SILICONE-HYDROGEL CONTACT LENS AND ITS MANUFACTURING METHOD

专利摘要:
Dimensionally stable silicone-hydrogel contact lenses are described dimensionally stable silicone-hydrogel contact lenses. the lenses are derived from a polymerizable composition including a first siloxane monomer representing by formula (1): (1) where m of formula (1) represents an integer from 3 to 10, n of formula (1) represents a number integer from 1 to 10, r¹ of formula (1) is an alkyl group with 1 to 4 carbon atoms and each r² of formula (1) is independently a hydrogen atom or a methyl group; the lenses also include units derived from a second siloxane monomer represented by formula (2): (2) where r¹ of formula (2) is selected from a hydrogen atom or a methyl group; r² of formula (2) is selected from any hydrogen atom or a hydrocarbon having from 1 to 4 carbon atoms; m of formula (2) represents an integer from 0 to 10; n of formula (2) represents an integer from 4 to 100; a and b represent integers of 1 or more; a + b is equal to 20-500; b / (a + b) is equal to 0.01 - 0.22; the configuration of the siloxane units includes a random configuration, the second siloxane monomer having an average meolecular weight number of at least 3,000 daltons, which is present in the polymerizable composition in an amount such that the ratio of the first siloxane monomer to the second monomer siloxane is at least 2: 1, based on unit parts by weight. lots of silicone-hydrogel contact lenses and methods for silicone-hydrogel contact lenses are also described.
公开号:BR112013022001B1
申请号:R112013022001-5
申请日:2012-02-23
公开日:2020-09-08
发明作者:Charles A. Francis；Ying Zheng；Li Yao；Yuan Xu；Arthur Back；Ye Hong；Charlie Chen
申请人:Coopervision International Holding Company, Lp；
IPC主号:

专利说明:

[0001] [001] This application claims the benefit in accordance with 35 USC § 119 (e) to the previous US Provisional Patent Application No. 61 / 447,164, filed on February 28, 2011, which is incorporated in its entirety by reference in this document. FIELD OF THE INVENTION
[0002] [002] This disclosure relates to silicone-hydrogel contact lenses and related compositions and methods. BACKGROUND OF THE INVENTION
[0003] [003] Commercially and clinically, silicone hydrogel contact lenses are a popular alternative to conventional hydrogel contact lenses (ie hydrogel contact lenses that do not contain silicone or silicone-containing ingredients). The presence of siloxanes in silicone-hydrogel contact lens formulations is believed to affect the properties of silicone-hydrogel contact lenses obtained from this. For example, the presence of a siloxane component in a contact lens is believed to result in a relatively higher oxygen permeability compared to a conventional hydrogel contact lens without a siloxane component. In addition, it is believed that the presence of a silicone component increases the likelihood of hydrophobic domains being present on the lens surface of a silicone hydrogel contact lens compared to a silicone hydrogel contact lens without a silicone component. silicone. Techniques were developed to overcome the problems of hydrophobicity of the surfaces of the silicone-hydrogel contact lens. Based on the popularity of silicone hydrogel contact lenses, there remains a need for new silicone hydrogel contact lenses that are ophthalmologically compatible.
[0004] [004] Some documents describing silicone hydrogel contact lenses include: US4711943, US5712327, US5760100, US7825170, US6867245, US20060063852, US20070296914, US7572841, US20090299022, US20090234089 and US20100249356, each of which is incorporated by reference to each in this document. SUMMARY
[0005] [005] It has been discovered that many silicone hydrogel contact lenses made during a contact lens development process can experience stability problems, such as unwanted changes in the physical dimensions of silicone hydrogel contact lenses over time . Such stability problems can affect the service life of silicone hydrogel contact lenses and compromise the manufacture of silicone hydrogel contact lenses on a commercial scale. The reduced stability of silicone hydrogel contact lenses, compared to conventional hydrogel contact lenses, can be attributed, at least in part, to the hydrolytic decomposition or degradation of siloxanes present in the formulations used to produce the contact lenses, or the siloxanes present in the polymerized contact lenses. From a manufacturing perspective, it is important that silicone hydrogel contact lenses remain dimensionally stable for long periods of time, so that the physical dimensions of the contact lenses remain within the specifications determined by regulatory agencies in relation to the life of product shelf.
[0006] [006] As an example, it was found that silicone-hydrogel contact lenses made from polymerizable compositions containing a single siloxane represented by formula (1):
[0007] [007] Based on this investigation, new silicone-hydrogel contact lenses were invented. Unlike approaches that have improved the dimensional stability of a silicone-hydrogel contact lens by manipulating the ingredients in the contact lens packaging solution or pH, this disclosure relates to the verification that, including a second represented siloxane by formula (2): where R1 of formula (2) is selected from a hydrogen atom or a methyl group; R2 of formula (2) is selected from 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 formula (2) represents an integer from 4 to 100; a and b represent integers of 1 or more; a + b is equal to 20-500; b / (a + b) is equal to 0.01-0.22; the configuration of the siloxane units includes a random configuration; and the second siloxane monomer having an average numerical molecular weight of at least 3,000 Daltons, can improve the dimensional stability of silicone hydrogel contact lenses that are made from formulations containing the siloxane of formula (1) and therefore result in silicone-hydrogel contact lenses that have a commercially acceptable shelf life.
[0008] [008] The present disclosure refers to new silicone-hydrogel contact lenses. A silicone-hydrogel contact lens, according to the present disclosure, comprises a polymeric lens body. The polymeric lens body is the product of the reaction of a polymerizable composition. The polymerizable composition comprises a plurality of ingredients that make up the lens, so that when the composition is polymerized, a polymeric lens body is obtained.
[0009] [009] In one example, the present disclosure relates to a polymerizable composition used to produce the silicone hydrogel contact lenses of the present invention. The polymerizable composition comprises a first siloxane monomer represented by formula (1):
[0010] [0010] In another example, the present disclosure also relates to a silicone-hydrogel contact lens that comprises a polymeric lens body which is the reaction product of a polymerizable composition. The polymerizable composition comprises a first siloxane monomer represented by formula (1):
[0011] [0011] Optionally in this example, the first siloxane monomer can have an average numerical molecular weight of 400 Daltons to 700 Daltons, or the second siloxane monomer can have an average numerical molecular weight greater than 7,000 Daltons, or both. The polymerizable composition also comprises at least one hydrophilic monomer, or at least one hydrophobic monomer, or at least one crosslinking agent, or any combination thereof. Also optionally in this example, when the polymerizable composition comprises at least one hydrophilic monomer, at least one hydrophilic monomer can be present in the polymerizable composition in an amount of 30 unit parts to 60 unit parts, or at least one hydrophilic monomer can include at least one vinyl-containing hydrophilic monomer, such as, for example, at least one amide-containing hydrophilic monomer with an N-vinyl group, or both. Also optionally in this example, when the polymerizable composition comprises at least one crosslinking agent, the at least one crosslinking agent can comprise a vinyl containing crosslinking agent. In a particular lens in this example, the silicone-hydrogel contact lens has an oxygen permeability of at least 55 barrers, an equilibrium water content of about 35% to about 65% by weight and a modulus of elasticity of about 0.2 MPa to about 0.9 MPa.
[0012] [0012] The present disclosure also relates to a batch of silicone hydrogel contact lenses comprising a plurality of contact lenses formed from polymeric lens bodies, which are the reaction product of the polymerizable composition described in the present invention. . The batch of silicone hydrogel contact lenses comprises the polymerizable composition described in paragraph [0009] above, or comprises a plurality of silicone hydrogel contact lenses described in paragraph [0010] above, or both, and has a variance of average dimensional stability less than plus or minus 3% (± 3.0%), where the variance of average dimensional stability is the variance of a value from a physical dimension, when measured at an initial time point on a day of a date of manufacture of the lens lot, and at a second time point, where the second time point is two weeks to seven years after the initial time point when the lot is stored at room temperature, or when the lot is stored at a higher temperature (that is, under accelerated life test conditions), the second time point is a time point representative of the batch storage from two weeks to seven years at room temperature, said stability variance average dimensional being an average of the dimensional stability variance determined for at least 20 individual lenses of the lot by the following equation (A): (Final Diameter - Original Diameter / Original Diameter) x 100 (A).
[0013] [0013] In one example, the conditions of the accelerated storage time test which is especially useful in determining the average dimensional stability variance dimensional stability variance are for 4 weeks at 70 degrees C, although other periods of time and temperature can be used .
[0014] [0014] The present disclosure is also directed to the methods of manufacturing a silicone-hydrogel contact lens. The manufacturing method comprises the steps of providing a polymerizable composition comprising a first siloxane monomer represented by the formula (1):
[0015] [0015] In any of the previous examples of polymerizable compositions, or polymeric lens bodies, or silicone hydrogel contact lenses, or lots of silicone hydrogel contact lenses, or methods of manufacturing contact details described in paragraphs [0009] to [0013] above, 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 a hydrogen atom or a methyl group. Examples of the second siloxane are described below; or the second siloxane monomer can be represented by formula (2), where in the second siloxane monomer, m of formula (2) is 0, n of formula (2) is an integer from 5 to 10, a is a integer 65 to 90, b is an integer 1 to 10 and R1 of the formula (2) is a methyl group; or both.
[0016] [0016] Additional modalities of the polymerizable compositions, polymeric lens bodies, present lenses, lens products, lots of lenses and methods of making contact lenses will be evident from the following description, Examples C1 and 1-25 and the claims. As can be seen from the preceding description and below, all the features described herein and each combination of two or more of such characteristics, and each combination of one or more values that define a range are included in the scope of the present invention, provided that the characteristics included in such a combination are not mutually inconsistent. In addition, any feature or combination of features or any value (s) defining a range can be specifically excluded from any embodiment of the present invention. DETAILED DESCRIPTION
[0017] [0017] As described in this document, it has now been verified that silicone-hydrogel contact lenses are formed from a polymerizable composition containing only a single siloxane monomer represented by formula (1):
[0018] [0018] As previously described, in the polymerizable compositions of the present disclosure, the first siloxane monomer and the second siloxane monomer are present in the polymerizable composition in a ratio of at least 2: 1, based on unit parts by weight. In other words, for each unit part by weight of the second siloxane monomer present in the polymerizable composition, 2 or more unit parts of the first siloxane monomer are also present in the polymerizable composition. According to the present disclosure, the first siloxane monomer and the second siloxane monomer can be present in the polymerizable composition in a ratio of about 2: 1 to about 10: 1, based on the unit parts by weight of the first monomer siloxane to the second siloxane monomer. In another example, the first siloxane monomer and the second siloxane monomer can be present in the polymerizable composition in a ratio of about 3: 1 to about 6: 1, based on unit parts by weight. In yet another example, the first siloxane monomer and the second siloxane monomer can be present in the polymerizable composition in a ratio of about 4: 1, based on unit parts by weight.
[0019] [0019] As used herein, "unit parts" is understood to be unit parts by weight. For example, to prepare a formulation described as comprising z unit parts of a siloxane monomer and unit parts of a hydrophilic monomer, the composition can be prepared by combining z grams of the siloxane monomer with y grams of the hydrophilic monomer to obtain a total of y + z grams of the polymerizable composition, or by combining z ounces of the 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 additionally comprises additional optional ingredients such as x unit parts of a crosslinking agent, x grams of the crosslinking agent are combined with z grams of the siloxane monomer y grams of the hydrophilic monomer to obtain a total of x + y + z grams of the polymerizable composition, and so on. 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 unit parts of the siloxane monomer, the y parts unitary parts of the hydrophilic monomer and x unitary parts of the crosslinker, w unitary parts of the first hydrophobic monomer and y unitary parts of the second hydrophobic monomer are combined to obtain a total amount of v + w + x + y + z parts of the polymerizable composition. It is understood that the unit parts of at least one hydrophobic monomer present in such a polymerisable is the sum of the unit parts of the first hydrophobic monomer and the unit parts of the second hydrophobic monomer, for example, v + w unit parts, in this example. Typically, a formula for a polymerizable composition will be composed of ingredients in amounts ranging from about 90 to about 110 unit parts by weight. When quantities of the components of the polymerizable composition are referred to in this document as being in unit parts, it should be understood that the unit parts of this component are based on a formula that provides a total weight of the composition ranging from about 90 to 110 unit parts. In one example, the unit parts by weight can be based on a formula that provides a total weight of the composition ranging from about 95 to 105 unit parts by weight, or from 98 to 102 unit parts by weight.
