HK1190795B

HK1190795B - Silicone hydrogel contact lenses having acceptable levels of energy loss

Info

Publication number: HK1190795B
Application number: HK14103885.6A
Authority: HK
Inventors: 刘荣华; 史新峰; 刘宇文; 查利．陈; 洪叶; 查尔斯．A．弗朗西斯; 姚莉; 阿瑟．巴克; 郑莹
Original assignee: Coopervision International Limited
Priority date: 2011-02-28
Filing date: 2012-02-23
Publication date: 2016-07-15

Description

Silicone hydrogel contact lenses with acceptable levels of energy loss

Cross reference to related applications

The present application claims the benefit of prior U.S. provisional patent application No. 61/447,197, filed 2011/2/28, in accordance with the provisions of 35u.s.c. § 119(e), which is incorporated herein by reference in its entirety.

Technical Field

The present invention relates to silicone hydrogel contact lenses and related compositions and methods.

Background

Commercially and clinically, silicone hydrogel contact lenses are a popular replacement for conventional hydrogel contact lenses (i.e., hydrogel contact lenses that do not contain silicone or silicone-containing components). It is believed that the presence of siloxanes in silicone hydrogel contact lens formulations can affect the properties of the silicone hydrogel contact lenses obtained therefrom. For example, it is believed that the presence of the silicone component in the contact lens results in a relatively high oxygen transmission rate as compared to conventional hydrogel contact lenses that do not contain the silicone component. In addition, it is believed that the presence of the silicone component increases the likelihood that hydrophobic domains will be present on the lens surface of the silicone hydrogel contact lens as compared to conventional hydrogel contact lenses that do not contain a silicone component. First generation silicone hydrogel contact lenses also provided high levels of oxygen even though the wettability of the lenses tended to be lower than desired. Various techniques have been developed to overcome the problem of hydrophobicity of the surface of silicone hydrogel contact lenses. Based on the popularity of silicone hydrogel contact lenses, there remains a need in the art for novel silicone hydrogel contact lenses that are ophthalmically compatible, such as novel silicone hydrogel contact lenses having acceptable levels of energy loss.

Some documents describing silicone hydrogel contact lenses include: US4711943, US5712327, US5760100, US7825170, US6867245, US20060063852, US20070296914, US7572841, US20090299022, US20090234089, and US20100249356, each of which is incorporated herein in its entirety by reference.

Disclosure of Invention

It has been found that polymerizable compositions can be prepared using a siloxane monomer having a particular structure in combination with a second siloxane monomer that is a double-terminal methacrylate-terminated polydimethylsiloxane having a number average molecular weight of at least 7,000 daltons, and that these polymerizable compositions can produce lenses having acceptable levels of energy loss when used to prepare silicone hydrogel contact lenses. Since the energy loss level of a silicone hydrogel contact lens can be related to the level of on-eye movement exhibited by the contact lens during wear, the energy loss level of the contact lens can have a significant impact on the ophthalmic acceptability of the contact lens.

Novel silicone hydrogel contact lenses have been invented. Unlike methods of improving the energy loss of silicone hydrogel contact lenses by adjusting the level of a single silicone macromer present in the contact lens, the present invention is related to the following findings: the inclusion of a second siloxane monomer, which is a double-terminal methacrylate-terminated polydimethylsiloxane having a number average molecular weight of at least 7,000 daltons, in the contact lens formulation can improve the energy loss of silicone hydrogel contact lenses made from formulations containing siloxanes of formula (1):

Wherein m in formula (1) represents an integer of 3 to 10, n in formula (1) represents an integer of 1 to 10, R in formula (1)¹Is an alkyl group having 1 to 4 carbon atoms, and R in the formula (1)²Is a hydrogen atom or a methyl group; and thus silicone hydrogel contact lenses with ophthalmically acceptable levels of energy loss can be produced. The present invention relates to novel silicone hydrogel contact lenses. According to the present invention, a silicone hydrogel contact lens includes a polymeric lens body. The polymeric lens body is the reaction product of a polymerizable composition. The polymerizable composition comprises a plurality of lens forming ingredients such that upon polymerization of the composition a polymerized lens body is obtained.

In one example, the present invention relates to polymerizable compositions for producing the silicone hydrogel contact lenses of the invention. The polymerizable composition includes a first siloxane monomer represented by formula (1):

wherein m in formula (1) represents an integer of 3 to 10, n in formula (1) represents an integer of 1 to 10, R in formula (1)¹Is an alkyl group having 1 to 4 carbon atoms, and each R in the formula (1)²Independently a hydrogen atom or a methyl group. In addition to the first siloxane monomer of formula (1), the polymerizable composition comprises a second siloxane monomer that is a double-terminal methacrylate-terminated polydimethylsiloxane having a number average molecular weight of at least 7,000 daltons. The amount of ingredients present in the polymerizable composition should be such that the resulting silicone hydrogel contact lens has an energy loss of about 25% to about 45% when fully hydrated. In one example, the energy loss may be about 27% to about 40%. In another example, the energy loss may be about 30% to about 37%.

In one example of the polymerizable composition, in the first siloxane monomer represented by formula (1), m in formula (1) is 4, n in formula (1) is 1, and R in formula (1)¹Is a butyl group. The first siloxane monomer represented by formula (1) can have a number average molecular weight of 400 daltons to 700 daltons.

In another example of the polymerizable composition, the polymerizable composition can comprise at least one crosslinker. The at least one crosslinking agent may be present in the polymerizable composition in a total amount of about 0.01 unit parts by weight to about 5.0 unit parts by weight. The at least one crosslinking agent may comprise or consist of at least one vinyl-containing crosslinking agent. The at least one vinyl-containing crosslinking agent can be present in the polymerizable composition in an amount of from about 0.01 unit parts to about 2.0 unit parts by weight, or from about 0.01 unit parts to about 0.5 unit parts. The ratio of the amount of the first siloxane monomer present in the polymerizable composition to the total amount of vinyl-containing crosslinker present in the polymerizable composition can be from 100:1 to 400:1 (based on parts by weight). The at least one vinyl-containing crosslinking agent may comprise or consist of at least one vinyl ether-containing crosslinking agent.

In another example, the polymerizable composition can comprise at least one hydrophilic monomer. The at least one hydrophilic monomer may comprise a hydrophilic amide monomer having one N-vinyl group.

The first siloxane monomer and the second siloxane monomer can be present in the polymerizable composition in the following amounts: the ratio of the amount of the first siloxane monomer present in the polymerizable composition to the amount of the second siloxane monomer present in the polymerizable composition is at least 3:1 (based on parts by weight). The total amount of siloxane monomer present in the polymerizable composition can be from about 30 weight unit parts to about 50 weight unit parts, for example from about 35 to about 40 weight unit parts, from about 33 weight unit parts to about 45 weight unit parts, or from about 35 weight unit parts to about 40 weight unit parts.

In one example, the second siloxane monomer can be a siloxane monomer represented by formula (2):

wherein R in formula (2)₁Selected from hydrogen or methyl; r in the formula (2)₂Selected from hydrogen or C_1-4A hydrocarbyl group; m in formula (2) represents an integer of 0 to 10; n in formula (2) represents an integer of 4 to 100; a and b in formula (2) represent an integer of 1 or more; a + b equals 20 to 500; b/(a + b) equals 0.01 to 0.22; and the configuration of the siloxane units comprises a random configuration, wherein the second siloxane monomer has a number average molecular weight of greater than 7,000 daltons. In one example of the siloxane of formula (2), m in formula (2) is 0, n in formula (2) is an integer of 5 to 10, a in formula (2) is an integer of 65 to 90, b in formula (2) is an integer of 1 to 10, and R in formula (2) ₁Is methyl.

In one example, the polymerizable composition can further comprise at least one third siloxane monomer. When the polymerizable composition comprises at least one third siloxane monomer, the third siloxane monomer can be a siloxane monomer represented by formula (3):

wherein R in formula (3)³Selected from hydrogen or methyl; m in formula (3) represents an integer of 0 to 10; and n in formula (3) represents an integer of 1 to 500. In one example of the siloxane of formula (3), R in formula (3)³Is a methyl group, m in formula (3) is 0, and n in formula (3) is an integer of 40 to 60.

The polymerizable composition can further comprise at least one hydrophilic monomer, or at least one hydrophobic monomer, or at least one crosslinking agent, or any combination thereof. In one example, the at least one hydrophilic monomer may comprise or consist of a hydrophilic amide monomer having at least one N-vinyl group (e.g., N-vinyl-N-methylacetamide (VMA)).

In another example, the present invention also relates to a silicone hydrogel contact lens comprising a polymerized lens body that is a reaction product of a polymerizable composition. The polymerizable composition comprises a first siloxane monomer represented by formula (1):

wherein m in formula (1) represents an integer of 3 to 10, n in formula (1) represents an integer of 1 to 10, R in formula (1) ¹Is an alkyl group having 1 to 4 carbon atoms, and each R in the formula (1)²Independently a hydrogen atom or a methyl group. In addition to the first siloxane monomer of formula (1), the polymerizable composition comprises a second siloxane monomer that is a double-terminal methacrylate-terminated polydimethylsiloxane having a number average molecular weight of at least 7,000 daltons. The silicone hydrogel contact lenses of this example have an energy loss of about 25% to about 45% when fully hydrated.

The present invention also relates to a batch of contact lenses comprising a plurality of contact lenses formed from polymeric lens bodies that are the reaction product of the polymerizable compositions described herein. In one example, the batch of silicone hydrogel contact lenses comprises a plurality of contact lenses described in any preceding claim, wherein the batch of silicone hydrogel contact lenses, when fully hydrated, has an average Equilibrium Water Content (EWC) of from about 30% wt/wt to about 70% wt/wt, or an average oxygen permeability of at least 55 barrers, or an average captive bubble dynamic advancing contact angle of less than 90 degrees, or an average captive bubble static contact angle of less than 70 degrees, or any combination thereof, based on an average of measurements for at least 20 individual lenses in the batch.

The present invention also relates to methods of manufacturing silicone hydrogel contact lenses. The method of manufacturing includes the step of providing a polymerizable composition including (a) a first siloxane monomer represented by formula (1):

wherein m in formula (1) represents an integer of 3 to 10, n in formula (1) represents an integer of 1 to 10, R in formula (1)¹Is an alkyl group having 1 to 4 carbon atoms, and each R in the formula (1)²Independently a hydrogen atom or a methyl group. In addition to the first siloxane monomer of formula (1), the polymerizable composition comprises a second siloxane monomer that is a double-terminal methacrylate-terminated polydimethylsiloxane having a number average molecular weight of at least 7,000 daltons. The method further comprises the steps of: polymerizing the polymerizable composition in the contact lens mold assembly to form a polymeric lens body; contacting the polymeric lens body with a washing solution to remove extractable material from the polymeric lens body; and hydrating the polymerized lens body to form the silicone hydrogel contact lens. When the polymerizable composition is polymerized to form a polymerized lens body, and the polymerized lens body is treated to form a fully hydrated silicone hydrogel contact lens, the silicone hydrogel contact lens can have an energy loss of about 25% to about 45% when fully hydrated. The method can further comprise packaging the polymeric lens body or the silicone hydrogel contact lens in a contact lens packaging solution in a contact lens package.

In one example of the method, the polymerizing step of the method can comprise polymerizing the polymerizable composition in a contact lens mold assembly having a molding surface formed from a non-polar thermoplastic polymer to form a polymeric lens body. In another example, the polymerizing step of the method can comprise polymerizing the polymerizable composition in a contact lens mold assembly having a molding surface formed from a polar thermoplastic polymer to form a polymeric lens body.

In one example of the method, the contacting step of the method can comprise contacting the polymeric lens body with a wash solution comprising at least one volatile organic solvent. In another example, the contacting step of the method can comprise contacting the polymeric lens body with a washing solution that is free of volatile organic solvents. In one particular example, the polymeric lens body and the silicone hydrogel contact lens comprising the polymeric lens body are not contacted with a liquid comprising a volatile organic solvent during manufacture.

In one example, the method can further comprise the step of autoclaving the contact lens package to sterilize the silicone hydrogel contact lens and the contact lens packaging solution.

In any of the foregoing polymerizable compositions, or polymerized lens bodies, or silicone hydrogel contact lenses, or batches of silicone hydrogel contact lenses, or methods of making contact lenses, the first siloxane monomer can be represented by formula (1), wherein m in formula (1) is 4, n in formula (1) is 1, and R in formula (1) is 1¹Is butyl, and each R in formula (1)²Independently a hydrogen atom or a methyl group. The second siloxane monomer of the polymerizable composition is a siloxane monomer having more than one polymerizable functional group, i.e., a multifunctional siloxane monomer, in fact, a difunctional siloxane monomer. The second siloxane is a siloxane monomer having a number average molecular weight of at least 7,000 daltons. Other examples of second siloxanes are described below.

The optional at least one crosslinker of the polymerizable composition may comprise a vinyl-containing crosslinker. For example, the optional at least one crosslinker can consist of a vinyl-containing crosslinker (i.e., all of the silicon-free crosslinkers present in the polymerizable composition are vinyl-containing crosslinkers).

Other embodiments of the polymerizable composition, the polymerized lens body, the present lenses, lens products, multi-batch lenses, and methods of manufacturing contact lenses are apparent from the following description, examples 1-28, and claims. As can be appreciated from the foregoing and the following description, each feature described herein, as well as each combination of two or more of such features, and each combination of one or more values defining a range, is included within the scope of the present invention provided that the features included in such combinations are not mutually inconsistent. In addition, any embodiment of the invention may not include any feature or combination of features or any value defining a range, among others.

Drawings

Detailed Description

As described herein, it has now been found that silicone hydrogel contact lenses can be formed from polymerizable compositions comprising a first siloxane monomer of formula (1) and a second siloxane monomer, which is a double-terminal methacrylate-terminated polydimethylsiloxane having a number average molecular weight of at least 7,000 daltons, and that these silicone hydrogel contact lenses can advantageously have an energy loss level of from about 25% to about 45% when fully hydrated.

The present contact lenses comprise or consist of a hydrated lens body comprising a polymeric component and a liquid component. The polymeric component comprises the following units: two or more siloxane monomers (i.e., a siloxane monomer of formula (1), a second siloxane monomer that is a double-terminal methacrylate-terminated polydimethylsiloxane having a number average molecular weight of at least 7,000 daltons, and optionally one or more other siloxane monomers), and one or more silicon-free reactive ingredients (i.e., one or more hydrophilic monomers, or one or more crosslinkers, or one or more hydrophobic monomers, or any combination thereof). Thus, it can be appreciated that the polymeric component is the reaction product of a polymerizable composition comprising two or more siloxane monomers (two or more siloxane monomers present as the siloxane monomer component of the composition) and one or more non-silicon reactive ingredients. Silicon-free reactive components as used herein are understood to be components which have a polymerizable double bond as part of their molecular structure but which do not have silicon atoms in their molecular structure. The polymerizable composition can be a monomer, a macromer, a prepolymer, a polymer, or any combination thereof. In addition to the first siloxane monomer of formula (1), the polymerizable composition further comprises a second siloxane monomer that is a double-terminal methacrylate-terminated polydimethylsiloxane having a number average molecular weight of at least 7,000 daltons. Optionally, the ingredients of the polymerizable composition can further comprise at least one hydrophilic monomer, or at least one hydrophobic monomer, or at least one third siloxane monomer, or any combination thereof. The at least one crosslinker, the at least one hydrophilic monomer and the at least one hydrophobic monomer of the polymerizable composition are to be understood as meaning silicon-free polymerizable constituents. As used herein, at least one crosslinker can be understood to comprise a single crosslinker, or to comprise a crosslinker component consisting of two or more crosslinkers. Similarly, the optional at least one hydrophilic monomer may be understood to comprise a single hydrophilic monomer, or to comprise a hydrophilic monomer component consisting of two or more hydrophilic monomers. The optional at least one hydrophobic monomer may be understood to comprise a single hydrophobic monomer, or to comprise a hydrophobic monomer component consisting of two or more hydrophobic monomers. The optional at least one third siloxane monomer can be understood to comprise a single third siloxane monomer, or to comprise a siloxane monomer component comprised of two or more siloxane monomers. Additionally, the polymerizable composition may 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 colorant, 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 colorant, at least one UV absorber or at least one chain transfer agent is understood to be a silicon-free component and may be a non-polymerizable component or a polymerizable component (i.e., a component having a polymerizable functional group as part of its molecular structure).

One example of the present invention relates to a silicone hydrogel contact lens, comprising: a polymerized lens body that is the reaction product of a polymerizable composition comprising (a) a first siloxane monomer represented by formula (1):

wherein m in formula (1) represents one integer of 3 to 10, n in formula (1) represents one integer of 1 to 10, R1 in formula (1) is an alkyl group having 1 to 4 carbon atoms, and R2 in formula (1) is a hydrogen atom or a methyl group; and (b) a second siloxane monomer that is a double-terminal methacrylate-terminated polydimethylsiloxane having a number average molecular weight of at least 7,000 daltons; wherein the silicone hydrogel contact lens has an energy loss of about 25% to about 45% when fully hydrated. Silicone hydrogel contact lenses can have an energy loss of about 27% to about 40% when fully hydrated.

The combination of the polymeric component and the liquid component is present as a hydrated lens body suitable for placement on a human eye. The hydrated lens body has an overall convex anterior surface and an overall concave posterior surface, and an Equilibrium Water Content (EWC) of greater than 10% (weight/weight, wt/wt). Thus, the present contact lenses can be understood as soft contact lenses, which as used herein refers to contact lenses that can fold upon themselves without breaking when fully hydrated.

As understood in the industry, a daily disposable contact lens is an unworn contact lens that is removed from a sealed sterile package (original package) made by the contact lens manufacturer, placed on a person's eye, and at the end of the day, the lens that the person has worn is removed and discarded. Typically, the lenses of a daily disposable contact lens are worn for a duration of 8 to 14 hours and are then discarded after being worn. The daily disposable lens is not washed or exposed to a wash solution prior to placement on the eye because it is sterile prior to opening the package. Daily disposable silicone hydrogel contact lenses are disposable silicone hydrogel contact lenses that are replaced daily. In contrast, non-daily disposable contact lenses are disposable contact lenses that are replaced less frequently than daily (e.g., weekly, biweekly, or monthly). The non-daily disposable contact lenses are removed from the eye and periodically rinsed with a rinsing solution, or worn continuously without removal from the eye. The present contact lenses can be daily-cast contact lenses or non-daily-cast contact lenses.

Upon application of a cycle of energy loading and energy release to a viscoelastic material (e.g., a silicone hydrogel material), the stress-strain curve will exhibit a phase delay or hysteresis loop due to the loss of energy (in the form of heat) from the system during cycling. The percent energy loss can be determined using a variety of methods known to those skilled in the art. For example, a sample may be stretched to 100% strain at a constant rate such as 50 mm/min and then returned to 0% strain. Plotting the percentage of tensile strain versus the tensile force applied to the sample will produce a curve showing a hysteresis loop. The percent energy loss of the material can be calculated using the following equation (B):

((energy)_{0% to 100% strain}-energy_{100% to 0% strain}) Energy/energy_{0% to 100% strain})×100(B)

Wherein the energy is_{0% to 100% strain}Means the energy applied to stretch the material to 100% strain, and the energy_{100% to 0% strain}Representing the energy released when the material returns from 100% strain to 0% strain.

In one example, the silicone hydrogel contact lens is a silicone hydrogel contact lens comprising a polymerized lens body that is a reaction product of a polymerizable composition comprising (a) a first siloxane monomer represented by formula (1):

wherein m in formula (1) represents one integer of 3 to 10, n in formula (1) represents one integer of 1 to 10, R1 in formula (1) is an alkyl group having 1 to 4 carbon atoms, and R2 in formula (1) is a hydrogen atom or a methyl group; and (b) a second siloxane monomer that is a double-terminal methacrylate-terminated polydimethylsiloxane having a number average molecular weight of at least 7,000 daltons; wherein the silicone hydrogel contact lens has an energy loss of about 25% to about 45% when fully hydrated, and the energy loss is calculated using equation (B):

Wherein the energy is_{0% to 100% strain}Represents the energy applied to stretch a sample of the lens to 100% strain at a constant rate, and the energy_{100% to 0% strain}Representing the energy released when a sample of the lens recovers from 100% strain to 0% strain.

The percent energy loss of the material is an indication of the elasticity of the tested material. A lower percentage of energy loss indicates that the material has a higher level of elasticity and is less viscous, while a higher percentage of energy loss indicates that the material has a lower level of elasticity and is more viscous. Elastomers with lower percentages of energy loss tend to be more "elastic" under force, while elastomers with higher percentages of energy loss tend to be more "compliant". For contact lenses, more "compliant" materials tend to move less on the eye, while more "elastic" materials tend to move more on the eye. It is important for corneal health to have a minimum level of on-eye movement. However, in order for the lens to provide vision improvement, the level of movement on the eye should be minimized so that the lens remains in place after blinking. Therefore, achieving the appropriate level of energy loss is an important factor in the development of silicone hydrogel contact lenses.

As described herein, it has been found that polymerizable compositions comprising a first siloxane monomer represented by formula (1) and a second siloxane, which is a double-terminal methacrylate-terminated polydimethylsiloxane having a number average molecular weight of at least 7,000 daltons, can be used to produce silicone hydrogel contact lenses having ophthalmically acceptable levels of energy loss. Silicone hydrogel contact lenses formed from polymers comprising a combination of polymerized units of a first siloxane and a second siloxane, optionally with polymerized units of a third siloxane monomer, or polymerized units of at least one crosslinker, or polymerized units of at least one hydrophilic monomer, or any combination thereof, can exhibit a level of on-eye movement when fully hydrated sufficient to promote good corneal health, while exhibiting a level of on-eye movement that is sufficiently low so that lenses formed from these materials provide good vision correction.

