# Patent

## Title
Silicone hydrogel contact lenses and related compositions and methods

## Abstract

Silicone hydrogel contact lenses are produced without using volatile organic solvents to extract materials from the polymerized contact lens bodies, and instead are washed with aqueous liquids. The silicone hydrogel contact lenses so produced have ophthalmically wettable lens surfaces. The hydrated silicone hydrogel contact lenses have diameters that are at least 24% larger than the diameters of the silicone hydrogel contact lenses prior to hydration or washing.

## Background
This application claims the benefit under 35 U.S.C. §119(e) of prior U.S. Provisional Patent Application No. 61/447,143, filed Feb. 28, 2011, which is incorporated in its entirety by reference herein.


FIELD
The present disclosure is directed to silicone hydrogel contact lenses and related compositions and methods.
BACKGROUND
Commercially and clinically, silicone hydrogel contact lenses are a popular alternative to conventional hydrogel contact lenses (i.e., hydrogel contact lenses that do not contain silicon or silicon-containing ingredients). The presence of hydrophobic ingredients, such as siloxanes and other hydrophobic reactive ingredients, in silicone hydrogel contact lens formulations is believed to contribute, at least in part, to the frequent occurrence of clinically ophthalmically unacceptable surface wettabilities associated with the development of new silicone hydrogel contact lenses.
The commercial manufacture of silicone hydrogel contact lenses frequently includes one or more washing steps using volatile organic solvents, such as alcohol, to remove unreacted or partially reacted chemicals, especially hydrophobic chemical ingredients, from the polymerized lens bodies prior to packaging. This is frequently referred to as an extraction process to remove extractable material from the polymerized silicone hydrogel contact lens product. The use of such organic extraction methods are commonly necessary in order to render the lens bodies acceptable for wear in the eye by removing potentially irritation or toxic materials from the lenses, and in some cases to increase the wettability of the lens surfaces. The use of volatile organic solvents facilitates removal of a component of the polymerized silicone hydrogel contact lens that has poor solubility in aqueous solutions or water. However, the use of volatile organic solvents presents safety risks to contact lens manufacturing sites, and can be associated with increased costs of goods. When an organic solvent, such as alcohol, is used to wash a silicone hydrogel contact lens, the contact lens increases in size or swells. For example, it is not uncommon for a pre-washed silicone hydrogel contact lens to have a first diameter, such as about 14.0 mm, and for the same silicone hydrogel contact lens to have a second diameter that is about twice as large as the first diameter after contacting the organic solvent, such as increasing to about 28.0 mm. Subsequent to swelling and washing with organic solvents, such lenses are then washed in aqueous solutions to remove the organic solvent and to reduce the size of the lens back to its original pre-swelled dimensions or dimensions close to its pre-swelled dimensions, for example within 10% of its original dimensions. Therefore, when using organic solvents, it is necessary to design the lens molds, and lens washing devices to take into account the changes in lens size resulting from washing. It is also necessary to process the swollen lenses so that they return to their initial size or close to their original size, such as about 14.0 mm in diameter.
In addition to extracting with volatile organic solvents, a variety of additional manufacturing techniques have been employed to make silicone hydrogel contact lenses having clinically ophthalmically compatible lens surfaces. For example, some silicone hydrogel contact lenses are treated with plasma to form a hydrophilic lens surface; some silicone hydrogel contact lenses are formed from a polymerizable lens formulation containing a hydrophilic polymeric internal wetting agent, such as polyvinyl pyrrolidone (PVP); some silicone hydrogel contact lenses are formed using polar resin contact lens molds instead of non-polar resin contact lens molds, and the lenses do not contain a hydrophilic polymeric internal wetting agent in the polymerizable lens formulation, and are not subject to plasma treatment; and some silicone hydrogel contact lenses are formed in non-polar resin molds and are provided with ophthalmically compatible lens surfaces based on chemical reactivity properties of the chemicals in the polymerizable lens formulation.
Based on the popularity of silicone hydrogel contact lenses, there continues to be a need for new silicone hydrogel contact lenses that are ophthalmically compatible.
Some documents describing silicone hydrogel contact lenses include: U.S. Pat. No. 4,711,943, U.S. Pat. No. 5,712,327, U.S. Pat. No. 5,760,100, U.S. Pat. No. 7,825,170, U.S. Pat. No. 6,867,245, US20060063852, US20070296914, U.S. Pat. No. 7,572,841, US20090299022, US20090234089, and US20100249356, each of which is incorporated in its entirety by reference herein.
SUMMARY
It has been realized that reducing or eliminating organic solvent-based extraction steps in the manufacture of silicone hydrogel contact lenses provides at least one opportunity to reduce costs associated with the manufacture of daily disposable silicone hydrogel contact lenses. However, by replacing organic solvent-based extraction steps, such as extracting silicone hydrogel contact lenses with alcohol-based media and the like, with aqueous washing steps, it has become apparent that new methods for manufacturing silicone hydrogel contact lenses of a predetermined target size are required.
New silicone hydrogel contact lenses and methods have been invented. The silicone hydrogel contact lenses and methods of the present invention have been formulated to allow the lens bodies to swell to dimensions which are significantly larger than their original molded dimensions when the lens bodies are exposed to water or aqueous solutions free of organic solvents, and to retain these larger dimensions during the manufacturing process and upon storage such that the dimensions of the resulting silicone hydrogel contact lenses have dimensions at least 24% larger than the dimensions of the polymeric lens body prior to contact with water or aqueous solutions free of organic solvents. In other words, unlike previous silicone hydrogel contact lenses, the lenses disclosed herein swell during wet processing of the lenses during the manufacturing process, and remain swollen following processing, rather than being swollen with an organic solvent during manufacturing and subsequently returning to a reduced size before being packaged and sterilized. By using the disclosed polymerizable compositions which unexpectedly have been found to result in lens bodies which are capable of both swelling significantly in aqueous environments and remaining swollen and dimensionally stable following wet processing, it has been found to be possible to remove significant amounts of irritating and toxic extractable materials from the lenses using aqueous solutions containing little or no organic solvents, and to produce wettable lens surfaces, while also producing silicone hydrogel contact lenses which remain dimensionally stable during storage.
In accordance with the lenses and methods of the disclosure, the present contact lenses comprise, or consist of, lens bodies comprising a polymeric component and a liquid component. The polymeric component comprises units of one or more siloxanes, and one or more non-siloxane reactive ingredients. It can therefore be understood that the polymeric component is the reaction product of a polymerizable composition comprising one or more siloxanes, and one or more non-siloxane reactive ingredients. The ingredients of the polymerizable composition can be monomers, macromers, pre-polymers, polymers, or combinations thereof. The combination of the polymeric component and the liquid component is present as a hydrated silicone hydrogel contact lens, which is suitable for placement on an eye of a person. The contact lens comprises a convex anterior surface and a concave posterior surface, and has an equilibrium water content (EWC) greater than 10% weight by weight (wt/wt). During the manufacture of the silicone hydrogel contact lenses, the lens bodies may not have been extracted with a volatile organic solvent, such as a liquid composition comprising, consisting essentially of, or consisting of, a volatile organic solvent. Examples of volatile organic solvents that are excluded from the manufacture of the present silicone hydrogel contact lenses to remove an extractable component from polymerized lens bodies include primary alcohols, secondary alcohols, tertiary alcohols, or any combination thereof. Unlike commercially available silicone hydrogel contact lenses, the present silicone hydrogel contact lenses may only be exposed to aqueous solutions that are free of volatile organic solvents to remove an extractable component from the polymerized lens bodies. The aqueous solutions may contain non-volatile organic ingredients, such as surfactants, wetting agents, anti-inflammatory agents, extraction aids, and the like, so long as the aqueous solution does not contain a volatile organic solvent. Thus, in one example, the present silicone hydrogel contact lenses can be understood to be aqueous extracted contact lenses. As discussed herein, an aqueous extracted contact lens is chemically and physically different and distinct from an organic solvent extracted contact lens.
The present silicone hydrogel contact lenses can comprise aqueous extracted lens bodies. The aqueous extracted lens bodies each have an anterior surface and an opposing posterior surface, the posterior surface being the surface adjacent to the corneal epithelium of an eye on which the lens body is located.
Thus, the inventors have invented new silicone hydrogel contact lenses with desirable properties to result in hydrated silicone hydrogel contact lenses of desired size or physical dimensions which are not necessarily dependent upon the use of volatile organic solvents to remove extractable material from the lens bodies during the manufacture thereof.
Thus, the silicone hydrogel contact lenses of the present disclosure can be produced without using volatile organic solvents to extract materials from the polymerized contact lens bodies, and instead are washed with aqueous liquids, although the polymerized contact lens bodies of the present disclosure may be washed with organic solvents or aqueous solutions of organic solvents. Regardless of the washing media used, the silicone hydrogel contact lenses of the present disclosure have wettable lens surfaces characterized by advancing contact angle values less than 120 degrees. In addition or alternatively, the wettability of the lens surfaces can be determined by observing that the present silicone hydrogel contact lenses can have water break up times (WBUTs) of about twenty seconds or more.
In accordance with the present disclosure, a method of manufacturing silicone hydrogel contact lenses comprises forming a lens body or forming lens bodies from polymerizable compositions. The lens body so formed is the reaction product of a polymerizable composition that comprises at least one siloxane monomer, at least one hydrophilic monomer, at least one hydrophobic monomer, and at least one cross-linking agent. The lens body is washed to remove extractable material from it. The washing can be performed by contacting the polymerized lens body with an aqueous liquid that is free of volatile organic solvent, or can be performed by contacting the polymerized lens body with a volatile organic solvent or with an aqueous solution of a volatile organic solvent. The lens body is packaged in a contact lens packaging containing an aqueous liquid, such as a contact lens packaging solution, and is sterilized, such as by autoclaving. The hydrated lens body has a lens surface wettability characterized by an advancing contact angle less than 120 degrees, and the hydrated lens body has a diameter (chord diameter) that is at least 24% larger than the diameter of the lens body prior to washing. In one example the hydrated lens body has a diameter that is from 24% greater to 40% greater than the diameter of the lens body prior to washing. In another example the hydrated lens body has a diameter that is from 26% greater to 36% greater than the diameter of the lens body prior to washing. In another example, the hydrated lens body has an advancing contact angle less than 90 degrees, and has a diameter that is from 24% to 40% greater, or from 26% to 36% greater than the diameter of the lens body prior to washing.
Another example of the present disclosure relates to silicone hydrogel contact lenses so produced, and the polymerizable compositions used in the present methods to produce the silicone hydrogel contact lenses.
Additional embodiments of the polymerizable compositions, present lenses, lens products, batches of lenses, and methods of manufacturing contact lenses will be apparent from the following description, Examples, and claims. As can be appreciated from the foregoing and following description, each and every feature described herein, and each and every combination of two or more of such features, and each and every combination of one or more values defining a range, are included within the scope of the present invention provided that the features included in such a combination are not mutually inconsistent. In addition, any feature or combination of features or any value(s) defining a range may be specifically excluded from any embodiment of the present invention.


DETAILED DESCRIPTION
As described herein, it has now been discovered that silicone hydrogel contact lenses can be produced with wettable lens surfaces, wherein the silicone hydrogel contact lens has a diameter that is at least 24% greater than the diameter of the polymerized lens body prior to washing. In one example, the silicone hydrogel contact lenses have been manufactured without contacting the polymerized silicone hydrogel contact lenses with one or more volatile organic solvents, especially during processing steps between separating the lenses from mold assemblies and packaging the lenses. Such wettable silicone hydrogel contact lenses can be produced without requiring a surface treatment of a polymerized lens body to achieve the wettability, without including a hydrophilic polymer in the formulation used to make the contact lenses, or without using an organic diluent in the formulation to reduce phase separation of hydrophobic and hydrophilic components of the formulation.
In accordance with the present disclosure, methods of manufacturing silicone hydrogel contact lenses are provided. The methods comprise a step of forming a lens body or lens bodies. The lens body is the reaction product of a polymerizable composition that comprises at least one siloxane monomer, at least one hydrophilic monomer, at least one hydrophobic monomer, and at least one cross-linking agent. The at least one siloxane monomer, at least one hydrophilic monomer, at least one hydrophobic monomer, and at least one cross-linking agent are present in the polymerizable composition in proportions such that, when polymerized to form a polymeric lens body, the resulting polymeric lens body, after hydration, has a diameter that is at least 24% greater than the diameter of the polymerized lens body prior to washing and hydration.
The lens body can be washed with an aqueous liquid free of a volatile organic solvent to remove dust or debris from the lens body, to remove extractable material from the lens body, and to hydrate the lens body. Thus, instead of using an alcohol-based extraction process, the present methods can employ an entirely aqueous extraction process. The methods can comprise a single washing step or can comprise more than one washing step. The washing can occur by immersing the lens body in a volume of aqueous washing liquid and allowing the lens to soak for a period of time. The lens body can be immersed one or more times for certain intervals. The aqueous liquid can be at room temperature (e.g., 20-25 degrees C.) or can be at a temperature between 20 degrees and 100 degrees. The immersion can be conducted by placing the lens body in a carrier or tray and immersing the carrier in a tank, or the immersion can be conducted in a contact lens package containing the washing liquid. At the time the lens body is first immersed, the lens body can be attached to one or more mold sections, or can be fully detached from the mold section(s) used to form the lens body. The washing liquid can also be manipulated to increase the rate of removal of the extractable material from the lens body, such as by delivering ultrasonic energy to the washing liquid containing the lens body. In some methods, the washing is performed by directing a flow of washing liquid over the lens body such that the extractable material is flushed from the lens body.
Alternatively, the lens body can be washed in a volatile organic solvent, or in an aqueous solution of a volatile organic solvent. In yet another example, the lens body need not be washed prior to hydration in packaging solution. For example, the lens body may not be contacted with any liquid during the manufacturing process prior to being contacted by packaging solution.
The washed lens body can then be packaged in a contact lens package, such as a blister pack or vial, containing an aqueous liquid, such as a contact lens packaging solution. The lens body in the contact lens package can be understood to be a hydrated lens body.
The sealed package containing the contact lens or lens body is then sterilized, such as by autoclaving and the like, as understood by persons of ordinary skill in the art.
It is observed that these new hydrated silicone hydrogel contact lenses so produced have a lens surface wettability characterized by an advancing contact angle less than 120 degrees and having a diameter (chord diameter) that is at least 24% larger than the diameter of the lens body prior to washing. Thus, prior to washing the lens body, the pre-washed lens body has a first diameter of Y, and after washing, the hydrated lens body has a second diameter that is at least 1.24×Y. In one example, the silicone hydrogel contact lenses so produced have a lens surface wettability characterized by an advancing contact angle less than 120 degrees and having a diameter (chord diameter) that is from 24% larger to 40% larger than the diameter of the lens body prior to washing. Thus, prior to washing the lens body, the pre-washed lens body has a first diameter of Y, and after washing, the hydrated lens body has a second diameter that is from 1.24×Y to 1.40×Y. In another example, silicone hydrogel contact lenses so produced have a lens surface wettability characterized by an advancing contact angle less than 120 degrees and having a diameter (chord diameter) that is at least 26% larger than the diameter of the lens body prior to washing. Thus, prior to washing the lens body, the pre-washed lens body has a first diameter of Y, and after washing, the hydrated lens body has a second diameter that is at least 1.26×Y. In yet another example, silicone hydrogel contact lenses so produced have a lens surface wettability characterized by an advancing contact angle less than 90 degrees and having a diameter (chord diameter) that is from 26% larger to 36% larger than the diameter of the lens body prior to washing. Thus, prior to washing the lens body, the pre-washed lens body has a first diameter of Y, and after washing, the hydrated lens body has a second diameter that is from 1.26×Y to 1.36×Y. This is unlike other silicone hydrogel contact lenses that are washed with organic solvents, such as alcohol, where the first diameter is Y, and the second diameter after washing is still Y, or is about Y, or is less than 1.20×Y. This is also unlike other silicone hydrogel contact lenses that swell when washed with organic solvents and return to their original dimensions or near their original dimensions when rinsed and hydrated in water. For example such lenses can have a diameter of Y before being washed in an organic solvent, can have a diameter of 1.5×Y when washed in an organic solvent, and, when subsequently rinsed and hydrated in water or packaging solution, return to having a diameter of Y or a diameter near Y, such as a diameter of 1.15×Y.
Unlike other methods using organic solvents, the present methods can include a step of forming contact lens mold inserts and contact lens molds that have diameters that are at least 24% smaller than the target size of the present silicone hydrogel contact lenses. In comparison, methods which employ organic solvents often include steps of designing inserts and contact lens molds that have diameters that are about equal to the target size of the organic solvent extracted and then hydrated silicone hydrogel contact lenses.
One example of a method of the present disclosure is a method of manufacturing silicone hydrogel contact lenses, comprising: forming a lens body that is the reaction product of a polymerizable composition that comprises at least one siloxane monomer, at least one hydrophilic monomer, at least one hydrophobic monomer, and at least one cross-linking agent; washing the lens body to remove extractable material from the lens body; packaging the washed lens body in a contact lens package containing an aqueous liquid resulting in a hydrated lens body; and sterilizing the contact lens package containing the packaged hydrated lens body; wherein the hydrated lens body has a lens surface wettability characterized by an advancing contact angle less than 120 degrees and has a diameter that is at least 24% larger than the diameter of the lens body prior to washing.
One example of a method of the present disclosure is a method of manufacturing silicone hydrogel contact lenses, comprising: forming a lens body that is the reaction product of a polymerizable composition that comprises at least one siloxane monomer, at least one hydrophilic monomer, at least one hydrophobic monomer, and at least one cross-linking agent; washing the lens body to remove extractable material from the lens body; packaging the washed lens body in a contact lens package containing an aqueous liquid resulting in a hydrated lens body; and sterilizing the contact lens package containing the packaged hydrated lens body; wherein the hydrated lens body has a lens surface wettability characterized by an advancing contact angle less than 90 degrees and has a diameter that is at least 26% larger than the diameter of the lens body prior to washing.
Another example of a method of the present disclosure is a method of manufacturing silicone hydrogel contact lenses, comprising: forming a lens body that is the reaction product of a polymerizable composition that comprises at least one siloxane monomer, at least one hydrophilic monomer, at least one hydrophobic monomer, and at least one cross-linking agent; washing the lens body with an aqueous liquid free of volatile organic solvent to remove extractable material from the lens body; packaging the washed lens body in a contact lens package containing an aqueous liquid resulting in a hydrated lens body; and sterilizing the contact lens package containing the packaged hydrated lens body; wherein the hydrated lens body has a lens surface wettability characterized by an advancing contact angle less than 120 degrees and has a diameter that is at least 24% larger than the diameter of the lens body prior to washing.
Yet another example of a method of the present disclosure is a method of manufacturing silicone hydrogel contact lenses, comprising: forming a lens body that is the reaction product of a polymerizable composition that comprises at least one siloxane monomer, at least one hydrophilic monomer, at least one hydrophobic monomer, and at least one cross-linking agent; washing the lens body with an aqueous liquid free of volatile organic solvent to remove extractable material from the lens body; packaging the washed lens body in a contact lens package containing an aqueous liquid resulting in a hydrated lens body; and sterilizing the contact lens package containing the packaged hydrated lens body; wherein the hydrated lens body has a lens surface wettability characterized by an advancing contact angle less than 90 degrees and has a diameter that is at least 26% larger than the diameter of the lens body prior to washing.
In one example of the present methods, the forming step can comprise cast molding the polymerizable composition in a non-polar resin contact lens mold assembly, such as a contact lens mold assembly made of polypropylene resin. One example of such a method is a method of manufacturing silicone hydrogel contact lenses, comprising: forming a lens body that is the reaction product of a polymerizable composition that comprises at least one siloxane monomer, at least one hydrophilic monomer, at least one hydrophobic monomer, and at least one cross-linking agent; cast molding the polymerizable composition in a non-polar resin contact lens mold assembly; washing the lens body to remove extractable material from the lens body; packaging the washed lens body in a contact lens package containing an aqueous liquid resulting in a hydrated lens body; and sterilizing the contact lens package containing the packaged hydrated lens body; wherein the hydrated lens body has a lens surface wettability characterized by an advancing contact angle less than 120 degrees and has a diameter that is at least 24% larger than the diameter of the lens body prior to washing. Another example of such a method is a method of manufacturing silicone hydrogel contact lenses, comprising: forming a lens body that is the reaction product of a polymerizable composition that comprises at least one siloxane monomer, at least one hydrophilic monomer, at least one hydrophobic monomer, and at least one cross-linking agent; cast molding the polymerizable composition in a non-polar resin contact lens mold assembly; washing the lens body with an aqueous liquid free of volatile organic solvent to remove extractable material from the lens body; packaging the washed lens body in a contact lens package containing an aqueous liquid resulting in a hydrated lens body; and sterilizing the contact lens package containing the packaged hydrated lens body; wherein the hydrated lens body has a lens surface wettability characterized by an advancing contact angle less than 120 degrees and has a diameter that is at least 24% larger than the diameter of the lens body prior to washing.
Each contact lens mold assembly comprises a first mold section and a second mold section. The first and second mold section are coupled together to provide a contact lens shaped cavity between the first and second mold section. The first mold section has a concave optical surface, which forms the anterior surface of the silicone hydrogel contact lens body. The first mold section may thus be understood to be a front surface mold section. The second mold section has a convex optical surface, which forms the posterior surface of the silicone hydrogel contact lens body. The second mold section may thus be understood to be a rear surface mold section.
The contact lens body can be formed in the contact lens mold assembly by polymerizing the contact lens formulation or polymerizable composition to form the silicone hydrogel contact lens body. The polymerization can occur by exposing the contact lens mold assembly to thermal radiation, ultraviolet radiation, visible light, and the like. As described herein, the polymerized contact lens bodies can be obtained by polymerizing a polymerizable composition in a contact lens mold assembly using thermal radiation, or ultraviolet radiation, or both. Typically, if thermal radiation is used, the polymerizable composition will include a thermal initiator. If ultraviolet radiation is used, the polymerizable composition will include an ultraviolet initiator. The curing times can vary depending on the silicone hydrogel contact lens being produced and frequently range from 20 minutes to 4 hours. In some methods, the curing can be achieved by providing a curing profile where a certain temperature or certain light intensity is provided for a certain amount of time before changing to another temperature or intensity for another amount of time.
The present methods can also comprise a step of demolding the contact lens mold assembly to produce a first mold section and a second mold section separated from the first mold section. The polymerized lens body remains attached to the first or second mold section. The polymerized lens body is then separated from the mold section to which it is attached to produce a delensed lens body. In some examples, the delensed lens body is separated from the mold section to which it is attached by contacting the polymerized lens body with an aqueous liquid free of volatile organic solvent or by mechanically removing the polymerized lens body without contacting the lens body with any liquid. One example of such a method is a method of manufacturing silicone hydrogel contact lenses, comprising: forming a lens body that is the reaction product of a polymerizable composition that comprises at least one siloxane monomer, at least one hydrophilic monomer, at least one hydrophobic monomer, and at least one cross-linking agent; cast molding the polymerizable composition in a contact lens mold assembly; separating the lens body from the mold assembly by mechanically removing the polymerized lens body without contact the lens body with any liquid; washing the lens body to remove extractable material from the lens body; packaging the washed lens body in a contact lens package containing an aqueous liquid resulting in a hydrated lens body; and sterilizing the contact lens package containing the packaged hydrated lens body; wherein the hydrated lens body has a lens surface wettability characterized by an advancing contact angle less than 120 degrees and has a diameter that is at least 24% larger than the diameter of the lens body prior to washing. Another example of such a method is a method of manufacturing silicone hydrogel contact lenses, comprising: forming a lens body that is the reaction product of a polymerizable composition that comprises at least one siloxane monomer, at least one hydrophilic monomer, at least one hydrophobic monomer, and at least one cross-linking agent; cast molding the polymerizable composition in a non-polar resin contact lens mold assembly; separating the lens body from the mold assembly by mechanically removing the polymerized lens body without contact the lens body with any liquid; washing the lens body to remove extractable material from the lens body; packaging the washed lens body in a contact lens package containing an aqueous liquid resulting in a hydrated lens body; and sterilizing the contact lens package containing the packaged hydrated lens body; wherein the hydrated lens body has a lens surface wettability characterized by an advancing contact angle less than 120 degrees and has a diameter that is at least 24% larger than the diameter of the lens body prior to washing.
As can be appreciated from the present disclosure, and unlike other silicone hydrogel contact lenses, in one example, the present methods result in silicone hydrogel contact lenses that have wettable lens surfaces without contacting the lens body with any volatile organic solvent after the lens body is formed and prior to sterilizing the lens body in the contact lens package. One example of such a method is a method of manufacturing silicone hydrogel contact lenses, comprising: forming a lens body that is the reaction product of a polymerizable composition that comprises at least one siloxane monomer, at least one hydrophilic monomer, at least one hydrophobic monomer, and at least one cross-linking agent; cast molding the polymerizable composition in a non-polar resin contact lens mold assembly; separating the lens body from the mold assembly by mechanically removing the polymerized lens body without contact the lens body with any liquid; washing the lens body with an aqueous liquid free of volatile organic solvent to remove extractable material from the lens body; packaging the washed lens body in a contact lens package containing an aqueous liquid resulting in a hydrated lens body; and sterilizing the contact lens package containing the packaged hydrated lens body; wherein the hydrated lens body has a lens surface wettability characterized by an advancing contact angle less than 120 degrees and has a diameter that is at least 24% larger than the diameter of the lens body prior to washing. Another example of such a method is a method of manufacturing silicone hydrogel contact lenses, comprising: forming a lens body that is the reaction product of a polymerizable composition that comprises at least one siloxane monomer, at least one hydrophilic monomer, at least one hydrophobic monomer, and at least one cross-linking agent; cast molding the polymerizable composition in a non-polar resin contact lens mold assembly; separating the lens body from the mold assembly by contacting the polymerized lens body with an aqueous liquid free of volatile organic solvent; washing the lens body with an aqueous liquid free of volatile organic solvent to remove extractable material from the lens body; packaging the washed lens body in a contact lens package containing an aqueous liquid resulting in a hydrated lens body; and sterilizing the contact lens package containing the packaged hydrated lens body; wherein the hydrated lens body has a lens surface wettability characterized by an advancing contact angle less than 120 degrees and has a diameter that is at least 24% larger than the diameter of the lens body prior to washing.
The silicone hydrogel contact lenses produced in accordance with the present methods, when fully hydrated, can have an oxygen permeability of at least 55 barrers, or an equilibrium water content from about 30% wt/wt to about 70% wt/wt, or a tensile modulus from about 0.2 MPa to about 0.9 MPa, or any combination thereof. In some examples, the silicone hydrogel contact lenses have an oxygen permeability of at least 55 barrers, and an equilibrium water content from about 30% wt/wt to about 70% wt/wt, and a tensile modulus from about 0.2 MPa to about 0.9 MPa. One example of such a method is a method of manufacturing silicone hydrogel contact lenses, comprising: forming a lens body that is the reaction product of a polymerizable composition that comprises at least one siloxane monomer, at least one hydrophilic monomer, at least one hydrophobic monomer, and at least one cross-linking agent; cast molding the polymerizable composition in a non-polar resin contact lens mold assembly; separating the lens body from the mold assembly; washing the lens body to remove extractable material from the lens body; packaging the washed lens body in a contact lens package containing an aqueous liquid resulting in a hydrated lens body; and sterilizing the contact lens package containing the packaged hydrated lens body; wherein the hydrated lens body has a lens surface wettability characterized by an advancing contact angle less than 120 degrees; has a diameter that is at least 24% larger than the diameter of the lens body prior to washing; and has an oxygen permeability of at least 55 barrers, or an equilibrium water content from about 30% wt/wt to about 70% wt/wt, or a tensile modulus from about 0.2 MPa to about 0.9 MPa, or any combination thereof. Another example of such a method is a method of manufacturing silicone hydrogel contact lenses, comprising: forming a lens body that is the reaction product of a polymerizable composition that comprises at least one siloxane monomer, at least one hydrophilic monomer, at least one hydrophobic monomer, and at least one cross-linking agent; cast molding the polymerizable composition in a non-polar resin contact lens mold assembly; separating the lens body from the mold assembly; washing the lens body to remove extractable material from the lens body; packaging the washed lens body in a contact lens package containing an aqueous liquid resulting in a hydrated lens body; and sterilizing the contact lens package containing the packaged hydrated lens body; wherein the hydrated lens body has a lens surface wettability characterized by an advancing contact angle less than 120 degrees; has a diameter that is at least 24% larger than the diameter of the lens body prior to washing; has an oxygen permeability of at least 55 barrers, an equilibrium water content from about 30% wt/wt to about 70% wt/wt, and a tensile modulus from about 0.2 MPa to about 0.9 MPa.
As stated herein, the polymerizable composition comprises at least one siloxane monomer, at least one hydrophilic monomer, at least one hydrophobic monomer, and at least one cross-linking agent. For example, polymerizable compositions may comprise a first siloxane monomer, a second siloxane monomer, one or more hydrophilic monomers, one or more hydrophobic monomers, and one or more cross-linking agents. Additional details and various examples of the ingredients of the polymerizable compositions and the amounts and relationship among the ingredients are described herein. As one example, many of the present polymerizable compositions are free of a diluent, or free of a hydrophilic polymer, or both. As another example, many of the present polymerizable compositions are free of N,N-dimethylacrylamide (DMA).
One example of the polymerizable composition of the present disclosure comprises a first siloxane monomer, a second siloxane monomer, at least one hydrophilic monomer, at least one hydrophobic monomer, and at least one cross-linking agent, wherein the polymerizable composition is free of a diluent. Another example of the polymerizable composition of the present disclosure comprises a first siloxane monomer, a second siloxane monomer, at least one hydrophilic monomer, at least one hydrophobic monomer, and at least one cross-linking agent, wherein the polymerizable composition is free of a pre-formed hydrophilic polymer. Another example of the polymerizable composition of the present disclosure comprises a first siloxane monomer, a second siloxane monomer, at least one hydrophilic monomer, at least one hydrophobic monomer, and at least one cross-linking agent, wherein the polymerizable composition is free of N,N-dimethylacrylamide (DMA). Yet another example of the polymerizable composition of the present disclosure comprises a first siloxane monomer, a second siloxane monomer, at least one hydrophilic monomer, at least one hydrophobic monomer, and at least one cross-linking agent, wherein the polymerizable composition is free of a diluent, is free of a pre-formed hydrophilic polymer, and is free of N,N-dimethylacrylamide (DMA). In some detail, the siloxane monomer(s) in the present polymerizable compositions may be monofunctional or multifunctional, such as bifunctional or trifunctional. A monofunctional siloxane monomer has a single polymerizable functional group, such as an acrylic group, methacrylic group, or vinyl group. A multifunctional siloxane monomer has two or more such polymerizable functional groups. The polymerizable functional group(s) can be present on a side chain of the siloxane monomer, on the main chain or backbone of the siloxane monomer, or both on side chains and main chain for multifunctional siloxane monomers. In some of the polymerizable compositions described herein, the first siloxane monomer is a monofunctional siloxane monomer, and the second siloxane monomer is a multifunctional siloxane monomer. In further examples, the number average molecular weight of the first siloxane monomer is less than 2,000 daltons, or less than 1,000 daltons, or from 400 to 700 daltons. In examples containing a second multifunctional siloxane monomer, the second siloxane monomer has a number average molecular weight greater than 3,000 daltons. Some second siloxane monomers have a number average molecular weight greater than 5,000 daltons, or greater than 9,000 daltons. Frequently, the second multifunctional siloxane monomers have a number average molecular weight less than 20,000 daltons. The first siloxane monomer can be present in an amount from 20 to 45 unit parts, or from 25 to 40 unit parts or from 27 to 35 unit parts of the polymerizable composition. Additional details of the siloxane monomer(s) useful in any of the present methods are described herein.
One example of the polymerizable composition of the present disclosure comprises a first siloxane monomer having a number average molecular weight of from 400 to 700 daltons, a second siloxane monomer, at least one hydrophilic monomer, and at least one cross-linking agent. Another example of the polymerizable composition of the present disclosure comprises a first siloxane monomer, a second siloxane monomer having a molecular weight greater than 5,000 daltons, at least one hydrophilic monomer, and at least one cross-linking agent. Another example of the polymerizable composition of the present disclosure comprises a first siloxane monomer having a number average molecular weight of from 400 to 700 daltons, a second siloxane monomer having a number average molecular weight greater than 5,000 daltons, at least one hydrophilic monomer, and at least one cross-linking agent. One example of the polymerizable composition of the present disclosure comprises a first siloxane monomer having a number average molecular weight of from 400 to 700 daltons, a second siloxane monomer which is a dual-end methacrylate end-capped polydimethylsiloxane having a number average molecular weight greater than 5,000 daltons, at least one hydrophilic monomer, and at least one cross-linking agent.
In some of the present methods, particular combinations of ingredients are provided. For example, the present silicone hydrogel contact lenses with wettable lens surfaces can be manufactured by including at least one hydrophilic vinyl-containing monomer, or at least one hydrophilic amide monomer having one N-vinyl group, or at least one hydrophilic vinyl-containing monomer and at least one vinyl-containing cross-linking agent in the polymerizable composition, or at least one hydrophilic amide monomer having one N-vinyl group and at least one vinyl-containing cross-linking agent, or at least one hydrophilic amide monomer having one N-vinyl group and at least one methacrylate-type cross-linking agent. In another example, the present silicone hydrogel contact lenses with wettable lens surfaces can be manufactured by including at least one hydrophilic vinyl ether-containing monomer and at least one vinyl ether-containing cross-linking agent in the polymerizable composition. Such vinyl-containing monomers and vinyl-containing cross-linking agents are distinguished from methacrylate type monomers and methacrylate type cross-linking agents based on their differing reactivity ratios, among other things.
One example of the polymerizable composition of the present disclosure comprises a first siloxane monomer, a second siloxane monomer, at least one hydrophilic monomer, at least one hydrophobic vinyl-containing monomer, and at least one cross-linking agent. Another example of the polymerizable composition of the present disclosure comprises a first siloxane monomer, a second siloxane monomer, at least one hydrophilic vinyl-containing monomer, at least one hydrophobic monomer, and at least one vinyl-containing cross-linking agent. Another example of the polymerizable composition of the present disclosure comprises a first siloxane monomer, a second siloxane monomer, at least one hydrophilic vinyl-containing monomer, at least one hydrophobic monomer, at least one vinyl-containing cross-linking agent, and at least one methacrylate-containing cross-linking agent. Another example of the polymerizable composition of the present disclosure comprises a first siloxane monomer, a second siloxane monomer, at least one hydrophilic amide monomer having one N-vinyl group, at least one hydrophobic monomer, and at least one cross-linking agent. Another example of the polymerizable composition of the present disclosure comprises a first siloxane monomer, a second siloxane monomer, at least one hydrophilic amide monomer having one N-vinyl group, at least one hydrophobic monomer, and at least one vinyl-containing cross-linking agent. Another example of the polymerizable composition of the present disclosure comprises a first siloxane monomer, a second siloxane monomer, at least one hydrophilic amide monomer having one N-vinyl group, at least one hydrophobic monomer, and at least one cross-linking agent, wherein the polymerizable composition is free of a diluent. Another example of the polymerizable composition of the present disclosure comprises a first siloxane monomer, a second siloxane monomer, at least one hydrophilic amide monomer having one N-vinyl group, at least one hydrophobic monomer, and at least one cross-linking agent, wherein the polymerizable composition is free of a pre-formed hydrophilic polymer. Another example of the polymerizable composition of the present disclosure comprises a first siloxane monomer, a second siloxane monomer, at least one hydrophilic amide monomer having one N-vinyl group, at least one hydrophobic monomer, and at least one cross-linking agent, wherein the polymerizable composition is free of N,N-dimethylacrylamide (DMA). Yet another example of the polymerizable composition of the present disclosure comprises a first siloxane monomer, a second siloxane monomer, at least one hydrophilic amide monomer having one N-vinyl group, at least one hydrophobic monomer, and at least one cross-linking agent, wherein the polymerizable composition is free of a diluent, is free of a pre-formed hydrophilic polymer, and is free of N,N-dimethylacrylamide (DMA).
In any of the present methods, a batch of sterilized silicone hydrogel contact lenses has an average diameter (i.e., average of each chord diameter for each silicone hydrogel contact lens or representative population of silicone hydrogel contact lenses) that is at least 24% greater than the average diameter of the same batch of silicone hydrogel contact lens bodies prior to the washing step of the present methods. Thus, the present silicone hydrogel contact lenses are produced at a certain size in a dry state, and after washing, the contact lenses have swollen to their final size, which is at least 24% greater than their size in the dry state. This is in contrast to silicone hydrogel contact lenses which swell when exposed to a volatile organic solvent and then return to their original size, or near their original size, when hydrated, including lenses that are produced with volatile organic solvent extraction steps. For example, in such silicone hydrogel contact lenses, the dry lenses are produced at a size that is substantially equal, and less than 24% different, than their final hydrated size. Thus, when such dry lenses are contacted with a volatile organic solvent, such as ethanol and the like, the individual contact lenses may swell to approximately twice their dry size, and then by removing the alcohol with aqueous solutions to produce a hydrated contact lens, the hydrated contact lens size has returned to its original size, within specified target dimensions.
In some examples, the silicone hydrogel contact lens is a cast molded silicone hydrogel contact lens without a plasma surface treatment or a polymeric internal wetting agent that is provided by including a hydrophilic polymer in a polymerizable composition used to form the silicone hydrogel contact lens. A cast molded contact lens is understood to be a contact lens polymerized from a polymerizable composition in a contact lens mold assembly comprising a first mold section and second mold section coupled together, as described herein.
The present silicone hydrogel contact lenses comprises a polymeric component and a liquid component. The polymeric component comprises units of at least one siloxane, units of at least one hydrophilic monomer, units of at least one hydrophobic monomer, and units of at least one cross-linking agent. In one example, the polymeric component comprises units of at least one siloxane having one or more functional acrylic groups, and units of one or more hydrophilic monomers having one or more functional non-acrylic vinyl groups.
Additional details of the present silicone hydrogel contact lenses, polymerizable compositions, and methods of manufacturing will now be described.
In one example, the present silicone hydrogel contact lenses are produced from polymerizable compositions comprising a first siloxane monomer represented by formula (1):




