DIV-CIP	5,364,405
	16884	5,147,395
	16885	5,152,789
	16891	5,197,636
	16892FWC	5,401,508
	16898	5,197,638
	16899	5,252,246
	16902	5,213,760
	16903	5,249,002
	16905CIP	5,392,653
	16906CIP	5,470,312
	16907	5,230,614
	16908	5,224,593
	16913CIP	5,303,023
	16916DIV	5,411,553
	16916	5,278,258
	16921	5,233,007
	16921FWC-DIV	5,420,213
	16925	5,462,968
	16926	5,326,898
	16927CON	5,391,753
	16927DIV	5,434,173
	16928	5,201,763
	16932CIP	5,422,073
	16936	5,420,295
	16937	5,268,387
	16937DIV	5,387,606
	16940	5,260,021
	16941	5,340,583
	16942FWC	5,387,394
	16943DIV	5,300,114
	16943	5,178,635
	16945	5,324,840
	16945CIP	5,475,113
	16946	5,281,227
	16948	5,268,624
	16949	5,384,606
	16950	5,320,256
	16950DIV	5,427,274
	16951	5,385,945
	16953	5,300,499
	16954FWC	5,324,180
	16955	5,352,708
	16956	5,332,730
	16957	5,312,842
	16959	5,468,778
	16960	5,328,933
	16961	5,284,472
	16963	5,375,698
	16965	5,389,383
	16967	5,331,073
	16967DIV-1	5,359,021
	16971	5,344,959
	16972	5,426,118
	16973	5,451,605
	16974	5,470,999
	16977	5,399,561
	16982	5,451,686
	16983	5,362,647
	16984	5,342,293
	16985	5,387,180
	16988	5,399,586
	16990	5,416,106
	16991	5,369,127
	16992	5,387,608
	16992DIV	5,457,131
	16995CIP	4,568,517
	17000	5,358,473
	17003	5,382,599
	17005	5,447,650
	17010	5,433,745
	17012	5,451,237
	17013	5,423,929
	17018	5,476,872
	17022	5,419,775
	17024	4,664,667
	17025	5,474,979
	17042	5,443,178
	17050	5,084,012
	17051	5,217,465
	17104	4,608,049
	17117	4,681,102
	17162	4,900,366
	17164	5,238,153
	17167	4,826,001

Claims

What is claimed is:

1. An optically clear, reinforced cross-linked silicone elastomer, comprising:

a polymer containing 12 to 18 mol percent diphenyl siloxane units, and end blockers containing siloxane units of the formula R₁,R₂,R₃—Si—O wherein R₁and R₂are alkyl, aryl or substituted alkyl or substituted aryl group, R₁and R₂being either identical or different from one another and wherein R₃is an alkenyl group, the balance of the polymer consisting of dimethyl siloxane units, the polymer having a degree of polymerization approximately between 100 to 2000, and the polymer having been cured by cross linking;

a trimethyl silyl treated silica reinforcer finely dispersed in the polymer, the elastomer having the physical properties of:

an optical refractive index which is at least 1.44;

a Type A durometer hardness value of at least 35;

a tensile strength of at least 500 psi, and

a tear strength of at least 20 pli.

2. The silicone elastomer of claim 1 wherein the R₁and R₂groups of the end blocking siloxane units are methyl, and the R₃group of the end blocking siloxane unit is vinyl.

3. The silicone elastomer of claim 2 wherein the polymer contains approximately 14 to 16 mol percent diphenyl siloxane units.

4. The silicone elastomer of claim 3 wherein the polymer contains approximately 15 mol percent diphenyl siloxane units.

5. The silicone elastomer of Claim 3 wherein the optical refractive index is at least 1.459.

6. The silicone elastomer of claim 3 wherein the ratio of polymer to the trimethyl silyl treated silica reinforcer is approximately 15 to 45 parts by weight of the reinforcer to 100 parts by weight of the polymer.

7. The silicone elastomer of claim 6 wherein the ratio of polymer to the trimethyl silyl treated silica reinforcer is approximately 27 parts of the reinforcer to 100 parts of the polymer.

8. The silicone elastomer of claim 3 having a type A durometer hardness value of approximately 38 to 40, a tensile strength of approximately 700 to 750 psi, and a tear strength of approximately 40 pli.