According to the present invention, the polymerizable composition used to produce the silicone hydrogel contact lenses of the invention comprises a first siloxane monomer represented by formula (1):

wherein m in formula (1) represents an integer of 3 to 10, n in formula (1) represents an integer of 1 to 10, R in formula (1) ¹Is an alkyl group having 1 to 4 carbon atoms, and each R in the formula (1)²Independently a hydrogen atom or a methyl group. The polymerizable composition also includes a second siloxane monomer that is a double-terminal methacrylate-terminated polydimethylsiloxane having a number average molecular weight of at least 7,000 daltons. The amount of ingredients present in the polymerizable composition should be such that the resulting silicone hydrogel contact lens has an energy loss of about 25% to about 45%, such as about 27% to about 40%, or about 30% to about 37%, when fully hydrated.

wherein m in formula (1) represents one integer of 3 to 10, n in formula (1) represents one integer of 1 to 10, R1 in formula (1) is an alkyl group having 1 to 4 carbon atoms, and R2 in formula (1) is a hydrogen atom or a methyl group; and (b) a second siloxane monomer that is a double-terminal methacrylate-terminated polydimethylsiloxane having a number average molecular weight of at least 7,000 daltons; wherein the silicone hydrogel contact lens has an energy loss of about 27% to about 40% when fully hydrated.

Further, according to the present invention, silicone hydrogel contact lenses having ophthalmically acceptable levels of energy loss can be formed from polymerizable compositions comprising: (a) a first siloxane monomer represented by formula (1):

wherein m in formula (1) represents an integer of 3 to 10, n in formula (1) represents an integer of 1 to 10, R in formula (1)¹Is an alkyl group having 1 to 4 carbon atoms, and each R in the formula (1)²Independently a hydrogen atom or a methyl group; and (b) a second siloxane monomer that is a double-terminal methacrylate-terminated polydimethylsiloxane having a number average molecular weight of at least 7,000 daltons. It has been found that by using a combination of a first siloxane monomer and a second siloxane monomer (alone or in combination with at least one crosslinker, or a third siloxane monomer, or a hydrophilic monomer, or a hydrophobic monomer, or any combination thereof), a polymerizable composition can be prepared that can be used to produce silicone hydrogel contact lenses that have an average energy loss level of about 25% to about 45%, or about 27% to about 40%, or 30% to about 37% when fully hydrated.

Wherein m in formula (1) represents one integer of 3 to 10, n in formula (1) represents one integer of 1 to 10, R1 in formula (1) is an alkyl group having 1 to 4 carbon atoms, and R2 in formula (1) is a hydrogen atom or a methyl group; (b) a second siloxane monomer that is a double-terminal methacrylate-terminated polydimethylsiloxane having a number average molecular weight of at least 7,000 daltons; and (c) at least one vinyl-containing crosslinking agent; wherein the silicone hydrogel contact lens has an energy loss of about 25% to about 45% when fully hydrated. Silicone hydrogel contact lenses can have an energy loss of about 27% to about 40% when fully hydrated. When the polymerizable composition includes at least one crosslinking agent, the total amount of crosslinking agent (i.e., the total unit parts of all crosslinking agents present in the polymerizable composition) can be in an amount of from about 0.01 unit parts to about 5 unit parts, or from about 0.1 unit parts to about 4 unit parts, or from about 0.3 unit parts to about 3.0 unit parts, or from about 0.2 unit parts to about 2.0 unit parts, or from about 0.6 unit parts to about 1.5 unit parts.

In one example, where the polymerizable composition of the present invention comprises at least one vinyl-containing crosslinking agent, the total amount of vinyl-containing crosslinking agent present in the polymerizable composition can be in an amount of from about 0.01 unit parts to about 2.0 unit parts, or from about 0.01 unit parts to about 0.80 unit parts, or from about 0.01 unit parts to about 0.30 unit parts, or from about 0.05 unit parts to about 0.20 unit parts, or in an amount of about 0.1 unit parts.

Where the polymerizable composition comprises a first siloxane monomer and a second siloxane monomer of formula (1) that is a double-terminal methacrylate-terminated polydimethylsiloxane having a number average molecular weight of at least 7,000 daltons and at least one crosslinker, the first siloxane monomer and the at least one crosslinker (i.e., a single crosslinker or a crosslinker component consisting of two or more crosslinkers) can be present in the polymerizable composition at a ratio of at least 10:1 (based on the total weight unit parts of the first siloxane monomer to the total weight unit parts of the at least one crosslinker (i.e., the sum of the unit parts of all vinyl-containing crosslinkers present in the polymerizable composition)). For example, the ratio may be at least 25:1 or at least 50:1 or at least 100:1 (based on parts by weight). In one example, the at least one crosslinker can comprise at least one vinyl-containing crosslinker and at least one methacrylate-containing crosslinker. In another example, the at least one crosslinking agent may consist of only one or more vinyl-containing crosslinking agents. In another example, the at least one crosslinking agent can comprise or consist of at least one vinyl ether-containing crosslinking agent. In yet another example, the at least one crosslinking agent may consist of only one or more vinyl-containing crosslinking agents. In a particular example, the at least one crosslinking agent can comprise or consist of at least one vinyl ether-containing crosslinking agent.

wherein m in formula (1) represents one integer of 3 to 10, n in formula (1) represents one integer of 1 to 10, R1 in formula (1) is an alkyl group having 1 to 4 carbon atoms, and R2 in formula (1) is a hydrogen atom or a methyl group; (b) a second siloxane monomer that is a double-terminal methacrylate-terminated polydimethylsiloxane having a number average molecular weight of at least 7,000 daltons; and (c) at least one vinyl-containing crosslinking agent; and (d) at least one methacrylate crosslinking agent; wherein the silicone hydrogel contact lens has an energy loss of about 25% to about 45% when fully hydrated. Silicone hydrogel contact lenses can have an energy loss of about 27% to about 40% when fully hydrated.

When the at least one crosslinking agent comprises or consists of at least one vinyl-containing crosslinking agent (i.e., a single vinyl-containing crosslinking agent or a vinyl-containing crosslinking agent component consisting of two or more vinyl-containing crosslinking agents), the first siloxane monomer and the at least one vinyl-containing crosslinking agent can be present in the polymerizable composition in a ratio of at least about 50:1 (based on the total number of unit parts of the first siloxane monomer to the total number of unit parts of the at least one vinyl-containing crosslinking agent (i.e., the sum of the unit parts of all vinyl-containing crosslinking agents present in the polymerizable composition). For example, the ratio may be about 50:1 to about 500:1, or about 100:1 to about 400:1, or about 200:1 to about 300:1 (based on parts by weight).

wherein m in formula (1) represents one integer of 3 to 10, n in formula (1) represents one integer of 1 to 10, R1 in formula (1) is an alkyl group having 1 to 4 carbon atoms, and R2 in formula (1) is a hydrogen atom or a methyl group; (b) a second siloxane monomer that is a double-terminal methacrylate-terminated polydimethylsiloxane having a number average molecular weight of at least 7,000 daltons; and (c) at least one vinyl-containing crosslinking agent; wherein the ratio of the amount of the first siloxane monomer present in the polymerizable composition to the total amount of vinyl-containing crosslinker present in the polymerizable composition is 100:1 to 400:1 (based on weight unit parts); and the silicone hydrogel contact lens has an energy loss of about 25% to about 45% when fully hydrated. Silicone hydrogel contact lenses can have an energy loss of about 27% to about 40% when fully hydrated.

When the polymerizable composition comprises a combination of a first siloxane monomer of formula (1), a second siloxane monomer that is a double-terminal methacrylate-terminated polydimethylsiloxane having a number average molecular weight of at least 7,000 daltons, and at least one crosslinking agent, the siloxane monomer and the at least one vinyl-containing monomer can be present in the polymerizable composition in a ratio of at least about 100:1 (based on the ratio of the total number of unit parts of each siloxane monomer present in the polymerizable composition (i.e., the sum of the unit parts of the first siloxane and second siloxane monomers and, if present, the third siloxane monomer, etc.) to the total number of unit parts of the at least one vinyl-containing crosslinking agent (i.e., the sum of the unit parts of all vinyl-containing crosslinking agents present in the polymerizable composition)). For example, the ratio may be about 50:1 to about 500:1, or about 100:1 to about 400:1, or about 200:1 to about 300:1 (based on parts by weight).

In one example, the total amount of siloxane monomers present in the polymerizable composition (i.e., the total unit parts of the first siloxane monomer and, if present, the second siloxane monomer and the at least one third siloxane monomer) can be in an amount of about 30 to 45 unit parts, or about 36 to 40 unit parts.

The first siloxane monomer of formula (1) has a molecular weight of 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. Further details of the first siloxane monomer are known from US20090299022, which is incorporated herein in its entirety by reference. As can be appreciated from formula (1), the first siloxane monomer has a single methacrylate polymerizable functional group present on one end of the siloxane monomer backbone.

wherein m in formula (1) represents an integer of 3 to 10, n in formula (1) represents an integer of 1 to 10, R1 in formula (1) is an alkyl group having 1 to 4 carbon atoms, and R2 in formula (1) is a hydrogen atom or a methyl group, and the number average molecular weight of the first siloxane monomer is 400 to 700 daltons; and (b) a second siloxane monomer that is a double-terminal methacrylate-terminated polydimethylsiloxane having a number average molecular weight of at least 7,000 daltons; wherein the silicone hydrogel contact lens has an energy loss of about 25% to about 45% when fully hydrated. Silicone hydrogel contact lenses can have an energy loss of about 27% to about 40% when fully hydrated.

In another example, the silicone hydrogel contact lens is a silicone hydrogel contact lens comprising a polymerized lens body that is a reaction product of a polymerizable composition comprising (a) a first siloxane monomer represented by formula (1):

wherein m in formula (1) represents an integer of 3 to 10, n in formula (1) represents an integer of 1 to 10, R1 in formula (1) is an alkyl group having 1 to 4 carbon atoms, and R2 in formula (1) is a hydrogen atom or a methyl group, and the number average molecular weight of the first siloxane monomer is 400 to 700 daltons; and (b) a second siloxane monomer that is a double-terminal methacrylate-terminated polydimethylsiloxane having a number average molecular weight of at least 7,000 daltons; and (c) at least one vinyl-containing crosslinking agent; wherein the silicone hydrogel contact lens has an energy loss of about 25% to about 45% when fully hydrated. Silicone hydrogel contact lenses can have an energy loss of about 27% to about 40% when fully hydrated.

In yet another example, the silicone hydrogel contact lens is a silicone hydrogel contact lens comprising a polymerized lens body that is a reaction product of a polymerizable composition comprising (a) a first siloxane monomer represented by formula (1):

Wherein m in formula (1) represents an integer of 3 to 10, n in formula (1) represents an integer of 1 to 10, R1 in formula (1) is an alkyl group having 1 to 4 carbon atoms, and R2 in formula (1) is a hydrogen atom or a methyl group, and the number average molecular weight of the first siloxane monomer is 400 to 700 daltons; and (b) a second siloxane monomer that is a double-terminal methacrylate-terminated polydimethylsiloxane having a number average molecular weight of from 7,000 daltons to at least 20,000 daltons; wherein the silicone hydrogel contact lens has an energy loss of about 25% to about 45% when fully hydrated. Silicone hydrogel contact lenses can have an energy loss of about 27% to about 40% when fully hydrated.

In one example of a contact lens of the invention, the first siloxane monomer can be represented by formula (1), wherein m in formula (1) is 4, n in formula (1) is 1, and R in formula (1)¹Is butyl, and each R in formula (1)²Independently a hydrogen atom or a methyl group. One example of the first siloxane monomer is identified herein in examples 1-28 as Si 1.

Wherein m in formula (1) is 4, n in formula (1) is 1, R in formula (1)¹Is butyl, and each R in formula (1)²Independently a hydrogen atom or a methyl group; and (b) a second siloxane monomer that is a double-terminal methacrylate-terminated polydimethylsiloxane having a number average molecular weight of at least 7,000 daltons; wherein the silicone hydrogel contact lens has an energy loss of about 25% to about 45% when fully hydrated. Silicone hydrogel contact lenses can have an energy loss of about 27% to about 40% when fully hydrated.

wherein m in formula (1) is 4, n in formula (1) is 1, R in formula (1)¹Is butyl, and each R in formula (1)²Independently a hydrogen atom or a methyl group, and the number average molecular weight of the first siloxane monomer is from 400 daltons to 700 daltons; and (b) a second siloxane monomer that is a double-terminal methacrylate-terminated polydimethylsiloxane having a number average molecular weight of at least 7,000 daltons; wherein the silicone hydrogel contact lens has an energy loss of about 25% to about 45% when fully hydrated. Silicone hydrogel contact lenses can have an energy loss of about 27% to about 40% when fully hydrated.

Molecular weight as used herein is understood to mean 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 monomer sample. Since the molar masses of the individual molecules in a monomer sample may differ slightly from one another, there may be a certain level of polydispersity in the sample. The term "molecular weight" as used herein refers to the number average molecular weight of a monomer or ingredient, as the siloxane monomer or any other monomer, macromer, prepolymer, or polymer in the polymerizable composition has polydispersity. As one example, a sample of siloxane monomers can have a number average molecular weight of about 15,000 daltons, but if the sample has polydispersity, the actual molecular weight of the individual monomers present in the sample can be in the range of 12,000 daltons to 18,000 daltons.

The number average molecular weight can be an absolute number average molecular weight as determined by proton Nuclear Magnetic Resonance (NMR) end group analysis as understood by one of skill in the art. Molecular weight may also be determined using gel permeation chromatography as understood by one of skill in the art, or may be provided by the supplier of the chemicals.

The first siloxane monomer, the second siloxane monomer, and, when present, the optional at least one third siloxane monomer comprise siloxane monomer components of the polymerizable composition each of the first siloxane monomer, or the second siloxane monomer, or the optional at least one third siloxane monomer, or any combination thereof, can be a hydrophilic siloxane monomer, or a hydrophobic siloxane monomer, or can have both hydrophilic and hydrophobic regions, depending on the number and location of any hydrophilic components (e.g., units of ethylene glycol, polyethylene glycol, etc.) present in the molecular structure of the siloxane monomer.

For example, the optional second siloxane monomer, or the optional at least one third siloxane monomer, or any combination thereof, can contain a hydrophilic component within the backbone of the siloxane molecule, can contain a hydrophilic component within one or more side chains of the siloxane molecule, or any combination thereof. For example, the siloxane monomer can have at least one ethylene glycol unit adjacent to a polymerizable functional group in the backbone of the siloxane molecule. As used herein, adjacent is understood to mean both directly adjacent and separated by only 10 or fewer carbon atoms. The at least one ethylene glycol unit adjacent to the polymerizable functional group in the backbone of the siloxane molecule can be separated from the polymerizable functional group by a carbon chain length of 1 to 5 units (i.e., wherein the ethylene glycol unit is bonded to the first carbon in a carbon chain length of 1 to 5 units and the polymerizable functional group is bonded to the last carbon in a carbon chain length of 1 to 5 units, in other words, the ethylene glycol unit and the polymerizable group are not directly adjacent but are separated by 1 to 5 carbon atoms). The siloxane monomer may have at least one ethylene glycol unit adjacent to the polymerizable functional groups present on both ends of the siloxane molecular backbone. The siloxane monomer can have at least one ethylene glycol unit present in at least one side chain of the siloxane molecule. The at least one ethylene glycol unit present in at least one side chain of the siloxane molecule can be part of a side chain bonded to a silicon atom in the backbone of the siloxane molecule. The siloxane molecules can have both at least one ethylene glycol unit adjacent to the polymerizable functional groups present on both ends of the siloxane molecule backbone, and at least one ethylene glycol unit present in at least one side chain of the siloxane molecule.

wherein m in formula (1) represents one integer of 3 to 10, n in formula (1) represents one integer of 1 to 10, R1 in formula (1) is an alkyl group having 1 to 4 carbon atoms, and R2 in formula (1) is a hydrogen atom or a methyl group; and (b) a second siloxane monomer that is a double-terminal methacrylate-terminated polydimethylsiloxane having at least one ethylene glycol unit adjacent to a polymerizable functional group present on both terminals of the siloxane molecule backbone and having a number average molecular weight of at least 7,000 daltons; wherein the silicone hydrogel contact lens has an energy loss of about 25% to about 45% when fully hydrated. Silicone hydrogel contact lenses can have an energy loss of about 27% to about 40% when fully hydrated.

The hydrophilicity or hydrophobicity of the monomer can be determined using conventional techniques (e.g., based on the water solubility of the monomer). For the purposes of the present invention, hydrophilic monomers are monomers which are significantly soluble in aqueous solutions at room temperature (e.g., about 20 ℃ to 25 ℃). For example, a hydrophilic monomer can be understood to be any monomer that is significantly completely soluble in 1 liter of water at 20 ℃ for 50 grams or more of the monomer (i.e., the monomer can be dissolved in water at a concentration of at least 5% wt/wt), as determined using standard shake flask methods known to those skilled in the art. Hydrophobic monomers as used herein are the following monomers: are significantly insoluble in aqueous solutions at room temperature, such that there are multiple separate visually discernible phases in the aqueous solution, or such that the aqueous solution appears cloudy and separates into two distinct phases over time upon standing at room temperature. By way of example, a hydrophobic monomer is understood to be any monomer that is significantly incapable of completely dissolving 50 grams of monomer in 1 liter of water at 20 ℃ (i.e., the monomer is dissolved in water at a concentration of less than 5% wt/wt).

In one example of the present invention, the second siloxane monomer, or optionally at least one third siloxane monomer, can be a multifunctional siloxane monomer. Where the second siloxane monomer has two functional groups (e.g., two methacrylate groups), it is a difunctional monomer.

The optional at least one third siloxane monomer may be a siloxane monomer in which a polymerizable functional group is present on one end of the monomer backbone. The third siloxane monomer may be a siloxane monomer having a polymerizable functional group on both ends of the monomer main chain. The third siloxane monomer can be a siloxane monomer in which a polymerizable functional group is present on at least one side chain of the monomer. The third siloxane monomer can be a siloxane monomer in which the polymerizable functional group is present on only one side chain of the monomer.

The optional at least one third siloxane monomer of the polymerizable composition can be an acrylate-containing siloxane monomer, in other words, a siloxane monomer having at least one acrylate polymerizable functional group as part of its molecular structure. In one example, the acrylate-containing siloxane monomer can be a methacrylate-containing siloxane monomer, i.e., a siloxane monomer having at least one methacrylate polymerizable functional group as part of its molecular structure.

The optional at least one third siloxane may be a siloxane monomer having a number average molecular weight of at least 3,000 daltons. In another example, the siloxane monomer can be a siloxane monomer having a 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 second siloxane monomer, or alternatively at least one third siloxane monomer, can be a siloxane monomer having a molecular weight of less than 20,000 daltons. In another example, the siloxane monomer can be a siloxane monomer having a molecular weight of less than 15,000 daltons, or less than 11,000 daltons, or less than 9,000 daltons, or less than 7,000 daltons, or less than 5,000 daltons.

The optional at least one third siloxane monomer can be a siloxane monomer having a molecular weight of 3,000 daltons to 20,000 daltons. In another example, the siloxane monomer can be a siloxane monomer having a molecular weight of 5,000 daltons to 20,000 daltons, or 5,000 daltons to 10,000 daltons, or 7,000 daltons to 15,000 daltons.

In one example, the optional at least one third siloxane monomer has more than one functional group and a number average molecular weight of at least 3,000 daltons.

The optional at least one third siloxane monomer may comprise a poly (organosiloxane) monomer or macromer or prepolymer, for example, 3- [ TRIS (trimethylsiloxy) silyl ] propylallyl carbamate, or 3- [ TRIS (trimethylsiloxy) silyl ] propyl vinyl carbamate, or trimethylsilylethyl carbonate vinyl ester, or trimethylsilylmethyl carbonate vinyl ester, or 3- [ TRIS (trimethylsiloxy) silyl ] propyl methacrylate (TRIS), or 3- (methacryloyloxy-2-hydroxypropoxy) propyl bis (trimethylsiloxy) methylsilane (SiGMA), or methyl bis (trimethylsiloxy) silylpropyl glycerol ethyl methacrylate (SiGEMA), or a polydimethylsiloxane having monomethacryloxypropyl ends (MCS-M11), MCR-M07, or polydimethylsiloxane (mPDMS) with monomethacryloxypropyl and mono-n-butyl termini, or any combination thereof. In one example of the polymerizable composition of the present disclosure, the optional at least one third siloxane can comprise one or more of the first siloxanes described herein, wherein the second siloxane monomer and the at least one third siloxane are different from the first siloxane present in the polymerizable composition based on molecular weight, molecular structure, or both molecular weight and structure. For example, the optional at least one third siloxane monomer can be a siloxane monomer of formula (1) having a different molecular weight than the first siloxane monomer or the second siloxane monomer in the polymerizable composition. In another example, the optional at least one third siloxane can comprise at least one siloxane disclosed in the following patents: US2007/0066706, US2008/0048350, US3808178, US4120570, US4136250, US4153641, US470533, US5070215, US5998498, US5760100, US6367929 and EP080539, the entire contents of which are incorporated herein by reference.

In another example of a contact lens of the invention, the optional at least one third siloxane monomer can be a double-terminal methacrylate-terminated polydimethylsiloxane having a number average molecular weight of at least 4,000 daltons. It is to be understood that the siloxane monomer is a difunctional monomer.

As an example of a difunctional siloxane monomer that may be used in the silicone hydrogel contact lenses of the present invention, the second siloxane monomer, or alternatively at least one third siloxane monomer, may be a siloxane monomer represented by formula (2):

wherein R in formula (2)₁Selected from a hydrogen atom or a methyl group; r in the formula (2)₂Selected from a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms; m in formula (2) represents an integer of 0 to 10; n in formula (2) represents an integer of 4 to 100; a and b represent an integer of 1 or more; a + b equals 20 to 500; b/(a + b) equals 0.01 to 0.22; and the configuration of the siloxane units includes a random configuration. In an example where the siloxane monomer is a monomer represented by formula (2), m in formula (2) is 0, n in formula (2) is an integer of 5 to 15, a is an integer of 65 to 90, b is an integer of 1 to 10, R in formula (2)₁Is methyl, and R in formula (2)₂Is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. One example of the siloxane monomer represented by formula (2) is abbreviated as Si2 in examples 1 to 28. The number average molecular weight of the siloxane monomer represented by formula (2) may be from about 9,000 daltons to about 10,000 daltons. In another example, the siloxane monomer represented by formula (2) can have a molecular weight of about 5,000 daltons to about 10,000 daltons. It can be appreciated that the siloxane represented by formula (2) is a difunctional siloxane having two terminal methacrylate polymerizable functional groups (i.e., a methacrylate group is present on each end of the siloxane backbone of the molecule). Further details of this siloxane monomer can be found in US20090234089, which is incorporated herein by reference in its entirety.

