hydrogel silicone contact lens, lot of said lens and method of manufacturing it

专利摘要:
HYDROGEL SILICON CONTACT LENSES WITH ACCEPTABLE LEVELS OF ENERGY LOSS Silicone hydrogel contact lenses with ophthalmologically acceptable levels of energy loss are described. The lenses are obtained from a polymerizable composition, including a first siloxane monomer represented by the general formula (1): where m of formula (1) represents an integer from 3 to 10, n of formula (1) represents an integer from 1 to 10, RA 1A of formula (1) is an alkyl group having 1 to 4 carbon atoms, and each RA 2A of formula (1) is, independently, either a hydrogen atom or a methyl group; the lenses also include units derived from a second siloxane monomer which is an end capped polydimethylsiloxane with methacrylate in two terminations with an average molecular weight of at least 7,000 Daltons. The average energy loss of silicone hydrogel contact lenses is around 30% to about 45%, when the lenses are fully hydrated. Lots of silicone hydrogel contact lenses and methods of making silicone hydrogel contact lenses are also described.
公开号:BR112013021871B1
申请号:R112013021871-1
申请日:2012-02-23
公开日:2021-01-05
发明作者:Ronghua Liu；Xinfeng Shi；Yumen Liu；Charlie Chen；Ye Hong；Charles A. Francis；Li Yao；Arthur Back；Ying Zheng
申请人:Coopervision International Holding Company, Lp；
IPC主号:

专利说明:

[001] This application claims priority benefit under 35 USC § 119 (e) of US Provisional Patent Application No. 61 / 447,197, filed on February 28, 2011, which is incorporated by reference in its entirety. Field of the Invention
[002] The present disclosure relates to silicone hydrogel contact lenses, related compositions and methods. Background of the Invention
[003] In the commercial and clinical scope, silicone hydrogel contact lenses are a popular alternative to conventional hydrogel contact lenses (for example, hydrogel contact lenses that do not contain silicone or ingredients containing silicone). It is believed that the presence of siloxanes in silicone hydrogel contact lens formulations affects the properties of the obtained silicone hydrogel contact lenses. For example, the presence of a siloxane component in a contact lens is believed to result in relatively higher oxygen permeability compared to a conventional hydrogel contact lens, without a siloxane component. . In addition, the presence of a silicone component is believed to increase the likelihood of hydrophobic domains being present on the lens surface of a silicone hydrogel contact lens, compared to a conventional hydrogel contact lens, without a silicone component. The first generation of silicone hydrogel contact lenses provides high levels of oxygen, although the wettability of the lenses tends to be less than you might want. Techniques have been developed to overcome the problems of hydrophobicity on the surfaces of silicone hydrogel contact lenses. Based on the popularity of silicone hydrogel contact lenses, there remains a need for new silicone hydrogel contact lenses that are ophthalmologically compatible, such that the new silicone hydrogel contact lenses have acceptable levels of loss of energy.
[004] Some documents describing silicone hydrogel contact lenses include: US 4,711,943, US 5,712,327, US 5,760,100, US 7,825,170, US 6,867,245, US 2006 / 0.063,852, US 2007 / 0.296.914, US 7,572,841, US 2009 / 0.299,022, US 2009 / 0.234,089 and US 2010 / 0.249,356, each of which is incorporated as a reference in its entirety. summary
[005] It has been discovered that polymerizable compositions can be prepared using siloxane monomers with a particular structure in combination with a second siloxane monomer, which is capped (end-capped) polydimethylsiloxane with methacrylate in two terminations with a molecular weight average of at least 7,000 Daltons, where these polymerizable compositions, when used to prepare silicone hydrogel contact lenses, can result in lenses with acceptable levels of energy loss. Since the level of energy loss of a silicone hydrogel contact lens may be related to the level of movement over the eye shown by the contact lens during use, the level of energy loss of a contact lens may have a significant effect on the ophthalmic acceptability of a contact lens.
[006] New silicone hydrogel contact lenses were invented. Unlike approaches that have improved the energy loss of a silicone hydrogel contact lens by adjusting the level of a single silicone macromer present in the contact lens, this disclosure refers to the discovery that inclusion of a second siloxane monomer, which is an end-capped polydimethylsiloxane with methacrylate in two terminations, with an average molecular weight of at least 7,000 Daltons, in the contact lens formulation, can improve the loss energy compared to silicone hydrogel contact lenses that are made from formulations containing the siloxane of the general formula (1):
where m of formula (1) represents an integer from 3 to 10, n of formula (1) represents an integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 atoms of carbon, and R2 of formula (1) is a hydrogen atom or a methyl group, and thus may result in silicone hydrogel contact lenses, which have ophthalmologically acceptable levels of energy loss. The present disclosure refers to new silicone hydrogel contact lenses. A silicone hydrogel contact lens, in accordance with the present disclosure, comprises a polymeric lens body. The polymeric body of the lens is the reaction product of a polymerizable composition. The polymerizable composition comprises a plurality of lens-forming components, such that when the composition is polymerized, a polymeric lens body is obtained.
[007] In one example, the present disclosure is directed to a polymerizable composition used to produce the present silicone hydrogel contact lenses. The polymerizable composition comprises a first siloxane monomer represented by the general formula (1):
where m of formula (1) represents an integer from 3 to 10, n of formula (1) represents an integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 atoms of carbon, and each R2 of formula (1) is, independently, either a hydrogen atom or a methyl group. In addition to the first siloxane monomer of the general formula (1), the polymerizable composition further comprises a second siloxane monomer which is a capped polydimethylsiloxane (end-capped) with methacrylate in two terminations, with an average molecular weight of at least 7,000 Daltons . The ingredients of the polymerizable composition can be present in amounts such that the resulting silicone hydrogel contact lens has, when fully hydrated, an energy loss of about 25% to about 45%. In one example, the loss of energy can be from about 27% to about 40%. In another example, the modulus of elasticity can be from about 30% to about 37%.
[008] In an example of the polymerizable composition, in the first siloxane monomer represented by the general formula (1), m of the formula (1) is 4, n of the formula (1) is 1, and R1 of the formula (1) is a group butyl. The first siloxane monomer represented by the general formula (1) can have an average molecular weight of 400 Daltons to 700 Daltons.
[009] In another example of the polymerizable composition, the polymerizable composition can comprise at least one crosslinking agent. At least one crosslinking agent can be present in the polymerizable composition in a total amount of about 0.01 units to about 5.0 units by weight. At least one crosslinking agent may comprise, or consist of, at least one vinyl containing crosslinking agent. At least one crosslinking agent containing vinyl may be present in the polymerizable composition in an amount of about 0.01 units to about 2.0 units by weight, or about 0.01 units to about 0 ,5 units. The ratio between an amount of the first siloxane monomer present in the polymerizable composition and a total amount of vinyl-containing crosslinking agents present in the polymerizable composition can be from 100: 1 to 400: 1, based on units by weight. At least one vinyl-containing crosslinking agent may comprise, or consist of, at least one vinyl ether-containing crosslinking agent.
[0010] In another example, the polymerizable composition can comprise at least one hydrophilic monomer. At least one hydrophilic monomer may comprise a hydrophilic amide monomer with an N-vinyl group.
[0011] The first siloxane monomer and the second siloxane monomer can be present in the polymerizable composition, such that the ratio between an amount of the first siloxane monomer present in the polymerizable composition and an amount of the second siloxane monomer present in the composition Polymerizable is at least 3: 1, based on units by weight. A total amount of siloxane monomers present in the polymerizable composition can be from about 30 units to about 50 units by weight, such as, for example, from about 35 to about 40 units, from about 33 units to about 45 units, or about 35 units to about 40 units by weight.
[0012] In one example, the second siloxane monomer can be a siloxane monomer represented by the general formula (2):
where R1 of formula (2) is selected from either hydrogen or a methyl group, R2 of formula (2) is selected from either a hydrogen or a C1-4 hydrocarbon group; m of formula (2) represents an integer from 0 to 10, n of general formula (2) represents an integer from 4 to 100; a and b of formula (2) represent integers of 1 or more, a + b is equal to 20 - 500, b / (a + b) is equal to 0.01 - 0.22, and the configuration of the siloxane units includes a random configuration, where the second siloxane monomer has an average molecular weight greater than 7000 Daltons. In an example of siloxane of general formula (2), m of formula (2) is 0, n of formula (2) is an integer from 5 to 10, that of formula (2) is an entire number of 65 - 90, b of formula (2) is an integer from 1 to 10, and R1 of formula (2) is a methyl group.
[0013] In one example, the polymerizable composition may further comprise at least a third siloxane monomer. When the polymerizable composition comprises at least a third siloxane monomer, the third siloxane monomer can be a siloxane monomer represented by the general formula (3):
where R3 of formula (3) is selected from either hydrogen or a methyl group; m of formula (3) represents an integer between 0 and 10, and n with formula (3) represents an integer from 1 to 500. In an example of siloxane of general formula (3), R3 of formula (3) is a methyl group, formula (3) is 0, and formula (3) is an integer from 40 to 60.
[0014] The polymerizable composition may 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, at least one hydrophilic monomer may comprise, or consist of, a hydrophilic amide monomer having at least one N-vinyl group, such as, for example, N-vinyl-N-methyl acetamide (VMA).
[0015] In another example, the present disclosure also refers to a silicone hydrogel contact lens, which comprises a polymeric lens body, which is the reaction product of a polymerizable composition. The polymerizable composition comprises a first siloxane monomer represented by the general formula (1):
where m of formula (1) represents an integer from 3 to 10, n of formula (1) represents an integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 atoms of carbon, and each R2 of formula (1) is, independently, either a hydrogen atom or a methyl group. In addition to the first siloxane monomer of the general formula (1), the polymerizable composition further comprises a second siloxane monomer which is a capped polydimethylsiloxane (end-capped) with methacrylate in two terminations with an average molecular weight of at least 7,000 Daltons. The hydrogel silicone contact lens of the present example, when fully hydrated, has an energy loss of about 25% to about 45%.
[0016] The present disclosure also refers to a group of contact lenses that comprises a plurality of contact lenses formed from polymeric bodies of the lenses, which are products of the reaction of the polymerizable composition described here. In one example, the batch of silicone hydrogel contact lenses, comprising a plurality of contact lenses according to any preceding claim, where the batch of silicone hydrogel contact lenses have, when completely hydrated, an average an equilibrium water content (EWC) of about 30% w / w to about 70% w / w, or an average oxygen permeability of at least 55 barrers, or an average forward contact angle dynamic by the captive bubble below 90 degrees, or mean static contact angle by the captive bubble below 70 degrees, or any combination of these, based on averages of values determined for at least 20 individual lenses in the batch.
[0017] The present disclosure also refers to the methods for the manufacture of a silicone hydrogel contact lens. The manufacturing method comprises the steps of providing a polymerizable composition, where said polymerizable composition comprises: (a) a first siloxane monomer represented by the general formula (1):
where m of formula (1) represents an integer from 3 to 10, n of formula (1) represents an integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 atoms of carbon, and each R2 of formula (1) is, independently, either a hydrogen atom or a methyl group. In addition to the first siloxane monomer of the general formula (1), the polymerizable composition further comprises a second siloxane monomer which is a capped polydimethylsiloxane (end-capped) with methacrylate in two terminations with an average molecular weight of at least 7,000 Daltons. The method also includes the polymerization steps of the polymerizable composition in a set of molds for contact lenses in order to form a polymeric lens body; to put the polymeric lens body in contact with a washing liquid to remove the extractable material from the lens polymeric body, and to hydrate the polymeric lens body to form a hydrogel silicon contact lens. When the polymerizable composition is polymerized to form a polymeric lens body, and the polymeric lens body is processed to form a fully hydrated silicone hydrogel contact lens, the silicone hydrogel contact lens, when completely hydrated, may have an energy loss of about 25% to about 45%. The method may further comprise packaging the polymeric lens body or silicone hydrogel contact lens in a contact lens packaging solution in a contact lens packaging.
[0018] In an example of the method, the polymerization step of the method may comprise the polymerization of the polymerizable composition in a set of molds for contact lenses that has a molding surface formed by a non-polar thermoplastic polymer so as to form a polymeric lens body. In another example, the polymerization step of the method may comprise the polymerization of the polymerizable composition in a set of molds for contact lenses with a molding surface formed by a polar thermoplastic polymer to form a polymeric lens body.
[0019] In an example of the method, the contact step of the method may comprise contacting the polymeric body of the lens with a washing liquid comprising at least one volatile organic solvent. In another example, the method contact step may comprise contacting the polymeric body of the lens with a washing liquid free of volatile organic solvent. In a particular example, the polymeric lens body, as well as the silicone hydrogel contact lens comprising the polymeric lens body, do not come into contact with a liquid comprising a volatile organic solvent during manufacture.
[0020] In one example, the method may further comprise the step of autoclaving the contact lens packaging for sterilizing the silicone hydrogel contact lenses and the contact lens packaging solution.
[0021] In any of the preceding polymerizable compositions, or polymeric lens bodies, or silicone hydrogel contact lenses, or lots of silicone hydrogel contact lenses or contact lens manufacturing methods, the first siloxane monomer can be represented by formula (1) where m of formula (1) is 4, n of formula (1) is 1, R1 of formula (1) is a butyl group, and each R2 of formula (1) is, independently , either a hydrogen atom or a methyl group. 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, i.e., a bifunctional siloxane monomer. The second siloxane is a siloxane monomer having an average molecular weight of at least 7,000 Daltons. Additional examples of the second siloxane are described below.
[0022] At least one optional crosslinking agent of the polymerizable composition can comprise a vinyl containing crosslinking agent. For example, at least one optional crosslinking agent may consist of a vinyl containing crosslinking agent (for example, all silicone-free crosslinking agents present in the polymerizable composition are vinyl containing crosslinking agents).
[0023] Additional embodiments of the polymerizable compositions, polymeric lens bodies, present lenses, lens products, lens lots, and contact lens manufacturing methods will be evident from the following disclosure, the Examples 1 to 28, and the claims. As can be seen from the previous and following disclosure, each feature described here, and each combination of two or more of such characteristics, and each combination of one or more values that define a range, are included within the scope of this provided that the characteristics included in such a combination are not mutually incompatible. In addition, any feature or combination of features or any value (s) that defines a range can be specifically excluded from any embodiment of the present invention. Detailed Disclosure
[0024] As described herein, it has recently been discovered that silicone hydrogel contact lenses can be formed from polymerizable compositions comprising a first siloxane monomer of the general formula (1) and a second siloxane monomer that is a polydimethylsiloxane capped (end-capped) with methacrylate in two terminations with an average molecular weight of at least 7,000 Daltons, and that these hydrogel silicone contact lenses, when fully hydrated, can advantageously have a level of energy loss from about 25% to about 45%.
[0025] The present contact lenses comprise, or consist of, hydrated lens bodies comprising a polymeric component and a liquid component. The polymeric component comprises units of two or more siloxane monomers (that is, a siloxane monomer of the general formula (1), a second siloxane monomer which is a capped (end-capped) polydimethylsiloxane with methacrylate in two terminations with a molecular weight average of at least 7,000 Daltons, and, optionally, one or more additional siloxane monomers) and one or more reactive ingredients without silicone (i.e., one or more hydrophilic monomers, or one or more crosslinking agents, or one or plus hydrophobic monomers, or any combination thereof). Therefore, it can be understood that the polymeric component is the reaction product of a polymerizable composition, comprising two or more siloxane monomers (two or more siloxane monomers presented as components of the composition's siloxane monomer), and one or more reactive ingredients without silicone. As used herein, a silicone-free reactive ingredient is understood to be an ingredient that has a polymerizable double bond as part of its molecular structure, but which does not have a silicon atom in its molecular structure. The ingredients of the polymerizable composition can be monomers, macromers, prepolymers and polymers, or any combination of these. In addition to the first siloxane monomer of the general formula (1), the polymerizable composition further comprises a second siloxane monomer which is an end capped polydimethylsiloxane with methacrylate in two terminations with an average molecular weight of at least 7,000 Daltons. Optionally, the ingredients of the polymerizable composition may further comprise at least one hydrophilic monomer or at least one hydrophobic monomer, or at least a third siloxane monomer, or any combination thereof. At least the cross-linking agent, at least one hydrophilic monomer, and at least the hydrophobic monomer of the polymerizable composition are to be understood as silicone-free polymerizable ingredients. As used herein, it can be understood that at least one crosslinking agent comprises a single crosslinking agent, or comprises a crosslinking agent component consisting of two or more crosslinking agents. Likewise, it can be understood that at least one optional hydrophilic monomer comprises a single hydrophilic monomer, or comprises a component of the hydrophilic monomer composed of two or more hydrophilic monomers. It can be understood that at least one optional hydrophobic monomer comprises a single hydrophobic monomer, or comprises a component of the hydrophobic monomer composed of two or more hydrophobic monomers. It can be understood that at least one optional third siloxane monomer comprises a single third siloxane monomer, or comprises a component of the third siloxane monomer composed of two or more siloxane monomers. In addition, 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 coloring agent , or at least a UV absorber, or at least a chain transfer agent, or any combination thereof. At least one optional initiator of at least one organic solvent, at least one surfactant, at least one oxygen scavenger, at least one coloring agent, at least one UV absorber, or at least one chain transfer agent , are understood as non-silicone ingredients, and can be non-polymerizable ingredients (or polymerizable ingredients, that is, ingredients that have a polymerizable functional group, as part of their molecular structure).
[0026] An example of the present disclosure is directed to a silicone hydrogel contact lens, comprising: a polymeric body of the lens, which is the reaction product of a polymerizable composition, where said polymerizable composition comprises: (a) a first siloxane monomer represented by the general formula (1):
where m of formula (1) represents an integer from 3 to 10, n of formula (1) represents an integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 atoms of carbon, and R2 of the formula (1) is a hydrogen atom or a methyl group, and (b) a second siloxane monomer which is a capped polydimethylsiloxane (end-capped) with methacrylate in two terminations with an average molecular weight of at least 7,000 Daltons, where the hydrogel silicone contact lens, when fully hydrated, has an energy loss of about 25% to about 45%. Silicone hydrogel contact lenses, when fully hydrated, can have an energy loss of about 27% to about 40%.
[0027] The combination of the polymeric component and the liquid component are present as a hydrated lens body, which is suitable for placing over a person's eye. The hydrated lens body has a generally convex anterior surface and a generally concave posterior surface, and has an equilibrium water content (EWC) of more than 10% weight by weight (w / w). Thus, it is understood that the contact lenses present are soft contact lenses, which, as used here, refer to contact lenses that, when fully hydrated, can be folded on themselves, without breaking.
[0028] As understood in the industry, daily disposable contact lenses are unused contact lenses, which are removed from their sealed and sterilized packaging (primary packaging), produced by a contact lens manufacturer, which are placed in the eye of person, and are removed and discarded at the end of the day after the person has used the lens. Normally, the duration of use of the lens for daily disposable contact lenses is 8 to 14 hours and then they are eliminated after use. Daily disposable lenses are not cleaned or exposed to cleaning solutions before being placed in the eye, as they are sterilized before opening the packaging. A daily disposable silicone hydrogel contact lens is a disposable silicone hydrogel contact lens that is replaced daily. In contrast, non-daily disposable contact lenses are disposable contact lenses that are replaced less frequently than daily (for example, weekly, bi-weekly or monthly). Non-daily disposable contact lenses are removed from the eye and washed with a cleaning solution, regularly, or are used continuously, without removing the eye. The contact lenses present can be either daily disposable contact lenses or non-daily disposable contact lenses.
[0029] When energy charge and discharge cycles are applied to viscoelastic materials, such as silicone hydrogel materials, the stress-strain curve will show a phase delay or hysteresis cycle due to system energy loss (in the form of heat) during the cycle. The percentage of energy loss can be determined using a number of methods known to those skilled in the art. For example, a sample can be stretched to 100% deformation and then return to 0% deformation at a constant rate, such as, for example, 50 mm / minute. Determining the percentage of tensile strain against the tensile strength applied to the sample will produce a graph showing the hysteresis cycle. The percentage of energy loss for the material can be calculated by the following equation (B): ((Energy from 0 to 100% deformation - Energy from 100 to 0% deformation) / Energy from 0 to 100% deformation ) x100 (B) where the energy from 0 to 100% deformation represents the energy applied to stretch the material to 100% deformation, and the energy from 100 to 0% deformation represents the energy released when the material returns to 0% from 100% deformation.
[0030] In one example, the silicone hydrogel contact lens is a silicone hydrogel contact lens, comprising: a polymeric body of the lens, which is the reaction product of a polymerizable composition, where said polymerizable composition comprises : (a) a first siloxane monomer represented by the general formula (1):
where m of formula (1) represents an integer from 3 to 10, n of formula (1) represents an integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 atoms of carbon, and R2 of the formula (1) is a hydrogen atom or a methyl group, and (b) a second siloxane monomer which is a capped polydimethylsiloxane (end-capped) with methacrylate in two terminations with an average molecular weight of at least 7,000 Daltons, where the hydrogel silicone contact lens, when fully hydrated, has an energy loss of about 25% to about 45%, and the energy loss is calculated using equation (B): (( Energy from 0 to 100% deformation - Energy from 100 to 0% deformation) / Energy from 0 to 100% deformation) x100 (B) where the energy from 0 to 100% deformation represents the energy applied to stretch a sample of the lens at 100% deformation at a constant rate, and the energy of 100 to 0% deformation represents the energy released when the lens sample returns to 0% from 100% deformation.
[0031] The percentage of energy loss for the material is an indicator of the elasticity of the material to be tested. The 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 low level of elasticity and is more viscous. Elastomers with lower percentages of energy loss tend to be more "bouncing" under force, while elastomers with higher percentages of energy loss tend to be more "compatible". For contact lenses, materials that are more “compatible” tend to move less over the eye, while materials that are more “bouncing” tend to move more over the eye. It is important for the health of the cornea to have a minimum level of movement over the eye. However, for a lens to provide improved vision, the level of movement over the eye must be minimized so that the lens remains in place after the blink of an eye. Thus, obtaining an adequate level of energy loss is an important factor in the development of a silicone hydrogel contact lens.
[0032] As described herein, it has been found that polymerizable compositions comprising a first siloxane monomer represented by the general formula (1) and a second siloxane which is a capped (end-capped) polydimethylsiloxane with methacrylate in two Terminations, with an average molecular weight of at least 7,000 Daltons, can be used to produce silicone hydrogel contact lenses having ophthalmologically acceptable levels of energy loss. Silicone hydrogel contact lenses formed from polymers comprising polymerized units of the first siloxane and the second siloxane, optionally in combination with the polymerized units of a third siloxane monomer or polymerized units of at least one crosslinking agent, or polymerized units of at least one hydrophilic monomer, or any combination thereof, when fully hydrated, may show adequate levels of movement over the eye in order to promote good corneal health, while exhibiting levels low enough movement of the lenses formed over the eye from these materials to provide good vision correction.
[0033] According to the present disclosure, the polymerizable composition used to produce the present silicone hydrogel contact lenses comprises a first siloxane monomer represented by the general formula (1):
where m of formula (1) represents an integer from 3 to 10, n of formula (1) represents an integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 atoms of carbon, and each R2 of formula (1) is, independently, either a hydrogen atom or a methyl group. The polymerizable composition further comprises a second siloxane monomer which is a polydimethylsiloxane capped (end-capped) with methacrylate in two terminations with an average molecular weight of at least 7,000 Daltons. The ingredients of the polymerizable composition can be present in such quantities that the resulting hydrogel silicone contact lens has, when fully hydrated, an energy loss of about 25% to about 45%, such as, for example, about 27% to about 40%, or about 30% to about 37%.
[0034] In one example, the silicone hydrogel contact lens is a silicone hydrogel contact lens, comprising: a polymeric body of the lens, which is the reaction product of a polymerizable composition, where said polymerizable composition comprises : (a) a first siloxane monomer represented by the general formula (1):
where m of formula (1) represents an integer from 3 to 10, n of formula (1) represents an integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 atoms of carbon, and R2 of the formula (1) is a hydrogen atom or a methyl group, and (b) a second siloxane monomer which is a capped polydimethylsiloxane (end-capped) with methacrylate in two terminations with an average molecular weight of at least 7,000 Daltons, where the hydrogel silicone contact lens, when fully hydrated, has an energy loss of about 27% to about 40%,
[0035] Also in accordance with the present disclosure, silicone hydrogel contact lenses with ophthalmologically acceptable levels of energy loss can be formed from a polymerizable composition containing (a) a first siloxane monomer represented by the general formula (1) :
where m of formula (1) represents an integer from 3 to 10, n of formula (1) represents an integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 atoms of carbon, and each R2 of the formula (1) is, independently, either a hydrogen atom or a methyl group, and (b) a second siloxane monomer which is an end-capped polydimethylsiloxane with methacrylate in two terminations with a weight molecular weight of at least 7,000 Daltons. It has been found that by using the combination of the first siloxane monomer and the second siloxane monomer, alone or in combination with at least one crosslinking agent, or a third siloxane monomer, or a hydrophilic monomer, or a hydrophobic monomer , or any combination thereof, it is possible to prepare polymerizable compositions that can be used to produce silicone hydrogel contact lenses that have, when fully hydrated, average levels of energy loss from about 25% to about 45%, or about 27% to about 40%, or 30% to about 37%.
[0036] In one example, the silicone hydrogel contact lens is a silicone hydrogel contact lens, comprising: a polymeric lens body, which is the product of the reaction of a polymerizable composition, where said polymerizable composition comprises : (a) a first siloxane monomer represented by the general formula (1):
where m of formula (1) represents an integer from 3 to 10, n of formula (1) represents an integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 atoms of carbon, and R2 of formula (1) is a hydrogen atom or a methyl group, (b) a second siloxane monomer which is a capped polydimethylsiloxane (end-capped) with methacrylate in two terminations with an average molecular weight of at least minus 7,000 Daltons, and (c) at least one crosslinking agent containing vinyl, where hydrogel silicone contact lenses, when fully hydrated, have an energy loss of about 25% to about 45%. Silicone hydrogel contact lenses, when fully hydrated, can have an energy loss of about 27% to about 40%. When the polymerizable composition comprises at least one crosslinking agent, the total amount of crosslinking agents (i.e., the total units of all crosslinking agents present in the polymerizable composition) can be an amount of about 0 , 01 units to about 5 units, or from about 0.1 units to about 4 units, or from about 0.3 units to about 3.0 units, or from about 0.2 units to about 2.0 units, or from about 0.6 units to about 1.5 units.
[0037] In one example, when the present polymerizable composition comprises at least one vinyl-containing crosslinking agent, the total amount of vinyl-containing crosslinking agents present in the polymerizable composition can be an amount from about 0.01 units to about 2 , 0 units, or from about 0.01 units to about 0.80 units, or from about 0.01 units to about 0.30 units, or from about 0.05 units to about 0.20 units, or in an amount of about 0.1 units.
[0038] When the polymerizable composition comprises the first siloxane monomer of the general formula (1) and the second siloxane monomer which is an end capped polydimethylsiloxane with methacrylate in two terminations with an average molecular weight of at least 7,000 Daltons, and at least one crosslinking agent, the first siloxane monomer and at least one crosslinking agent (i.e., a single crosslinking agent or a crosslinking agent component consisting of two or more crosslinking agents) may be present in the polymerizable composition in a ratio of at least 10: 1 based on the total units by weight between the first siloxane monomer and the total units, by weight, of at least one crosslinking agent (that is, the sum of the units of all vinyl-containing crosslinking agents present in the polymerizable composition). For example, the ratio can be at least 25: 1 or at least 50: 1 or at least 100: 1 based on units by weight. In one example, at least one crosslinking agent can comprise at least one vinyl containing crosslinking agent, and at least one methacrylate crosslinking agent. In another example, at least one crosslinking agent can consist of just one or more crosslinking agents containing vinyl. In another example, at least one cross-linking agent may comprise or consist of at least one cross-linking agent containing vinyl ether. In yet another example, at least one crosslinking agent can be composed of just one or more vinyl containing crosslinking agents. In a particular example, at least one crosslinking agent may comprise or consist of at least one crosslinking agent containing vinyl ether.
[0039] In one example, the silicone hydrogel contact lens is a silicone hydrogel contact lens, comprising: a polymeric lens body, which is the product of the reaction of a polymerizable composition, where said polymerizable composition comprises : (a) a first siloxane monomer represented by the general formula (1):
where m of formula (1) represents an integer from 3 to 10, n of formula (1) represents an integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 atoms of carbon, and R2 of formula (1) is a hydrogen atom or a methyl group, (b) a second siloxane monomer which is a capped polydimethylsiloxane (end-capped) with methacrylate in two terminations with an average molecular weight of at least least 7,000 Daltons, and (c) at least one crosslinking agent containing vinyl, and (d) at least one methacrylate crosslinking agent, where hydrogel silicone contact lenses, when fully hydrated, have a loss of energy from about 25% to about 45%. Hydrogel silicone contact lenses, when fully hydrated, can have an energy loss of about 27% to about 40%.
[0040] When 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 consisting of two or more crosslinking agents containing vinyl), the first siloxane monomer and at least one crosslinking agent containing vinyl can be present in the polymerizable composition in the ratio of at least about 50: 1 based on the ratio between a total number of units of the first siloxane monomer and a total number of units of at least one of the vinyl containing crosslinking agent (i.e., the sum of the units of all vinyl containing crosslinking agents present in the polymerizable composition). For example, the ratio can 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 units per Weight.
[0041] In one example, the silicone hydrogel contact lens is a silicone hydrogel contact lens, comprising: a polymeric lens body, which is the reaction product of a polymerizable composition, where said polymerizable composition comprises : (a) a first siloxane monomer represented by the general formula (1):
where m of formula (1) represents an integer from 3 to 10, n of formula (1) represents an integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 atoms of carbon, and R2 of formula (1) is a hydrogen atom or a methyl group, (b) a second siloxane monomer which is a capped polydimethylsiloxane (end-capped) with methacrylate in two terminations with an average molecular weight of at least at least 7,000 Daltons, and (c) at least one crosslinking agent containing vinyl; where the ratio between an amount of the first siloxane monomer present in the polymerizable composition and a total amount of vinyl-containing crosslinking agents present in the polymerizable composition is 100: 1 to 400: 1 based on units by weight, and contact lenses Hydrogel silicone, when fully hydrated, has an energy loss of about 25% to about 45%. Silicone hydrogel contact lenses, when fully hydrated, can have an energy loss of about 27% to about 40%.
[0042] When the polymerizable composition comprises a first siloxane monomer of the general formula (1), the second siloxane monomer, which is an end capped polydimethylsiloxane with methacrylate in two terminations with an average molecular weight of at least 7,000 Daltons , in combination with at least one crosslinking agent, siloxane monomers, and at least one vinyl-containing monomer, can be present in the polymerizable composition in the ratio of at least about 100: 1 based on the ratio between the total number of units of each siloxane monomer present in the polymerizable composition (that is, the sum of the parts of the first siloxane units and the second siloxane monomer and, if present, the third siloxane monomer, etc.) and the total number of units of at least one vinyl containing crosslinking agent (i.e., the sum of the units of all vinyl containing crosslinking agents present in the polymerizable composition). For example, the ratio can 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 units by weight.
[0043] In one example, a total amount of siloxane monomers present in the polymerizable composition (ie, the total units of the first siloxane monomer and, if present, a second siloxane monomer, and at least a third monomer siloxane) can be an amount of about 30 to 45 units, or about 36 to 40 units.
[0044] The molecular weight of the first siloxane monomer of the general formula (1) is less than 2,000 Daltons. In one example, the molecular weight of the first siloxane monomer can be less than 1,000 Daltons. In another example, the molecular weight of the first siloxane monomer can be 400 to 700 Daltons. Additional details of the first siloxane monomer can be understood from US 2009 / 0.299.022, the complete content of which is incorporated herein by reference. As may be desired from formula (1), the first siloxane monomer has a single functional polymerizable group of methacrylate present at one end of the main chain of the siloxane monomer.
[0045] In one example, the silicone hydrogel contact lens is a silicone hydrogel contact lens, comprising: a polymeric lens body, which is the reaction product of a polymerizable composition, where said polymerizable composition comprises : (a) a first siloxane monomer represented by the general formula (1):
where m of formula (1) represents an integer from 3 to 10, n of formula (1) represents an integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 atoms of carbon, and R2 of formula (1) is a hydrogen atom or a methyl group, and the first siloxane monomer has an average molecular weight of 400 Daltons to 700 Daltons, and (b) a second siloxane monomer which is polydimethylsiloxane capped (end-capped) with methacrylate in two terminations with an average molecular weight of at least 7,000 Daltons, where silicone hydrogel contact lenses, when fully hydrated, have an energy loss of about 25% to about 45% . Hydrogel silicone contact lenses, when fully hydrated, can have an energy loss of about 27% to about 40%.
[0046] In another example, the silicone hydrogel contact lens is a silicone hydrogel contact lens, comprising: a polymeric lens body, which is the reaction product of a polymerizable composition, where said polymerizable composition comprises : (a) a first siloxane monomer represented by the general formula (1):
where m of formula (1) represents an integer from 3 to 10, n of formula (1) represents an integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 atoms of carbon, and R2 of formula (1) is a hydrogen atom or a methyl group, and the first siloxane monomer has an average molecular weight of 400 Daltons, at 700 Daltons, (b) a second siloxane monomer which is a polydimensional capillary tilsiloxane (end-capped) with methacrylate in two terminations with an average molecular weight of at least 7,000 Daltons, and (c) at least one vinyl-containing crosslinking agent, where the hydrogel silicone contact lenses, when completely hydrated, have an energy loss of about 25% to about 45%. Silicone hydrogel contact lenses, when fully hydrated, can have an energy loss of about 27% to about 40%.
[0047] In yet another example, the silicone hydrogel contact lens is a silicone hydrogel contact lens, comprising: a polymeric body of the lens, which is the reaction product of a polymerizable composition, where said polymerizable composition comprises: (a) a first siloxane monomer represented by the general formula (1):
where m of formula (1) represents an integer from 3 to 10, n of formula (1) represents an integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 atoms of carbon, and R2 of formula (1) is a hydrogen atom or a methyl group, and the first siloxane monomer has an average molecular weight of 400 Daltons, at 700 Daltons, and (b) a second siloxane monomer which is a polyd - end-capped methylsiloxane with methacrylate in two terminations with an average molecular weight of 7,000 Daltons to 20,000 Daltons, where silicone hydrogel contact lenses, when fully hydrated, have an energy loss of around 25% 45%. Silicone hydrogel contact lenses, when fully hydrated, can have an energy loss of about 27% to about 40%.
[0048] In an example of the contact lenses present, the first siloxane monomer can be represented by formula (1) where m of formula (1) is 4, n of formula (1) is 1, R1 of formula (1) it is a butyl group and each R2 of the formula (1) is, independently, either a hydrogen atom or a methyl group. An example of such a first siloxane monomer is identified herein as Si1 in Examples 1 to 28.
[0049] In one example, the silicone hydrogel contact lens is a silicone hydrogel contact lens, comprising: a polymeric body of the lens, which is the reaction product of a polymerizable composition, where said polymerizable composition comprises : (a) a first siloxane monomer represented by the general formula (1):
where m of formula (1) is 4, n of formula (1) is 1, R1 of formula (1) is a butyl group, and each R2 of formula (1) is, independently, both an atom of hi - hydrogen or a methyl group; and (b) a second siloxane monomer which is an end capped polydimethylsiloxane with methacrylate in two terminations with an average molecular weight of at least 7,000 Daltons, in which the hydrogel silicone contact lenses, when fully hydrated, have an energy loss of about 25% to about 45%. Silicone hydrogel contact lenses, when fully hydrated, can have an energy loss of about 27% to about 40%.
[0050] In another example, the silicone hydrogel contact lens is a silicone hydrogel contact lens, comprising: a polymeric lens body, which is the reaction product of a polymerizable composition, where said polymerizable composition comprises : (a) a first siloxane monomer represented by the general formula (1):
where m of formula (1) is 4, n of formula (1) is 1, R1 of formula (1) is a butyl group, and each R2 of formula (1) is, independently, both an atom of hi - drogen or a methyl group, and the first siloxane monomer has an average molecular weight of 400 Daltons, to 700 Daltons, and (b) a second siloxane monomer which is a capped polydimethylsiloxane (end-capped) with methacrylate in two terminations with an average molecular weight of at least 7,000 Daltons, where silicone hydrogel contact lenses, when fully hydrated, have an energy loss of about 25% to about 45%. Hydrogel silicone contact lenses, when fully hydrated, can have an energy loss of about 27% to about 40%.
[0051] As used herein, it is to be understood that the molecular weight refers to the average molecular weight. The average molecular weight is the common arithmetic mean or average of the molecular weights of the individual molecules present in a monomer sample. As the individual molecules in a sample of the monomer may vary slightly in terms of molar masses relative to each other, some degree of polydispersity may be present in the sample. As used herein, when the siloxane monomer, or any other monomer, macromer, prepolymer or polymer, of the polymerizable composition is polydispersed, the term "molecular weight" refers to the number of the average molecular weight of the monomer or ingredient. As an example, a sample of the siloxane monomer may have an average molecular weight of about 15,000 Daltons, but if the sample is polydispersed, the actual molecular weights of the individual monomers present in the sample can range from 12,000 Daltons to 18,000 Daltons .
[0052] The average molecular weight can be the absolute average molecular weight, as determined by the analysis of the nuclear proton magnetic resonance (NMR) of the terminal group, as understood by people with knowledge in the art. Molecular weights can also be determined using gel permeation chromatography, as understood by persons skilled in the art, or can be supplied by chemical suppliers.
[0053] The first siloxane monomer, the second siloxane monomer and, when present, at least one third optional siloxane monomer, comprise the components of the siloxane monomer of the polymerizable composition. Each first siloxane monomer, or second siloxane monomer, or at least an optional third siloxane monomer, or any combination thereof, may be a hydrophilic siloxane monomer or a hydrophobic siloxane monomer, or they can have both hydrophilic and hydrophobic regions, depending on the amount and location of any hydrophilic components, such as the ethylene glycol, polyethylene glycol and the like units present in the molecular structure of siloxane monomers.
[0054] For example, the optional second siloxane monomer, or at least an optional third siloxane monomer, or any combination thereof, may contain hydrophilic components in the main chain of the siloxane molecule, may contain hydrophilic components within a 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 on the main chain of the siloxane molecule. As used herein, adjacent is understood to be immediately adjacent and separated only by 10 or less carbon atoms. At least one ethylene glycol unit adjacent to a polymerizable functional group on the main chain of the siloxane molecule can be separated from the polymerizable functional group by a carbon chain of 1 to 5 units in length (that is, when the ethylene glycol units are linked to the first carbon in the carbon chain of 1 to 5 units in length, and the polymerizable functional group is linked to the last carbon in the carbon chain of 1 to 5 units in length. In other words, the ethylene glycol units of the polymerizable group are not is immediately adjacent, but separated by 1 to 5 carbon atoms). The siloxane monomer can have at least one ethylene glycol unit adjacent to the polymerizable functional groups present at both ends of the main chain of the siloxane molecule. The siloxane monomer can have at least one ethylene glycol moiety present in at least one side chain of the siloxane molecule. At least one ethylene glycol unit present in at least one side chain of the siloxane molecule can be part of a side chain attached to a silicon atom in the main chain of the siloxane molecule. The siloxane molecule can have both at least one ethylene glycol unit adjacent to the polymerizable functional groups present at both ends of the main chain of the siloxane molecule, and at least one ethylene glycol unit present in at least one side chain of the siloxane. siloxane molecule.
[0055] In one example, the silicone hydrogel contact lens is a silicone hydrogel contact lens, comprising: a polymeric lens body, which is the product of the reaction of a polymerizable composition, where said polymerizable composition comprises : (a) a first siloxane monomer represented by the general formula (1):
where m of formula (1) represents an integer from 3 to 10, n of formula (1) represents an integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 atoms of carbon, and R2 of formula (1) is a hydrogen atom or a methyl group, and (b) a second siloxane monomer which is a capped polydimethylsiloxane with methacrylate in two terminations with at least one units of ethylene glycol adjacent to the polymerizable functional group at the 2 ends of the main chain of the siloxane molecule and the average molecular weight of at least 7,000 Daltons, where the hydrogel silicone contact lenses, when fully hydrated, have an energy loss of about 25% to about 45%. Silicone hydrogel contact lenses, when fully hydrated, can have an energy loss of about 27% to about 40%
[0056] The hydrophilicity or hydrophobicity of a monomer can be determined using conventional techniques, such as, for example, based on the water solubility of the monomer. For the purposes of the present disclosure, a hydrophilic monomer is a monomer that is visibly soluble in an aqueous solution at room temperature (for example, about 20 to 25 ° C). For example, a hydrophilic monomer can be understood as any monomer for every 50 grams or more of the monomer is visible and completely soluble in 1 liter of water at 20 ° C (that is, the monomer is soluble at a level of at least 5% w / w in water), as determined by the use of the standard bottle shaking method, as known to those skilled in the art. A hydrophobic monomer, as used herein, is a monomer that is visibly insoluble in an aqueous solution at room temperature, such that the separate, visually identifiable phases are present in the aqueous solution, or in such a way that the aqueous solution it becomes cloudy and separates into 2 distinct phases over time after resting at room temperature. For example, a hydrophobic monomer can be understood as a monomer for every 50 grams of monomer is not visible and completely soluble in 1 liter of water at 20 ° C (that is, the monomer is soluble at a level below 5% w / w in water).
[0057] In an example of the present disclosure, the second siloxane monomer or at least an optional third siloxane monomer can be a multifunctional siloxane monomer. As the second siloxane monomer has two functional groups, such as methacrylate groups, it is a bifunctional monomer.
[0058] At least one optional third siloxane monomer can be a siloxane monomer having a polymerizable functional group present at one end of the monomer backbone. The third siloxane monomer may be a siloxane monomer having a polymerizable functional group at both ends of the monomer main chain. The third siloxane monomer can be a siloxane monomer having a polymerizable functional group, present in at least one side chain of the monomer. The third siloxane monomer can be a siloxane monomer having a polymerizable functional group present in only one side chain of the monomer.
[0059] At least one third optional siloxane monomer of the polymerizable composition can be an acrylate-containing siloxane monomer, in other words, a siloxane monomer having at least one polymerizable functional acrylate group as part of its molecular structure. In one example, the acrylate-containing siloxane monomer may be a siloxane monomer containing methacrylate, that is, a siloxane monomer having at least one functional and polymerizable methacrylate group as part of its molecular structure.
[0060] At least one optional third siloxane monomer can be a siloxane monomer having an average molecular weight of at least 3,000 Daltons. In another example, the siloxane monomer may 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.
[0061] The second siloxane monomer or at least an optional third siloxane monomer can be a siloxane monomer having a molecular weight of less than 20,000 Daltons. In another example, the siloxane monomer may 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.
[0062] At least one optional 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 may be a siloxane monomer having a molecular weight of 5,000 Daltons to 20,000 Daltons, or from 5,000 Daltons to 1,000,000 Daltons, or from 7,000 Daltons to 15,000 Daltons.
[0063] In one example, at least an optional third siloxane monomer has more than one functional group and has an average molecular weight of at least 3,000 Daltons.
[0064] At least one optional third siloxane monomer may include poly (organosiloxane) monomers or macromers or prepolymers, such as, for example, 3 - [tris (trimethylsiloxy) silyl] -propyl allyl carbamate, or 3 - [tris (trimethylsiloxy) silyl] propyl vinyl, or vinyl trimethyl silyl ethyl carbonate, or vinyl trimethyl silyl methyl, or 3 - [tris (trimethylsilyloxy) silyl] propyl (TRIS), or 3- methacryloxy-2-hydroxypropyloxy) propylbis (trimethylsiloxy) methylsilane (Sigma), or methyl di (trimethylsiloxy) silyl propyl glycerol ethyl (SiGEMA), or mono-methacryloxypropyl polydimethylsiloxane-M (MCS-11), MCR (MCS) finished mono-methacryloxypropyl mono-n-butyl-polydimethylsiloxane (mPDMS), or any combination thereof. In an example of a polymerizable composition of the present disclosure, at least an optional third siloxane monomer may contain one or more of the first siloxanes described herein, where the second siloxane monomer and at least a third siloxane differ from the first siloxane present in the polymerizable composition based on molecular weight, molecular structure, or both molecular weights and structures. For example, at least a third optional siloxane monomer can be a siloxane monomer of the general formula (1) having a different molecular weight than the first siloxane monomer or the second siloxane monomer of the polymerizable composition. In another example, at least a third optional siloxane monomer may comprise at least one of the siloxanes disclosed in the following patents: US 2007 / 0.066,706, US 2008 / 0.048,350, US 3,808,178, US 4,120. 570, US 4,136,250, US 4,153,641, US 470,533, US 5,070,215, US 5,998,498, US 5,760,100, US 6,367,929 and EP 080,539, the entire contents of which are hereby incorporated by reference.
[0065] In another example of the contact lenses present, at least a third optional siloxane monomer can be an end-capped polydimethylsiloxane with methacrylate in two terminations with an average molecular weight of at least 4,000 Daltons. Such siloxane monomers are understood to be bifunctional.
[0066] As an example of a bifunctional siloxane monomer useful for the present silicone hydrogel contact lenses, the second siloxane monomer or at least an optional third siloxane monomer can be a siloxane monomer represented by the general formula (2) :
where R1 of formula (2) is selected from either the hydrogen atom or a methyl group, R2 of formula (2) is selected from either a hydrogen atom or a hydrocarbon group with 1 to 4 carbon atoms; m of formula (2) represents an integer from 0 to 10; n of the general formula (2) represents an integer from 4 to 100; a and b represent integers of 1 or more, a + b is equal to 20 to 500, b / (a + b) is equal to 0.01 to 0.22, and the siloxane unit configuration includes a random configuration. In an example where the monomer is a siloxane monomer represented by the general formula (2), m of the formula (2) is 0, n of the formula (2) is an integer from 5 to 15, a is an integer 65 to 90, b is an integer from 1 to 10, R1 of formula (2) is a methyl group, and R2 of formula (2) is either a hydrogen atom or a hydrocarbon group with 1 to 4 carbon atoms - bono. An example of a siloxane monomer, as represented by the general formula (2), is abbreviated as Si2 in Examples 1 to 28. The average molecular weight for this siloxane monomer represented by the general formula (2) can be from about 9,000 Daltons to about 10,000 Daltons. In another example, the siloxane monomer represented by the general formula (2) can have a molecular weight of about 5,000 Daltons to about 10,000 Daltons. It may be desired that the siloxane represented by the general formula (2) is a bifunctional siloxane that has two methacrylate terminal polymerizable functional groups (ie, a methacrylate group present at each end of the main chain of the siloxane molecule). Additional details of this siloxane monomer can be found in US 2009 / 0.234.089, the complete content of which is incorporated herein by reference.
[0067] In one example, the silicone hydrogel contact lens is a silicone hydrogel contact lens, comprising: a polymeric lens body, which is the reaction product of a polymerizable composition, where said polymerizable composition comprises : (a) a first siloxane monomer represented by the general formula (1):
where m of formula (1) represents an integer from 3 to 10, n of formula (1) represents an integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 atoms of carbon, and R2 of formula (1) is a hydrogen atom or a methyl group, and (b) a second siloxane monomer represented by the general formula (2):
where R of formula (2) is selected from either the hydrogen atom or a methyl group, R of formula (2) is selected from either a hydrogen atom or a hydrocarbon group with 1 to 4 carbon atoms; m of formula (2) represents an integer from 0 to 10; n of the general formula (2) represents an integer from 4 to 100; a and b represent integers of 1 or more, a + b is equal to 20 to 500, b / (a + b) is equal to 0.01 to 0.22, and the siloxane unit configuration includes a random configuration and the second siloxane monomer has an average molecular weight of at least 7,000 Daltons, where silicone hydrogel contact lenses, when fully hydrated, have an energy loss of about 25% to about 45%. Silicone hydrogel contact lenses, when fully hydrated, can have an energy loss of about 27% to about 40%.
[0068] In another example, the silicone hydrogel contact lens is a silicone hydrogel contact lens, comprising: a polymeric lens body, which is the product of the reaction of a polymerizable composition, where said polymerizable composition comprises : (a) a first siloxane monomer represented by the general formula (1):
where m of formula (1) represents an integer from 3 to 10, n of formula (1) represents an integer from 1 to 10, R1 of formula (1) is an alkyl group having 1 to 4 carbon atoms, and R2 of formula (1) is a hydrogen atom or a methyl group, and (b) a second siloxane monomer represented by the general formula (2):
where m of formula (2) is 0, n of formula (2) is an integer from 5 to 15, a is an integer from 65 to 90, b is an integer from 1 to 10, R1 of formula (2) is a methyl group, and R2 of formula (2) is either a hydrogen atom or a hydrocarbon group with 1 to 4 carbon atoms, the siloxane unit configuration includes a random configuration, and the second siloxane monomer has an average molecular weight of at least 7000 Daltons; where silicone hydrogel contact lenses, when fully hydrated, have an energy loss of about 25% to about 45%. Silicone hydrogel contact lenses, when fully hydrated, can have an energy loss of about 27% to about 40%.
[0069] In yet another example, the silicone hydrogel contact lens is a silicone hydrogel contact lens, comprising: a polymeric lens body, which is the product of the reaction of a polymerizable composition, where said polymerizable composition comprises: (a) a first siloxane monomer represented by the general formula (1):
where m of formula (1) represents an integer from 3 to 10, n of formula (1) represents an integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 atoms of carbon, R2 of formula (1) is a hydrogen atom or a methyl group, and the first siloxane monomer has an average molecular weight of 400 Daltons to 700 Daltons, and (b) a second siloxane monomer represented by the general formula ( two):
where R1 of formula (2) is selected from either the hydrogen atom or a methyl group, R2 from formula (2) is selected from either a hydrogen atom or a hydrocarbon group with 1 to 4 carbon atoms; m of formula (2) represents an integer from 0 to 10; n of the general formula (2) represents an integer from 4 to 100; a and b represent integers of 1 or more, a + b is equal to 20 to 500, b / (a + b) is equal to 0.01 to 0.22, and the siloxane unit configuration includes a random configuration and the second siloxane monomer has an average molecular weight of at least 7,000 Daltons, where silicone hydrogel contact lenses, when fully hydrated, have an energy loss of about 25% to about 45%. Silicone hydrogel contact lenses, when fully hydrated, can have an energy loss of about 27% to about 40%.
[0070] As another example of a bifunctional siloxane monomer useful for the present hydrogel silicone contact lens, at least a third optional siloxane monomer can be represented by formula (3):
where R3 is selected either from the hydrogen atom or a methyl group, a formula (3) represents an integer from 0 to 10, and with formula (3) represents an integer from 1 to 500. In one example , the second siloxane monomer is represented by formula 3, and R3 is a methyl group, but formula (3) is 0, and formula (3) is an integer from 40 to 60.
[0071] In another example, at least an optional third siloxane monomer can be a bifunctional siloxane monomer represented by the general formula (4), and is abbreviated as Si3 in Examples 1 to 28 (available from Ge-lest, Inc., Cary, PA with product code: DMS R18):