[0020] [0020] The present contact lenses comprise, or consist of, hydrated lens bodies that comprise a polymeric component and a liquid component. The polymeric component comprises units of two or more siloxane monomers (i.e., a siloxane monomer of formula (1), a second siloxane monomer of formula (2) and, optionally, one or more additional siloxane monomers) and one or more polymerizable ingredients that are not silicone (i.e., one or more hydrophilic monomers, one or more hydrophobic monomers, one or more crosslinking agents 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 present as the siloxane monomer component of the composition) and one or more reactive ingredients other than silicone. As used in this document, a reactive ingredient that is not silicone is understood to be an ingredient that has a polymerizable double bond as part of its molecular structure, but that does not have a silicon atom in its molecular structure. The ingredients of the polymerizable composition can be monomers, macromers, prepolymers, polymers or any combination thereof. In addition to the first siloxane monomer of formula (1), the polymerizable composition further includes a second siloxane monomer, or at least one cross-linking agent, or a second siloxane monomer and at least one cross-linking agent. The at least one cross-linking agent, the at least one hydrophilic monomer and the at least one hydrophobic monomer of the polymerizable composition are understood to be non-silicon polymerizable ingredients. As used herein, the at least one crosslinking agent can be understood to comprise a single crosslinking agent, or comprising a crosslinking agent component composed of two or more crosslinking agents. Likewise, at least one hydrophilic monomer can be understood as a single hydrophilic monomer, or comprising a hydrophilic monomer component composed of two or more hydrophilic monomers. At least one hydrophobic monomer is understood to mean a single hydrophobic monomer, or comprising a hydrophobic monomer component composed of two or more hydrophobic monomers. The at least one optional third siloxane monomer can be understood to be a single third siloxane monomer, or comprising a third siloxane monomer component composed of two or more siloxane monomers. In addition, the polymerizable composition may optionally include at least one initiator, at least one organic diluent, at least one surfactant, at least one oxygen remover, at least one dyeing agent, at least one UV absorber, at least one agent chain transfer, or any combination thereof. The at least one optional initiator, at least one organic diluent, at least one surfactant, at least one oxygen remover, at least one dyeing agent, at least one UV absorber, or at least one chain transfer agent are comprised as non-silicon ingredients, and may be non-polymerizable ingredients or polymerizable ingredients (i.e., ingredients having a polymerizable functional group as part of their molecular structure).
[0021] [0021] The combination of the polymeric component and the liquid component is present as a hydrated lens body, which is suitable to be placed in 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% by weight by weight (w / w). Thus, the present contact lenses can be understood as being soft contact lenses which, as used in this document, refer to contact lenses which, when fully hydrated, can be folded over themselves, without breaking.
[0022] [0022] As understood in the industry, a disposable daily contact lens is an unused contact lens that is removed from its sealed and sterile packaging (main package) produced by a contact lens manufacturer, placed in a person's eye, and is removed and discarded after the person wears the lens at the end of the day. Typically, the duration of use of the lens for daily disposable contact lenses is eight to fourteen hours, and they are then eliminated after wear. Daily disposable lenses are not cleaned or exposed to cleaning solutions before being placed in the eye, as they are sterile before the package is opened. 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, biweekly or monthly). Non-daily disposable contact lenses are either removed from the eye and cleaned with a cleaning solution regularly or are used continuously, without being removed from the eye. The present contact lenses can be daily disposable contact lenses or non-daily disposable contact lenses.
[0023] [0023] In one example, the polymerizable composition of the present disclosure comprises a first siloxane monomer represented by formula (1):
[0024] [0024] The present disclosure also refers to a new silicone-hydrogel contact lens or new silicone-hydrogel contact lenses. A silicone-hydrogel contact lens, according to the present disclosure, comprises a polymeric lens body. The polymeric lens body is the product of the reaction of a polymerizable composition or contact lens formulation. The polymerizable composition used to produce the present silicone hydrogel lens or contact lenses comprises a first siloxane monomer represented by formula (1):
[0025] [0025] As used in this document, a molecular weight is understood to refer to the average numerical molecular weight. The average numerical molecular weight is the simple arithmetic mean or the average of the molecular weights of the individual molecules present in the sample of a monomer. Since the individual molecules in a monomer sample may vary slightly from each other, in terms of molar mass, some level of polydispersity may be present in the sample. As used herein, when the second siloxane monomer, or any other monomer, macromer, prepolymer or polymer of the polymerizable composition is polydispersed, the term "molecular weight" refers to the average numerical molecular weight of the monomer or ingredient. For example, a sample of the second siloxane monomer may have an average numerical molecular weight of about 15,000 Daltons, but if the sample is polydispersed, the actual molecular weights of the present individual monomers can range from 12,000 Daltons to 18,000 Daltons.
[0026] [0026] The average numerical molecular weight can be the absolute average numerical molecular weight, as determined by the group analysis of the end by proton nuclear magnetic resonance (NMR), as understood by those normally skilled in the art. Molecular weights can also be determined using gel permeation chromatography, as understood by those of ordinary skill in the art, or can be supplied by chemical suppliers.
[0027] [0027] The molecular weight of the first siloxane monomer 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 US20090299022, the entire contents of which are hereby incorporated by reference. As can be seen from formula (1), the first siloxane monomer has a single polymerizable methacrylate functional group present at one end of the siloxane monomer backbone.
[0028] [0028] An example of a polymerizable composition according to the present disclosure is composed of a first siloxane monomer represented by the formula (1):
[0029] [0029] In an example of the present contact lenses, the second siloxane monomer can have an average numerical molecular weight of at least 4,000 Daltons, at least 7,000 Daltons, at least 9,000 Daltons or at least 11,000 Daltons. The average numerical molecular weight of the second siloxane monomer can be less than 20,000 Daltons. Thus, in some contexts, the second siloxane monomer can be considered a macromer, but it will be referred to as a monomer in this document, since it forms a unitary part of a polymer formed with the other reactive components of the polymerizable composition.
[0030] [0030] Another example of a polymerizable composition according to the present disclosure is composed of a first siloxane monomer represented by the formula (1):
[0031] [0031] Yet another example of a polymerizable composition according to the present disclosure is composed of a first siloxane monomer represented by the formula (1):
[0032] [0032] As previously stated, the polymerizable composition also comprises at least one hydrophilic monomer, or at least one hydrophobic monomer, or at least one cross-linking agent, or any combination thereof. As used in this document, the three types of prior chemical substances are non-silicon chemicals (that is, chemicals whose molecular structure does not include a silicon atom) and are therefore different from the siloxane monomers present in the polymerizable compositions. The polymerizable compositions can be understood to include at least two siloxane monomers and other hydrophilic monomers without silicon, or hydrophobic monomers without silicon, or cross-linking agents without silicon, or any combination thereof, although, optionally, the polymerizable composition can further comprise at least a third siloxane monomer.
[0033] [0033] The first siloxane monomer, the second siloxane monomer and at least an optional third siloxane monomer comprise the siloxane monomer component of the polymerizable composition. Each of the first siloxane monomer, second siloxane monomer or optional third siloxane monomer, or any combination thereof, may be a hydrophilic siloxane monomer, a hydrophobic siloxane monomer or may have hydrophilic regions and hydrophobic regions, depending on the amount and the location of all hydrophilic components, such as ethylene glycol, polyethylene glycol units and the like, present in the molecular structure of siloxane monomers. For example, the 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 in one or more side chains of the molecule siloxane, or any combination thereof. For example, the siloxane monomer may contain at least one ethylene glycol unit adjacent to a polymerizable functional group on the main chain of the siloxane molecule. As used in this document, adjacent means both immediately adjacent and separated by only 10 carbon atoms or less. The 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 1 to 5 units in length (ie, where the ethylene glycol unit is attached to the first carbon in the carbon chain of 1 to 5 units in length, and the polymerizable functional group is attached to the last carbon in the carbon chain of 1 to 5 units in length, in other words, the ethylene glycol unit and the polymerizable group are not immediately adjacent , but are 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 unit present in at least one side chain of the siloxane molecule. The at least one ethylene glycol unit present in at least one side chain of the siloxane molecule may be part of a side chain attached to a silicon atom in the main chain of the siloxane molecule. The siloxane molecule may 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 and at least one ethylene glycol unit present in at least one side chain of the siloxane molecule.
[0034] [0034] The hydrophilicity or hydrophobicity of a monomer can be determined using conventional techniques, such as, for example, based on the aqueous solubility of the monomer. For the purposes of the present disclosure, a hydrophilic monomer is a monomer that is visibly soluble in aqueous solution, at room temperature (for example, from about 20 to 25 degrees C). For example, a hydrophilic monomer can be understood to be any monomer for which 50 grams or more of the monomer is visibly fully soluble in 1 liter of water at 20 degrees C (that is, the monomer is soluble at a level of at least 5 % w / w in water) as determined using a standard shake bottle method, as known to those of ordinary skill in the art. A hydrophobic monomer, as used in the present invention, is a monomer that is visibly insoluble in an aqueous solution at room temperature, so that the separate visually identifiable phases are present in the aqueous solution, or so that the aqueous solution appears cloudy and becomes separates into two distinct phases over time, after resting at room temperature. For example, a hydrophobic monomer can be understood to be any monomer for which 50 grams of the monomer are not visibly fully soluble in 1 liter of water at 20 degrees C (that is, the monomer is soluble at a level less than 5% w / p in water).
[0035] [0035] In an example of the present contact lenses, the first siloxane monomer can be represented by formula (1), where m of formula (1) is 4, n of formula (1) is 1, R1 of formula (1 ) is a butyl group and each R2 of the formula (1) is independently a hydrogen atom or a methyl group. An example of such a first siloxane monomer is identified in the present invention as Si1, in Examples C1 and 1-25. An example of a polymerizable composition used to produce the present silicone hydrogel lens or contact lenses comprises a first siloxane monomer represented by formula (1):
[0036] [0036] Another example of a polymerizable composition used to produce the present silicone hydrogel lens or contact lenses comprises a first siloxane monomer represented by formula (1):
[0037] [0037] Yet another example of a polymerizable composition used to produce the present silicone hydrogel lens or contact lenses comprises a first siloxane monomer represented by formula (1):
[0038] [0038] As previously defined, in the present silicone-hydrogel contact lenses, the second siloxane monomer is represented by the formula (2):
[0039] [0039] An example of a polymerizable composition used to produce the present silicone hydrogel lens or contact lenses comprises a first siloxane monomer represented by formula (1):
[0040] [0040] 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 a hydrogen atom or a hydrocarbon group having from 1 to 4 carbon atoms and the second siloxane has an average numerical molecular weight of at least 7,000 Daltons. The first siloxane monomer and the second siloxane monomer are present in the polymerizable composition in a ratio of at least 2: 1 based on unit parts by weight. The polymerizable composition also comprises at least one hydrophilic monomer, or at least one hydrophobic monomer, or at least one crosslinking agent, or any combination thereof. Optionally in this example, at least one hydrophilic monomer can comprise a vinyl-containing hydrophilic monomer, including an amide-containing hydrophilic monomer with an N-vinyl group; or it may comprise a vinyl-containing crosslinking agent, or both.