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

wherein R in formula (2)₁Selected from a hydrogen atom or a methyl group; r in the formula (2)₂Selected from a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms; m in formula (2) represents an integer of 0 to 10; n in formula (2) represents an integer of 4 to 100; a and b represent an integer of 1 or more; a + b equals 20 to 500; b/(a + b) equals 0.01 to 0.22; and the configuration of the siloxane units comprises a random configuration, and the second siloxane monomer has a number average molecular weight of at least 7,000 daltons; wherein the silicone hydrogel contact lens has an energy loss of about 25% to about 45% when fully hydrated. Silicone hydrogel contact lenses can have an energy loss of about 27% to about 40% when fully hydrated.

wherein m in formula (2) is 0, n in formula (2) is an integer of 5 to 15, a is an integer of 65 to 90, b is an integer of 1 to 10, R in formula (2)₁Is methyl, and R in formula (2)₂Is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms; the configuration of the siloxane units includes a random configuration; and the second siloxane monomer has a number average molecular weight of at least 7,000 daltons; wherein the silicone hydrogel contact lens has an energy loss of about 25% to about 45% when fully hydrated. Silicone hydrogel contact lenses can have an energy loss of about 27% to about 40% when fully hydrated.

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

wherein R in formula (2)₁Selected from a hydrogen atom or a methyl group; r in the formula (2)₂Selected from a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms; m in formula (2) represents an integer of 0 to 10; n in formula (2) represents an integer of 4 to 100; a and b represent an integer of 1 or more; a + b equals 20 to 500; b/(a + b) equals 0.01 to 0.22; and the configuration of the siloxane units includes a random configuration,and the second siloxane monomer has a number average molecular weight of at least 7,000 daltons; wherein the silicone hydrogel contact lens has an energy loss of about 25% to about 45% when fully hydrated. Silicone hydrogel contact lenses can have an energy loss of about 27% to about 40% when fully hydrated.

As another example of difunctional siloxane monomers that may be used in the silicone hydrogel contact lenses of the present invention, the optional at least one third siloxane monomer may be represented by formula (3):

Wherein R is³Selected from a hydrogen atom or a methyl group, m in formula (3) represents an integer of 0 to 10, and n in formula (3) represents an integer of 1 to 500. In one example, the second siloxane monomer is represented by formula (3), and R³Is methyl, m in formula (3) is 0, and n in formula (3) is an integer of 40 to 60.

In another example, the optional at least one third siloxane monomer can be a difunctional siloxane monomer represented by formula (4), and abbreviated as Si3 in examples 1-28 (obtained as product code DMS-R18 from gallet (Gelest), Morrisville (Morrisville), PA):

in one example, the siloxane of formula (4) has a number average molecular weight of about 4,000 to about 4,500 daltons.

Another example of a siloxane monomer that may be used as the optional at least one third siloxane monomer may include a monofunctional siloxane monomer having at least one urethane linkage, such as a monofunctional siloxane monomer represented by formula (5):

wherein n in formula (5) is 0 to 30, or 10 to 15. In one example, the siloxane monomer can be a monomer of formula (5), wherein n in formula (5) is 12 to 13 and its molecular weight is about 1,500 daltons. The monofunctional siloxane monomer is described in US6,867,245, which case is incorporated herein by reference.

Yet another example of a siloxane monomer that may be used as the optional at least one third siloxane monomer may include a difunctional siloxane monomer having at least two urethane linkages, such as a difunctional siloxane monomer represented by formula (6):

wherein n in formula (6) is an integer from about 100 to 150, m in formula (6) is an integer from about 5 to about 15, h is an integer from about 2 to 8, and p is an integer from about 5 to about 10. Other examples of such difunctional siloxane monomers and methods of making compounds of formula (6) are described in U.S. patent No. 6,867,245, which is incorporated herein by reference. In a particular example, the siloxane monomer can be a difunctional siloxane monomer having two urethane linkages and a molecular weight greater than about 5,000 daltons (e.g., a molecular weight greater than about 10,000 daltons, or a molecular weight greater than about 15,000 daltons).

In one example of the present contact lenses, the optional at least one third 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 siloxane monomer can have a number average molecular weight of less than 20,000 daltons. Thus, in some instances, the second siloxane monomer can be considered a macromer, but will be referred to herein as a monomer because it forms 1 unit part of a polymer with the other reactive components in the polymerizable composition.

In one example, the first siloxane monomer and the second siloxane monomer can be present in the polymerizable composition in the following amounts: the ratio of the first siloxane monomer to the second siloxane monomer is at least 1:1 (based on unit parts), or at least 2:1 (based on unit parts). For example, the first siloxane monomer and the second siloxane monomer can be present in the polymerizable composition in a ratio of about 2:1 to about 10:1 (based on unit parts). In another example, the first siloxane monomer and the second siloxane monomer can be present in the polymerizable composition in a ratio of about 3:1 to about 6:1 (based on unit parts). In one 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).

wherein m in formula (1) represents one integer of 3 to 10, n in formula (1) represents one integer of 1 to 10, R1 in formula (1) is an alkyl group having 1 to 4 carbon atoms, and R2 in formula (1) is a hydrogen atom or a methyl group; (b) a second siloxane monomer that is a double-terminal methacrylate-terminated polydimethylsiloxane having a number average molecular weight of at least 7,000 daltons; wherein the ratio of the amount of the first siloxane monomer present in the polymerizable composition to the amount of the second siloxane monomer present in the polymerizable composition is at least 3:1 (based on parts by weight), and the silicone hydrogel contact lens has an energy loss of about 25% to about 45% when fully hydrated. Silicone hydrogel contact lenses can have an energy loss of about 27% to about 40% when fully hydrated.

The total amount of siloxane monomer present in the polymerizable composition (e.g., the sum of the unit parts of the first siloxane monomer, the second siloxane monomer, and any other optional siloxane monomers present in the polymerizable composition) can be from about 10 unit parts to about 60 unit parts, or from about 25 unit parts to about 50 unit parts, or from about 35 unit parts to about 40 unit parts.

The polymerizable composition of the present invention can be understood to comprise a first component consisting of a first siloxane monomer of formula (1), a second siloxane monomer which is a double-terminal methacrylate-terminated polydimethylsiloxane having a number average molecular weight of at least 7,000 daltons, and a second component comprising at least one third siloxane monomer, or at least one crosslinker, or at least one hydrophilic monomer, or at least one hydrophobic monomer, or any combination thereof. Optionally, at least one crosslinker may be present as a single crosslinker, or may be present as a crosslinker component comprising two or more single crosslinkers. The crosslinker and crosslinker components used herein are silicon-free crosslinkers and thus are distinct from the multifunctional siloxane monomers that may be present in the polymerizable composition.

Unit parts as used herein are understood to mean unit parts by weight. For example, to prepare a formulation described as comprising z unit parts of a siloxane monomer and y unit parts of a hydrophilic monomer, a composition can be prepared by: combining z grams of silicone monomer with y grams of hydrophilic monomer to obtain a total of y + z grams of polymerizable composition, or combining z ounces of silicone with y ounces of hydrophilic monomer to obtain a total of y + z ounces of polymerizable composition, and so forth. Where the composition further comprises other optional ingredients (e.g., x unit parts of a crosslinker), x grams of the crosslinker are combined with z grams of a siloxane monomer and y grams of a hydrophilic monomer to obtain a total of x + y + z grams of the polymerizable composition, and so on. Where the composition comprises other optional ingredients comprising an ingredient component consisting of two ingredients, e.g., a hydrophobic monomer component consisting of a first hydrophobic monomer and a second hydrophobic monomer, w unit parts of the first hydrophobic monomer and v unit parts of the second hydrophobic monomer are combined to obtain a total amount of v + w + x + y + z unit parts of the polymerizable composition, in addition to z unit parts of the siloxane monomer, y unit parts of the hydrophilic monomer, and x unit parts of the crosslinking agent. It is understood that the unit parts of the at least one hydrophobic monomer present in the polymerizable composition is the sum of the unit parts of the first hydrophobic monomer and the unit parts of the second hydrophobic monomer, e.g., v + w unit parts in this example. Typically, the formulation of the polymerizable composition will consist of ingredients in amounts totaling from about 90 to about 110 unit parts by weight. When the amounts of the components in the polymerizable composition are recited herein in unit parts, it is understood that the unit parts of these components are based on formulations that provide a total weight of the composition in the range of about 90 to 110 unit parts. In one example, the unit parts by weight can be based on a formulation that provides a total weight of the composition ranging from about 95 to 105 unit parts by weight, or about 98 to 102 unit parts by weight.

According to the invention, a crosslinker is understood to be a monomer having more than one polymerizable functional group (e.g. two or three or four polymerizable functional groups) as part of its molecular structure, i.e. a multifunctional monomer, such as a difunctional or trifunctional or tetrafunctional monomer. Silicon-free crosslinkers that may be used in the polymerizable compositions disclosed herein include, for example, but are not limited to, 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 divinylbenzene and trivinylbenzene, or trimethylolpropane tri (meth) acrylate, or neopentylglycol tetra (meth) acrylate, or bisphenol a di (meth) acrylate, or methylenebis (meth) acrylamide, or triallyl phthalate and diallyl phthalate, or any combination thereof. Crosslinkers as disclosed in examples 1-28 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 crosslinking agent can have a molecular weight of less than 1500 daltons, or less than 1000 daltons, or less than 500 daltons, or less than 200 daltons.

In one example, the crosslinker or crosslinker component can comprise or consist of a vinyl-containing crosslinker. As used herein, a vinyl-containing crosslinking 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, wherein each of the at least two polymerizable carbon-carbon double bonds present in the vinyl polymerizable functional groups of the vinyl-containing crosslinking agent is less reactive than the carbon-carbon double bonds present in the acrylate or methacrylate polymerizable functional groups. Although as understood herein, carbon-carbon double bonds are present in the acrylate and methacrylate polymerizable functional groups, crosslinkers comprising one or more acrylate or methacrylate polymerizable groups (e.g., acrylate-containing crosslinkers or methacrylate-containing crosslinkers) are not considered vinyl-containing crosslinkers. Polymerizable functional groups having a carbon-carbon double bond that is less reactive than the carbon-carbon double bond of the acrylate or methacrylate polymerizable group include, for example, vinyl amide, vinyl ester, vinyl ether, and allyl ester polymerizable functional groups. Thus, vinyl-containing crosslinkers as used herein include, for example, crosslinkers having at least two polymerizable functional groups selected from: vinyl amides, vinyl ethers, vinyl esters, allyl esters, and any combination thereof. The mixed vinyl-containing crosslinking agent used herein is the following crosslinking agent: at least one polymerizable carbon-carbon double bond (i.e., at least one vinyl polymerizable functional group) having a weaker reactivity than the carbon-carbon double bond present in the acrylate or methacrylate polymerizable functional group is present in the structure, and at least one polymerizable functional group having a carbon-carbon double bond having a reactivity at least equivalent to the carbon-carbon double bond in the acrylate or methacrylate polymerizable functional group is present in the structure.

When present in the polymerizable composition, the vinyl-containing crosslinking agent or crosslinker component may be present in an amount of from about 0.01 unit parts to about 2.0 unit parts, or from about 0.01 unit parts to about 0.80 unit parts, or from about 0.01 unit parts to about 0.30 unit parts, or from about 0.05 unit parts to about 0.20 unit parts, or in an amount of about 0.1 unit parts.

In one example, the crosslinker or crosslinker component can comprise or consist of a non-vinyl crosslinker (i.e., a crosslinker that is not a vinyl crosslinker). For example, the non-vinyl crosslinker or crosslinker component can comprise or consist of an acrylate-containing crosslinker (i.e., a crosslinker having at least two acrylate polymerizable functional groups), or a methacrylate-containing crosslinker (i.e., at least two methacrylate polymerizable functional groups), or at least one acrylate-containing crosslinker and at least one methacrylate-containing crosslinker.

When present in the polymerizable composition, no vinyl crosslinker or crosslinker may be present in an amount of from about 0.01 unit parts to about 5 unit parts, or from about 0.1 unit parts to about 4 unit parts, or from about 0.3 unit parts to about 3.0 unit parts, or from about 0.2 unit parts to about 2.0 unit parts.

The crosslinker component may comprise or consist of a combination of two or more crosslinkers each having a different polymerizable functional group. For example, the crosslinker component can comprise a vinyl-containing crosslinker and an acrylate-containing crosslinker. The crosslinker component may comprise a vinyl-containing crosslinker and a methacrylate-containing crosslinker. The crosslinker component may comprise or consist of a vinyl ether-containing crosslinker and a methacrylate-containing crosslinker.

In one example, the polymerizable composition of the present disclosure can optionally comprise at least one hydrophilic monomer. Hydrophilic monomers are understood to be non-silicone polymerizable components which have only one polymerizable functional group present in their molecular structure. The polymerizable composition can comprise a single hydrophilic monomer, or can comprise two or more hydrophilic monomers in the form of a hydrophilic monomer component. Silicon-free hydrophilic monomers that can be used as the hydrophilic monomer or hydrophilic monomer component in the polymerizable compositions disclosed herein include, for example, acrylamide-containing monomers, or acrylate-containing monomers, or acrylic-containing monomers, or methacrylate-containing monomers, or methacrylic-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 silicon-free monomer.

wherein m in formula (1) represents one integer of 3 to 10, n in formula (1) represents one integer of 1 to 10, R1 in formula (1) is an alkyl group having 1 to 4 carbon atoms, and R2 in formula (1) is a hydrogen atom or a methyl group; (b) a second siloxane monomer that is a double-terminal methacrylate-terminated polydimethylsiloxane having a number average molecular weight of at least 7,000 daltons; and (c) at least one hydrophilic monomer; wherein the silicone hydrogel contact lens has an energy loss of about 25% to about 45% when fully hydrated. Silicone hydrogel contact lenses can have an energy loss of about 27% to about 40% when fully hydrated.

Examples of hydrophilic monomers that may be included in the polymerizable compositions of the present disclosure may include, for example, 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 polyethylene glycol monomethacrylate, or methacrylic acid, or acrylic acid, or any combination thereof.

wherein m in formula (1) represents one integer of 3 to 10, n in formula (1) represents one integer of 1 to 10, R1 in formula (1) is an alkyl group having 1 to 4 carbon atoms, and R2 in formula (1) is a hydrogen atom or a methyl group; (b) a second siloxane monomer that is a double-terminal methacrylate-terminated polydimethylsiloxane having a number average molecular weight of at least 7,000 daltons; and (c) at least one hydrophilic vinyl-containing monomer; wherein the silicone hydrogel contact lens has an energy loss of about 25% to about 45% when fully hydrated. Silicone hydrogel contact lenses can have an energy loss of about 27% to about 40% when fully hydrated.

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 that can be provided in the polymerizable composition include, but are not limited to, 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-beta-alanine N-vinyl ester, or 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 in the polymerizable composition can comprise or consist of a hydrophilic amide monomer. The hydrophilic amide monomer may be a hydrophilic amide monomer having one N-vinyl group, such as 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-methylacetamide (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.

wherein m in formula (1) represents one integer of 3 to 10, n in formula (1) represents one integer of 1 to 10, R1 in formula (1) is an alkyl group having 1 to 4 carbon atoms, and R2 in formula (1) is a hydrogen atom or a methyl group; (b) a second siloxane monomer that is a double-terminal methacrylate-terminated polydimethylsiloxane having a number average molecular weight of at least 7,000 daltons; and (c) at least one hydrophilic amide monomer having one N-vinyl group; wherein the silicone hydrogel contact lens has an energy loss of about 25% to about 45% when fully hydrated. Silicone hydrogel contact lenses can have an energy loss of about 27% to about 40% when fully hydrated.

wherein m in formula (1) represents one integer of 3 to 10, n in formula (1) represents one integer of 1 to 10, R1 in formula (1) is an alkyl group having 1 to 4 carbon atoms, and R2 in formula (1) is a hydrogen atom or a methyl group; and (b) a second siloxane monomer that is a double-terminal methacrylate-terminated polydimethylsiloxane having a number average molecular weight of at least 7,000 daltons; and the polyoxide composition is free of N, N-Dimethylacrylamide (DMA); wherein the silicone hydrogel contact lens has an energy loss of about 25% to about 45% when fully hydrated. Silicone hydrogel contact lenses can have an energy loss of about 27% to about 40% when fully hydrated.

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, but are not limited to, 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 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 polymerizable functional group different from 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, where 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 amide-free monomers (i.e., one or more monomers each of which does not have an amide functional group as part of its molecular structure). 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 monomers (i.e., one or more monomers, each of which does not have a vinyl polymerizable functional group as part of its molecular structure). In another example, where 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 amide-free monomers. Where the first hydrophilic monomer or monomer component comprises or consists of one or more acrylate-free monomers (i.e., one or more monomers, each of which does not have an acrylate or methacrylate polymerizable functional group as part of its molecular structure), 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. Where the first hydrophilic monomer or monomer component comprises or consists of one or more vinyl ether-free monomers (i.e., one or more monomers, each of which does not have a vinyl ether polymerizable functional group as part of its molecular structure), 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, where 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 may comprise VMA and the second hydrophilic monomer may comprise BVE. The first hydrophilic monomer may comprise VMA and the second hydrophilic monomer may comprise EGVE. The first hydrophilic monomer may comprise VMA and the second hydrophilic monomer may comprise DEGVE. The first hydrophilic monomer may comprise VMA, and the second hydrophilic monomer component may comprise EGVE and DEGVE.

Similarly, the first hydrophilic monomer may be VMA, and the second hydrophilic monomer or monomer component may 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 may be VMA and the second hydrophilic monomer may be EGVE. The first hydrophilic monomer may comprise VMA and the second hydrophilic monomer may 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 silicon-free hydrophilic vinyl-containing monomer can have any molecular weight, such as a molecular weight of 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 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 of 30 to 60 unit parts of the polymerizable composition. The hydrophilic monomer or monomer component can be present in the polymerizable composition in a unit part by weight of 40 to 55, or 45 to 50. Where 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 of 0.1 to 20 unit parts of the polymerizable composition. For example, in a total amount of 30 to 60 unit parts of the hydrophilic monomer or monomer component present in the polymerizable composition, the first hydrophilic monomer or monomer component can comprise 29.9 to 40 unit parts and the second hydrophilic monomer or monomer component can comprise 0.1 to 20 unit parts. 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, wherein the carbon-carbon double bond in the vinyl polymerizable functional group is less reactive than the carbon-carbon double bond present in the acrylate or methacrylate polymerizable functional group under free radical polymerization. In other words, monomers comprising a single acrylate or methacrylate polymerizable group are not considered to be vinyl-containing monomers, although as understood herein, carbon-carbon double bonds are present in acrylate and methacrylate groups. Examples of the polymerizable group having a carbon-carbon double bond (which is less reactive than the carbon-carbon double bond in the acrylate or methacrylate polymerizable group) include vinyl amide, vinyl ether, vinyl ester, and allyl ester polymerizable groups. Thus, examples of vinyl-containing monomers useful herein 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 invention may optionally comprise at least one silicon-free hydrophobic monomer. Hydrophobic monomers are understood to be non-silicone polymerizable constituents which have only one polymerizable functional group present in their molecular structure. The at least one hydrophobic monomer of the polymerizable composition can be one hydrophobic monomer, or can comprise a hydrophobic monomer component consisting of at least two hydrophobic monomers. Examples of hydrophobic monomers that can be used in the polymerizable compositions disclosed herein include, but are not limited to, acrylate-containing hydrophobic monomers or methacrylate-containing hydrophobic monomers, or any combination thereof. Examples of hydrophobic monomers include, but are not limited to, 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 vinyl toluene, 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 may comprise or consist of MMA or EGMA or both.

wherein m in formula (1) represents one integer of 3 to 10, n in formula (1) represents one integer of 1 to 10, R1 in formula (1) is an alkyl group having 1 to 4 carbon atoms, and R2 in formula (1) is a hydrogen atom or a methyl group; (b) a second siloxane monomer that is a double-terminal methacrylate-terminated polydimethylsiloxane having a number average molecular weight of at least 7,000 daltons; and (c) at least one hydrophobic monomer; wherein the silicone hydrogel contact lens has an energy loss of about 25% to about 45% when fully hydrated. Silicone hydrogel contact lenses can have an energy loss of about 27% to about 40% when fully hydrated.

When present in the polymerizable composition, the hydrophobic monomer or monomer component can be present in an amount of about 5 to about 25 unit parts, or about 10 to about 20 unit parts.

In one example, the hydrophobic monomer component can comprise at least two hydrophobic monomers each having a different polymerizable functional group. 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 may 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 may 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 unit parts of MMA to unit parts of EGMA present in the polymerizable composition can be from about 6:1 to about 1: 1. The ratio of unit parts of MMA to EGMA present in the polymerizable composition may be about 2:1 (based on unit parts of MMA to unit parts of EGMA).

The polymerizable composition may 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 absorbers, or one or more colorants, or one or more oxygen scavengers, or one or more chain transfer agents, or any combination thereof. These optional ingredients may be polymerizable or non-polymerizable ingredients. In one example, the polymerizable composition can be free of diluents, in this regard, it is free of any organic diluents that achieve miscibility between the silicone and other lens forming ingredients (e.g., optional hydrophilic monomers, hydrophobic monomers, and crosslinking agents). Additionally, many of the polymerizable compositions of the present invention are substantially free of water (e.g., contain no more than 3.0% or 2.0% by weight water). The polymerizable compositions disclosed herein can optionally comprise one or more organic diluents, i.e., the polymerizable compositions can comprise an organic diluent, or can comprise an organic diluent component comprising two or more organic diluents. Organic diluents that may optionally be included in the polymerizable compositions of the present invention include alcohols, including lower alcohols, such as, but not limited to, 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 of 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.