wherein m of formula (1) represents one integer from 3 to 10, n of formula (1) represents one integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 carbon atoms, and each R2 of formula (1) is independently either a hydrogen atom or a methyl group. One example of the polymerizable composition of the present disclosure comprises a first siloxane monomer represented by formula (1):





wherein m of formula (1) represents one integer from 3 to 10, n of formula (1) represents one integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 carbon atoms, and each R2 of formula (1) is independently either a hydrogen atom or a methyl group; a second siloxane monomer, at least one hydrophilic vinyl-containing monomer, at least one hydrophobic monomer, and at least one cross-linking agent. Another example of the polymerizable composition of the present disclosure comprises a first siloxane monomer represented by formula (1):





wherein m of formula (1) represents one integer from 3 to 10, n of formula (1) represents one integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 carbon atoms, and each R2 of formula (1) is independently either a hydrogen atom or a methyl group; a second siloxane monomer having a number average molecular weight greater than 5,000 daltons, at least one hydrophilic vinyl-containing monomer, at least one hydrophobic, and at least one cross-linking agent. Another example of the polymerizable composition of the present disclosure comprises a first siloxane monomer represented by formula (1):





wherein m of formula (1) represents one integer from 3 to 10, n of formula (1) represents one integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 carbon atoms, and each R2 of formula (1) is independently either a hydrogen atom or a methyl group; a second siloxane monomer having a number average molecular weight of at last 5,000 daltons, at least one hydrophilic amide monomer having one N-vinyl group, at least one hydrophobic monomer, and at least one cross-linking agent. Yet another example of the polymerizable composition of the present disclosure comprises a first siloxane monomer represented by formula (1):





wherein m of formula (1) represents one integer from 3 to 10, n of formula (1) represents one integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 carbon atoms, and each R2 of formula (1) is independently either a hydrogen atom or a methyl group, the first siloxane monomer having a number average molecular weight of from 400 daltons to 700 daltons; a second siloxane monomer having a number average molecular weight of at last 5,000 daltons, at least one hydrophilic amide monomer having one N-vinyl group, at least one hydrophobic monomer, and at least one cross-linking agent. In any of the present methods and polymerizable compositions, the polymerizable composition can comprise at least two siloxane monomers, and the second siloxane monomer can have a number average molecular weight of at least 3,000 daltons. In some methods, compositions, and contact lenses, the second siloxane monomer is a dual-end methacrylate end-capped polydimethylsiloxane having a number average molecular weight of at least 4,000 daltons. One example of the polymerizable composition of the present disclosure comprises a first siloxane monomer represented by formula (1):





wherein m of formula (1) represents one integer from 3 to 10, n of formula (1) represents one integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 carbon atoms, and each R2 of formula (1) is independently either a hydrogen atom or a methyl group; a second siloxane monomer which is a dual-end methacrylate end-capped polydimethylsiloxane having a number average molecular weight of at last 5,000 daltons, at least one hydrophilic amide monomer having one N-vinyl group, at least one hydrophobic monomer, and at least one cross-linking agent.

In some examples of the present methods, polymerizable compositions, and silicone hydrogel contact lenses, the second siloxane monomer is represented by formula (2):




wherein R1 is selected from either hydrogen or a methyl group; R2 is selected from either of hydrogen or a C1-4 hydrocarbon group; m represents an integer of from 0 to 10; n represents an integer of from 4 to 100; a and b represent integers of 1 or more; a+b is equal to 20-500; b/(a+b) is equal to 0.01-0.22; and the configuration of siloxane units includes a random configuration. One example of the polymerizable composition of the present disclosure comprises a first siloxane monomer; a second siloxane monomer represented by formula (2):





wherein R1 is selected from either hydrogen or a methyl group; R2 is selected from either of hydrogen or a C1-4 hydrocarbon group; m represents an integer of from 0 to 10; n represents an integer of from 4 to 100; a and b represent integers of 1 or more; a+b is equal to 20-500; b/(a+b) is equal to 0.01-0.22; and the configuration of siloxane units includes a random configuration; at least one hydrophilic vinyl-containing monomer, at least one hydrophobic monomer, and at least one cross-linking agent. Another example of the polymerizable composition of the present disclosure comprises a first siloxane monomer; a second siloxane monomer represented by formula (2):





wherein R1 is selected from either hydrogen or a methyl group; R2 is selected from either of hydrogen or a C1-4 hydrocarbon group; m represents an integer of from 0 to 10; n represents an integer of from 4 to 100; a and b represent integers of 1 or more; a+b is equal to 20-500; b/(a+b) is equal to 0.01-0.22; and the configuration of siloxane units includes a random configuration; at least one hydrophilic amide monomer having one N-vinyl group, at least one hydrophobic monomer, and at least one cross-linking agent. Another example of the polymerizable composition of the present disclosure comprises a first siloxane monomer represented by formula (1):





wherein m of formula (1) represents one integer from 3 to 10, n of formula (1) represents one integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 carbon atoms, and each R2 of formula (1) is independently either a hydrogen atom or a methyl group; a second siloxane monomer represented by formula (2):





wherein R1 is selected from either hydrogen or a methyl group; R2 is selected from either of hydrogen or a C1-4 hydrocarbon group; m represents an integer of from 0 to 10; n represents an integer of from 4 to 100; a and b represent integers of 1 or more; a+b is equal to 20-500; b/(a+b) is equal to 0.01-0.22; and the configuration of siloxane units includes a random configuration; at least one hydrophilic amide monomer having one N-vinyl group, at least one hydrophobic monomer, and at least one cross-linking agent. Yet another example of the polymerizable composition of the present disclosure comprises a first siloxane monomer represented by formula (1):





wherein m of formula (1) represents one integer from 3 to 10, n of formula (1) represents one integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 carbon atoms, and each R2 of formula (1) is independently either a hydrogen atom or a methyl group, the first siloxane monomer have a number average molecular weight of from 400 daltons to 700 daltons; a second siloxane monomer represented by formula (2):





wherein R1 is selected from either hydrogen or a methyl group; R2 is selected from either of hydrogen or a C1-4 hydrocarbon group; m represents an integer of from 0 to 10; n represents an integer of from 4 to 100; a and b represent integers of 1 or more; a+b is equal to 20-500; b/(a+b) is equal to 0.01-0.22; and the configuration of siloxane units includes a random configuration, the second siloxane monomer having a number average molecular weight greater than 5,000 daltons; at least one hydrophilic amide monomer having one N-vinyl group, at least one hydrophobic monomer, and at least one cross-linking agent. The first siloxane monomer and the second siloxane monomer can be present in the polymerizable composition at a ratio of at least 2:1 based on unit parts by weight. In other words, for every unit part by weight of the second siloxane monomer present in the polymerizable composition, 2 or more unit parts of the first siloxane monomer are also present in the polymerizable composition. In accordance with the present disclosure, the first siloxane monomer and the second siloxane monomer can be present in the polymerizable composition in a ratio from about 2:1 to about 10:1 based on unit parts by weight of the first siloxane monomer to the second siloxane monomer. In another example, the first siloxane monomer and the second siloxane monomer can be present in the polymerizable composition in a ratio from about 3:1 to about 6:1 based on unit parts by weight. In yet another example, the first siloxane monomer and the second siloxane monomer can be present in the polymerizable composition in a ratio of about 4:1 based on unit parts by weight. One example of the polymerizable composition of the present disclosure comprises a first siloxane monomer represented by formula (1):





wherein m of formula (1) represents one integer from 3 to 10, n of formula (1) represents one integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 carbon atoms, and each R2 of formula (1) is independently either a hydrogen atom or a methyl group; a second siloxane monomer represented by formula (2):





wherein R1 is selected from either hydrogen or a methyl group; R2 is selected from either of hydrogen or a C1-4 hydrocarbon group; m represents an integer of from 0 to 10; n represents an integer of from 4 to 100; a and b represent integers of 1 or more; a+b is equal to 20-500; b/(a+b) is equal to 0.01-0.22; and the configuration of siloxane units includes a random configuration; at least one hydrophilic monomer, at least one hydrophobic monomer, and at least one cross-linking agent, wherein the first siloxane monomer and the second siloxane monomer are present in the polymerizable composition in a ratio from about 2:1 to about 10:1 based on unit parts by weight of the first siloxane monomer to the second siloxane monomer. Yet another example of the polymerizable composition of the present disclosure comprises a first siloxane monomer represented by formula (1):





wherein m of formula (1) represents one integer from 3 to 10, n of formula (1) represents one integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 carbon atoms, and each R2 of formula (1) is independently either a hydrogen atom or a methyl group, the first siloxane monomer have a number average molecular weight of from 400 daltons to 700 daltons; a second siloxane monomer represented by formula (2):





wherein R1 is selected from either hydrogen or a methyl group; R2 is selected from either of hydrogen or a C1-4 hydrocarbon group; m represents an integer of from 0 to 10; n represents an integer of from 4 to 100; a and b represent integers of 1 or more; a+b is equal to 20-500; b/(a+b) is equal to 0.01-0.22; and the configuration of siloxane units includes a random configuration, the second siloxane monomer having a number average molecular weight greater than 5,000 daltons; at least one hydrophilic amide monomer having one N-vinyl group, at least one hydrophobic monomer, and at least one cross-linking agent, wherein the first siloxane monomer and the second siloxane monomer are present in the polymerizable composition in a ratio from about 2:1 to about 10:1 based on unit parts by weight of the first siloxane monomer to the second siloxane monomer. As used herein, ‘unit parts’ is understood to mean unit parts by weight. For example, to prepare a formulation described as comprising x unit parts of a first siloxane monomer and y unit parts of a second siloxane monomer, the composition can be prepared by combining x grams of the first siloxane with y grams of the second siloxane to obtain a total of x+y grams of polymerizable composition, or by combining x ounces of the first siloxane with y ounces of the second siloxane to obtain a total of x+y ounces of polymerizable composition, and so on. When the composition further comprises additional optional ingredients such as, for example, z unit parts of a cross-linking agent, z grams of the cross-linking agent are combined with x grams of the first siloxane monomer and y grams of the second siloxane to obtain a total of x+y+z grams of polymerizable composition, and so on. Typically, a formula for a polymerizable composition will be composed of ingredients in amounts totaling from about 90 to about 110 unit parts by weight. When amounts of components of the polymerizable composition are recited herein as being in unit parts, it is to be understood that the unit parts of these components are based on a formula providing a total weight of the composition ranging from about 90 to 110 unit parts. In one example, the unit parts by weight can be based on a formula providing a total weight of the composition ranging from about 95 to 105 unit parts by weight, or from about 98 to 102 unit parts by weight.