9. The silicone elastomer of claim 3 wherein the degree of polymerization is approximately 250 .

10. An optically clear, reinforced cross-linked silicone elastomer, comprising:

a polymer containing 12 to 18 mol percent of aryl substituted siloxane units of the formula R₄,R₅—Si—O wherein R₄and R₅are identical with one another or are different from one another and represent phenyl, or mono- or di- lower alkyl substituted phenyl groups, and end blockers containing siloxane units of the formula R₁,R₂,R₃—Si—O wherein R₁and R₂are alkyl, aryl or substituted alkyl or substituted aryl group, R₁and R₂being either identical or different from one another and wherein R₃is an alkenyl group, the balance of the polymer consisting of dialkyl siloxane units of the formula R₆,R₇—Si—O wherein R₆and R₇are identical with one another or are different from one another and are methyl or ethyl groups, the polymer having a degree of polymerization approximately between 100 to 2000, and the polymer having been cured by cross linking;

a trimethyl silyl treated silica reinforcer finely dispersed in the polymer, the cross-linked elastomer having the physical properties of:

an optical refractive index which is at least 1.44;

a Type A durometer hardness value of at least 35;

a tensile strength of at least 500 psi, and

a tear strength of at least 20 pli.

11. The elastomer of claim 10 wherein the R₄and R₅groups are phenyl groups.

12. The elastomer of claim 10 wherein the R₁and R₂groups are methyl.

13. The elastomer of claim 10 wherein the R₁And R₂groups are methyl, the R₃group is vinyl.

14. The elastomer of claim 10 wherein the R₆and R₇groups are methyl.

15. The elastomer of claim 10 wherein the degree of polymerization is approximately 250 .

16. The elastomer of claim 10 wherein the ratio of the reinforcer to the polymer is approximately 15 to 45 part per weight for 100 parts of the polymer.

17. The elastomer of claim 10 further comprising a ultra violet light absorbing agent covalently linked to the cross linked elastomer.

18. An optically clear, reinforced polyayloxane base comprising:

a copolymer having 12 to 18 mol percent diphenyl siloxane units, and end blockers containing siloxane units of the formula R₁,R₂,R₃—Si—O wherein R₁and R₂are alkyl, aryl or substituted alkyl or substituted aryl group, R₁and R₂being either identical or different from one another and wherein R₃is an alkenyl group, the balance consisting of dimethyl siloxane units, the polymer having a degree of polymerization approximately between 100 to 2000;

a trimethyl silyl treated silica reinforcer finely dispersed in the copolymer, the weight ratio of the reinforcer to the copolymer being approximately 15 to 45 parts for 100 parts of the copolymer, the base having an optical refractive index of at least 1.44 and a viscosity of approximately 35,000 to 80,000 cp and is capable of being cured by cross-linking such that the physical properties of the cured cross-linked base include:

an optical refractive index which is at least 1.44;

a Type A durometer hardness value of at least 35;

a tensile strength of at least 500 psi, and

a tear strength of at least 20 pli.

19. The base of claim 18 wherein R₁and R₂are methyl, and R₃is vinyl.

20. The base of claim 19 wherein the degree of polymerization of the copolymer is approximately 250 .

21. The base of claim 19 wherein the weight ratio of the reinforcer to the copolymer in approximately 27 parts for 100 parts of the polymer.

22. The base of claim 19 wherein the copolymer comprises approximately 15 mol percent diphenyl siloxane units.

23. The base of claim 22 having an optical refractive index of at least 1.459.

24. An optically clear, reinforced polysiloxane base consisting essentially of:

a copolymer having 12 to 18 mol percent of aryl substituted siloxane units of the formula R₄,R₅—Si—O wherein R₄and R₅are identical with one another or are different iron one another and represent phenyl, or mono- or di- lower alkyl substituted phenyl groups, and end blockers containing siloxane units of the formula R₁,R₂,R₃—Si—O wherein R₁and R₂are alkyl, aryl or substituted alkyl or substituted aryl group, R₁and R₂being either identical or different from one another and wherein R₃is an alkenyl group, the balance of the polymer consisting of dialkyl siloxane units of the formula R₆,R₇—Si—O wherein R₆and R₇are identical with one another or are different from one another and are methyl or ethyl groups, the polymer having a degree of polymerization approximately between 100 to 2000;

an optical refractive index which is at least 1.44;

a Type A durometer hardness value of at least 35;

a tensile strength of at least 500 psi, and

a tear strength of at least 20 pli.