[0072] In one example, the siloxane of the general formula (4) has an average molecular weight of about 4,000 to about 4,500 Daltons.
[0073] Another example of a siloxane monomer that can be used as at least an optional third siloxane monomer can include monofunctional siloxane monomers with at least one urethane bond, such as that of the represented monofunctional siloxane monomers by the general formula (5):
where n of formula (5) is 0 to 30, or 10 to 15. In one example, the siloxane monomer can be the monomer of formula (5) where n of formula (5) is 12 to 13 and having a weight molecular weight of about 1,500 Daltons. Such monofunctional siloxane monomers are described in US Patent 6,867,245, which is incorporated herein by reference.
[0074] Yet another example of a siloxane monomer that can be used as at least an optional third siloxane monomer can include bifunctional siloxane monomers having at least 2 urethane bonds, such as the bifunctional siloxane monomers represented by the general formula ( 6):
where n of formula (6) is an integer of about 100 to 150, m of formula (6) is an integer of about 5 to about 15, h represents an integer of about 2 to 8 , ep is an integer from about 5 to about 10. The additional example of such a bifunctional siloxane monomer and methods of preparing the compounds of the general formula (6) are described in US Patent No. 6,867,245, which is incorporated herein by reference. In a particular example, the siloxane monomer may be a bifunctional siloxane monomer having 2 urethane bonds and have a molecular weight greater than about 5000 Daltons, such as, for example, a molecular weight greater than about 10,000 Daltons, or a molecular weight greater than about 15,000 Daltons.
[0075] In an example of the contact lenses shown, at least an optional third siloxane monomer can have an average molecular weight of at least 4,000 Daltons, or at least 7,000 Daltons, at least 9,000 Daltons, at least 11,000 Daltons. The average molecular weight of the siloxane monomer can be less than 20,000 Daltons. Thus, in some contexts, the second siloxane monomer may be considered a macromer, but will be referred to here as a monomer, as it forms a part of a polymer unit formed with the other reactive components of the polymerizable composition.
[0076] In one example, the first siloxane monomer and the second siloxane monomer can be present in the polymerizable composition in amounts such that the ratio between the first siloxane monomer and the second siloxane monomer is at least 1: 1, based on the units, or is at least 2: 1 based on the units. For example, the first siloxane monomer and the second siloxane monomer can be present in the polymerizable composition in the ratio of about 2: 1 to about 10: 1 based on the units. In another example, the first siloxane monomer and the second siloxane monomer can be present in the polymerizable composition in the ratio of about 3: 1 to about 6: 1 based on the units. 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 the units.
[0077] In one example, the silicone hydrogel contact lens is a silicone hydrogel contact lens, comprising: a polymeric lens body, which is the reaction product of a polymerizable composition, where said polymerizable composition comprises : (a) a first siloxane monomer represented by the general formula (1):
where m of formula (1) represents an integer from 3 to 10, n of formula (1) represents an integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 atoms of carbon, and R2 of formula (1) is a hydrogen atom or a methyl group, (b) a second siloxane monomer which is a capped polydimethylsiloxane (end-capped) with methacrylate in two terminations with an average molecular weight of at least minus 7,000 Daltons, where the ratio between an amount of the first siloxane monomer present in the polymerizable composition and an amount of the second siloxane monomer present in the polymerizable composition is at least 3: 1 based on units by weight, and where the Hydrogel silicone contact lenses, when fully hydrated, have an energy loss of about 25% to about 45%. Silicone hydrogel contact lenses, when fully hydrated, can have an energy loss of about 27% to about 40%.
[0078] The total amount of siloxane monomers present in the polymerizable composition (for example, the sum of the units 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 to about 60 units, or from about 25 to about 50 units, or from about 35 to about 40 units.
[0079] The polymerizable compositions of the present disclosure can be understood as comprising a first component consisting of a first siloxane monomer of the general formula (1), a second siloxane monomer which is a capped (end-capped) polydimethylsiloxane with methacrylate in two endings with an average molecular weight of at least 7,000 Daltons, and a second component comprising at least a third siloxane monomer, or at least one cross-linking agent, or at least one hydrophilic monomer or at least a hydrophobic monomer, or any combination thereof. At least one optional crosslinking agent can be present as a single crosslinking agent, or it can be present as a component of the crosslinking agent comprising two or more individual crosslinking agents. As used herein, the crosslinking agent and the crosslinking agent component are silicone-free crosslinking agents and are thus different from the multifunctional siloxane monomers that may be present in the polymerizable composition.
[0080] As used here, the units are understood as units by weight. For example, to prepare a described formulation comprising z units of a siloxane monomer and units of a hydrophilic monomer, the composition can be prepared by combining z grams of the siloxane monomer with y grams of the hydrophilic monomer for obtaining a total of y + z grams of the polymerizable composition, or by combining z ounces of siloxane with y ounces of the hydrophilic monomer to obtain a total of y + z ounces of the polymerizable composition, and so on. When the composition further comprises optional optional ingredients, such as, for example, x units of a crosslinking agent, x grams of the crosslinking agent are combined with z grams of the siloxane monomer and grams of hydrophilic monomer to obtain a total of x + y + z grams of the polymerizable composition, and so on. When the composition comprises an optional additional ingredient comprising an ingredient component composed of two ingredients, such as, for example, a hydrophobic monomer component consisting of a first hydrophobic monomer and a second hydrophobic monomer, in addition to the z monomer units of siloxane, y units of hydrophilic monomer and x units of crosslinking agents, w units of the first hydrophobic monomer and v units of the second hydrophobic monomer are combined to obtain a total amount of v + w + x + y + z units of the polymerizable composition. It is understood that the units of at least one hydrophobic monomer present in such a polymerizable composition is the sum of the units of the first hydrophobic monomer and the units of the second hydrophobic monomer, for example, v + w units in this example. Typically, a formula for a polymerizable composition will be composed of ingredients in quantities that total from about 90 to about 110 units by weight. When the amount of the components of the polymerizable composition is said to be units here, it is to be understood that the units of these components are based on a formula that provides a total weight of the composition ranging from about 90 to 110 units. In one example, units by weight can be based on a formula that provides a total weight of the composition ranging from about 95 to 105 units by weight, or from about 98 to 102 units by weight.
[0081] According to the present disclosure, a crosslinking agent is understood to be a monomer that has more than one polymerizable functional group as part of its molecular structure, such as two, three or four polymerizable functional groups, that is, a multifunctional monomer such as, a bifunctional or trifunctional or tetrafunctional monomer. Silicone-free crosslinking agents that can be used in the polymerizable compositions described herein include, for example, without limitation, lower alkyl (meth) acrylate, or lower alkylene glycol di- (meth) acrylate, or di- (meth) acrylate of poly (lower alkylene) alkylene glycol, or lower alkylene di (meth) acrylate, or divinyl ether or divinyl sulfone, or di- and trivinylbenzene, or trimethyl propane tri (meth) acrylate, or tetra (met) pentaerythritol acrylate or bisphenol-A di- (meth) acrylate or methylenebis (meth) acrylamide, trialyl phthalate or diallyl phthalate, or any combination thereof. Crosslinking agents, as described in Examples 1 to 28, include, for example, ethylene glycol dimethacrylate (EGDMA), or triethylene glycol dimethacrylate (TEGDMA), or triethylene glycol divinyl ether (TEGDVE), or any combination of these themselves. In one example, the crosslinking agent may have a molecular weight of less than 1,500 Daltons, or less than 1,000 Daltons, or less than 500 Daltons, or less than 200 Daltons.
[0082] In one example, the crosslinking agent or crosslinking agent component may comprise or consist of a vinyl containing crosslinking agent. As used herein, a vinyl-containing crosslinking agent is a monomer with at least 2 carbon-carbon polymerizable double bonds (that is, at least two polymerizable vinyl functional groups) presented, in their molecular structure, where at least minus each of the 2 carbon-carbon polymerizable double bonds present in the vinyl polymerizable functional groups of the vinyl-containing crosslinking agent is less reactive than a carbon-carbon double bond present in an acrylate or group methacrylate polymerizable functional. Although carbon-carbon double bonds are present in the polymerizable functional groups of acrylate and methacrylate, as understood herein, crosslinking agents that comprise one or more polymerizable acrylate or methacrylate groups (for example, one that contains the acrylate crosslinking or a methacrylate containing crosslinking agent) are not considered to be vinyl containing crosslinking agents. Polymerizable functional groupings with carbon-carbon double bonds, which are less reactive than carbon-carbon double bonds of acrylate or methacrylate polymerizable groups include, for example, polymerizable functional groups of vinyl amide, vinyl ester , vinyl ether and allyl ester. Thus, as used herein, vinyl containing crosslinking agents include, for example, crosslinking agents with at least two polymerizable functional groups selected from a vinyl amide, vinyl ester, vinyl ether and allyl ester, and any combination of these . As used herein, a crosslinking agent containing mixed vinyl is a crosslinking agent having at least one polymerizable carbon-carbon double bond (that is, at least one functional group of polymerizable vinyl), present in its structure, which is less reactive than the carbon-carbon double bond present in a polymerizable functional group of acrylate or methacrylate, and at least one polymerizable functional group present in its structure that has a carbon-carbon double bond, which is at least as reactive as the carbon-carbon double bond in a functional polymerizable group of acrylate or methacrylate.
[0083] When present in the polymerizable composition, the vinyl containing crosslinking agent or crosslinking agent component can be present in an amount of about 0.01 units to about 2.0 units, or about 0.01 units to about 0.80 units of units, or between about 0.01 units to about 0.30 units of units, or from about 0.05 units to about 0.20 units, or an amount of about 0.1 units.
[0084] In one example, the crosslinking agent or crosslinking agent component may comprise or consist of a non-vinyl crosslinking agent, that is, a crosslinking agent which is a crosslinking agent without containing vinyl. For example, the crosslinking agent or non-vinyl crosslinking component may comprise or consist of an acrylate copolymer containing crosslinking agent (i.e., a crosslinking agent having at least two polymerizable functional acrylate groups) ), or a crosslinking agent containing methacrylate (ie at least two polymerizable methacrylate functional groups), or at least one crosslinking agent containing acrylate and at least one crosslinking agent containing methacrylate.
[0085] When present in the polymerizable composition, the non-vinyl crosslinking agent or crosslinking agent can be present in an amount of about 0.01 units to about 5 units, or about 0.1 units at about 4 units, or from about 0.3 units to about 3.0 units, or from about 0.2 units to about 2.0 units.
[0086] The crosslinking agent component may comprise or consist of a combination of two or more crosslinking agents, each of which has a different polymerizable functional group. For example, the crosslinking agent component can include a vinyl containing crosslinking agent and an acrylate crosslinking agent. The crosslinking agent component can include a crosslinking agent containing vinyl and a crosslinking group containing methacrylate. The crosslinking agent component may comprise or consist of a crosslinking agent containing vinyl ether, and a crosslinking agent containing methacrylate.
[0087] In one example, the polymerizable compositions of the present disclosure may optionally comprise at least one hydrophilic monomer. It is understood that the hydrophilic monomer is a non-polymerizable silicone ingredient having only one polymerizable functional group present in its molecular structure. The polymerizable compositions can comprise a single hydrophilic monomer, or can comprise two or more hydrophilic monomers present as the hydrophilic monomer component. Silicone-free hydrophilic monomers, which can be used as the hydrophilic monomer or the component of the hydrophilic monomer in the polymerizable compositions described herein, include, for example, acrylamide, monomers containing acrylamide, or monomers containing acrylates, or monomers containing acrylic acid, or monomers containing methacrylate, or monomers containing methacrylic acid, or any combination thereof. In one example, the component of the hydrophilic monomer or monomer may comprise or consist of a hydrophilic monomer containing methacrylate. It is understood that the hydrophilic monomer or component of the hydrophilic monomer is a silicone-free monomer.
[0088] In one example, the silicone hydrogel contact lens is a silicone hydrogel contact lens, comprising: a polymeric lens body, which is the product of the reaction of a polymerizable composition, where said polymerizable composition comprises : (a) a first siloxane monomer represented by the general formula (1):
where m of formula (1) represents an integer from 3 to 10, n of formula (1) represents an integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 atoms of carbon, and R2 of formula (1) is a hydrogen atom or a methyl group, (b) a second siloxane monomer which is a capped polydimethylsiloxane (end-capped) with methacrylate in two terminations with an average molecular weight of at least at least 7,000 Daltons, and (c) at least one hydrophilic monomer; where silicone hydrogel contact lenses, when fully hydrated, have an energy loss of about 25% to about 45%. Silicone hydrogel contact lenses, when fully hydrated, can have an energy loss of about 27% to about 40%.
[0089] Examples of hydrophilic monomers that can be included in the present polymerizable compositions include, for example, N, N-dimethylacrylamide (DMA), or 2-hydroxyethyl acrylate, or 2-hydroxyethyl methacrylate (HEMA) or 2-methacrylate -hydroxypropyl, 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 of these.
[0090] In one example, the silicone hydrogel contact lens is a silicone hydrogel contact lens, comprising: a polymeric lens body, which is the product of the reaction of a polymerizable composition, where said polymerizable composition comprises : (a) a first siloxane monomer represented by the general formula (1):
where m of formula (1) represents an integer from 3 to 10, n of formula (1) represents an integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 atoms of carbon, and R2 of formula (1) is a hydrogen atom or a methyl group, (b) a second siloxane monomer which is a capped polydimethylsiloxane (end-capped) with methacrylate in two terminations with an average molecular weight of at least minus 7,000 Daltons, and (c) at least one hydrophilic monomer containing vinyl, where silicone hydrogel contact lenses, when fully hydrated, have an energy loss of about 25% to about 45%. Silicone hydrogel contact lenses, when fully hydrated, can have an energy loss of about 27% to about 40%.
[0091] In one example, the hydrophilic monomer or hydrophilic monomer component may comprise or consist of a vinyl-containing monomer. Examples of hydrophilic vinyl-containing monomers that can be supplied in the polymerizable compositions include, without limitation, N-vinyl formamide, or N-vinyl acetamide, or N-vinyl-N-ethyl acetamide, or N-vinyl isopropylmide or N-vinyl acetamide -N-methyl (VMA), or N-vinyl-pyrrolidone (NVP), or N-vinyl caprolactam, formamide or N-vinyl-N-ethyl, or N-vinyl-formamide, or N-2-hydroxyethyl vinyl carbamate , or N-carboxy-β-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 of themselves.
[0092] In another example, the hydrophilic monomer or component of the hydrophilic monomer of the polymerizable composition may comprise or consist of a hydrophilic amide monomer. The hydrophilic amide monomer may be a hydrophilic monomer with an N-vinyl amide group, such as, for example, N-vinyl formamide, or N-vinyl acetamide, or N-vinyl-N-ethyl acetamide, or N-vinyl iso - propylmide, or N-vinyl-N-methyl acetamide (VMA), or N-vinyl pyrrolidone (NVP), or N-vinyl caprolactam, or any combination thereof. In one example, the hydrophilic monomer or hydrophilic monomer component comprises N-vinyl-N-methyl acetamide (VMA). For example, the monomer or hydrophilic monomer component may comprise or consist of VMA. In a particular example, the hydrophilic monomer can be VMA.
[0093] In one example, the silicone hydrogel contact lens is a silicone hydrogel contact lens, comprising: a polymeric body of the lens, which is the product of the reaction of a polymerizable composition, where said polymerizable composition comprises : (a) a first siloxane monomer represented by the general formula (1):
where m of formula (1) represents an integer from 3 to 10, n of formula (1) represents an integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 atoms of carbon, and R2 of formula (1) is a hydrogen atom or a methyl group, (b) a second siloxane monomer which is a capped polydimethylsiloxane (end-capped) with methacrylate in two terminations with an average molecular weight of at least minus 7,000 Daltons, and (c) at least one hydrophilic monomer amide with an N-vinyl group, where hydrogel silicone contact lenses, when fully hydrated, have an energy loss of about 25% to about 45 %. Silicone hydrogel contact lenses, when fully hydrated, can have an energy loss of about 27% to about 40%.
[0094] In another example, the silicone hydrogel contact lens is a silicone hydrogel contact lens, comprising: a polymeric body of the lens, which is the product of the reaction of a polymerizable composition, where said polymerizable composition comprises : (a) a first siloxane monomer represented by the general formula (1):
where m of formula (1) represents an integer from 3 to 10, n of formula (1) represents an integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 atoms of carbon, and R2 of the formula (1) is a hydrogen atom or a methyl group, and (b) a second siloxane monomer which is a capped polydimethylsiloxane (end-capped) with methacrylate in two terminations with an average molecular weight of at least 7,000 Daltons, where the polymerizable composition is free of N, N-dimethylacrylamide (DMA), and where silicone hydrogel contact lenses, when fully hydrated, have an energy loss of about 25% to about 45% . Silicone hydrogel contact lenses, when fully hydrated, can have an energy loss of about 27% to about 40%.
[0095] In another example, the hydrophilic monomer or component of the vinyl-containing monomer may comprise or consist of a monomer containing vinyl ether. Examples of monomers containing vinyl ether include, without limitation, vinyl 1,4-butanediol 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 vinyl hydrophilic component comprises or consists of DEGVE.
[0096] In yet another example, the vinyl-containing hydrophilic monomer component may comprise or consist of a combination of a first hydrophilic monomer or hydrophilic monomer component, and a second hydrophilic monomer or hydrophilic monomer component. In one example, the first hydrophilic monomer has a different polymerizable functional group than the second hydrophilic monomer. In another example, each monomer of the first hydrophilic monomer has a different polymerizable functional group than the second hydrophilic monomer. In another example, the first hydrophilic monomer has a different polymerizable functional group from each monomer of the component of the second hydrophilic monomer. In yet another example, each component monomer of the first hydrophilic monomer has a different polymerizable functional group from each component monomer of the second hydrophilic monomer.
[0097] For example, when the first hydrophilic monomer or component of the hydrophilic monomer comprises or consists of one or more amides containing amide, the second monomer or component of the hydrophilic monomer may comprise or consist of one or more non-amide monomers (that is, one or more monomers of each do not have a functional amide group as part of their molecular structures). According to another example, when the first monomer or component of the hydrophilic monomer comprises or consists of one or more monomers containing vinyl, the second monomer or component of the hydrophilic monomer may comprise one or more non-vinyl monomers (for example, one or more monomers of each does not have a functional polymerizable vinyl group as part of their molecular structures). In another example, when the first monomer or component of the hydrophilic monomer comprises or consists of one or more amide monomers where each has an N-vinyl group, the second monomer or component of the hydrophilic monomer may comprise or consist of in one or more non-amide monomers. When the first monomer or component of the hydrophilic monomer comprises or consists of one or more monomers without acrylate (that is, one or more monomers of each do not have a polymerizable functional group of acrylate or methacrylate as part of their molecular structures), the second monomer or component of the hydrophilic monomers may comprise or consist of one or more acrylate monomers that contain, or one or more monomers containing methacrylate, or any combination thereof. When the first monomer or component of the hydrophilic monomer comprises or consists of one or more monomers not containing vinyl ether (that is, one or more monomers of each do not have a polymerizable vinyl ether functional group as part of their molecular structures), the second monomer or component of the hydrophilic monomer may comprise or consist of one or more monomers containing vinyl ether. In a particular example, the first monomer or component of the hydrophilic monomer may comprise or consist of one or more amide-containing monomers, each having an N-vinyl group, and the second monomer or component of the hydrophilic monomer may comprise or consist of one or more monomers containing vinyl ether.
[0098] In an example, when the first monomer or component of the hydrophilic monomer comprises or consists of a hydrophilic monomer containing amide has an N-vinyl group, the second monomer or component of the hydrophilic monomer may comprise or consist of a monomer containing vinyl ether. In a particular example, the first hydrophilic monomer can comprise VMA, and the second monomer or component of the hydrophilic monomer can comprise BVE or EGVE or DEGVE or any combination thereof. The first hydrophilic monomer can comprise VMA and the second hydrophilic monomer can comprise BVE. The first hydrophilic monomer can comprise VMA and the second hydrophilic monomer can comprise EGVE. The first hydrophilic monomer can comprise VMA and the second hydrophilic monomer can comprise DEGVE. The first hydrophilic monomer can comprise VMA, and the component of the second hydrophilic monomer can comprise EGVE and DEGVE.
[0099] Likewise, the first hydrophilic monomer can be VMA, and the second hydrophilic monomer or component of the monomer can comprise BVE or EGVE or DEGVE or any combination thereof. The first hydrophilic monomer can be VMA and the second hydrophilic monomer can be BVE. The first hydrophilic monomer can be VMA and the second hydrophilic monomer can be EGVE. The first hydrophilic monomer can comprise VMA and the second hydrophilic monomer can be DEGVE. The first hydrophilic monomer can be VMA, and the component of the second hydrophilic monomer can be a combination of EGVE and DEGVE.
[00100] In another example, the hydrophilic monomer containing vinyl without silicon can have any molecular weight, such as a molecular weight less than 400 Daltons, or less than 300 Daltons, or less than 250 Daltons, or less than 200 Daltons tones, or less than 150 Daltons, or about 75 to about 200 Daltons.
[00101] When a hydrophilic monomer or a component of the hydrophilic monomer is present in the polymerizable composition, the component of the hydrophilic monomer or monomer can be present in the polymerizable composition in an amount of 30 to 60 units of the polymerizable composition. The monomer or component of the hydrophilic monomer can be present in the polymerizable composition of 40 to 55 units, or from 45 to 50 units by weight. When the hydrophilic monomer component of the polymerizable composition comprises a first hydrophilic monomer or component of the monomer, and a second monomer or component of the hydrophilic monomer, the second monomer or component of the hydrophilic monomer may be present in the polymerizable composition in a quanti - from 0.1 to 20 units of the polymerizable composition. For example, of the total amount ranging from 30 to 60 units of monomer or component of the hydrophilic monomer present in the polymerizable composition, 29.9 to 40 units may comprise the first monomer or component of the hydrophilic monomer, and from 0, 1 to 20 units can comprise the second monomer or component of the hydrophilic monomer. In another example, the second monomer or component of the hydrophilic monomer may be present in the polymerizable composition from 1 to 15 units, or from 2 to 10 units, or from 3 to 7 units.
[00102] As used herein, a vinyl-containing monomer is a monomer with a single polymerizable carbon-carbon double bond (ie, a functional polymerizable vinyl group) present in its molecular structure, where, when subjected to polymerization by free radicals, the carbon-carbon double bond in the polymerizable functional vinyl group is less reactive than the carbon-carbon double bond present in an acrylate or methacrylate polymerizable functional group. In other words, although a carbon-carbon double bond is present in acrylate and methacrylate groups, as understood herein, monomers comprising a single polymerizable acrylate or methacrylate group are not considered vinyl-containing monomers. Examples of groups having carbon-carbon double bonds, which are less reactive than the carbon-carbon double bonds of the acrylate or methacrylate groups include the polymerizable vinyl amide, vinyl ether, vinyl ester, and allyl ester groups. Thus, as used herein, examples of vinyl containing monomers include monomers having a polymerizable group with a single vinyl amide, a single vinyl ether, a single vinyl ester, or a single allyl ester.
[00103] In addition, the polymerizable compositions of the present disclosure may optionally comprise at least one hydrophobic monomer without silicone. It is understood that the hydrophobic monomer is a non-polymerizable silicone ingredient having only one polymerizable functional group present in its molecular structure. At least one hydrophobic monomer of the polymerizable composition can be a single hydrophobic monomer, or it can comprise a component of the hydrophobic monomer composed of at least two hydrophobic monomers. Examples of hydrophobic monomers that can be used in the polymerizable compositions described herein include, without limitation, hydrophobic monomers containing acrylate or hydrophobic monomers containing methacrylate, or any combination thereof. Examples of hydrophobic monomers include, without limitation, methyl acrylate or ethyl acrylate, or propyl acrylate, or isopropyl, cyclohexyl acrylate or 2-ethylhexyl acrylate or methylate or methyl methacrylate (MMA), or ethyl methacrylate, or propyl methacrylate, or butyl acrylate, or vinyl acetate or vinyl propionate or vinyl butyrate, vinyl valerate, or styrene, or chloroprene, or vinyl chloride or vinylidene chloride, or acrylonitrile ; ethylene glycidyl methacrylate (EGMA), or any combination thereof. In a particular example, the hydrophobic monomer or monomer component may comprise or consist of MMA, or EGMA, or both.
[00104] In one example, the silicone hydrogel contact lens is a silicone hydrogel contact lens, comprising: a polymeric lens body, which is the reaction product of a polymerizable composition, where said polymerizable composition comprises : (a) a first siloxane monomer represented by the general formula (1):
where m of formula (1) represents an integer from 3 to 10, n of formula (1) represents an integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 atoms of carbon, and R2 of formula (1) is a hydrogen atom or a methyl group, (b) a second siloxane monomer which is a capped polydimethylsiloxane (end-capped) with methacrylate in two terminations with an average molecular weight of hair minus 7,000 Daltons, and (c) at least one hydrophobic monomer, where silicone hydrogel contact lenses, when fully hydrated, have an energy loss of about 25% to about 45%. Silicone hydrogel contact lenses, when fully hydrated, can have an energy loss of about 27% to about 40%.
[00105] When present in the polymerizable composition, the component of the hydrophobic monomer or monomer may be present in an amount of about 5 to about 25 units, or about 10 to about 20 units.
[00106] In one example, the hydrophobic monomer component can comprise at least two hydrophobic monomers, each of which has a different polymerizable functional group. In another example, the hydrophobic monomer component can comprise at least two hydrophobic monomers having the same polymerizable functional group. The component of the hydrophobic monomer can comprise or consist of two hydrophobic monomers, both of which have the same polymerizable functional group. In one example, the hydrophobic monomer component can comprise or consist of two hydrophobic monomers containing methacrylate. The hydrophobic monomer component can comprise or consist of MMA and EGMA. In one example, at least two hydrophobic monomers of the hydrophobic monomer component may comprise or consist of MMA and EGMA, and the ratio between the MMA units and the EGMA units present in the polymerizable composition can be about 6: 1 to about 1: 1. The ratio of the MMA and EGMA units present in the polymerizable composition can be about 2: 1 based on the MMA units by the EGMA units.
[00107] The polymerizable composition may optionally include one or more organic thinners, one or more polymerization initiators (i.e., ultraviolet (UV) light initiators, or thermal initiators, or both), or one or more agents UV absorbers, or one or more coloring agents, or one or more oxygen scavengers, or one or more chain transfer agents, or any combination thereof. These optional ingredients can be polymerizable or non-polymerizable ingredients. In one example, polymerizable compositions may be free of diluent that does not contain any organic solvent to obtain miscibility between siloxanes and other lens-forming ingredients, such as hydrophilic monomers, hydrophobic monomers, agents optional crosslinking elements. In addition, many of the polymerizable compositions shown are essentially free of water (for example, they contain no more than 3.0% or 2.0% water by weight). The polymerizable compositions described herein may optionally comprise one or more organic solvents, that is, the polymerizable composition may comprise an organic diluent, or may comprise a component of the organic diluent comprising two or more organic solvents. Organic diluents that can optionally be included in the present polymerizable compositions include alcohols, including lower alcohols, such as, for example, without limitation, pentanol or hexanol, or octanol or decanol, or any combination thereof. When included, the organic diluent or organic diluent component can be supplied in the polymerizable composition in an amount of about 1 to about 70 units, or from about 2 units to about 50 units, or from about 5 units to about 30 units.
[00108] The present polymerizable compositions 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. The polymerization initiators that can be included in the present polymerizable compositions include, for example, azo compounds, or organic peroxides, or both. Initiators that may be present in the polymerizable composition include, for example, without limitation, benzoyl or benzyl dimethyl acetal, or alpha ethyl, alpha-diethoxyacetophenone, or 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, or peroxide of benzoin, or t-butyl peroxide, or azo-bis-isobutyronitrile or azo-bis-dimethyl valero-nitrile, or any combination thereof. UV photoinitiators can include, for example, phosphine oxides, such as diphenyl (2,4,6-trimethyl benzoyl) phosphine oxide, or benzoin methyl ether, or a ketone hydroxy or Darocur (available from BASF, Florham Park, NJ, USA) or Irgacur (also available from BASF), or any combination of these. In many of Examples 1 to 28 disclosed herein, the polymerization initiator is the 2,2'-azo-bis-2-methyl propanonitrile thermal initiator (VAZO- 64 from El DuPont de Nemours & Co., Wilmington, DE, USA). Other thermoinitiators used can include 2,2'-azo-bis (2,4-dimethylpentanonitrile) (VAZO-52) and 1,1'-azo-bis (cyanocyclohexane) (VAZO-88). The polymerization initiator or a starting component can be present in the polymerizable composition in an amount of about 0.01 units to about 2.0 units, or in an amount of about 0.1 units to about 1.0 units, or from about 0.2 units to about 0.6 units by weight.
[00109] Optionally, the present polymerizable compositions may comprise one or more UV absorbing agents, that is, the polymerizable composition may comprise a UV absorbing agent, or it may comprise a component of the UV absorbing agent which comprises two or more UV absorbing agents. UV absorbing agents that can be included in the present polymerizable compositions include, for example, benzophenones or benzotriazoles, or any combination thereof. In many of Examples 1 to 28 disclosed herein, the UV absorbing agent is 2 - (4-benzoyl-3-hydroxyphenoxy) ethyl acrylate (UV-416) or 2 - (3 - (2H-benzotriazole-2) acrylate -yl) -4-hydroxy-phenyl) of ethyl (NORBLOC ® 7966 from Noramco, Athens, GA, USA). The UV-absorbing agent or UV-absorbing agent component may be present in the polymerizable composition in an amount of about 0.01 units to about 5.0 units, or in an amount of about 0.1 units to about 3.0 units, or from about 0.2 units to about 2.0 units per weight.
[00110] The polymerizable compositions of the present disclosure can also optionally include at least one coloring agent (i.e., a coloring agent or a coloring agent component comprising two or more coloring agents), which is provided in both the products of colored and clear lenses. In one example, the coloring agent can be a reactive dye or an effective pigment that produces color in the product resulting from the lens. The coloring agent component or the coloring agent of the polymerizable composition may comprise a polymerizable coloring agent, or it may comprise a non-polymerizable coloring agent, or any combination thereof. The polymerizable coloring agent can be a coloring agent, the molecular structure of which comprises a polymerizable functional group, or it can be a coloring agent, the molecular structure of which includes both a monomer part and a dye part, i.e. , the coloring agent can be a coloring monomer compound. The molecular structure of the staining agent may comprise a functional beta-sulfone group, or may comprise a functional triazine group. Coloring agents may include, for example, VAT Blue 6 (7,16-Dichloro-6,15-dihydroanthrazine-5, 9,14,18-tetrone), or 1-amino-4- [3- ( ethyl sufonyl beta sulfate) Anilio] anthraquinone-2-sulfonic (CI Reactive Blue 19, LD-19), or a Reactive Blue 19 dye monomer compound and hydroxyethyl methacrylate (RB-19 HEMA), or 1, 4-bis [4 - [(2 - methacryl-oxyethyl) phenylamine] anthraquinone (Reactive Blue 246, RB-246, available from Arran Chemical Company, Atlone, Ireland), or 1,4-bis [(2-hydroxyethyl ester) ) -amino] -9,10 anthracenedodione-bis (2-propenoic) (LD-247), or Reactive Blue 4, RB-4, or a Reactive Blue 4 dye monomer compound and hydroxyethyl methacrylate (RB-4 HEMA or "Blue HEMA"), or any combination thereof. In one example, the coloring agent component or coloring agent may comprise a polymerizable coloring agent. The polymerizable coloring agent component can comprise, for example, RB-246 or RB-274 or RB-4 HEMA, or RB-19 HEMA, or any combination thereof. Examples of dye monomer compounds include RB-4 HEMA and RB-19 HEMA. Additional examples of dye monomer compounds are described in US 5,944,853 and US 7,216,975, both of which are incorporated in their entirety by reference. Other exemplary coloring agents are disclosed, for example, in US Patent Application Publication No. 2008 / 0.048.350, the disclosure of which is incorporated in its entirety here by reference. In many of the examples 1 - 28 disclosed herein, the blue coloring agent is a reactive dye, such as that described in US 4,997,897, the disclosure of which is incorporated in its entirety here by reference. Other coloring agents suitable for use according to the present invention are phthalocyanine pigments, such as blue phthalocyanine or green phthalocyanine, or chromium-cobalt-alumina oxide, or chromium oxides, or various iron oxides for the colors red, yellow, brown and black, or any combination of these. Opacifying agents, such as titanium dioxide, can also be incorporated. For certain applications, a combination of agents with different color shades can be used as the component of the color agent. If used, the coloring agent component or coloring agent can be present in the polymerizable composition in an amount ranging from about 0.001 units to about 15.0 units, that is, about 0.005 units to about 10.0 units, that is, about 0.01 units to about 8.0 units.
[00111] The polymerizable compositions of the present disclosure may optionally comprise at least one oxygen scavenger, that is, an oxygen scavenger or an oxygen scavenger component comprising two or more oxygen scavengers. Examples of oxygen scavengers that can be included as the oxygen scavenger or an oxygen scavenger component of the present polymerizable compositions include, for example, vitamin E, or phenolic compounds, or compounds containing phosphite, or compounds phosphine, or amine oxide compounds, or any combination thereof. For example, the oxygen scavenger or an oxygen scavenger component may consist of, or comprise, a phosphine-containing compound. In many of the examples 1 - 28 disclosed herein, the oxygen scavenger or an oxygen scavenger component is a phosphine-containing compound, such as triphenyl phosphine, or a polymerizable form of triphenyl-phosphine, such as diphenyl- (P -vinylphenyl) phosphine.
[00112] Chain transfer is a polymerization reaction in which the activity of a growing polymer chain is transferred to another molecule, reducing the average molecular weight of the final polymer. The polymerizable compositions of the present disclosure can optionally comprise at least one chain transfer agent, i.e., it can comprise a chain transfer agent, or it can comprise a chain transfer agent component which comprises at least two chain transfer agents. Examples of chain transfer agents that can be included as the chain transfer agent, or the chain transfer component of the presented polymerizable compositions include, for example, thiol compounds, or halogenated hydrocarbon compounds, or C3 - C5 hydrocarbons, or any combination thereof. In many of the examples 1 - 28 described herein, the chain transfer agent is allyloxy ethanol. When present in the polymerizable composition, the chain transfer agent or chain transfer agent component can be present in an amount of about 0.01 units to about 1.5 units, for example, about 0.1 units to about 0.5 units.
[00113] The contact lenses of the present disclosure are ophthalmologically acceptable contact lenses because they are configured to be placed or arranged on a cornea of a human or animal eye. As used herein, an ophthalmologically acceptable contact lens is understood to be a contact lens that has at least one of a number of different properties, as described below. An ophthalmologically acceptable contact lens can be formed by, and packaged in, ophthalmologically acceptable ingredients in such a way that the lens is non-cytotoxic and does not release irritating and / or toxic ingredients during use. An ophthalmologically acceptable contact lens may have a level of clarity in the optical zone of the lens (ie the part of the lens that provides vision correction) sufficient for its intended use in contact with the cornea of an eye, for example, by means of a transmission coefficient of at least 80%, or at least 90%, or at least 95% of visible light. An ophthalmologically acceptable contact lens may have sufficient mechanical properties to facilitate the handling and care of the lens for a period of time based on its expected lifetime. For example, its modulus of elasticity, tensile strength, and elongation may be sufficient to support insertion, use, removal and, optionally, cleaning over the expected duration of the lens. The level of these suitable properties will vary, depending on the expected lifetime and use of the lens (for example, disposable daily single-use lens, multiple monthly use, etc.). An ophthalmologically acceptable contact lens can have an effective ion flow or suitable to substantially inhibit or substantially prevent corneal staining, such as corneal staining more severe than superficial or moderate corneal staining after continuous use of the lens on a cornea for 8 hours or more. An ophthalmologically acceptable contact lens may have a sufficient degree of oxygen permeability to allow oxygen to reach the cornea of an eye, while using the lens, in an amount sufficient for the long-term health of the cornea. An ophthalmologically acceptable contact lens can be a lens that does not cause substantial or undue swelling of the cornea of an eye using the lens, for example, no more than about 5% or 10% corneal swelling after be placed over a cornea of one eye during sleep throughout the night. An ophthalmologically acceptable contact lens can be a lens that allows sufficient movement of the lens over the cornea of an eye using the lens in order to facilitate tear flow between the lens and the eye, in other words, it does not cause adhesion of the lens over the eye with sufficient force to prevent normal lens movement and to have a sufficiently low level of movement over the eye to allow vision correction. An ophthalmologically acceptable contact lens can be a lens that allows the use of a lens over the eye, without undue or significant discomfort and / or irritation and / or pain. An ophthalmologically acceptable contact lens can be a lens that substantially inhibits or prevents the deposition of sufficient lipids and / or proteins to cause the lens wearer to remove it because of such deposits. An ophthalmologically acceptable contact lens can have at least one of a water content, or a surface wettability, or a module or design, or any combination of these, which are effective in facilitating the ophthalmologically compatible use of the lenses contact lens wearer for at least one day. It is to be understood that ophthalmologically compatible use refers to the use of a lens by a lens wearer with little or no discomfort, and little or no corneal staining. People with knowledge in the art can determine whether an ophthalmologically acceptable contact lens can be achieved using conventional clinical methods, such as those exercised by an ophthalmologist.
[00114] In an example of the present disclosure, contact lenses can have their surfaces wettable and ophthalmologically acceptable. For example, the contact lens may have wettable and ophthalmologically acceptable surfaces when the polymerizable composition used to form the polymeric body of the lens is free of an internal wetting agent, or when the polymerizable composition used to form the polymeric body of the lens is free of an organic diluent, or when the polymeric body of the lens is extracted in water or an aqueous solution free of volatile organic solvent, or when the polymeric body of the lens is free of a plasma surface treatment, or any combination thereof.
[00115] An approach used in the technique to increase the wettability of contact lens surfaces is to apply treatments to the lens surfaces, or modify the lens surfaces. In accordance with the present disclosure, silicone hydrogel contact lenses can have wettable and ophthalmologically acceptable surfaces without the presence of surface treatment or surface modification. Surface treatments include, for example, plasma treatment and corona treatments, which increase the hydrophilicity of the lens surface. Although it is possible to apply one or more plasma surface treatments to current lens bodies, it is not necessary to do so to obtain a hydrogel silicone contact lens having wettable and ophthalmologically acceptable surfaces when the lenses are fully hydrated. In other words, in one example, the silicone hydrogel contact lenses of the present disclosure may be free from plasma surface treatment or corona treatment.
[00116] Surface modifications include attaching wetting agents to the lens surface, such as, for example, attaching a wetting agent, such as a hydrophilic polymer, to at least one surface of the lens by chemical bonding or another form of chemical interaction. In some cases, the wetting agent can be attached to the lens surface, as well as at least part of the polymeric matrix of the lens, that is, at least part of the lens mass, by chemical bonding or some other form of chemical interaction. The wettable and ophthalmologically acceptable surfaces of the lens of the present disclosure may be wettable and ophthalmologically acceptable, without the presence of a wetting agent (for example, a polymeric material or a non-polymeric material) attached at least to the lens surface. Although it is possible to attach one or more wetting agents to current lenses, it is not necessary to obtain a silicone hydrogel contact lens having wettable and ophthalmologically acceptable surfaces when the lenses are fully hydrated. Thus, in one example, the lenses of the present disclosure may comprise wetting agents, such as, for example, hydrophilic polymers and include polyvinylpyrrolidone attached to a surface of the lens. In addition, in another example, the silicone hydrogel contact lenses of the present disclosure can be free of a wetting agent attached to the lens surface.
[00117] Another method of increasing the wettability of the lens is to physically retain a wetting agent inside the lens body or on contact lenses, such as introducing the wetting agent into the lens body when the lens body is swollen, and then return the lens body to a less swollen state, thereby trapping a part of a wetting agent in the lens body. The wetting agent may be permanently trapped within the lens body, or it may be released from the lens over time, such as during use. The wettable and ophthalmologically acceptable surfaces of the lens of the present disclosure can be wettable and ophthalmologically acceptable, without the presence of a wetting agent (for example, a polymeric material or a non-polymeric material) physically retained in the lens body after the formation of the lens. polymeric lens body. Although it is possible to physically retain one or more wetting agents in current lenses, it is not necessary to do so in order to obtain a silicone hydrogel contact lens having its wettable and ophthalmologically acceptable surfaces when fully hydrated. Thus, in one example, the lenses of the present disclosure may comprise wetting agents, such as, for example, hydrophilic polymers and include polyvinylpyrrolidone retained within the lenses. In addition, the silicone hydrogel contact lenses of the present disclosure can be free of a wetting agent physically trapped inside the lens. As used herein, physically retained refers to the immobilization of a wetting agent, or other ingredients, in the polymeric matrix of the lenses with little or no chemical bond or chemical interaction between the wetting agent and either component and the polymeric matrix. This is the opposite of ingredients that are chemically linked to the polymeric matrix, whether by covalent bonds, ionic bonds, Van der Waals forces, and the like.
[00118] Another approach used in the technique to increase the humidity of silicone hydrogel contact lenses includes the addition of one or more wetting agents to the polymerizable composition. In one example, the wetting agent can be a polymeric wetting agent. However, the contact lenses of the present disclosure may have wettable and ophthalmologically acceptable surfaces of the lens when the polymerizable composition used to form the polymeric lens body is free of a wetting agent. Although it is possible to include one or more wetting agents in the present polymerizable compositions to increase the wettability of the silicone hydrogel contact lenses of the present disclosure, it is not necessary to do so in order to obtain a silicone hydrogel contact lens having its surfaces wettable and ophthalmologically acceptable. In other words, in one example, the silicone hydrogel contact lenses of the present disclosure can be formed from polymerizable compositions free of wetting agents. In addition, in another example, the polymerizable compositions of the present invention may further comprise a wetting agent.
[00119] In one example, the wetting agent can be an internal wetting agent. The internal wetting agent can be attached within at least a part of the polymeric matrix of the lens. For example, the internal wetting agent can be bonded within at least part of the polymeric matrix of the lens through chemical bonding or another form of chemical interaction. In some cases, the wetting agent can also be attached to the lens surface. The internal wetting agent can comprise a polymeric material or a non-polymeric material. Although it is possible to connect one or more internal wetting agents within the polymeric matrix of current lenses, it is not necessary to do so in order to obtain a silicone hydrogel contact lens having its wettable and ophthalmologically acceptable surfaces when fully hydrated. Thus, in one example, the lenses of the present disclosure may comprise internal wetting agents attached to at least part of the polymeric matrix of the lens. In addition, in another example, the silicone hydrogel contact lenses of the present disclosure can be free of an internal wetting agent attached to at least part of the polymeric matrix of the lens.
[00120] In another example, the wetting agent can be an internal polymeric wetting agent. The polymeric internal wetting agent can be present in the polymeric body of the lens as part of a network of interpenetrating polymers (IPN), or a semi-IPN. A network of interpenetrating polymers is formed by at least two polymers, each of which is cross-linked to itself, but none of them are cross-linked. Likewise, a semi-IPN is formed by at least two polymers, at least one of which is cross-linked with each other, but not with the other polymer, and the other is neither cross-linked nor with other polymers. In an example of the present disclosure, the contact lens may have its surfaces wettable and ophthalmologically acceptable, when the polymeric lens body is free of an internal polymeric wetting agent present in the lens body such as an IPN or a semi-IPN. In addition, the contact lens may comprise an internal polymeric wetting agent present in the lens body as an IPN or a semi-IPN.
[00121] In yet another example, the wetting agent can be a bonding compound present in the polymerizable composition used to form the lens body, or a bonding agent physically trapped inside the polymeric body of the lens after the body the lens has been formed. When the wetting agent is a bonding compound, after polymerizing the lens body or trapping the bonding agent in the polymeric lens body, the bonding compound can later bind a second wetting agent to the lens body when the lens body comes into contact with wetting agent. Bonding can occur as part of the manufacturing process, for example, as a washing process, or it can happen when the lens body comes into contact with a packaging solution. The bond can take the form of an ionic bond, or a covalent bond, or a Van der Waals form of attraction. The binding agent may comprise a part or group of boric acid in such a way that a part or group of the polymerized boronic acid is present in the polymeric body of the lens, or in such a way that a part or group of the boronic acid is present. physically retained in the polymeric body of the lens. For example, when the binding agent comprises a form of boronic acid, the second wetting agent may comprise a form of poly (vinyl alcohol), which is attached to the form of boronic acid. Optionally, it is understood that the silicone hydrogel contact lenses of the present disclosure are free of bonding agents. In one example, silicone hydrogel contact lenses can be free of boronic acid parts or groups, including polymerized boronic acid parts or groups, that is, specifically, silicone hydrogel contact lenses can be formed from of a polymerizable composition free of a boronic acid form such as, for example, a polymerizable form of boronic acid including vinyl phenyl boronic acid (VPB), can be formed of a polymer free of units derived from a form polymerizable boronic acid, such as vinyl phenyl boronic acid (VPB) and the polymeric lens body and silicone hydrogel contact lenses can be free of a boronic acid form, including the polymeric or non-polymeric form of boronic acid, physically held in them. In addition, the polymerizable composition, or the polymeric body of the lens, or the silicone hydrogel contact lens, or any combination thereof, may comprise at least one bonding agent.
[00122] In addition to the inclusion of wetting agents in the polymerizable composition and the modification of lens surfaces, the washing of polymeric lens bodies in volatile organic solvents or in aqueous solutions of volatile organic solvent has been used to increase wettability lens surfaces. Although it is possible to wash the present polymeric bodies of the lenses in a volatile organic solvent or an aqueous solution of a volatile organic solvent, in accordance with the present disclosure, it is not necessary to do so in order to obtain a silicone hydrogel contact lens having its wettable and ophthalmologically acceptable surfaces when fully hydrated. In other words, in one example, the silicone hydrogel contact lenses of the present invention have not been exposed to a volatile organic solvent, including a solution of a volatile organic solvent, as part of a manufacturing process. In one example, the silicone hydrogel contact lenses of the present invention can be formed from a polymerizable composition free of a wetting agent, or the polymeric body of the lens and / or hydrated contact lens can be free of a wetting agent, either without surface treatment or free from surface modification, or not being exposed to a volatile organic solvent, during the manufacturing process, or any combination thereof. Instead, for example, silicone hydrogel contact lenses can be washed in a washing liquid free of a volatile organic solvent, such as, for example, water or an aqueous solution free of volatile organic solvent, including volatile lower alcohol-free liquid.
[00123] The use of volatile organic solvents to extract the bodies from the lenses contributes significantly to the costs of production, due to factors such as the cost of organic solvents, the costs of disposal of solvents, the need to use explosion-proof production, the need to remove solvents from the lenses before packaging, and the like. However, developing polymerizable compositions capable of consistently producing contact lenses with wettable and ophthalmologically acceptable surfaces of the lenses when extracted in aqueous liquids free of volatile organic solvents, can be a challenge. For example, it is common to find non-wetting regions present on the surfaces of contact lenses that have been extracted in aqueous liquids free of volatile organic solvents.
[00124] As discussed earlier, in an example of the present disclosure, contact lenses are contact lenses that were not exposed to a volatile organic solvent, such as a lower alcohol, during their manufacture. In other words, the washing, moisturizing and extraction liquids used in such lenses, as well as all liquids used during wet demoulding 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 do not come into contact with a volatile organic solvent may comprise a vinyl-containing hydrophilic monomer or monomer component, such as, for example, a hydrophilic monomer containing vinyl ether . The component of the vinyl-containing hydrophilic monomer or monomer may include, for example, VMA. Monomers containing vinyl ether can include, for example, BVE, or EGVE or DEGVE, or any combination thereof. In a particular example, the monomer containing vinyl ether may be a monomer containing vinyl ether more hydrophilic than BVE, such as, for example, DEGVE. In another example, the hydrophilic monomer component of the polymerizable composition may be a mixture of a first hydrophilic monomer which is a vinyl-containing monomer, but which is not a vinyl ether-containing monomer, and a second hydrophilic monomer, which is an ether-containing monomer vinyl. These mixtures include, for example, mixtures of VMA and one or more vinyl ethers, such as, for example, BVE, or DEGVE or EGVE, or any combination thereof.
[00125] When present, the hydrophilic monomer or monomer component containing vinyl ether can be present in the polymerizable composition in an amount of about 1 to about 15 units, or about 3 to about 10 units. When presented as a mixture of a hydrophilic monomer containing vinyl, which is not a vinyl ether, the component part of the monomer or hydrophilic monomer containing vinyl, which is not a vinyl ether, and that of the component of the hydrophilic monomer or monomer containing vinyl ether 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 ratio en - three units by weight of the component of the monomer or hydrophilic monomer containing vinyl, which is not a vinyl ether, and the units by weight of the component of the monomer or hydrophilic monomer containing vinyl ether.
[00126] Another approach for the production of contact lenses with wettable and ophthalmologically acceptable surfaces according to the present disclosure, in particular lenses extracted in a liquid free of volatile organic solvent, including lenses that did not come into contact with a volatile organic solvent during manufacture, it may be to limit the amount of a crosslinking agent or vinyl containing crosslinking agent component in the polymerizable composition. For example, a crosslinking agent or vinyl containing crosslinking agent component may be present in the polymerizable composition in an amount of about 0.01 to about 0.80 units, or 0.01 to about 0.30 units, or from about 0.05 to about 0.20 units, or in an amount of about 0.1 units. In one example, a crosslinking agent or vinyl containing crosslinking agent component may be present in the polymerizable composition in an effective amount that produces a contact lens with a better wettability over a contact lens produced from of the same polymerizable composition, but containing an amount of crosslinking agent or vinyl containing crosslinking agent component greater than about 2.0 units, or greater than 1.0 units, or greater than about 0.8 units, or greater about 0.5 units, or greater than about 0.3 units.
[00127] While limiting the amount of crosslinking agent or vinyl containing crosslinking agent may improve moisture, in one example, the inclusion of a crosslinking agent or vinyl containing crosslinking 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, a crosslinking agent or crosslinking agent component containing vinyl may be present in the polymerizable composition in an effective amount that produces a contact lens having a better dimensional stability compared to a contact lens. tact produced from the same polymerizable composition, but without the crosslinking agent or vinyl containing crosslinking agent component.
[00128] Another approach also for the production of contact lenses with wettable and ophthalmologically acceptable surfaces, according to the present disclosure, in particular for lenses washed in a liquid free of a volatile organic solvent, may be to include a quantity of a crosslinking agent or vinyl bonding agent component in the polymerizable composition based on the ratio of units by weight of the hydrophilic monomer containing vinyl or the monomer component present in the composition and units by weight of the crosslinking agent or crosslinking agent component containing vinyl in the present composition. For example, the total units of the hydrophilic monomer or vinyl-containing monomer component and the total units parts of the vinyl-containing crosslinking agent or cross-linking agent may be present in the polymerizable composition in a ratio greater than about 125: 1 , or from about 150: 1 to about 625: 1 or from about 200: 1 to about 600: 1 or from about 250: 1 to about 500: 1 or from about 450: 1 to about 500: 1, based on the ratio between the units by weight of all hydrophilic monomers containing vinyl present in the polymerizable composition and the total units by weight of all vinyl containing crosslinking agents present in the polymerizable composition.
[00129] In one example, the contact lenses of the present disclosure are ophthalmologically compatible silicone hydrogel contact lenses. Many different criteria can be assessed to determine whether or not a contact lens is ophthalmologically compatible, as will be discussed later. In one example, ophthalmologically acceptable contact lenses have wettable and ophthalmologically acceptable surfaces when fully hydrated. It is understood that a silicone hydrogel contact lens having a wettable and ophthalmologically acceptable surface refers to a silicone hydrogel contact lens that does not negatively affect the tear film of a lens wearer's eye to a degree that provide the lens user with an experience or report of discomfort associated with placing or using the silicone hydrogel contact lens in an eye.
[00130] An example of the disclosed polymerizable composition may be miscible when initially prepared, and may remain miscible over a period of time suitable for the commercial manufacture of contact lenses, such as, for example, for about 2 weeks, or about 1 week, or about 5 days. Typically, when polymerized and transformed into contact lenses, miscible and polymerizable compositions result in contact lenses that have ophthalmologically acceptable clarity.
[00131] The approaches commonly used to increase the miscibility of hydrophilic monomers and siloxane monomers include the addition of organic diluents in the polymerizable composition in order to act as compatibilizers between hydrophilic monomers and siloxane monomers that are typical more hydrophobic, or using only low molecular weight siloxane monomers (for example, molecular weights less than 2,500 Daltons). In one example, the use of the first siloxane, as described above, makes it possible to include both the second high molecular weight siloxane and a high level of an optional or more hydrophilic monomers in the polymerizable compositions of the present disclosure. And, while it is possible to include one or more organic diluents in the present polymerizable compositions described herein, it may not be necessary to do so in order to obtain a miscible polymerizable composition in accordance with the present disclosure. In other words, in one example, the silicone hydrogel contact lenses of the present disclosure are formed from polymerizable compositions that are free of an organic diluent.
[00132] In one example, the silicone hydrogel contact lens is a silicone hydrogel contact lens, comprising: a polymeric body of the lens, which is the product of the reaction of a polymerizable composition, where said polymerizable composition comprises : (a) a first siloxane monomer represented by the general formula (1):
where m of formula (1) represents an integer from 3 to 10, n of formula (1) represents an integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 atoms of carbon, and R2 of the formula (1) is a hydrogen atom or a methyl group, and (b) a second siloxane monomer which is a capped polydimethylsiloxane (end-capped) with methacrylate in two terminations with an average molecular weight of at least 7,000 Daltons, where the polymerizable composition is free of an organic solvent, and where silicone hydrogel contact lenses, when fully hydrated, have an energy loss of about 25% to about 45%. Silicone hydrogel contact lenses, when fully hydrated, can have an energy loss of about 27% to about 40%.
[00133] Various methods of measuring contact angles are known to those skilled in the art, including the captive bubble method. The contact angle can be a static or dynamic contact angle. The silicone hydrogel contact lenses of the present invention can have an average dynamic contact contact angle through the captive bubble of less than 120 degrees, such as, for example, less than 90 degrees when fully hydrated, less than 80 degrees when completely hydrated, less than 70 degrees, when fully hydrated, or less than 65 degrees, when fully hydrated, or less than 60 degrees, when completely hydrated, or less than 50 degrees when completely hydrated. The silicone hydrogel contact lenses of the present invention can have an average static contact angle through the captive bubble of less than 70 degrees when fully hydrated, or less than 60 degrees when fully hydrated, or less than 55 degrees when completely hydrated. hydrated, or less than 50 degrees when fully hydrated, or less than 45 degrees when fully hydrated.
[00134] In accordance with the present disclosure, silicone hydrogel contact lenses can have, when fully hydrated, the equilibrium water content (EWC) of about 30% to about 70%. For example, contact lenses can 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. EWC determination methods are known to those skilled in the art, and can be based on the loss of weight of a lens during the drying process.
[00135] The contact lenses present 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 lenses can have an oxygen permeability of about 55 barrers to about 135 barrers, or from about 60 barrers to about 120 barrers, or from about 65 barrers to about 90 barrers, or from about from 50 barrers to about 75 barrers. Various methods of determining oxygen permeability are known to those skilled in the art.
[00136] The contact lenses present can have an oxygen permeability of at least 55 barrers (DK> 55 barrers), or an EWC of about 30% to about 70%, or a medium dynamic contact angle by the captive bubble below 70 degrees, or an average static contact angle by the captive bubble below 55 degrees, or any combination of these. In one example, contact lenses can have an oxygen permeability of at least 60 barrers (DK> 60 barrers), or an EWC of about 35% to about 65%, or an average dynamic forward contact angle across captive bubble below 70 degrees, or mean static contact angle through the captive bubble below 55 degrees, or any combination of these. In another example, the contact lenses present may have an oxygen permeability of at least 65 barrers, or an EWC of about 45% to about 65%, or an average dynamic forward contact angle through the captive bubble. less than 70 degrees, or an average angle of static contact through the captive bubble less than 55 degrees, or any combination thereof.
[00137] In one example, the contact lenses present have an oxygen permeability of at least 55 barrers, an EWC of about 30% to about 70%, an average dynamic forward contact angle through the lower captive bubble at 70 degrees, and an average angle of static contact through the captive bubble below 55 degrees.
[00138] The present contact lenses, when completely hydrated, can have an ionic flux less than about 8.0 x 10-3 mm2 / min, or less than about 7.0 x 10-3 mm2 / min , or less than about 5.0 x 10-3 mm2 / min. Various methods of determining ionic flux are conventional and are known to those skilled in the art.
[00139] The silicone hydrogel contact lenses of the present disclosure may have, when fully hydrated, an average tensile modulus of about 0.20 MPa to about 0.90 MPa. For example, the average modulus may be about 0.30 MPa to about 0.80 MPa, or between about 0.40 MPa to about 0.75 MPa, or between about 0.50 MPa to about 0.70 MPa.
[00140] As used here, it is understood that the module of a contact lens or the lens body refers to the traction module, also known as the Young's module. It is a measure of the stiffness of an elastic material. The voltage module can be measured using a method according to ANSI Z80.20. In one example, the voltage module can be measured using an Instron Model 3342 or Model 3343 mechanical test system.
[00141] In one example, the contact lenses present may have an extractable wet component. The extractable wet component is determined based on the weight lost during methanol extraction from contact lenses that were fully hydrated and sterilized before drying and the extraction test. The extractable wet component may comprise polymerizable ingredients of the polymerizable composition that have not reacted or have partially reacted. The extractable wet component consists of materials extractable by organic solvent that remain in the lens body after the lens body has been fully processed to form a sterile contact lens formed from polymerizable compositions that comprise non-polymerizable ingredients. For lenses extracted during manufacture, either by an extraction liquid, which comprises a volatile organic solvent, or an extraction liquid free of an organic solvent, in most cases, substantially all non-polymerizable ingredients will have been removed from the lens body, and thus, the wet extractable component may consist essentially of extractable components formed from polymerizable reactive ingredients of the polymerizable composition, that is, polymerizable components that did not react and polymerizable ingredients that partially reacted. In lenses made from a diluent-free polymerizable composition, the extractable wet component may be present in the contact lens in an amount between about 1% w / w, about 15% w / w, or about 2% w / w about 10% w / w, or about 3% w / w about 8% w / w based on the dry weight of the lens body, before the extraction test. In lenses made from a polymerizable composition comprising a diluent, the extractable wet component may consist of a part of the diluent, as well as polymerizable ingredients that have not reacted and partially reacted, and may be present in the contact lens in an amount between about 1% w / w about 20% w / w, or about 2% w / w about 15% w / w of the lens, or between about 3% w / w and about 10% w / w based in the dry weight of the lens body, before the extraction test.
[00142] In one example, the contact lenses present have an extractable dry component. The extractable dry component is determined based on the weight lost during methanol extraction from the polymeric bodies of the lenses that have not been washed, extracted (as part of a manufacturing process), hydrated or sterilized before drying and extraction. The extractable dry component may comprise polymerizable ingredients of the polymerizable composition that have not reacted or partially reacted. When optional non-polymerizable ingredients, such as diluents and the like, are present in the polymerizable composition, the extractable dry component can also comprise the non-polymerizable ingredients.
[00143] In lenses made from a diluent-free polymerizable composition, the extractable dry component of the lens consists mainly of extractable dry components from the polymerizable ingredients of the polymerizable composition (i.e., polymerizable ingredients that have not reacted or partially reacted), and may also include dry extractable materials from optional non-polymerizable components present in small amounts in the polymerizable composition (eg less than 3% w / w), such as, for example, coloring agents, sequestering agents oxygen, and the like. In lenses made from a diluent-free polymerizable composition, the extractable dry component can be present in the polymeric body of the lens in an amount of about 1% w / w to about 30% w / w of the lens body or about 2% w / w about 25% w / w, or about 3% w / w about 20% w / w, or about 4% w / w about 15 % w / w, or 2% w / w less than 10% w / w based on the dry weight of the lens body, before the pull test.
[00144] In lenses made from a polymerizable composition comprising a large amount (for example, more than 3% w / w) of an optional non-polymerizable ingredient, such as a diluent, the dry component ex - traceable composed of extractable materials from the reactive ingredients, as well as extractable components from the non-polymerizable ingredients of the polymerizable composition. The total amount of extractable dry components from the reactive ingredients and non-polymerizable ingredients present in the contact lens can be an amount of about 1% w / w, about 75% w / w, or about 2% w / w about 50% w / w of the lens, or about 3% w / w about 40% w / w, or about 4% w / w about 20% w / w, or about from 5% to about 10% based on the dry weight of the polymeric body of the lens, before the extraction test. The total amount of dry extractable components from the polymerizable ingredients (ie, polymerizable ingredients that have not reacted or partially reacted) can be an amount of about 1% w / w to about 30% w / w of the body of the lens, or about 2% w / w about 25% w / w, or about 3% w / w about 20% w / w, or about 4% w / w about 15% w / w, or 2% w / w less than 10% w / w based on the dry weight of the lens body, before the extraction test.
[00145] Certain specific examples of silicone hydrogel contact lenses will now be described, in accordance with the present teachings.
[00146] As an example (Example A), a silicone hydrogel contact lens comprises a polymeric lens body, which is the reaction product of a polymerizable composition comprising a first siloxane monomer represented by the general formula (1 ):
where m of formula (1) represents an integer from 3 to 10, n of formula (1) represents an integer from 1 to 10, R1 is an alkyl group having 1 to 4 carbon atoms, and each R2 of the formula (1) is, independently, either a hydrogen atom or a methyl group, a second siloxane monomer which is a polydimethylsiloxane capped (end-capped) with methacrylate in two endings with an average molecular weight of at least 7,000 Daltons, and a second optional component comprising a third siloxane monomer or at least one crosslinking agent or at least one hydrophilic monomer or at least one hydrophobic monomer, or any combination thereof; where contact lenses have an energy loss of about 30% to about 40% when fully hydrated. In one example, when the polymerizable composition comprises the third siloxane monomer, the third siloxane monomer may be a third siloxane monomer having more than one functional group, and having an average molecular weight of at least 3,000 Daltons. In another example, when the polymerizable composition comprises at least one crosslinking agent, at least the crosslinking agent can consist of at least one vinyl containing crosslinking agent.
[00147] As a second example (Example B), a silicone hydrogel contact lens comprises a polymeric lens body, which is the reaction product of a polymerizable composition, as described in example A, wherein the other polymerizable composition comprises a monomer or component of the hydrophilic monomer. In one example, the component of the hydrophilic monomer or monomer may be present in the polymerizable composition in an amount of about 30 units to about 60 units.
[00148] As a third example (Example C), a silicone hydrogel contact lens comprises a polymeric lens body, which is the reaction product of a polymerizable composition, as described in Example A or B, wherein the composition The polymerizable material further comprises a monomer or component of the hydrophobic monomer, specifically, the hydrophilic monomer comprising or consisting of methyl methacrylate (MMA).
[00149] As a fourth example (Example D), a silicone hydrogel contact lens comprises a polymeric lens body, which is the reaction product of a polymerizable composition, as described in Example A or B or C, and wherein the polymerizable composition further comprises a crosslinking agent or vinyl containing crosslinking agent component. In one example, the crosslinking agent or crosslinking agent component may comprise or consist of crosslinking agent or crosslinking agent component containing vinyl ether, specifically the crosslinking agent or crosslinking agent component may comprise or consist of divinyl triethylene glycol ether (TEGVE).
[00150] As a fifth example (Example E), a silicone hydrogel contact lens comprises a polymeric lens body, which is the reaction product of a polymerizable composition, as described in Example A or B or C or D, wherein the polymerizable composition further comprises a thermal initiator or thermal initiator component.
[00151] As a sixth example (Example F), a silicone hydrogel contact lens comprises a polymeric lens body, which is the reaction product of a polymerizable composition, as described in Example A or B or C or D or E, wherein the polymerizable composition further comprises an oxygen scavenger or oxygen scavenger component.
[00152] As a seventh example (Example G), a silicone hydrogel contact lens comprises a polymeric lens body, which is the reaction product of a polymerizable composition, as described in Example A or B or C or D or E or F, wherein the additional polymerizable composition comprises a UV absorbing agent or UV absorbing agent component.
[00153] As an eighth example (Example H), a silicone hydrogel contact lens comprises a polymeric lens body, which is the reaction product of a polymerizable composition, as described in Example A or B or C or D or E or F or G, wherein the polymerizable composition further comprises a coloring agent or coloring agent component.
[00154] As a ninth example (example I), a silicone hydrogel contact lens comprises a polymeric body of the lens, which is the reaction product of a polymerizable composition, as described in Example A or B or C or D or E or F or G or H, wherein the polymerizable composition further comprises a second siloxane monomer represented by the general formula (2), where R1 of the formula (2) is selected either from a hydrogen atom or a group methyl, R2 of the formula (2) is selected from either a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms; m of formula (2) represents an integer between 0 and 10, n of general formula (2) represents an integer from 4 to 100; a and b represent integers of 1 or more, a + b is equal to 20 to 500, b / (a + b) is equal to 0.01 to 0.22, and the siloxane unit configuration includes a random configuration . As an example, the second siloxane monomer can be represented by the general formula (2), where m of formula (2) is 0, n of formula (2) is an integer from 5 to 10, a is an integer of 65 to 90, b is an integer from 1 to 10, R1 of formula (2) is a methyl group, and R2 of formula (2) is either a hydrogen atom or a hydrocarbon group with 1 to 4 atoms of carbon.
[00155] As a tenth example (Example J), a silicone hydrogel contact lens comprises a polymeric lens body, which is the reaction product of a polymerizable composition, as described in Example A or B or C or D or E or F or G or H or I, wherein the polymerizable composition further comprises a crosslinking agent or crosslinking agent component containing methacrylate, specifically the crosslinking agent or crosslinking agent component may comprise or consist of ethylene glycol dimethacrylate (EGDMA). In this example, when the polymerizable composition further comprises a crosslinking agent containing vinyl ether, as part of the crosslinking agent component, more specifically the crosslinking agent component may comprise or consist of divinyl triethylene glycol ether (TGDVE) in combination with a crosslinking agent containing methacrylate, which may specifically comprise or consist of ethylene glycol dimethacrylate (EGDMA). In this example, it can be seen that the polymerizable composition comprises two crosslinking agents, each with different reactivity ratios, that is, the polymerizable composition comprises a crosslinking agent component comprising or consisting of a crosslinking agent containing vinyl and a methacrylate-containing crosslinking agent, where the methacrylate-containing crosslinking agent has polymerizable functional groups that are more reactive and react at a faster rate than the polymerizable vinyl functional groups present in the vinyl containing crosslinking agent .
[00156] As an eleventh example (example K), a silicone hydrogel contact lens comprises a polymeric lens body, which is the reaction product of a polymerizable composition, as described in Example A or B or C or D or E or F or G or H or I or J, wherein the polymerizable composition further comprises a chain transfer agent or chain transfer agent component which may specifically comprise or consist of allyloxy ethanol (AE).
[00157] As a twelfth example (example L), a silicone hydrogel contact lens comprises a polymeric lens body, which is the reaction product of a polymerizable composition, as described in Example A or B or C or D or E or F or G or H or I or J or K, wherein the polymerizable composition further comprises a hydrophobic monomer, or component of the hydrophobic monomer, which may comprise or consist specifically of ethylene glycidyl methacrylate (EGMA).
[00158] As a thirteenth example (Example M), a silicone hydrogel contact lens comprises a polymeric lens body, which is the reaction product of a polymerizable composition, as described in Example A or B or C or D or E or F or G or H or I or J or K or L, wherein the polymerizable composition further comprises a monomer or component of the hydrophilic monomer containing vinyl ether, for example, the monomer or monomer component hydrophilic containing vinyl ether may 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.
[00159] As a fourteenth example (example N), a silicone hydrogel contact lens comprises a polymeric lens body, which is the reaction product of a polymerizable composition, as described in Example A or B or C or D or E or F or G or H or I or J or K or L or M, where the contact lens has its wettable and ophthalmologically acceptable surfaces when the polymerizable composition used to form the lens is free of a modifying agent. - internal lens, or when the polymerizable composition used to form the polymeric lens body is free of an organic thinner, or when the polymeric lens body is extracted in a liquid free of a volatile organic solvent, or when the lens is free of a plasma surface treatment, or any combination thereof.
[00160] In any or each of the preceding examples A - N, as well as any or all of the other examples described herein, the amount of the first siloxane monomer can be from 20 to 45 units of the polymerizable composition. The amount of the first siloxane monomer can be 25 to 40 units of the polymerizable composition. The amount of the first siloxane monomer can be from 27 to 35 units of the polymerizable composition.
[00161] In any or each of the preceding examples A - N, as well as any or all of the other examples described herein, the amount of the optional second siloxane monomer can be from 1 to 20 units of the polymerizable composition. The amount of the second siloxane monomer can be from 2 to 15 units of the polymerizable composition. The amount of the second siloxane monomer can be 5 and 13 units of the polymerizable composition. In another example, the ratio between the units of the first siloxane monomer and the second siloxane can be at least 1: 1 or at least 2: 1.
[00162] In any or each of the preceding examples A - N, as well as any or all of the other examples described herein, the amount of monomer or component of the hydrophilic monomer present in the polymerizable composition can be from 1 to 60 units of the polymerizable composition. The hydrophilic monomer component can contain 4 to 60 units of the polymerizable composition. When the hydrophilic monomer consists of or includes VMA, it can be present in an amount of 30 units to 60 units. The VMA can be present in the polymerizable composition in an amount of about 40 units to about 50 units. When hydrophilic monomers, N, N-dimethylacrylamide (DMA), 2-hydroxyethyl methacrylate (HEMA), 2-hydroxybutyl methacrylate (HOB), or any combination thereof are present in the polymerizable composition, such as the hydrophilic monomer in component of the hydrophilic monomer, each or all may be present in amounts of about 3 to about 10 units.
[00163] In any or each of the preceding examples A - N, as well as any or all of the other examples described here, the amount of monomer or component of the hydrophobic monomer present in the polymerizable composition can be from 1 to 30 units of polymerizable composition. For example, the total amount of monomer or component of the hydrophobic monomer can be from about 5 to about 20 units of the polymerizable composition. In polymerizable compositions, where the hydrophobic MMA monomer is present as a hydrophobic monomer, or as part of the hydrophobic monomer component, MMA can be present in an amount of about 5 to about 20 units, or about 8 to about 15 units.
[00164] In any or each of the preceding examples A - N, as well as any or all of the other examples described herein, the amount of crosslinking agent or components of the crosslinking agent present in the polymerizable composition may be 0 , 01 to 4 units of the polymerizable composition. TEGDVE can be present in quantities of 0.01 to 1.0 units. EGDMA can be present in quantities of 0.01 to 1.0 units. TEGDMA can be present in quantities from 0.1 to 2.0 units. Each of these silicone-free crosslinking agents can be present alone or in any combination in the polymerizable composition.
[00165] In any or each of the preceding examples A - N, as well as any or all of the other examples described here, when the polymerizable composition contains EGMA, BVE, DEGVE, EGVE, or any combination thereof, each one of them are present in quantities of 1 units to 20 units of the polymerizable composition. EGMA can be present in a quantity of about 2 units to about 15 units. BVE can be present in an amount of 1 units to about 15 units. BVE can be present in an amount of about 3 units to about 7 units. DEGVE can be present in an amount of 1 units to about 15 units. DEGVE can be present in an amount of about 7 units to about 10 units. EGVE can be present in an amount of 1 units to about 15 units, or in an amount of about 3 units to about 7 units.
[00166] In any or each of the preceding examples AN, as well as any or all of the other examples described herein, the other optional components, such as initiators or initiator component, coloring agents or coloring agent components , UV-absorbing agents or components of the UV-absorbing agent, oxygen scavengers or components of the oxygen scavengers, chain transfer agents or chain transfer agent components, each can be present in amounts of about 0.01 units to about 3 units. An initiator or component of the initiator may be present in the polymerizable composition in an amount of 0.1 units to 1.0 units. When a thermal initiator or a component of the thermal initiator is present, such as Vazo-64, it can be present in an amount of about 0.3 to about 0.5 units. The coloring agent or components of the coloring agent can be present in amounts of 0.01 unit to 1.0 unit. When reactive dyes are used as coloring agents or as part of a coloring agent component, such as Reactive Blue 246 or Reactive Blue 247, each can be present in quantities of about 0.01 units. The UV-absorbing agents or components of the UV-absorbing agent can be present in quantities of 0.1 units to 2.0 units. For example, the UV absorbing agent (UV1) described in Examples 1 to 28 below, can be present in an amount of about 0.8 to about 1.0 units, such as 0.9 units, or the agent UV absorber (UV2) described in Examples 1 to 28 below, can be present in an amount of 0.5 units to 2.5 units, for example, from about 0.9 units to about 2 , 1 units. Oxygen scavengers or oxygen scavenger components can be present in quantities from 0.1 units to 1.0 units. As an example, when triphenylphosphine (TPP) or diphenyl (P-vinylphenyl) phosphine (PTPP) or any combination of these is used as an oxygen scavenger or an oxygen scavenger component in the polymerizable composition, each or combination it can be present in an amount from 0.3 parts units to 0.7 units, such as about 0.5 units. Chain transfer reagents or components of chain transfer reagents can be present in the polymerizable composition in an amount of 0.1 units to 2.0 units, and in many of Examples 1 to 28 below it is present in an amount of 0 , 2 units to 1.6 units. For example, the allyloxy ethanol (AE) chain transfer reagent may be present in an amount of about 0.3 to about 1.4 units.
[00167] In any or each of the preceding examples A - N, as well as any or all of the other examples described here, silicone hydrogel contact lenses can be free of a wetting agent, which is present in the polymerizable composition, either in the polymeric body of the lens, or in the silicone hydrogel contact lens. Likewise, the silicone hydrogel contact lens can have lens surfaces that are free from surface treatment or surface modification. However, in another example, the hydrogel silicone contact lens may include at least one wetting agent (i.e., a single wetting agent or two or more wetting agents present as a wetting agent component) in the polymerizable composition, in the polymeric lens body, or silicone hydrogel contact lens. The hydrogel silicone contact lens can have the lens surface treated or modified. In addition, or alternatively, any or each of the preceding examples A - N, as well as any or all of the other examples of silicone hydrogel contact lenses described herein, the contact lenses can be understood as free from a binding agent such as, for example, a form of boronic acid.
[00168] In another example, new polymerizable compositions are provided, including each and every polymerizable composition described here with reference to silicone hydrogel contact lenses and methods. Polymerizable compositions can be free of diluent in which an organic solvent is not contained, such as alcohols and the like, which can help to reduce the phase separation of the polymerizable composition. However, such polymerizable compositions without diluent can still contain one or more chain transfer agents, such as allyloxy ethanol. However, if desired, the polymerizable composition can include a diluent or a diluent component, which can be present in an amount of 1 to 20 units.
[00169] As described herein, the present silicone hydrogel contact lenses, which form the polymeric bodies of the lenses comprising units derived from a first siloxane monomer represented by the general formula (1) and a second siloxane monomer , or at least one crosslinking agent, or both; when fully hydrated, an average equilibrium water content (EWC) of about 30% w / w about 70% w / w, or an average oxygen permeability of at least 55 barrers, or mean forward contact angle dynamic by the captive bubble below 70 degrees, or an average static contact angle by the captive bubble below 55 degrees, or any combination of these, based on the mean values determined for at least 20 individual lenses in the batch. Thus, the present disclosure also refers to a group of silicone hydrogel contact lenses.
[00170] As used herein, a batch of silicone hydrogel contact lenses refers to a group of 2 or more silicone hydrogel contact lenses, and often a group refers to at least 10, or at least at least 100, or at least 1000 silicone hydrogel contact lenses. According to the present disclosure, a batch of silicone hydrogel contact lenses comprises a plurality of any of the silicone hydrogel contact lenses described herein.
[00171] In one example, the batch of silicone hydrogel contact lenses comprises a plurality of contact lenses, in accordance with the present disclosure, in which the batch of silicone hydrogel contact lenses has at least two selected values from the average oxygen permeability of at least 55 barrers, an average tensile modulus of about 0.2 MPa to about 0.9 MPa, when fully hydrated, when an average dynamic forward contact angle through the bubble less than 70 degrees, when fully hydrated, and an average static contact angle through the captive bubble less than 55 degrees, when fully hydrated, based on the mean values determined for at least 20 individual lenses in the batch .
[00172] In one example, the batch of silicone hydrogel contact lenses comprises a plurality of contact lenses, where each of the contact lenses comprises a polymeric lens body, which is the reaction product of a polymerizable composition, where said polymerizable composition comprises: (a) a first siloxane monomer represented by the general formula (1):
where m of formula (1) represents an integer from 3 to 10, n of formula (1) represents an integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 atoms of carbon, and R2 of the formula (1) is a hydrogen atom or a methyl group, and (b) a second siloxane monomer which is a capped polydimethylsiloxane (end-capped) with methacrylate in two terminations with an average molecular weight of at least 7,000 Daltons, where silicone hydrogel contact lenses, when fully hydrated, have an energy loss of about 25% to about 45%, where the batch of silicone hydrogel contact lenses have, when completely hydrated, an average equilibrium water content (EWC) of about 30% w / w to about 70% w / w, or an average oxygen permeability of at least 55 barrers, or an average dynamic forward contact angle through the bubble less than 70 degrees, or an average static contact angle through the captive bubble below 55 degrees, or any combination thereof, based on the averages of the values determined for at least 20 individual lenses in the lot. In one example, when a group of lenses is initially tested shortly after manufacture and then tested again at a later time, it may show a change in its average physical dimensions. As the batches of lenses, according to the present disclosure, are dimensionally stable, they can present an acceptable level of change in their average physical dimensions. As used here, it is understood that the dimensional stability variance is a variation of a value of a physical dimension and a value of the physical dimension determined when the batch of lenses is initially tested right after its manufacture, and the determined physical dimension value, when the lens lot is tested again at a later time. The later moment can be, for example, from at least 2 weeks after the initial moment, up to 7 years after the initial moment. Lot hydrogel silicone contact lenses have an average variance in dimensional stability of less than plus or minus three percent (± 3.0%) based on the average lens diameter measurements of a representative number of lenses a from the batch, such as, for example, 20 lenses from the batch. For a batch of lenses, a dimensional stability of average variance less than plus or minus three percent (± 3.0%), where the average variance of dimensional stability is the variance of a physical dimension value, when measured in an initial moment within the first day from the date of manufacture of the lens batch, and a second moment, which is 2 weeks to six years after the initial moment, when the batch is stored at room temperature , or, when the batch is stored at a higher temperature (that is, under conditions of accelerated shelf life testing), the second moment is a representative point of the time of storage of the batch from 2 weeks to 7 years at room temperature, the batch is then considered to be dimensionally stable. In one example, accelerated shelf-life testing conditions that are especially useful for determining the average dimensional stability variance are 4 weeks at 70 ° C, although other periods of time and other temperatures may be used . The average variation in dimensional stability is determined by calculating the average deviations from the individual dimensional stability for each of the representative lenses, using the actual diameters of the representative lenses initially measured (Original diameter), and the actual diameters of the representative lenses measured. after storage at room temperature or under accelerated shelf-life conditions (final diameter). The representative lenses measured initially and the representative lenses measured after storage may be the same or may be different. As used here, the average variance of dimensional stability is represented as a percentage (%). The individual variances of dimensional stability are determined using the following equation (A):