As discussed herein, the present contact lenses comprise, or consist of, hydrated lens bodies comprising a polymeric component and a liquid component. The polymeric component can comprise units of two or more siloxanes, and one or more non-silicon reactive ingredients. It can therefore be understood that the polymeric component can be the reaction product of a polymerizable composition comprising two or more siloxanes (the siloxane monomer component of the composition), and one or more non-silicon reactive ingredients. As used herein, a non-silicon reactive ingredient is understood to be an ingredient which has a polymerizable double bond as part of its molecular structure, but which does not have a silicon atom in its molecular structure. The ingredients of the polymerizable composition can be monomers, macromers, pre-polymers, polymers, or any combination thereof. Optionally, the ingredients of the polymerizable composition can further include at least one hydrophilic monomer, or at least one hydrophobic monomer, or at least one cross-linking agent. The at least one hydrophilic monomer, at least one hydrophobic monomer and at least one cross-linking agent are understood to be silicon-free reactive ingredients. As used herein, the at least one hydrophilic monomer can be understood to comprise a single hydrophilic monomer, or to comprise a hydrophilic monomer component composed of two or more hydrophilic monomers. Similarly, the at least one hydrophobic monomer can be understood to comprise a single hydrophobic monomer, or to comprise a hydrophobic monomer component composed of two or more hydrophobic monomers. The at least one cross-linking agent can be understood to comprise a single cross-linking agent, or to comprise a cross-linking agent component composed of two or more cross-linking agents. Additionally, the polymerizable composition can optionally include at least one initiator, or at least one organic diluent, or at least one surfactant, or at least one oxygen scavenger, or at least one tinting agent, or at least one UV absorber, or at least one chain transfer agent, or any combination thereof. The optional at least one initiator, at least one organic diluent, at least one surfactant, at least one oxygen scavenger, at least one tinting agent, at least one UV absorber, or at least one chain transfer agent are understood to be non-silicon ingredients, and can be either non-polymerizable ingredients or polymerizable ingredients (i.e., ingredients having a polymerizable functional group as part of their molecular structure).
In some examples of the present methods, polymerizable compositions, and silicone hydrogel contact lenses, the at least one cross-linking agent comprises (i) a vinyl-containing cross-linking agent, and (ii) an acrylate-containing cross-linking agent or a methacrylate-containing cross-linking agent. In other examples, the at least one cross-linking agent can consist of a vinyl-containing cross-linking agent.
In some examples of the present methods, polymerizable compositions, and silicone hydrogel contact lenses, the at least one hydrophilic monomer comprises a vinyl-containing monomer.
In any of the present methods, the amount of the extractable material removed from the lens body during the washing step is less than 15% (w/w) of the dry weight of the lens body, and the extractable material consists essentially of unreacted monomer, partially reacted monomer, or both. For example, non-reactive, removable ingredients, such as diluents and the like are not included in this amount. One method in accordance with the present disclosure is a method of manufacturing silicone hydrogel contact lenses, comprising: forming a lens body that is the reaction product of a polymerizable composition that comprises at least one siloxane monomer, at least one hydrophilic monomer, at least one hydrophobic monomer, and at least one cross-linking agent; washing the lens body to remove extractable material from the lens body; packaging the washed lens body in a contact lens package containing an aqueous liquid resulting in a hydrated lens body; and sterilizing the contact lens package containing the packaged hydrated lens body; wherein the hydrated lens body has a lens surface wettability characterized by an advancing contact angle less than 120 degrees and has a diameter that is at least 24% larger than the diameter of the lens body prior to washing, and wherein an amount of the extractable material removed from the lens body during the washing step is less than 15% (w/w) of the dry weight of the lens body, the extractable material consists essentially of unreacted monomer, partially reacted monomer, or both.
The combination of the polymeric component and the liquid component are present as a hydrated lens body, which is suitable for placement on an eye of a person. The hydrated lens body has a generally convex anterior surface and a generally concave posterior surface, and has an equilibrium water content (EWC) greater than 10% weight by weight (wt/wt). Thus, the present contact lenses can be understood to be soft contact lenses, which as used herein, refers to contact lenses that, when fully hydrated, can be folded upon themselves without breaking.
The present contact lenses can be either daily disposable contact lenses or non-daily disposable contact lenses.
In one example, the polymerizable composition of the present methods comprises a first siloxane monomer represented by formula (1):




wherein m of formula (1) represents one integer from 3 to 10, n of formula (1) represents one integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 carbon atoms, and each R2 of formula (1) is independently either a hydrogen atom or a methyl group. In other words, on a single molecule of the siloxane monomer represented by formula 1, the first R2 of formula (1), (the R2 which is closest to the R1 end group on the left side of the molecule), can be either a hydrogen atom or a methyl group, and the second R2 of formula (1) (the R2 which is part of the methacrylate end group on the right side of the molecule), can also be either a hydrogen atom or a methyl group, regardless of whether the first R2 of formula (1) is a hydrogen atom or a methyl group. The polymerizable composition also comprises a second siloxane monomer. The first siloxane monomer and the second siloxane monomer are present in the polymerizable composition at a ratio of at least 2:1 based on unit parts by weight. The second siloxane monomer has more than one polymerizable functional group (i.e., is a multifunctional siloxane monomer) and has a number average molecular weight of at least 3,000 daltons. If the second siloxane monomer has two polymerizable functional groups, such as two methacrylate groups, it is a bifunctional monomer. If the second siloxane monomer has three polymerizable functional groups, it is a trifunctional monomer. The polymerizable composition also comprises at least one hydrophilic monomer, or at least one hydrophobic monomer, or at least one cross-linking agent, or any combination thereof.

The present disclosure also relates to a new silicone hydrogel contact lens or to new silicone hydrogel contact lenses. A silicone hydrogel contact lens in accordance with the present disclosure comprises a polymeric lens body. The polymeric lens body is the reaction product of a polymerizable composition or contact lens formulation. The polymerizable composition comprises at least one siloxane monomer, at least one hydrophilic monomer, at least one hydrophobic monomer, and at least one cross-linking agent. The lens body of the silicone hydrogel contact lens was washed with an aqueous liquid free of volatile organic solvent to remove extractable material from the lens body, and is hydrated with an aqueous liquid. The hydrated lens body has a lens surface wettability characterized by an advancing contact angle less than 120 degrees, and the hydrated lens body has a diameter that is at least 24% larger than the diameter of the lens body prior to washing.
In some examples, the at least one cross-linking agent comprises a vinyl-containing cross-linking agent; and an acrylate-containing cross-linking agent or a methacrylate-containing cross-linking agent. In some examples, the at least one cross-linking agent comprises at least one vinyl-containing cross-linking agent present in the polymerizable composition in an amount from about 0.01 unit parts to about 2.0 unit parts by weight.
In any of the present silicone hydrogel contact lenses, or polymerizable compositions used to produce the present silicone hydrogel contact lens or lenses a first siloxane monomer represented by formula (1):




wherein m of formula (1) represents one integer from 3 to 10, n of formula (1) represents one integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 carbon atoms, and each R2 of formula (1) is independently either a hydrogen atom or a methyl group can be provided.

In any of the present silicone hydrogel contact lenses, the polymerizable composition comprises at least two siloxane monomers, and the second siloxane monomer is a siloxane monomer having a number average molecular weight of at least 3,000 daltons. In some silicone hydrogel contact lenses and polymerizable compositions, the second siloxane monomer is a dual-end methacrylate end-capped polydimethylsiloxane having a number average molecular weight of at least 4,000 daltons.
In some examples of the present silicone hydrogel contact lenses and polymerizable compositions, the second siloxane monomer is represented by formula (2):




wherein R1 of formula (2) is selected from either a hydrogen atom or a methyl group; R2 of formula (2) is selected from either of hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms; m of formula (2) represents an integer of from 0 to 10; n of formula (2) represents an integer of from 4 to 100; a and b represent integers of 1 or more; a+b is equal to 20-500; b/(a+b) is equal to 0.01-0.22; and the configuration of siloxane units includes a random configuration.

The first siloxane monomer and the second siloxane monomer can be present in the polymerizable composition at a ratio of at least 2:1 based on unit parts by weight. The polymerizable composition also comprises at least one hydrophilic monomer, or at least one hydrophobic monomer, or at least one cross-linking agent, or any combination thereof.
As used herein, a molecular weight is understood to refer to the number average molecular weight. The number average molecular weight is the ordinary arithmetic mean or average of the molecular weights of the individual molecules present in the sample of a monomer. As the individual molecules in a sample of monomer may vary slightly from one another in molar mass, some level of polydispersity may be present in the sample. As used herein, when the second siloxane monomer, or any other monomer, macromer, pre-polymer, or polymer, of the polymerizable composition is polydisperse, the term “molecular weight” refers to the number average molecular weight of the monomer or ingredient. As one example, a sample of the second siloxane monomer can have a number average molecular weight of about 15,000 daltons, but if the sample is polydisperse, the actual molecular weights of the individual monomers present in the sample may range from 12,000 daltons to 18,000 daltons.
The number average molecular weight can be the absolute number average molecular weight as determined by proton nuclear magnetic resonance (NMR) end group analysis, as understood by persons of ordinary skill in the art. Molecular weights may also be determined using gel permeation chromatography, as understood by persons of ordinary skill in the art, or may be provided by suppliers of the chemicals.
The molecular weight of the first siloxane monomer represented by formula (1) is less than 2,000 daltons. In one example, the molecular weight of the first siloxane monomer can be less than 1,000 daltons. In another example, the molecular weight of the first siloxane monomer can be from 400 to 700 daltons. Additional details of the first siloxane monomer can be understood from US20090299022, the entire content of which is hereby incorporated by reference. As can be appreciated from formula (1), the first siloxane monomer has a single methacrylic polymerizable end group.
In one example of the present contact lenses, the second siloxane monomer can have a number average molecular weight of at least 4,000 daltons, or at least 7,000 daltons, or at least 9,000 daltons, or at least 11,000 daltons. The number average molecular weight of the second siloxane monomer can be greater than 5,000 daltons, or from 5,000 daltons to 20,000 daltons. In another example, the number average molecular weight of the second siloxane monomer can be greater than 7,000 daltons, or from 7,000 daltons to 20,000 daltons. The number average molecular weight of the second siloxane monomer can be less than 20,000 daltons. Thus, in some contexts, the second siloxane monomer can be considered a macromer or prepolymer, but it will be referred to as a monomer herein since it forms a unit part of a polymer formed with the other reactive components of the polymerizable composition.
The polymerizable composition also comprises at least one hydrophilic monomer, or at least one hydrophobic monomer, or at least one cross-linking agent, or any combination thereof. As used herein, the preceding three types of chemicals are non-silicon chemicals (i.e., chemicals whose molecular structure does not include a silicon atom) and thus are different from the siloxane monomers present in the polymerizable compositions. The polymerizable compositions can be understood to comprise at least two siloxane monomers, and other non-silicon hydrophilic monomers, or non-silicon hydrophobic monomers, or non-silicon cross-linking agents, or any combination thereof, although, optionally, the polymerizable composition can further comprise at least a third siloxane monomer.
The first siloxane monomer, the second siloxane monomer and the optional at least one third siloxane monomer comprise the siloxane monomer component of the polymerizable composition. Each of the first siloxane monomer, or the second siloxane monomer, or the optional third siloxane monomer, or any combination thereof, can be a hydrophilic siloxane monomer, or a hydrophobic siloxane monomer, or can have both hydrophilic regions and hydrophobic regions, depending on the amount and location of any hydrophilic components, such as units of ethylene glycol, polyethylene glycol and the like, present in the molecular structure of the siloxane monomers. For example, the second siloxane monomer, or the optional at least one third siloxane monomer, or any combination thereof, can contain hydrophilic components within the main chain of the siloxane molecule, can contain hydrophilic components within one or more side chains of the siloxane molecule, or any combination thereof. For example, the siloxane monomer can have at least one unit of ethylene glycol adjacent to a polymerizable functional group in the main chain of the siloxane molecule. The at least one unit of ethylene glycol adjacent to a polymerizable functional group in the main chain of the siloxane molecule can be separated from the polymerizable functional group by a carbon chain 1-10 units in length (i.e., where the ethylene glycol unit is bonded to the first carbon in the chain, and the polymerizable functional group is bonded to the last carbon in the chain). The siloxane monomer can have at least one unit of ethylene glycol adjacent to polymerizable functional groups present on both ends of the main chain of the siloxane molecule. The siloxane monomer can have at least one unit of ethylene glycol present in at least one side chain of the siloxane molecule. The at least one unit of ethylene glycol present in at least one side chain of the siloxane molecule can be part of a side chain bonded to a silicon atom of the main chain of the siloxane molecule. The siloxane molecule can have both at least one unit of ethylene glycol adjacent to polymerizable functional groups present on both ends of the main chain of the siloxane molecule, and at least one unit of ethylene glycol present in at least one side chain of the siloxane molecule.
One example of the polymerizable composition of the present disclosure comprises a first siloxane monomer represented by formula (1):




wherein m of formula (1) represents one integer from 3 to 10, n of formula (1) represents one integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 carbon atoms, and each R2 of formula (1) is independently either a hydrogen atom or a methyl group; a second siloxane monomer; at least one hydrophilic monomer, at least one hydrophobic monomer, and at least one cross-linking agent, wherein the polymerizable composition is free of a siloxane represented by formula (4):





Another example of the polymerizable composition of the present disclosure comprises a first siloxane monomer represented by formula (1):




wherein m of formula (1) represents one integer from 3 to 10, n of formula (1) represents one integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 carbon atoms, and each R2 of formula (1) is independently either a hydrogen atom or a methyl group; a second siloxane monomer at least one unit of ethylene glycol adjacent to a polymerizable functional group in the main chain of the second siloxane molecule and having a number average molecular weight of from 5,000 daltons to 20,000 daltons; at least one hydrophilic monomer, at least one hydrophobic monomer, and at least one cross-linking agent.

The hydrophilicity or hydrophobicity of a monomer can be determined using conventional techniques, such as, for example, based on the monomer's aqueous solubility. For purposes of the present disclosure, a hydrophilic monomer is a monomer that is visibly soluble in an aqueous solution at room temperature (e.g. about 20-25 degrees C.). For example, a hydrophilic monomer can be understood to be any monomer for which 50 grams of the monomer are visibly fully soluble in 1 liter of water at 20° C. (i.e., ≧5% soluble in water) as determined using a standard shake flask method as known to persons of ordinary skill in the art. A hydrophobic monomer, as used herein, is a monomer that is visibly insoluble in an aqueous solution at room temperature, such that separate, visually identifiable phases are present in the aqueous solution, or such that the aqueous solution appears cloudy and separates into two distinct phases over time after sitting at room temperature. For example, a hydrophobic monomer can be understood to be any monomer for which 50 grams of the monomer are not visibly fully soluble in 1 liter of water at 20° C.
In one example of the present contact lenses, the first siloxane monomer can be represented by formula (1) where m of formula (1) is 4, n of formula (1) is 1, R1 of formula (1) is a butyl group, and each R2 of formula (1) is independently either a hydrogen atom or a methyl group. One example of such a first siloxane monomer is identified herein as Si1 in the Examples.
One example of the polymerizable composition of the present disclosure comprises a first siloxane monomer represented by formula (1):




wherein m of formula (1) is 4, n of formula (1) is 1, R1 of formula (1) is a butyl group, and each R2 of formula (1) is independently either a hydrogen atom or a methyl group; a second siloxane monomer having a number average molecular weight greater than 5,000 daltons; at least one hydrophilic monomer, at least one hydrophobic monomer, and at least one cross-linking agent.

In another example of the present contact lenses, the second siloxane monomer can be a dual-end methacrylate end-capped polydimethylsiloxane having a number average molecular weight of at least 4,000 daltons, or of at least 5,000 daltons, or of at least 7,000 daltons. It will be understood that such siloxane monomers are bifunctional.
As an example of a bifunctional siloxane monomer useful in the present silicone hydrogel contact lenses, the second siloxane monomer can be represented by formula (2):




wherein R1 of formula (2) is selected from either hydrogen atom or a methyl group; R2 of formula (2) is selected from either of hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms; m of formula (2) represents an integer of from 0 to 10; n of formula (2) represents an integer of from 4 to 100; a and b represent integers of 1 or more; a+b is equal to 20-500; b/(a+b) is equal to 0.01-0.22; and the configuration of siloxane units includes a random configuration. In one example in which the second siloxane monomer is a monomer represented by formula (2), m of formula (2) is 0, n of formula (2) is an integer from 5 to 15, a is an integer from 65 to 90, b is an integer from 1 to 10, R1 of formula (2) is a methyl group, and R2 of formula (2) is either a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. One example of such a second siloxane monomer as represented by formula (2) is abbreviated Si2 in the Examples. The number average molecular weight for this second siloxane monomer represented by formula (2) can be from about 9,000 daltons to about 10,000 daltons. In another example, the second siloxane monomer represented by formula (2) can have a molecular weight from about 5,000 daltons to about 10,000 daltons. It can be appreciated that the second siloxane represented by formula (2) is a bifunctional siloxane having two terminal methacrylic groups. Additional details of this second siloxane monomer can be found in US20090234089, the entire content of which is incorporated herein by reference. One example of the polymerizable composition of the present disclosure comprises a first siloxane monomer; a second siloxane monomer represented by formula (2):





wherein R1 is selected from either hydrogen or a methyl group; R2 is selected from either of hydrogen or a C1-4 hydrocarbon group; m of formula (2) is 0, n of formula (2) is an integer from 5 to 15, a is an integer from 65 to 90, b is an integer from 1 to 10, R1 of formula (2) is a methyl group, and R2 of formula (2) is either a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms; and the configuration of siloxane units includes a random configuration; at least one hydrophilic vinyl-containing monomer, at least one hydrophobic monomer, and at least one cross-linking agent. Another example of the polymerizable composition of the present disclosure comprises a first siloxane monomer having a number average molecular weight of from 400 daltons to 700 daltons; a second siloxane monomer represented by formula (2):





wherein R1 is selected from either hydrogen or a methyl group; R2 is selected from either of hydrogen or a C1-4 hydrocarbon group; m of formula (2) is 0, n of formula (2) is an integer from 5 to 15, a is an integer from 65 to 90, b is an integer from 1 to 10, R1 of formula (2) is a methyl group, and R2 of formula (2) is either a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms; and the configuration of siloxane units includes a random configuration; at least one hydrophilic vinyl-containing monomer, at least one hydrophobic monomer, and at least one cross-linking agent. Yet another example of the polymerizable composition of the present disclosure comprises a first siloxane monomer having a number average molecular weight of from 400 daltons to 700 daltons; a second siloxane monomer represented by formula (2):





wherein R1 is selected from either hydrogen or a methyl group; R2 is selected from either of hydrogen or a C1-4 hydrocarbon group; m of formula (2) is 0, n of formula (2) is an integer from 5 to 15, a is an integer from 65 to 90, b is an integer from 1 to 10, R1 of formula (2) is a methyl group, and R2 of formula (2) is either a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms; and the configuration of siloxane units includes a random configuration; at least one hydrophilic amide monomer having at least one N-vinyl group, at least one hydrophobic monomer, and at least one cross-linking agent.

As another example of a bifunctional siloxane monomer useful in the present silicone hydrogel contact lenses, the second siloxane monomer can be represented by formula (3):




wherein R3 is selected from either a hydrogen atom or a methyl group, m of formula (3) represents an integer from 0 to 15, and n of formula (3) represents an integer from 1 to 500. In one example, the siloxane monomer is represented by formula (3), and R3 is a methyl group, m of formula (3) is 0, and n of formula (3) is one integer from 40 to 60.

The second siloxane monomer of this example is represented by formula (4), and is abbreviated Si3 in the Examples (available from Gelest, Inc. (Morrisville, Pa., USA) as product code DMS-R18):




The siloxane of formula (4) can have a number average molecular weight from about 4,000 to about 4,500 daltons.
One example of the polymerizable composition of the present disclosure comprises a first siloxane monomer; a second siloxane monomer at least one hydrophilic vinyl-containing monomer, at least one hydrophobic monomer, and at least one cross-linking agent, wherein the polymerizable composition is free of a siloxane monomer represented by formula (4):




Another example of a second siloxane monomer that can be included in the present polymerizable compositions is represented by formula (5) below:




wherein n of formula (5) is an integer from 100 to 140, m of formula (5) is an integer from 6-9, h of formula (5) is an integer from 3-6, and the Mn=12,800, and the Mw=16,200. The siloxane monomer of formula (5) has a chemical name of α-ω-Bis(methacryloyloxyethyl iminocarboxy ethyloxypropyl)-poly(dimethylsiloxane)-poly (trifluoropropylmethylsiloxane)-poly (ω-methoxy-poly(ethyleneglycol)propylmethylsiloxane).

In some polymerizable compositions that include the siloxane monomer of formula (5), a monofunctional siloxane monomer can be provided in the composition as represented by formula (6)




wherein n of formula (6) is an integer from 13-16, and the molecular weight is about 1500 daltons. The monofunctional siloxane monomer of formula (6) has a chemical name of α-Methacryloyloxyethyliminocarboxyethyloxypropyl-poly(dimethylsiloxy)-butyldimethylsilane.

One example of the polymerizable composition of the present disclosure comprises a first siloxane monomer represented by formula (6)




wherein n of formula (6) is an integer from 13-16, and the molecular weight is about 1500 daltons; 3-[tris (trimethylsilyloxy)silyl]propyl methacrylate (TRIS); at least one hydrophilic monomer; at least one hydrophobic monomer; and at least one cross-linking agent; wherein the polymerizable composition is free of N,N-dimethylacrylamide (DMA). Another example of the polymerizable composition of the present disclosure comprises a first siloxane monomer represented by formula (6)





wherein n of formula (6) is an integer from 13-16, and the molecular weight is about 1500 daltons; 3-[tris (trimethylsilyloxy)silyl]propyl methacrylate (TRIS); at least one hydrophilic vinyl-containing monomer; at least one hydrophobic monomer; and at least one cross-linking agent, wherein the polymerizable composition is free of N,N-dimethylacrylamide (DMA). Another example of the polymerizable composition of the present disclosure comprises a first siloxane monomer represented by formula (6)





wherein n of formula (6) is an integer from 13-16, and the molecular weight is about 1500 daltons; 3-[tris (trimethylsilyloxy)silyl]propyl methacrylate (TRIS); at least one hydrophilic amide monomer having at least one N-vinyl group; at least one hydrophobic monomer; and at least one cross-linking agent, wherein the polymerizable composition is free of N,N-dimethylacrylamide (DMA). Yet another example of the polymerizable composition of the present disclosure comprises a first siloxane monomer represented by formula (6)





wherein n of formula (6) is an integer from 13-16, and the molecular weight is about 1500 daltons; 3-[tris (trimethylsilyloxy)silyl]propyl methacrylate (TRIS); at least one hydrophilic amide monomer having at least one N-vinyl group; at least one hydrophobic monomer; and at least one methacrylate-containing cross-linking agent, wherein the polymerizable composition is free of N,N-dimethylacrylamide (DMA).