25. The base of claim 24 wherein the R₄and R₅groups are both phenyl.

26. The base of claim 24 wherein the R₁and R₂units are both methyl and R₃is vinyl.

27. The base of claim 24 wherein the R₆and R₇units are both methyl.

28. The base of claim 24 wherein the R₄and R₅groups are both phenyl, R₁, R₂, R₆and R₇are methyl and R₃is vinyl, and wherein the copolymer contains approximately 15 mol percent diphenyl siloxane units.

29. The base of claim 28 wherein the weight ratio of the reinforcer to the base is approximately 27 parts of the reinforcer to 100 parts of the copolymer, and wherein the degree of polymerization of the copolymer is approximately 250 .

30. The base of claim 29 having an optical refractive index of at least 1.459.

31. An intraocular lens body suitable for surgical implantation into the human eye, the lens body being an optically clear reinforced cross-linked silicone elastomer which comprises:

a polymer containing 12 to 18 mol percent diphenyl siloxane units, and end blockers containing siloxane units of the formula R₁,R₂,R₃—Si—O wherein R₁and R₂are alkyl, aryl or substituted alkyl or substituted aryl group, R₁and R₂being either identical or different from one another and wherein R₃is an alkenyl group, the balance of the polymer consisting of dimethyl siloxane units, the polymer having a degree of polymerization approximately between 100 to 2000;

a trimethyl silyl treated silica reinforcer finely dispersed in the polymer, the reinforcer having a weight ratio of approximately 15 to 45 parts to 100 part of the polymer, the lens body having the physical properties of:

an optical refractive index which is at least 1.44;

a Type A durometer hardness value of at least 35;

a tensile strength of at least 500 psi, and

a tear strength of at least 20 pli.

32. The intraocular lens of claim 31 wherein the R₁and R₂groups of the end blocking siloxane units of the polymer are methyl, and the R₃group of the end blocking siloxane unit is vinyl and wherein the polymer contains approximately 14 to 16 mol percent diphenyl siloxane units.

33. The intraocular lens of claim 32 wherein the polymer contains approximately 15 mol percent diphenyl siloxane units, has a degree of polymerization of approximately 250, the ratio of polymer to the trimethyl silyl treated silica reinforcer is approximately 27 parts of the reinforcer to 100 parts of the polymer and wherein the optical refractive index of the lens body is at least 1.459.

34. The intraocular lens of claim 33 having a type A durometer hardness value of approximately 38 to 40, a tensile strength of approximately 700 to 750 psi, and a tear strength of approximately 40 pli.

35. An intraocular lens body suitable for surgical implantation into the human eye, the lens body being an optically clear reinforced cross-linked silicone elastomer which comprises:

a polymer containing 12 to 18 mol percent of aryl substituted siloxane units of the formula R₄,R₅—Si—O wherein R₄and R₅are identical with one another or are different from one another and represent phenyl, or mono- or di- lower alkyl substituted phenyl groups, and end blockers containing siloxane units of the formula R₁,R₂,R₃—Si—O wherein R₁and R₂are alkyl, aryl or substituted alkyl or substituted aryl group, R₁and R₂being either identical or different from one another and wherein R₃is an alkenyl group, the balance of the polymer consisting of dialkyl siloxane units of the formula R₆,R₇—Si—O wherein R₆and R₇are identical with one another or are different from one another and are methyl or ethyl groups, the polymer having a degree of polymerization approximately between 100 to 2000;

an optical refractive index which is at least 1.44;

a Type A durometer hardness value of at least 35;

a tensile strength of at least 500 psi, and

a tear strength of at least 20 pli.

36. The intraocular lens of claim 10 wherein the R₄and R₅groups are phenyl groups, the R₁and R₂groups are methyl, the R₃group is vinyl, and the R₆and R₇groups are methyl.

37. The intraocular lens of claim 36 wherein the polymer has a degree of polymerization of approximately 250 .

38. The intraocular lens of claim 36 wherein the ratio of the reinforcer to the polymer is approximately 27 parts per weight of the reinforcer for 100 parts per weight of the polymer.

39. The intraocular lens of claim 36 further comprising a ultra violet light absorbing agent covalently linked to the cross linked elastomer.

40. The intraocular lens of claim 38 having a type A durometer hardness value of approximately 38 to 40, a tensile strength of approximately 700 to 750 psi, and a tear strength of approximately 40 pli.