The polymerizable composition of the present invention may optionally comprise one or more polymerization initiators, i.e., the polymerizable composition may comprise an initiator, or may comprise an initiator component comprising two or more polymerization initiators. Polymerization initiators that may be included in the polymerizable compositions of the present invention include, for example, azo compounds or organic peroxides or both. Initiators that may be present in the polymerizable composition include, for example, but are not limited to, benzoin ethyl ether, or benzyl dimethyl ketal, or α, α diethoxyacetophenone, or 2,4, 6-trimethylbenzoyl diphenylphosphine oxide, or benzoin peroxide, or t-butyl peroxide, or azobisisobutyronitrile, or azobisdimethylvaleronitrile, or any combination thereof. The UV photoinitiator may include, for example, a phosphine oxide such as diphenyl (2,4, 6-trimethylbenzoyl) phosphine oxide, or benzoin methyl ether, or 1-hydroxycyclohexyl phenyl ketone, or Darocur (available from BASF, florham park, NJ, usa), or gorgeous (Irgacur) (also available from BASF), or any combination thereof. In many of examples 1-28 disclosed herein, the polymerization initiator is the thermal initiator 2, 2' -azobis-2-methylpropanenitrile (VAZO-64 from dupont nemours & Co.), Wilmington, state of terawa (DE), usa. Other commonly used thermal initiators may include 2,2 '-azobis (2, 4-dimethylvaleronitrile) (VAZO-52) and 1, 1' -azobis (cyanocyclohexane) (VAZO-88). The polymerization initiator or initiator component can be present in the polymerizable composition in an amount of from about 0.01 to about 2.0 unit parts by weight, or from about 0.1 to about 1.0 unit parts by weight, or from about 0.2 to about 0.6 unit parts by weight.

Optionally, the polymerizable compositions of the present inventionOne or more UV absorbers may be included, i.e., the polymerizable composition may include a UV absorber, or may include a UV absorber component including two or more UV absorbers. UV absorbers that may be included in the polymerizable compositions of the present invention include, for example, benzophenone, or benzotriazole, or any combination thereof. In many of examples 1-28 disclosed herein, the UV absorber is 2- (4-benzoyl-3-hydroxyphenoxy) ethyl acrylate (UV-416) or 2- (3- (2H-benzotriazol-2-yl) -4-hydroxy-phenyl) ethyl methacrylate (nobilex @)7966 from Nolamaceae (Noramco), Athens (Athens), Georgia (GA), USA. The UV absorber or UV absorber component can be present in the polymerizable composition in an amount of from about 0.01 unit parts by weight to about 5.0 unit parts by weight, or from about 0.1 unit parts by weight to about 3.0 unit parts by weight, or from about 0.2 unit parts by weight to about 2.0 unit parts by weight.

The polymerizable compositions of the present invention can also optionally include at least one colorant (i.e., one colorant or a colorant component comprising two or more colorants), but encompass tinted and clear lens products. In one example, the colorant can be a reactive dye or pigment effective to provide color to the resulting lens product. The colorant or colorant component in the polymerizable composition can comprise a polymerizable colorant, or can comprise a non-polymerizable colorant, or any combination thereof. The polymerizable colorant may be a colorant whose molecular structure contains a polymerizable functional group, or may be a colorant whose molecular structure includes both a monomer portion and a dye portion, i.e., the colorant may be a monomer-dye compound. The molecular structure of the colorant may comprise a beta sulfone functional group, or may comprise a triazine functional group. Colorants can include, for example, VAT blue 6(7, 16-dichloro-6, 15-dihydroanthracene azine-5, 9,14, 18-tetrone), or 1-amino-4- [3- (. beta. -sulfatoethylsulfonyl) anilino ] -2-anthraquinone sulfonic acid (c.i. reactive blue 19, RB-19), or a monomer-dye compound of reactive blue 19 with hydroxyethyl methacrylate (RB-19HEMA), or 1, 4-bis [4- [ (2-methacryloyl-oxyethyl) phenylamino ] anthraquinone (reactive blue 246, RB-246, available from arran chemical company, alslon (Athlone), Ireland (Ireland)), or 1, 4-bis [ (2-hydroxyethyl) amino ] -9, 10-anthracenedione bis (2-propenoic acid) ester (RB-247), or reactive blue 4(RB-4), or a monomer-dye compound of reactive blue 4 and hydroxyethyl methacrylate (RB-4HEMA or "blue HEMA"), or any combination thereof. In one example, the colorant or colorant component can comprise a polymerizable colorant. The polymerizable colorant component can comprise, for example, RB-246, or RB-274, or RB-4HEMA, or RB-19HEMA, or any combination thereof. Examples of monomer-dye compounds include RB-4HEMA and RB-19 HEMA. Further examples of monomer-dye compounds are described in US5944853 and US 72169975, both of which are incorporated herein by reference in their entirety. Other exemplary colorants are disclosed, for example, in U.S. patent application publication No. 2008/0048350, the disclosure of which is incorporated herein by reference in its entirety. In many of examples 1-28 disclosed herein, the colorant is a reactive blue dye, such as those described in US4997897, the entire disclosure of which is incorporated herein by reference. Other suitable colorants for use in accordance with the present invention are phthalocyanine pigments (e.g., phthalocyanine blue or phthalocyanine green), or chromium-aluminum-cobalt oxide, or chromium oxide, as well as various red, yellow, brown, and black iron oxides, or any combination thereof. Opacifiers such as titanium dioxide may also be included. For some applications, combinations of colorants having different colors may be employed as the colorant component. If employed, the colorant or colorant 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 from about 0.005 unit parts to about 10.0 unit parts, or from about 0.01 unit parts to about 8.0 unit parts.

The polymerizable composition of the present invention may 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 that may be included as an oxygen scavenger or oxygen scavenger component of the polymerizable composition of the present invention include, for example, vitamin E, or a phenolic compound, or a phosphite compound, or a phosphine compound, or an amine oxide compound, or any combination thereof. For example, the oxygen scavenger or oxygen scavenger component may consist of or comprise a phosphine-containing compound. In many of examples 1-28 disclosed herein, the oxygen scavenger or oxygen scavenger component is a phosphine-containing compound, such as triphenylphosphine, or a polymerizable form of triphenylphosphine, such as diphenyl (p-vinylphenyl) phosphine.

Chain transfer is a polymerization reaction that transfers the activity of a growing polymer chain to another molecule, thereby reducing the average molecular weight of the final polymer. The polymerizable composition of the present invention may optionally comprise at least one chain transfer agent, i.e., may comprise one chain transfer agent or may comprise a chain transfer agent component comprising at least two chain transfer agents. Examples of chain transfer agents that may be included as chain transfer agents or chain transfer components of the polymerizable compositions of the present invention include, for example, thiol compounds, or halocarbon compounds, or C3 to C5 hydrocarbons, or any combination thereof. In many of examples 1-28 disclosed herein, the chain transfer agent is allyloxyethanol. When present in the polymerizable composition, the chain transfer agent or chain transfer agent component may be present in an amount of 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.

The contact lenses of the present invention are ophthalmically acceptable contact lenses in that they are configured to be placed or disposed on the cornea of an animal or human eye. An ophthalmically acceptable contact lens as used herein is understood to be a contact lens having at least one of a plurality of different properties as described below. An ophthalmically acceptable contact lens can be formed from and packaged in ophthalmically acceptable ingredients such that the lens is non-cytotoxic and does not release irritating and/or toxic ingredients during wear. An ophthalmically acceptable contact lens can have a clarity in the lens optic zone (i.e., the portion of the lens that provides vision correction) sufficient for its intended use in contact with the cornea of an eye, e.g., a light transmission of at least 80%, or at least 90%, or at least 95%. Ophthalmically acceptable contact lenses can have sufficient mechanical properties to facilitate lens handling and care over a duration based on their expected lifetime. For example, its modulus, tensile strength, and elongation may be sufficient to withstand insertion, wearing, removal, and optionally cleaning during the lens' expected lifetime. The level of these suitable properties will vary depending on the intended life and use of the lens (e.g., disposable, multiple use per month, etc.). An ophthalmically acceptable contact lens can have an effective or appropriate ion current to substantially inhibit or substantially prevent corneal staining, e.g., corneal staining that is more severe than superficial or moderate corneal staining, after 8 or more hours of continuous lens wear on the cornea. Ophthalmically acceptable contact lenses can have sufficient oxygen permeability levels to allow oxygen to reach the cornea of the eye wearing the lens in an amount sufficient to maintain long-term corneal health. An ophthalmically acceptable contact lens can be one that does not cause significant or excessive corneal edema of the eye on which the lens is worn, e.g., no more than about 5% or 10% corneal edema after being worn on the cornea of the eye during overnight sleep. An ophthalmically acceptable contact lens can be a lens that 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, without adhering the lens to the eye with sufficient force to impede normal lens movement, and with a sufficiently low level of movement on the eye to allow vision correction. An ophthalmically acceptable contact lens can be a lens that permits the lens to be worn on-eye without excess or significant discomfort and/or irritation and/or pain. An ophthalmically acceptable contact lens can be a lens that inhibits or substantially prevents the deposition of lipids and/or proteins sufficiently to allow the lens wearer to remove the lens due to the deposition. The ophthalmically acceptable contact lenses can have at least one water content, or surface wettability, or modulus or design, or any combination thereof, effective to promote ophthalmically compatible contact lens wear by contact lens wearers for at least one day. Ophthalmically compatible wear is understood to mean that the lens wearer produces little or no discomfort when wearing the lens and little or no corneal staining occurs. Conventional clinical methods can be used to determine whether a contact lens is ophthalmically acceptable, such as those implemented by an eye care practitioner and as will be appreciated by those skilled in the art.

In one example of the invention, a contact lens may have an ophthalmically acceptably wettable lens surface. For example, a contact lens can have an ophthalmically acceptably wettable lens surface when the polymerizable composition used to form the polymeric lens body does not contain an internal wetting agent, or when the polymerizable composition used to form the polymeric lens body does not contain an organic diluent, or when the polymeric lens body is extracted in water or an aqueous solution that does not contain a volatile organic solvent, or when the polymeric lens body is not surface plasma treated, or any combination thereof.

One method commonly used in the art to increase the wettability of a contact lens surface is to apply a treatment to or modify the lens surface. According to the present invention, silicone hydrogel contact lenses can have ophthalmically acceptably wettable lens surfaces without surface treatment or surface modification. Surface treatments include, for example, plasma and corona treatments that increase the hydrophilicity of the lens surface. While one or more surface plasmon treatments may be applied to the present lens bodies, this is not necessary to obtain silicone hydrogel contact lenses having ophthalmically acceptably wettable lens surfaces when fully hydrated. In other words, in one example, the present silicone hydrogel contact lenses may not be surface plasma or corona treated.

Surface modification includes binding a wetting agent to the lens surface, for example, binding a wetting agent such as a hydrophilic polymer to at least the lens surface by chemical bonding or other forms of chemical interaction. In some cases, the wetting agent can be bound to the lens surface and at least a portion of the polymeric matrix of the lens (i.e., at least a portion of the lens body) by chemical bonding or other forms of chemical interaction. An ophthalmically acceptably wettable lens surface of the present invention can have ophthalmically acceptable wettability in the absence of a wetting agent (e.g., a polymeric or non-polymeric material) at least bound to the lens surface. While one or more wetting agents may be incorporated into the lenses of the invention, this is not necessary to obtain silicone hydrogel contact lenses having ophthalmically acceptably wettable lens surfaces when fully hydrated. Thus, in one example, the lenses of the invention can comprise a wetting agent, e.g., a hydrophilic polymer and including polyvinylpyrrolidone, bound to the lens surface. Alternatively, in another example, the silicone hydrogel contact lenses of the invention may be free of wetting agents bound to the lens surface.

Another approach to increasing the wettability of a lens is to physically entrap wetting agents within the lens body or contact lens, for example, by: the wetting agent is introduced into the lens body as the lens body expands and then the lens body is returned to a less expanded state, thereby trapping a portion of the wetting agent within the lens body. The wetting agent may be permanently trapped within the lens body, or may be released from the lens over time (e.g., during wear). An ophthalmically acceptably wettable lens surface of the present invention can have ophthalmically acceptable wettability without the presence of wetting agents (e.g., polymeric or non-polymeric materials) physically entrapped in the lens body after formation of the polymeric lens body. While one or more wetting agents may be physically entrapped in the lenses of the invention, this is not necessary to obtain silicone hydrogel contact lenses having ophthalmically acceptably wettable lens surfaces when fully hydrated. Thus, in one example, the lenses of the invention may comprise a wetting agent entrapped within the lens, for example, a hydrophilic polymer and including polyvinylpyrrolidone. Alternatively, the silicone hydrogel contact lenses of the invention may be free of wetting agents physically entrapped within the lenses. Physical entrapment, as used herein, means that the wetting agent or other ingredient is immobilized in the polymeric matrix of the lens with little or no chemical bonding or interaction between the wetting agent and or other ingredient and the polymeric matrix. This is in contrast to components that are chemically bonded to the polymeric matrix by, for example, ionic bonding, covalent bonding, van der waals forces, and the like.

Another method commonly used in the industry 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, when the polymerizable composition used to form the polymeric lens body is free of wetting agents, the contact lenses of the invention can have an ophthalmically acceptably wettable lens surface. While one or more wetting agents may be included in the polymerizable compositions of the present invention to increase the wettability of the silicone hydrogel contact lenses of the present invention, this is not necessary to obtain silicone hydrogel contact lenses having ophthalmically acceptably wettable lens surfaces. In other words, in one example, the present silicone hydrogel contact lenses can be formed from a polymerizable composition that does not contain a wetting agent. Alternatively, in another example, the polymerizable composition 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 incorporated within at least a portion of the polymeric matrix of the lens. For example, the internal wetting agent can be incorporated within at least a portion of the lens polymeric matrix by chemical bonding or other forms of chemical interaction. In some cases, wetting agents can also bind to the lens surface. The internal wetting agent may comprise a polymeric material or a non-polymeric material. While one or more internal wetting agents may be incorporated within the polymeric matrix of the lenses of the invention, this is not necessary to obtain silicone hydrogel contact lenses having an ophthalmically acceptably wettable lens surface when fully hydrated. Thus, in one example, the lenses of the invention can comprise an internal wetting agent bound to at least a portion of the lens polymeric matrix. Alternatively, in another example, the silicone hydrogel contact lenses of the invention can be free of an internal wetting agent bound to at least a portion of the lens polymeric matrix.

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. Interpenetrating polymer networks are formed from at least two polymers, each crosslinked to itself, but not to each other. Similarly, a semi-IPN is formed from at least two polymers, at least one of which is cross-linked to itself but not to the other, and the other is neither cross-linked to itself nor to each other. In one example of the invention, a contact lens can have an ophthalmically acceptably wettable lens surface when the polymeric lens body is free of an internal polymeric wetting agent present in the lens body in the form of an IPN or semi-IPN. Alternatively, the contact lens can comprise an internal polymeric wetting agent in the form of an IPN or semi-IPN present in the lens body.

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 that is physically trapped within the polymerized lens body after the lens body has been formed. Where the wetting agent is a linking compound, after polymerization of the lens body or entrapment of the linking agent in the polymerized lens body, the linking compound can then link the wetting agent to the lens body upon contact of the lens body with a second wetting agent. The linking can be performed as part of the manufacturing process (e.g., as a washing process), or can be performed while the lens body is in contact with the packaging solution. The linkage may be in the form of an ionic or covalent bond, or in the form of van der waals attraction. The linking agent can comprise organoboronic acid(s) moieties or groups, such that the polymeric organoboronic acid moieties or groups are present in the polymeric lens body, or such that the organoboronic acid moieties or groups are physically entrapped in the polymeric lens body. For example, where the chain linking agent comprises an organic boronic acid form, the second wetting agent may comprise a poly (vinyl alcohol) form bound to the organic boronic acid form. Optionally, the silicone hydrogel contact lenses of the present invention can be understood to be free of a linking agent. In one example, the silicone hydrogel contact lenses can be free of organoboronic acid moieties or groups (including polymerized organoboronic acid moieties or groups), i.e., in particular, the silicone hydrogel contact lenses can be formed from polymerizable compositions that are free of organoboronic acid forms (e.g., polymerizable forms of organoboronic acids, including vinylphenyl organoboronic acids (VPBs)), can be formed from polymers that are free of units derived from polymerizable forms of organoboronic acids (e.g., vinylphenyl organoboronic acids (VPBs)), and the polymerized lens bodies and the silicone hydrogel contact lenses can be free of organoboronic acid forms (including polymerized or non-polymerized forms of organoboronic acids) 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 addition to including wetting agents and modifying the lens surface in the polymerizable composition, washing the polymeric lens body in a volatile organic solvent or an aqueous solution of a volatile organic solvent has also been used to increase the wettability of the lens surface. Although the polymeric lens bodies of the present invention can be washed in a volatile organic solvent or an aqueous solution of a volatile organic solvent in accordance with the present invention, this is not necessary to obtain silicone hydrogel contact lenses having an ophthalmically acceptably wettable lens surface when fully hydrated. In other words, in one example, the silicone hydrogel contact lenses of the present invention are not exposed to (as part of the manufacturing process) a volatile organic solvent (including a solution of) the volatile organic solvent. In one example, the silicone hydrogel contact lenses of the present invention can be formed from a polymerizable composition that is free of wetting agents, or the polymerized lens body and/or hydrated contact lens can be free of wetting agents, or free of surface treatment, or free of surface modification, or free of exposure to volatile organic solvents during the manufacturing process, or any combination thereof. In contrast, for example, the silicone hydrogel contact lens can be washed in a volatile organic solvent-free wash solution (e.g., water or an aqueous solution free of volatile organic solvents, including volatile lower alcohol-free liquids).

The use of volatile organic solvents to extract the lens body significantly increases production costs due to factors such as: the cost of organic solvents, the cost of disposing of solvents, the need to employ explosion-proof production equipment, the need to remove solvents from the lens prior to packaging, and the like. However, it can be challenging to develop polymerizable compositions that consistently produce contact lenses having ophthalmically acceptably wettable lens surfaces upon extraction in an aqueous liquid that is free of volatile organic solvents. For example, the presence of unwetted areas is often found on the lens surface of contact lenses that have been extracted in aqueous liquids that are free of volatile organic solvents.

As previously discussed, in one example of the invention, the contact lens is one that has not been exposed to volatile organic solvents (e.g., lower alcohols) during manufacture. In other words, the washing, extraction and hydration liquids used for the lenses and all liquids used in wet demolding, or wet delensing, or washing, or any other manufacturing step are free of volatile organic solvents. In one example, the polymerizable composition used to form these lenses that are not in contact with volatile organic solvents can comprise a hydrophilic vinyl-containing monomer or monomer component, e.g., a hydrophilic vinyl ether-containing monomer. The vinyl-containing hydrophilic monomer or monomer component can include, for example, VMA. The vinyl ether containing monomer may include, for example, BVE, or EGVE, or DEGVE, or any combination thereof. In a particular example, the vinyl ether-containing monomer can be a vinyl ether-containing monomer that is more hydrophilic than BVE, e.g., DEGVE. In another example, the hydrophilic monomer component in the polymerizable composition can be a mixture of a first hydrophilic monomer that is a vinyl-containing monomer but not a vinyl ether-containing monomer and a second hydrophilic monomer that is a vinyl ether-containing monomer. The mixture includes, for example, a mixture of VMA and one or more vinyl ethers (e.g., 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 of from about 1 to about 15 unit parts, or from about 3 to about 10 unit parts. When present in admixture with a hydrophilic vinyl-containing monomer that is not a vinyl ether, the portion of the hydrophilic vinyl-containing monomer or monomer component that is not a vinyl ether and the hydrophilic vinyl ether-containing monomer or monomer component can be present in the polymerizable composition in a ratio of at least 3:1, or from about 3:1 to about 15:1, or about 4:1, based on the weight unit parts of the hydrophilic vinyl-containing monomer or monomer component that is not a vinyl ether to the weight unit parts of the hydrophilic vinyl ether-containing monomer or monomer component.

Another method of producing the present contact lenses having ophthalmically acceptably wettable lens surfaces, particularly lenses extracted in liquids free of volatile organic solvents and including lenses that are not contacted with volatile organic solvents during manufacture, can be to limit the amount of vinyl-containing crosslinking agent or crosslinker component included in the polymerizable composition. For example, the vinyl-containing crosslinking agent or crosslinker component can be present in the polymerizable composition in an amount of from about 0.01 to about 0.80 unit parts, or from 0.01 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, the vinyl-containing crosslinking agent or crosslinker component can be present in the polymerizable composition in an amount effective to produce a contact lens having enhanced wettability compared to a contact lens produced from the same polymerizable composition but in an amount 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.

While limiting the amount of vinyl-containing crosslinking agent or crosslinker component can improve wettability, in one example, the inclusion of a vinyl-containing crosslinking agent or crosslinker component in the polymerizable composition can improve the dimensional stability of the resulting contact lens formed from the polymerizable composition. Thus, in some polymerizable compositions, the vinyl crosslinker or crosslinker component 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 crosslinker or crosslinker component.

Yet another method of producing the contact lenses of the invention having ophthalmically acceptably wettable surfaces, particularly lenses washed in liquids free of volatile organic solvents, can be to include an amount of a vinyl-containing crosslinking agent or crosslinker component in the polymerizable composition based on the ratio of the weight unit parts of hydrophilic vinyl-containing monomer or monomer component present in the composition to the weight unit parts of vinyl-containing crosslinking agent or crosslinker component present in the composition. For example, the total unit parts of the hydrophilic vinyl-containing monomer or monomer component and the total unit parts of the vinyl-containing crosslinking agent or crosslinker component can be present in the polymerizable composition at a ratio of 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 weight unit parts of all hydrophilic vinyl-containing monomers present in the polymerizable composition to the total weight unit parts of all vinyl-containing crosslinking agents present in the polymerizable composition.