[0041] [0041] Another example of a polymerizable composition used to produce the present silicone hydrogel lens or contact lenses comprises a first siloxane monomer represented by formula (1):
[0042] [0042] Polymerizable compositions used to prepare silicone hydrogel contact lenses may also include additional ingredients other than those described above. For example, as discussed above, a polymerizable composition can include at least a third siloxane monomer. The polymerizable compositions may comprise a third siloxane monomer, or may include a third siloxane monomer component, where the third siloxane monomer component comprises two or more siloxane monomers, each of which is different from the first siloxane monomer and the second siloxane monomer of the polymerizable composition. Examples of the third siloxane monomer or the third siloxane monomer component may comprise (poly) organosiloxane monomers or macromers or prepolymers, such as, for example, 3- [tris (trimethylsiloxy) silyl] propylalyl carbamate, or carbamate 3- [tris (trimethylsiloxy) silyl] propylvinyl, or trimethylsilylethylvinyl carbonate or trimethylsilylmethylvinyl carbonate, or 3- [tris (trimethylsilyloxy) silyl] propyl (TRIS), or 3-methymethylsiloxy-2-hydroxypropyloxy (propyl) propyl ) methylsilane (SiGMA) or methyldi (trimethylsiloxy) silylpropylglycerethyl (SiGEMA) or polydimethylsiloxane terminated in monomethacryloxypropyl (MCS-M11), MCR-M07 or polydimethylsiloxane terminated in mono-n-butylated mono-n-butyl compound themselves. In an example of a polymerizable composition of the present disclosure, the at least a third siloxane can comprise one or more of the first siloxanes described herein or the second siloxanes described herein, wherein the at least one third siloxane differs from the first siloxane and the second siloxane present in the polymerizable composition based on molecular weight, molecular formula, or molecular weight and formula. For example, the third siloxane monomer may be a siloxane monomer of formula (1), with a different molecular weight compared to the first siloxane monomer of the polymerizable composition. In another example, at least a third siloxane can comprise at least one of the siloxanes disclosed in the following patents: US2007 / 0066706, US2008 / 0048350, US3808178, US4120570, US4136250, US4153641, US470533, US5070215, US5998498, US5998498, US572939100, US660 the contents of which are incorporated by reference in this document.
[0043] [0043] The total amount of siloxane monomers present in the polymerizable composition (for example, the sum of the unit parts of the first siloxane monomer, the second siloxane monomer and any other optional siloxane monomers present in the polymerizable composition) can be about 10 to about 60 unit parts, about 25 to about 50 unit parts, or about 35 to about 40 unit parts.
[0044] [0044] As previously established, optionally, the polymerizable compositions of the present disclosure may comprise at least one hydrophilic monomer. A hydrophilic monomer is a polymerizable ingredient without silicon, 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. Hydrophilic monomers without silicon that can be used as the hydrophilic monomer or hydrophilic monomer component in the polymerizable compositions disclosed herein include, for example, acrylamide-containing monomers, acrylate-containing monomers, acrylic acid-containing monomers, methacrylate-containing monomers or methacrylic acid-containing monomers any combination of them. In one example, the hydrophilic monomer or monomer component may comprise or consist of a hydrophilic monomer containing methacrylate. It is understood that the hydrophilic monomer or hydrophilic monomer component is a non-silicon monomer. Examples of hydrophilic monomers that can be included in the present polymerizable compositions can include, for example, N, N-dimethylacrylamide (DMA), 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate (HEMA), 2-hydroxypropyl methacrylate, methacrylate 2-hydroxybutyl (HOB), 2-hydroxybutyl acrylate, 4-hydroxybutylacrylateoglycerol methacrylate, 2-hydroxyethylmethacrylamide, polyethylene glycol monomethacrylate, methacrylic acid or acrylic acid, or any combination thereof.
[0045] [0045] 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 polymerizable compositions include, without limitation, N-vinylformamide, N-vinylacetamide, N-vinyl-N-ethylacetamide, N-vinylisopropylamide, N-vinyl-N-methylacetamide (VMA), N -vinylpyrrolidone (NVP), N-vinylcaprolactam, N-vinyl-N-ethylformamide, N-vinylformamide, N-2-hydroxyethylvinyl carbamate, N-carboxy ^ -alanine-N-vinyl ester, 1,4-butanediolvinyl ether ( BVE), ethylene glycolinyl ether (EGVE), diethylene glycolinyl ether (DEGVE) or any combination thereof.
[0046] [0046] In another example, the hydrophilic monomer or hydrophilic monomer component of the polymerizable composition may comprise or consist of a hydrophilic amide monomer. The hydrophilic amide monomer can be a hydrophilic amide monomer with an N-vinyl group, such as, for example, N-vinylformamide, N-vinylacetamide, N-vinyl-N-ethylacetamide, N-vinylisopropylamide, N-vinyl-N- methylacetamide (VMA), N-vinylpyrrolidone (NVP), N-vinylcaprolactam or any combination thereof. In one example, the hydrophilic monomer or the component of the hydrophilic monomer component N-vinyl-N-methylacetamide (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.
[0047] [0047] In one example, the polymerizable composition of the present disclosure comprises a first siloxane monomer represented by formula (1):
[0048] [0048] In another example, the polymerizable composition of the present disclosure comprises a first siloxane monomer represented by formula (1):
[0049] [0049] In another example, the polymerizable composition of the present disclosure comprises a first siloxane monomer represented by formula (1):
[0050] [0050] In another example, the vinyl-containing hydrophilic monomer or monomer component may comprise or consist of a monomer containing vinyl ether. Examples of monomers containing vinyl ether include, without limitation, 1,4-butanediolvinyl ether (BVE), or ethylene glycolinyl ether (EGVE), or diethylene glycolinyl ether (DEGVE) or any combination thereof. In one example, the hydrophilic monomer component comprises or consists of BVE. In another example, the hydrophilic monomer component comprises or consists of EGVE. In yet another example, the hydrophilic vinyl component comprises or consists of DEGVE.
[0051] [0051] In yet another example, the vinyl-containing hydrophilic monomer component may comprise or consist of a combination of a first hydrophilic monomer or component and a second hydrophilic monomer or hydrophilic monomer component. In one example, the first hydrophilic monomer has a different polymerizable functional group than the second hydrophilic monomer. In another example, each monomer of the first hydrophilic monomer has a different polymerizable functional group than the second hydrophilic monomer. In another example, the first hydrophilic monomer has a different polymerizable functional group than each monomer in the second component of the hydrophilic monomer. In yet another example, each monomer of the first hydrophilic monomer component has a different polymerizable functional group than each monomer of the second hydrophilic monomer component.
[0052] [0052] For example, when the first monomer or component of the hydrophilic monomer comprises or consists of one or more monomers containing amide, the second monomer or component of the hydrophilic monomer may comprise or consist of one or more monomers without amide (i.e., a or more monomers, each without an amide functional group as part of its molecular structures). As 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 monomers without vinyl (i.e., one or more monomers, each one of which without a polymerizable vinyl functional group as part of its molecular structures). In another example, when the first monomer or component of the hydrophilic monomer comprises or consists of one or more amide monomers, each of which has an N-vinyl group, the second monomer or component of the hydrophilic monomer may comprise or consist of one or more monomers without amide. When the first monomer or component of the hydrophilic monomer consists of one or more monomers without acrylate (that is, one or more monomers that do not have a polymerizable acrylate or methacrylate functional group as part of their molecular structures), the second monomer or component of the monomer hydrophilic may comprise or consist of one or more monomers containing acrylate, one or more monomers containing methacrylate, any combination thereof. When the first hydrophilic monomer or components comprise or consist of one or more monomers containing non-vinyl ether (i.e., one or more monomers, each without a polymerizable functional group of vinyl ether 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 of which has 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.
[0053] [0053] In an example, when the first monomer or component of the hydrophilic monomer comprises or consists of a hydrophilic monomer containing amide with 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, EGVE or DEGVE, or any combination thereof. The first hydrophilic monomer can comprise VMA and the second hydrophilic monomer can comprise BVE. The first hydrophilic monomer can comprise VMA and the second hydrophilic monomer can comprise EGVE. The first hydrophilic monomer can comprise VMA and the second hydrophilic monomer can comprise DEGVE. The first hydrophilic monomer can comprise VMA and the second component of the hydrophilic monomer can comprise EGVE and DEGVE.
[0054] [0054] Likewise, the first hydrophilic monomer can be VMA and the second monomer or component of the hydrophilic monomer can comprise BVE, EGVE or DEGVE, or any combination thereof. The first hydrophilic monomer can be VMA and the second hydrophilic monomer can be BVE. The first hydrophilic monomer can be VMA and the second hydrophilic monomer can be EGVE. The first hydrophilic monomer can comprise VMA and the second hydrophilic monomer can be DEGVE. The first hydrophilic monomer can be VMA and the second component of the hydrophilic monomer can be a combination of EGVE and DEGVE.
[0055] [0055] In another example, the hydrophilic monomer containing vinyl without silicon may have a molecular weight such as a molecular weight less than 400 Daltons, less than 300 Daltons, less than 250 Daltons, less than 200 Daltons or less than 150 Daltons, or about 75 to about 200 Daltons.
[0056] [0056] When a hydrophilic monomer or a component of the hydrophilic monomer is present in the polymerizable composition, the monomer or component of the hydrophilic monomer can be present in the polymerizable composition in an amount of 30 to 60 unit parts of the polymerizable composition. The monomer or component of the hydrophilic monomer can be present in the polymerizable composition of 40 to 55 unit parts, or from 45 to 50 unit parts by weight. When the hydrophilic monomer component of the polymerizable composition comprises a first monomer or component of the hydrophilic monomer and a second monomer or component of the hydrophilic monomer, the second monomer or component of the hydrophilic monomer can be present in the polymerizable composition in an amount of 0.1 to 20 unit parts of the polymerizable composition. For example, from the total amount of 30 to 60 unit parts of monomer or component of the hydrophilic monomer present in the polymerizable composition, 29.9 to 40 unit parts can comprise the first monomer or component of the hydrophilic monomer, and from 0.1 to 20 unitary parts may 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 of 1 to 15 unit parts, 2 to 10 unit parts or 3 to 7 unit parts.
[0057] [0057] In one example, the polymerizable composition of the present disclosure comprises a first siloxane monomer represented by formula (1):
[0058] [0058] In another example, the polymerizable composition of the present disclosure comprises a first siloxane monomer represented by formula (1):
[0059] [0059] In another example, the polymerizable composition of the present disclosure comprises a first siloxane monomer represented by formula (1):
[0060] [0060] As used in this document, a vinyl-containing monomer is a monomer with a single polymerizable carbon-carbon double bond (ie, a polymerizable vinyl functional group) present in its molecular structure, where, under free radical polymerization, the carbon-carbon double bond in the polymerizable vinyl functional group is less reactive than the carbon-carbon double bond present in an acrylate or in a polymerizable methacrylate functional group. In other words, although a carbon-carbon double bond is present in the acrylate and methacrylate groups, as understood in the present invention, monomers comprising a single polymerizable acrylate or methacrylate group are not considered to be vinyl-containing monomers. Examples of polymerizable groups containing carbon-carbon double bonds that are less reactive than the carbon-carbon double bonds of polymerizable groups of acrylate or methacrylate include the groups of vinylamide, vinyl ether, vinyl ester and allyl ester. Thus, as used in the present invention, examples of vinyl-containing monomers include monomers with a single polymerizable group of vinylamide, a single vinyl ether, a single vinyl ester or a single allyl ester.
[0061] [0061] Furthermore, the polymerizable compositions of the present disclosure can optionally comprise at least one hydrophobic monomer without silicon. A hydrophobic monomer is a polymerizable ingredient without silicon, having only one polymerizable functional group present in its molecular structure. The at least one hydrophobic monomer of the polymerizable composition can be a hydrophobic monomer, or it can comprise a hydrophobic monomer component composed of at least two hydrophobic monomers. Examples of hydrophobic monomers that can be used in the polymerizable compositions disclosed herein include, without limitation, hydrophobic monomers containing acrylate or hydrophobic monomers containing methacrylate, or any combination thereof. Examples of hydrophobic monomers include, without limitation, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate (MMA), ethyl methacrylate, propyl methacrylate, butyl acrylate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, styrene, or chloroprene, vinyl chloride, vinylidene or acrylonitrile chloride, 1-butene, butadiene, methacrylonitrile, viniltoluene, ether vinylethyl, perfluoro-hexylethylthiocarbonylaminoethyl methacrylate, isobornyl methacrylate, trifluorethyl methacrylate, hexafluorisopropyl methacrylate or hexafluorbutyl methacrylate, or the same methylene glycol ether methacrylate (any of the same). In a particular example, the hydrophobic monomer or monomer component may comprise or consist of MMA, EGMA or both.