[00173] On average, the diameters of the hydrogel silicone contact lenses in the batch vary by less than three percent, in any direction of a target value (± 3.0%). As an example, if a contact lens has a target diameter (string diameter) of 14.20 mm, the present batch of silicone hydrogel contact lenses will have an average diameter (population average in the batch) of 13.77 mm at 14.63 mm. In one example, the dimensional stability variance is less than plus or minus two percent (± 2.0%). As an example, if a contact lens has a target diameter (string diameter) of 14.20 mm, the present batch of silicone hydrogel contact lenses will have an average diameter (population average in the batch) of 13.92 mm at 14.48 mm. Preferably, the average diameter of the batch of silicone hydrogel contact lenses does not vary by more or less 0.20 mm from the target diameter, which is normally 13.00 mm to 15.00 mm.
[00174] In accelerated shelf-life tests, the average variation in dimensional stability can be determined in contact lenses that have been stored for a period of time at an elevated temperature, such as above 40 ° C, including, for example, 50 ° C or 55 ° C, or 65 ° C, or 70 ° C or 80 ° C or 95 ° C, and so on. Or, the average dimensional stability can be determined on contact lenses that have been stored for a period of time at room temperature (for example, about 20 to 25 ° C).
[00175] For accelerated shelf-life tests, the following formula can be used to determine the number of months of storage at a particular temperature, which are equivalent to storage for a desired period of time, at room temperature : Desired shelf life = [N x 2y] + n (B), where N = number of months of storage under accelerated conditions 2y = acceleration factor y = (test temperature - 25 ° C) / 10 ° C n = lens age (in months) at start of test
[00176] Based on this equation, the following storage times have been calculated: 6 months of storage at 35 ° C is equivalent to one year of aging at 25 ° C, 3 months of storage at 45 ° C is equivalent to 1 year of aging at 25 ° C, 3 months of storage at 55 ° C is equivalent to 2 years of aging at 25 ° C, and 3 months of storage at 65 ° C is equivalent to 4 years of aging at 25 ° C .
[00177] The present disclosure also provides methods of manufacturing silicone hydrogel contact lenses. According to the present teachings, the method comprises providing a polymerizable composition. The polymerizable composition, or a contact lens formulation, comprises a first siloxane monomer represented by the general formula (1):
where m of formula (1) represents an integer from 3 to 10, n of formula (1) represents an integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 atoms of carbon, and each R2 of formula (1) is, independently, either a hydrogen atom or a methyl group. In addition to the first siloxane monomer of the general formula (1), the polymerizable composition further comprises a second siloxane monomer, or at least one cross-linking agent, or both. The ingredients of the polymerizable composition can be present in amounts such that the resulting hydrogel silicone contact lenses have, when fully hydrated, an equilibrium water content (EWC) of about 30% w / w about 70 % w / w, such as, for example, from about 45% w / w to about 65% w / w or from about 50% w / w to about 67% w / w, or from about 50% to about 63%, or about 55% w / w and about 65% w / w.
[00178] The method can also comprise a polymerization step of the polymerizable composition to form a polymeric lens body. The polymerization step of the polymerizable composition can be carried out in a set of contact lens molds. The polymerizable composition can be molded between molds formed by a thermoplastic polymer. The thermoplastic polymer used to form the molding surfaces of the mold may comprise a polar polymer, or may comprise a non-polar polymer. In addition, the polymerizable composition can be formed on a lens using various methods known to those skilled in the art, such as spin casting, injection molding, which form a polymerized rod that is subsequently turned to form a body of the lens, etc.
[00179] The method can also comprise the contact of the polymeric body of the lens with a washing liquid to remove the extractable material, such as the unreacted monomers, the non-crosslinked materials that would otherwise not be physically immobilized in the polymeric body of the lens, thinners and the like. The washing liquid can be a liquid free of a volatile organic solvent, or it can comprise a volatile organic solvent (for example, it can be a volatile organic solvent or a solution of a volatile organic solvent).
[00180] According to the present disclosure, the polymeric lens body can be packaged together with a contact lens packaging solution in a contact lens packaging, such as a protective blister pack or vial. glass. After packaging, the packaging can be sealed and the polymeric lens body and the contact lens packaging solution can be sterilized, for example, by autoclaving the sealed packaging, to produce a hydrogel silicone contact lens product. .
[00181] The present method may also include repeating the steps to produce a plurality of silicone hydrogel contact lenses.
[00182] In any of the present methods, namely a first siloxane monomer can be supplied in the polymerizable composition, such as a monomer represented by formula (1), where m of formula (1) is 4, n of formula (1) is 1, R1 of formula (1) is a butyl group, and each R2 of formula (1) is, independently, either a hydrogen atom or a methyl group.
[00183] In any of the present methods, the second siloxane monomer or at least an optional third siloxane monomer can be represented by formula (2):
where R1 of formula (2) is selected from either the hydrogen atom or a methyl group, R2 from formula (2) is selected from either a hydrogen atom or a hydrocarbon group having from 1 to 4 carbon atoms; m of formula (2) represents an integer between 0 and 10, n of general formula (2) represents an integer from 4 to 100; a and b represent whole numbers of 1 or more, a + b is equal to 20 to 500, b / (a + b) is equal to 0.01 to 0.22, and the siloxane unit configuration includes a random configuration. As an example, the siloxane monomer can be represented by the general formula (2), where m of formula (2) is 0, n of formula (2) is an integer from 5 to 15, a is an integer of 65 to 90, b is an integer from 1 to 10, R1 of formula (2) is a methyl group, and R2 of formula (2) is either a hydrogen atom or a hydrocarbon group with 1 to 4 carbon atoms .
[00184] In the present methods, the step of contacting the polymeric body of the lens with a washing liquid can be understood as being an extraction step, because the extractable materials can be removed from the polymeric body of the lens during the process . When the washing liquid comprises water or an aqueous solution free of volatile organic solvent, the contact step is understood to be both an extraction step and a hydration step. In another example of method, the contact step may comprise contacting the polymeric body of the lens with a washing liquid comprising a volatile organic solvent, such as a liquid containing a primary alcohol, such as methanol, ethanol, n-propyl alcohol, and the like. The washing liquid can contain a secondary alcohol, such as isopropyl alcohol, and the like. The use of a washing liquid containing one or more volatile organic solvents can be useful in removing hydrophobic materials from the polymeric body of the lens, and therefore can increase the wettability of the resulting silicon hydrogel contact lens. . Such methods can be understood as extraction steps based on volatile organic solvents. In other methods, the contact step comprises bringing the polymeric body of the lens into contact with an aqueous washing liquid, which is free of a volatile organic solvent. Such methods can be understood as fully aqueous washing steps, since volatile organic solvents are not included in the washing liquid. The water-based washing liquid that can be used in such methods includes water, such as deionized water, saline solutions, buffered solutions, or aqueous solutions containing surfactants or other non-volatile ingredients that can improve the removal of hydrophobic components from the polymeric bodies of the contact lenses, or they can reduce the distortion of the polymeric bodies of the contact lenses, compared to using only deionized water.
[00185] After washing, contact lenses can be placed in packaging, such as plastic blister packs, with a packaging solution, such as a buffered saline solution, which may or may not contain surfactants, anti-inflammatory agents, anti-microbial agents, contact lens wetting agents, and the like, and can be sealed and sterilized. The packaging solution used to package the hydrogel silicone contact lenses of the present disclosure may comprise a wetting agent to increase the humidity of the lens surfaces. However, it should be understood that the surfaces of the silicone hydrogel lenses of the present disclosure have wettable and ophthalmologically acceptable surfaces prior to contact with a packaging solution comprising a wetting agent, since the use of a wetting agent in the solution of packaging is only to increase the humidity of the surfaces are already wettable and ophthalmologically acceptable, and therefore it is not necessary to provide it to the contact lens with a wettable and ophthalmologically acceptable surface.
[00186] In another example, new polymerizable compositions are provided, including each polymerizable composition described herein in reference to silicone hydrogel contact lenses and methods. The polymerizable compositions can be diluent or solvent free, that is, they do not contain an organic solvent, such as alcohols and the like, which can help to reduce the phase separation of the polymerizable composition. However, such polymerizable compositions without diluent may still contain one or more chain transfer agents, such as allyloxy ethanol. However, if desired, the polymerizable composition can include a diluent, which can be present in an amount of 1 to 20 units.
[00187] As described herein, the present silicone hydrogel contact lenses, which consist of polymeric lens bodies, comprise units derived from a first siloxane monomer represented by the general formula (1), a second siloxane monomer which is a end capped polydimethylsiloxane with methacrylate in two endings with an average molecular weight of at least 7,000 Daltons. In one example, the second siloxane monomer can be a second siloxane monomer represented by the general formula (2), and silicone hydrogel lenses, when fully hydrated, have energy losses of around 25% at about from 45%, or from about 27% to about 40%, or from about 30% to about 37%. Thus, the present disclosure also relates to a batch of silicone hydrogel contact lenses.
[00188] As used herein, a batch of silicone hydrogel contact lenses refers to a group of 2 or more silicone hydrogel contact lenses, and often a group refers to at least 10, or at least at least 100, or at least 1,000 silicone hydrogel contact lenses. According to the present disclosure, a batch of silicone hydrogel contact lenses comprises a plurality of silicone hydrogel contact lenses described herein.
[00189] In one example, the batch of silicone hydrogel contact lenses comprises a plurality of contact lenses, in accordance with the present disclosure, where the batch of silicone hydrogel contact lenses, when completely hydrated, have a average energy loss of about 25% to about 45%, or about 27% to about 40%, or about 30% to about 37%.
[00190] In another example, the lot of silicone hydrogel contact lenses comprises a plurality of contact lenses, in accordance with the present disclosure, where the lot of silicone hydrogel contact lenses, when completely hydrated, have an equilibrium water content (EWC) of 30% to 70%, or an average oxygen permeability of at least 55 barrers, or an average tensile module of about 0.2 MPa at about 0.9 MPa, an average dynamic forward contact angle through the captive bubble below 70 degrees, or an average static contact angle through the captive bubble below 55 degrees, based on the mean values determined for at least 20 individual lenses in the lot.
[00191] In yet another example, batch contact lenses can have an average variance of dimensional stability based on the average lens diameter measurements of a representative number of lenses from the batch, such as, for example , 20 lenses from the lot. For a lot of lenses, an average dimensional stability variance of less than plus or minus three percent (± 3.0%), over a period of 2 weeks to 7 years when stored at room temperature or, when stored under term test Accelerated validity conditions, for a period of time and temperature equivalent to storage from 2 weeks to 7 years at room temperature, are considered to be a dimensionally stable batch. In one example, accelerated shelf-life tests are especially useful for determining the average variance of dimensional stability is 4 weeks at 70 ° C, although other periods of time and temperatures may be used. The average variation in dimensional stability is determined by calculating the average deviations of the individual dimensional stability for each of the representative lenses, using the actual diameters of the representative lenses initially measured (Original diameter), and the actual diameters of the representative lenses measured after storage at room temperature or under accelerated shelf-life conditions (final diameter). As used here, the average variance of dimensional stability is represented as a percentage (%). The individual variances of dimensional stability are determined using the following equation (A):