In one example, the contact lenses of the invention are ophthalmically compatible silicone hydrogel contact lenses. As will be discussed below, many different criteria may be evaluated to determine whether a contact lens is ophthalmically compatible. In one example, an ophthalmically acceptable contact lens has an ophthalmically acceptable wettable surface when fully hydrated. A silicone hydrogel contact lens having an ophthalmically acceptably wettable surface can be understood to refer to a silicone hydrogel contact lens that adversely affects the tear film of the lens wearer's eye to an extent that does not cause the lens wearer to experience or report discomfort associated with placement or wearing of the silicone hydrogel contact lens on the eye.

Examples of the disclosed polymerizable compositions can be miscible at the time of initial preparation, and can remain miscible for a period of time sufficient for industrial manufacture of contact lenses (e.g., about 2 weeks, or about 1 week, or about 5 days). Typically, upon polymerization and processing into contact lenses, the miscible polymerizable compositions produce contact lenses having ophthalmically acceptable clarity.

Commonly used methods of increasing the miscibility of silicone monomers and hydrophilic monomers include adding an organic diluent to the polymerizable composition to act as a compatibilizer (compatibiliser) between the hydrophilic monomer and the generally more hydrophobic silicone monomer, or using only silicone monomers having low molecular weights (e.g., molecular weights below 2500 daltons). In one example, the use of the above-described first siloxane allows for the inclusion of both a high molecular weight second siloxane and high levels of optional one or more hydrophilic monomers in the polymerizable composition of the present invention. Moreover, while one or more organic diluents may be included in the polymerizable compositions of the present invention disclosed herein, such may not be necessary to obtain a miscible polymerizable composition of the present invention. In other words, in one example, the silicone hydrogel contact lenses of the present invention are formed from a polymerizable composition that is free of organic diluents.

wherein m in formula (1) represents one integer of 3 to 10, n in formula (1) represents one integer of 1 to 10, R1 in formula (1) is an alkyl group having 1 to 4 carbon atoms, and R2 in formula (1) is a hydrogen atom or a methyl group; and (b) a second siloxane monomer that is a double-terminal methacrylate-terminated polydimethylsiloxane having a number average molecular weight of at least 7,000 daltons; wherein the polymerizable composition is free of diluent, and wherein the silicone hydrogel contact lens has an energy loss of about 25% to about 45% when fully hydrated. Silicone hydrogel contact lenses can have an energy loss of about 27% to about 40% when fully hydrated.

Various methods of measuring contact angle are known to those skilled in the art, including bubble trapping. The contact angle may be a static or dynamic contact angle. The silicone hydrogel contact lenses of the invention can have a captive bubble dynamic advancing contact angle of less than 120 degrees, 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. The silicone hydrogel contact lenses of the invention can have a captive bubble static contact angle 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.

According to the present invention, silicone hydrogel contact lenses can have an Equilibrium Water Content (EWC) of about 30% to about 70% when fully hydrated. For example, a contact lens may have an EWC of about 45% to about 65%, or about 50% to about 63%, or about 50% to about 67%, or about 55% to about 65% by weight when fully hydrated. Methods of determining EWC are known to those skilled in the art and can be based on the weight loss of the lens during the drying process.

The contact lenses of the invention may 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 lens may have an oxygen permeability of about 55 to about 135, or about 60 to about 120, or about 65 to about 90, or about 50 to about 75 bara. Various methods of measuring oxygen permeability are known to those skilled in the art.

The contact lenses of the invention may have an oxygen permeability of at least 55 barrers (Dk ≧ 55 barrers), or an EWC of about 30% to about 70%, or a captive bubble dynamic advancing contact angle of less than 70 degrees, or a captive bubble static contact angle of less than 55 degrees, or any combination thereof. In one example, the contact lens may have an oxygen permeability of at least 60 barrers (Dk ≧ 60 barrers), or an EWC of about 35% to about 65%, or a captive bubble dynamic advancing contact angle of less than 70 degrees, or a captive bubble static contact angle of less than 55 degrees, or any combination thereof. In another example, the present contact lenses can have an oxygen permeability of at least 65 barrers, or an EWC of about 45% to about 65%, or a captive bubble dynamic advancing contact angle of less than 70 degrees, or a captive bubble static contact angle of less than 55 degrees, or any combination thereof.

In one example, the present contact lenses have an oxygen permeability of at least 55 barrers, an EWC of about 30% to about 70%, a captive bubble dynamic advancing contact angle of less than 70 degrees, and a captive bubble static contact angle of less than 55 degrees.

The present contact lenses can have less than about 8.0 x 10 when fully hydrated^-3mm²A/min, or less than about 7.0X 10^-3mm²A/min, or less than about 5.0X 10^-3mm²Ion flow/min. Various methods of determining ion current are conventional and known to those skilled in the art.

The silicone hydrogel contact lenses of the invention, when fully hydrated, can have an average tensile modulus of about 0.20MPa to about 0.90 MPa. For example, the average modulus can be from about 0.30MPa to about 0.80MPa, or from about 0.40MPa to about 0.75MPa, or from about 0.50MPa to about 0.70 MPa.

The modulus of a contact lens or lens body as used herein is understood to mean the tensile modulus, also known as Young's modulus. Which is a measure of the stiffness of an elastic material. Tensile modulus can be measured using a method that meets ANSIZ80.20 standards. In one example, the tensile modulus may be measured using an Instron model 3342 or 3343 mechanical testing system.

In one example, the present contact lenses can have a wet extractable component. The wet extractable component was determined based on the weight loss of the contact lens during methanol extraction, which had 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. For lenses formed from polymerizable compositions comprising non-polymerizable ingredients, the wet extractable component is comprised of an organic solvent extractable material that remains in the lens body after the lens body has been completely treated to form a sterilized contact lens. For lenses that are extracted in either an extraction solution containing a volatile organic solvent or an extraction solution without an organic solvent during manufacture, in most cases, substantially all of the non-polymerizable components will have been removed from the lens body, and the wet extractable component can thus consist essentially of extractable components formed from the reactive polymerizable components (i.e., unreacted polymerizable components and partially reacted polymerizable components) in the polymerizable composition. In lenses prepared from polymerizable compositions without diluents, the wet extractable component can be present in the contact lens in an amount of 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 the extraction test. In lenses made from polymerizable compositions comprising diluents, the wet extractable component can consist of a portion of the diluent and unreacted and partially reacted polymerizable ingredients, and can be present in the contact lens in an amount of from about 1% wt/wt to about 20% wt/wt, or from about 2% wt/wt to about 15% wt/wt, or from about 3% wt/wt to about 10% wt/wt of the lens based on the dry weight of the lens body prior to the extraction test.

In one example, the present contact lenses have a dry extractable component. The dry extractable component is determined based on the weight loss of the polymeric lens body during methanol extraction, which has not been washed, extracted (as part of the manufacturing process), hydrated, or sterilized prior to drying and extraction testing. The dry extractable component can comprise unreacted or partially reacted polymerizable ingredients of the polymerizable composition. Where optional non-polymerizable ingredients such as diluents are present in the polymerizable composition, the dry extractable component may further comprise non-polymerizable ingredients.

In lenses made from a diluent-free polymerizable composition, the dry extractable component of the lens consists essentially of the dry extractable component contributed by the polymerizable ingredients in the polymerizable composition (i.e., unreacted or partially reacted polymerizable ingredients), and may also include a small amount (e.g., less than 3% wt/wt) of dry extractable material contributed by optional non-polymerizable components (e.g., colorants, oxygen scavengers, etc.) present in the polymerizable composition. In lenses made from polymerizable compositions without diluents, the dry extractable component can be present in the polymerized lens body in an amount from about 1% wt/wt to about 30% wt/wt, 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 the extraction test.

In lenses made from polymerizable compositions that contain significant amounts (e.g., greater than 3% wt/wt) of optional non-polymerizable ingredients such as diluents, the dry extractable component is made up of extractable material contributed by reactive ingredients as well as extractable components contributed by non-polymerizable ingredients in the polymerizable composition. The total amount of reactive and non-polymerizable components contributing dry extractable components present in the contact lens can be comprised of an amount of from about 1% wt/wt to about 75% wt/wt, or from about 2% wt/wt to about 50% wt/wt, 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% of the lens based on the dry weight of the polymeric lens body prior to the extraction test. The total amount of dry extractable components contributed by the polymerizable ingredients (i.e., unreacted or partially reacted polymerizable ingredients) can be in an amount of from about 1% wt/wt to about 30% wt/wt, 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 of the lens body based on the dry weight of the lens body prior to the extraction test.

Certain specific examples of silicone hydrogel contact lenses will now be described in accordance with the teachings of the present disclosure.

As one example (example a), a silicone hydrogel contact lens comprises a polymerized lens body that is the reaction product of a polymerizable composition comprising a first siloxane monomer represented by formula (1):

Wherein m in formula (1) represents an integer of 3 to 10, n in formula (1) represents an integer of 1 to 10, R¹Is an alkyl group having 1 to 4 carbon atoms, and each R in the formula (1)²Independently a hydrogen atom or a methyl group; a second siloxane monomer that is a double-terminal methacrylate-terminated polydimethylsiloxane having a number average molecular weight of at least 7,000 daltons; and optionally a second component comprising a third siloxane monomer or at least one cross-linking agent or at least one hydrophilic monomer or at least one hydrophobic monomer or any combination thereof; wherein the contact lens has an energy loss of about 30% to about 40% when fully hydrated. In one example, inWhen the polymerizable composition comprises a third siloxane monomer, the third siloxane monomer can be a third siloxane monomer having more than one functional group and a number average molecular weight of at least 3,000 daltons. In another example, where the polymerizable composition comprises at least one crosslinker, the at least one crosslinker can consist of at least one vinyl-containing crosslinker.

As a second example (example B), a silicone hydrogel contact lens comprises a polymerized lens body that is the reaction product of the polymerizable composition described in example a, and wherein the polymerizable composition further comprises a hydrophilic monomer or monomer component. In one example, the hydrophilic monomer or monomer component can be present in the polymerizable composition in an amount of from about 30 unit parts to about 60 unit parts.

As a third example (example C), a silicone hydrogel contact lens comprises a polymerized lens body that is the reaction product of the polymerizable composition as described in examples a or B, and wherein the polymerizable composition further comprises a hydrophobic monomer or monomer component, specifically, a hydrophilic monomer comprises or consists of Methyl Methacrylate (MMA).

As a fourth example (example D), a silicone hydrogel contact lens comprises a polymerized lens body that is the reaction product of the polymerizable composition as in examples a or B or C, and wherein the polymerizable composition further comprises a vinyl-containing crosslinking agent or crosslinker component. In one example, the crosslinker or crosslinker component can comprise or consist of a vinyl ether-containing crosslinker or crosslinker component, specifically the crosslinker or crosslinker component can comprise or consist of triethylene glycol divinyl ether (TEGVE).

As a fifth example (example E), a silicone hydrogel contact lens comprises a polymerized lens body that is the reaction product of the polymerizable composition as in examples a or B or C or D, and wherein the polymerizable composition further comprises a thermal initiator or thermal initiator component.

As a sixth example (example F), a silicone hydrogel contact lens comprises a polymerized lens body that is the reaction product of the polymerizable composition as in examples a or B or C or D or E, and wherein the polymerizable composition further comprises an oxygen scavenger or an oxygen scavenger component.

As a seventh example (example G), a silicone hydrogel contact lens comprises a polymerized lens body that is the reaction product of the polymerizable composition as in examples a or B or C or D or E or F, and wherein the polymerizable composition further comprises a UV absorber or UV absorber component.

As an eighth example (example H), a silicone hydrogel contact lens comprises a polymeric lens body that is the reaction product of the polymerizable composition as in examples a or B or C or D or E or F or G, and wherein the polymerizable composition further comprises a colorant or a colorant component.

As a ninth example (example I), a silicone hydrogel contact lens comprises a polymerized lens body that is the reaction product of the polymerizable composition as in examples a or B or C or D or E or F or G or H, and wherein the polymerizable composition further comprises a second siloxane monomer represented by formula (2), wherein R in formula (2) ₁Selected from a hydrogen atom or a methyl group; r in the formula (2)₂Selected from hydrogen or a hydrocarbon group having 1 to 4 carbon atoms; m in formula (2) represents an integer of 0 to 10; n in formula (2) represents an integer of 4 to 100; a and b represent an integer of 1 or more; a + b equals 20 to 500; b/(a + b) equals 0.01 to 0.22; and the configuration of the siloxane units includes a random configuration. As an example, the second siloxane monomer can be represented by formula (2), wherein m in formula (2) is 0, n in formula (2) is an integer from 5 to 10, a is an integer from 65 to 90, b is an integer from 1 to 10, R in formula (2)₁Is methyl, and R in formula (2)₂Is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.

As a tenth example (example J), a silicone hydrogel contact lens comprises a polymerized lens body that is the reaction product of the polymerizable composition as in examples 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 methacrylate-containing crosslinker or crosslinker component, specifically the crosslinker or crosslinker component can comprise or consist of Ethylene Glycol Dimethacrylate (EGDMA). In this example, where the polymerizable composition also includes a vinyl ether-containing crosslinker as part of the crosslinker component, specifically the crosslinker component can comprise or consist of a combination of triethylene glycol divinyl ether (TGDVE) and a methacrylate-containing crosslinker, which can specifically comprise or consist of Ethylene Glycol Dimethacrylate (EGDMA). In this example, it can be appreciated that the polymerizable composition comprises two crosslinkers, each having a different reactivity ratio, i.e., the polymerizable composition contains a crosslinker component comprising or consisting of a vinyl-containing crosslinker and a methacrylate-containing crosslinker having polymerizable functional groups that are more reactive and therefore react at a faster rate than the vinyl-containing polymerizable functional groups present in the vinyl-containing crosslinker.

As an eleventh example (example K), a silicone hydrogel contact lens comprises a polymerized lens body that is the reaction product of the polymerizable composition as in examples 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 chain transfer agent or chain transfer agent component, which can specifically comprise or consist of Allyloxyethanol (AE).

As a twelfth example (example L), a silicone hydrogel contact lens comprises a polymerized lens body that is the reaction product of the polymerizable composition as in examples 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 hydrophobic monomer or hydrophobic monomer component that can specifically comprise or consist of ethylene glycol methyl ether methacrylate (EGMA).

As a thirteenth example (example M), a silicone hydrogel contact lens comprises a polymerized lens body that is the reaction product of the polymerizable composition as in examples a or B or C or D or E or F or G or H or I or J or K or L, and wherein the polymerizable composition further comprises a hydrophilic vinyl ether-containing monomer or monomer component, e.g., 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.

As a fourteenth example (example N), a silicone hydrogel contact lens comprises a polymerized lens body that is the reaction product of the polymerizable compositions as described in examples a or B or C or D or E or F or G or H or I or J or K or L or M, wherein the contact lens has an ophthalmically acceptably wettable lens surface when the polymerizable composition used to form the lens does not contain an internal wetting agent, or when the polymerizable composition used to form the polymerized lens body does not contain an organic diluent, or when the polymerized lens body is extracted in a liquid that does not contain a volatile organic solvent, or when the lens is not surface plasma treated, or any combination thereof.

In any or each of the above examples a-N, 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 27 to 35 unit parts of the polymerizable composition.

In any or each of the above examples a-N, as well as any or all of the other examples disclosed herein, the amount of the optional second siloxane monomer can comprise 1 to 20 unit parts of the polymerizable composition. 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 another example, the ratio of unit parts of the first siloxane monomer to the second siloxane can be at least 1:1, or at least 2: 1.

In any or each of the above examples a-N, as well as any or all of the other examples disclosed herein, the amount of 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 comprise from 4 to 60 unit parts of the polymerizable composition. Where the hydrophilic monomer comprises or consists of VMA, it can be present in an amount of 30 unit parts to 60 unit parts. The VMA can be present in the polymerizable composition in an amount of about 40 unit parts to about 50 unit parts. Where a hydrophilic monomer (i.e., N-Dimethylacrylamide (DMA), 2-hydroxyethyl methacrylate (HEMA), or 2-hydroxybutyl methacrylate (HOB), or any combination thereof) is present in the polymerizable composition as the hydrophilic monomer in the hydrophilic monomer component, each or all may be present in an amount of about 3 to about 10 unit parts.

In any or each of the above examples a-N, as well as any or all of the other examples disclosed herein, the hydrophobic monomer or monomer component can be present in the polymerizable composition in an amount of 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 where the hydrophobic monomer MMA is present as a hydrophobic monomer or as part of a hydrophobic monomer component, MMA may be present in amounts of from about 5 to about 20 unit parts, or from about 8 to about 15 unit parts.

In any or each of the above examples a-N, as well as any or all of the other examples disclosed herein, the crosslinker or crosslinker component can be present in the polymerizable composition in an amount of 0.01 to 4 unit parts of the polymerizable composition. TEGDVE may be present in an amount of 0.01 to 1.0 unit parts. EGDMA may be present in an amount of 0.01 to 1.0 unit parts. TEGDMA may be present in an amount of 0.1 to 2.0 unit parts. Each of these silicon-free crosslinkers can be present in the polymerizable composition alone or in any combination.

In any or each of the above examples a-N, and any or all other examples disclosed herein, when the polymerizable composition contains EGMA, BVE, DEGVE, EGVE, or any combination thereof, each is present in an amount of 1 unit part to 20 unit parts of the polymerizable composition. EGMA may be present in an amount of about 2 unit parts to about 15 unit parts. BVE can be present in an amount of from 1 unit part to about 15 unit parts. BVE can be present in an amount of about 3 unit parts to about 7 unit parts. DEGVE may be present in an amount of 1 unit part to about 15 unit parts. DEGVE may be present in an amount of about 7 unit parts to about 10 unit parts. EGVE may be present in an amount of from 1 unit part to about 15 unit parts, or in an amount of from about 3 unit parts to about 7 unit parts.

In any or each of the above examples a-N, as well as in any or all of the other examples disclosed herein, other optional components (e.g., an initiator or initiator component, a colorant or colorant component, a UV absorber or UV absorber component, an oxygen scavenger or oxygen scavenger component, or a chain transfer agent or chain transfer agent component) can each be present in an amount of from about 0.01 unit parts to about 3 unit parts. The initiator or initiator component may be present in the polymerizable composition in an amount of from 0.1 unit parts to 1.0 unit parts. When present, the thermal initiator or thermal initiator component (e.g., Vazo-64) may be present in an amount of from about 0.3 to about 0.5 unit parts. The colorant or colorant component may be present in an amount of from 0.01 unit parts to 1 unit part. When a reactive dye (e.g., reactive blue 246 or reactive blue 247) is used as a colorant or as part of a colorant component, it can each be present in an amount of about 0.01 unit parts. The UV absorber or UV absorber component can be present in an amount of 0.1 unit parts to 2.0 unit parts. For example, the UV absorber UV1 described in examples 1-28 below may be present in an amount of about 0.8 to about 1.0 unit parts (e.g., 0.9 unit parts); or the UV absorber UV2 described in examples 1-28 below may be present in an amount of 0.5 unit parts to 2.5 unit parts (e.g., about 0.9 unit parts to about 2.1 unit parts). The oxygen scavenger or oxygen scavenger component may be present in an amount of from 0.1 unit parts to 1.0 unit parts. By way of example, where Triphenylphosphine (TPP) or diphenyl (p-vinylphenyl) phosphine (pTPP), or any combination thereof, is used as the oxygen scavenger or oxygen scavenger component in the polymerizable composition, each or the combination may be present in an amount of from 0.3 unit parts to 0.7 unit parts (e.g., about 0.5 unit parts). The chain transfer agent or chain transfer agent component may be present in the polymerizable composition in an amount of from 0.1 unit parts to 2.0 unit parts, and in many of examples 1-28 below in an amount of from 0.2 unit parts to 1.6 unit parts. For example, the chain transfer agent Allyloxyethanol (AE) may be present in an amount of about 0.3 to about 1.4 unit parts.

In any or each of the above examples a-N, as well as in any or all other examples disclosed herein, the silicone hydrogel contact lens can be free of a wetting agent present in the polymerizable composition, or present in the polymerized lens body, or present in the silicone hydrogel contact lens. Similarly, silicone hydrogel contact lenses can have lens surfaces that are not surface treated or surface modified. 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 wetting agent components) in the polymerizable composition, in the polymerized lens body, or in the silicone hydrogel contact lens. Silicone hydrogel contact lenses may have treated or modified lens surfaces. Additionally or alternatively, any or each of the foregoing examples a-N, as well as any or all other examples of the silicone hydrogel contact lenses disclosed herein, the contact lenses can be understood to be free of a linking agent (e.g., an organoboronic acid form).

In another example, novel polymerizable compositions are provided, including each (eachanendegy) polymerizable composition described herein with reference to silicone hydrogel contact lenses and methods. The polymerizable composition can be free of diluents, which in this regard are free of organic solvents, such as alcohols and the like, that can help reduce phase separation of the polymerizable composition. However, the diluent-free polymerizable composition may still contain one or more chain transfer agents, such as allyloxyethanol. However, if desired, the polymerizable composition can include a diluent or diluent component, which can be present in an amount of 1 to 20 unit parts.

As described herein, the silicone hydrogel contact lenses of the invention comprise a polymeric lens body comprising units derived from a first siloxane monomer and a second siloxane monomer represented by formula (1), or at least one crosslinking agent, or both; the contact lenses, when fully hydrated, have an average Equilibrium Water Content (EWC) of from about 30% wt/wt to about 70% wt/wt, or an average oxygen permeability of at least 55 barrers, or an average captive bubble dynamic advancing contact angle of less than 70 degrees, or an average captive bubble static contact angle of less than 55 degrees, or any combination thereof, based on an average of values determined for at least 20 individual lenses in the batch. Accordingly, the present invention also relates to a batch of silicone hydrogel contact lenses.