[0062] [0062] When present in the polymerizable composition, the hydrophobic monomer or monomer component may be present in an amount of about 5 to about 25 unit parts, or about 10 to about 20 unit parts.
[0063] [0063] In one example, the hydrophobic monomer component can comprise at least two hydrophobic monomers, each with different polymerizable functional groups. In another example, the hydrophobic monomer component can comprise at least two hydrophobic monomers, each with the same polymerizable functional group. The hydrophobic monomer component can comprise or consist of two hydrophobic monomers, both with 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 an 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 of unitary parts of MMA to unitary parts of EGMA present in the polymerizable composition can be about 6: 1 to about 1: 1. The ratio of the single parts of MMA and EGMA present in the polymerizable composition can be about 2: 1, based on the single parts of MMA to the single parts of EGMA.
[0064] [0064] Optionally, the polymerizable composition can further comprise at least one crosslinking agent. The polymerizable composition can comprise a cross-linking agent, or it can comprise a cross-linking component comprised of at least two cross-linking agents. As used herein, a crosslinking agent is a silicon-free crosslinking agent and is therefore different from the multifunctional siloxane monomers that may be present in the polymerizable compositions.
[0065] [0065] According to the present disclosure, a crosslinking agent is 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 monomer multifunctional, such as a bifunctional, trifunctional or tetrafunctional monomer. Silicon-free crosslinking agents that can be used in the polymerizable compositions disclosed in the present invention include, for example and without limitation, allyl (meth) acrylate, lower alkylene glycol di (meth) acrylate, (polyalkylene) glycol di (meth) acrylate (lower), lower alkylene di (meth) acrylate, divinyl ether, divinylsulfone, di and trivinylbenzene, trimethylolpropane tri (meth) acrylate, pentaerythritol (meth) acrylate, bisphenol A (meth) acrylate, methylenebis (met ) acrylamide, trialyl phthalate and diaryl phthalate, or any combination thereof. Cross-linking agents, as disclosed in Examples C1 and 1-25, include, for example, ethylene glycol dimethacrylate (EGDMA), triethylene glycol dimethacrylate (TEGDMA), triethylene glycolvinyl ether (TEGDVE) or any combination thereof. In one example, the crosslinking agent may have a molecular weight of less than 1500 Daltons, less than 1000 Daltons, less than 500 Daltons or less than 200 Daltons.
[0066] [0066] In one example, the crosslinking agent can be a vinyl containing crosslinking agent. As used herein, a vinyl-containing crosslinking agent is a monomer that has at least two polymerizable carbon-carbon double bonds (that is, at least two polymerizable vinyl functional groups) present in its molecular structure, where each of the at least two polymerizable carbon-carbon bonds present in the polymerizable vinyl functional groups is less reactive than a carbon-carbon double bond present in a polymerizable acrylate or methacrylate functional group. Although carbon-carbon double bonds are present in the polymerizable acrylate and methacrylate functional groups, as comprised in the present invention, crosslinking agents comprising one or more polymerizable acrylate or methacrylate group (for example, an acrylate-containing crosslinking agent or an agent crosslinkers containing methacrylate) are not considered to be vinyl containing crosslinking agents. Polymerizable functional groups having carbon-carbon double bonds are less reactive than polymerizable carbon-carbon double bonds of polymerizable acrylate or methacrylate groups include, for example, polymerizable functional groups of vinylamide, vinyl ester, vinyl ether and allyl ester. Thus, as used in the present invention, vinyl-containing crosslinking agents include, for example, crosslinking agents with at least two polymerizable functional groups selected from a vinylamide, vinyl ether, vinyl ester, allyl ester and any combination thereof. As used in this document, a crosslinking agent containing mixed vinyl is a crosslinking agent that has at least one polymerizable carbon-carbon double bond (i.e., at least one polymerizable vinyl functional group) present in its structure that is less reactive than that the carbon-carbon double bond present in a polymerizable acrylate or methacrylate functional group, and at least one polymerizable functional group present in its structure with a carbon-carbon double bond that is at least as reactive as the carbon-carbon double bond in a polymerizable acrylate or methacrylate functional group.
[0067] [0067] In one example, the crosslinking agent or crosslinking agent component can comprise a vinyl containing crosslinking agent. For example, the crosslinking agent or component of the vinyl containing crosslinking agent may comprise or consist of a crosslinking agent containing vinyl ether. In another example, the crosslinking agent or crosslinking agent component may comprise or consist of an acrylate-containing crosslinking agent (i.e., a crosslinking agent that has at least two polymerizable acrylate functional groups), or a crosslinking agent containing methacrylate (i.e., at least two methacrylate polymerizable functional groups), or at least one acrylate-containing crosslinking agent and at least one methacrylate-containing crosslinking agent.
[0068] The crosslinking agent component may comprise or consist of two or more crosslinking agents, each of which has a different polymerizable functional group. For example, the crosslinking agent component can comprise a vinyl containing crosslinking agent, and an acrylate containing crosslinking agent. The crosslinking agent component can comprise a vinyl containing crosslinking agent and a methacrylate crosslinking group. The crosslinking agent component can comprise or consist of a crosslinking agent containing vinyl ether and a crosslinking agent containing methacrylate.
[0069] [0069] Optionally, the polymerizable composition of the present disclosure can comprise or consist of a crosslinking agent or crosslinking agent component containing vinyl and can be free of a crosslinking agent without non-vinyl silicon. In other words, in this example, the polymerizable composition comprises the first siloxane monomer, the second siloxane monomer and at least one crosslinking agent, wherein at least one crosslinking agent consists of at least one vinyl containing crosslinking agent (or i.e., a single vinyl containing crosslinking agent or a vinyl containing crosslinking component comprising two or more vinyl containing crosslinking agents), since no vinyl containing crosslinking agent is present in the polymerizable composition. In other words, in this example, there are no non-vinyl crosslinking agents present in the polymerizable composition.
[0070] [0070] In one example, the polymerizable composition of the present disclosure comprises a first siloxane monomer represented by formula (1):
[0071] [0071] In another example, the polymerizable composition of the present disclosure comprises a first siloxane monomer represented by formula (1):
[0072] [0072] The crosslinking agent or optional crosslinking agent component can be present in the polymerizable composition in an amount of 0.01 to 10.0 unit parts, for example, from 0.05 to 5.0 unit parts, from 0.1 to 2.0 unit parts, 0.2 to 1.0 unit part or 0.3 to 0.8 unit part. In one example, when the crosslinking agent or crosslinking agent component comprises a vinyl containing crosslinking agent, the crosslinking agent or vinyl containing crosslinking component may be present in the polymerizable composition in an amount of 0.01 to 0 , 50 unit parts, such as 0.05 to 0.30 unit parts or 0.1 to 0.2 unit parts. When the at least one crosslinking agent is a crosslinking agent or crosslinking agent component containing acrylate or containing methacrylate, the crosslinking agent or crosslinking agent component containing acrylate or containing methacrylate can be present in the polymerizable composition in an amount of 0.1 to 2.0 unit parts, such as 0.3 to 1.2 unit parts or 0.5 to 0.8 unit parts. When a combination of a crosslinking agent or crosslinking agent component containing vinyl, and a crosslinking agent or crosslinking agent component containing acrylate or containing methacrylate is used, the crosslinking agent or crosslinking agent component of vinyl and the crosslinking agent or crosslinking agent component containing acrylate or containing methacrylate can be present in the polymerizable composition in a ratio of 1: 2 to 1:20, or from 1: 3 to 1:12, or from 1: 4 to 1: 7 based on the weight ratio of the unitary parts of the crosslinking agent or vinyl containing crosslinking agent component to the unitary parts of the crosslinking agent or crosslinking agent component containing acrylate or containing methacrylate.
[0073] [0073] The polymerizable composition can optionally include one or more organic diluents, one or more polymerization initiators (i.e., ultraviolet (UV) initiators or thermal initiators, or both), one or more UV absorbing agents, one or more dyeing agents, one or more oxygen scavengers, one or more chain transfer agents or any combination thereof. These optional ingredients can be reactive or non-reactive ingredients. In one example, polymerizable compositions may be free of diluent, so they do not contain any organic diluent to achieve miscibility between siloxanes and the other ingredients that make up the lens, such as optional hydrophilic monomers, hydrophobic monomer and crosslinking agents. In addition, many of the present polymerizable compositions are essentially water-free (for example, they contain no more than 3.0% or 2.0% water by weight).
[0074] [0074] The polymerizable compositions disclosed in this document can optionally comprise one or more organic diluents, that is, the polymerizable composition can comprise an organic diluent, or it can comprise a component of the organic diluent that comprises two or more organic diluents. Organic diluents that can optionally be included in the present polymerizable compositions include alcohols, including lower alcohols, such as, for example and without limitation, pentanol, hexanol, 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 unit parts, or from about 2 unit parts to about 50 unit parts, or about 5 unit parts to about 30 unit parts.
[0075] [0075] Approaches commonly employed to increase the miscibility of siloxane monomers and hydrophilic monomers include the addition of organic diluents to the polymerizable composition to act as compatibility agents between hydrophilic monomers and siloxane monomers that are typically more hydrophobic, or using only low molecular weight siloxane monomers (eg molecular weight less than 2500 Daltons). The use of the first siloxane as described above makes it possible to include both a second high molecular weight siloxane and a high level of one or more hydrophilic monomers in the polymerizable compositions of the present disclosure. And while it is possible to include one or more organic diluents in the present polymerizable compositions disclosed in this document, it may not be necessary to do this in order to obtain a miscible polymerizable composition according to the present disclosure. In other words, in one example, the silicone-hydrogel contact lenses of the present disclosure are formed from polymerizable compositions, which are free of an organic diluent.
[0076] [0076] An example of the disclosed polymerizable composition may be miscible when it is initially prepared, and may remain miscible over a period of time suitable for the commercial manufacture of contact lenses, such as, for example, for 2 weeks, 1 week or 5 days. Usually, when polymerized and processed in contact lenses, miscible polymerizable compositions form contact lenses with ophthalmologically acceptable clarities.
[0077] [0077] The present polymerizable compositions can optionally include one or more polymerization initiators, that is, the polymerizable composition can comprise an initiator, or it can include an initiator component that comprises two or more polymerization initiators. The polymerization initiators that can be included in the present polymerizable compositions include, for example, azo compounds, organic peroxides or both. Initiators that may be present in the polymerizable composition include, for example and without limitation, benzoimethyl ether, benzildimethyl ketal, alpha, alpha-diethoxyacetophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzoin peroxide, t-butyl peroxide, azobisisututyl nitrile or azobisdimethylvaleronitrile, or any combination thereof. UV photoinitiators may include, for example, phosphine oxides such as diphenyl (2,4,6-trimethylbenzoyl) phosphine, benzoinmethyl ether, 1-hydroxycyclohexylphenylketone or Darocur (available from BASF, Florham Park, NJ, USA) , or Irgacur (also available from BASF), or any combination thereof. In many of the examples C1 and 1-25 disclosed in this document, the polymerization initiator is the 2,2'-azobis-2-methylpropanonitrile thermal initiator (VAZO-64, obtained from EI DuPont de Nemours & Co., Wilmington, DE , USA). Other commonly used thermoinitiators can include 2,2'-azobis (2,4-dimethylpentanonitrile) (VAZO-52) and 1,1'-azobis (cyanocyclohexane) (VAZO-88). The initiator or polymerization initiator component may be present in the polymerizable composition in an amount of about 0.01 unit part to about 2.0 unit parts, or in an amount of about 0.1 unit part to about 1.0 unit part, or from about 0.2 unit part to about 0.6 unit part by weight.