[00192] On average, the diameters of the silicone hydrogel contact lenses in the batch vary by less than three percent, in either direction of a target value (± 3.0%). As an example, if a contact lens has a target diameter (string diameter) of 14.20 mm, the present batch of silicone hydrogel contact lenses will have an average diameter (population average in the batch) of 13.77 mm at 14.63 mm. In one example, the dimensional stability variance is less than plus or minus two percent (± 2.0%). As an example, if a contact lens has a target diameter (string diameter) of 14.20 mm, the present batch of silicone hydrogel contact lenses will have an average diameter (population average in the batch) of 13.92 mm at 14.48 mm. Preferably, the average diameter of the batch of silicone hydrogel contact lenses does not vary by more or less 0.20 mm from the target diameter, which is normally 13.00 mm to 15.00 mm.
[00193] In accelerated shelf-life tests, the average variation in dimensional stability can be determined in contact lenses that have been stored for a period of time at an elevated temperature, such as above 40 ° C, including, for example, 50 ° C or 55 ° C, or 65 ° C, or 70 ° C or 80 ° C or 95 ° C, and so on. Or, the average dimensional stability can be determined on contact lenses that have been stored for a period of time at room temperature (for example, about 20 to 25 ° C).
[00194] For accelerated shelf-life tests, the following formula can be used to determine the number of months of storage at a particular temperature, which are equivalent to storage for a desired period of time, at room temperature : Desired shelf life = [N x 2y] + n (B), where N = number of months of storage under accelerated conditions 2y = acceleration factor y = (test temperature - 25 ° C) / 10 ° C n = lens age (in months) at start of test
[00195] Based on this equation, the following storage times have been calculated: 6 months of storage at 35 ° C is equivalent to one year of aging at 25 ° C, 3 months of storage at 45 ° C is equivalent to 1 year of aging at 25 ° C, 3 months of storage at 55 ° C is equivalent to 2 years of aging at 25 ° C, and 3 months of storage at 65 ° C is equivalent to 4 years of aging at 25 ° C .
[00196] The present disclosure also provides methods of manufacturing silicone hydrogel contact lenses. According to the present teachings, the method comprises providing a polymerizable composition. The polymerizable composition, or a contact lens formulation, comprises a first siloxane monomer represented by the general formula (1):
where m of formula (1) represents an integer from 3 to 10, n of formula (1) represents an integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 atoms of carbon, and each R2 of formula (1) is, independently, either a hydrogen atom or a methyl group. The polymerizable composition further comprises a second siloxane monomer. Silicone hydrogel contact lenses manufactured using the methods of the present disclosure, have energy losses of about 25% to about 45%, when fully hydrated, such as, for example, energy losses of about 27% to about 40% when fully hydrated, or energy losses of about 30% to about 37%, when fully hydrated. In one example, the second siloxane monomer may be a siloxane monomer having more than one functional group and having an average molecular weight of at least 3,000 Daltons. In one example, the method is a method of fabricating a hydrogel silicone contact lens, which comprises: providing a miscible polymerizable composition, wherein said polymerizable composition comprises: (a) a first re siloxane monomer - presented by the general formula (1):
where m of formula (1) represents an integer from 3 to 10, n of formula (1) represents an integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 atoms of carbon, and R2 of the formula (1) is a hydrogen atom or a methyl group, and (b) a second siloxane monomer which is a capped polydimethylsiloxane (end-capped) with methacrylate in two terminations with an average molecular weight of at least 7,000 Daltons. The polymerization of the polymerizable composition in a set of molds for contact lenses forms a polymeric lens body; which is then placed in contact with a washing liquid to remove the extractable material from the polymeric lens body, and the polymeric lens body is then packaged in a contact lens packaging solution in a contact lens packaging, where silicone hydrogel contact lenses have an energy loss of about 25% to about 45% when completely hydrated.
[00197] The method can also comprise a polymerization step of the polymerizable composition to form a polymeric lens body. In the methods described in Examples 1 to 28 of the present disclosure, the polymerization step of the polymerizable composition is conducted in a set of molds for contact lenses. The polymerizable composition can be molded between molds formed by a thermoplastic polymer. The thermoplastic polymer used to form the molding surfaces of the mold may comprise a polar polymer, or may comprise a non-polar polymer. In other methods, the polymerizable composition can be formed on a lens using various methods known in the art, such as spin casting, injection molding, which form a polymerized rod that is subsequently turned to form a lens body , etc.
[00198] The method can also comprise the contact of the polymeric body of the lens with a washing liquid to remove the extractable material, such as the unreacted monomers, the non-crosslinked materials that would otherwise not be physically immobilized in the polymeric body of the lens, thinners and the like.
[00199] In one example, the method is a method of manufacturing a silicone hydrogel contact lens, which comprises: providing a miscible polymerizable composition, wherein said polymerizable composition comprises: (a) a first siloxane monomer represented by the general formula (1):
where m of formula (1) represents an integer from 3 to 10, n of formula (1) represents an integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 atoms of carbon, and R2 of the formula (1) is a hydrogen atom or a methyl group, and (b) a second siloxane monomer which is a capped polydimethylsiloxane (end-capped) with methacrylate in two terminations with an average molecular weight of at least 7,000 Daltons. The polymerization of the polymerizable composition in a set of molds for contact lenses forms a polymeric lens body; which is then placed in contact with a washing liquid to remove the extractable material from the polymeric body of the lens, where the contact step comprises bringing the polymeric body of the lens into contact with a washing liquid, which is free of a volatile organic solvent, and then pack the polymeric lens body in a contact lens packaging solution in a contact lens packaging, where silicone hydrogel contact lenses have a loss of energy from about 25% to about 45% when fully hydrated.
[00200] According to the present method, the polymeric lens body can be packaged in a contact lens packaging solution in a contact lens packaging, such as a protective blister or glass bottle. After packaging, the packaging can be sealed and the polymeric lens body and contact lens packaging solution can be sterilized, for example, by autoclaving the sealed packaging.
[00201] The present method may also include 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, for example, an average energy loss of about 27% to about 40%, when fully hydrated, or an average energy loss of about 30% to around 37%, when fully hydrated.
[00202] In one example, the method is a method of making a silicone hydrogel contact lens, which comprises: providing a miscible polymerizable composition, wherein said polymerizable composition comprises: (a) a first siloxane monomer represented by the general formula (1):
where m of formula (1) represents an integer from 3 to 10, n of formula (1) represents an integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 atoms of carbon, and R2 of the formula (1) is a hydrogen atom or a methyl group, and (b) a second siloxane monomer which is a capped polydimethylsiloxane (end-capped) with methacrylate in two terminations with an average molecular weight of at least 7,000 Daltons. The polymerization of the polymerizable composition in a set of molds for contact lenses forms a polymeric lens body; which is then placed in contact with a washing liquid to remove the extractable material from the polymeric lens body, and the polymeric lens body is then packaged in a contact lens packaging solution in a contact lens packaging, where silicone hydrogel contact lenses have an energy loss of about 27% to about 40%, or about 30% to about 37%, when fully hydrated.
[00203] In another example, the method is a method of manufacturing a silicone hydrogel contact lens, which comprises: providing a miscible polymerizable composition, wherein said polymerizable composition comprises: (a) a first siloxane monomer represented by general formula (1):
where m of formula (1) represents an integer from 3 to 10, n of formula (1) represents an integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 atoms of carbon, and R2 of the formula (1) is a hydrogen atom or a methyl group, and (b) a second siloxane monomer which is a capped polydimethylsiloxane (end-capped) with methacrylate in two terminations with an average molecular weight of at least 7,000 Daltons. The polymerization of the polymerizable composition in a set of molds for contact lenses forms a polymeric lens body; which is then placed in contact with a washing liquid to remove the extractable material from the polymeric lens body, and the polymeric lens body is then packaged in a contact lens packaging solution in a contact lens packaging, where silicone hydrogel contact lenses have an energy loss of about 25% to about 45%, when fully hydrated, and the energy loss is calculated using equation (B): ((Energy 0 to 100% deformation - Energy 100 to 0% deformation) / Energy 0 to 100% deformation) x100 (B) where the energy 0 to 100% deformation represents the energy applied to stretch a lens sample at 100% deformation at a constant rate, and the energy from 100 to 0% deformation represents the energy released when the lens sample returns to 0% from 100% deformation.
[00204] Optionally, the polymeric lens bodies of the plurality of silicone hydrogel contact lenses can have a dimensional stability variance less than plus or minus three percent, over a period of 2 weeks to 7 years, where said dimensional stability variance (%) is determined from the lens diameter by the following equation (B):