As used herein, a batch of silicone hydrogel contact lenses refers to a set of two or more silicone hydrogel contact lenses, and typically, a batch refers to at least 10, or at least 100, or at least 1,000 silicone hydrogel contact lenses. According to the present invention, a batch of silicone hydrogel contact lenses comprises a plurality of any of the silicone hydrogel contact lenses described herein.

In one example, the batch of silicone hydrogel contact lenses comprises a plurality of contact lenses of the invention, wherein the batch of silicone hydrogel contact lenses has at least two average values selected from the group consisting of: an average oxygen permeability of at least 55 barrers, an average tensile modulus of from about 0.2MPa to about 0.9MPa when fully hydrated, an average captive bubble dynamic advancing contact angle of less than 70 degrees when fully hydrated, and an average captive bubble static contact angle of less than 55 degrees when fully hydrated.

In one example, the batch of silicone hydrogel contact lenses comprises a plurality of contact lenses, wherein each contact lens comprises a polymerized lens body that is a reaction product of a polymerizable composition comprising (a) a first siloxane monomer represented by formula (1):

wherein m in formula (1) represents one integer of 3 to 10, n in formula (1) represents one integer of 1 to 10, R1 in formula (1) is an alkyl group having 1 to 4 carbon atoms, and R2 in formula (1) is a hydrogen atom or a methyl group; and (b) a second siloxane monomer that is a double-terminal methacrylate-terminated polydimethylsiloxane having a number average molecular weight of at least 7,000 daltons; wherein the silicone hydrogel contact lens has an energy loss of about 25% to about 45% when fully hydrated; and wherein the batch of silicone hydrogel contact lenses, when fully hydrated, has an average Equilibrium Water Content (EWC) of from about 30% wt/wt to about 70% wt/wt, or an average oxygen permeability of at least 55 barrers, or an average captive bubble dynamic advancing contact angle of less than 70 degrees, or an average captive bubble static contact angle of less than 55 degrees, or any combination thereof, based on an average of measurements for at least 20 individual lenses in the batch. In one example, a batch of lenses may exhibit a change in average physical dimension when first tested shortly after manufacture and then tested again at a subsequent point in time. Where multiple batches of lenses of the invention are dimensionally stable, they may exhibit an acceptable level of variation in average physical dimension. As used herein, dimensional stability difference is understood to mean the difference in physical dimension value between the physical dimension value determined when the batch of lenses is first tested shortly after their manufacture and the physical dimension value when the batch of lenses is tested again at a subsequent point in time. The subsequent time point can be, for example, at least 2 weeks after the initial time point to as long as 7 years after the initial time point. The batches of silicone hydrogel contact lenses have a mean dimensional stability difference of less than +/-3% (± 3.0%) based on averaging lens diameter measurements for a representative number of lenses in the batch (e.g., 20 lenses in the batch). For a batch of lenses, a mean dimensional stability difference of less than +/-3% (± 3.0%) is considered a dimensionally stable batch, wherein the mean dimensional stability difference is measured at an initial time point within one day of the date of manufacture of the batch of lenses and at a second time point (wherein the second time point is the initial time point when the batch is stored at room temperature) Two weeks to seven years after the dotting; or the difference in physical dimension values when the batch is stored at a higher temperature (i.e., under accelerated shelf life test conditions), the second time point being a time point representing when the batch is stored at room temperature for two weeks to seven years). In one example, an accelerated shelf life test condition that is particularly useful for determining the difference in average dimensional stability is 4 weeks at 70 ℃, although other time periods and other temperatures may be used. The mean dimensional stability difference is the actual diameter (diameter) of a representative lens using the first measurement_Initial) And the actual diameter (diameter) of a representative lens measured at room temperature or after storage under accelerated shelf life conditions_{Finally, the product is processed}) Determined by averaging the individual dimensional stability differences for each representative lens. The representative lens measured for the first time and the representative lens measured after storage may be the same lens or may be different lenses. The average dimensional stability difference as used herein is expressed in percent (%). The individual dimensional stability differences were determined using the following equation (a):

((diameter)_{Finally, the product is processed}Diameter of_Initial) Diameter_Initial)×100(A)。

On average, the batch of silicone hydrogel contact lenses varied in diameter by less than 3% (± 3.0%) in either direction of the target value. As one example, if the contact lens has a target diameter (chord diameter) of 14.20mm, the present batch of silicone hydrogel contact lenses will have an average diameter (average of the population in the batch) of 13.77mm to 14.63 mm. In one example, the dimensional stability difference is less than +/-2% (+ -2.0%). As one example, if the contact lens has a target diameter (chord diameter) of 14.20mm, the present batch of silicone hydrogel contact lenses will have an average diameter (average of the population in the batch) of 13.92mm to 14.48 mm. Preferably, the mean diameter of the batch of silicone hydrogel contact lenses does not vary more than +/-0.20mm from the target diameter (typically 13.00mm to 15.00 mm).

In accelerated shelf life studies, the difference in average dimensional stability of contact lenses that have been stored at elevated temperatures (e.g., above 40 ℃, including, for example, 50 ℃, or 55 ℃, or 65 ℃, or 70 ℃, or 80 ℃, or 95 ℃, etc.) for a period of time can be determined. Alternatively, the average dimensional stability of a contact lens that has been stored at room temperature (e.g., about 20 ℃ to 25 ℃) for a period of time can be determined.

For accelerated shelf life studies, the number of storage months at a particular temperature corresponding to a desired length of storage at room temperature can be determined using the following formula:

acceptable shelf life = [ N × 2 =^y]+n(B)

Wherein

N = number of storage months under accelerated conditions

2^y= acceleration factor

y = (test temperature-25 ℃)/10 ℃

n = lens age (in months) at the beginning of the study.

Based on this equation, the following storage times have been calculated: storage at 35 ℃ for 6 months corresponds to aging at 25 ℃ for 1 year, storage at 45 ℃ for 3 months corresponds to aging at 25 ℃ for 1 year, storage at 55 ℃ for 3 months corresponds to aging at 25 ℃ for 2 years, and storage at 65 ℃ for 3 months corresponds to aging at 25 ℃ for 4 years.

The present invention also provides methods of manufacturing silicone hydrogel contact lenses. According to the teachings of the present disclosure, the method comprises providing a polymerizable composition. The polymerizable composition or contact lens formulation comprises a first siloxane monomer represented by formula (1):

Wherein m in formula (1) represents an integer of 3 to 10, n in formula (1) represents an integer of 1 to 10, R in formula (1)¹Is an alkyl group having 1 to 4 carbon atoms, and each R in the formula (1)²Independently a hydrogen atom or a methyl group. In addition to the first siloxane monomer of formula (1), the polymerizable composition comprises a second siloxane monomer, or at least one crosslinker, or both. The ingredients are present in the polymerizable composition in amounts such that the resulting silicone hydrogel contact lens, when fully hydrated, has an average Equilibrium Water Content (EWC) of about 30% wt/wt to about 70% wt/wt (e.g., about 45% wt/wt to about 65% wt/wt, or about 50% wt/wt to about 67% wt/wt, or about 50% wt/wt to about 63% wt/wt, or about 55% wt/wt to about 65% wt/wt).

The method can further comprise the step of polymerizing the polymerizable composition to form a polymerized lens body. The step of polymerizing the polymerizable composition can be carried out in a contact lens mold assembly. The polymerizable composition can be cast molded between molds formed from thermoplastic polymers. The thermoplastic polymer used to form the molding surface of the mold may comprise a polar polymer, or may comprise a non-polar polymer. Alternatively, the polymerizable composition can be formed into a lens via various methods known to those skilled in the art, such as spin casting, injection molding, forming a polymeric rod, and then lathing to form a lens body, and the like.

The method can also include contacting the polymeric lens body with a washing solution to remove extractable materials, such as unreacted monomers, uncrosslinked materials that were not physically immobilized in the polymeric lens body, diluents, and the like. The wash liquid may be a liquid that is free of volatile organic solvents, or may comprise a volatile organic solvent (e.g., may be a volatile organic solvent or a solution of a volatile organic solvent).

According to the present invention, the polymeric lens body can be packaged in a contact lens package (e.g., a blister package or a glass vial) with a contact lens packaging solution. After packaging, the package can be sealed and the polymeric lens body and contact lens packaging solution sterilized, for example, by autoclaving the sealed package, to produce a silicone hydrogel contact lens product.

The present methods may further comprise repeating the steps to produce a plurality of silicone hydrogel contact lenses.

In any of the methods of the present invention, a particular first siloxane monomer, for example, a monomer represented by formula (1), wherein m in formula (1) is 4, n in formula (1) is 1, and R in formula (1) is provided in the polymerizable composition¹Is butyl, and each R in formula (1)²Independently a hydrogen atom or a methyl group.

In any of the methods of the present invention, the second siloxane monomer, or optionally at least one third siloxane monomer, can be represented by formula (2):

wherein R in formula (2)₁Selected from a hydrogen atom or a methyl group; r in the formula (2)₂Selected from hydrogen or a hydrocarbon group having 1 to 4 carbon atoms; m in formula (2) represents an integer of 0 to 10; n in formula (2) represents an integer of 4 to 100; a and b represent an integer of 1 or more; a + b equals 20 to 500; b/(a + b) equals 0.01 to 0.22; and the configuration of the siloxane units includes a random configuration. As an example, the siloxane monomer may be represented by formula (2), wherein m in formula (2) is 0, n in formula (2) is an integer of 5 to 15, a is an integer of 65 to 90, b is an integer of 1 to 10, R in formula (2)₁Is methyl, and R in formula (2)₂Is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.

In the methods of the present invention, the step of contacting the polymeric lens body with a washing solution can be understood to be an extraction step, since extractable material can be removed from the polymeric lens body during the process. Where the wash liquor comprises water or an aqueous solution free of volatile organic solvents, the contacting step is understood to be both an extraction step and a hydration step. In another example of the method, the contacting step can comprise contacting the polymeric lens body with a wash solution comprising a volatile organic solvent, such as a liquid containing a primary alcohol (e.g., methanol, ethanol, n-propanol, etc.). The wash solution may contain secondary alcohols such as isopropanol and the like. The use of a wash solution containing one or more volatile organic solvents can facilitate removal of hydrophobic materials from the polymeric lens body, and thus can increase the wettability of the resulting silicone hydrogel contact lens. The process can be understood as an extraction step based on volatile organic solvents. In other methods, the contacting step comprises contacting the polymeric lens body with an aqueous wash solution that is free of volatile organic solvents. The process can be understood as a completely aqueous washing step since no volatile organic solvent is included in the washing liquid. Water-based wash liquids that may be used in the method include water (e.g., deionized water), saline solutions, buffer solutions, or aqueous solutions containing surfactants or other non-volatile components that may improve the removal of hydrophobic components from, or may reduce the deformation of, the polymeric contact lens body compared to the use of deionized water alone.

After washing, the contact lens can be placed in a package (e.g., a plastic blister package) containing a packaging solution (e.g., a buffered saline solution), which may or may not contain surfactants, anti-inflammatory agents, antimicrobial agents, contact lens wetting agents, and the like; and can be sealed and sterilized. The packaging solutions used to package the silicone hydrogel contact lenses of the present invention may include a wetting agent to increase the wettability of the lens surface. However, it should be understood that the lens surface of the silicone hydrogel contact lenses of the present invention has an ophthalmically acceptably wettable surface prior to contact with a packaging solution comprising a wetting agent, and that the wetting agent is used in the packaging solution only to increase the wettability of a surface that is already ophthalmically acceptably wettable, and thus, there is no need to provide an ophthalmically acceptably wettable surface to the contact lens.

In another example, novel polymerizable compositions are provided, including each (eachanendegy) polymerizable composition described herein with reference to silicone hydrogel contact lenses and methods. The polymerizable composition can be free of diluents or solvents, and in this regard, is free of organic solvents, such as alcohols and the like, that can help reduce phase separation of the polymerizable composition. However, the diluent-free polymerizable composition may still contain one or more chain transfer agents, such as allyloxyethanol. However, if desired, the polymerizable composition can include a diluent, which can be present in an amount of 1 to 20 unit parts.

As described herein, the silicone hydrogel contact lenses of the invention comprise a polymeric lens body comprising units derived from a first siloxane monomer represented by formula (1), a second siloxane monomer that is a double-terminal methacrylate-terminated polydimethylsiloxane having a number average molecular weight of at least 7,000 daltons. In one example, the second siloxane monomer can be a second siloxane monomer represented by formula (2), and the silicone hydrogel lens has an energy loss of about 25% to about 45%, or about 27% to about 40%, or about 30% to about 37% when fully hydrated. Accordingly, the present invention also relates to a batch of silicone hydrogel contact lenses.

In one example, the batch of silicone hydrogel contact lenses comprises a plurality of the contact lenses of the invention, wherein the batch of silicone hydrogel contact lenses has an average energy loss of about 25% to about 45%, or about 27% to about 40%, or about 30% to about 37% when fully hydrated.

In another example, the batch of silicone hydrogel contact lenses comprises a plurality of contact lenses of the invention, wherein the batch of silicone hydrogel contact lenses, when fully hydrated, has an average Equilibrium Water Content (EWC) of from 30% to 70%, or an average oxygen permeability of at least 55 barrers, or an average tensile modulus of from about 0.2MPa to about 0.9MPa, or an average captive bubble dynamic advancing contact angle of less than 70 degrees, or an average captive bubble static contact angle of less than 55 degrees, or any combination thereof, based on an average of measurements on at least 20 individual lenses in the batch.

In yet another example, the batch of contact lenses can have an average dimensional stability difference based on averaging lens diameter measurements for a representative number of lenses in the batch (e.g., 20 lenses in the batch). For a batch of lenses, a mean dimensional stability difference of less than +/-3% (± 3.0%) is considered a dimensionally stable batch when stored at room temperature for a period of two weeks to seven years, or under accelerated shelf life testing conditions of a period and temperature comparable to two weeks to seven years of storage at room temperature. In one example, an accelerated shelf life test condition that is particularly useful for determining the difference in average dimensional stability is 4 weeks at 70 ℃, although other time periods and temperatures may be used. The difference in average dimensional stability is at room temperature or prior to storage under accelerated shelf life conditions (diameter) _Initial) And thereafter (diameter)_{Finally, the product is processed}) The actual diameter of the representative lens of (a) is determined by averaging the individual dimensional stability differences for each representative lens. The average dimensional stability difference as used herein is expressed in percent (%). The individual dimensional stability differences were determined using the following equation (a):

On average, the batch of silicone hydrogel contact lenses varied in diameter by less than 3% (± 3.0%) in either direction of the target value. As one example, if the contact lens has a target diameter (chord diameter) of 14.20mm, the present batch of silicone hydrogel contact lenses will have an average diameter (average of the population in the batch) of 13.77mm to 14.63 mm. The dimensional stability difference can be less than +/-2% (± 2.0%). As one example, if the contact lens has a target diameter (chord diameter) of 14.20mm, the present batch of silicone hydrogel contact lenses will have an average diameter (average of the population in the batch) of 13.92mm to 14.48 mm. Preferably, the mean diameter of the batch of silicone hydrogel contact lenses does not vary more than +/-0.20mm from the target diameter (typically 13.00mm to 15.00 mm).

For accelerated shelf life studies, the number of storage months at a particular temperature corresponding to a desired length of storage at room temperature can be determined using the following formula, which is represented by the following formula (C):

acceptable shelf life = [ N × 2 =^y]+n(C)

Wherein

N = number of storage months under accelerated conditions

2^y= acceleration factor

y = (test temperature-25 ℃)/10 ℃

n = lens age (in months) at the beginning of the study.

Wherein m in formula (1) represents an integer of 3 to 10, n in formula (1) represents an integer of 1 to 10, R in formula (1)¹Is an alkyl group having 1 to 4 carbon atoms, and each R in the formula (1)²Independently a hydrogen atom or a methyl group. The polymerizable composition further comprises a second siloxane monomer. Silicone hydrogel contact lenses made using the methods of the present invention have an energy loss of about 25% to about 45% when fully hydrated, such as about 27% to about 40% when fully hydrated, or about 30% to about 37% when fully hydrated. In one example, the second siloxane monomer can be a siloxane monomer having more than one functional group and a number average molecular weight of at least 3,000 daltons. In one example, the method is a method of manufacturing a silicone hydrogel contact lens, comprising: providing a miscible polymerizable composition comprising (a) a first siloxane monomer represented by formula (1):

wherein m in formula (1) represents an integer of 3 to 10, n in formula (1) represents an integer of 1 to 10, R in formula (1)¹Is an alkyl group having 1 to 4 carbon atoms, and R in the formula (1)²Is a hydrogen atom or a methyl group; and (b) a second siloxane monomer that is a double-terminal methacrylate-terminated polydimethylsiloxane having a number average molecular weight of at least 7,000 daltons; polymerizing the polymerizable composition in the contact lens mold assembly to form a polymeric lens body; contacting the polymeric lens body with a washing solution to remove extractable material from the polymeric lens body; and packaging the polymeric lens body in a contact lens packaging solution in a contact lens package; wherein the silicone hydrogel contact lens has an energy loss of about 25% to about 45% when fully hydrated.

The method can further comprise the step of polymerizing the polymerizable composition to form a polymerized lens body. In the methods described in examples 1-28 of the present disclosure, the step of polymerizing the polymerizable composition is carried out in a contact lens mold assembly. The polymerizable composition can be cast molded between molds formed from thermoplastic polymers. The thermoplastic polymer used to form the molding surface of the mold may comprise a polar polymer, or may comprise a non-polar polymer. In some other methods, the polymerizable composition can be formed into a lens via various methods known in the art, such as spin casting, injection molding, forming a polymeric rod, and then lathing to form a lens body, and the like.

The method can also include contacting the polymeric lens body with a washing solution to remove extractable materials, such as unreacted monomers, uncrosslinked materials that were not physically immobilized in the polymeric lens body, diluents, and the like.

In one example, the method is a method of manufacturing a silicone hydrogel contact lens, comprising: providing a miscible polymerizable composition comprising (a) a first siloxane monomer represented by formula (1):

Wherein m in formula (1) represents an integer of 3 to 10, n in formula (1) represents an integer of 1 to 10, R in formula (1)¹Is an alkyl group having 1 to 4 carbon atoms, and R in the formula (1)²Is a hydrogen atom or a methyl group; and (b) a second siloxane monomer that is a double-terminal methacrylate-terminated polydimethylsiloxane having a number average molecular weight of at least 7,000 daltons; polymerizing the polymerizable composition in the contact lens mold assembly to form a polymeric lens body; contacting the polymeric lens body with a washing liquid to remove extractable material from the polymeric lens body, wherein the contacting step comprises contacting the polymeric lens body with a washing liquid that is free of volatile organic solvents; and packaging the polymerized lens body in a contact lens packageIn the contact lens packaging solution of (1); wherein the silicone hydrogel contact lens has an energy loss of about 25% to about 45% when fully hydrated.

According to the present methods, polymeric lens bodies can be packaged in contact lens packaging solutions in contact lens packages (e.g., blister packs or glass vials). After packaging, the package can be sealed and the polymeric lens body and contact lens packaging solution sterilized, for example, by autoclaving the sealed package.

The present methods may further comprise repeating the steps to produce a plurality of silicone hydrogel contact lenses. The plurality of silicone hydrogel contact lenses have an average energy loss of about 25% to about 45% when fully hydrated, such as about 27% to about 40% when fully hydrated, or about 30% to about 37% when fully hydrated.

wherein m in formula (1) represents an integer of 3 to 10, n in formula (1) represents an integer of 1 to 10, R in formula (1)¹Is an alkyl group having 1 to 4 carbon atoms, and R in the formula (1)²Is a hydrogen atom or a methyl group; and (b) a second siloxane monomer that is a double-terminal methacrylate-terminated polydimethylsiloxane having a number average molecular weight of at least 7,000 daltons; polymerizing the polymerizable composition in the contact lens mold assembly to form a polymeric lens body; contacting the polymeric lens body with a washing solution to remove extractable material from the polymeric lens body; and packaging the polymeric lens body in a contact lens packaging solution in a contact lens package; wherein the silicone hydrogel contact lens is in When fully hydrated, has an energy loss of about 27% to about 40%, or about 30% to about 37%.

In another example, the method is a method of manufacturing a silicone hydrogel contact lens, comprising: providing a miscible polymerizable composition comprising (a) a first siloxane monomer represented by formula (1):

wherein m in formula (1) represents an integer of 3 to 10, n in formula (1) represents an integer of 1 to 10, R in formula (1)¹Is an alkyl group having 1 to 4 carbon atoms, and R in the formula (1)²Is a hydrogen atom or a methyl group; and (b) a second siloxane monomer that is a double-terminal methacrylate-terminated polydimethylsiloxane having a number average molecular weight of at least 7,000 daltons; polymerizing the polymerizable composition in the contact lens mold assembly to form a polymeric lens body; contacting the polymeric lens body with a washing solution to remove extractable material from the polymeric lens body; and packaging the polymeric lens body in a contact lens packaging solution in a contact lens package; wherein the silicone hydrogel contact lens has an energy loss of about 25% to about 45% when fully hydrated, and wherein the energy loss is calculated using equation (B):

((energy) _{0% to 100% strain}-energy_{100% to 0% strain}) Energy/energy_{0% to 100% strain})×100(B)

Optionally, the polymeric lens bodies of the plurality of silicone hydrogel contact lenses have a dimensional stability difference of less than +/-3% over a period of two weeks to seven years, the dimensional stability difference (%) being determined from the lens diameter by the following equation (B):

((diameter)_{Finally, the product is processed}Diameter of_Initial) Diameter_Initial)×100(B)。

wherein m in formula (1) represents an integer of 3 to 10, n in formula (1) represents an integer of 1 to 10, R in formula (1)¹Is an alkyl group having 1 to 4 carbon atoms, and R in the formula (1)²Is a hydrogen atom or a methyl group, and the first siloxane monomer has a number average molecular weight of 400 daltons to 700 daltons; and (b) a second siloxane monomer that is a double-terminal methacrylate-terminated polydimethylsiloxane having a number average molecular weight of at least 7,000 daltons; polymerizing the polymerizable composition in the contact lens mold assembly to form a polymeric lens body; contacting the polymeric lens body with a washing solution to remove extractable material from the polymeric lens body; and packaging the polymeric lens body in a contact lens packaging solution in a contact lens package; wherein the silicone hydrogel contact lens has an energy loss of about 25% to about 45% when fully hydrated.