The polymerizable compositions used to prepare the present silicone hydrogel contact lenses can also include additional ingredients other than those described above. For example, some polymerizable compositions can include at least one third siloxane monomer. The polymerizable compositions can comprise one third siloxane monomer, or can comprise a third siloxane monomer component where the third siloxane monomer component is comprised of two or more siloxane monomers, each of which differ from the first siloxane monomer and the second siloxane monomer of the polymerizable composition. Examples of the third siloxane monomer or third siloxane monomer component can include poly (organosiloxane) monomers or macromers or prepolymers, such as, for example, 3-[tris(trimethylsiloxy)silyl]propyl allyl carbamate, or 3-[tris(trimethylsiloxy)silyl]propyl vinyl carbamate, or trimethylsilylethyl vinyl carbonate, or trimethylsilylmethyl vinyl carbonate, or 3-[tris (trimethylsilyloxy)silyl]propyl methacrylate (TRIS), or 3-methaycryloxy-2-hydroxypropyloxy)propylbis(trimethylsiloxy)methylsilane (SiGMA), or methyldi (trimethylsiloxy)silylpropylglycerolethyl methacrylate (SiGEMA), or monomethacryloxypropyl terminated polydimethylsiloxane (MCS-M11), MCR-M07, or monomethacryloxypropyl terminated mono-n-butyl terminated polydimethyl siloxane (mPDMS), or any combination thereof. In one example of a polymerizable composition of the present disclosure, the at least one third siloxane can comprise one or more of the first siloxanes described herein or the second siloxanes described herein, wherein the at least one third siloxane differs from the first siloxane and the second siloxane present in the polymerizable composition based on molecular weight, molecular formula, or both molecular weight and formula. For example, the third siloxane monomer can be a siloxane monomer of formula (1) having a different molecular weight than the first siloxane monomer of the polymerizable composition. In another example, the at least one third siloxane can comprise at least one of the siloxanes disclosed in the following patents: US2007/0066706, US2008/0048350, U.S. Pat. No. 3,808,178, U.S. Pat. No. 4,120,570, U.S. Pat. No. 4,136,250, U.S. Pat. No. 4,153,641, U.S. Pat. No. 470,533, U.S. Pat. No. 5,070,215, U.S. Pat. No. 5,998,498, U.S. Pat. No. 5,760,100, U.S. Pat. No. 6,367,929, and EP080539, the entire content of which are hereby incorporated by reference.
As previously stated, optionally, the polymerizable compositions of the present disclosure can comprise at least one hydrophilic monomer. The polymerizable compositions can comprise a single hydrophilic monomer, or can comprise two or more hydrophilic monomers present as the hydrophilic monomer component. Non-silicon hydrophilic monomers which can be used as the hydrophilic monomer or the hydrophilic monomer component in the polymerizable compositions disclosed herein include, for example, acrylamide-containing monomers, or acrylate-containing monomers, or acrylic acid-containing monomers, or methacrylate-containing monomers, or methacrylic acid-containing monomers, or any combination thereof. In one example, the hydrophilic monomer or monomer component can comprise or consist of a methacrylate-containing hydrophilic monomer. It is understood that the hydrophilic monomer or hydrophilic monomer component is a non-silicon monomer. Examples of hydrophilic monomers which can be included in the present polymerizable compositions can include, for example, N,N-dimethylacrylamide (DMA), or 2-hydroxyethyl acrylate, or 2-hydroxyethyl methacrylate (HEMA), or 2-hydroxypropyl methacrylate, or 2-hydroxybutyl methacrylate (HOB), or 2-hydroxybutyl acrylate, or 4-hydroxybutyl acrylate, or glycerol methacrylate, or 2-hydroxyethyl methacrylamide, or polyethyleneglycol monomethacrylate, or methacrylic acid, or acrylic acid, or any combination thereof.
In one example, the hydrophilic monomer or hydrophilic monomer component can comprise or consist of a vinyl-containing monomer. Examples of hydrophilic vinyl-containing monomers which can be provided in the polymerizable compositions include, without limitation, N-vinyl formamide, or N-vinyl acetamide, or N-vinyl-N-ethyl acetamide, or N-vinyl isopropylamide, or N-vinyl-N-methyl acetamide (VMA), or N-vinyl pyrrolidone (NVP), or N-vinyl caprolactam, or N-vinyl-N-ethyl formamide, or N-vinyl formamide, or N-2-hydroxyethyl vinyl carbamate, or N-carboxy-β-alanine N-vinyl ester, 1,4-butanediol vinyl ether (BVE), or ethylene glycol vinyl ether (EGVE), or diethylene glycol vinyl ether (DEGVE), or any combination thereof.
In another example, the hydrophilic monomer or hydrophilic monomer component of the polymerizable composition can comprise or consist of a hydrophilic amide monomer. The hydrophilic amide monomer can be a hydrophilic amide monomer having one N-vinyl group, such as, for example, N-vinyl formamide, or N-vinyl acetamide, or N-vinyl-N-ethyl acetamide, or N-vinyl isopropylamide, or N-vinyl-N-methyl acetamide (VMA), or N-vinyl pyrrolidone (NVP), or N-vinyl caprolactam, or any combination thereof. In one example, the hydrophilic monomer or hydrophilic monomer component comprises N-vinyl-N-methyl acetamide (VMA). For example, the hydrophilic monomer or monomer component can comprise or consist of VMA. In one particular example, the hydrophilic monomer can be VMA.
In another example, the hydrophilic vinyl-containing monomer or monomer component can comprise or consist of a vinyl ether-containing monomer. Examples of vinyl ether-containing monomers include, without limitation, 1,4-butanediol vinyl ether (BVE), or ethylene glycol vinyl ether (EGVE), or diethylene glycol vinyl ether (DEGVE), or any combination thereof. In one example, the hydrophilic monomer component comprises or consists of BVE. In another example, the hydrophilic monomer component comprises or consists of EGVE. In yet another example, the hydrophilic vinyl component comprises or consists of DEGVE. In one particular example, the vinyl ether-containing monomer can be a vinyl ether-containing monomer which is more hydrophilic than BVE, such as, for example, DEGVE. In another example, the hydrophilic monomer of the polymerizable composition can be a mixture of a first hydrophilic monomer which is a vinyl-containing monomer but which is not a vinyl ether-containing monomer, and a second hydrophilic monomer which is a vinyl ether containing monomer. Such mixtures include, for example, mixtures of VMA and one or more vinyl ethers such as, for example, BVE, or DEGVE, or EGVE, or any combination thereof.
When present, the hydrophilic vinyl ether-containing monomer can be present in the polymerizable composition in an amount from about 1 to about 15 unit parts, or from about 3 to about 10 unit parts. When present as a mixture with a hydrophilic vinyl-containing monomer which is not a vinyl ether, the hydrophilic vinyl-containing monomer which is not a vinyl ether and the hydrophilic vinyl ether-containing monomer can be present in the polymerizable composition at a ratio of at least 3:1, or from about 3:1 to about 15:1, or of about 4:1 based on the ratio of the unit parts of the hydrophilic vinyl-containing monomer which is not a vinyl ether to the unit parts of the hydrophilic vinyl ether-containing monomer.
In yet another example, the hydrophilic vinyl-containing monomer component can comprise or consist of a combination of a first hydrophilic monomer or monomer component, and a second hydrophilic monomer or hydrophilic monomer component. In one example, the first hydrophilic monomer has a different polymerizable functional group than the second hydrophilic monomer. In another example, each monomer of the first hydrophilic monomer has a different polymerizable functional group than the second hydrophilic monomer. In another example, the first hydrophilic monomer has a different polymerizable functional group than each monomer of the second hydrophilic monomer component. In yet another example, each monomer of the first hydrophilic monomer component has a different polymerizable functional group than each monomer of the second hydrophilic monomer component.
For example, when the first hydrophilic monomer or monomer component comprises or consists of one or more amide-containing monomers, the second hydrophilic monomer or monomer component can comprise or consist of one or more non-amide monomers (i.e., one or more monomers each of which do not have an amide functional group as part of their molecular structures). As another example, when the first hydrophilic monomer or monomer component comprises or consists of one or more vinyl-containing monomers, the second hydrophilic monomer or monomer component can comprise one or more non-vinyl-containing monomers (i.e., one or more monomers each of which do not have a vinyl polymerizable functional group as part of their molecular structures). In another example, when the first hydrophilic monomer or monomer component comprises or consists of one or more amide monomers each having an N-vinyl group, the second hydrophilic monomer or monomer component can comprise or consist of one or more non-amide monomers. When the first hydrophilic monomer or monomer component comprise or consists of one or more non-acrylate monomers (i.e., one or more monomers each of which do not have an acrylate or methacrylate polymerizable functional group as part of their molecular structures), the second hydrophilic monomer or monomer component can comprise or consist of one or more acrylate-containing monomers, or one or more methacrylate-containing monomers, or any combination thereof. When the first hydrophilic monomer or monomer components comprises or consists of one or more non-vinyl ether-containing monomers (i.e., one or more monomers each of which do not have a vinyl ether polymerizable functional group as part of their molecular structures), the second hydrophilic monomer or monomer component can comprise or consist of one or more vinyl ether-containing monomers. In a particular example, the first hydrophilic monomer or monomer component can comprise or consist of one or more amide-containing monomers each having an N-vinyl group, and the second hydrophilic monomer or monomer component can comprise or consist of one or more vinyl ether-containing monomers.
In one example, when the first hydrophilic monomer or monomer component comprises or consists of a hydrophilic amide-containing monomer having one N-vinyl group, the second hydrophilic monomer or monomer component can comprise or consist of a vinyl ether-containing monomer. In a particular example, the first hydrophilic monomer can comprise VMA, and the second hydrophilic monomer or monomer component can comprise BVE or EGVE or DEGVE or any combination thereof. The first hydrophilic monomer can comprise VMA and the second hydrophilic monomer can comprise BVE. The first hydrophilic monomer can comprise VMA and the second hydrophilic monomer can comprise EGVE. The first hydrophilic monomer can comprise VMA and the second hydrophilic monomer can comprise DEGVE. The first hydrophilic monomer can comprise VMA, and the second hydrophilic monomer component can comprise EGVE and DEGVE.
Similarly, the first hydrophilic monomer can be VMA, and the second hydrophilic monomer or monomer component can comprise BVE or EGVE or DEGVE or any combination thereof. The first hydrophilic monomer can be VMA and the second hydrophilic monomer can be BVE. The first hydrophilic monomer can be VMA and the second hydrophilic monomer can be EGVE. The first hydrophilic monomer can comprise VMA and the second hydrophilic monomer can be DEGVE. The first hydrophilic monomer can be VMA, and the second hydrophilic monomer component can be a combination of EGVE and DEGVE.
In another example, the non-silicon hydrophilic vinyl-containing monomer can have any molecular weight, such as a molecular weight less than 400 daltons, or less than 300 daltons, or less than 250 daltons, or less than 200 daltons, or less than 150 daltons, or from about 75 to about 200 daltons.
When a hydrophilic monomer or a hydrophilic monomer component is present in the polymerizable composition, the hydrophilic monomer or monomer component can be present in the polymerizable composition in an amount from 30 to 60 unit parts of the polymerizable composition. The hydrophilic monomer or monomer component can be present in the polymerizable composition from 40 to 55 unit parts, or from 45 to 50 unit parts by weight. When the hydrophilic monomer component of the polymerizable composition comprises a first hydrophilic monomer or monomer component and a second hydrophilic monomer or monomer component, the second hydrophilic monomer or monomer component can be present in the polymerizable composition in an amount from 0.1 to 20 unit parts of the polymerizable composition. For example, of the total amount of from 30 to 60 unit parts of hydrophilic monomer or monomer component present in the polymerizable composition, 29.9 to 40 unit parts can comprise the first hydrophilic monomer or monomer component, and 0.1 to 20 unit parts can comprise the second hydrophilic monomer or monomer component. In another example, the second hydrophilic monomer or monomer component can be present in the polymerizable composition from 1 to 15 unit parts, or from 2 to 10 unit parts, or from 3 to 7 unit parts.
As used herein, a vinyl-containing monomer is a monomer having a single polymerizable carbon-carbon double bond (i.e., a vinyl polymerizable functional group) present in its molecular structure, where, under free radical polymerization, the carbon-carbon double bond in the vinyl polymerizable functional group is less reactive than the carbon-carbon double bond present in an acrylate or a methacrylate polymerizable functional group. In other words, although a carbon-carbon double bond is present in acrylate groups and methacrylate groups, as understood herein, monomers comprising a single acrylate or methacrylate polymerizable group are not considered to be vinyl-containing monomers. Examples of polymerizable groups having carbon-carbon double bonds which are less reactive than the carbon-carbon double bonds of acrylate or methacrylate polymerizable groups include vinyl amide, vinyl ether, vinyl ester, and allyl ester polymerizable groups. Thus, as used herein, examples of vinyl-containing monomers include monomers having a single vinyl amide, a single vinyl ether, a single vinyl ester, or a single allyl ester polymerizable group.
In addition, the polymerizable compositions of the present disclosure can optionally comprise at least one non-silicon hydrophobic monomer. The at least one hydrophobic monomer of the polymerizable composition can be one hydrophobic monomer, or can comprise a hydrophobic monomer component composed of at least two hydrophobic monomers. Examples of hydrophobic monomers that can be used in the polymerizable compositions disclosed herein, include, without limitation, acrylate-containing hydrophobic monomers, or methacrylate-containing hydrophobic monomers, or any combination thereof. Examples of hydrophobic monomers include, without limitation, methyl acrylate, or ethyl acrylate, or propyl acrylate, or isopropyl acrylate, or cyclohexyl acrylate, or 2-ethylhexyl acrylate, or methyl methacrylate (MMA), or ethyl methacrylate, or propyl methacrylate, or butyl acrylate, or vinyl acetate, or vinyl propionate, or vinyl butyrate, or vinyl valerate, or styrene, or chloroprene, or vinyl chloride, or vinylidene chloride, or acrylonitrile, or 1-butene, or butadiene, or methacrylonitrile, or vinyltoluene, or vinyl ethyl ether, or perfluorohexylethylthiocarbonylaminoethyl methacrylate, or isobornyl methacrylate, or trifluoroethyl methacrylate, or hexafluoroisopropyl methacrylate, or hexafluorobutyl methacrylate, or ethylene glycol methyl ether methacrylate (EGMA), or any combination thereof. In one particular example, the hydrophobic monomer or monomer component can comprise or consist of methyl methacrylate, or ethylene glycol methyl ether methacrylate, or both.
When present in the polymerizable composition, the hydrophobic monomer or monomer component can be present in an amount from about 5 to about 25 unit parts, or from about 10 to about 20 unit parts.
In one example, the hydrophobic monomer component can comprise at least two hydrophobic monomers each having different polymerizable functional groups. In another example, the hydrophobic monomer component can comprise at least two hydrophobic monomers each having the same polymerizable functional group. The hydrophobic monomer component can comprise or consist of two hydrophobic monomers, both having the same polymerizable functional group. In one example, the hydrophobic monomer component can comprise or consist of two hydrophobic methacrylate-containing monomers. The hydrophobic monomer component can comprise or consist of MMA and EGMA. In one example, the at least two hydrophobic monomers of the hydrophobic monomer component can comprise or consist of MMA and EGMA, and the ratio of the amounts of MMA and EGMA present in the polymerizable composition can be from about 6:1 to about 1:1 based on the unit parts of MMA to the unit parts of EGMA. The ratio of the unit parts of MMA and EGMA present in the polymerizable composition can be about 2:1 based on the unit parts of MMA to the unit parts of EGMA.
Optionally, the polymerizable composition can further comprise at least one cross-linking agent. The polymerizable composition can comprise one cross-linking agent, or can comprise a cross-linking agent component comprised of at least two cross-linking agents. As used herein, a cross-linking agent is a non-silicon cross-linking agent and thus is different from multifunctional siloxane monomers which may be present in the polymerizable compositions.
In accordance with the present disclosure, a cross-linking agent is understood to be a monomer having more than one polymerizable functional group as part of its molecular structure, such as two or three or four polymerizable functional groups, i.e., a multifunctional monomer such as a bifunctional or trifunctional or tetrafunctional monomer. Non-silicon cross-linking agents that can be used in the polymerizable compositions disclosed herein include, for example, without limitation, allyl (meth)acrylate, or lower alkylene glycol di(meth)acrylate, or poly(lower alkylene) glycol di(meth)acrylate, or lower alkylene di(meth)acrylate, or divinyl ether, or divinyl sulfone, or di- and trivinylbenzene, or trimethylolpropane tri(meth)acrylate, or pentaerythritol tetra(meth)acrylate, or bisphenol A di(meth)acrylate, or methylenebis(meth)acrylamide, or triallyl phthalate and diallyl phthalate, or any combination thereof. Cross-linking agents, as disclosed in the Examples, include, for example, ethylene glycol dimethacrylate (EGDMA), or triethylene glycol dimethacrylate (TEGDMA), or triethylene glycol divinyl ether (TEGDVE), or any combination thereof. In one example, the cross-linking agent can have a molecular weight less than 1500 daltons, or less than 1000 daltons, or less than 500 daltons, or less than 200 daltons.
In one example, the cross-linking agent can be a vinyl-containing cross-linking agent. As used herein, a vinyl-containing cross-linking agent is a monomer having at least two polymerizable carbon-carbon double bonds (i.e., at least two vinyl polymerizable functional groups) present in its molecular structure, where each of the at least two polymerizable carbon-carbon double bonds present in the vinyl polymerizable functional groups of the vinyl-containing cross-linking agent is less reactive than a carbon-carbon double bond present in an acrylate or methacrylate polymerizable functional group. Although carbon-carbon double bonds are present in acrylate and methacrylate polymerizable functional groups, as understood herein, cross-linking agents comprising one or more acrylate or methacrylate polymerizable group (e.g., an acrylate-containing cross-linking agent or a methacrylate-containing cross-linking agent) are not considered to be vinyl-containing cross-linking agents. Polymerizable functional groups having carbon-carbon double bonds which are less reactive than the carbon-carbon double bonds of acrylate or methacrylate polymerizable groups include, for example, vinyl amide, vinyl ester, vinyl ether and allyl ester polymerizable functional groups. Thus, as used herein, vinyl-containing cross-linking agents include, for example, cross-linking agents having at least two polymerizable functional groups selected from a vinyl amide, a vinyl ether, a vinyl ester, an allyl ester, and any combination thereof. As used herein, a mixed vinyl-containing cross-linking agent is a cross-linking agent having at least one polymerizable carbon-carbon double bond (i.e., at least one vinyl polymerizable functional group) present in its structure which is less reactive than the carbon-carbon double bond present in an acrylate or methacrylate polymerizable functional group, and at least one polymerizable functional group present in its structure having a carbon-carbon double bond which is at least as reactive as the carbon-carbon double bond in an acrylate or methacrylate polymerizable functional group.
In one example, the cross-linking agent or cross-linking agent component can comprise a vinyl-containing cross-linking agent. For example, the vinyl-containing cross-linking agent or cross-linking agent component can comprise or consist of a vinyl ether-containing cross-linking agent. In another example, the cross-linking agent or cross-linking agent component can comprise or consist of an acrylate-containing cross-linking agent (i.e., a cross-linking agent having at least two acrylate polymerizable functional groups), or a methacrylate-containing cross-linking agent (i.e., at least two methacrylate polymerizable functional groups), or at least one acrylate-containing cross-linking agent and at least one methacrylate-containing cross-linking agent.
The cross-linking agent component can comprise or consist of a combination of two or more cross-linking agents, each of which has a different polymerizable functional group. For example, the cross-linking agent component can comprise one vinyl-containing cross-linking agent, and one acrylate-containing cross-linking agent. The cross-linking agent component can comprise one vinyl-containing cross-linking agent and one methacrylate-containing cross-linking group. The cross-linking agent component can comprise or consist of one vinyl ether-containing cross-linking agent, and one methacrylate-containing cross-linking agent. One example of the polymerizable composition of the present disclosure comprises a first siloxane monomer; a second siloxane monomer; at least one hydrophilic amide monomer having at least one N-vinyl group; at least one hydrophobic monomer; and at least vinyl-containing one cross-linking agent, and at least one acrylate-containing or methacrylate-containing cross-linking agent. Another example of the polymerizable composition of the present disclosure comprises a first siloxane monomer; a second siloxane monomer; at least one hydrophilic amide monomer having at least one N-vinyl group; at least one hydrophobic monomer; and at least vinyl-containing one cross-linking agent, and at least one acrylate-containing or methacrylate-containing cross-linking agent, wherein the polymerizable composition is free of N,N-dimethylacrylamide (DMA).
Optionally, the polymerizable composition of the present disclosure can comprise or consist of at least one vinyl-containing cross-linking agent or cross-linking agent component, and can be free of a non-silicon vinyl-free cross-linking agent. In other words, in this example, the polymerizable composition comprises the first siloxane monomer, the second siloxane monomer, and at least one cross-linking agent, wherein the at least one cross-linking agent consists of at least one vinyl-containing cross-linking agent (i.e., a single vinyl-containing cross-linking agent or a vinyl-containing cross-linking agent component comprised of two or more vinyl-containing cross-linking agents), as no non-silicone cross-linking agents other than vinyl-containing cross-linking agents are present in the polymerizable composition. In other words, in this example, no non-vinyl-containing cross-linking agents are present in the polymerizable composition.
The optional cross-linking agent or cross-linking agent component can be present in the polymerizable composition in an amount from 0.01 to 10.0 unit parts, such as, for example, from 0.05 to 5.0 unit parts, or from 0.1 to 2.0 unit parts, or from 0.2 to 1.0 unit parts, or from 0.3 to 0.8 unit parts. In one example, when the cross-linking agent or cross-linking agent component comprises a vinyl-containing cross-linking agent, the vinyl-containing cross-linking agent or cross-linking agent component can be present in the polymerizable composition in an amount from 0.01 to 0.80 unit parts, such as, for example, 0.05 to 0.30 unit parts or from 0.1 to 0.2 unit parts. When the at least one cross-linking agent is a acrylate-containing or methacrylate-containing cross-linking agent or cross-linking agent component, the acrylate-containing or methacrylate-containing cross-linking agent or cross-linking agent component can be present in the polymerizable composition in an amount from 0.1 to 2.0 unit parts, such as, for example, 0.3 to 1.2 unit parts or from 0.5 to 0.8 unit parts. When a combination of a vinyl-containing cross-linking agent or cross-linking agent component, and an acrylate-containing or methacrylate-containing cross-linking agent or cross-linking agent component is used, the vinyl-containing cross-linking agent or cross-linking agent component and the acrylate-containing or methacrylate-containing cross-linking agent or cross-linking agent component can be present in the polymerizable composition in a ratio from 1:2 to 1:20, or from 1:3 to 1:12, or from 1:4 to 1:7 based on the ratio by weight of the unit parts of the vinyl-containing cross-linking agent or cross-linking agent component to the unit parts of the acrylate-containing or methacrylate-containing cross-linking agent or cross-linking component.
While in some polymerizable compositions limiting the amount of vinyl-containing cross-linking agent can improve wettability, in many cases, the inclusion of a vinyl-containing cross-linking agent in the polymerizable composition can also improve the dimensional stability of the resulting contact lens formed from the polymerizable composition. Thus, in some polymerizable compositions, a vinyl-containing cross-linking agent can be present in the polymerizable composition in an amount effective to produce a contact lens having improved dimensional stability as compared to a contact lens produced from the same polymerizable composition but without the vinyl-containing cross-linking agent.
Yet another approach for producing contact lenses having ophthalmically acceptably wettable surfaces in accordance with the present disclosure, can be to include an amount of a vinyl-containing cross-linking agent in the polymerizable composition based on the ratio of the unit parts of the hydrophilic vinyl-containing monomer present in the composition to the unit parts of the vinyl-containing cross-linking agent present in the composition. For example, the unit parts of the hydrophilic vinyl-containing monomer and the unit parts of the vinyl-containing cross-linking agent can be present in the polymerizable composition in a ratio greater than about 125:1, or from about 150:1 to about 625:1, or from about 200:1 to about 600:1, or from about 250:1 to about 500:1, or from about 450:1 to about 500:1, based on the ratio of the unit parts of the hydrophilic vinyl-containing monomer to the unit parts of the vinyl-containing cross-linking agent.
The polymerizable composition can optionally include one or more organic diluents, one or more polymerization initiators (i.e., ultraviolet (UV) initiators or thermal initiators, or both), or one or more UV absorbing agents, or one or more tinting agents, or one or more oxygen scavengers, or one or more chain transfer agents, or any combination thereof. These optional ingredients can be reactive or non-reactive ingredients. In at least one example, the polymerizable compositions can be diluent-free in that they do not contain any organic diluent to achieve miscibility between the siloxanes and the other lens forming ingredients, such as the optional hydrophilic monomers, hydrophobic monomer, and cross-linking agents. In addition, many of the present polymerizable compositions are essentially free of water (e.g., contain no more than 3.0% or 2.0% water by weight).
The polymerizable compositions disclosed herein can optionally comprise one or more organic diluents, i.e., the polymerizable composition can comprise an organic diluent, or can comprise an organic diluent component comprising two or more organic diluents. Organic diluents that can optionally be included in the present polymerizable compositions include alcohols, including lower alcohols, such as, for example, without limitation, pentanol, or hexanol, or octanol, or decanol, or any combination thereof. When included, the organic diluent or organic diluent component can be provided in the polymerizable composition in an amount from about 1 to about 70 unit parts, or from about 2 unit parts to about 50 unit parts, or from about 5 unit parts to about 30 unit parts.
Approaches commonly employed to increase the miscibility of siloxane monomers and hydrophilic monomers include adding organic diluents to the polymerizable composition to act as compatiblizers between the hydrophilic monomers and the siloxane monomers which typically are more hydrophobic, or using only siloxane monomers having low molecular weights (e.g., molecular weights below 2500 daltons). The use of the first siloxane as described above makes it possible to include both a high molecular weight second siloxane and a high level of one or more hydrophilic monomers in the polymerizable compositions of the present disclosure. And while it is possible to include one or more organic diluents in the present polymerizable compositions disclosed herein, it may not be necessary to do so in order to obtain a miscible polymerizable composition in accordance with the present disclosure. In other words, in at least one example, the silicone hydrogel contact lenses of the present disclosure are formed from polymerizable compositions which are free of an organic diluent.
An example of the disclosed polymerizable composition can be miscible when initially prepared, and can remain miscible over a period of time adequate for the commercial manufacture of contact lenses, such as, for example, 2 weeks, or 1 week, or 5 days. Typically, when polymerized and processed into contact lenses, miscible polymerizable compositions result in contact lenses having ophthalmically acceptable clarities.
The present polymerizable compositions can optionally comprise one or more polymerization initiators, i.e., the polymerizable composition can comprise an initiator, or can comprise an initiator component comprising two or more polymerization initiators. Polymerization initiators that can be included in the present polymerizable compositions include, for example, azo compounds, or organic peroxides, or both. Initiators that can be present in the polymerizable composition include, for example, without limitation, benzoin ethyl ether, or benzyl dimethyl ketal, or alpha,alpha-diethoxyacetophenone, or 2,4,6-trimethylbenzoyl diphenyl phosphine axide, or benzoin peroxide, or t-butyl peroxide, or azobisisobutyronitorile, or azobisdimethylvaleronitorile, or any combination thereof. UV photoinitiators can include, for example, phosphine oxides such as diphenyl (2,4,6-trimethyl benzoyl)phosphine oxide, or benzoin methyl ether, or 1-hydroxycyclohexylphenyl ketone, or Darocur (available from BASF, Florham Park, N.J., USA), or Irgacur (also available from BASF), or any combination thereof. In many of Examples disclosed herein, the polymerization initiator is the thermal initiator 2,2′-azobis-2-methyl propanenitrile (VAZO-64 from E.I. DuPont de Nemours & Co., Wilmington, Del., USA). Other commonly used thermoinitiators can include 2,2′-azobis(2,4-dimethylpentanenitrile) (VAZO-52) and 1,1′-azo bis(cyanocyclohexane) (VAZO-88). The polymerization initiator or initiator component can be present in the polymerizable composition in an amount from about 0.01 unit parts to about 2.0 unit parts, or in an amount from about 0.1 unit parts to about 1.0 unit parts, or from about 0.2 unit parts to about 0.6 unit parts by weight.
Optionally, the present polymerizable compositions can comprise one or more UV absorbing agents, i.e., the polymerizable composition can comprise an UV absorbing agent, or can comprise an UV absorbing agent component comprising two or more UV absorbing agents. UV absorbing agents that can be included in the present polymerizable compositions include, for example, benzophenones, or benzotriazoles, or any combination thereof. In many of the Examples disclosed herein, the UV absorbing agent is 2-(4-Benzoyl-3-hydroxyphenoxy)ethyl acrylate (UV-416) or 2-(3-(2H-benzotriazol-2-YL)-4-hydroxy-phenyl)ethyl methacrylate (NORBLOC® 7966 from Noramco, Athens, Ga., USA). The UV absorbing agent or UV absorbing agent component can be present in the polymerizable composition in an amount from about 0.01 unit parts to about 5.0 unit parts, or in an amount from about 0.1 unit parts to about 3.0 unit parts, or from about 0.2 unit parts to about 2.0 unit parts by weight.
The polymerizable compositions of the present disclosure can also optionally include at least one tinting agent (i.e., one tinting agent or a tinting agent component comprising two or more tinting agents), although both tinted and clear lens products are contemplated. In one example, the tinting agent can be a reactive dye or pigment effective to provide color to the resulting lens product. The tinting agent or tinting agent component of the polymerizable composition can comprise a polymerizable tinting agent, or can comprise a non-polymerizable tinting agent, or any combination thereof. The polymerizable tinting agent can be a tinting agent whose molecular structure comprises a polymerizable functional group, or can be a tinting agent whose molecular structure includes both a monomer portion and a dye portion, i.e., the tinting agent can be a monomer-dye compound. Tinting agents can include, for example, VAT Blue 6 (7,16-Dichloro-6,15-dihydroanthrazine-5,9,14,18-tetrone), or 1-Amino-4-[3-(beta-sulfatoethylsulfonyl)amino]-2-anthraquinonesulfonic acid (C. I. Reactive Blue 19, RB-19), or a monomer-dye compound of Reactive Blue 19 and hydroxyethylmethacrylate (RB-19 HEMA), or 1,4-bis[4-[(2-methacryl-oxyethyl)phenylamino]anthraquinone (Reactive Blue 246, RB-246, available from Arran Chemical Company, Athlone, Ireland), or 1,4-Bis[(2-hydroxyethyl)amino]-9,10-anthracenedione bis(2-propenoic)ester (RB-247), or Reactive Blue 4, RB-4, or a monomer-dye compound of Reactive Blue 4 and hydroxyethyl methacrylate (RB-4 HEMA or “Blue HEMA”), or any combination thereof. In one example, the tinting agent or tinting agent component can comprise a polymerizable tinting agent. The polymerizable tinting agent component can comprise, for example, RB-246, or RB-247, or RB-4 HEMA, or RB-19 HEMA, or any combination thereof. Examples of monomer-dye compounds include RB-4 HEMA and RB-19 HEMA. Additional examples of monomer-dye compounds are described in U.S. Pat. No. 5,944,853 and U.S. Pat. No. 7,216,975, both of which are incorporated in their entirety by reference herein. Other exemplary tinting agents are disclosed, for example, in U.S. Patent Application Publication No. 2008/0048350, the disclosure of which is incorporated in its entirety herein by reference. In many of the Examples disclosed herein, the tinting agent is a reactive blue dye, such as those described in U.S. Pat. No. 4,997,897, the disclosure of which is incorporated in its entirety herein by reference. Other suitable tinting agents for use in accordance with the present invention are phthalocyanine pigments such as phthalocyanine blue, or phthalocyanine green, or chromic-alumina-cobaltous oxide, or chromium oxides, or various iron oxides for red, yellow, brown and black colors, or any combination thereof. Opaquing agents such as titanium dioxide can also be incorporated. For certain applications, a combination of tinting agents having different colors can be employed as the tinting agent component. If employed, the tinting agent or tinting agent component can be present in the polymerizable composition in an amount ranging from about 0.001 unit parts to about 15.0 unit parts, or about 0.005 unit parts to about 10.0 unit parts, or about 0.01 unit parts to about 8.0 unit parts.
The polymerizable compositions of the present disclosure can optionally comprise at least one oxygen scavenger, i.e., one oxygen scavenger or an oxygen scavenger component comprising two or more oxygen scavengers. Examples of oxygen scavengers which can be included as the oxygen scavenger or oxygen scavenger component of the present polymerizable compositions include, for example, Vitamin E, or phenolic compounds, or phosphite compounds, or phosphine compounds, or amine oxide compounds, or any combination thereof. For example, the oxygen scavenger or oxygen scavenger component can consist of or comprise a phosphine-containing compound. In many of the Examples disclosed herein, the oxygen scavenger or oxygen scavenger component is a phosphine-containing compound, such as triphenyl phosphine, or a polymerizable form of triphenyl phosphine, such as diphenyl(P-vinylphenyl)phosphine.
Chain transfer is a polymerization reaction in which the activity of a growing polymer chain is transferred to another molecule, reducing the average molecular weight of the final polymer. The polymerizable compositions of the present disclosure can optionally comprise at least one chain transfer agent, i.e., can comprise one chain transfer agent or can comprise a chain transfer agent component comprising at least two chain transfer agents. Examples of chain transfer agents which can be included as the chain transfer agent or the chain transfer component of the present polymerizable compositions include, for example, thiol compounds, or halocarbon compounds, or C3-C5 hydrocarbons, or any combination thereof. In many of the Examples disclosed herein, the chain transfer agent is allyloxy ethanol. When present in the polymerizable composition, the chain transfer agent or chain transfer agent component can be present in an amount from about 0.01 unit parts to about 1.5 unit parts, for example from about 0.1 unit parts to about 0.5 unit parts.
In one example, the silicone hydrogel contact lenses of the present disclosure can have relatively high equilibrium water contents (EWC)s. Methods of determining EWC are known to those of ordinary skill in the art, and can be based on weight loss from a lens during a drying process. For example, the silicone hydrogel contact lenses can have, when fully hydrated, an equilibrium water content from 20% to 75% by weight. The present contact lenses can have an EWC from about 30% to about 70%, or from about 45% to about 65%, or from about 50% to about 63%, or from about 50% to about 67%, or from about 55% to about 65% by weight.
The present contact lenses can have an oxygen permeability (or Dk) of at least 55 barrers (Dk≧55 barrers), or an oxygen permeability of at least 60 barrers (Dk≧60 barrers), or an oxygen permeability of at least 65 barrers (Dk≧65 barrers). The lenses can have an oxygen permeability from about 55 barrers to about 135 barrers, or from about 60 barrers to about 120 barrers, or from about 65 barrers to about 90 barrers, or from about 50 barrers to about 75 barrers. Various methods of determining oxygen permeability are known to those of ordinary skill in the art.
The silicone hydrogel contact lenses of the present disclosure have, when fully hydrated, an average tensile modulus about 0.20 MPa to about 0.90 MPa. For example, the average modulus can be from about 0:30 MPa to about 0.80 MPa, or from about 0.40 MPa to about 0.75 MPa, or from about 0.50 MPa to about 0.70 MPa.
As used herein, the modulus of a contact lens or lens body is understood to refer to the tensile modulus, also known as Young's modulus. It is a measure of the stiffness of an elastic material. The tensile modulus can be measured using a method in accordance with ANSI Z80.20 standard. In one example, the tensile modulus can be measured using an Instron Model 3342 or Model 3343 mechanical testing system.
The present contact lenses can have an oxygen permeability of at least 55 barrers (Dk≧55 barrers), or an EWC from about 30% to about 70%, or a tensile modulus from about 0.2 MPa to about 0.9 MPa, or any combination thereof. In one example, the contact lenses can have an oxygen permeability of at least 60 barrers (Dk≧60 barrers), or an EWC from about 35% to about 65%, or a tensile modulus from about 0.3 MPa to about 0.8 MPa, or any combination thereof. In another example, the present contact lenses can have an oxygen permeability of at least 60 barrers, or an EWC from about 45% to about 65%, or a tensile modulus from about 0.40 MPa to about 0.75 MPa, or any combination thereof.
In one example, the present contact lenses have an oxygen permeability of at least 55 barrers, an EWC from about 30% to about 70%, and a tensile modulus from about 0.2 MPa to about 0.9 MPa.
The silicone hydrogel contact lenses of the present disclosure can have, when fully hydrated, an average percentage of energy loss from about 25% to about 40%. For example, the average percentage of energy loss can be from about 27% to about 40%, or can be from about 30% to about 37%.
As used herein, percentage of energy loss is a measure of the energy lost as heat when energy loading and unloading cycles are applied to viscoelastic materials. Percentage of energy loss can be determined using a number of methods known to those of ordinary skill in the art. For example, the force involved in stretching a sample to 100% strain, and then returning it to 0% at a constant rate can be determined and used to calculate the percentage energy loss for the material.
The present contact lenses can have an ionoflux less than about 8.0×10−3 mm2/min, or less than about 7.0×10−3 mm2/min, or less than about 5.0×10−3 mm2/min. Various methods of determining ionoflux are conventional and are known to those of ordinary skill in the art.
Silicone hydrogel contact lenses of the present invention can have captive bubble dynamic advancing contact angles of less than 120 degrees, such as, for example, less than 90 degrees when fully hydrated, less than 80 degrees when fully hydrated, less than 70 degrees when fully hydrated, or less than 65 degrees when fully hydrated, or less than 60 degrees when fully hydrated, or less than 50 degrees when fully hydrated.
Silicone hydrogel contact lenses of the present invention can have captive bubble static contact angles of less than 70 degrees when fully hydrated, or less than 60 degrees when fully hydrated, or less than 55 degrees when fully hydrated, or less than 50 degrees when fully hydrated, or less than 45 degrees when fully hydrated.
In one example, the present contact lenses can have a wet extractable component. The wet extractable component is determined based on the weight lost during methanol extraction of contact lenses which have been fully hydrated and sterilized prior to drying and extraction testing. The wet extractable component can comprise unreacted or partially reacted polymerizable ingredients of the polymerizable composition. As the wet extractable component consists of extractable materials remaining in the lens body after the lens body has been fully processed to form a sterilized contact lens, for lenses formed from polymerizable compositions comprising non-reactive ingredients, it can be assumed that substantially all of the non-reactive ingredients have been removed from the lens body during its processing, and so the wet extractable component consists essentially of extractable components formed from reactive ingredients of the polymerizable composition, i.e., unreacted polymerizable components and partially reacted polymerizable ingredients. In lenses made from a polymerizable composition free of a diluent, the wet extractable component can be present in the contact lens in an amount from about 1% wt/wt to about 15% wt/wt, or from about 2% wt/wt to about 10% wt/wt, or from about 3% wt/wt to about 8% wt/wt based on the dry weight of the lens body prior to extraction testing. In lenses made from a polymerizable composition comprising a diluent, the wet extractable component may consist of a portion of the diluent as well as unreacted and partially reacted polymerizable ingredients, and can be present in the contact lens in an amount from about 1% wt/wt to about 20% wt/wt, or from about 2% wt/wt to about 15% wt/wt of the lens, or from about 3% wt/wt to about 10% wt/wt based on the dry weight of the lens body prior to extraction testing.
In one example, the present contact lenses have a dry extractable component. The dry extractable component is determined based on the weight lost during extraction in methanol of polymeric lens bodies which have not been washed, extracted (as part of a manufacturing process), hydrated or sterilized prior to the drying and extraction testing. The dry extractable component can comprise unreacted or partially reacted polymerizable ingredients of the polymerizable composition. When optional non-reactive ingredients such as diluents and the like are present in the polymerizable composition, the dry extractable component may further comprise the non-reactive ingredients.
In lenses made from a polymerizable composition free of a diluent, the dry extractable component of the lens consists primarily of dry extractable components contributed by polymerizable ingredients of the polymerizable composition (i.e., unreacted or partially reacted polymerizable ingredients), and may also include dry extractable materials contributed by optional non-polymerizable components present in the polymerizable composition in small amounts (e.g., less than 3% wt/wt), such as, for example, initiators, tinting agents, oxygen scavengers, and the like. In lenses made from a polymerizable composition free of a diluent, the dry extractable component can be present in the polymeric lens body in an amount from about 1% wt/wt to about 30% wt/wt of the lens body, or from about 2% wt/wt to about 25% wt/wt, or from about 3% wt/wt to about 20% wt/wt, or from about 4% wt/wt to about 15% wt/wt, or from 2% wt/wt to less than 10% wt/wt based on the dry weight of the lens body prior to extraction testing.