[0078] [0078] 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 may comprise a component of the UV absorbing agent comprising two or more UV absorbing agents. UV-absorbing agents that can be included in the present polymerizable compositions include, for example, benzophenones, benzotriazoles or any combination thereof. In many of the C1 and 1-25 examples disclosed herein, the UV-absorbing agent is 2- (4-benzoyl-3-hydroxyphenoxy) ethyl acrylate (UV-416) or 2- (3- (2H-) methacrylate benzotriazol-2-yl) -4-hydroxyphenyl) ethyl (NORBLOC® 7966, obtained 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 unitary to about 5.0 unitary parts, or in an amount of about 0, 1 unit part to about 3.0 unit parts, or from about 0.2 unit part to about 2.0 unit parts by weight.
[0079] [0079] The polymerizable compositions of the present disclosure may also optionally include at least one dyeing agent (i.e., dyeing agent or a dyeing agent component comprising two or more dyeing agents), although the dyed product and the clear lens are contemplated. In one example, the dyeing agent can be an effective reactive dye or pigment to impart color to the resulting lens product. The dyeing agent or dyeing agent component of the polymerizable composition may comprise a polymerizable dyeing agent, or it may comprise a non-polymerizable dyeing agent, or any combination thereof. The polymerizable dyeing agent can be a dyeing agent whose molecular structure comprises a polymerizable functional group, or it can be a dyeing agent whose molecular structure includes a monomer portion and an ink portion, i.e., the dyeing agent can be a monomer-dye compound. The molecular structure of the dyeing agent can comprise a beta-sulfone functional group, or it can comprise a triazine functional group. Dyeing agents may include, for example, Blue VAT 6 (7,16-dichloro-6,15-dihydroanthrazine-5,9,14,18-tetrone) or 1-amino-4- [3- (beta - sulfatoethylsufonyl) anilio] -2-anthraquinonesulfonic (Reactive Blue CI 19, RB-19), or a monomer-dye compound of Reactive Blue 19 and hydroxyethylmethacrylate (RB-19, HEMA) or 1,4-bis [4 - [( 2-methacryloxyethyl) phenylamino] anthraquinone (Reactive Blue 246, RB-246, available from Arran Chemical Company, Athlone, Ireland), or 1,4-bis [(2-hydroxyethyl) amino] bis (2-propenoic) ester] -9,10-anthracenedione (RB-247), or Reactive Blue 4, RB-4 or a Reactive Blue 4 monomer-dye compound and hydroxyethyl methacrylate (RB-4 HEMA or "Blue HEMA”), or any combination In one example, the dyeing agent or the dyeing agent component may comprise a polymerizable dyeing agent The polymerizable dyeing agent component may comprise, for example, RB-246, RB-274, RB-4 HEMA or RB-19 HEMA, or any combination of the esmos. Examples of monomer-dye compounds include RB-4 HEMA and RB-19 HEMA. Additional examples of monomer-dye compounds are described in US5944853 and US7216975, both of which are incorporated in their entirety by reference herein. Other exemplary dyeing agents are disclosed, for example, in United States International Patent Application Publication No. 2008/0048350, the disclosure of which is incorporated in its entirety by reference in the present invention. In many of the examples C1 and 1-25 disclosed in this document, the dyeing agent is a reactive blue dye, as described in US4997897, the disclosure of which is incorporated in its entirety by reference in the present invention. Other dyeing agents suitable for use according to the present invention are phthalocyanine pigments, such as phthalocyanine blue, phthalocyanine green, chromium-alumina-cobaltous oxide, chromium oxides or various iron oxides for the colors red, yellow, brown and black , or any combination thereof. Opacifying agents, such as titanium dioxide, can also be incorporated. For certain applications, a combination of dyeing agents with different colors can be used as the component of the dyeing agent. If used, the dyeing agent or dyeing agent component can be present in the polymerizable composition in an amount ranging from about 0.001 unit part to about 15.0 unit parts, or from about 0.005 unit part to about 10.0 unit parts, or from about 0.01 unit parts to about 8.0 unit parts.
[0080] [0080] The polymerizable compositions of the present disclosure may optionally comprise at least one oxygen scavenger, i.e., 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 the oxygen scavenger component of the present polymerizable compositions include, for example, vitamin E or phenolic compounds, phosphite compounds, phosphine compounds or amine oxide compounds, or any combination of them. For example, the oxygen scavenger or the oxygen scavenger component may consist of or comprise a phosphine-containing compound. In many of the examples C1 and 1-25 disclosed herein, the oxygen scavenger or oxygen scavenger component is a phosphine-containing compound, such as triphenylphosphine, or a polymerizable form of triphenylphosphine, such as diphenyl (P-viniphenyl) phosphine.
[0081] [0081] Chain transfer is a polymerization reaction in which the activity of an increasing 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 include at least one chain transfer agent, or it can comprise a component of the chain transfer agent, or it can comprise at least two chain transfer agents. Examples of chain transfer agents that can be included as the chain transfer agent of the present polymerizable compositions include, for example, thiol compounds, or halogen compounds or C3-C5 hydrocarbons, or any combination thereof. In many of the examples C1 and 1-25 disclosed herein, the chain transfer agent is allyloxyethanol. 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 unit part to about 1.5 unit part, for example, about 0.1 unit part to about 0.5 unit part.
[0082] [0082] In one example, the silicone-hydrogel contact lenses of the present disclosure may have high levels of equilibrium water (EWC) s. Methods for determining EWC are known to those of ordinary skill in the art, and can be based on the loss of weight of a lens during a drying process. For example, silicone-hydrogel contact lenses can have, when fully hydrated, a water content in the balance of 20% to 75% by weight. The present contact lenses can have an EWC of about 30% to about 70%, or from about 45% to about 65%, or from about 50% to about 63%, or about 50% about 67% or about 55% to about 65% by weight.
[0083] [0083] The present contact lenses can have an oxygen permeability (or Dk) of at least 55 barrers (Dk> 55 barrers), or an oxygen permeability of at least 60 barrers (Dk> 60 barrers) or a permeability to oxygen of at least 65 barrers (Dk> 65 barrers). The lenses can have an oxygen permeability of about 55 barrers to about 135 barrers, or about 60 barrers to about 120 barrers, or about 65 barrers to about 90 barrers or about 50 barrers to about of 75 barrers. Various methods of determining oxygen permeability are known to those of ordinary skill in the art.
[0084] [0084] The silicone-hydrogel contact lenses of the present disclosure have, when fully hydrated, an average elastic modulus of about 0.20 MPa to about 0.90 MPa. For example, the average modulus may be from about 0.30 MPa to about 0.80 MPa, or from about 0.40 MPa to about 0.75 MPa, or from about 0.50 MPa to about 0.70 MPa.
[0085] [0085] As used in the present invention, it is understood that the modulus of a lens or of a contact lens body refers to the elastic modulus, also known as Young's modulus. It is a measure of the stiffness of an elastic material. The elastic modulus can be measured using a method according to the ANSI Z80.20 standard. In one example, the elastic modulus can be measured using an Instron Model 3342 or Model 3343 mechanical test system.
[0086] [0086] The present contact lenses can have an oxygen permeability of at least 55 barrers (Dk> 55 barrers), or an EWC of about 30% to about 70%, or an elastic module of about 0.2 MPa at about 0.9 MPa, or any combination thereof. 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 elastic modulus of about 0.3 MPa to about 0.8 MPa, or any combination thereof. In another example, the present contact lenses can have an oxygen permeability of at least 60 barrers, or an EWC of about 45% to about 65% or an elastic module from about 0.40 MPa to about 0.75 MPa, or any combination thereof.
[0087] [0087] In one example, the present contact lenses have an oxygen permeability of at least 55 barrers, an EWC of about 30% to about 70% and an elastic modulus of about 0.2 MPa to about 0 , 9 MPa.
[0088] [0088] The silicone-hydrogel contact lenses of the present disclosure can have, when fully hydrated, an average energy loss percentage of about 25% to about 40%. For example, the average percentage of energy loss can be from about 27% to about 40%, or it can be from about 30% to about 37%.
[0089] [0089] As used in the present invention, the percentage of energy loss is a measure of the energy lost as heat when the energy charge and discharge cycles are applied to viscoelastic materials. The percentage of energy loss can be determined using a variety of methods known to those of ordinary skill in the art. For example, the force involved in stretching a sample up to 100% elongation and then returning it to 0% at a constant rate can be determined and used to calculate the percentage energy loss for the material.
[0090] [0090] The present contact lenses can have 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 of ordinary skill in the art.
[0091] [0091] The silicone-hydrogel contact lenses of the present invention may have dynamic bubble contact advance angles of less than 120 degrees, such as, for example, less than 90 degrees, when fully hydrated, less than 80 degrees, when fully hydrated, less than 70 degrees, when fully hydrated, or less than 65 degrees, when fully hydrated, or less than 60 degrees, when fully hydrated, or less than 50 degrees, when fully hydrated.
[0092] [0092] The silicone-hydrogel contact lenses of the present invention may have static contact angles of trapped bubble less than 70 degrees when fully hydrated or less than 60 degrees when fully hydrated or less than 55 degrees when fully hydrated hydrated, or less than 50 degrees, when fully hydrated, or less than 45 degrees, when fully hydrated.
[0093] [0093] In one example, the present contact lenses may have a wet extractable component. The wet extractable component is determined based on the weight lost during methanol extraction from contact lenses that were fully hydrated and sterilized prior to drying and the extraction test. The wet extractable component can comprise unreacted or partially reacted polymerizable ingredients of the polymerizable composition. The wet extractable component consists of extractable materials with organic solvent remaining in the lens body, after being fully processed to form a sterile contact lens, for lenses formed from polymerizable compositions that comprise non-polymerizable ingredients. For lenses extracted during manufacture in an extraction liquid that 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 then, the wet extractable component can essentially consist of extractable components formed from reactive polymerizable ingredients of the polymerizable composition, that is, unreacted polymerizable components and partially reacted polymerizable ingredients. In lenses made with a polymerizable composition free of a diluent, the wet extractable component can be present in the contact lens in an amount of about 1% w / w, about 15% w / w, or about 2% w / w for 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 of a polymerizable composition comprising a diluent, the wet extractable component may consist of a portion of the diluent, as well as unreacted and partially reacted polymerizable ingredients, and may be present in the contact lens in an amount of about 1% w / w about 20% w / w, or about 2% w / w about 15% w / w of the lens, or about 3% w / w about 10% w / w based on the dry weight of the lens body before the extraction test.
[0094] [0094] In one example, the present contact lenses may have a wet extractable component. The dry extractable component is determined based on the weight lost during methanol extraction from polymeric lens bodies that have not been washed, extracted (as part of a manufacturing process), hydrated or sterilized prior to the drying and extraction test. The dry extractable component can comprise unreacted or partially reacted polymerizable ingredients of the polymerizable composition.
[0095] [0095] The wet extractable component may comprise polymerizable ingredients that have not reacted or that have partially reacted, of the polymerizable composition. When optional non-polymerizable ingredients, such as thinners and the like, are present in the polymerizable composition, the dry extractable component may further comprise non-polymerizable ingredients.
[0096] [0096] In lenses made of a diluent-free polymerizable composition, the dry extractable component of the lens essentially consists of dry extractable components contributed by polymerizable ingredients of the polymerizable composition (or polymerizable ingredients that have not reacted or have partially reacted) and may also include dry extractable materials contributed by optional nonpolymerizable components present in the polymerisable composition in small quantities (eg less than 3% w / w), such as, for example, dyeing agents, oxygen removers and the like. In lenses made from a diluent-free polymerizable composition, the dry extractable component may be present in the polymeric lens body in an amount of about 1% w / w to about 30% w / w of the lens body, or about from 2% w / w to about 25% w / w, or from about 3% w / w to about 20% w / w, or from about 4% w / w to 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.
[0097] [0097] In lenses made from a polymerizable composition comprising a large amount (for example, greater than 3% w / w) of an optional non-polymerizable ingredient, such as a diluent, the dry extractable component consists of extractable materials contributed by non-polymeric ingredients polymerizable components of the polymerizable composition. The total amount of dry extractable components contributed by reactive ingredients and non-polymerizable ingredients present in the contact lens can consist of an amount 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 5% to about 10% based on the dry weight of the polymeric lens body before the extraction test. The total amount of dry extractable components contributed by polymerizable ingredients (ie, unreacted or partially reacted polymerizable ingredients) can be 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 extraction test.