In any of the methods of the present invention, the second siloxane monomer can be represented by formula (2):

wherein R in formula (2)₁Selected from hydrogen or methyl; r in the formula (2)₂Selected from hydrogen or a hydrocarbon group having 1 to 4 carbon atoms; m in formula (2) represents an integer of 0 to 10; n in formula (2) represents an integer of 4 to 100; a and b represent an integer of 1 or more; a + b equals 20 to 500; b/(a + b) equals 0.01 to 0.22; and the configuration of the siloxane units includes a random configuration. As an example, the second siloxane monomer can be represented by formula (2), wherein m in formula (2) is 0, n in 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, R in formula (2)₁Is methyl, and R in formula (2)₂Is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.

In the method of the invention, the step of contacting the polymeric lens body with the washing liquid may be understood as an extraction step, since extractable material is removed from the polymeric lens body. In another example of the method, the contacting step comprises contacting the polymeric lens body with a wash solution comprising a volatile organic solvent, such as a liquid containing a primary alcohol (e.g., methanol, ethanol, n-propanol, etc.). The wash solution may contain secondary alcohols such as isopropanol and the like. The use of a wash solution containing one or more volatile organic solvents can aid in the removal of hydrophobic materials from the polymeric lens body. The extraction step can be understood as an alcohol-based extraction step. In another example of the method, the contacting step can comprise contacting the polymeric lens body with an aqueous wash solution that is free of volatile organic solvents. The extraction step may be understood as an aqueous extraction step. Aqueous wash solutions useful in the methods include, for example, water, such as deionized water, saline solutions, buffer solutions, or aqueous solutions containing surfactants or other non-volatile components that improve the removal of hydrophobic components from, or reduce the deformation of, the polymeric contact lens body compared to the use of deionized water alone. In one example, the surface of the lens body of the present invention may have an ophthalmically acceptably wettable surface when washed with an aqueous wash solution.

After washing, the contact lens can be placed in a package (e.g., a plastic blister package) containing a packaging solution (e.g., a buffered saline solution), which may or may not contain surfactants, anti-inflammatory agents, antimicrobial agents, contact lens wetting agents, and the like; and may be sealed and sterilized.

Examples of the invention

The following examples 1-28 illustrate certain aspects and advantages of the present invention, which should not be construed as limiting.

As can be readily determined by review of the following examples, none of the example formulations contained an organic diluent. Meanwhile, all example formulations contained no N, N-Dimethylacrylamide (DMA). Additionally, all of the example formulations below do not contain polymeric wetting agents. Furthermore, all example formulations included at least one hydrophilic amide monomer having one N-vinyl group. Most example formulations include a second siloxane that is a double-terminal methacrylate-terminated polydimethylsiloxane having a number average molecular weight of at least 7,000 daltons.

The following chemicals are mentioned in examples 1 to 28 and may be mentioned by their abbreviations.

Si 1: 2-methyl-2- [3- (9-butyl-1, 1,3,3,5,5,7,7,9, 9-decamethylpentasiloxane-1-yl) propoxy ] ethyl 2-acrylate (CAS number 1052075-57-6). (Si1 was obtained as product number X-22-1622 from Shin-Etsu chemical Co., Ltd., Tokyo, Japan (Japan)).

Si 2: α, ω -bis (methacryloxypropyl) -poly (dimethylsiloxane) -poly (ω -methoxy-poly (ethyleneglycol) propylmethylsiloxane) (the synthesis of this compound can be carried out as described in US20090234089, which is incorporated herein by reference)

Si 3: methacryloxypropyl terminated poly (dimethylsiloxane) (CAS number 58130-03-3; DMS-R18, obtained from Leersite Corp.)

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-hydroxybutyl 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-allyloxyethanol (CAS number 111-45-5)

V-64: 2, 2' -azobis-2-methylpropanenitrile (CAS number 78-67-1)

UV 1: acrylic acid 2- (4-benzoyl-3-hydroxyphenoxy) ethyl ester (CAS number 16432-81-8)

UV 2: 2- (3- (2H-benzotriazol-2-yl) -4-hydroxy-phenyl) ethyl methacrylate (CAS number 96478-09-0)

RBT 1: 1, 4-bis [4- (2-methacryloyloxyethyl) phenylamino ] anthraquinone (CAS number 121888-69-5)

RBT 2: 1, 4-bis [ (2-hydroxyethyl) amino ] -9, 10-anthracenedione bis (2-propenoic acid) ester (CAS registry number 109561071)

TPP: triphenylphosphine (CAS number 603-35-0)

pTPP: polymerizable TPP: diphenyl (p-vinylphenyl) phosphine (CAS number 40538-11-2)

Silicone hydrogel contact lens manufacturing and testing procedures

For each example, the chemical compounds described in examples 1-28 were weighed out in amounts corresponding to the unit parts and combined to form a mixture. The mixture was filtered into a bottle through a 0.2 to 5.0 micron syringe filter. The mixture was stored for a maximum of about 2 weeks. The mixture is understood to be a polymerizable silicone hydrogel contact lens precursor composition, or a polymerizable composition as used herein. In examples 1 to 28, the amounts of ingredients listed are given in parts by weight of the polymerizable composition.

A volume of polymerizable composition is cast molded by placing the composition in contact with the lens defining surface of the female mold member. In all of the following examples 1 to 28, the molding surface of the female mold member was formed of a nonpolar resin, specifically, polypropylene. The male mold member is placed in contact with the female mold member to form a contact lens mold assembly comprising a contact lens shaped cavity containing a polymerizable composition. In the following examples 1 to 28, the molding surface of the male mold member was formed of a nonpolar resin, specifically, polypropylene.

The contact lens mold assembly was placed in a nitrogen rinse oven to thermally cure the polymerizable composition. For all examples 1-28, the contact lens mold assembly was exposed to a temperature of at least about 55 ℃ for about 2 hours. Examples of curing profiles (curingprofiles) that can be used to cure the silicone hydrogel contact lenses described herein include exposing the contact lens mold assembly to a temperature of 55 ℃ for 40 minutes, to 80 ℃ for 40 minutes, and to 100 ℃ for 40 minutes. Other contact lenses may be manufactured with the same cure profile, but without using a first temperature of 55 ℃, which may be 65 ℃.

After polymerizing the polymerizable composition to form a polymeric lens body contained in the mold assembly, the contact lens mold assembly is demolded to separate the male and female mold members. The polymeric lens body remains attached to the male or female mold. A dry demolding process that does not contact the mold assembly with a liquid medium may be used, or a wet demolding process that contacts the mold assembly with a liquid medium (e.g., water or an aqueous solution) may be used. Mechanical dry demolding methods may involve applying mechanical force to a portion of one or both mold members to separate the mold members. In all of the following examples 1 to 28, the dry demolding method was used.

The polymeric lens body is then delensed from the male or female mold to produce a delensed polymeric lens body. In one example of a delensing process, a polymeric lens body can be delensed from a male mold member using a dry delensing process by: for example, manually stripping the lens from the male mold member; or compressing the male mold member and directing gas to the male mold member and the polymeric lens body and lifting the dry polymeric lens body from the male mold member with a vacuum device and discarding the male mold member. In other methods, the polymeric lens body can be delensed using a wet delensing method by contacting the dry polymeric lens body with a liquid release medium (e.g., water or an aqueous solution). For example, the male mold member with the polymeric lens body attached thereto can be immersed in a container containing a liquid until the polymeric lens body is separated from the male mold member. Alternatively, a volume of liquid release medium can be added to the female mold to soak the polymeric lens body in the liquid and separate the lens body from the female mold member. In the following examples 1 to 28, the dry delensing method was used. After separation, the lens body can be manually lifted from the mold member using tweezers or using a vacuum device and placed in a tray.

The delensed lens product is then washed to remove extractable material from the polymeric lens body, and the product is hydrated. The extractable material includes polymerizable components (e.g., monomers, or crosslinkers, or any optional polymerizable ingredients (e.g., colorants or UV blockers), or combinations thereof) present in the polymerizable composition that remain in the polymerized lens body in unreacted form, in partially reacted form, or in uncrosslinked form, or any combination thereof, after polymerization of the lens body and prior to extraction of the lens body. The extractable material can also include any non-polymerizable ingredients present in the polymerizable composition, such as any optional non-polymerizable colorant, or UV blocker, or diluent, or chain transfer agent, or any combination thereof, that remains present in the polymerized lens body after polymerization of the polymerized lens body and prior to extraction of the polymerized lens body.

In another method, for example, a method involving delensing by compressing a male mold member and directing a stream of gas toward the male mold member, a delensed polymeric contact lens body can be placed in a cavity of a lens carrier or tray, wherein the delensed polymeric lens body can then be contacted with one or more volumes of an extraction fluid (e.g., an aqueous extraction fluid free of a volatile organic solvent, such as deionized water or an aqueous solution of a surfactant such as Tween (Tween)80, or an organic solvent-based extraction fluid (e.g., ethanol), or an aqueous solution of a volatile organic solvent (e.g., ethanol)).

In other methods, such as those involving wet delensing by contacting the mold and lens with a liquid release medium, the delensed polymeric contact lens body can be washed with a wash solution free of volatile organic solvents, such as lower alcohols, e.g., methanol, ethanol, or any combination thereof, to remove extractable components from the lens body. For example, the delensed polymeric contact lens body can be washed by contacting the lens body with an aqueous wash solution free of volatile organic solvents (e.g., deionized water, or a surfactant solution, or a saline solution, or a buffer solution, or any combination thereof) to remove extractable components from the lens body. The washing may be performed in the final contact lens package, or may be performed in a wash tray or wash tank.

In examples 1-28 below, after the dry demolding and dry delensing steps, the dry delensing lens body is placed in a cavity of a tray, and the delensing polymeric lens body is extracted and hydrated by contacting the polymeric lens body with one or more volumes of an extraction solution. The extraction and hydration liquid used in the extraction and hydration process is composed of: a) a combination of a volatile organic solvent-based extract with a volatile organic solvent-free hydration liquid, or b) a volatile organic solvent-free extraction and hydration liquid, i.e. a complete water-based extraction and hydration liquid. Specifically, in the following examples 1 to 5, the extraction and hydration process comprises, in order, at least two extraction steps performed in separate portions of ethanol, at least one extraction step performed in a portion of 50:50wt/wt ethanol: aqueous solution of tween 80, at least three extraction and hydration steps performed in separate portions of deionized water solution of tween 80, wherein each extraction step or extraction and hydration step lasts about 5 minutes to 3 hours. In examples 6-25 below, the extraction and hydration process used comprised at least three extraction and hydration steps performed in separate portions of a deionized water solution of tween 80, wherein the temperature of the tween 80 solution portion ranges from room temperature to about 90 ℃, and wherein each extraction and hydration step lasts from about 15 minutes to about 3 hours.

The washed, extracted and hydrated lenses are then individually placed in contact lens blister packages containing a phosphate buffered saline packaging solution. The blister pack is sealed and sterilized by autoclaving.

After sterilization, lens properties such as contact angle (including dynamic and static contact angles), oxygen permeability, ion flux, modulus, elongation, tensile strength, water content, and the like are determined as described herein.

For the present contact lenses, contact angles, including dynamic and static contact angles, can be determined using conventional methods known to those skilled in the art. For example, the advancing and receding contact angles of the contact lenses provided herein can be measured using conventional droplet shape methods, such as the sitting drop method or the captive bubble method.

In the following examples 1-28, the advancing and receding contact angles of silicone hydrogel contact lenses were determined using a Kruss (Kruss) DSA100 instrument (Kruss gmbh, Hamburg) and as described in the following references: d.a. brandreth (d.a. brandreth): "dynamic contact angle and contact angle hysteresis (dynamic contact angle and contact angle hysteresis)", journal of colloid and interface science (journal of colloids and interface science), volume 62, 1977, pages 205 to 212; and r. naproski (r.knapikowski), m. kudre (m.kudra): "measurement of contact angle (Kontaktwilkelmessung. nemchdeWilhelmy-Prinzip-Einstastatischer Anasatzzur Feiherbeuriteung)" by error evaluation via William principle statistical method, chemical technique (chem. Technik), Vol.45, 1993, pp.179 to 185; and U.S. patent No. 6,436,481, which are incorporated herein by reference.

As an example, advancing and receding contact angles were determined using a bubble trap method with phosphate buffered saline (PBS; pH = 7.2). The lenses were laid flat on a quartz surface and rehydrated with PBS for at least 10 minutes prior to testing. An automatic injection system is used to place air bubbles on the lens surface. The size of the air bubble is increased and decreased to obtain a receding angle (plateau obtained when the bubble size is increased) and an advancing angle (plateau obtained when the bubble size is decreased).

The modulus, elongation and tensile strength values of the lenses of the invention can be determined using conventional methods known to those skilled in the art, for example, according to test methods of ANSIZ 80.20. The modulus, elongation and tensile strength values reported herein were determined using an instron 3342 or 3343 mechanical testing system (instron corporation, Norwood (Norwood), MA, usa) and blue hill (Bluehill) materials testing software, where a custom rectangular contact lens cut mold was used to prepare rectangular sample strips. Modulus, elongation and tensile strength are measured in a room having a relative humidity of at least 70%. Lenses intended for testing were soaked in Phosphate Buffered Saline (PBS) for at least 10 minutes prior to testing. The central strip of the lens is cut using a cutting die while the lens is held concave side up. The thickness of the strip was measured using a calibrated gauge (reed electronic thickness gauge, reed development, inc., CastroValley, CA, usa). The strips were loaded into the grips of a calibrated instron apparatus using tweezers and the strips were fitted on at least 75% of the grip surface of each grip. Test methods designed to determine the mean and standard deviation of the maximum load (N), tensile strength (MPa), strain at maximum load (% elongation), and tensile modulus (MPa) were run and the results recorded.

The percent energy loss of the silicone hydrogel contact lenses of the invention can be determined using conventional methods known to those skilled in the art. For the following examples 1-28, the percent energy loss was determined using an instron model 3343 (instron corporation, norwood, ma, usa) mechanical testing system using a 10N force transducer (instron model 2519-. The energy loss is measured in a room with a relative humidity of at least 70%. Prior to testing, each lens was soaked in Phosphate Buffered Saline (PBS) for at least 10 minutes. The lenses are loaded into the jaws of a calibrated instron apparatus using tweezers, and the lenses are loaded vertically between the jaws as symmetrically as possible so that the lenses fit on at least 75% of the jaw surface of each jaw. A test designed to determine the energy required to stretch the lens to 100% strain at a rate of 50 mm/min and then return it to 0% strain was then run on the lens. Only one test is performed on a single lens. After the test is completed, the energy loss is calculated using the following equation: lost energy (%) = (energy to 100% strain-energy recovered to 0% strain)/energy to 100% strain x 100%.

The ion current of the lenses of the invention can be determined using conventional methods known to those skilled in the art. For the lenses in examples 1-28 below, ion current was measured using a technique substantially similar to the "ion current technique" described in U.S. patent 5,849,811, which is incorporated herein by reference. The hydrated lens was allowed to equilibrate in deionized water for at least 10 minutes prior to measurement. The lens to be measured is placed in the lens holding device between the convex and concave portions. The male and female portions include a flexible sealing ring between the lens and the respective male or female portion. After placing the lens in the lens holder, the lens holder is then placed in the threaded cap. The cap is screwed onto the glass tube to define the supply chamber. The supply chamber was filled with 16ml of a 0.1M NaCl solution. The receiving chamber was filled with 80ml of deionized water. The leads of the conductivity meter were immersed in deionized water in 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 maintained at about 35 ℃. Finally, the supply chamber is immersed in the receiving chamber so that the NaCl solution in the supply chamber is level with the water in the receiving chamber. After the temperature in the receiving chamber had equilibrated to 35 ℃, the conductivity was measured every 2 minutes for at least 10 minutes. The conductivity is substantially linear with time data and is used to calculate the ion flow value of the lens tested.

The oxygen transmission rate (Dk) of the lenses of the invention can be determined using conventional methods known to those skilled in the art. For example, the Dk value may be used under the model name FunkangCommercially available instruments for the oxygen permeation system (Ox-TranSystem) (membrane health (Mocon) corporation, Minneapolis (Minneapolis), MN (MN), usa) are determined, for example, using the membrane health method as described in U.S. patent No. 5,817,924, which is incorporated herein by reference. The Dk values for the lenses in examples 1-28 below were determined using the method described in Brilliant (Chhabra) et al (2007), Single lens polarographic measurements of oxygen transmission rate (Dk) for high transmission soft contact lenses (Ashingle-Ensporograspherentityinformationablity (Dk) for HyperTransmissibleContactles BioMaterial 28: 4331-4342, which is incorporated herein by reference.

The Equilibrium Water Content (EWC) of the lenses of the invention can be determined using conventional methods known to those skilled in the art. For the lenses in examples 1-28 below, the hydrated silicone hydrogel contact lenses were removed from the aqueous liquid, wiped to remove excess surface water and weighed. The weighed lenses can then be dried in an oven at 80 ℃ and under vacuum, and the dried lenses are 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 (%) was (weight difference/hydrated weight) × 100.

The percentage of wet extractable or dry extractable components in the lens can be determined by extracting the lens in an organic solvent that does not dissolve the polymeric lens body according to methods known to those skilled in the art. For the lenses in examples 1 to 28 below, the soxhlet extraction method was used for extraction in methanol. For the determination of wet extractable components, samples of fully hydrated and sterilized contact lenses (e.g., at least 5 lenses per batch) were prepared by removing excess packaging solution from each lens and drying it overnight in a vacuum oven at 80 ℃. For determination of dry extractable components, samples of polymeric lens bodies were prepared without washing, extraction, hydration or sterilization by drying the lens bodies overnight in a vacuum oven at 80 ℃. Upon drying and cooling, each lens was weighed to determine its initial dry weight (W1). Each lens was then placed in a porous stackable Teflon (Teflon) sleeve and the sleeves were stacked to form an extraction column with an empty sleeve placed at the top of the column. The extraction column was placed in a small soxhlet extractor attached to a condenser and a round bottom flask containing 70ml to 80ml methanol. Water was circulated through the condenser and methanol was heated until it boiled gently. The lenses were extracted for at least 4 hours from the time of first appearance of condensed methanol. The extracted lenses were dried again overnight in a vacuum oven at 80 ℃. Upon drying and cooling, each lens was weighed to obtain the dry weight of the extracted lens (W2), and the following calculation was performed on each lens to determine the percentage of wet extractable components: [ (W1-W2)/W1] x 100.

Example 1

The polymerizable compositions were obtained by mixing and filtering the following chemical compounds in the amounts specified using the procedures described in the silicone hydrogel contact lens manufacturing and testing procedures given above.

Chemical Compounds (abbreviations)	Unit parts
		Si1	30
Si3	3
		VMA	45
EGMA	7

MMA	15
		TEGDMA	0.8
AE	0.5
		V-64	0.3
UV1	0.9

A batch of silicone hydrogel contact lenses was prepared and tested using this formulation according to the manufacturing procedures and testing methods described in the silicone hydrogel contact lens manufacturing and testing procedures using a dry demolding method, a dry delensing method, and a washing method using a washing solution comprising a volatile organic solvent-based extract and a hydration solution consisting of a liquid free of volatile organic solvents. These contact lenses contain units derived from two siloxane monomers, Si1 and Si 3. This batch of contact lenses had an acceptable average percent energy loss.

In addition, the batches of silicone hydrogel contact lenses had an average EWC of 30% wt/wt to 70% wt/wt when fully hydrated, when tested at the beginning of the shelf life study.

Example 2

Chemical Compounds (abbreviations)	Unit parts
		Si1	30
Si3	3
		VMA	45
EGMA	7
		MMA	15
EGDMA	0.5
		TEGDVE	0.1
AE	0.8
		V-64	0.3
UV2	0.9
		RBT1	0.01
TPP	0.5

In addition, when tested at the beginning of the shelf life study, these lenses had an EWC of 52% wt/wt, a modulus of 0.63MPa, and 3.62(× 10) when fully hydrated^-3mm²/min) ion flow.

Example 3

Chemical Compounds (abbreviations)	Unit parts
		Si1	30
Si3	3
		VMA	45
EGMA	7
		MMA	15
EGDMA	0.5
		TEGDVE	0.1
AE	1.4
		V-64	0.5
UV2	0.9
		RBT1	0.01
TPP	0.5

Additionally, these silicone hydrogel contact lenses, when fully hydrated, have an EWC of about 52% wt/wt, a modulus of about 0.58MPa, a wet extractable content of about 0.67%, a captive bubble static contact angle of about 30 degrees, and a captive bubble dynamic advancing contact angle of about 50.1 degrees, when tested at the beginning of the shelf life study.

Example 4

Chemical Compounds (abbreviations)

Unit parts

Si1	30
		Si2	10
VMA	45
		EGMA	7
MMA	15
		EGDMA	0.5
TEGDVE	0.1
		AE	1.4
V-64	0.5
		UV2	0.9
RBT1	0.01
		TPP	0.5

A batch of silicone hydrogel contact lenses was prepared and tested using this formulation according to the manufacturing procedures and testing methods described in the silicone hydrogel contact lens manufacturing and testing procedures using a dry demolding method, a dry delensing method, and a washing method using a washing solution comprising a volatile organic solvent-based extract and a hydration solution consisting of a liquid free of volatile organic solvents. These contact lenses contain units derived from two siloxane monomers, Si1 and Si 2. This batch of contact lenses had an acceptable average percent energy loss.