In lenses made from a polymerizable composition comprising a large amount (e.g., more than 3% wt/wt) of an optional non-reactive ingredient such as a diluent, the dry extractable component consists of extractable materials contributed by reactive ingredients as well as extractable components contributed by non-polymerizable ingredients of the polymerizable composition. The total amount of dry extractable components contributed by reactive ingredients and non-polymerizable ingredients present in the contact lens can consist of an amount from about 1% wt/wt to about 75% wt/wt, or from about 2% wt/wt to about 50% wt/wt of the lens, or from about 3% wt/wt to about 40% wt/wt, or from about 4% wt/wt to about 20% wt/wt, or from about 5% to about 10% based on the dry weight of the polymeric lens body prior to extraction testing. The total amount of dry extractable components contributed by polymerizable ingredients (i.e., unreacted or partially reacted polymerizable ingredients) can be an amount from about 1% wt/wt to about 30% wt/wt of the lens body, or from about 2% wt/wt to about 25% wt/wt, or from about 3% wt/wt to about 20% wt/wt, or from about 4% wt/wt to about 15% wt/wt, or from 2% wt/wt to less than 10% wt/wt based on the dry weight of the lens body prior to extraction testing.
The contact lenses of the present disclosure, as they are configured to be placed or disposed on a cornea of an animal or human eye, are ophthalmically acceptable contact lenses. As used herein, an ophthalmically acceptable contact lens is understood to be a contact lens having at least one of a number of different properties as described below. An ophthalmically acceptable contact lens can be formed of, and packaged in, ophthalmically acceptable ingredients such that the lens is not cytotoxic and does not release irritating and/or toxic ingredients during wear. An ophthalmically acceptable contact lens can have a level of clarity in the optic zone of the lens (i.e., the portion of the lens providing vision correction) sufficient for its intended use in contact with the cornea of an eye, for example, a transmittance of at least 80%, or at least 90%, or at least 95% of visible light. An ophthalmically acceptable contact lens can have sufficient mechanical properties to facilitate lens handling and care for a duration of time based on its intended lifetime. For example, its modulus, tensile strength, and elongation can be sufficient to withstand insertion, wear, removal and, optionally, cleaning over the intended lifetime of the lens. The level of these properties which are appropriate will vary depending upon the intended lifetime and usage of the lens (e.g., single use daily disposable, multiple use monthly, etc). An ophthalmically acceptable contact lens can have an effective or appropriate ionoflux to substantially inhibit or substantially prevent corneal staining, such as corneal staining more severe than superficial or moderate corneal staining after continuous wear of the lens on a cornea for 8 or more hours. An ophthalmically acceptable contact lens can have a level of oxygen permeability sufficient to allow oxygen to reach the cornea of an eye wearing the lens in an amount sufficient for long term corneal health. An ophthalmically acceptable contact lens can be a lens which does not cause substantial or undue corneal swelling in an eye wearing the lens, for example, no more than about 5% or 10% corneal swelling after being worn on a cornea of an eye during an overnight sleep. An ophthalmically acceptable contact lens can be a lens which allows movement of the lens on the cornea of an eye wearing the lens sufficient to facilitate tear flow between the lens and the eye, in other words, does not cause the lens to adhere to the eye with sufficient force to prevent normal lens movement, and that has a low enough level of movement on the eye to allow vision correction. An ophthalmically acceptable contact lens can be a lens which allows wearing of the lens on the eye without undue or significant discomfort and/or irritation and/or pain. An ophthalmically acceptable contact lens can be a lens which inhibits or substantially prevents lipid and/or protein deposition sufficient to cause the lens wearer to remove the lens because of such deposits. An ophthalmically acceptable contact lens can have at least one of a water content, or a surface wettability, or a modulus or a design, or any combination thereof, that is effective to facilitate ophthalmically compatible wearing of the contact lens by a contact lens wearer at least for one day. Ophthalmically compatible wearing is understood to refer to the wearing of a lens by a lens wearer with little or no discomfort, and with little or no occurrence of corneal staining. Determining whether a contact lens is ophthalmically acceptable can be achieved using conventional clinical methods, such as those performed by an eye care practitioner, and as understood by persons of ordinary skill in the art.
The present contact lenses have ophthalmically acceptably wettable lens surfaces. For example, the contact lenses can have the ophthalmically acceptably wettable lens surfaces when the polymerizable composition used to form the polymeric lens body is free of an internal wetting agent, or when the polymerizable composition used to form the polymeric lens body is free of an organic diluent, or when the polymeric lens body is extracted in water or an aqueous solution free of a volatile organic solvent, or when the polymeric lens body is free of a surface plasma treatment, or any combination thereof.
One approach commonly used in the art to increase the wettability of contact lens surfaces is to apply treatments to the lens surfaces or to modify the lens surfaces. In accordance with the present disclosure, the silicone hydrogel contact lenses can have ophthalmically acceptably wettable lens surfaces without the presence of a surface treatment or surface modification. Surface treatments include, for example, plasma and corona treatments which increase the hydrophilicity of the lens surface. While it is possible to apply one or more surface plasma treatments to the present lens bodies, it is not necessary to do so in order to obtain a silicone hydrogel contact lens having ophthalmically acceptably wettable lens surfaces when fully hydrated. In other words, in one example, the silicone hydrogel contact lenses of the present disclosure can be free of a surface plasma or corona treatment.
Surface modifications include binding wetting agents to the lens surface, such as, for example, binding a wetting agent such as a hydrophilic polymer to at least a lens surface by chemical bonding or another form of chemical interaction. In some cases, the wetting agent may be bound to the lens surface as well as a least a portion of the polymeric matrix of the lens, i.e., at least a portion of the bulk of the lens, by chemical bonding or another form of chemical interaction. The ophthalmically acceptably wettable lens surfaces of the present disclosure can be ophthalmically acceptably wettable without the presence of a wetting agent (e.g., a polymeric material or a non-polymeric material) bound to at least the lens surface. While it is possible to bind one or more wetting agents to the present lenses, it is not necessary to do so in order to obtain a silicone hydrogel contact lens having ophthalmically acceptably wettable lens surfaces when fully hydrated. Thus, in one example, the lenses of the present disclosure can comprise wetting agents, such as, for example, hydrophilic polymers and including polyvinyl pyrrolidone, bound to a surface of the lens. Alternatively, in another example, the silicone hydrogel contact lenses of the present disclosure can be free of a wetting agent bound to the lens surface.
Another method of increasing lens wettability is to physically entrap a wetting agent within the lens body or contact lens, such as by introducing the wetting agent into the lens body when the lens body is swollen, and then returning the lens body to a less swollen state, thereby entrapping a portion of a wetting agent within the lens body. The wetting agent can be permanently trapped within the lens body, or can be released from the lens over time, such as during wear. The ophthalmically acceptably wettable lens surfaces of the present disclosure can be ophthalmically acceptably wettable without the presence of a wetting agent (e.g., a polymeric material or a non-polymeric material) physically entrapped in the lens body following formation of the polymeric lens body. While it is possible to physically entrap one or more wetting agents in the present lenses, it is not necessary to do so in order to obtain a silicone hydrogel contact lens having ophthalmically acceptably wettable lens surfaces when fully hydrated. Thus, in one example, the lenses of the present disclosure can comprise wetting agents, such as, for example, hydrophilic polymers and including polyvinyl pyrrolidone, entrapped within the lenses. Alternatively, the silicone hydrogel contact lenses of the present disclosure can be free of a wetting agent physically entrapped within the lens. As used herein, physically entrapped refers to immobilizing a wetting agent, or other ingredient, in the polymeric matrix of the lens with little or no chemical bonding or chemical interaction being present between the wetting agent and or other ingredient and the polymeric matrix. This is in contrast to ingredients that are chemically bound to the polymeric matrix, such as by ionic bonds, covalent bonds, van der Waals forces, and the like.
Another approach commonly used in the art to increase the wettability of silicone hydrogel contact lenses includes adding one or more wetting agents to the polymerizable composition. In one example, the wetting agent can be a polymeric wetting agent. However, the contact lenses of the present disclosure can have ophthalmically acceptably wettable lens surfaces when the polymerizable composition used to form the polymeric lens body is free of a wetting agent. While it is possible to include one or more wetting agents in the present polymerizable compositions to increase the wettability of the silicone hydrogel contact lenses of the present disclosure, it is not necessary to do so in order to obtain a silicone hydrogel contact lens having ophthalmically acceptably wettable lens surfaces. In other words, in one example, the silicone hydrogel contact lenses of the present disclosure can be formed from polymerizable compositions free of wetting agents. Alternatively, in another example, the polymerizable compositions of the present invention can further comprise a wetting agent.
In one example, the wetting agent can be an internal wetting agent. The internal wetting agent can be bound within at least a portion of the polymeric matrix of the lens. For example, the internal wetting agent can be bound within at least a portion of the polymeric matrix of the lens by chemical bonding or another form of chemical interaction. In some cases, the wetting agent may be bound to the lens surface as well. The internal wetting agent can comprise a polymeric material or a non-polymeric material. While it is possible to bind one or more internal wetting agents within the polymeric matrix of the present lenses, it is not necessary to do so in order to obtain a silicone hydrogel contact lens having ophthalmically acceptably wettable lens surfaces when fully hydrated. Thus, in one example, the lenses of the present disclosure can comprise internal wetting agents bound to at least a portion of the polymeric matrix of the lens. Alternatively, in another example, the silicone hydrogel contact lenses of the present disclosure can be free of an internal wetting agent bound to at least a portion of the polymeric matrix of the lens.
In another example, the wetting agent can be an internal polymeric wetting agent. The internal polymeric wetting agent can be present in the polymeric lens body as part of an interpenetrating polymer network (IPN) or a semi-IPN. An interpenetrating polymer network is formed by at least two polymers, each of which is cross-linked to itself, but none of which are cross-linked to each other. Similarly, a semi-IPN is formed by at least two polymers, at least one of which is cross-linked to itself but not to the other polymer, and the other of which is not cross-linked either to itself or the other polymer. In one example of the present disclosure, the contact lens can have ophthalmically acceptably wettable lens surfaces when the polymeric lens body is free of an internal polymeric wetting agent present in the lens body as an IPN or a semi-IPN. Alternatively, the contact lens can comprise an internal polymeric wetting agent present in the lens body as an IPN or a semi-IPN.
In yet another example, the wetting agent can be a linking compound present in the polymerizable composition used to form the lens body, or a linking agent physically entrapped within the polymeric lens body after the lens body has been formed. When the wetting agent is a linking compound, after polymerization of the lens body or entrapment of the linking agent in the polymeric lens body, the linking compound can subsequently link a second wetting agent to the lens body when the lens body is contacted by the wetting agent. The linking can occur as part of the manufacturing process, for example as a washing process, or can take place when the lens body is contacted by a packaging solution. The linking can take the form of an ionic bond, or a covalent bond, or a form of van der Waals attraction. The linking agent can comprise a boronic acid moiety or group such that a polymerized boronic acid moiety or group is present in the polymeric lens body, or such that a boronic acid moiety or group is physically entrapped in the polymeric lens body. For example, when the linking agent comprises a form of boronic acid, the second wetting agent can comprise a form of poly(vinyl alcohol) which becomes bound to the form of boronic acid. Optionally, silicone hydrogel contact lenses of the present disclosure can be understood to be free of linking agents. In one example, the silicone hydrogel contact lenses can be free of boronic acid moieties or groups, including polymerized boronic acid moieties or groups, that is, specifically, the silicone hydrogel contact lenses can be formed from a polymerizable composition free of a form of boronic acid such as, for example, a polymerizable form of boronic acid including vinyl phenyl boronic acid (VPB), can be formed of a polymer free of units derived from a polymerizable form of boronic acid such as vinyl phenyl boronic acid (VPB), and the polymeric lens body and the silicone hydrogel contact lenses can be free of a form of boronic acid, including polymeric or non-polymeric form of boronic acid, physically entrapped therein. Alternatively, the polymerizable composition, or the polymeric lens body, or the silicone hydrogel contact lens, or any combination thereof, can comprise at least one linking agent.
In one example, the silicone hydrogel contact lenses of the present disclosure have not been exposed to a volatile organic solvent or a solution of a volatile organic solvent as part of a manufacturing process. In one example, the silicone hydrogel contact lenses of the present disclosure can be formed from a polymerizable composition free of a wetting agent, or the polymeric lens body and/or hydrated contact lens can be free of a wetting agent, or free of surface treatment, or free of a surface modification, or was not exposed to a volatile organic solvent or a solution of a volatile organic solvent during the manufacturing process, or any combination thereof. Instead, for example, the silicone hydrogel contact lenses can be extracted in water or an aqueous solution free of a volatile organic solvent, such as, for example, free of a volatile lower alcohol.
The use of volatile organic solvents to extract lens bodies contributes significantly to production costs, due to factors such as the cost of the organic solvents, the cost of disposal of the solvents, the need to employ explosion-proof production equipment, the need to remove the solvents from the lenses prior to packaging, and the like. However, development of polymerizable compositions capable of consistently producing contact lenses with ophthalmically acceptably wettable lens surfaces when extracted in aqueous media free of volatile organic solvents can be challenging. For example, it is common to find non-wetting regions present on the lens surfaces of contact lenses which have been extracted in aqueous media free of volatile organic solvents, as discussed herein.
As previously discussed, in one example, the contact lenses disclosed herein are contact lenses which have not been exposed to a volatile organic solvent, such as a lower alcohol, during their manufacture. In other words, the extraction media used for such lenses, as well as all liquids used during wet demolding, or wet delensing, or washing, or any other manufacturing step, are all free of volatile organic solvents. In one example, the polymerizable composition used to form these entirely aqueous media extracted lenses can comprise a hydrophilic vinyl-containing monomer or monomer component, such as, for example, a hydrophilic vinyl ether-containing monomer. The vinyl-containing hydrophilic monomer or monomer component can include, for example, VMA. The vinyl ether-containing monomers can include, for example, BVE, or EGVE, or DEGVE, or any combination thereof. In one particular example, the vinyl ether-containing monomer can be a vinyl ether-containing monomer which is more hydrophilic than BVE, such as, for example, DEGVE. In another example, the hydrophilic monomer component of the polymerizable composition can be a mixture of a first hydrophilic monomer which is a vinyl-containing monomer but which is not a vinyl ether-containing monomer, and a second hydrophilic monomer which is a vinyl ether-containing monomer. Such mixtures include, for example, mixtures of VMA and one or more vinyl ethers such as, for example, BVE, or DEGVE, or EGVE, or any combination thereof.
When present, the hydrophilic vinyl ether-containing monomer or monomer component can be present in the polymerizable composition in an amount from about 1 to about 15 unit parts, or from about 3 to about 10 unit parts. When present as a mixture with a hydrophilic vinyl-containing monomer which is not a vinyl ether, the portion of the hydrophilic vinyl-containing monomer or monomer component which is not a vinyl ether and the hydrophilic vinyl ether-containing monomer or monomer component can be present in the polymerizable composition at a ratio of at least 3:1, or from about 3:1 to about 15:1, or of about 4:1 based on the ratio of the unit parts by weight of the hydrophilic vinyl-containing monomer or monomer component which is not a vinyl ether to the unit parts by weight of the hydrophilic vinyl ether-containing monomer or monomer component.
Another approach for producing contact lenses having ophthalmically acceptably wettable lens surfaces in accordance with the present disclosure, particularly lenses extracted in a liquid media free of a volatile organic solvent, can be to limit the amount of a vinyl-containing cross-linking agent or cross-linking agent component included in the polymerizable composition. For example, a vinyl-containing cross-linking agent or cross-linking agent component can be present in the polymerizable composition in an amount from about 0.01 to about 0.80 unit parts, or from 0.05 to about 0.30 unit parts, or from about 0.05 to about 0.20 unit parts, or in an amount of about 0.1 unit parts. In one example, a vinyl-containing cross-linking agent or cross-linking agent component can be present in the polymerizable composition in an amount effective to produce a contact lens having improved wettability as compared to a contact lens produced from the same polymerizable composition but having an amount of the vinyl-containing cross-linking agent or cross-linking agent component greater than about 2.0 unit parts, or greater than 1.0 unit parts, or greater than about 0.8 unit parts, or greater than about 0.5 unit parts, or greater than about 0.3 unit parts.
Certain specific examples of silicone hydrogel contact lenses will now be described, in accordance with the present teachings.
As one example (example A), a silicone hydrogel contact lens comprises a polymeric lens body that is the reaction product of a polymerizable composition comprising a first monofunctional siloxane monomer, such as the siloxane monomer represented by formula (1), wherein m of formula (1) represents one integer from 3 to 10, n of formula (1) represents one integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 carbon atoms, and each R2 of formula (1) is independently either a hydrogen atom or a methyl group; a second siloxane monomer having more than one polymerizable functional group and that has a number average molecular weight of at least 5,000 daltons; and a hydrophilic amide monomer or monomer component having one N-vinyl group, specifically the hydrophilic monomer comprises or consists of N-vinyl-N-methyl acetamide (VMA), wherein the first siloxane monomer and second siloxane monomer are present in the composition at a ratio of 2:1 based on unit parts by weight. This example of a silicone hydrogel contact lens of the present disclosure is a silicone hydrogel contact lenses, comprising: a lens body that is the reaction product of a polymerizable composition that comprises at least one siloxane monomer represented by formula (1), wherein m of formula (1) represents one integer from 3 to 10, n of formula (1) represents one integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 carbon atoms, and each R2 of formula (1) is independently either a hydrogen atom or a methyl group; a second siloxane monomer having more than one polymerizable functional group and that has a number average molecular weight of at least 5,000 daltons; and a hydrophilic amide monomer or monomer component having one N-vinyl group, at least one hydrophobic monomer, and at least one cross-linking agent; wherein the first siloxane monomer and second siloxane monomer are present in the composition at a ratio of 2:1 based on unit parts by weight, the lens body is washed to remove extractable material from the lens body, and is hydrated with an aqueous liquid, and the hydrated lens body has a lens surface wettability characterized by an advancing contact angle less than 120 degrees, and the hydrated lens body has a diameter that is at least 24% larger than the diameter of the lens body prior to washing. Another example of a silicone hydrogel contact lens of the present disclosure is a silicone hydrogel contact lenses, comprising: a lens body that is the reaction product of a polymerizable composition that comprises at least one siloxane monomer represented by formula (1), wherein m of formula (1) represents one integer from 3 to 10, n of formula (1) represents one integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 carbon atoms, and each R2 of formula (1) is independently either a hydrogen atom or a methyl group; a second siloxane monomer having more than one polymerizable functional group and that has a number average molecular weight of at least 5,000 daltons; N-vinyl-N-methyl acetamide (VMA), at least one hydrophobic monomer, and at least one cross-linking agent; wherein the first siloxane monomer and second siloxane monomer are present in the composition at a ratio of 2:1 based on unit parts by weight, the lens body is washed to remove extractable material from the lens body, and is hydrated with an aqueous liquid, and the hydrated lens body has a lens surface wettability characterized by an advancing contact angle less than 120 degrees, and the hydrated lens body has a diameter that is at least 24% larger than the diameter of the lens body prior to washing.
As a second example (example B), a silicone hydrogel contact lens comprises a polymeric lens body that is the reaction product of a polymerizable composition as described in example A, and wherein the polymerizable composition further comprises a hydrophobic monomer or monomer component, specifically the hydrophilic monomer comprises or consists of methyl methacrylate (MMA). This example of a silicone hydrogel contact lens of the present disclosure is a silicone hydrogel contact lenses, comprising: a lens body that is the reaction product of a polymerizable composition that comprises at least one siloxane monomer represented by formula (1), wherein m of formula (1) represents one integer from 3 to 10, n of formula (1) represents one integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 carbon atoms, and each R2 of formula (1) is independently either a hydrogen atom or a methyl group; a second siloxane monomer having more than one polymerizable functional group and that has a number average molecular weight of at least 5,000 daltons; and a hydrophilic amide monomer or monomer component having one N-vinyl group, methyl methacrylate (MMA), and at least one cross-linking agent; wherein the first siloxane monomer and second siloxane monomer are present in the composition at a ratio of 2:1 based on unit parts by weight, the lens body is washed to remove extractable material from the lens body, and is hydrated with an aqueous liquid, and the hydrated lens body has a lens surface wettability characterized by an advancing contact angle less than 120 degrees, and the hydrated lens body has a diameter that is at least 24% larger than the diameter of the lens body prior to washing. Another example of a silicone hydrogel contact lens of the present disclosure is a silicone hydrogel contact lenses, comprising: a lens body that is the reaction product of a polymerizable composition that comprises at least one siloxane monomer represented by formula (1), wherein m of formula (1) represents one integer from 3 to 10, n of formula (1) represents one integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 carbon atoms, and each R2 of formula (1) is independently either a hydrogen atom or a methyl group; a second siloxane monomer having more than one polymerizable functional group and that has a number average molecular weight of at least 5,000 daltons; N-vinyl-N-methyl acetamide (VMA), methyl methacrylate (MMA), and at least one cross-linking agent; wherein the first siloxane monomer and second siloxane monomer are present in the composition at a ratio of 2:1 based on unit parts by weight, the lens body is washed to remove extractable material from the lens body, and is hydrated with an aqueous liquid, and the hydrated lens body has a lens surface wettability characterized by an advancing contact angle less than 120 degrees, and the hydrated lens body has a diameter that is at least 24% larger than the diameter of the lens body prior to washing.
As a third example (example C), a silicone hydrogel contact lens comprises a polymeric lens body that is the reaction product of a polymerizable composition as described in example A or B, and wherein the polymerizable composition further comprises a vinyl ether-containing cross-linking agent or cross-linking agent component, specifically the cross-linking agent or cross-linking agent component comprises or consists of triethylene glycol divinyl ether (TEGVE). This example of a silicone hydrogel contact lens of the present disclosure is a silicone hydrogel contact lenses, comprising: a lens body that is the reaction product of a polymerizable composition that comprises at least one siloxane monomer represented by formula (1), wherein m of formula (1) represents one integer from 3 to 10, n of formula (1) represents one integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 carbon atoms, and each R2 of formula (1) is independently either a hydrogen atom or a methyl group; a second siloxane monomer having more than one polymerizable functional group and that has a number average molecular weight of at least 5,000 daltons; and a hydrophilic amide monomer or monomer component having one N-vinyl group, at least one hydrophobic monomer, and at least one vinyl-containing cross-linking agent; wherein the first siloxane monomer and second siloxane monomer are present in the composition at a ratio of 2:1 based on unit parts by weight, the lens body is washed to remove extractable material from the lens body, and is hydrated with an aqueous liquid, and the hydrated lens body has a lens surface wettability characterized by an advancing contact angle less than 120 degrees, and the hydrated lens body has a diameter that is at least 24% larger than the diameter of the lens body prior to washing. Another example of a silicone hydrogel contact lens of the present disclosure is a silicone hydrogel contact lenses, comprising: a lens body that is the reaction product of a polymerizable composition that comprises at least one siloxane monomer represented by formula (1), wherein m of formula (1) represents one integer from 3 to 10, n of formula (1) represents one integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 carbon atoms, and each R2 of formula (1) is independently either a hydrogen atom or a methyl group; a second siloxane monomer having more than one polymerizable functional group and that has a number average molecular weight of at least 5,000 daltons; N-vinyl-N-methyl acetamide (VMA), at least one hydrophobic monomer, and at least one vinyl-containing cross-linking agent; wherein the first siloxane monomer and second siloxane monomer are present in the composition at a ratio of 2:1 based on unit parts by weight, the lens body is washed to remove extractable material from the lens body, and is hydrated with an aqueous liquid, and the hydrated lens body has a lens surface wettability characterized by an advancing contact angle less than 120 degrees, and the hydrated lens body has a diameter that is at least 24% larger than the diameter of the lens body prior to washing.
As a fourth example (example D), a silicone hydrogel contact lens comprises a polymeric lens body that is the reaction product of a polymerizable composition as described in example A or B or C, and wherein the polymerizable composition further comprises a thermal initiator or thermal initiator component.
As a fifth example (example E), a silicone hydrogel contact lens comprises a polymeric lens body that is the reaction product of a polymerizable composition as described in example A or B or C or D, and wherein the polymerizable composition further comprises an oxygen scavenger or oxygen scavenger component.
As a sixth example (example F), a silicone hydrogel contact lens comprises a polymeric lens body that is the reaction product of a polymerizable composition as described in example A or B or C or D or E, and wherein the polymerizable composition further comprises a UV blocker or UV blocker component.
As a seventh example (example G), a silicone hydrogel contact lens comprises a polymeric lens body that is the reaction product of a polymerizable composition as described in example A or B or C or D or E or F, and wherein the polymerizable composition further comprises a tinting agent or tinting agent component.
As an eighth example (example H), a silicone hydrogel contact lens comprises a polymeric lens body that is the reaction product of a polymerizable composition as described in example A or B or C or D or E or F or G, and wherein the second siloxane monomer is represented by formula (2), wherein R1 of formula (2) is selected from either hydrogen atom or a methyl group; R2 of formula (2) is selected from either of hydrogen or a hydrocarbon group having 1 to 4 carbon atoms; m of formula (2) represents an integer of from 0 to 10; n of formula (2) represents an integer of from 4 to 100; a and b represent integers of 1 or more; a+b is equal to 20-500; b/(a+b) is equal to 0.01-0.22; and the configuration of siloxane units includes a random configuration. As one example, the second siloxane monomer can be represented by formula (2), wherein m of formula (2) is 0, n of formula (2) is one integer from 5 to 10, a is one integer from 65 to 90, b is one integer from 1 to 10, R1 of formula (2) is a methyl group, and R2 of formula (2) is either a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.
As a ninth example (example I), a silicone hydrogel contact lens comprises a polymeric lens body that is the reaction product of a polymerizable composition as described in example A or B or C or D or E or F or G or H, and wherein the polymerizable composition further comprises a methacrylate-containing cross-linking agent or cross-linking agent component, specifically the cross-linking agent or agent component comprises or consists of ethylene glycol dimethacrylate (EGDMA). In this example, when the polymerizable composition also comprises a vinyl ether-containing cross-linking agent as part of the cross-linking agent component, specifically the cross-linking agent component can comprise or consist of triethylene glycol divinyl ether (TGDVE) in combination with a methacrylate-containing cross-linking agent, which can specifically comprise or consist of ethylene glycol dimethacrylate (EGDMA). In this example, it can be appreciated that the polymerizable composition comprises two cross-linking agents, each having different reactivity ratios, i.e., the polymerizable composition comprises a cross-linking agent component comprising or consisting of a vinyl-containing cross-linking agent and a methacrylate-containing cross-linking agent, the methacrylate-containing cross-linking agent having polymerizable functional groups which are more reactive and which thus react at a faster rate than the vinyl polymerizable functional groups present in the vinyl-containing cross-linking agent.
As a tenth example (example J), a silicone hydrogel contact lens comprises a polymeric lens body that is the reaction product of a polymerizable composition as described in example A or B or C or D or E or F or G or H or I, and wherein the polymerizable composition further comprises a chain transfer agent or chain transfer agent component which can specifically comprise or consist of allyloxy ethanol (AE).
As an eleventh example (example K), a silicone hydrogel contact lens comprises a polymeric lens body that is the reaction product of a polymerizable composition as described in example A or B or C or D or E or F or G or H or I or J, and wherein the polymerizable composition further comprises a hydrophobic monomer or hydrophobic monomer component which can specifically comprise or consist of ethylene glycol methyl ether methacrylate (EGMA).
As a twelfth example (example L), a silicone hydrogel contact lens comprises a polymeric lens body that is the reaction product of a polymerizable composition as described in example A or B or C or D or E or F or G or H or I or J or K, and wherein the polymerizable composition further comprises a hydrophilic vinyl ether-containing monomer or monomer component, for example, the hydrophilic vinyl ether-containing monomer or monomer component can comprise or consist of 1,4-butanediol vinyl ether (BVE), or ethylene glycol vinyl ether (EGVE), or diethylene glycol vinyl ether (DEGVE), or any combination thereof.
In any or each of the foregoing examples A-L, as well as any or all other examples disclosed herein, the amount of the first siloxane monomer can be from 20 to 45 unit parts of the polymerizable composition. The amount of the first siloxane monomer can be from 25 to 40 unit parts of the polymerizable composition. The amount of the first siloxane monomer can be from 27 to 35 unit parts of the polymerizable composition.
In any or each of the foregoing examples A-L, as well as any or all other examples disclosed herein, the amount of the second siloxane monomer can be from 1 to 20 unit parts of the polymerizable composition, as long as the ratio of 2:1 based on unit parts by weight of the first siloxane to the second siloxane is maintained. The amount of the second siloxane monomer can be from 2 to 15 unit parts of the polymerizable composition. The amount of the second siloxane monomer can be from 5 to 13 unit parts of the polymerizable composition.
In any or each of the foregoing examples A-L, as well as any or all other examples disclosed herein, the amount of the hydrophilic monomer or monomer component present in the polymerizable composition can be from 1 to 60 unit parts of the polymerizable composition. The hydrophilic monomer component can constitute from 4 to 60 unit parts of the polymerizable composition. When the hydrophilic monomer comprises or consists of the VMA, it can be present in an amount from 30 unit parts to 60 unit parts. VMA can be present in the polymerizable composition in an amount from about 40 unit parts to about 50 unit parts. When the hydrophilic monomers, N,N-dimethylacrylamide (DMA), 2-hydroxyethyl methacrylate (HEMA), or 2-hydroxylbutyl methacrylate (HOB), or any combination thereof are present in the polymerizable composition as the hydrophilic monomer in the hydrophilic monomer component, each or all can be present in amounts from about 3 to about 10 unit parts.
In any or each of the foregoing examples A-L as well as any or all other examples disclosed herein, the amount of the hydrophobic monomer or monomer component present in the polymerizable composition can be from 1 to 30 unit parts of the polymerizable composition. For example, the total amount of hydrophobic monomer or monomer component can be from about 5 to about 20 unit parts of the polymerizable composition. In polymerizable compositions in which the hydrophobic monomer MMA is present as the hydrophobic monomer or as part of the hydrophobic monomer component, the MMA can be present in an amount from about 5 to about 20 unit parts, or from about 8 to about 15 unit parts.
In any or each of the foregoing examples A-L, as well as any or all other examples disclosed herein, the amount of the cross-linking agent or cross-linking agent component present in the polymerizable composition can be from 0.01 to 4 unit parts of the polymerizable composition. TEGDVE can be present in amounts from 0.01 to 1.0 unit parts. EGDMA can be present in amounts from 0.01 to 1.0 unit parts. TEGDMA can be present in amounts from 0.1 to 2.0 unit parts. Each of these non-silicon cross-linking agents can be present alone or in any combination in the polymerizable composition.
In any or each of the foregoing examples A-L, as well as any or all other examples disclosed herein, when the polymerizable composition contains EGMA, BVE, DEGVE, EGVE, or any combination thereof, they are each present in amounts from 1 unit part to 20 unit parts of the polymerizable composition. EGMA can be present in an amount from about 2 unit parts to about 15 unit parts. BVE can be present in an amount from 1 unit part to about 15 unit parts. BVE can be present in an amount from about 3 unit parts to about 7 unit parts. DEGVE can be present in an amount from 1 unit part to about 15 unit parts. DEGVE can be present in an amount from about 7 unit parts to about 10 unit parts. EGVE can be present in an amount from 1 unit part to about 15 unit parts, or in an amount from about 3 unit parts to about 7 unit parts.
In any or each of the foregoing examples A-L, as well as any or all other examples disclosed herein, the other optional components, such as initiators or initiator component, tinting agents or tinting agent components, UV absorbing agents or UV absorbing agent components, oxygen scavengers or oxygen scavenger components, or chain transfer agents or chain transfer agent components, can each be present in amounts from about 0.01 unit parts to about 3 unit parts. An initiator or initiator component can be present in the polymerizable in an amount from 0.1 unit parts to 1.0 unit parts. When a thermal initiator or thermal initiator component is present, such as Vazo-64, it can be present in an amount from about 0.3 to about 0.5 unit parts. Tinting agents or tinting agent components can be present in amounts from 0.01 unit parts to 1 unit part. When reactive dyes are used as tinting agents or as part of a tinting agent component, such as Reactive Blue 246 or Reactive Blue 247, they can each be present in amounts of about 0.01 unit parts. UV absorbing agents or UV absorbing agent components can be present in amounts from 0.1 unit parts to 2.0 unit parts. For example, the UV absorbing agent UV1 described in the Examples below can be present in an amount from about 0.8 to about 1.0 unit parts, such as 0.9 unit parts; or the UV absorbing agent UV2 described in the Examples below, can be present in an amount from 0.5 unit parts to 2.5 unit parts, such as from about 0.9 unit parts to about 2.1 unit parts. Oxygen scavengers or oxygen scavenger components can be present in amounts from 0.1 unit parts to 1.0 unit parts. As an example, when triphenyl phosphine (TPP) or diphenyl(P-vinylphenyl)phosphine (pTPP) or any combination thereof is used as an oxygen scavenger or oxygen scavenger component in the polymerizable composition, each or the combination can be present in an amount from 0.3 unit parts to 0.7 unit parts, such as about 0.5 unit parts. Chain transfer reagents or chain transfer reagent components can be present in the polymerizable composition in an amount from 0.1 unit parts to 2.0 unit parts, and in many of the Examples below is present in an amount from 0.2 unit parts to 1.6 unit parts. For example, the chain transfer reagent allyloxy ethanol (AE) can be present in an amount from about 0.3 to about 1.4 unit parts.
In any or each of the foregoing examples A-L, as well as any or all other examples disclosed herein, the silicone hydrogel contact lenses can be free of a wetting agent that is present in the polymerizable composition, or in the polymeric lens body, or in the silicone hydrogel contact lens. Similarly, the silicone hydrogel contact lens can have lens surfaces that are free of a surface treatment or a surface modification. However, in another example, the silicone hydrogel contact lens can include at least one wetting agent (i.e., a single wetting agent or two or more wetting agents present as a wetting agent component) in the polymerizable composition, in the polymeric lens body, or in the silicone hydrogel contact lens. The silicone hydrogel contact lens can have treated or modified lens surfaces. In addition or alternatively, any or each of the foregoing examples A-L, as well as any or all other examples of silicone hydrogel contact lenses disclosed herein, the contact lenses can be understood to be free of a linking agent such as, for example, a form of boronic acid.
In another example, new polymerizable compositions are provided, including each and every polymerizable composition described herein in reference to the silicone hydrogel contact lenses and methods. The polymerizable compositions can be diluent-free in that they do not contain an organic solvent, such as alcohols and the like, which can help reduce phase separation of the polymerizable composition. However, such diluent-free polymerizable compositions can still contain one or more chain transfer agents, such as allyloxy ethanol. However, if desired, the polymerizable composition can include a diluent or a diluent component, which can be present in an amount from 1 to 20 unit parts.
As described herein, the present silicone hydrogel contact lenses which comprise polymeric lens bodies that comprise units derived from a first siloxane monomer represented by formula (1) and a second siloxane monomer having more than one polymerizable functional group and having a number average molecular weight of at least 3,000 daltons, such as those represented by formulas (2), (3), or (4), are dimensionally stable. The present disclosure also relates to a batch of silicone hydrogel contact lenses.
As used herein, a batch of silicone hydrogel contact lenses refers to a group of twenty or more silicone hydrogel contact lenses, and frequently, a batch refers to at least 20, or at least 100, or at least 1,000 silicone hydrogel contact lenses. In accordance with the present disclosure, a batch of silicone hydrogel contact lenses comprises at least 20 of any of the silicone hydrogel contact lenses described herein.
When initially tested shortly after manufacturing and then tested again at a later time point, a batch of lenses can exhibit a change in its average physical dimensions. As batches of lenses in accordance with the present disclosure are dimensionally stable, they can exhibit an acceptable level of change in their average physical dimensions. As used herein, dimensional stability variance is understood to refer to a variance in a value of a physical dimension between a value of the physical dimension determined when the batch of lenses is initially tested shortly after its manufacture, and the value of the physical dimension determined when the batch of lenses is tested again at a later time point. The later time point can be, for example, from at least 2 weeks after the initial time point, to up to 7 years after the initial time point. The silicone hydrogel contact lenses of the batch have an average dimensional stability variance of less than plus or minus three percent (±3.0%) based on averaging the lens diameter measurements of a representative number of lenses from the batch, such as, for example, 20 lenses from the batch. For a batch of lenses, an average dimensional stability variance of less than plus or minus three percent (±3.0%), where the average dimensional stability variance is the variance in a value of a physical dimension when measured at an initial time point within one day of a manufacturing date of the batch of lenses, and at a second time point, where the second time point is from two weeks to seven years after the initial time point when the batch is stored at room temperature, or, when the batch is stored at a higher temperature (i.e., under accelerated shelf life testing conditions), the second time point is a time point representative of storage of the batch from two weeks to seven years at room temperature, is considered to be a dimensionally stable batch. In one example, accelerated shelf life testing conditions which are especially useful in determining average dimensional stability variance are for 4 weeks at 70 degrees C., although other periods of time and other temperatures can be used. The average dimensional stability variance is determined by averaging the individual dimensional stability variances for each of the representative lenses using the actual diameters of representative lenses measured initially (DiameterOriginal) and the actual diameters of representative lenses measured following (DiameterFinal) storage at room temperature or under accelerated shelf life conditions. The representative lenses measured initially and the representative lenses measured following storage can be the same lenses or can be different lenses. As used herein, the average dimensional stability variance is represented as a percent (%). The individual dimensional stability variances are determined using the following equation (A):