[0098] [0098] The contact lenses of the present disclosure, once they are configured to be placed or arranged in a cornea of the human or animal eye, are ophthalmologically acceptable contact lenses. As used in the present invention, an ophthalmologically acceptable contact lens is a contact lens that has at least one of a variety of different properties, as described below. An ophthalmologically acceptable contact lens can be formed from, and packaged in ophthalmologically acceptable ingredients, so that the lens is non-cytotoxic and does not release irritating and / or toxic ingredients during wear. 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 the eye, for example, a transmittance 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 handling and caring for the lens for a period of time based on its expected lifetime. For example, its modulus, elastic strength and elongation may be sufficient to withstand insertion, wear, removal and, optionally, cleaning during the expected life of the lens. The level of these suitable properties will vary depending on the intended life and use of the lens (for example, single-use disposable daily, various uses, monthly, etc.). An ophthalmologically acceptable contact lens can have an effective or appropriate ion flux to substantially inhibit or substantially prevent corneal staining, such as corneal staining more severe than superficial or moderate corneal staining after continuous wear of the lens on the cornea for 8 hours or more. An ophthalmologically acceptable contact lens may have a level of oxygen permeability sufficient to allow oxygen to reach the cornea of the eye using the lens in sufficient quantity for the long-term health of the cornea. An ophthalmologically acceptable contact lens can be a lens that does not cause substantial or undue corneal swelling in an eye with the lens, for example, no more than about 5% or 10% of the corneal swelling after being used on a cornea of the eye during the night sleep period. An ophthalmologically acceptable contact lens can be a lens that allows the lens to move over the cornea of the eye using enough lens to facilitate the flow of tears between the lens and the eye, in other words, that does not allow the lens to stick to eyes with sufficient strength to prevent normal lens movement, and having a low enough level of movement in the eye to allow vision correction. An ophthalmologically acceptable contact lens can be a lens that allows use in the eye without discomfort and / or irritation and / or pain that is too much or undue. An ophthalmologically acceptable contact lens can be a lens that substantially inhibits or prevents sufficient lipid and / or protein deposition to cause the lens wearer to remove the lens because of such deposits. An ophthalmologically acceptable contact lens may have at least one of a water content, or a surface wettability, or a module or design, or any combination thereof, that is effective in facilitating the ophthalmologically compatible use of the contact lens by a contact lens wearer for at least a day. It is understood that the ophthalmologically compatible use refers to the wear of a lens by a lens wearer with little or no discomfort, and with little or no occurrence of corneal staining. It is possible to determine whether a contact lens is ophthalmologically acceptable using conventional clinical methods, such as those performed by an eye care professional, and as understood by those normally skilled in the art.
[0099] [0099] In an example of the present disclosure, the contact lens may have ophthalmologically acceptable wetted lens surfaces. For example, the contact lens may have ophthalmologically acceptable wetted lens surfaces when the polymerizable composition used to form the lens is free of a wetting agent, or when the polymerizable composition used to form the lens is free of an organic solvent, or when the polymeric lens body is free of a wetting agent, or when the polymeric lens body is washed, extracted and hydrated in extraction liquid free of a volatile organic solvent, or when the lens is free of surface treatment or modification of the surface, or any combination thereof. The contact lens may have ophthalmologically acceptable wetted lens surfaces when the polymerizable composition used to form the lens is free of an internal wetting agent, or when the polymerizable composition used to form the lens is free of an organic thinner, or when the polymeric lens body comes into contact only with liquids free of volatile organic solvents during manufacture, or when the polymeric lens body is exempt from plasma surface treatment, or any combination thereof.
[0100] [00100] An approach commonly used in the art to increase the wettability of contact lens surfaces is to apply treatments to the lens surfaces or modify the lens surfaces. According to the present disclosure, silicone hydrogel contact lenses can have ophthalmologically acceptable moisturizing lens surfaces without the presence of a surface treatment or surface modification. Surface treatments include, for example, crown plasma treatments that increase the hydrophilicity of the lens surface. Although it is possible to apply one or more plasma surface treatments to the present lens bodies, it is not necessary to do so to obtain a silicone hydrogel contact lens with ophthalmologically acceptable lens surfaces when fully hydrated. In other words, in one example, the silicone hydrogel contact lenses of the present disclosure may be exempt from a plasma or crown surface treatment.
[0101] [00101] Surface modifications include wetting agents that bond to the lens surface, such as, for example, binding to a wetting agent, such as a hydrophilic polymer to at least one lens surface by chemical bonding or other form of chemical interaction. In some cases, the wetting agent can be attached to the lens surface as well as to at least a portion of the polymeric matrix of the lens, that is, at least a portion of the lens mass, by chemical bonding or other form of chemical interaction. Ophthalmologically acceptable wetted lens surfaces can be ophthalmologically acceptable wetting without the presence of a wetting agent (e.g., 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 the lenses of the present invention, it is not necessary to do so to obtain a silicone hydrogel contact lens with ophthalmologically acceptable lens 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 including polyvinylpyrrolidone attached to a lens surface. Alternatively, in another example, the silicone hydrogel contact lenses of the present disclosure may be free of a wetting agent attached to the surface of the lens.
[0102] [00102] Another method of increasing the wetting capacity of the lens is to physically trap a wetting agent within the lens body or contact lens, such as by introducing the wetting agent into the lens body when the lens body swells, and, then, returning the lens body to a less swollen state, thereby trapping a portion of a wetting agent within the lens body. The wetting agent can be permanently trapped inside the lens body, or it can be released from the lens over time, such as during wear. The ophthalmologically acceptable wetted lens surfaces of the present disclosure can be ophthalmologically acceptable wetted without the presence of a wetting agent (for example, a polymeric material or a non-polymeric material) physically trapped in the lens body after the polymeric lens body is formed. Although it is possible to physically trap one or more wetting agents in the present lenses, it is not necessary to do this to obtain a silicone-hydrogel contact lens with ophthalmologically acceptable lens 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 including polyvinylpyrrolidone trapped within the lenses. Alternatively, the silicone hydrogel contact lenses of the present disclosure may be free of a wetting agent physically trapped within the lens. As used in the present invention, physically entrapped refers to the immobilization of a wetting agent, or other ingredient, in the polymeric matrix of the lens with little or no chemical bonding or chemical interaction occurring between the wetting agent and / or another ingredient and the polymeric matrix . This is unlike the ingredients that are chemically linked to the polymeric matrix, such as by ionic bonds, covalent bonds, van der Waals forces and the like.
[0103] [00103] Another approach commonly used in the art to increase the wettability 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 ophthalmologically acceptable moisturizing lens surfaces 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 this to obtain a silicone-hydrogel contact lens with ophthalmologically wettable lens surfaces 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. Alternatively, in another example, the polymerizable compositions of the present invention can further comprise a wetting agent.
[0104] [00104] In one example, the wetting agent can be an internal wetting agent. The internal wetting agent can be bonded within at least a part of the polymeric matrix of the lens. For example, the internal wetting agent can be bound within at least part of the polymeric matrix of the lens by chemical bonding or other form of chemical interaction. In some cases, the wetting agent may 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 bind one or more internal wetting agents within the polymeric matrix of the present lenses, it is not necessary to do this to obtain a silicone hydrogel contact lens with ophthalmologically acceptable lens 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. Alternatively, in another example, the silicone hydrogel contact lenses of the present disclosure may be free of an internal wetting agent, attached to at least a part of the polymeric matrix of the lens.
[0105] [00105] In another example, the wetting agent can be an internal polymeric wetting agent. The internal polymeric wetting agent can be present in the polymeric lens body as part of an interpenetrating polymer (IPN) network or a semi-IPN. An interpenetrating polymer network is formed by at least two polymers, each of which is cross-linked with itself, but neither is cross-linked with the other. Likewise, a semi-IPN is formed by at least two polymers, at least one of which is cross-linked with itself, but not with the other polymer, and the other is not cross-linked with itself or with the other polymer. In an example of the present disclosure, the contact lens may have ophthalmologically acceptable moisturizing lens surfaces when the polymeric lens body is free of an internal polymeric wetting agent present in the lens body as an IPN or a semi-IPN. Alternatively, the contact lens may comprise an internal polymeric wetting agent present in the lens body as an IPN or a semi-IPN.
[0106] [00106] In yet another example, the wetting agent can be a binding compound present in the polymerizable composition used to form the lens body, or a binding agent physically trapped within the polymeric lens body after the lens body is formed. When the wetting agent is a binding compound, after polymerization of the lens body or entrapment of the binding agent in the polymeric lens body, the binding compound can subsequently bind a second wetting agent to the lens body when the lens body is in contact by the wetting agent. Bonding can occur as part of the manufacturing process, for example, as a washing process, or it can occur when the lens body comes into contact with a packaging solution. The bond can take the form of an ionic bond, a covalent bond, or a van der Waals form of attraction. The binding agent may comprise a portion of the boronic acid or group so that a portion of polymerized boronic acid or group is present in the polymeric lens body, or so that a portion of the boronic acid or group is physically trapped in the lens body polymeric. 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 binds to the form of boronic acid. Optionally, it can be 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 portions or groups, including polymerized portions or groups of boronic acid, that is, specifically, silicone hydrogel contact lenses can be formed from one polymerizable composition free of a boronic acid form, such as, for example, a polymerizable form of boronic acid including vinylphenylboronic acid (VPB), can be formed of a polymer free of units derived from a polymerizable form of boronic acid such as vinylphenylboronic acid ( VPB), and the polymeric lens body and silicone-hydrogel contact lenses may be free of a boronic acid form, including the polymeric or non-polymeric form of boronic acid, physically trapped in it. Alternatively, the polymerizable composition, or the polymeric lens body, or the silicone-hydrogel contact lens, or any combination thereof, may include at least one bonding agent.
[0107] [00107] In addition to including wetting agents in the polymerizable composition and modifying the lens surfaces, washing the polymeric lens bodies in volatile organic solvents or aqueous solutions of volatile organic solvent has been used to increase the wettability of the lens surfaces. While it is possible to wash the present polymeric lens body in a volatile organic solvent or in an aqueous solution of a volatile organic solvent, according to the present disclosure, it is not necessary to do this to obtain a silicone hydrogel contact lens with surfaces ophthalmologically acceptable lenses when fully hydrated. In other words, in one example, the silicone hydrogel contact lenses of the present invention were not 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 lens body and / or the hydrated contact lens can be free of an agent humectant, either free from surface treatment or free from surface modification, or was not 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 washing liquids free of a volatile organic solvent, such as, for example, water or aqueous solution free of a volatile organic solvent, that is, a liquid free of volatile lower alcohol.
[0108] [00108] The use of volatile organic solvents to extract lens bodies contributes significantly to production costs, due to factors such as the cost of organic solvents, the cost of solvent disposal, the need to use explosion-proof production equipment , the need to remove from the lenses before packaging and the like. However, the development of polymerizable compositions capable of consistently producing contact lenses with ophthalmologically acceptable moisturizing lens surfaces when extracted in aqueous liquids free of volatile organic solvents can be challenging. For example, it is common to find non-wetting regions present on the lens surfaces of contact lenses that have been extracted from the lens in aqueous liquids free of volatile organic solvents.
[0109] [00109] 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 manufacture. In other words, the washing, extracting and hydrating liquids used for such lenses, as well as all liquids used during wet demoulding, or removing the wet lens, or washing, or any other manufacturing step, are all solvent-free. volatile organics. In one example, the polymerizable composition used to form such lenses that are not contacted by 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 monomer or component of the vinyl-containing hydrophilic monomer may include, for example, VMA. Monomers containing vinyl ether can include, for example, BVE, EGVE, DEGVE or any combination thereof. In a particular example, the vinyl ether-containing monomer may be a vinyl ether-containing monomer that is 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. Such mixtures include, for example, mixtures of VMA and one or more vinyl ethers such as, for example, BVE, DEGVE or EGVE, or any combination thereof.