In addition, these silicone hydrogel contact lenses, when fully hydrated, had an EWC of 53% wt/wt to 54% wt/wt, a modulus of about 0.43MPa, a moisture extractable content of about 1.23% wt/wt, a bubble trap static contact angle of about 38 degrees, about 5 when tested at the beginning of the shelf life study 0.0 degree of dynamic advancing contact angle of trapped bubble, 2.5-3.0 (x 10)^-3mm²/min), Dk of 70 barrers, elongation of about 450%, tensile strength of 1.40MPa, percent transmittance of 98%, energy loss of 36%, and swelling factor of about 21%. The polymeric lens body has a dry extractable content of about 17% wt/wt when tested prior to extraction and hydration.

Example 5

Chemical Compounds (abbreviations)	Unit parts
		Si1	30
Si2	10
		VMA	48
EGMA	7
		MMA	15

EGDMA	0.5
		TEGDVE	0.1
AE	1.4
		V-64	0.5
UV2	0.9
		RBT1	0.01
TPP	0.5

A batch of silicone hydrogel contact lenses was prepared and tested using this formulation according to the manufacturing procedures and testing methods described in the silicone hydrogel contact lens manufacturing and testing procedures using a dry demolding method, a dry delensing method, and a washing method using a washing solution comprising a volatile organic solvent-based extract and a hydration solution consisting of a liquid free of volatile organic solvents. These contact lenses contain units derived from two siloxane monomers, Si1 and Si 2. This batch of contact lenses had acceptable average dimensional stability, and had acceptable average tensile modulus.

In addition, in shelf lifeThese silicone hydrogel contact lenses, when tested at the beginning of the study, had an oxygen permeability of greater than 60 barrers, an EWC of about 53% wt/wt, about 2.90(× 10) when fully hydrated^-3mm²/min), a modulus of about 0.40MPa, an elongation of about 425%, a tensile strength of about 1.4MPa, a static captive bubble contact angle of about 37 degrees, a dynamic captive bubble advancing contact angle of about 48 to 52 degrees, a light transmittance of about 98%, a wet extractable content of about 1.30% wt/wt, an energy loss of about 35% to about 36%, and a swelling factor of about 21%, and has an average dimensional stability difference of less than +/-3.0% after storage for at least 2 weeks at 80 ℃.

Example 6

Chemical Compounds (abbreviations)	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 and tested using this formulation according to the manufacturing and testing procedures described in the silicone hydrogel contact lens manufacturing and testing procedures using a dry demolding method, a dry delensing method, and a washing method using an extraction and hydration liquid consisting of an extract that was free of volatile organic solvents. This batch of lenses was not exposed to volatile organic solvents during their manufacture. These contact lenses contain units derived from two siloxane monomers, Si1 and Si 3. This batch of contact lenses had an acceptable average percent energy loss.

In addition, these silicone hydrogel contact lenses have an EWC of about 55% wt/wt, about 3.1(× 10) when fully hydrated, when tested at the beginning of the shelf life study^-3mm²Min), a Dk of about 72 barrers, a modulus of about 0.70MPa, an elongation of about 345%, a tensile strength of about 2.4MPa, a water break time of more than 20 seconds, a wet extractable component of about 3.9% wt/wt and an energy loss of about 40%, and has an average dimensional stability difference of less than +/-3.0% after storage for more than 2 weeks at 80 ℃. The polymeric lens body has about 11% wt/wt of dry extractable components when tested prior to extraction and hydration.

Example 7

Chemical Compounds (abbreviations)	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

In addition, these silicone hydrogel contact lenses have an EWC of about 58% wt/wt, about 4.14(× 10) when fully hydrated, when tested at the beginning of the shelf life study^-3mm²Min), a modulus of about 0.77MPa, an elongation of about 349%, a tensile strength of about 1.75MPa, a water burst time of greater than 20 seconds, a wet extractable content of about 4.42% wt/wtAmount and about 41% energy loss, and has a mean dimensional stability difference of less than +/-3.0% after storage for at least 2 weeks at 80 ℃.

Example 8

Chemical Compounds (abbreviations)	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 and tested using this formulation according to the manufacturing and testing procedures described in the silicone hydrogel contact lens manufacturing and testing procedures using a dry demolding method, a dry delensing method, and a washing method using an extraction and hydration liquid consisting of an extract that was free of volatile organic solvents. This batch of lenses was not exposed to volatile organic solvents during their manufacture. These contact lenses contain units derived from two siloxane monomers, Si1 and Si 2. This batch of contact lenses had an acceptable average percent energy loss.

In addition, these silicone hydrogel contact lenses have an EWC of about 55% wt/wt, about 4.19(× 10) when fully hydrated, when tested at the beginning of the shelf life study^-3mm²Min), a modulus of about 0.61MPa, an elongation of about 275%, a tensile strength of about 1.51MPa, a water burst time of greater than 20 seconds, and a wet extractable component of about 4.10% wt/wt, and has an average dimensional stability difference of less than +/-3.0% for more than 2 weeks at 80 ℃.

Example 9

Chemical Compounds (abbreviations)	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

In addition, these silicone hydrogel contact lenses have an EWC of about 58% wt/wt, about 2.75(× 10) when fully hydrated, when tested at the beginning of the shelf life study^-3mm²Min), a modulus of about 0.66MPa, an elongation of about 216%, a tensile strength of about 0.87MPa, a water burst time of greater than 20 seconds, and a wet extractable component of about 4.56% wt/wt, and has an average dimensional stability difference of less than +/-3.0% after 6 days of storage at 95 ℃.

Example 10

Chemical Compounds (abbreviations)	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

In addition, these silicone hydrogel contact lenses have an EWC of about 56% wt/wt, about 3.54(× 10) when fully hydrated, when tested at the beginning of the shelf life study^-3mm²Min), a modulus of about 0.57MPa, an elongation of about 310%, a tensile strength of about 1.90MPa, a water burst time of greater than 20 seconds, a wet extractable component of about 4.74% wt/wt, and an energy loss of about 34% to 36%, and has an average dimensional stability difference of less than +/-3.0% after 7 days of storage at 80 ℃. The polymeric lens body has about 14.39% wt/wt of dry extractable components when tested prior to extraction and hydration.

Example 11

Chemical Compounds (abbreviations)	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

In addition, these silicone hydrogel contact lenses have an EWC of about 57% wt/wt, about 3.68(× 10) when fully hydrated, when tested at the beginning of the shelf life study^-3mm²Min), a modulus of about 0.69MPa, an elongation of about 314%, a tensile strength of about 1.30MPa, a water burst time of greater than 20 seconds, a wet extractable component of about 1.81% wt/wt, and an energy loss of about 34%, and has an average dimensional stability difference of less than +/-3.0% after 14 days of storage at 80 ℃.

Example 12

Chemical Compounds (abbreviations)	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 and tested using this formulation according to the manufacturing and testing procedures described in the silicone hydrogel contact lens manufacturing and testing procedures using a dry demolding method, a dry delensing method, and a washing method using an extraction and hydration liquid consisting of an extract that was free of volatile organic solvents. This batch of lenses was not exposed to volatile organic solvents during their manufacture. These contact lenses contain units derived from three siloxane monomers, Si1, Si2, and Si 3. This batch of contact lenses had an acceptable average percent energy loss.

In addition, these silicone hydrogel contact lenses have an EWC of about 55% wt/wt, about 3.06(× 10) when fully hydrated, when tested at the beginning of the shelf life study^-3mm²Min), a modulus of about 0.85MPa, an elongation of about 284%, a tensile strength of about 1.88MPa, a water burst time of greater than 20 seconds, a wet extractable component of about 2.38% wt/wt, and an energy loss of about 36%, and has an average dimensional stability difference of less than +/-3.0% after 14 days of storage at 80 ℃.

Example 13

Chemical Compounds (abbreviations)	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

In addition, these silicone hydrogel contact lenses have an EWC of about 54% wt/wt, about 3.57(× 10) when fully hydrated, when tested at the beginning of the shelf life study^-3mm²Min), a modulus of about 0.66MPa, an elongation of about 274%, a tensile strength of about 1.40MPa, and a moisture extractable content of about 3.8% wt/wt, and has a difference in average dimensional stability of less than +/-3.0% after storage for 7 days at 80 ℃.

Example 14

Chemical Compounds (abbreviations)	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

Additionally, these silicone hydrogel contact lenses, when fully hydrated, have a modulus of about 0.81MPa, an elongation of about 351%, a tensile strength of about 1.61MPa, and an EWC of 30% wt/wt to 70% wt/wt, and have a mean dimensional stability difference of less than +/-3.0% at 80 ℃ for 14 days, when tested at the beginning of the shelf life study.

Example 15

Chemical Compounds (abbreviations)	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

In addition, these silicone hydrogel contact lenses have about 3.33(× 10) when fully hydrated, when tested at the beginning of the shelf life study^-3mm²Min), a modulus of about 0.74MPa, and an elongation of about 222%, and has a mean dimensional stability difference of less than +/-3.0% for 14 days at 80 ℃.

Example 16

Chemical Compounds (abbreviations)	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

Additionally, these silicone hydrogel contact lenses, when fully hydrated, have an EWC of about 57% wt/wt, a modulus of about 0.70MPa, an energy loss of about 40%, and a captive bubble dynamic advancing contact angle of about 50 degrees to about 60 degrees, when tested at the beginning of the shelf life study, and have an average dimensional stability difference of less than +/-3.0% at 80 ℃ for 14 days.

Example 17

Chemical Compounds (abbreviations)	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

Additionally, these silicone hydrogel contact lenses have an EWC of about 56% wt/wt, a modulus of about 0.50MPa, and a captive bubble dynamic advancing contact angle of about 47 degrees to about 51 degrees when fully hydrated, and have an average dimensional stability difference of less than +/-3.0% at 80 ℃ for 4.4 weeks, when tested at the beginning of the shelf life study.

Example 18

Chemical Compounds (abbreviations)	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

Additionally, these silicone hydrogel contact lenses have an EWC of about 55% wt/wt, a modulus of about 0.60MPa, and a captive bubble dynamic advancing contact angle of about 47 degrees to about 55 degrees when fully hydrated, and have an average dimensional stability difference of less than +/-3.0% after 2 weeks of storage at 80 ℃, when tested at the beginning of the shelf life study.

Example 19

Chemical Compounds (abbreviations)	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

Additionally, these silicone hydrogel contact lenses, when fully hydrated, have an EWC of about 55% wt/wt to about 56% wt/wt, a modulus of about 0.71MPa, and a captive bubble dynamic advancing contact angle of about 45 degrees to about 47 degrees, when tested at the beginning of the shelf life study, and have an average dimensional stability difference of less than +/-3.0% for at least 2 weeks at 80 ℃.

Example 20

Chemical Compounds (abbreviations)	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

Additionally, these silicone hydrogel contact lenses have an EWC of about 56% wt/wt and a modulus of about 0.65MPa when fully hydrated, and have a mean dimensional stability difference of less than +/-3.0% at 80 ℃ for 2 weeks, when tested at the beginning of the shelf life study.

Example 21

Chemical Compounds (abbreviations)	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

Additionally, these silicone hydrogel contact lenses have an EWC of about 55% wt/wt to about 56% wt/wt, a modulus of about 0.53MPa, a captive bubble dynamic advancing contact angle of about 51 degrees to about 53 degrees, and an energy loss of about 34% when fully hydrated, and have an average dimensional stability difference of less than +/-3.0% at 80 ℃ for 4.4 weeks, when tested at the beginning of the shelf life study.

Example 22

The polymerizable silicone composition was obtained by mixing and filtering the following chemical compounds in the amounts specified using the procedures described in the silicone hydrogel contact lens manufacturing and testing procedures given above.

Chemical Compounds (abbreviations)	Unit parts
		Si1	29
Si2	8
		VMA	42
MMA	8
		EGMA	6
DEGVE	7
		EGDMA	0.6
TEGDVE	0.1
		V-64	0.5
UV2	1.7
		RBT2	0.01
pTPP	0.5
		AE	0.4

In addition, these silicone hydrogel contact lenses, when fully hydrated, had an EWC of 57% wt/wt to 58% wt/wt, about 2.9(× 10) when tested at the beginning of the shelf life study^-3mm²Min), a modulus of about 0.7MPa, an elongation of about 300%, a tensile strength of about 1.5MPa, a captive bubble dynamic advancing contact angle of about 44 degrees to about 48 degrees, a wet extractable component of about 5.10% wt/wt, and an energy loss of about 32% to about 33%, and has an average dimensional stability difference of less than +/-3.0% after storage of 4.4 at 80 ℃. The polymeric lens body has about 12.2% wt/wt of dry extractable components when tested prior to extraction and hydration.

Example 23

Chemical Compounds (abbreviations)	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

In addition, these silicone hydrogel contact lenses, when fully hydrated, had an EWC of about 55% wt/wt to about 56% wt/wt, about 4.1(× 10) when tested at the beginning of the shelf life study^-3mm²Min), a modulus of about 0.6MPa, an elongation of about 275%, a tensile strength of about 1.2MPa, a captive bubble dynamic advancing contact angle of about 55 degrees to about 58 degrees, a wet extractable component of about 4.6% wt/wt, an energy loss of about 31% to about 32%, and a swelling factor of about 27%, and has an average dimensional stability difference of less than +/-3.0% after storage for 4.4 weeks at 80 ℃. The polymeric lens body has about 10.6% wt/wt of dry extractable components when tested prior to extraction and hydration.

Example 24

Chemical Compounds (abbreviations)	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

In addition, these silicone hydrogel contact lenses have an EWC of about 61% wt/wt, about 3.8(× 10) when fully hydrated, when tested at the beginning of the shelf life study^-3mm²Min), a modulus of about 0.5MPa, an elongation of about 279%, a tensile strength of about 1.2MPa, a captive bubble dynamic advancing contact angle of about 45 to about 47 degrees, a wet extractable component of about 4.55% wt/wt, and an energy loss of about 30 to about 33%, and storage at 80 deg.C There was a mean dimensional stability difference of less than +/-3.0% after 14 days of storage. The polymeric lens body has about 13.65% wt/wt of dry extractable components when tested prior to extraction and hydration.

Example 25

Chemical Compounds (abbreviations)	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

In addition, these silicone hydrogel contact lenses, when fully hydrated, had an EWC of about 55% wt/wt to about 57% wt/wt, about 3.6(× 10) when tested at the beginning of the shelf life study ^-3mm²Min), a modulus of about 0.7MPa, an elongation of about 285%, a tensile strength of about 1.3MPa, a captive bubble dynamic advancing contact angle of about 47 degrees to about 53 degrees, a wet extractable component of about 4.10% wt/wt, and an energy loss of about 34% to about 35%, and has an average dimensional stability difference of less than +/-3.0% after 14 days of storage at 80 ℃. When tested prior to extraction and hydration, the polymeric lens body was found to have about 9.80% wt/wt of dry extractable components.

Example 26

Chemical Compounds (abbreviations)	Unit parts
		Si1	31
Si2	5
		VMA	40
MMA	10
		EGMA	5
BVE	9
		TEGDVE	0.1
EGDMA	1.0
		V-64	0.5
UV2	0.9
		RBT2	0.01
pTPP	0.5

In particular, these silicone hydrogel contact lenses have an energy loss of about 36% to about 38% when fully hydrated, when tested at the beginning of the shelf life study.

Example 27

Chemical Compounds (abbreviations)	Unit parts
		Si1	26
Si2	10
		VMA	40
MMA	10
		EGMA	5
BVE	9
		TEGDVE	0.1
TEGDMA	1.0
		V-64	0.5
UV2	0.9
		RBT2	0.01
pTPP	0.5

In addition, these silicone hydrogel contact lenses have an EWC of about 56% wt/wt, about 3.6(× 10) when fully hydrated, when tested at the beginning of the shelf life study ^-3mm²Min), a modulus of about 0.46MPa, an elongation of about 196%, a tensile strength of about 0.6MPa, about 7.28% wt/wt of a wet extractable component, and an energy loss of about 34% to about 38%. When tested prior to extraction and hydration, the polymeric lens body was found to have about 17.87% wt/wt of dry extractable components.

Example 28

Chemical Compounds (abbreviations)	Unit parts
		Si1	21
Si2	15
		VMA	40
MMA	10
		EGMA	5
BVE	9
		TEGDVE	0.1
TEGDMA	1.0
		V-64	0.5
UV2	0.9
		RBT2	0.01
pTPP	0.5

In addition, these silicone hydrogel contact lenses have about 6.4(× 10) when fully hydrated when tested at the beginning of the shelf life study^-3mm²Min), a modulus of about 0.51MPa, an elongation of about 200%, a tensile strength of about 0.67MPa, and an energy loss of about 32% to about 34%.

While the disclosure herein refers to certain illustrated embodiments, it is to be understood that these embodiments are presented by way of example and not limitation. While exemplary embodiments are discussed, the intent of the foregoing detailed description should be construed to cover all modifications, alterations, and equivalents of those embodiments as may fall within the spirit and scope of the invention as defined by the other disclosure.

A number of publications and patents are cited above. Each of the publications and patents cited herein is incorporated by reference in its entirety.

Claims

1. A silicone hydrogel contact lens, comprising:

a polymerized lens body that is the reaction product of a polymerizable composition comprising

(a) A first siloxane monomer represented by formula (1):

wherein m in formula (1) represents one of 3 to10, n in formula (1) represents an integer of 1 to 10, R in formula (1)¹Is an alkyl group having 1 to 4 carbon atoms, and R in the formula (1)²Is a hydrogen atom or a methyl group; and

(b) a second siloxane monomer that is a double-terminal methacrylate-terminated polydimethylsiloxane having a number average molecular weight of at least 7,000 daltons;

wherein the silicone hydrogel contact lens has an energy loss of 25% to 45% when fully hydrated.

2. The contact lens of claim 1, wherein the silicone hydrogel contact lens has an energy loss of 27% to 40% when fully hydrated.

3. The contact lens of claim 1, wherein the energy loss is calculated using equation (B):

Wherein the energy is_{0% to 100% strain}Represents the energy applied to stretch a sample of the lens to 100% strain at a constant rate, and the energy _{100% to 0% strain}Representing the energy released when the sample of the lens recovers from 100% strain to 0% strain.

4. The contact lens of claim 1, wherein in the first siloxane monomer, m in formula (1) is 4, n in formula (1) is 1, and R in formula (1) is¹Is butyl, and each R in formula (1)²Independently a hydrogen atom or a methyl group.

5. The contact lens of claim 1, wherein the first siloxane monomer has a number average molecular weight of 400 to 700 daltons.

6. The contact lens of claim 1, wherein the polymerizable composition further comprises at least one crosslinker.

7. The contact lens of claim 6, wherein the at least one crosslinking agent comprises a vinyl-containing crosslinking agent.

8. The contact lens of claim 7, wherein the total amount of vinyl-containing cross-linking agent present in the polymerizable composition is from 0.01 to 2.0 unit parts by weight.

9. The contact lens of claim 8, wherein the ratio of the amount of the first siloxane monomer present in the polymerizable composition to the total amount of vinyl-containing crosslinker present in the polymerizable composition is 100: 1 to 400: 1, based on weight unit parts.

10. The contact lens of claim 1, wherein the polymerizable composition further comprises at least one hydrophilic monomer.

11. The contact lens of claim 10, wherein the at least one hydrophilic monomer comprises a hydrophilic amide monomer having one N-vinyl group.

12. The contact lens of claim 1, wherein the ratio of the amount of the first siloxane monomer present in the polymerizable composition to the amount of the second siloxane monomer present in the polymerizable composition is at least 3: 1, based on weight unit parts.

13. The contact lens of claim 1, wherein the total amount of siloxane monomers present in the polymerizable composition is 35 to 40 weight unit parts.

14. The contact lens of claim 1, wherein the second siloxane monomer is represented by formula (2):

wherein R in formula (2)₁Selected from hydrogen or methyl; r in the formula (2)₂Selected from hydrogen or C_1-4A hydrocarbyl group; m represents an integer of 0 to 10; n in formula (2) represents an integer of 4 to 100; a and b in formula (2) represent an integer of 1 or more; a + b equals 20 to 500; b/(a + b) equals 0.01 to 0.22; and the configuration of the siloxane units includes a random configuration.

15. The contact lens of claim 14, wherein in the second siloxane monomer, m in formula (2) is 0, n in formula (2) is an integer from 5 to 10, a in formula (2) is an integer from 65 to 90, b in formula (2) is an integer from 1 to 10, and R in formula (2) is₁Is methyl.

16. A batch of silicone hydrogel contact lenses comprising a plurality of the contact lenses of claim 1, wherein the batch of silicone hydrogel contact lenses, when fully hydrated, has an average equilibrium water content EWC of from 30% wt/wt to 70% wt/wt, or an average oxygen permeability of at least 55 barrers, or an average captive bubble dynamic advancing contact angle of less than 70 degrees, or an average captive bubble static contact angle of less than 55 degrees, or any combination thereof, based on an average of values determined for at least 20 individual lenses in the batch.

17. A method of manufacturing a silicone hydrogel contact lens, comprising:

providing a miscible polymerizable composition comprising

(a) A first siloxane monomer represented by formula (1):

wherein m in formula (1) represents an integer of 3 to 10, n in formula (1) represents an integer of 1 to 10, R in formula (1) ¹Is an alkyl group having 1 to 4 carbon atoms, and R in the formula (1)²Is a hydrogen atom or a methyl group; and

polymerizing the polymerizable composition in a contact lens mold assembly to form a polymeric lens body;

contacting the polymeric lens body with a washing solution to remove extractable material from the polymeric lens body; and

packaging the polymeric lens body in a contact lens packaging solution in a contact lens package;

18. The method of claim 17, wherein the contacting step comprises contacting the polymeric lens body with a washing solution that is free of volatile organic solvents.

19. The method of claim 17, wherein the first siloxane monomer has a number average molecular weight of 400 to 700 daltons.

20. The method of claim 17, wherein the energy loss is calculated using equation (B):

Wherein the energy is_{0% to 100% strain}Means applied by stretching a sample of the lens to 100% strain at a constant rateEnergy of (2), and energy_{100% to 0% strain}Representing the energy released when the sample of the lens recovers from 100% strain to 0% strain.