((DiameterFinal−DiameterOriginal)/DiameterOriginal)×100  (A).

On average, the diameters of the silicone hydrogel contact lenses of the batch vary by less than three percent in either direction of a target value (±3.0%). As one example, if a contact lens has a target diameter (chord diameter) of 14.20 mm, the present batch of silicone hydrogel contact lenses will have an average diameter (average of the population in the batch) from 13.77 mm to 14.63 mm. In one example, the dimensional stability variance is less than plus or minus two percent (±2.0%). As one example, if a contact lens has a target diameter (chord diameter) of 14.20 mm, the present batch of silicone hydrogel contact lenses will have an average diameter (average of the population in the batch) from 13.92 mm to 14.48 mm. Preferably, the average diameter of the batch of silicone hydrogel contact lenses does not vary by more than plus or minus 0.20 mm from the target diameter, which is commonly from 13.00 mm to 15.00 mm.
In accelerated shelf life studies, the average dimensional stability variance can be determined for contact lenses that were stored for a period of time at an elevated temperature, such as above 40 degrees C., including, for example, 50 degrees C., or 55 degrees C., or 65 degrees C., or 70 degrees C., or 80 degrees C., or 95 degrees C., and the like. Or, the average dimensional stability can be determined for contact lenses that were stored for a period of time at room temperature (e.g., about 20-25 degrees C.).
For accelerated shelf life studies, the following formula can be used to determine the number of months of storage at a particular temperature that are equivalent to storage for a desired length of time at room temperature:

Desired shelf life=[N×2y]+n  (B)

    
    
        where
        N=number of months of storage under accelerated conditions
        2y=acceleration factor
        y=(test temperature−25° C.)/10° C.
        n=age of lenses (in months) at start of the study.
    
    


Based on this equation, the following storage times have been calculated: 6 months of storage at 35 degrees C. is equivalent to 1 year aging at 25 degrees C., 3 months of storage at 45 degrees C. is equivalent to 1 year of aging at 25 degrees C., 3 months of storage at 55 degrees C. is equivalent to 2 years of aging at 25 degrees C., and 3 months of storage at 65 degrees C. is equivalent to 4 years of aging at 25 degrees C.
As discussed herein, the present disclosure also provides methods of manufacturing silicone hydrogel contact lenses. In accordance with the present teachings, some of the present methods comprise providing a polymerizable composition. In some examples of the present methods, the polymerizable composition, or contact lens formulation, comprises a first siloxane monomer represented by formula (1):




wherein m of formula (1) represents one integer from 3 to 10, n of formula (1) represents one integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 carbon atoms, and each R2 of formula (1) is independently either a hydrogen atom or a methyl group. The polymerizable composition also comprises a second siloxane monomer having more than one polymerizable functional group and having a number average molecular weight of at least 3,000 daltons. The first siloxane monomer and the second siloxane monomer are present in the polymerizable composition at a ratio of at least 2:1 based on unit parts. The polymerizable composition also comprises at least one hydrophilic monomer, or at least one hydrophobic monomer, or at least one cross-linking agent, or any combination thereof.