[00205] In another example, the method is a method of manufacturing a silicone hydrogel contact lens, which comprises: providing a miscible polymerizable composition, wherein said polymerizable composition comprises:
where m of formula (1) represents an integer from 3 to 10, n of formula (1) represents an integer from 1 to 10, R1 of formula (1) is an alkyl group having from 1 to 4 atoms of carbon, and R2 of the formula (1) is a hydrogen atom or a methyl group, and the first siloxane monomer has an average molecular weight of 400 Daltons to 700 Daltons, and (b) a second siloxane monomer which is a polydi- methylsiloxane capped (end-capped) with methacrylate in two terminations with an average molecular weight of at least 7,000 Daltons. The polymerization of the polymerizable composition in a set of molds for contact lenses forms a polymeric lens body; which is then placed in contact with a washing liquid to remove the extractable material from the polymeric lens body, and the polymeric lens body is then packaged in a contact lens packaging solution in a contact lens package, where silicone hydrogel contact lenses have an energy loss of about 25% to about 45%, when fully hydrated
[00206] In any of the present methods, namely a first siloxane monomer can be supplied in the polymerizable composition, such as a monomer represented by formula (1) where m of formula (1) is 4, n of formula (1) is 1, R1 of formula (1) is a butyl group, and each R2 of formula (1) is, independently, either a hydrogen atom or a methyl group.
[00207] In any of the present methods, the second siloxane monomer can be represented by the formula (2):
where R1 of formula (2) is selected from either the hydrogen atom or a methyl group, R2 from formula (2) is selected from either a hydrogen atom or a hydrocarbon group having from 1 to 4 carbon atoms; m of formula (2) represents an integer between 0 and 10, n of general formula (2) represents an integer from 4 to 100; a and b represent whole numbers of 1 or more, a + b is equal to 20 to 500, b / (a + b) is equal to 0.01 to 0.22, and the siloxane unit configuration includes a random configuration. As an example, the siloxane monomer can be represented by the general formula (2), where m of formula (2) is 0, n of formula (2) is an integer from 5 to 15, a is an integer of 65 to 90, b is an integer from 1 to 10, R1 of formula (2) is a methyl group, and R2 of formula (2) is either a hydrogen atom or a hydrocarbon group with 1 to 4 carbon atoms .
[00208] In the present methods, the step of contacting the polymeric body of the lens with a washing liquid can be understood as being an extraction step, because the extractable materials can be removed from the polymeric body of the lens. In another example of method, the contact step comprises bringing the polymeric lens body into contact with a washing liquid comprising a volatile organic solvent, such as a liquid containing a primary alcohol, such as methanol, ethanol, alcohol -propyl, and the like. The washing liquid may contain a secondary alcohol, such as isopropyl alcohol, and the like. The use of a washing liquid containing one or more volatile organic solvents can be useful for the removal of hydrophobic materials from the polymeric body of the lens. These extraction steps can be understood as alcohol-based extraction steps. In another example of method, the contact step may comprise contacting the polymeric lens body with an aqueous washing liquid, which is free of a volatile organic solvent. These extraction steps can be understood as water-based extraction steps. The water-based washing liquid that can be used in such methods includes water, such as deionized water, saline solutions, buffered solutions, or aqueous solutions containing surfactants or other non-volatile ingredients that can improve the removal of hydrophobic components from the polymeric bodies of the contact lenses, or they can reduce the distortion of the polymeric bodies of the contact lenses, compared to using only deionized water. In one example, when washed with a water-based washing liquid, the surfaces of the lens bodies of the present disclosure may have wettable and ophthalmologically acceptable surfaces.
[00209] After washing, contact lenses can be placed in packaging, such as plastic blister packs, with a packaging solution, such as a buffered saline solution, which may or may not contain surfactants , anti-inflammatory agents, anti-microbial agents, contact lens wetting agents, and the like, and can be sealed and sterilized. EXAMPLES
[00210] Examples 1 to 28 below illustrate certain aspects and advantages of the present invention, therefore, they should not be understood as limitations.
[00211] As can be easily determined by an evaluation of the Examples below, all formulations of the Examples are free of an organic diluent. In addition, all the formulations of the Examples are free of N, N-dimethylacrylamide (DMA). In addition, all the formulations in the Examples below are free of a polymeric wetting agent. In addition, all the formulations of the Examples comprise at least one hydrophilic amide monomer with an N-vinyl group. Most of the formulations of the Examples comprise a second siloxane which is a polydimethylsiloxane capped (end-capped) with methacrylate in two terminations with an average molecular weight of at least 7,000 Daltons.
[00212] The following chemicals, which are referred to in Examples 1 to 28, can be referred to by their abbreviations. Si1: 2-propenoic acid, 2-methyl-, 2- [3- (9-butyl-1,1,3,3,5,5,7,7,9,9- decamethylpentasiloxane-1-yl) propoxy] ethyl ester (CAS number :: 1052075-57-6). (Si1 was obtained from Shin-Etsu Chemical Co., Ltd., Tokyo, Japan, under product number X-22-1622). Si2: α, w-bis (methacryloxypropyl) -poly (dimethylsiloxane) - poly (w-methoxy-poly (ethylenegylcol) propylmethylsiloxane) (the synthesis of this compound can be carried out as described in US 2009 / 0.234.089, which is incorporated herein by reference) Si3: poly (dimethylsiloxane), finished methacryloxypropyl (CAS number :: 58130-3-3; DMS-R18 available from Gelest) VMA: N-vinyl-N-methylacetamide (CAS number: 003195786) DMA: N , N-dimethylacrylamide (CAS number: 2680/03/07) HEMA: 2-hydroxyethyl methacrylate (CAS number: 868-77-9) HOB: 2-hydroxylbutyl methacrylate (CAS number: 29008-35-3) EGMA: ethylene glycidyl 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 (Number CAS: 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) TEGD VE: triethylene glycol divinyl ether (CAS number: 765-12-8) AE: 2-Allyloxy ethanol (CAS number: 111-45-5) V-64: 2,2 'methyl azobis propanonitrile (CAS number: 78-67 -1) UV1: 2 - (4-benzoyl-3-hydroxyphenoxy) ethyl acrylate (CAS number: 16432-81- 8) UV2: 2 - (3 - (2H-benzotriazol-2-yl) -4-hydroxy- phenyl) ethyl methacrylate (CAS number: 96478-09-0) RBT1: 1,4-Bis [4 - (2-methacryloxyethyl) -phenylamine] anthraquinone (CAS number: 121888-69-5) RBT2: 1, 4-Bis [(2-hydroxyethyl) -amine] -9.10 anthracenedodione-bis (2-propenoic) ester (CAS Reg. No. 109561071) TPP: triphenyl phosphine (CAS number: 603-35-0) PTPP: TPP polymerizable: diphenyl (P-vinylphenyl) phosphine (CAS number: 40538- 11-2) Procedure for Testing and Manufacturing of Hydro-Gel Silicone Contact Lens
[00213] The chemical compounds set forth in Examples 1 to 28 were, for each example, weighed in quantities corresponding to the units described, and were combined to form a mixture. The mixture was filtered through a 0.2 - 5.0 μ syringe filter inside a bottle. The mixtures were stored for up to about 2 weeks. Mixtures are understood to be the precursor polymerizable compositions of silicone hydrogel contact lenses, or as used herein, polymerizable compositions. In Examples 1 to 28, the indicated amounts of the ingredients are given as units by weight of the polymerizable composition.
[00214] A volume of the polymerizable composition was molded by placing the composition in contact with the lens defining surface of the female mold. In all Examples 1 to 28 below, the molding surface of the female mold was formed from a non-polar resin, specifically polypropylene. The male mold was placed in contact with the female mold to form a contact lens mold assembly comprising a cavity in the shape of the contact lens containing the polymerizable composition. In Examples 1 to 28 below, the forming surface of the male mold was formed from a non-polar resin, specifically, polypropylene.
[00215] The sets of molds for contact lenses were placed in an oven under nitrogen flow (nitrogen flushed oven) in order to allow the polymerizable composition to cure thermally. For all Examples 1 to 28, the contact lens mold sets were exposed to temperatures of at least about 55 ° C for about 2 hours. Examples of curing profiles that can be used to cure silicone hydrogel contact lenses described here include exposing contact lens mold sets to temperatures of 55 ° C for 40 minutes, to 80 ° C for 40 minutes and 100 ° C for 40 minutes. Other contact lenses can be made with the same curing profile, but instead of the first temperature being 55 ° C, this can be 65 ° C.
[00216] After the polymerization of the polymerizable composition forms a polymeric lens body contained in a mold set, the mold sets for contact lenses were demoulded to separate the male and female molds. The polymeric body of the lens remained adhered to the male or female mold. A dry demoulding process, where the mold sets are not brought into contact with a liquid medium, can be used, or a wet demolding process, where the mold set is brought into contact with a liquid medium, such as, for example, water or an aqueous solution, can be used. A mechanical dry demoulding process may involve applying mechanical force to part of one or both molds in order to separate the molds. In all of Examples 1 to 28 below, a dry demolding process was used.
[00217] The polymeric lens body was then laminated (delensed) from the male or female mold to produce a laminated polymeric lens body (delensed). In an example of a delensing method, the polymeric lens body can be laminated from the male mold using a dry delensing process, as well as by manually peeling the lens from the male mold or by compression of the male mold by directing a gas to the male mold and the polymeric body of the lens, which raises the dry polymeric body of the lens with a vacuum device from the male mold, which is then discarded. In other methods, the polymeric body of the lens can be laminated (delensed) using a wet lamination (delensing) process that causes the dry polymeric body of the lens to come into contact with a liquid release medium, such as water or an aqueous solution. For example, a male mold with the polymeric lens body attached can be immersed in a container containing liquid until the polymeric lens body separates from the male mold. Or, 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. In Examples 1 to 28 below, a dry rolling process (delensing) was used. After separation, the lens body can be lifted manually from the mold using tweezers or using a vacuum device and placed inside a tray.
[00218] The laminated lens product (delensed) was then washed to remove extractable materials from the polymeric body of the lens, and hydrated. Extractable materials include polymerizable components, such as, for example, monomers or crosslinking agents, or any optional polymerizable ingredients, such as paints or UV blockers, or combinations thereof, present in the polymerizable composition that remain present in the poly body - lens lens in an unreacted form, in a form that reacted partially, or in a non-crosslinked form, or any combination thereof, after polymerization of the lens body and before extraction of the lens body. Extractable materials may also include any non-polymerizable ingredients present in the polymerizable composition, for example, any optional non-polymerizable agents, or coloring agents or UV blockers, or diluents, or chain transfer agent, or any combination thereof. , remaining in the polymeric body of the lens after polymerization of the polymeric body of the lens, but before extraction of the polymeric body from the lens.
[00219] In another method, such as a method that involves lamination (delensing) by compression of the male mold or directing a gas to the male mold, the polymerized bodies of the laminated contact lenses (delensed) can be placed in carrier cavities or lens trays where the polymeric bodies of the laminated lens (delensed) can then come into contact with one or more volumes of an extraction liquid, such as an aqueous extraction liquid free of a volatile organic solvent, for example , deionized water, or an aqueous solution of a surfactant, such as Tween 80, or an extraction liquid based on organic solvent, such as ethanol, or an aqueous solution of a volatile organic solvent, such as ethanol.
[00220] In other methods, such as those involving wet lamination (delensing) through contact of the lens and the mold with a liquid release medium, the polymerized bodies of the laminated contact lenses (delensed) can be washed to remove the components extractable from the lens bodies using a washing liquid that is free of a volatile organic solvent, such as a lower alcohol, for example, methanol, ethanol, or any combination thereof. For example, the polymerized bodies of laminated (de-lensed) contact lenses can be washed to remove extractable components from the contact lens bodies with an aqueous washing liquid free of volatile organic solvent, such as, for example, deionized water, or a surfactant solution, or a saline solution, or a buffer solution, or any combination of these. Washing can take place in the final contact lens package, or it can take place in a washing tray or in a washing tank.
[00221] In the following Examples 1 to 28, after the steps of dry demoulding and dry lamination (delensing), the bodies of the dried laminated (de-lensed) lenses were placed in the cavities of the trays, and the polymeric bodies of the lenses were laminated (delensed) and hydrated by contacting the polymeric bodies of the lenses with one or more volumes of extraction liquids. The extraction and hydration liquids used in the extraction and hydration process consisted of a) a combination of extraction liquids based on volatile organic solvents and hydration liquids free of volatile organic solvents, or b) extraction and hydration liquids free of volatile organic solvents, that is, the extraction and hydration liquids are totally water based. Specifically, in Examples 1 to 5 below, the extraction and hydration process is formed by at least 2 extraction steps in separate parts of ethanol, followed by at least one step of extracting a part of 50: 50 in ethanol p / p: solution of Tween 80 in water, followed by at least three stages of extraction and hydration in separate parts of a solution of Tween 80 in deionized water, where each stage of extraction or extraction and hydration lasted about 5 minutes to 3 hours. In Examples 6 - 25 below, the extraction and hydration process used is based at least on three extraction and hydration steps in separate parts of a Tween 80 solution in deionized water, where the temperature of the Tween solution 80 of the parts ranged from room temperature to about 90 ° C, where each hydration and extraction step lasted about 15 minutes to about 3 hours.
[00222] The washed, extracted and hydrated lenses were then individually placed in protective contact lens blisters with a saline phosphate buffer packaging solution. The protective packaging (blister) was sealed and sterilized by autoclaving.
[00223] After sterilization, properties, such as the contact angle of the lenses, including the dynamic and static contact angle, oxygen permeability, ionic flux, modulus, elongation, tensile strength, the content of water, and the like were determined, as described herein.
[00224] For the contact lenses present, the contact angles, including dynamic and static contact angles, can be determined using routine methods, known to people with knowledge in the art. For example, the advanced contact angle and the recessed contact angle of the contact lenses provided here can be measured using a conventional drop-shaped method, such as the sessile drop method or the captive bubble method.
[00225] In the following Examples 1 to 28, the forward and backward contact angles of the silicone hydrogel contact lenses were determined using a DSA 100 Kruss instrument (Kruss GmbH, Hamburg), and as described in DA Brandreth: "" Dynamic contact angles and contact angle hysteresis ", Journal of Colloid and Interface Science, vol. 62, 1977, pp. 205 - 212 and R. Knapikowski, M. Kudra: Kontaktwinkelmessungen nach dem Wilhelmy-Prinzip-Ein statistischer Ansatz zur Fehierbeurteilung ", Chem. Technik, vol. 45, 1993, pp. 179 - 185, and US Patent No. 6,436,481, which are hereby incorporated by reference.
[00226] As an example, the forward contact angle and the recessed contact angle were determined using a captive bubble method using phosphate buffered saline (PBS, pH = 7.2). The lens was flattened on a quartz surface and rehydrated with PBS for at least 10 minutes before testing. An air bubble was placed on a lens surface using an automated sealing system. The size of the air bubble was increased and decreased to obtain the recessed angle (the level obtained by increasing the size of the bubbles) and the advanced angle (the level obtained by decreasing the size of the bubbles).
[00227] The modulus, elongation, and tensile strength values of the present lenses can be determined using routine methods, known to those skilled in the art, such as, for example, a test method according to ANSI Z80.20 . The modulus, elongation, and tensile strength values reported here were determined using an Inserton Model 3342 or Model 3343 mechanical test system (Instron Corporation, Norwood, MA, USA) and Blue Hill Materials Testing Software, using a contact lens constructed with a custom rectangular cut to sample the rectangular strip. The modulus, elongation and tensile strength were determined inside a chamber with a relative humidity of at least 70%. The lens to be tested was soaked in phosphate buffered saline (PBS) for at least 10 minutes before testing. While the concave side of the lens was held up, the central strip of the lens was cut using the cutting blade. The strip thickness was determined using a calibrated gauge (Rehder electronic thickness gauge, Rehder Development Company, Castro Valley, CA, USA). Using tweezers, the strip was placed on the claws of the calibrated Instron device, with the mounting strip occupying at least 75% of the claw surface of each claw. A test method designed to determine the maximum load (N), the tensile strength (MPa), the strain at maximum load (% elongation) and the mean and standard deviation of the modulus of elasticity (MPa), was performed, and the results were recorded.
[00228] The percentage of energy loss of the present silicone hydrogel contact lenses can be determined using routine methods, known to those skilled in the art. For Examples 1 to 28 below, the percentage energy loss was determined using an Instron Model 3343 mechanical test system (Instron Corporation, Norwood, MA, USA), with a 10N force transducer (Instron model No 2519-101) and Bluehill Materials Testing Software, including a TestProfiler module. The energy loss was determined inside a chamber with a relative humidity of at least 70%. Before testing, each lens was soaked in a phosphate buffered saline (PBS) for at least 10 minutes. Using tweezers, the lens was placed in the calibrated Instron device's claws, with the lens placed vertically between the claws as symmetrically as possible so that the lens fits and occupies at least 75% of the claw surface of each claw . A test designed to determine the energy required to stretch the lens to 100% deformation and then return to 0% deformation at a rate of 50 mm / minute was then performed on the lens. The test was performed only once on a single lens. Once the test was completed, the energy loss was calculated using the following equation: (Deformation energy from 0 to 100% - Deformation energy from 100 to 0%) / Deformation energy from 0 to 100%) x 100 (B)
[00229] The ionic flow of the present lenses can be determined using routine methods, known to those skilled in the art. For the lenses of Examples 1 to 28 below, the ionic flux was measured using a technique substantially similar to the "Ionic flux Technique", described in US Patent No. 5,849,811, which is incorporated herein by reference. Before measurement, a hydrated lens was equilibrated in deionized water for at least 10 minutes. The lens to be measured was placed in a lens retention device, between the male and female portions. The male and female portions include flexible seal rings that have been positioned between the lens and the respective male or female part. After placing the lens on the lens holding device, a screw cap was then placed on the lens holding device. The cap was screwed into a glass tube to define a donor chamber. The donor chamber was filled with 16 mL of 0.1 M NaCl solution. The recipient chamber was filled with 80 mL of deionized water. The conductivity meter connections were immersed in the deionized water of the receiving chamber and a stir bar was added to the receiving chamber. The receiving chamber was placed in a water bath and the temperature was maintained at about 35 ° C. Finally, the donor chamber was immersed in the receiving chamber in such a way that the NaCI solution inside the donor chamber was leveled with water inside the receiving chamber. Since the temperature inside the receiving chamber was equilibrated at 35 ° C, conductivity measurements were made every 2 minutes for at least 10 minutes. The conductivity versus time data were substantially linear, and it was used to calculate the ionic flux value for the tested lenses.
[00230] The oxygen permeability (Dk) of the present lenses can be determined using routine methods, known to those skilled in the art. For example, the Dk value can be determined using a commercially available instrument under the designation of the Mocon Ox-Tran ® System model (Mocon Inc., Minneapolis, MN, USA), for example, using the Mocon method, as described in US Patent No. 5,817,924, which is incorporated herein by reference. The Dk values of the lenses in the following Examples 1 to 28 were determined using the method described by Chhabra et al. (2007), A single-lens polarographic meas- urement of oxygen permeability (Dk) for hypertransmissible soft contact lenses. Biomaterials 28: 4331 - 4342, which is incorporated herein by reference.
[00231] The equilibrium water content (EWC) of the present lenses can be determined using routine methods, known to those skilled in the art. For the lenses of the following Examples 1 to 28, a hydrated silicone hydrogel contact lens was removed from an aqueous liquid, dried to remove excess water from the surface, and weighed. The heavy lens was then dried in a furnace at 80 ° C under a vacuum, and the dry lens was then weighed. The weight difference was determined by subtracting the dry lens weight from the hydrated lens weight. The water content (%) is the (difference in weight / hydrated weight) x 100.
[00232] The percentage of the extractable wet component or extractable dry component of a lens can be determined by extracting the lenses in an organic solvent in which the polymeric body of the lens is not soluble, in accordance with methods known to experts in the matter. For the lenses of Examples 1 to 28 below, a methanol extraction was used using a Sohxlet extraction process. For the determination of wet extractable components, a sample (for example, at least 5 lenses per lot) of fully hydrated and sterilized contact lenses was prepared by removing excess solution from the packaging of each lens. and drying overnight in a vacuum oven at 80 ° C. To determine the dry extractable components, a sample of the polymeric lens bodies that had not been washed, extracted, hydrated or sterilized was prepared by drying the lens bodies overnight in a vacuum oven at 80 ° C . After drying and cooling, each lens was weighed to determine its initial dry weight (W1). Each lens was then placed on a perforated, stackable Teflon thimble, and the thimbles were stacked to form an extraction column with an empty thimble placed on top of the column. The extraction column was placed in a small Sohxlet extractor connected to a condenser and a round bottom flask containing 70 - 80 mL of methanol. The water was circulated through the condenser and the methanol was heated to a gentle boil. The lenses were extracted for at least 4 hours from the moment the first condensed methanol appeared. The lenses were extracted again and dried overnight in a vacuum oven at 80 ° C. After drying and cooling, each lens was weighed to obtain the dry weight of the extracted lens (W2), and the following calculation was performed for each lens to determine the percentage of the extractable wet component: [(W1-W2) / W1 ] x 100. EXAMPLE 1
[00233] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in specified quantities, using the procedure described in the Test and Manufacturing Procedure for the Silicone Hydrogel Contact Lens above.