[0110] [00110] When present, the monomer or monomeric component containing hydrophilic vinyl ether can be present in the polymerizable composition in an amount of about 1 to about 15 unit parts, or about 3 to about 10 unit parts. When present as a mixture with a hydrophilic monomer containing vinyl that is not a vinyl ether, the portion of the monomer or monomer component containing hydrophilic vinyl ether that is not a vinyl ether and the monomer or monomer component containing hydrophilic vinyl ether may be present in the composition polymerizable in a ratio of at least 3: 1, or from about 3: 1 to about 15: 1, or from about 4: 1 based on the ratio of the unit parts by weight of the monomer or hydrophilic monomeric component that is not a vinyl ether for the unit parts by weight of the monomer or monomer component containing hydrophilic vinyl ether.
[0111] [00111] Another approach for producing contact lenses with ophthalmologically acceptable wettable lens surfaces in accordance with the present disclosure, particularly lenses extracted in a liquid free of a volatile organic solvent and including lenses that do not come into contact with a solvent volatile organic during manufacture, it may be to limit the amount of a vinyl-containing cross-linking agent or cross-linking agent included 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 unit part, or about 0.01 to about 0 , 30 unit part, or from about 0.05 to about 0.20 unit part, or in an amount of about 0.1 unit part. In one example, a vinyl-containing crosslinking agent or crosslinking agent component may be present in the polymerizable composition in an amount effective to produce a contact lens with improved wettability compared to the contact lens produced from the same polymerizable composition, but having an amount of the vinyl-containing crosslinking agent or crosslinking agent greater than about 2.0 unit parts, or greater than about 1.0 unit part, the greater than about 0.8 unit parts, or greater than about 0.5 unit part, or greater than about 0.3 unit part.
[0112] [00112] Although limiting the amount of the crosslinking agent or component of the vinyl containing crosslinking agent can improve wettability, in one example, the inclusion of a crosslinking agent or component of the vinyl containing crosslinking agent 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 vinyl containing crosslinking agent component may be present in the polymerizable in an amount effective to produce a contact lens that has improved dimensional stability compared to a contact lens produced from same polymerizable composition, but without the crosslinking agent or vinyl containing crosslinking agent component.
[0113] [00113] Yet another approach for producing contact lenses with ophthalmologically acceptable wettable surfaces in accordance with the present disclosure, particularly lenses washed with a liquid free of volatile organic solvent, may be to include an amount of a crosslinking agent or agent component crosslinking agent containing vinyl in the polymerizable composition based on the ratio of the unit parts by weight of the vinyl containing hydrophilic monomer or monomer component present in the composition to the unit parts by weight of the crosslinking agent or component of the vinyl containing crosslinking agent present in the composition. For example, the total unit parts of the hydrophilic monomer or monomer component and the total unit parts of the vinyl-containing crosslinking agent or crosslinking agent may be present in the polymerizable composition in a ratio greater than about 125: 1, or about 150: 1 to about 625: 1, or from about 200: 1 to about 600: 1, or from about 250: 1 to about 500: 1, or from about 450: 1 to about 500: 1, based on the ratio of the unit parts by weight of all the vinyl-containing hydrophilic monomers present in the polymerizable composition to the total unit parts by weight of all the vinyl-containing crosslinking agents present in the polymerizable composition.
[0114] [00114] Some specific examples of silicone hydrogel contact lenses will now be described, according to the present teachings.
[0115] [00115] 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 formula (1), wherein 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 with 1 to 4 carbon atoms and each R2 of formula (1) is independent of a hydrogen atom or a methyl group; a second siloxane monomer represented by formula (2):
[0116] [00116] 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, and wherein the polymerizable composition comprises further a monomer or hydrophobic monomer component, specifically the hydrophobic monomer may comprise or consist of methyl methacrylate (MMA).
[0117] [00117] 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, and in which The polymerizable composition further comprises a crosslinking agent or crosslinking agent component containing vinyl ether, specifically the crosslinking agent or crosslinking agent component may comprise or consist of triethylene glycolvinyl ether (TEGVE).
[0118] [00118] As a fourth example (example D), a silicone hydrogel contact lens comprises a polymeric lens body that is the reaction product of a polymerizable composition, as described in example A, B or C, and in which the polymerizable composition further comprises a thermal initiator or a component of the thermal initiator.
[0119] [00119] 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, B, C or D, and wherein the polymerizable composition further comprises an oxygen scavenger or oxygen scavenger component.
[0120] [00120] As a sixth example (example F), a silicone hydrogel contact lens comprises a polymeric lens body that is the reaction product of a polymerizable composition, as described in example A, B, C, D or E , and wherein the polymerizable composition further comprises a UV-absorbing agent or UV-absorbing agent component.
[0121] [00121] As a seventh example (example G), a silicone hydrogel contact lens comprises a polymeric lens body that is the reaction product of a polymerizable composition, as described in example A, B, C, D, E or F, and wherein the polymerizable composition further comprises a dyeing agent or a dyeing agent component.
[0122] [00122] 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, B, C, D, E , F or G, and where the second siloxane monomer is represented by formula (2), where R1 of formula (2) is selected from a hydrogen atom or a methyl group; R2 of formula (2) is selected from 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 formula (2) represents an integer from 4 to 100; a and b represent integers of 1 or more; a + b is equal to 20-500; b / (a + b) is equal to 0.01-0.22; the configuration of the siloxane units includes a random configuration. As an example, the second siloxane monomer can be represented by 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 a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.
[0123] [00123] As a ninth example (example I), a silicone hydrogel contact lens comprises a polymeric lens body which is the reaction product of a polymerizable composition, as described in example A, B, C, D, E , F, G or H, and 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 an ethylene glycol dimethacrylate (EGDMA ). In this example, when the polymerizable composition also comprises a crosslinking agent containing vinyl ether as part of the crosslinking agent component, specifically the crosslinking agent component can comprise or consist of triethylene glycolvinyl ether (TGDVE), together with a crosslinking agent containing methacrylate, which may comprise or consist specifically 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 that comprises or consists of a vinyl containing crosslinking agent and a crosslinking agent containing methacrylate means the crosslinking agent containing methacrylate having polymerizable functional groups that are more reactive and therefore react at a higher rate than the polymerizable functional vinyl groups present in the vinyl containing crosslinking agent.
[0124] [00124] As a tenth example (example J), a silicone hydrogel contact lens comprises a polymeric lens body that is the reaction product of a polymerizable composition, as described in example A, B, C, D, E , F, G, H or I, and wherein the polymerizable composition further comprises a chain transfer agent or chain transfer agent component that can specifically comprise or consist of allyloxyethanol (AE).
[0125] [00125] 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, B, C, D , E, F, G, H, I or J, and wherein the polymerizable composition further comprises a hydrophobic monomer or a component of the hydrophobic monomer which may comprise or specifically consist of ethylene glycol methyl ether (EGMA) methacrylate.
[0126] [00126] 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, B, C, D , E, F, G, H, I, J or K, and wherein the polymerizable composition further comprises a monomer or component of the monomer containing hydrophilic vinyl ether, for example, the monomer or component of the monomer containing hydrophilic vinyl ether comprises or consists of in 1,4-butanediolvinyl ether (BVE), or ethylene glycolinyl ether (EGVE), or diethylene glycolinyl ether (DEGVE), or any combination thereof.
[0127] [00127] In any or each of the previous examples A to L, as well as in any or all of the other examples disclosed in this document, the first siloxane monomer can have an average numerical molecular weight of 400 Daltons to 700 Daltons.
[0128] [00128] In any or each of the previous examples A to L, as well as in any or all of the other examples disclosed in this document, the polymerizable composition can comprise at least one hydrophilic monomer. The at least one hydrophilic monomer can be present in the polymerizable composition in an amount of 30 unit parts to 60 unit parts. The at least one hydrophilic monomer can comprise at least one vinyl-containing hydrophilic monomer. The at least one vinyl-containing hydrophilic monomer can be at least one amide-containing hydrophilic monomer with an N-vinyl group.
[0129] [00129] In any or all of the previous examples A to L, as well as in any or all of the other examples disclosed in this document, the polymerizable composition comprises at least one crosslinking agent, and at least one crosslinking agent. crosslinking may comprise at least one vinyl containing crosslinking agent.
[0130] [00130] In any or all of the previous examples A to L, as well as in any or all of the other examples disclosed in this document, the amount of the first siloxane monomer can be from 20 to 45 unit parts of the polymerizable composition . The amount of the first siloxane monomer can be 25 to 40 unit parts of the polymerizable composition. The amount of the first siloxane monomer can be from 27 to 35 unit parts of the polymerizable composition.
[0131] [00131] In any or each of the previous examples A to L, as well as in any or all of the other examples disclosed in this document, the amount of the second siloxane monomer can be from 1 to 20 unit parts of the polymerizable composition, as long as the 2: 1 ratio, based on unit parts by weight of the first siloxane to the second siloxane, is maintained. The amount of the second siloxane monomer can be from 2 to 15 unit parts of the polymerizable composition. The amount of the second siloxane monomer can be from 5 to 13 unit parts of the polymerizable composition.
[0132] [00132] In any or each of the previous examples A to L, as well as in any or all of the other examples disclosed in this document, the amount of the hydrophilic monomer or component present in the polymerizable composition can be from 1 to 60 unit parts of the polymerizable composition. The hydrophilic monomer component can comprise 4 to 60 unit parts of the polymerizable composition. When the hydrophilic monomer comprises or consists of VMA, it can be present in an amount of 30 unit parts to 60 unit parts. VMA can be present in the polymerizable composition in an amount of about 40 unit parts to about 50 unit parts. When hydrophilic monomers, N, N-dimethylacrylamide (DMA), 2-hydroxyethyl methacrylate (HEMA), or 2-hydroxybutyl methacrylate (HOB), or any combination thereof are present in the polymerizable composition as the hydrophilic monomer in the component hydrophilic monomer, each or all may be present in amounts of about 3 to about 10 unit parts.
[0133] [00133] In any or each of the previous examples A to L, as well as in any or all of the other examples disclosed in this document, the amount of the hydrophilic monomer or component present in the polymerizable composition can be from 1 to 30 unit parts of the polymerizable composition. For example, the total amount of the hydrophobic monomer or monomer component can be from about 5 to about 20 unit parts of the polymerizable composition. In polymerizable compositions in which the hydrophobic monomer MMA is present as the hydrophobic monomer or as a part of the hydrophobic monomer component, MMA can be present in an amount of about 5 to about 20 unit parts, or about 8 to about 15 unit parts.
[0134] [00134] In any or each of the previous examples A to L, as well as in any or all of the other examples disclosed in this document, the amount of the crosslinking agent or crosslinking agent component in the polymerizable composition can be 0.01 to 4 unit parts of the polymerizable composition. TEGDVE can be present in amounts of 0.01 to 1.0 unit parts. EGDMA can be present in quantities of 0.01 to 1.0 unit parts. TEGDMA can be present in quantities of 0.1 to 2.0 unit parts. Each of these silicon-free crosslinking agents can be present alone or in any combination in the polymerizable composition.
[0135] [00135] In any or all of the previous examples A to L, as well as in any or all of the other examples disclosed in this document, when the polymerizable composition contains EGMA, BVE, DEGVE, EGVE or any combination thereof, each one of them can be present in quantities of 1 unit part to 20 unit parts of the polymerizable composition. EGMA can be present in an amount of about 2 unit parts to about 15 unit parts. BVE can be present in an amount of 1 unit part to about 15 unit parts. BVE can be present in an amount of about 3 unit parts to about 7 unit parts. DEGVE can be present in an amount of 1 unit part to about 15 unit parts. DEGVE can be present in an amount of about 7 unit parts to about 10 unit parts. EGVE can be present in an amount of 1 unit part to about 15 unit parts, or in an amount of about 3 unit parts to about 7 unit parts.