The method can also comprise a step of polymerizing the polymerizable composition to form a polymeric contact lens body. The step of polymerizing the polymerizable composition can be conducted in a contact lens mold assembly. The polymerizable composition can be cast molded between molds formed of a thermoplastic polymer. The thermoplastic polymer used to form the molding surfaces of the mold can comprise a polar polymer, or can comprise a non-polar polymer. Alternatively, the polymerizable composition can be formed into a lens via various methods known to those of ordinary skill in the art, such as spin casting, injection molding, forming a polymerized rod that is subsequently lathed to form a lens body, etc.
The method also comprises contacting the polymeric lens body with an aqueous washing liquid to remove extractable material, such as unreacted monomers, uncross-linked materials that are otherwise not physically immobilized in the polymeric contact lens body, diluents, and the like.
In accordance with the present disclosure, the polymeric contact lens body can be packaged along with a contact lens packaging solution in a contact lens package, such as a blister pack or glass vial. Following packaging, the package can be sealed and the polymeric contact lens body and the contact lens packaging solution can be sterilized, for example, by autoclaving the sealed package, to produce a silicone hydrogel contact lens product.
In the present methods, the step of contacting the polymeric contact lens body with a washing liquid can be understood to be an extraction step because extractable materials can be removed from the polymeric contact lens body during the process. In the present methods, the contacting step comprises contacting the polymeric contact lens body with an aqueous washing liquid that is free of a volatile organic solvent. Such methods may be understood to be entirely aqueous washing steps, as no volatile organic solvents are included in the washing liquid. Water-based washing liquids that can be used in such methods include water, such as deionized water, saline solutions, buffered solutions, or aqueous solutions containing surfactants or other non-volatile ingredients that can improve the removal of hydrophobic components from the polymeric contact lens bodies, or can reduce distortion of the polymeric contact lens bodies, compared to the use of deionized water alone.
After washing, the contact lenses can be placed in packages, such as plastic blister packs, with a packaging solution, such as a buffered saline solution, which may or may not contain surfactants, anti-inflammatory agents, anti-microbial agents, contact lens wetting agents, and the like, and can be sealed and sterilized.
EXAMPLES
The following Examples illustrate certain aspects and advantages of the present invention, which should be understood not to be limited thereby.
As can be readily determined by a review of the Examples below, all of the Example formulations are free of an organic diluent. Also, all of the Example formulations are free of N,N-dimethylacrylamide (DMA). Additionally, all of the Example formulations below are free of a polymeric wetting agent. Furthermore, all of the Example formulations comprise at least one hydrophilic amide monomer having one N-vinyl group. A majority of the Example formulations comprise a second siloxane which is a dual-end methacrylate end-capped polydimethylsiloxane having a number average molecular weight of at least 5,000 daltons.
The following chemicals are referred to in Examples C1 and 1-25, and may be referred to by their abbreviations.
Si1: 2-propenoic acid, 2-methyl-, 2-[3-(9-butyl-1,1,3,3,5,5,7,7,9,9-decamethylpentasiloxane-1-yl)propoxy]ethyl ester (CAS number of 1052075-57-6). (Si1 was obtained from Shin-Etsu Chemical Co., Ltd., Tokyo, Japan, as product number X-22-1622).
Si2: α,ω-Bis (methacryloxypropyl)-poly(dimethyl siloxane)-poly(co-methoxy-poly(ethylenegylcol)propylmethylsiloxane) (the synthesis of this compound can be performed as described in US20090234089, which is incorporated herein by reference)
Si3: Poly(dimethyl siloxane), methacryloxypropyl terminated (CAS number 58130-03-3; DMS-R18 available from Gelest)
VMA: N-vinyl-N-methylacetamide (CAS number 003195786)
DMA: N,N-dimethylacrylamide (CAS number 2680-03-7)
HEMA: 2-hydroxyethyl methacrylate (CAS number 868-77-9)
HOB: 2-hydroxylbutyl methacrylate (CAS number 29008-35-3)
EGMA: Ethylene glycol methyl ether methacrylate (CAS number 6976-93-8)
MMA: Methyl methacrylate (CAS number 80-62-6)
EGDMA: Ethylene glycol dimethacrylate (CAS number 97-90-5)
TEGDMA: triethylene glycol dimethacrylate (CAS number 109-16-0)
BVE: 1,4-butanediol vinyl ether (CAS number 17832-28-9)
DEGVE: diethylene glycol vinyl ether (CAS number 929-37-3)
EGVE: ethylene glycol vinyl ether (CAS number 764-48-7)
TEGDVE: triethylene glycol divinyl ether (CAS number 765-12-8)
AE: 2-Allyloxy ethanol (CAS number 111-45-5)
V-64: 2,2′-Azobis-2-methyl propanenitrile (CAS number 78-67-1)
UV1: 2-(4-benzoyl-3-hydroxyphenoxy)ethyl acrylate (CAS number 16432-81-8)
UV2: 2-(3-(2H-benzotriazol-2-YL)-4-hydroxy-phenyl)ethyl methacrylate (CAS number 96478-09-0)
RBT1: 1,4-Bis[4-(2-methacryloxyethyl)phenylamino]anthroquinone (CAS number 121888-69-5)
RBT2: 1,4-Bis[(2-hydroxyethyl)amino]-9,10-anthracenedione bis(2-propenoic)ester (CAS Reg. No. 109561071)
TPP: Triphenyl phosphine (CAS number 603-35-0)
pTPP: polymerizable TPP: diphenyl(P-vinylphenyl)phosphine (CAS number 40538-11-2)
Silicone Hydrogel Contact Lens Fabrication and Testing Procedure
The chemical compounds set forth in Examples were, for each example, weighed out in amounts corresponding to the described unit parts, and combined to form a mixture. The mixture was filtered through a 0.2-5.0 micron syringe filter into a bottle. Mixtures were stored for up to about 2 weeks. The mixtures are understood to be polymerizable silicone hydrogel contact lens precursor compositions, or as used herein, polymerizable compositions. In the Examples, the listed amounts of ingredients are given as unit parts of the polymerizable composition by weight.
A volume of the polymerizable composition was cast molded by placing the composition in contact with a lens defining surface of a female mold member. In all of the following Examples, the molding surface of the female mold member was formed of a non-polar resin, specifically polypropylene, although polar resins, such as PBT could also be used. A male mold member was placed in contact with the female mold member to form a contact lens mold assembly comprising a contact lens shaped cavity containing the polymerizable composition. In the following Examples, the molding surface of the male mold member was formed of a non-polar resin, specifically polypropylene.
Contact lens mold assemblies were placed in a nitrogen flushed oven to allow the precursor compositions to thermally cure. For all of the Examples, the contact lens mold assemblies were exposed to temperatures of at least about 55° C. for about 2 hours. Examples of curing profiles which can be used to cure silicone hydrogel contact lenses described herein include exposing the contact lens mold assemblies to temperatures of 55° C. for 40 minutes, 80° C. for 40 minutes, and 100° C. for 40 minutes. Other contact lenses can be made with the same curing profile, but instead of the first temperature being at 55° C., it can be at 65° C.
After polymerizing the polymerizable compositions, the contact lens mold assemblies were demolded to separate the male and female mold members. The polymerized contact lens body remained adhered to the male mold or the female mold. A dry demolding process where the mold assembly is not contacted with a liquid medium can be used, or a wet demolding process where the mold assembly is contacted with a liquid medium such as, for example, water or an aqueous solution, can be used. A mechanical dry demolding process can involve applying mechanical force to a portion of one or both of the mold members in order to separate the mold members. In all of the following Examples, a dry demolding process was used.
The polymerized contact lens body was then delensed from the male mold or female mold to produce a delensed polymerized contact lens body. In one example of a delensing method, the polymerized contact lens body can be delensed from the male mold member using a dry delensing process, such as by manually peeling the lens from the male mold member or by compressing the male mold member and directing a gas toward the male mold member and the polymerized contact lens body, and lifting the dry polymerized contact lens body with a vacuum device from the male mold member, which is discarded. In other methods, the polymerized contact lens body can be delensed using a wet delensing process by contacting the dry polymerized contact lens body with a liquid releasing medium, such as water or an aqueous solution. For example, a male mold member with the attached polymerized contact lens body can be dipped into a receptacle containing a liquid until the polymerized contact lens body separates from the male mold member. Or, a volume of liquid releasing medium can be added to the female mold to soak the polymerized contact lens body in the liquid and to separate the lens body from the female mold member. In the following Examples, a dry delensing process was used. Following separation, the lens body can be lifted from the mold member manually using tweezers or using a vacuum device and placed into a tray.
The delensed lens product was then washed to remove extractable materials from the polymerized contact lens body, and hydrated. Extractable materials included polymerizable components such as, for example, monomers, or cross-linking agents, or any optional polymerizable ingredients such as tints or UV blockers, or combinations thereof, present in the polymerizable composition which remain present in the polymeric lens body in an unreacted form, in a partially reacted form, or in an uncross-linked form, or any combination thereof, following polymerization of the lens body and prior to extraction of the lens body. Extractable materials may have also included any non-polymerizable ingredients present in the polymerizable composition, for example, any optional non-polymerizable tinting agents, or UV blockers, or diluents, or chain transfer agent, or any combination thereof, remaining present in the polymeric lens body following polymerization of the polymeric lens body but prior to extraction of the polymeric lens body.
In another method, such as a method involving delensing by compression of the male mold member and directing gas flow toward the male mold member, the delensed polymerized contact lens bodies can be placed in cavities of lens carriers or trays where the delensed polymeric lens bodies can then be contacted with one or more volumes of an extraction media, such as an aqueous extraction media free of a volatile organic solvent, for example deionized water or an aqueous solution of a surfactant such as Tween 80.
In other methods, such as those involving wet delensing by contacting the mold and lens with a liquid releasing medium, the delensed polymerized contact lens bodies can be washed to remove extractable components from the lens bodies using a washing liquid that is free of a volatile organic solvent, such as a lower alcohol, for example, methanol, ethanol, or any combination thereof. For example, the delensed polymerized contact lens bodies can be washed to remove extractable components from the lens bodies by contacting the lens bodies with aqueous washing media free of a volatile organic solvent, such as, for example, deionized water, or a surfactant solution, or a saline solution, or a buffer solution, or any combination thereof. The washing can take place in the final contact lens package, or can take place a in washing tray or a washing tank.
In the following Examples, following the dry demolding and dry delensing steps, the dry delensed lens bodies were placed in cavities of trays, and the delensed polymeric lens bodies were extracted and hydrated by contacting the polymeric lens bodies with one or more volumes of extraction media. The extraction and hydration media used in the extraction and hydration process consisted of volatile organic solvent-free extraction and hydration media, i.e., entirely aqueous-based extraction and hydration media. Specifically, in the Examples below, the extraction and hydration process used comprised at least three extraction and hydration steps in separate portions of a solution of Tween 80 in deionized water, wherein the temperature of the Tween 80 solution of the portions ranged from room temperature to about 90 degrees C., and wherein each extraction and hydration step lasted from about 15 minutes to about 3 hours.
Washed, extracted and hydrated lenses were then placed individually in contact lens blister packages with a phosphate buffered saline packaging solution. The blister packages were sealed and sterilized by autoclaving.
Following sterilization, lens properties such as contact angle, including dynamic and static contact angle, oxygen permeability, ionoflux, modulus, elongation, tensile strength, water content, and the like were determined, as described herein.
For the present contact lenses, contact angles including dynamic and static contact angles, can be determined using routine methods known to persons of ordinary skill in the art. For example, the advancing contact angle and receding contact angle of the contact lenses provided herein can be measured using a conventional drop shape method, such as the sessile drop method or captive bubble method.
In the following Examples, the advancing and receding contact angle of silicone hydrogel contact lenses was determined using a Kruss DSA 100 instrument (Kruss GmbH, Hamburg), and as described in D. A. Brandreth: “Dynamic contact angles and contact angle hysteresis”, Journal of Colloid and Interface Science, vol. 62, 1977, pp. 205-212 and R. Knapikowski, M. Kudra: Kontaktwinkelmessungen nach dem Wilhelmy-Prinzip-Ein statistischer Ansatz zur Fehierbeurteilung”, Chem. Technik, vol. 45, 1993, pp. 179-185, and U.S. Pat. No. 6,436,481, all of which are incorporated by reference herein.
As an example, the advancing contact angle and receding contact angle was be determined using a captive bubble method using phosphate buffered saline (PBS; pH=7.2). The lens was flattened onto a quartz surface and rehydrated with PBS for at least 10 minutes before testing. An air bubble was placed onto a lens surface using an automated syringe system. The size of the air bubble was increased and decreased to obtain the receding angle (the plateau obtained when increasing the bubble size) and the advancing angle (the plateau obtained when decreasing the bubble size).
The modulus, elongation, and tensile strength values of the present lenses can be determined using routine methods known to persons of ordinary skill in the art, such as, for example, a test method in accordance with ANSI Z80.20. The modulus, elongation, and tensile strength values reported herein were determined by using an Instron Model 3342 or 3343 mechanical testing system (Instron Corporation, Norwood, Mass., USA) and Bluehill Materials Testing Software, using a custom built rectangular contact lens cutting die to prepare the rectangular sample strip. The modulus, elongation and tensile strength were determined inside a chamber having a relative humidity of least 70%. The lens to be tested was soaked in phosphate buffered solution (PBS) for at least 10 minutes prior to testing. While holding the lens concave side up, a central strip of the lens was cut using the cutting die. The thickness of the strip was determined using a calibrated gauge (Rehder electronic thickness gauge, Rehder Development Company, Castro Valley, Calif., USA). Using tweezers, the strip was loaded into the grips of the calibrated Instron apparatus, with the strip fitting over at least 75% of the grip surface of each grip. A test method designed to determine the maximum load (N), the tensile strength (MPa), the strain at maximum load (% elongation) and the mean and standard deviation of the tensile modulus (MPa) was run, and the results were recorded.
The percent energy loss of the present silicone hydrogel contact lenses can be determined using routine methods known to persons of ordinary skill in the art. For the following Examples, the percent energy loss was determined using an Instron Model 3343 (Instron Corporation, Norwood, Mass., USA) mechanical testing system, with a 10N force transducer (Instron model no. 2519-101) and Bluehill Materials Testing Software including a TestProfiler module. The energy loss was determined inside a chamber having a relative humidity of least 70%. Before testing, each lens was soaked in phosphate buffered solution (PBS) for at least 10 minutes. Using tweezers, the lens was loaded into the grips of the calibrated Instron apparatus, with the lens loaded vertically between the grips as symmetrically as possible so that the lens fit over at least 75% of the grip surface of each grip. A test designed to determine the energy required to stretch the lens to 100% strain and then return it to 0% strain at a rate of 50 mm/minute was then run on the lens. The test was conducted only once on a single lens. Once the test was finished, energy loss was calculated using the following equation: Lost Energy (%)=(Energy to 100% strain−Energy to return to 0% strain)/Energy to 100% strain×100%.
The ionoflux of the present lenses can be determined using routine methods known to persons of ordinary skill in the art. For the lenses of the following Examples, the ionoflux was measured using a technique substantially similar to the “Ionoflux Technique” described in U.S. Pat. No. 5,849,811, which is incorporated by reference herein. Prior to measurement, a hydrated lens was equilibrated in deionized water for at least 10 minutes. The lens to be measured was placed in a lens-retaining device, between male and female portions. The male and female portions included flexible sealing rings which were positioned between the lens and the respective male or female portion. After positioning the lens in the lens-retaining device, the lens-retaining device was then placed in a threaded lid. The lid was screwed onto a glass tube to define a donor chamber. The donor chamber was filled with 16 ml of 0.1 molar NaCl solution. A receiving chamber was filled with 80 ml of deionized water. Leads of the conductivity meter were immersed in the deionized water of the receiving chamber and a stir bar was added to the receiving chamber. The receiving chamber was placed in a water bath and the temperature was held at about 35° C. Finally, the donor chamber was immersed in the receiving chamber such that the NaCl solution inside the donor chamber was level with the water inside the receiving chamber. Once the temperature inside the receiving chamber was equilibrated to 35 degrees C., measurements of conductivity were taken every 2 minutes for at least 10 minutes. The conductivity versus time data was substantially linear, and was used to calculate the ionoflux value for the lenses tested.
The oxygen permeability (Dk) of the present lenses can be determined using routine methods known to persons of ordinary skill in the art. For example, the Dk value can be determined using the Mocon Method, as described in U.S. Pat. No. 5,817,924, which is incorporated by reference herein. The Dk values of the lenses of the following Examples were determined using a commercially available instrument under the model designation of MOCON® Ox-Tran System (Mocon Inc., Minneapolis, Minn., USA).
The equilibrium water content (EWC) of the present lenses can be determined using routine methods known to persons of ordinary skill in the art. For the lenses of the following Examples a hydrated silicone hydrogel contact lens was removed from an aqueous liquid, wiped to remove excess surface water, and weighed. The weighed lens was then dried in an oven at 80 degrees C. under a vacuum, and the dried lens was then weighed. The weight difference was determined by subtracting the weight of the dry lens from the weight of the hydrated lens. The water content (%) is the (weight difference/hydrated weight)×100.
The percentage of the wet extractable component or dry extractable component in a lens can be determined by extracting the lenses in an organic solvent in which the polymeric lens body is not soluble in accordance to methods known to those of ordinary skill in the art. For the lenses of the following Examples, an extraction in methanol using a Sohxlet extraction process was used. For determination of the wet extractable component, a sample (e.g., at least 5 lenses per lot) of fully hydrated and sterilized contact lenses was prepared by removing excess packaging solution from each lens and drying them overnight in an 80° C. vacuum oven. For determination of the dry extractable component, a sample of polymeric lens bodies which had not been washed, extracted, hydrated or sterilized was prepared by drying the lens bodies overnight in an 80° C. vacuum oven. When dried and cooled, each lens was weighed to determine its initial dry weight (W1). Each lens was then placed in a perforated, stackable Teflon thimble, and the thimbles were stacked to form an extraction column with an empty thimble placed at the top of the column. The extraction column was placed into a small Sohxlet extractor attached to a condenser and a round bottom flask containing 70-80 ml methanol. Water was circulated through the condenser and the methanol was heated until it gently boiled. The lenses were extracted for at least 4 hours from the time condensed methanol first appeared. The extracted lenses were again dried overnight at 80° C. in a vacuum oven. When dried and cooled, each lens was weighed to obtain the dry weight of the extracted lens (W2), and the following calculation was made for each lens to determine the percent wet extractables: [(W1−W2)/W1]×100.
Example 1
A polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified amounts, using the procedure described in the Silicone Hydrogel Contact Lens Fabrication and Testing Procedure given above.














Chemical




Compound



(Abbrev.)
Unit parts



















Si1
32



Si3
4



VMA
40



EGMA
5



MMA
12



TEGDMA
1.0



TEGDVE
0.3



BVE
7



V-64
0.5



UV2
0.9



RBT2
0.01



pTPP
0.5










A batch of silicone hydrogel contact lenses was prepared using this formulation and tested in accordance with the fabrication procedure and test methods described in the Silicone Hydrogel Contact Lens Fabrication and Testing Procedure, using a dry demolding process, a dry delensing process, and an extraction and hydration process which used extraction and hydration media which consisted of volatile organic solvent-free extraction media. The lenses of this batch were not exposed to a volatile organic solvent during their manufacture. These contact lenses contained units derived from two siloxane monomers, Si1 and Si3. This batch of contact lenses had acceptable average dimensional stability variance.
In addition, these silicone hydrogel contact lenses had, when fully hydrated, an EWC of about 55% wt/wt, an ionoflux from about 3.1 (×10−3 mm2/min), a Dk of about 72 barrers, a modulus of about 0.70 MPa, an elongation of about 345%, a tensile strength of about 2.4 MPa, a water break up time greater than 20 seconds, a wet extractable component of about 3.9% wt/wt, and an energy loss of about 40% when tested at the start of the shelf life study, and had an average dimensional stability variance less than plus or minus 3.0% after storage for more than 2 weeks at 80 degrees C. When tested prior to extraction and hydration, the polymeric lens bodies had a dry extractable component of about 11% wt/wt.
Example 2
A polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified amounts, using the procedure described in the Silicone Hydrogel Contact Lens Fabrication and Testing Procedure given above.














Chemical




Compound



(Abbrev.)
Unit parts



















Si1
32



Si3
4



VMA
50



MMA
14



TEGDMA
0.8



TEGDVE
0.2



V-64
0.5



UV2
0.9



RBT2
0.01



pTPP
0.5










A batch of silicone hydrogel contact lenses was prepared using this formulation and tested in accordance with the fabrication procedure and test methods described in the Silicone Hydrogel Contact Lens Fabrication and Testing Procedure, using a dry demolding process, a dry delensing process, and an extraction and hydration process which used extraction and hydration media which consisted of volatile organic solvent-free extraction media. The lenses of this batch were not exposed to a volatile organic solvent during their manufacture. These contact lenses contained units derived from two siloxane monomers, Si1 and Si3. This batch of contact lenses had acceptable average dimensional stability variance.
In addition, these silicone hydrogel contact lenses, when fully hydrated, had an EWC of about 58% wt/wt, an ionoflux from about 4.14 (×10−3 mm2/min), a modulus of about 0.77 MPa, an elongation of about 349%, a tensile strength of about 1.75 MPa, a water break up time greater than 20 seconds, a wet extractable content of about 4.42% wt/wt, and an energy loss of about 41% when tested at the start of the shelf life study, and had an average dimensional stability variance less than plus or minus 3.0% after storage for at least 2 weeks at 80 degrees C.
Example 3
A polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified amounts, using the procedure described in the Silicone Hydrogel Contact Lens Fabrication and Testing Procedure given above.














Chemical




Compound



(Abbrev.)
Unit parts



















Si1
23



Si2
15



VMA
40



MMA
10



EGMA
5



BVE
7



TEGDMA
1.0



TEGDVE
0.1



V-64
0.5



UV2
0.9



RBT2
0.01



pTPP
0.5










A batch of silicone hydrogel contact lenses was prepared using this formulation and tested in accordance with the fabrication procedure and test methods described in the Silicone Hydrogel Contact Lens Fabrication and Testing Procedure, using a dry demolding process, a dry delensing process, and extraction an extraction and hydration process which used extraction and hydration media which consisted of volatile organic solvent-free extraction media. The lenses of this batch were not exposed to a volatile organic solvent during their manufacture. These contact lenses contained units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had acceptable average dimensional stability variance.
In addition, these silicone hydrogel contact lenses, when fully hydrated, had an EWC of about 55% wt/wt, an ionoflux from about 4.19 (×10−3 mm2/min), a modulus of about 0.61 MPa, an elongation of about 275%, a tensile strength of about 1.51 MPa, a water break up time greater than 20 seconds, and a wet extractable component of about 4.10% wt/wt when tested at the start of the shelf life study, and had an average dimensional stability variance less than plus or minus 3.0% for more than 2 weeks at 80 degrees C.
Example 4
A polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified amounts, using the procedure described in the Silicone Hydrogel Contact Lens Fabrication and Testing Procedure given above.














Chemical




Compound



(Abbrev.)
Unit parts



















Si1
23



Si2
15



VMA
45



MMA
10



BVE
7



TEGDMA
1.0



TEGDVE
0.1



V-64
0.5



UV2
0.9



RBT2
0.01



pTPP
0.5










A batch of silicone hydrogel contact lenses was prepared using this formulation and tested in accordance with the fabrication procedure and test methods described in the Silicone Hydrogel Contact Lens Fabrication and Testing Procedure, using a dry demolding process, a dry delensing process, and an extraction and hydration process which used extraction and hydration media which consisted of volatile organic solvent-free extraction media. The lenses of this batch were not exposed to a volatile organic solvent during their manufacture. These contact lenses contained units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had acceptable average dimensional stability variance.
In addition, these silicone hydrogel contact lenses, when fully hydrated, had an EWC of about 58% wt/wt, an ionoflux from about 2.75 (×10−3 mm2/min), a modulus of about 0.66 MPa, an elongation of about 216%, a tensile strength of about 0.87 MPa, a water break up time greater than 20 seconds, and a wet extractable component of about 4.56% wt/wt when tested at the start of the shelf life study, and had an average dimensional stability variance less than plus or minus 3.0% after storage for 6 days at 95 degrees C.
Example 5
A polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified amounts, using the procedure described in the Silicone Hydrogel Contact Lens Fabrication and Testing Procedure given above.














Chemical




Compound



(Abbrev.)
Unit parts



















Si1
26



Si2
10



VMA
40



MMA
12



EGMA
5



BVE
7



TEGDMA
1.2



TEGDVE
0.1



V-64
0.5



UV2
0.9



RBT2
0.01



pTPP
0.5










A batch of silicone hydrogel contact lenses was prepared using this formulation and tested in accordance with the fabrication procedure and test methods described in the Silicone Hydrogel Contact Lens Fabrication and Testing Procedure, using a dry demolding process, a dry delensing process, and an extraction and hydration process which used extraction and hydration media which consisted of volatile organic solvent-free extraction media. The lenses of this batch were not exposed to a volatile organic solvent during their manufacture. These contact lenses contained units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had acceptable average dimensional stability variance.
In addition, these silicone hydrogel contact lenses, when fully hydrated, had an EWC of about 56% wt/wt, an ionoflux from about 3.54 (×10−3 mm2/min), a modulus of about 0.57 MPa, an elongation of about 310%, a tensile strength of about 1.90 MPa, a water break up time greater than 20 seconds, a wet extractable component of about 4.74% wt/wt, and an energy loss from about 34 to 36% when tested at the start of the shelf life study, and had an average dimensional stability variance less than plus or minus 3.0% after storage for 7 days at 80 degrees C. When tested prior to extraction and hydration, the polymeric lens bodies had a dry extractable component of about 14.39% wt/wt.
Example 6
A polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified amounts, using the procedure described in the Silicone Hydrogel Contact Lens Fabrication and Testing Procedure given above.














Chemical Compound (Abbrev.)
Unit parts



















Si1
26



Si2
10



VMA
45



MMA
12



EGMA
2



BVE
5



TEGDMA
1.2



TEGDVE
0.2



V-64
0.5



UV2
0.9



RBT2
0.01



pTPP
0.5










A batch of silicone hydrogel contact lenses was prepared using this formulation and tested in accordance with the fabrication procedure and test methods described in the Silicone Hydrogel Contact Lens Fabrication and Testing Procedure, using a dry demolding process, a dry delensing process, and an extraction and hydration process which used extraction and hydration media which consisted of volatile organic solvent-free extraction media. The lenses of this batch were not exposed to a volatile organic solvent during their manufacture. These contact lenses contained units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had acceptable average dimensional stability variance.
In addition, these silicone hydrogel contact lenses, when fully hydrated, had an EWC of about 57% wt/wt, an ionoflux from about 3.68 (×10−3 mm2/min), a modulus of about 0.69 MPa, an elongation of about 314%, a tensile strength of about 1.30 MPa, a water break up time greater than 20 seconds, a wet extractable component of about 1.81% wt/wt, and an energy loss of about 34% when tested at the start of the shelf life study, and had an average dimensional stability variance less than plus or minus 3.0% after storage for 14 days at 80 degrees C.
Example 7
A polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified amounts, using the procedure described in the Silicone Hydrogel Contact Lens Fabrication and Testing Procedure given above.