[00234] A batch of silicone hydrogel contact lenses was prepared using this formulation and tested according to the manufacturing procedure and test methods described in the Test and Manufacturing Procedure for the Silicone Hydrogel Contact Lens, using a demoulding process dry, dry lamination process (delensing), and a washing process that uses washing liquids comprising extraction liquids based on volatile organic solvents and hydration liquids consisting of liquids free of volatile organic solvents . These contact lenses contain units derived from two siloxane monomers, Si1 and Si3. This batch of contact lenses had an acceptable percentage of average energy loss.
[00235] In addition, the batch of silicone hydrogel contact lenses, when fully hydrated, had an average EWC of 30% w / w to 70% w / w, when tested at the beginning of the shelf-life test. EXAMPLE 2
[00236] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in specified quantities, using the procedure described in the Test and Manufacturing Procedure for the Silicone Hydrogel Contact Lens above.

[00237] A batch of silicone hydrogel contact lenses was prepared using this formulation and tested according to the manufacturing procedure and test methods described in the Test and Manufacturing Procedure for the Silicone Hydrogel Contact Lens, using a demoulding process dry, dry lamination process (delensing), and a washing process that uses washing liquids comprising extraction liquids based on volatile organic solvents and hydration liquids consisting of liquids free of volatile organic solvents . These contact lenses contain units derived from two siloxane monomers, Si1 and Si3. This batch of contact lenses had an acceptable percentage of average energy loss.
[00238] In addition, these lenses, when fully hydrated, had an EWC of 52% w / w, a modulus of 0.63 MPa, and an ion flux of 3.62 (x10-3 mm2 / min) when tested at the beginning of the shelf-life test. EXAMPLE 3
[00239] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in specified quantities, using the procedure described in the Test and Manufacturing Procedure for the Silicone Hydrogel Contact Lens above:


[00240] A batch of silicone hydrogel contact lenses was prepared using this formulation and tested according to the manufacturing procedure and test methods described in the Test and Manufacturing Procedure for the Silicone Hydrogel Contact Lens, using a demoulding process dry, dry lamination process (delensing), and a washing process that uses washing liquids comprising extraction liquids based on volatile organic solvents and hydration liquids consisting of liquids free of volatile organic solvents . These contact lenses contain units derived from two siloxane monomers, Si1 and Si3. This batch of contact lenses had an acceptable percentage of average energy loss.
[00241] Furthermore, these hydrogel silicone contact lenses, when fully hydrated, had an EWC of about 52% w / w, a module of about 0.58 MPa, a wet extractable component of about 0.67 %, a mean angle of static contact by the captive bubble of about 30 degrees, and a dynamic and advanced contact angle by the method of the captive bubble of about 50.1 degrees, when tested at the beginning of the lifetime test. -shelf. EXAMPLE 4
[00242] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in specified quantities, using the procedure described in the Test and Manufacturing Procedure for the Silicone Hydrogel Contact Lens above:

[00243] A batch of silicone hydrogel contact lenses was prepared using this formulation and tested according to the manufacturing procedure and test methods described in the Test and Manufacturing Procedure for the Silicone Hydrogel Contact Lens, using a demoulding process dry, dry lamination process (delensing), and a washing process that uses washing liquids comprising extraction liquids based on volatile organic solvents and hydration liquids consisting of liquids free of volatile organic solvents . These contact lenses contain units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had an acceptable percentage of average energy loss.
[00244] In addition, these hydrogel silicone contact lenses, when fully hydrated, had an EWC of 53% w / w 54% w / w, a module of about 0.43 MPa, with a wet extractable component of about 1.23% w / w, an average static contact angle through the captive bubble of about 38 degrees, dynamic and advanced contact angle using the captive bubble method of about 50.0 degrees, an ionic flow of 2 , 5 - 3.0 (x10-3 mm2 / min), a Dk of 70 barrers, a length of about 450%, tensile strength of 1.40 MPa, with a transmittance percentage of 98% , a loss of energy of 36%, and a swelling factor of about 21%, when tested at the beginning of the shelf-life test. When tested before extraction and hydration, the polymeric bodies of the lenses had an extractable dry component of about 17% w / w. EXAMPLE 5
[00245] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in specified quantities, using the procedure described in the Test and Manufacturing Procedure for the Silicone Hydrogel Contact Lens above:

[00246] A batch of silicone hydrogel contact lenses was prepared using this formulation and tested according to the manufacturing procedure and test methods described in the Test and Manufacturing Procedure for the Silicone Hydrogel Contact Lens, using a demoulding process dry, dry lamination process (delensing), and a washing process that uses washing liquids comprising extraction liquids based on volatile organic solvents and hydration liquids consisting of liquids free of volatile organic solvents . These contact lenses contain units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had an acceptable percentage of average energy loss.
[00247] Furthermore, these hydrogel silicone contact lenses had, when fully hydrated, a higher oxygen permeability of 60 barrers, an EWC of about 53% w / w, an ion flow of about 2.90 (x10 -3 mm2 / min), an elastic modulus of about 0.40 MPa, an elongation of about 425%, a tensile strength of about 1.4 MPa, with an average static contact angle by the captive bubble of about 37 degrees, a dynamic contact angle advanced by the captive bubble method of about 48 to 52 degrees, a light transmittance of about 98%, an extractable wet component of about 1.30% w / p, an energy loss of about 35% to about 36%, and a swelling factor of about 21%, when tested at the beginning of the shelf-life test, and had an average dimensional stability less than plus or minus 3.0% variation after storage for at least 2 weeks at 80 ° C. EXAMPLE 6
[00248] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in specified quantities, using the procedure described in the Test and Manufacturing Procedure for the Silicone Hydrogel Contact Lens above:

[00249] A batch of silicone hydrogel contact lenses was prepared using this formulation and tested according to the manufacturing procedure and test methods described in the Test and Manufacturing Procedure for the Silicone Hydrogel Contact Lens, using a demoulding process dry, dry lamination process (delensing), and a washing process that uses extraction and hydration liquids consisting of extraction liquids free of volatile organic solvents. The lenses in this batch were not exposed to the volatile organic solvent during manufacture. These contact lenses contain units derived from two siloxane monomers, Si1 and Si3. This batch of contact lenses had an acceptable percentage of average energy loss.
[00250] Furthermore, these silicone hydrogel contact lenses had, when fully hydrated, an EWC of about 55% w / w, an ion flow of about 3.1 (x10-3 mm2 / min), a Dk of about 72 barrers, a module of about 0.70 MPa, an elongation of about 345%, a tensile strength of about 2.4 MPa, a breaking time of more than 20 seconds and, an extractable wet component of about 3.9% w / w, and an energy loss of about 40%, when tested at the beginning of the shelf-life test, and had an average variation in dimensional stability less than more or less 3.0% after storage for more than 2 weeks at 80 ° C. When tested before extraction and hydration, the polymeric lens bodies had an extractable dry component of about 11% w / w. EXAMPLE 7
[00251] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in specified quantities, using the procedure described in the Test and Manufacturing Procedure for the Silicone Hydrogel Contact Lens above:


[00252] A batch of silicone hydrogel contact lenses was prepared using this formulation and tested according to the manufacturing procedure and test methods described in the Test and Manufacturing Procedure for the Silicone Hydrogel Contact Lens, using a demoulding process dry, dry lamination process (delensing), and a washing process that uses extraction and hydration liquids consisting of extraction liquids free of volatile organic solvents. The lenses in this batch were not exposed to the volatile organic solvent during manufacture. These contact lenses contain units derived from two siloxane monomers, Si1 and Si3. This batch of contact lenses had an acceptable percentage of average energy loss.
[00253] In addition, these hydrogel silicone contact lenses, when fully hydrated, had an EWC of about 58% w / w, an ion flow of about 4.14 (x10-3 mm2 / min), a module of about 0.77 MPa, an elongation of about 349%, a tensile strength of about 1.75 MPa, with a water break time of more than 20 seconds and with an extractable wet component of about 4.42% w / w, and an energy loss of about 41%, when tested at the beginning of the shelf-life test, and had an average variation in dimensional stability less than plus or minus 3.0 % after storage for at least 2 weeks at 80 ° C. EXAMPLE 8
[00254] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in specified quantities, using the procedure described in the Test and Manufacturing Procedure for the Silicone Hydrogel Contact Lens above:


[00255] A batch of silicone hydrogel contact lenses was prepared using this formulation and tested according to the manufacturing procedure and test methods described in the Test and Manufacturing Procedure for the Silicone Hydrogel Contact Lens, using a demoulding process dry, dry lamination process (delensing), and a washing process that uses extraction and hydration liquids consisting of extraction liquids free of volatile organic solvents. The lenses in this batch were not exposed to the volatile organic solvent during manufacture. These contact lenses contain units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had an acceptable percentage of average energy loss.
[00256] In addition, these hydrogel silicone contact lenses, when fully hydrated, had an EWC of about 55% w / w, an ion flow of about 4.19 (x10-3 mm2 / min), a module of about 0.61 MPa, an elongation of about 275%, a tensile strength of about 1.51 MPa, a water break time of more than 20 seconds and an extractable wet component of about 4.10% w / w, when tested at the beginning of the shelf-life test, and had an average variation in dimensional stability of less than about 3.0% for more than 2 weeks at 80 ° C. EXAMPLE 9
[00257] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in specified quantities, using the procedure described in the Test and Manufacturing Procedure for the Silicone Hydrogel Contact Lens above:

[00258] A batch of silicone hydrogel contact lenses was prepared using this formulation and tested according to the manufacturing procedure and test methods described in the Test and Manufacturing Procedure for the Silicone Hydrogel Contact Lens, using a demoulding process dry, dry lamination process (delensing), and a washing process that uses extraction and hydration liquids consisting of extraction liquids free of volatile organic solvents. The lenses in this batch were not exposed to the volatile organic solvent during manufacture. These contact lenses contain units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had an acceptable percentage of average energy loss.
[00259] In addition, these hydrogel silicone contact lenses, when fully hydrated, had an EWC of about 58% w / w, an ion flux of about 2.75 (x10-3 mm2 / min), a module of about 0.66 MPa, an elongation of about 216%, a tensile strength of about 0.87 MPa, a water break time of more than 20 seconds and an extractable wet component of about 4.56% w / w, when tested at the beginning of the shelf-life test, and had an average variation in dimensional stability of less than plus or minus 3.0% after storage for six days at 95 ° C. EXAMPLE 10
[00260] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in specified quantities, using the procedure described in the Test and Manufacturing Procedure for the Silicone Hydrogel Contact Lens above:

[00261] A batch of silicone hydrogel contact lenses was prepared using this formulation and tested according to the manufacturing procedure and testing methods described in the Test and Manufacturing Procedure for the Silicone Hydrogel Contact Lens, using a demoulding process dry, dry lamination process (delensing), and a washing process that uses extraction and hydration liquids consisting of extraction liquids free of volatile organic solvents. The lenses in this batch were not exposed to the volatile organic solvent during manufacture. These contact lenses contain units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had an acceptable percentage of average energy loss.
[00262] In addition, these hydrogel silicone contact lenses, when fully hydrated, had an EWC of about 56% w / w, an ion flow of about 3.54 (x10-3 mm2 / min), a module of about 0.57 MPa, an elongation of about 310%, a tensile strength of about 1.90 MPa, a water break time of more than 20 seconds and an extractable wet component of about of 4.74% w / w, and an energy loss of around 34 to 36%, when tested at the beginning of the shelf-life test, and had an average variation in dimensional stability less than plus or minus 3, 0% after storage for 7 days at 80 ° C. When tested before extraction and hydration, the polymeric bodies of the lenses had a dry extractable component of about 14.39% w / w. EXAMPLE 11
[00263] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in specified quantities, using the procedure described in the Test and Manufacturing Procedure for the Silicone Hydrogel Contact Lens above:

[00264] A batch of silicone hydrogel contact lenses was prepared using this formulation and tested according to the manufacturing procedure and test methods described in the Test Procedure and Manufacturing of the Silicone Hydrogel Contact Lens, using a demoulding process dry, dry lamination process (delensing), and a washing process that uses extraction and hydration liquids consisting of extraction liquids free of volatile organic solvents. The lenses in this batch were not exposed to the volatile organic solvent during manufacture. These contact lenses contain units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had an acceptable percentage of average energy loss.
[00265] In addition, these silicone hydrogel contact lenses, when fully hydrated, had an EWC of about 57% w / w, an ion flow of about 3.68 (x10-3 mm2 / min), a module of about 0.69 MPa, an elongation of about 314%, a tensile strength of about 1.30 MPa, a water break time of more than 20 seconds, an extractable wet component of about 1.81% w / w, and a loss of energy of about 34%, when tested at the beginning of the shelf-life test, and had an average variation in dimensional stability less than plus or minus 3 , 0% after storage for 14 days at 80 ° C. EXAMPLE 12
[00266] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in specified quantities, using the procedure described in the Test and Manufacturing Procedure for the Silicone Hydrogel Contact Lens above:

[00267] A batch of silicone hydrogel contact lenses was prepared using this formulation and tested according to the manufacturing procedure and test methods described in the Test Procedure and Manufacturing of the Silicone Hydrogel Contact Lens, using a demoulding process dry, dry lamination process (delensing), and a washing process that uses extraction and hydration liquids consisting of extraction liquids free of volatile organic solvents. The lenses in this batch were not exposed to the volatile organic solvent during manufacture. These contact lenses contain units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had an acceptable percentage of average energy loss.
[00268] Furthermore, these silicone hydrogel contact lenses, when fully hydrated, had an EWC of about 55% w / w, an ion flow of about 3.06 (x10-3 mm2 / min), a module of about 0.85 MPa, an elongation of about 284%, a tensile strength of about 1.88 MPa, a water break time greater than 20 seconds, a wet extractable component of about 2.38% w / w, and an energy loss of around 36%, when tested at the beginning of the shelf-life test, and had an average variation in dimensional stability less than plus or minus 3 , 0% after storage for 14 days at 80 ° C. EXAMPLE 13
[00269] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in specified quantities, using the procedure described in the Test and Manufacturing Procedure for the Silicone Hydrogel Contact Lens above:


[00270] A batch of silicone hydrogel contact lenses was prepared using this formulation and tested according to the manufacturing procedure and test methods described in the Test and Manufacturing Procedure for the Silicone Hydrogel Contact Lens, using a demoulding process dry, dry lamination process (delensing), and a washing process that uses extraction and hydration liquids consisting of extraction liquids free of volatile organic solvents. The lenses in this batch were not exposed to the volatile organic solvent during manufacture. These contact lenses contain units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had an acceptable percentage of average energy loss.
[00271] In addition, these hydrogel silicone contact lenses, when fully hydrated, had an EWC of about 54% w / w, an ion flow of about 3.57 (x10-3 mm2 / min), a module of about 0.66 MPa, an elongation of about 274%, a tensile strength of about 1.40 MPa, and an extractable wet component of about 3.8% w / w, when tested at the beginning from the shelf-life test, and had an average variation in dimensional stability less than plus or minus 3.0% after storage for 7 days at 80 ° C. EXAMPLE 14
[00272] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in specified quantities, using the procedure described in the Test and Manufacturing Procedure for the Silicone Hydrogel Contact Lens above:


[00273] A batch of silicone hydrogel contact lenses was prepared using this formulation and tested according to the fabrication procedure and test methods described in the Test and Fabrication Procedure for the Silicone Hydrogel Contact Lens, using a demoulding process dry, dry lamination process (delensing), and a washing process that uses extraction and hydration liquids consisting of extraction liquids free of volatile organic solvents. The lenses in this batch were not exposed to the volatile organic solvent during manufacture. These contact lenses contain units derived from the three siloxane monomers, Si1, Si2 and Si3. This batch of contact lenses had an acceptable percentage of average energy loss.
[00274] In addition, these hydrogel silicone contact lenses, when fully hydrated, had a modulus of about 0.81 MPa, an elongation of about 351%, a tensile strength of about 1.61 MPa , and EWC of 30% w / w 70% w / w when tested at the beginning of the shelf-life test, and had an average variation in dimensional stability of less than plus or minus 3.0% for 14 days at 80 ° Ç. EXAMPLE 15
[00275] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in specified quantities, using the procedure described in the Test and Manufacturing Procedure for the Silicone Hydrogel Contact Lens above:


[00276] A batch of silicone hydrogel contact lenses was prepared using this formulation and tested according to the manufacturing procedure and test methods described in the Test Procedure and Manufacturing of the Silicone Hydrogel Contact Lens, using a demoulding process dry, dry lamination process (delensing), and a washing process that uses extraction and hydration liquids consisting of extraction liquids free of volatile organic solvents. The lenses in this batch were not exposed to the volatile organic solvent during manufacture. These contact lenses contain units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had an acceptable percentage of average energy loss.
[00277] In addition, these silicone hydrogel contact lenses, when fully hydrated, had an ionic flow of about 3.33 (x10-3 mm2 / min), a modulus of about 0.74 MPa, and an elongation about 222% when tested at the beginning of the shelf-life test, and had an average variation in dimensional stability of less than plus or minus 3.0% for 14 days at 80 ° C. EXAMPLE 16
[00278] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in specified quantities, using the procedure described in the Test and Manufacturing Procedure for the Silicone Hydrogel Contact Lens above:

[00279] A batch of silicone hydrogel contact lenses was prepared using this formulation and tested according to the manufacturing procedure and test methods described in the Test and Manufacturing Procedure for the Silicone Hydrogel Contact Lens, using a demoulding process dry, dry lamination process (delensing), and a washing process that uses extraction and hydration liquids consisting of extraction liquids free of volatile organic solvents. The lenses in this batch were not exposed to the volatile organic solvent during manufacture. These contact lenses contain units derived from two siloxane monomers, Si1 and Si3. This batch of contact lenses had an acceptable percentage of average energy loss.
[00280] Furthermore, these hydrogel silicone contact lenses, when fully hydrated, had an EWC of about 57% w / w, a module of about 0.70 MPa, with an energy loss of about 40% , and dynamic and advanced contact angle by the captive bubble method of about 50 degrees to about 60 degrees when tested at the beginning of the shelf-life test, and had an average variance of dimensional stability less than more or less 3.0%, for 14 days at 80 ° C. EXAMPLE 17
[00281] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in specified quantities, using the procedure described in the Test and Manufacturing Procedure for the Silicone Hydrogel Contact Lens above:

[00282] A batch of silicone hydrogel contact lenses was prepared using this formulation and tested according to the manufacturing procedure and test methods described in the Test and Manufacturing Procedure for the Silicone Hydrogel Contact Lens, using a demoulding process dry, dry lamination process (delensing), and a washing process that uses extraction and hydration liquids consisting of extraction liquids free of volatile organic solvents. The lenses in this batch were not exposed to the volatile organic solvent during manufacture. These contact lenses contain units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had an acceptable percentage of average energy loss.
[00283] Furthermore, these hydrogel silicone contact lenses, when fully hydrated, had an EWC of about 56% w / w, a module of about 0.50 MPa, and a dynamic and advanced contact angle by the method of the captive bubble of about 47 to about 51 degrees, when tested at the beginning of the shelf-life test, and had a mean variation in dimensional stability of less than about 3.0% for 4.4 weeks at 80 ° C. EXAMPLE 18
[00284] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in specified quantities, using the procedure described in the Test and Manufacturing Procedure for the Silicone Hydrogel Contact Lens above:

[00285] A batch of silicone hydrogel contact lenses was prepared using this formulation and tested according to the manufacturing procedure and test methods described in the Test Procedure and Manufacture of Silicone Hydrogel Contact Lens, using a demoulding process dry, dry lamination process (delensing), and a washing process that uses extraction and hydration liquids consisting of extraction liquids free of volatile organic solvents. The lenses in this batch were not exposed to the volatile organic solvent during manufacture. These contact lenses contain units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had an acceptable percentage of average energy loss.
[00286] In addition, these hydrogel silicone contact lenses, when fully hydrated, had an EWC of about 55% w / w, a module of about 0.60 MPa, and a dynamic and advanced contact angle by the method of the captive bubble of about 47 degrees to about 55 degrees when tested at the beginning of the shelf-life test, and had an average variation in dimensional stability of less than plus or minus 3.0% after storage for 2 weeks at 80 ° C. EXAMPLE 19
[00287] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in specified quantities, using the procedure described in the Test and Manufacturing Procedure for the Silicone Hydrogel Contact Lens above:

[00288] A batch of silicone hydrogel contact lenses was prepared using this formulation and tested according to the manufacturing procedure and test methods described in the Test Procedure and Manufacturing of the Silicone Hydrogel Contact Lens, using a demoulding process dry, dry lamination process (delensing), and a washing process that uses extraction and hydration liquids consisting of extraction liquids free of volatile organic solvents. The lenses in this batch were not exposed to the volatile organic solvent during manufacture. These contact lenses contain units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had an acceptable percentage of average energy loss.
[00289] In addition, these hydrogel silicone contact lenses, when fully hydrated, had an EWC of about 55% w / w and about 56% w / w, a modulus of about 0.71 MPa, and an angle dynamic contact and advanced by the captive bubble method from about 45 degrees to about 47 degrees when tested at the beginning of the shelf-life test, and had an average variation in dimensional stability less than plus or minus 3, 0% for at least 2 weeks at 80 ° C. EXAMPLE 20
[00290] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in specified quantities, using the procedure described in the Test and Manufacturing Procedure for the Silicone Hydrogel Contact Lens above:

[00291] A batch of silicone hydrogel contact lenses was prepared using this formulation and tested according to the manufacturing procedure and test methods described in the Test and Manufacturing Procedure for the Silicone Hydrogel Contact Lens, using a demoulding process dry, dry lamination process (delensing), and a washing process that uses extraction and hydration liquids consisting of extraction liquids free of volatile organic solvents. The lenses in this batch were not exposed to the volatile organic solvent during manufacture. These contact lenses contain units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had an acceptable percentage of average energy loss.
[00292] Furthermore, these hydrogel silicone contact lenses, when fully hydrated, had an EWC of about 56% w / w, and a module of about 0.65 MPa, when tested at the beginning of the test shelf life, and had an average variation in dimensional stability of less than plus or minus 3.0% for 2 weeks at 80 ° C. EXAMPLE 21
[00293] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in specified quantities, using the procedure described in the Test and Manufacturing Procedure for the Silicone Hydrogel Contact Lens above:

[00294] A batch of silicone hydrogel contact lenses was prepared using this formulation and tested according to the fabrication procedure and test methods described in the Test and Fabrication Procedure for the Silicone Hydrogel Contact Lens, using a demoulding process dry, dry lamination process (delensing), and a washing process that uses extraction and hydration liquids consisting of extraction liquids free of volatile organic solvents. The lenses in this batch were not exposed to the volatile organic solvent during manufacture. These contact lenses contain units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had an acceptable percentage of average energy loss.
[00295] Furthermore, these hydrogel silicone contact lenses, when fully hydrated, had an EWC of about 55% w / w and about 56% w / w, a module of about 0.53 MPa, an angle of dynamic and advanced contact by the captive bubble method from about 51 degrees to about 53 degrees, and an energy loss of about 34%, when tested at the beginning of the shelf-life test, and had an average variation in dimensional stability less than plus or minus 3.0% for 4.4 weeks at 80 ° C. EXAMPLE 22
[00296] A polymerizable silicone composition was obtained by mixing and filtering the following chemical compounds in the specified quantities, using the procedure described in the Hydrogelacima Silicone Contact Lens Test and Fabrication Procedure indicated:

[00297] A batch of silicone hydrogel contact lenses was prepared using this formulation and tested according to the manufacturing procedure and test methods described in the Test and Manufacturing Procedure for the Silicone Hydrogel Contact Lens, using a demoulding process dry, dry lamination process (delensing), and a washing process that uses extraction and hydration liquids consisting of extraction liquids free of volatile organic solvents. The lenses in this batch were not exposed to the volatile organic solvent during manufacture. These contact lenses contain units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had an acceptable percentage of average energy loss.
[00298] In addition, these hydrogel silicone contact lenses, when fully hydrated, had an EWC of 57% w / w and 58% w / w, an ion flow of about 2.9 (x10-3 mm2 / min) , a module of about 0.7 MPa, an elongation of about 300%, a tensile strength of about 1.5 MPa, dynamic and advanced contact angle by the captive bubble method of about 44 degrees a about 48 degrees, an extractable wet component of about 5.10% w / w, and an energy loss of about 32% to about 33%, when tested at the beginning of the shelf-life test, and had an average variation in dimensional stability of less than about 3.0% after storage for 4.4 weeks at 80 ° C. When tested before extraction and hydration, the polymeric bodies of the lenses had a dry extractable component of about 12.2% w / w. EXAMPLE 23
[00299] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in specified quantities, using the procedure described in the Test and Manufacturing Procedure for the Silicone Hydrogel Contact Lens above:


[00300] A batch of silicone hydrogel contact lenses was prepared using this formulation and tested according to the manufacturing procedure and test methods described in the Test Procedure and Manufacturing of the Silicone Hydrogel Contact Lens, using a demoulding process dry, dry lamination process (delensing), and a washing process that uses extraction and hydration liquids consisting of extraction liquids free of volatile organic solvents. The lenses in this batch were not exposed to the volatile organic solvent during manufacture. These contact lenses contain units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had an acceptable percentage of average energy loss.
[00301] Furthermore, these hydrogel silicone contact lenses, when fully hydrated, had an EWC of about 55% w / w and about 56% w / w, an ion flow of about 4.1 (x10-3 mm2 / min), a modulus of about 0.6 MPa, an elongation of about 275%, a tensile strength of about 1.2 MPa, dynamic contact angle advanced by the captive bubble method of about 55 degrees to about 58 degrees, an extractable wet component of about 4.6% w / w, an energy loss of about 31% to about 32%, and a swelling factor of about 27% when tested at the beginning of the shelf-life test, and had an average variation in dimensional stability of less than about 3.0% after storage for 4.4 weeks at 80 ° C. When tested before extraction and hydration, the polymeric bodies of the lenses had a dry extractable component of about 10.6% w / w. EXAMPLE 24
[00302] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in specified quantities, using the procedure described in the Test and Manufacturing Procedure for the Silicone Hydrogel Contact Lens above:

[00303] A batch of silicone hydrogel contact lenses was prepared using this formulation and tested according to the manufacturing procedure and test methods described in the Test and Manufacturing Procedure for the Silicone Hydrogel Contact Lens, using a demoulding process dry, dry lamination process (delensing), and a washing process that uses extraction and hydration liquids consisting of extraction liquids free of volatile organic solvents. The lenses in this batch were not exposed to the volatile organic solvent during manufacture. These contact lenses contain units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had an acceptable percentage of average energy loss.
[00304] Furthermore, these silicone hydrogel contact lenses, when fully hydrated, had an EWC of about 61% w / w, an ion flow of about 3.8 (x10-3 mm2 / min), a module about 0.5 MPa, an elongation of about 279%, a tensile strength of about 1.2 MPa, dynamic contact angle and advanced by the captive bubble method from about 45 degrees to about 47 degrees, an extractable wet component of about 4.55% w / w, and an energy loss of about 30% to about 33% when tested at the beginning of the shelf-life test, and had an average variation dimensional stability less than plus or minus 3.0% after storage for 14 days at 80 ° C. When tested before extraction and hydration, the polymeric bodies of the lenses had an extractable dry component of about 13.65% w / w. EXAMPLE 25
[00305] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in specified quantities, using the procedure described in the Test and Manufacturing Procedure for the Silicone Hydrogel Contact Lens above:

[00306] A batch of silicone hydrogel contact lenses was prepared using this formulation and tested according to the manufacturing procedure and test methods described in the Test and Manufacturing Procedure for the Silicone Hydrogel Contact Lens, using a demoulding process dry, dry lamination process (delensing), and a washing process that uses extraction and hydration liquids consisting of extraction liquids free of volatile organic solvents. The lenses in this batch were not exposed to the volatile organic solvent during manufacture. These contact lenses contain units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had an acceptable percentage of average energy loss.
[00307] Furthermore, these silicone hydrogel contact lenses, when fully hydrated, had an EWC of about 55% w / w and about 57% w / w, an ion flow of about 3.6 (x10-3 mm2 / min), a modulus of about 0.7 MPa, an elongation of about 285%, a tensile strength of about 1.3 MPa, a dynamic contact angle advanced by the captive bubble method of about 47 degrees to about 53 degrees, an extractable wet component of about 4.10% w / w, and a loss of energy from about 34% to about 35% when tested at the beginning of the life test- shelf stability, and had an average dimensional stability variance of less than plus or minus 3.0% after storage for 14 days at 80 ° C. When tested before extraction and hydration, the polymeric bodies of the lenses had the components dry extractables of about 9.80% w / w. EXAMPLE 26
[00308] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in specified quantities, using the procedure described in the Test and Manufacturing Procedure for the Silicone Hydrogel Contact Lens above:

[00309] A batch of silicone hydrogel contact lenses was prepared using this formulation and tested according to the manufacturing procedure and test methods described in the Test and Manufacturing Procedure for the Silicone Hydrogel Contact Lens, using a demoulding process dry, dry lamination process (delensing), and a washing process that uses extraction and hydration liquids consisting of extraction liquids free of volatile organic solvents. The lenses in this batch were not exposed to the volatile organic solvent during manufacture. These contact lenses contain units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had an acceptable percentage of average energy loss.
[00310] Specifically, these silicone hydrogel contact lenses, when fully hydrated, had an energy loss of about 36% to about 38%, when tested at the beginning of the shelf-life test. EXAMPLE 27
[00311] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in specified quantities, using the procedure described in the Test and Manufacturing Procedure for the Silicone Hydrogel Contact Lens above:

[00312] A batch of silicone hydrogel contact lenses was prepared using this formulation and tested according to the fabrication procedure and test methods described in the Test and Fabrication Procedure for the Silicone Hydrogel Contact Lens, using a demoulding process dry, dry lamination process (delensing), and a washing process that uses extraction and hydration liquids consisting of extraction liquids free of volatile organic solvents. The lenses in this batch were not exposed to the volatile organic solvent during manufacture. These contact lenses contain units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had an acceptable percentage of average energy loss.
[00313] Furthermore, these hydrogel silicone contact lenses, when fully hydrated, had an EWC of about 56% w / w, an ion flow of about 3.6 (x10-3 mm2 / min), a module of about 0.46 MPa, an elongation of about 196%, a tensile strength of about 0.6 MPa, an extractable wet component of about 7.28% w / w, and a loss about 34% to about 38% when tested at the beginning of the shelf-life test. When tested before extraction and hydration, the polymeric bodies of the lenses had a dry extractable component of about 17.87% w / w. EXAMPLE 28
[00314] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in specified quantities, using the procedure described in the Test and Fabrication Procedure for the Hydrogelacima Silicon Contact Lens indicated.

[00315] A batch of silicone hydrogel contact lenses was prepared using this formulation and tested according to the manufacturing procedure and test methods described in the Test and Manufacturing Procedure for the Silicone Hydrogel Contact Lens, using a demoulding process dry, dry lamination process (delensing), and a washing process that uses extraction and hydration liquids consisting of extraction liquids free of volatile organic solvents. The lenses in this batch were not exposed to the volatile organic solvent during manufacture. These contact lenses contain units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had an acceptable percentage of average energy loss.
[00316] Furthermore, these hydrogel silicone contact lenses, when fully hydrated, had an ionic flow of about 6.4 (x10-3 mm2 / min), a module of about 0.51 MPa, with an elongation about 200%, a tensile strength of about 0.67 MPa, and an energy loss of about 32% to about 34%, when tested at the beginning of the shelf-life test.
[00317] Although the disclosure here refers to certain illustrated embodiments, it is to be understood that these embodiments are presented by way of example and not by way of limitation. The purpose of the previously detailed disclosure, while discussing exemplary embodiments, should be interpreted to cover all modifications, alternatives and equivalents of the embodiments that may be within the spirit and scope of the invention, as defined by the additional disclosure.
[00318] A number of publications and patents have been cited previously. Each of the publications and patents cited here is incorporated in its entirety as a reference.

权利要求:
Claims (15)
[0001]
1. Silicone hydrogel contact lens, comprising: a polymeric lens body which is the reaction product of a polymerizable composition, said polymerizable composition comprising: (a) a first siloxane monomer represented by formula (1):
[0002]
2. Contact lens, according to claim 1, CHARACTERIZED by the fact that the hydrogel silicone contact lens, when completely hydrated, has an energy loss of 27% to 40%.
[0003]
3. Contact lens, according to claim 1 or 2, CHARACTERIZED by the fact that, in the first siloxane monomer, m of the formula (1) is 4, n of the formula (1) is 1, R1 of the formula (1) is a butyl group, and each R2 of formula (1) is, independently, a hydrogen atom or a methyl group.
[0004]
4. Contact lens according to any one of claims 1 to 3, CHARACTERIZED by the fact that the average numerical molecular weight of the first siloxane monomer is 400 Daltons to 700 Daltons.
[0005]
Contact lens according to any one of claims 1 to 4, CHARACTERIZED by the fact that the polymerizable composition further comprises at least one crosslinking agent, such as a vinyl containing crosslinking agent.
[0006]
6. Contact lens, according to claim 5, CHARACTERIZED by the fact that a total amount of vinyl-containing crosslinking agents present in the polymerizable composition is 0.01 unit parts to 2.0 unit parts by weight, and wherein a ratio of an amount of the first siloxane monomer present in the polymerizable composition to the total amount of vinyl-containing crosslinking agents present in the polymerizable composition is optionally 100: 1 to 400: 1, based on unit parts by weight .
[0007]
Contact lens according to any one of claims 1 to 6, CHARACTERIZED by the fact that the polymerizable composition further comprises at least one hydrophilic monomer, such as a hydrophilic amide monomer having an N-vinyl group.
[0008]
8. Contact lens according to any one of claims 1 to 7, CHARACTERIZED by the fact that a ratio between an amount of the first siloxane monomer present in the polymerizable composition to a quantity of the second siloxane monomer present in the polymerizable composition is at least 3: 1 based on unit parts by weight.
[0009]
9. Contact lens according to any one of claims 1 to 8, CHARACTERIZED by the fact that a total amount of siloxane monomers present in the polymerizable composition is 35 to 40 unit parts by weight.
[0010]
10. Contact lens according to any one of claims 1 to 9, CHARACTERIZED by the fact that the second siloxane monomer is represented by the formula (2):
[0011]
11. Contact lens, according to claim 10, CHARACTERIZED by the fact that in the second siloxane monomer, m of formula (2) is 0, n of formula (2) is an integer from 5 to 10, that of formula (2) is an integer from 65 to 90, b from formula (2) is an integer from 1 to 10 and R1 from formula (2) is a methyl group.
[0012]
12. Lot of silicone hydrogel contact lenses CHARACTERIZED by the fact that it comprises a plurality of contact lenses, as defined in any of claims 1 to 11, in which the lot of hydrogel silicone contact lenses has , when fully hydrated, an average equilibrium water content (EWC) of 30% by weight to 70% by weight, or an average oxygen permeability of at least 55 Barrers, or an average dynamic forward contact angle through captive bubble below 70 degrees, or an average static contact angle through the captive bubble below 55 degrees, or any combination thereof, based on the averages of the values determined for at least 20 individual lenses in the batch.
[0013]
13. Method of manufacturing a silicone hydrogel contact lens, CHARACTERIZED by the fact that it comprises: providing a miscible polymerizable composition, said polymerizable composition comprising: (a) a first siloxane monomer represented by formula (1):
[0014]
14. Method according to claim 13, CHARACTERIZED by the fact that the contact step comprises contacting the polymeric lens body with a washing liquid that is free of a volatile organic solvent.
[0015]
15. Method, according to claim 13 or 14, CHARACTERIZED by the fact that the first siloxane monomer is, as defined in claim 3 or 4. (2) where R1 of formula (2) is selected both from hydrogen or a methyl group, R2 of formula (2) is selected from either a hydrogen or a C1-4 hydrocarbon group; m of formula (2) represents an integer from 0 to 10, n of general formula (2) represents an integer from 4 to 100; a and b of formula (2) represent integers of 1 or more, a + b is equal to 20 - 500, b / (a + b) is equal to 0.01 - 0.22, and the configuration of the siloxane units includes a random configuration, where the second siloxane monomer has an average molecular weight greater than 7000 Daltons. In an example of siloxane of general formula (2), m of formula (2) is 0, n of formula (2) is an integer from 5 to 10, that of formula (2) is an integer

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同族专利:

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公开号 | 公开日

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AU2012223592A1|2013-09-12|

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JP5842297B2|2016-01-13|

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US20130261216A1|2013-10-03|

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MX2013009217A|2014-09-08|

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US20120220690A1|2012-08-30|

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EP2681616B1|2019-01-23|

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CA2828458C|2017-04-11|

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TW201239451A|2012-10-01|

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KR101743801B1|2017-06-05|

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SG10201402884XA|2014-07-30|

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CN103620480B|2015-12-09|

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CN103620480A|2014-03-05|

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CA2828458A1|2012-09-07|

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US8481662B2|2013-07-09|

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BR112013021871A2|2017-03-28|

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HUE043683T2|2019-09-30|

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WO2012118681A2|2012-09-07|

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ES2719850T3|2019-07-16|

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EP2681616A4|2017-12-06|

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MY164188A|2017-11-30|

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WO2012118681A3|2013-12-12|

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JP2014513812A|2014-06-05|

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KR20140009399A|2014-01-22|

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US8658748B2|2014-02-25|

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HK1190795A1|2014-07-11|

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EP2681616A2|2014-01-08|

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GB2502502A|2013-11-27|

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SG192230A1|2013-09-30|

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AU2012223592B2|2014-10-30|

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GB201316967D0|2013-11-06|

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TWI506334B|2015-11-01|

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法律状态:
2018-12-18| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-11-26| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-11-17| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-01-05| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 23/02/2012, OBSERVADAS AS CONDICOES LEGAIS. |

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2021-09-21| B25G| Requested change of headquarter approved|Owner name: COOPERVISION INTERNATIONAL HOLDING COMPANY, LP (BB) |

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2021-10-13| B25A| Requested transfer of rights approved|Owner name: COOPERVISION INTERNATIONAL LIMITED (GB) |

优先权:

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申请号 | 申请日 | 专利标题

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US201161447197P| true| 2011-02-28|2011-02-28|

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US61/447,197|2011-02-28|

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PCT/US2012/026222|WO2012118681A2|2011-02-28|2012-02-23|Silicone hydrogel contact lenses having acceptable levels of energy loss|

---