Chemical Compound (Abbrev.)
Unit parts



















Si1
26



Si3
2



Si2
10



VMA
45



MMA
12



BVE
5



TEGDMA
1.2



TEGDVE
0.2



V-64
0.5



UV2
0.9



RBT2
0.01



pTPP
0.5










A batch of silicone hydrogel contact lenses was prepared using this formulation and tested in accordance with the fabrication procedure and test methods described in the Silicone Hydrogel Contact Lens Fabrication and Testing Procedure, using a dry demolding process, a dry delensing process, and an extraction and hydration process which used extraction and hydration media which consisted of volatile organic solvent-free extraction media. The lenses of this batch were not exposed to a volatile organic solvent during their manufacture. These contact lenses contained units derived from three siloxane monomers, Si1, Si2 and Si3. This batch of contact lenses had acceptable average dimensional stability variance.
In addition, these silicone hydrogel contact lenses, when fully hydrated, had an EWC of about 55% wt/wt, an ionoflux from about 3.06 (×10−3 mm2/min), a modulus of about 0.85 MPa, an elongation of about 284%, a tensile strength of about 1.88 MPa, a water break up time greater than 20 seconds, a wet extractable component of about 2.38% wt/wt, and an energy loss of about 36% when tested at the start of the shelf life study, and had an average dimensional stability variance less than plus or minus 3.0% after storage for 14 days at 80 degrees C.
Example 8
A polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified amounts, using the procedure described in the Silicone Hydrogel Contact Lens Fabrication and Testing Procedure given above.














Chemical Compound (Abbrev.)
Unit parts



















Si1
26



Si2
10



VMA
40



MMA
12



EGMA
5



BVE
7



TEGDMA
1.3



TEGDVE
0.2



V-64
0.5



UV2
0.9



RBT2
0.01



pTPP
0.5










A batch of silicone hydrogel contact lenses was prepared using this formulation and tested in accordance with the fabrication procedure and test methods described in the Silicone Hydrogel Contact Lens Fabrication and Testing Procedure, using a dry demolding process, a dry delensing process, and an extraction and hydration process which used extraction and hydration media which consisted of volatile organic solvent-free extraction media. The lenses of this batch were not exposed to a volatile organic solvent during their manufacture. These contact lenses contained units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had acceptable average dimensional stability variance.
In addition, these silicone hydrogel contact lenses, when fully hydrated, had an EWC of about 54% wt/wt, an ionoflux from about 3.57 (×10−3 mm2/min), a modulus of about 0.66 MPa, an elongation of about 274%, a tensile strength of about 1.40 MPa, and a wet extractable content of about 3.8% wt/wt when tested at the start of the shelf life study, and had an average dimensional stability variance less than plus or minus 3.0% after storage for 7 days at 80 degrees C.
Example 9
A polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified amounts, using the procedure described in the Silicone Hydrogel Contact Lens Fabrication and Testing Procedure given above.














Chemical Compound (Abbrev.)
Unit parts



















Si1
26



Si3
2



Si2
10



VMA
45



MMA
12



BVE
5



TEGDMA
1.1



TEGDVE
0.2



V-64
0.5



UV2
0.9



RBT2
0.01



pTPP
0.5










A batch of silicone hydrogel contact lenses was prepared using this formulation and tested in accordance with the fabrication procedure and test methods described in the Silicone Hydrogel Contact Lens Fabrication and Testing Procedure, using a dry demolding process, a dry delensing process, and an extraction and hydration process which used extraction and hydration media which consisted of volatile organic solvent-free extraction media. The lenses of this batch were not exposed to a volatile organic solvent during their manufacture. These contact lenses contained units derived from three siloxane monomers, Si1, Si2 and Si3. This batch of contact lenses had acceptable average dimensional stability variance.
In addition, these silicone hydrogel contact lenses, when fully hydrated, had a modulus of about 0.81 MPa, an elongation of about 351%, a tensile strength of about 1.61 MPa, and EWC from 30% wt/wt to 70% wt/wt when tested at the start of the shelf life study, and had an average dimensional stability variance less than plus or minus 3.0% for 14 days at 80 degrees C.
Example 10
A polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified amounts, using the procedure described in the Silicone Hydrogel Contact Lens Fabrication and Testing Procedure given above.














Chemical Compound (Abbrev.)
Unit parts



















Si1
26



Si3
2



Si2
10



VMA
40



EGMA
15



BVE
7



TEGDMA
1.6



TEGDVE
0.2



V-64
0.5



UV2
0.9



RBT2
0.01



pTPP
0.5










A batch of silicone hydrogel contact lenses was prepared using this formulation and tested in accordance with the fabrication procedure and test methods described in the Silicone Hydrogel Contact Lens Fabrication and Testing Procedure, using a dry demolding process, a dry delensing process, and an extraction and hydration process which used extraction and hydration media which consisted of volatile organic solvent-free extraction media. The lenses of this batch were not exposed to a volatile organic solvent during their manufacture. These contact lenses contained units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had acceptable average dimensional stability variance.
In addition, these silicone hydrogel contact lenses, when fully hydrated, had an ionoflux from about 3.33 (×10−3 mm2/min), a modulus of about 0.74 MPa, and an elongation of about 222% when tested at the start of the shelf life study, and had an average dimensional stability variance less than plus or minus 3.0% for 14 days at 80 degrees C.
Example 11
A polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified amounts, using the procedure described in the Silicone Hydrogel Contact Lens Fabrication and Testing Procedure given above.














Chemical Compound (Abbrev.)
Unit parts



















Si1
32



Si3
4



VMA
45



MMA
13



EGMA
3



BVE
3



TEGDMA
1.0



TEGDVE
0.2



V-64
0.5



UV2
1.3



RBT2
0.01



pTPP
0.5










A batch of silicone hydrogel contact lenses was prepared using this formulation and tested in accordance with the fabrication procedure and test methods described in the Silicone Hydrogel Contact Lens Fabrication and Testing Procedure, using a dry demolding process, a dry delensing process, and an extraction and hydration process which used extraction and hydration media which consisted of volatile organic solvent-free extraction media. The lenses of this batch were not exposed to a volatile organic solvent during their manufacture. These contact lenses contained units derived from two siloxane monomers, Si1 and Si3. This batch of contact lenses had acceptable average dimensional stability variance.
In addition, these silicone hydrogel contact lenses, when fully hydrated, had an EWC of about 57% wt/wt, a modulus of about 0.70 MPa, an energy loss of about 40%, and a captive bubble dynamic advancing contact angle of from about 50 to about 60 degrees when tested at the start of the shelf life study, and had an average dimensional stability variance less than plus or minus 3.0% for 14 days at 80 degrees C.
Example 12
A polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified amounts, using the procedure described in the Silicone Hydrogel Contact Lens Fabrication and Testing Procedure given above.














Chemical Compound (Abbrev.)
Unit parts



















Si1
26



Si2
10



VMA
40



MMA
12



EGMA
5



BVE
7



TEGDMA
1.2



TEGDVE
0.2



V-64
0.5



UV2
1.3



RBT2
0.01



pTPP
0.5










A batch of silicone hydrogel contact lenses was prepared using this formulation and tested in accordance with the fabrication procedure and test methods described in the Silicone Hydrogel Contact Lens Fabrication and Testing Procedure, using a dry demolding process, a dry delensing process, and an extraction and hydration process which used extraction and hydration media which consisted of volatile organic solvent-free extraction media. The lenses of this batch were not exposed to a volatile organic solvent during their manufacture. These contact lenses contained units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had acceptable average dimensional stability variance.
In addition, these silicone hydrogel contact lenses, when fully hydrated, had an EWC of about 56% wt/wt, a modulus of about 0.50 MPa, and a captive bubble dynamic advancing contact angle of from about 47 to about 51 degrees when tested at the start of the shelf life study, and had an average dimensional stability variance less than plus or minus 3.0% for 4.4 weeks at 80 degrees C.
Example 13
A polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified amounts, using the procedure described in the Silicone Hydrogel Contact Lens Fabrication and Testing Procedure given above.














Chemical Compound (Abbrev.)
Unit parts



















Si1
26



Si2
10



VMA
40



MMA
12



EGMA
5



BVE
3



EGDMA
0.5



TEGDVE
0.1



V-64
0.5



UV2
1.3



RBT2
0.01



pTPP
0.5










A batch of silicone hydrogel contact lenses was prepared using this formulation and tested in accordance with the fabrication procedure and test methods described in the Silicone Hydrogel Contact Lens Fabrication and Testing Procedure, using a dry demolding process, a dry delensing process, and an extraction and hydration process which used extraction and hydration media which consisted of volatile organic solvent-free extraction media. The lenses of this batch were not exposed to a volatile organic solvent during their manufacture. These contact lenses contained units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had acceptable average dimensional stability variance.
In addition, these silicone hydrogel contact lenses, when fully hydrated, had an EWC of about 55% wt/wt, a modulus of about 0.60 MPa, and a captive bubble dynamic advancing contact angle of from about 47 to about 55 degrees when tested at the start of the shelf life study, and had an average dimensional stability variance less than plus or minus 3.0% after storage for 2 weeks at 80 degrees C.
Example 14
A polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified amounts, using the procedure described in the Silicone Hydrogel Contact Lens Fabrication and Testing Procedure given above.














Chemical Compound (Abbrev.)
Unit parts



















Si1
29



Si2
8



VMA
42



MMA
14



DEGVE
7



EGDMA
0.6



TEGDVE
0.08



V-64
0.5



UV2
1.3



RBT2
0.01



pTPP
0.5










A batch of silicone hydrogel contact lenses was prepared using this formulation and tested in accordance with the fabrication procedure and test methods described in the Silicone Hydrogel Contact Lens Fabrication and Testing Procedure, using a dry demolding process, a dry delensing process, and an extraction and hydration process which used extraction and hydration media which consisted of volatile organic solvent-free extraction media. The lenses of this batch were not exposed to a volatile organic solvent during their manufacture. These contact lenses contained units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had acceptable average dimensional stability variance.
In addition, these silicone hydrogel contact lenses, when fully hydrated, had an EWC from about 55% wt/wt to about 56% wt/wt, a modulus of about 0.71 MPa, and a captive bubble dynamic advancing contact angle of from about 45 to about 47 degrees when tested at the start of the shelf life study, and had an average dimensional stability variance less than plus or minus 3.0% for at least 2 weeks at 80 degrees C.
Example 15
A polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified amounts, using the procedure described in the Silicone Hydrogel Contact Lens Fabrication and Testing Procedure given above.














Chemical Compound (Abbrev.)
Unit parts



















Si1
29



Si2
8



VMA
44



MMA
14



EGVE
5



EGDMA
0.6



TEGDVE
0.15



V-64
0.5



UV2
1.3



RBT2
0.01










A batch of silicone hydrogel contact lenses was prepared using this formulation and tested in accordance with the fabrication procedure and test methods described in the Silicone Hydrogel Contact Lens Fabrication and Testing Procedure, using a dry demolding process, a dry delensing process, and an extraction and hydration process which used extraction and hydration media which consisted of volatile organic solvent-free extraction media. The lenses of this batch were not exposed to a volatile organic solvent during their manufacture. These contact lenses contained units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had acceptable average dimensional stability variance.
In addition, these silicone hydrogel contact lenses, when fully hydrated, had an EWC of about 56% wt/wt, and a modulus of about 0.65 MPa when tested at the start of the shelf life study, and had an average dimensional stability variance less than plus or minus 3.0% for 2 weeks at 80 degrees C.
Example 16
A polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified amounts, using the procedure described in the Silicone Hydrogel Contact Lens Fabrication and Testing Procedure given above.














Chemical Compound (Abbrev.)
Unit parts



















Si1
29



Si2
8



VMA
45



MMA
13



HEMA
4



EGDMA
0.5



TEGDVE
0.1



V-64
0.5



UV2
1.7



RBT2
0.01



pTPP
0.5



AE
0.3










A batch of silicone hydrogel contact lenses was prepared using this formulation and tested in accordance with the fabrication procedure and test methods described in the Silicone Hydrogel Contact Lens Fabrication and Testing Procedure, using a dry demolding process, a dry delensing process, and an extraction and hydration process which used extraction and hydration media which consisted of volatile organic solvent-free extraction media. The lenses of this batch were not exposed to a volatile organic solvent during their manufacture. These contact lenses contained units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had acceptable average dimensional stability variance.
In addition, these silicone hydrogel contact lenses, when fully hydrated, had an EWC of from about 55% wt/wt to about 56% wt/wt, a modulus of about 0.53 MPa, a captive bubble dynamic advancing contact angle of from about 51 to about 53 degrees, and an energy loss of about 34% when tested at the start of the shelf life study, and had an average dimensional stability variance less than plus or minus 3.0% for 4.4 weeks at 80 degrees C.
Example 17
A polymerizable silicone composition was obtained by mixing and filtering the following chemical compounds in the specified amounts, using the procedure described in the Silicone Hydrogel Contact Lens Fabrication and Testing Procedure given above.














Chemical Compound (Abbrev.)
Unit parts



















Si1
29



Si2
8



VMA
42



MMA
8



EGMA
6



DELVE
7



EGDMA
0.6



TEGDVE
0.1



V-64
0.5



UV2
1.7



RBT2
0.01



pTPP
0.5



AE
0.4










A batch of silicone hydrogel contact lenses was prepared using this formulation and tested in accordance with the fabrication procedure and test methods described in the Silicone Hydrogel Contact Lens Fabrication and Testing Procedure, using a dry demolding process, a dry delensing process, and an extraction and hydration process which used extraction and hydration media which consisted of volatile organic solvent-free extraction media. The lenses of this batch were not exposed to a volatile organic solvent during their manufacture. These contact lenses contained units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had acceptable average dimensional stability variance.
In addition, these silicone hydrogel contact lenses, when fully hydrated, had an EWC from 57% wt/wt to 58% wt/wt, an ionoflux of about 2.9 (×103 mm2/min), a modulus of about 0.7 MPa, an elongation of about 300%, a tensile strength of about 1.5 MPa, a captive bubble dynamic advancing contact angle of from about 44 to about 48 degrees, a wet extractable component of about 5.10% wt/wt, and an energy loss from about 32% to about 33% when tested at the start of the shelf life study, and had an average dimensional stability variance less than plus or minus 3.0% after storage for 4.4 weeks at 80 degrees C. When tested prior to extraction and hydration, the polymeric lens bodies had a dry extractable component of about 12.2% wt/wt.
Example 18
A polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified amounts, using the procedure described in the Silicone Hydrogel Contact Lens Fabrication and Testing Procedure given above.














Chemical Compound (Abbrev.)
Unit parts



















Si1
29



Si2
8



VMA
45



HOB
7



EGMA
10



EGDMA
0.5



TEGDVE
0.1



V-64
0.5



UV2
1.7



RBT2
0.01



pTPP
0.5



AE
0.3










A batch of silicone hydrogel contact lenses was prepared using this formulation and tested in accordance with the fabrication procedure and test methods described in the Silicone Hydrogel Contact Lens Fabrication and Testing Procedure, using a dry demolding process, a dry delensing process, and an extraction and hydration process which used extraction and hydration media which consisted of volatile organic solvent-free extraction media. The lenses of this batch were not exposed to a volatile organic solvent during their manufacture. These contact lenses contained units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had acceptable average dimensional stability variance.
In addition, these silicone hydrogel contact lenses, when fully hydrated, had an EWC from about 55% wt/wt to about 56% wt/wt, an ionoflux of about 4.1 (×103 mm2/min), a modulus of about 0.6 MPa, an elongation of about 275%, a tensile strength of about 1.2 MPa, a captive bubble dynamic advancing contact angle of from about 55 to about 58 degrees, a wet extractable component of about 4.6% wt/wt, an energy loss from about 31% to about 32%, and a swell factor of about 27% when tested at the start of the shelf life study, and had an average dimensional stability variance less than plus or minus 3.0% for after storage for 4.4 weeks at 80 degrees C. When tested prior to extraction and hydration, the polymeric lens bodies had a dry extractable component of about 10.6% wt/wt.
Example 19
A polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified amounts, using the procedure described in the Silicone Hydrogel Contact Lens Fabrication and Testing Procedure given above.














Chemical Compound (Abbrev.)
Unit parts



















Si1
30



Si2
7



VMA
44



MMA
8



EGMA
6



BVE
4



DEGVE
10



EGDMA
0.6



TEGDVE
0.1



V-64
0.5



UV2
1.8



RBT2
0.01



pTPP
0.5










A batch of silicone hydrogel contact lenses was prepared using this formulation and tested in accordance with the fabrication procedure and test methods described in the Silicone Hydrogel Contact Lens Fabrication and Testing Procedure, using a dry demolding process, a dry delensing process, and an extraction and hydration process which used extraction and hydration media which consisted of volatile organic solvent-free extraction media. The lenses of this batch were not exposed to a volatile organic solvent during their manufacture. These contact lenses contained units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had acceptable average dimensional stability variance.
In addition, these silicone hydrogel contact lenses, when fully hydrated, had an EWC of about 61% wt/wt, an ionoflux of about 3.8 (×10−3 mm2/min), a modulus of about 0.5 MPa, an elongation of about 279%, a tensile strength of about 1.2 MPa, a captive bubble dynamic advancing contact angle of from about 45 to about 47 degrees, a wet extractable component of about 4.55% wt/wt, and an energy loss from about 30% to about 33% when tested at the start of the shelf life study, and had an average dimensional stability variance less than plus or minus 3.0% after storage for 14 days at 80 degrees C. When tested prior to extraction and hydration, the polymeric lens bodies had a dry extractable component of about 13.65% wt/wt.
Example 20
A polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified amounts, using the procedure described in the Silicone Hydrogel Contact Lens Fabrication and Testing Procedure given above.














Chemical Compound (Abbrev.)
Unit parts



















Si1
30



Si2
7



VMA
45



MMA
12



EGMA
5



BVE
5



TEGDMA
1.4



TEGDVE
0.2



V-64
0.5



UV2
1.8



RBT2
0.01



pTPP
0.5










A batch of silicone hydrogel contact lenses was prepared using this formulation and tested in accordance with the fabrication procedure and test methods described in the Silicone Hydrogel Contact Lens Fabrication and Testing Procedure, using a dry demolding process, a dry delensing process, and an extraction and hydration process which used extraction and hydration media which consisted of volatile organic solvent-free extraction media. The lenses of this batch were not exposed to a volatile organic solvent during their manufacture. These contact lenses contained units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had acceptable average dimensional stability variance.
In addition, these silicone hydrogel contact lenses, when fully hydrated, had an EWC from about 55% wt/wt to about 57% wt/wt, an ionoflux of about 3.6 (×103 mm2/min), a modulus of about 0.7 MPa, an elongation of about 285%, a tensile strength of about 1.3 MPa, a captive bubble dynamic advancing contact angle of from about 47 to about 53 degrees, a wet extractable component of about 4.10% wt/wt, and an energy loss from about 34% to about 35% when tested at the start of the shelf life study, and had an average dimensional stability variance less than plus or minus 3.0% after storage for 14 days at 80 degrees C. When tested prior to extraction and hydration, the polymeric lens bodies were found to have a dry extractable component of about 9.80% wt/wt.
Although the disclosure herein refers to certain illustrated embodiments, it is to be understood that these embodiments are presented by way of example and not by way of limitation. The intent of the foregoing detailed description, although discussing exemplary embodiments, is to be construed to cover all modifications, alternatives, and equivalents of the embodiments as may fall within the spirit and scope of the invention as defined by the additional disclosure.
A number of publications and patents have been cited hereinabove. Each of the cited publications and patents are hereby incorporated by reference in their entireties.

## Claims

1. A method of manufacturing silicone hydrogel contact lenses, comprising:
forming a lens body that is the reaction product of a polymerizable composition that comprises at least one siloxane monomer, at least one hydrophilic monomer, at least one hydrophobic monomer, at least one cross-linking agent, and that is free of diluent;
washing the lens body to remove extractable material from the lens body;
packaging the washed lens body in a contact lens package containing an aqueous liquid resulting in a hydrated lens body; and
sterilizing the contact lens package containing the packaged hydrated lens body;
wherein the hydrated lens body has a lens surface wettability characterized by an advancing contact angle less than 120 degrees and has a diameter that is at least 24% larger than the diameter of the lens body prior to washing.

2. The method of claim 1, wherein the washing comprises washing the lens body with an aqueous liquid free of volatile organic solvent.

3. The method of claim 1, wherein the hydrated lens body has an advancing contact angle less than 90 degrees.

4. The method of claim 1, wherein the forming comprises cast molding the polymerizable composition in a non-polar resin contact lens mold assembly.

5. The method of claim 1, further comprising demolding the contact lens mold assembly to produce a first mold section and a second mold section separated from the first mold section, wherein the polymerized lens body remains attached to the first or second mold section; and separating the polymerized lens body from the mold section to which it is attached to produce a delensed lens body.

6. The method of claim 5, wherein the delensed lens body is separated from the mold section to which it is attached by contacting the polymerized lens body with an aqueous liquid free of volatile organic solvent or by mechanically removing the polymerized lens body without contacting the lens body with any liquid.

7. The method of claim 1, wherein the lens body is not contacted with any volatile organic solvent after the lens body is formed and prior to sterilizing the lens body in the contact lens package.

8. The method of claim 1, wherein the polymerizable composition comprises a first siloxane monomer represented by formula (1):



wherein m of formula (1) represents one integer from 3 to 10, n of formula (1) represents one integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 carbon atoms, and each R2 of formula (1) is independently either a hydrogen atom or a methyl group; and
a second siloxane monomer having a number average molecular weight greater than 5,000 daltons.

9. The method of claim 8, wherein the second siloxane monomer is a dual-end methacrylate end-capped polydimethylsiloxane.

10. The method of claim 1, wherein the polymerizable composition comprises a first siloxane monomer having a number average molecular weight of from 400 daltons to 700 daltons, and a second siloxane monomer is represented by formula (2):



wherein R1 of formula (2) is selected from either a hydrogen atom or a methyl group; R2 of formula (2) is selected from either of hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms; m of formula (2) represents an integer of from 0 to 10; n of formula (2) represents an integer of from 4 to 100; a and b represent integers of 1 or more; a+b is equal to 20-500; b/(a+b) is equal to 0.01-0.22; and the configuration of siloxane units includes a random configuration.

11. A method of manufacturing silicone hydrogel contact lenses, comprising:
forming a lens body that is the reaction product of a polymerizable composition that comprises at least one hydrophobic monomer, at least one cross-linking agent,
a siloxane monomer represented by formula (6):




wherein n of formula (6) is an integer from 13-16, and the molecular weight is about 1500 daltons, and
3-[tris (trimethylsilyloxy) silyl]propyl methacrylate (TRIS);
wherein the polymerizable composition is free of N,N-dimethylacrylamide (DMA);
washing the lens body to remove extractable material from the lens body;
packaging the washed lens body in a contact lens package containing an aqueous liquid resulting in a hydrated lens body; and
sterilizing the contact lens package containing the packaged hydrated lens body;
wherein the hydrated lens body has a lens surface wettability characterized by an advancing contact angle less than 120 degrees and has a diameter that is at least 24% larger than the diameter of the lens body prior to washing.

12. The method of claim 1, wherein the at least one cross-linking agent comprises a cross-linking agent component comprising a vinyl-containing cross-linking agent in combination with an acrylate-containing cross-linking agent or a methacrylate-containing cross-linking agent.

13. The method of claim 1, wherein the at least one hydrophilic monomer comprises a hydrophilic vinyl-containing monomer.

14. The method claim 13, wherein the hydrophilic vinyl-containing monomer comprises a hydrophilic amide monomer having one N-vinyl group.

15. The method of claim 1, wherein the polymerizable composition is free of a diluent, or free of a pre-formed hydrophilic polymer, or free of N,N-dimethylacrylamide (DMA), or any combination thereof.

16. A silicone hydrogel contact lens, comprising:
a lens body that is the reaction product of a polymerizable composition that comprises at least one siloxane monomer, at least one hydrophilic monomer, at least one hydrophobic monomer, and at least one cross-linking agent;
wherein the lens body is washed to remove extractable material from the lens body, and is hydrated with an aqueous liquid, and the hydrated lens body has a lens surface wettability characterized by an advancing contact angle less than 120 degrees, and the hydrated lens body has a diameter that is at least 24% larger than the diameter of the lens body prior to washing.

17. The contact lens of claim 16, wherein the lens body is washed with an aqueous liquid free of volatile organic solvent to remove extractable material from the lens body.

18. The contact lens of claim 16, which has an oxygen permeability of at least 55 barrers, or an equilibrium water content from about 30% wt/wt to about 70% wt/wt, or a tensile modulus from about 0.2 MPa to about 0.9 MPa, or any combination thereof.

19. The contact lens of claim 16, wherein the polymerizable composition comprises a first siloxane monomer having a number average molecular weight of from 400 daltons to 700 daltons, and a second siloxane monomer having a number average molecular weight of greater than 5,000 daltons.

20. The contact lens of claim 16, wherein the polymerizable composition is free of N,N-dimethylacrylamide (DMA).

21. The contact lens of claim 16, wherein the polymerizable composition is free of diluent.