[0136] [00136] In any or each of the previous examples A to L, as well as in any or all of the other examples disclosed in this document, the other optional components, such as initiators or initiator component, dyeing agents or components of the dyeing agent, UV-absorbing agents or UV-absorbing agent components, oxygen scavengers or oxygen scavenger components, or chain transfer agents or chain transfer agent components can each be present in amounts of about 0.01 unit parts to about 3 unit parts. An initiator or component of the initiator may be present in the polymerizable in an amount of 0.1 unit part to 1.0 unit part. When a thermal initiator or thermal initiator component is present, such as Vazo-64, it can be present in an amount of about 0.3 to about 0.5 unit parts. Dyeing agents or dyeing agent components can be present in amounts of 0.01 unitary to 1 unitary part. When reactive dyes are used as dyeing agents or as part of a dyeing agent component, such as Reactive Blue 246 or Reactive Blue 247, each of them can be present in amounts of about 0.01 unit part. UV-absorbing agents or UV-absorbing agent components can be present in amounts of 0.1 unit to 2.0 unit parts. For example, the UV-absorbing agent UV1 described in Examples C1 and 1-25 below can be present in an amount of about 0.8 to about 1.0 unit part, such as 0.9 unit part; or the UV-absorbing agent UV2 described in Examples C1 and 1-25 below can be present in an amount of 0.5 unit parts to 2.5 unit parts, from about 0.9 unit parts to about 2, 1 unit parts. Oxygen removers or oxygen remover components may be present in amounts of 0.1 unit to 1.0 part unit. As an example, when triphenylphosphine (TPP) or diphenyl (P-vinylphenyl) phosphine (pTPP), or any combination thereof is used as an oxygen scavenger or oxygen scavenger component in the polymerizable composition, each or the combination can be present in an amount of 0.3 unit parts to 0.7 unit parts, such as about 0.5 unit parts. Chain transfer reagents or chain transfer reagent components may be present in the polymerizable composition in an amount of 0.1 unit part to 2.0 unit part, and in many of examples C1 and 1-25 below, they are present in a quantity from 0.2 unit part to 1.6 unit part. For example, the allyloxyethanol chain transfer reagent (AE) can be present in an amount of about 0.3 to about 1.4 unit parts.
[0137] [00137] In any or all of the previous examples A to L, as well as in any or all of the other examples disclosed in this document, silicone hydrogel contact lenses may be free of a wetting agent that is present in the polymerizable composition, or in the polymeric lens body or in the silicone-hydrogel contact lens. Likewise, the silicone-hydrogel contact lens may have lens surfaces that are free from surface treatment or surface modification. However, in another example, the silicone hydrogel 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 body polymeric lens or silicone hydrogel contact lens. The silicone-hydrogel contact lens can have the lens surfaces treated or modified. In addition or alternatively, any or each of the foregoing examples AL, as well as any or all of the other examples of silicone hydrogel contact lenses disclosed in the present invention, contact lenses can be understood to be free of a spray agent. binding, such as, for example, a form of boronic acid.
[0138] [00138] In another example, new polymerizable compositions are provided, including each and each polymerizable composition described herein in reference to silicone hydrogel contact lenses and methods. Polymerizable compositions can be diluent-free, in that 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 diluent-free polymerizable compositions may still contain one or more chain transfer agents, such as allyloxyethanol. 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 unit parts.
[0139] [00139] As described in the present invention, the present silicone-hydrogel contact lenses, comprising polymeric lens bodies comprising units derived from a first siloxane monomer, represented by formula (1) and a second siloxane monomer, represented by formula (2), and with an average numerical molecular weight of at least 3,000 Daltons, like those represented by formulas (2), (3), or (4), are dimensionally stable. The present disclosure also refers to a batch of silicone hydrogel contact lenses.
[0140] [00140] As used in this document, a batch of silicone hydrogel contact lenses refers to a group of two or more silicone hydrogel contact lenses, and often, a batch refers to at least 10, 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 any of the silicone hydrogel contact lenses described in the present invention.
[0141] [00141] When initially tested shortly after manufacture and when tested again at a later time, a batch of lenses may exhibit a change in their average physical dimensions. As the batches of lenses according to the present disclosure are dimensionally stable, they can exhibit an acceptable level of change in their average physical dimensions. As used in this document, variance of dimensional stability is understood as a variance in a value of a physical dimension between a value of the determined physical dimension when the batch of lenses is initially tested right after its manufacture, and the value of the physical dimension determined when the lens batch is retested at a later point in time. The last time point can be, for example, at least 2 weeks after the start time point, up to 7 years after the start time point. Lot silicone hydrogel contact lenses have an average dimensional stability variance of less than plus or minus three percent (± 3.0%) based on the average lens diameter measurements of a representative number of lenses in the lot , such as, for example, 20 lenses in the batch. For a lot of lenses, an average dimensional stability variance less than plus or minus three percent 3% (± 3.0), where the average dimensional stability variance is the variance in a physical dimension value when measured in a starting time point within one day of a lens batch manufacturing date, and at a second time point, where the second time point is two weeks to seven years after the starting time point when the batch is stored at room temperature, or when the batch is stored at a higher temperature (that is, under accelerated life test conditions), the second time point is a time point representative of the batch storage from two weeks to seven years at room temperature, it is considered as a dimensionally stable lot. In one example, the conditions of the accelerated storage time test which is especially useful in determining the average dimensional stability variance are 4 weeks at 70 degrees C, although other periods of time and temperature can be used. The average dimensional stability variance is determined by the average of the individual dimensional stability variances for each of the representative lenses using the actual diameters of the representative lenses measured initially (Original diameter) and the actual diameters of the representative lenses measured after storage (Final Diameter) at room temperature or under conditions of accelerated storage time. The representative lenses measured initially and the representative lenses measured after storage can be the same lenses or they can be different lenses. As used in this document, the average dimensional stability variance is represented as a percentage (%). The variances of individual dimensional stability are determined using the following equation (A): ((Final Diameter - Original diameter / Original diameter) x 100 (A).
[0142] [00142] On average, the diameters of the silicone-hydrogel contact lenses in the batch vary by less than three percent in any direction from a target value (± 3.0%). As an example, if a contact lens has a target diameter (rope diameter) of 14.20 mm, the current 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 (rope diameter) of 14.20 mm, the current 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 commonly from 13.00 mm to 15.00 mm.
[0143] [00143] In accelerated storage time studies, the average dimensional stability variance can be determined for contact lenses that have been stored for a period of time at an elevated temperature, such as above 40 degrees C, including, for example, 50 degrees C, 55 degrees C, 65 degrees C, 70 degrees C, 80 degrees C, 95 degrees C and the like. Or the average dimensional stability can be determined for contact lenses that have been stored for a period of time at room temperature (for example, about 20 to 25 degrees C).
[0144] [00144] For accelerated storage time studies, the following formula can be used to determine the number of months of storage at a particular temperature that are equivalent to storage for a desired period of time at room temperature: Desired storage time = [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 = age of the lenses (in months) at baseline
[0145] [00145] Based on this equation, the following storage times were calculated: 6 months of storage at 35 degrees C equals 1 year of aging at 25 degrees C, 3 months of storage at 45 degrees C equals 1 year of aging at 25 degrees C, 3 months of storage at 55 degrees C equals 2 years of aging at 25 degrees C and 3 months of storage at 65 degrees C equals 4 years of aging at 25 degrees C.
[0146] [00146] 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 contact lens formulation, comprises a first siloxane monomer represented by formula (1):
[0147] [00147] 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 contact lens mold assembly. The polymerizable composition can be molded between molds formed of a thermoplastic polymer. The thermoplastic polymer used to form the molding surfaces of the mold may comprise a polar polymer, or may include a non-polar polymer. Alternatively, the polymerizable composition can be formed on a lens by various methods known to those of ordinary skill in the art, such as by casting, injection molding, forming a polymerized rod that is later turned to form a lens body, etc.
[0148] [00148] The method may also comprise bringing the polymeric lens body into contact with a washing liquid to remove extractable material, such as unreacted monomers, non-crosslinked materials that are otherwise not physically immobilized in the body of polymeric lens, thinners and the like.
[0149] [00149] 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 blister or glass bottle packaging. After packaging, the package can be sealed and the polymeric lens body and the contact lens packaging solution can be sterilized, for example, by autoclaving the sealed package, to produce a silicone hydrogel contact lens product.
[0150] [00150] The present method can further comprise repeating the steps to produce a plurality of silicone-hydrogel contact lenses. The polymeric lens bodies of the plurality of silicone-hydrogel contact lenses have an average dimensional stability variance of less than plus or minus three percent (± 3.0%) over a period of time from two weeks to seven years, at said average dimensional stability variance being a normal average of the individual dimensional stability variance values (%) determined from the lens diameter of each representative lens by the following equation (A): (Final Diameter - Original Diameter / Original Diameter) x 100 (A).
[0151] [00151] In any of the present methods, a first particular siloxane monomer can be provided 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 a hydrogen atom or a methyl group.
[0152] [00152] In all of the present methods, the second siloxane monomer is represented by the formula (2):
[0153] [00153] In the present methods, the step of contacting the polymeric lens body with a washing liquid can be understood as an extraction step, because extractable materials can be removed from the polymeric lens body during the process. When the washing liquid comprises water or an aqueous solution free of a volatile organic solvent, the contact step can be understood as an extraction step and a hydration step. In another example of the method, the contact step may comprise contacting the polymeric lens body 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. Some washing liquids may contain a secondary alcohol, such as isopropyl alcohol and the like. Using a washing liquid containing one or more volatile organic solvents can be useful in removing hydrophobic materials from the polymeric lens body and thus can increase the wettability of the resulting silicone-hydrogel contact lens. Such methods can be understood as being extraction steps based on volatile organic solvents. In other methods, the contact step comprises bringing the polymeric lens body into contact with an aqueous washing liquid that is free of volatile organic solvent. Such methods can be understood as being completely aqueous washing steps, since no volatile organic solvent is included in the washing liquid. Water-based washing liquids that can be used in such methods include water, such as deionized water, saline solutions, buffered solutions or aqueous solutions containing surfactants or other non-volatile ingredients that can improve the removal of hydrophobic components from lens bodies. polymeric contact, or can reduce distortion of the polymeric bodies of contact lenses compared to using only deionized water.
[0154] [00154] After washing, contact lenses can be placed in packages, such as in plastic blister packs, with a packaging solution, such as a buffered saline solution, which may or may not contain surfactants, anti-inflammatory agents, antimicrobial agents, contact lens wetting agents and the like, and can be sealed and sterilized. EXAMPLES
[0155] [00155] The following examples C1 and 1-25 illustrate certain aspects and advantages of the present invention, which should be understood as not being limited in this way.
[0156] [00156] As can be easily determined by a review of the Examples below, all exemplary formulations are free of an organic diluent. In addition, all Example formulations are free of N, N-dimethylacrylamide (DMA). In addition, all of the Example formulations below are free of a polymeric wetting agent. In addition, all Example formulations comprise at least one hydrophilic amide monomer with an N-vinyl group. Most of the Example formulations (Ex. 4 to 5, 8 to 13, 15 and 17 to 25) comprise a second siloxane having a structure represented by formula (2);
[0157] [00157] The following chemicals are referred to in examples C1 and 1-25, and 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-decamethyl pentassiloxane-1-yl) ethyl ester propoxy] of 2-propenoic acid (CAS number 1052075-57-6). (Si1 was obtained from Shin-Etsu Chemical Co., Ltd., Tokyo, Japan, as product number X-22-1622). Si2: α, ω-bis (methacryloxypropyl) -poly (dimethylsiloxane) -poly (ω-methoxypoly (ethylene glycol) propylmethylsiloxane) (the synthesis of this compound can be performed as described in US20090234089, which is incorporated by reference in this document) Si3: poly (dimethylsiloxane), finished in methacryloxypropyl (CAS number 58130-03-3; DMS-R18, available from Gelest) VMA: N-vinyl-N-methylacetamide (CAS number 003195786) DMA: N, N-dimethylacrylamide (CAS number 2680-03-7) HEMA: 2-hydroxyethyl methacrylate (CAS number 868-77-9) HOB: 2-hydroxybutyl methacrylate (CAS number 29008-35-3) EGMA: ethylene glycol methyl ether methacrylate (CAS number 6976-93-8) MMA: methyl methacrylate (CAS number 80-62-6) EGDMA: ethylene glycol dimethacrylate (CAS number 97-90-5) TEGDMA: triethylene glycol dimethacrylate (CAS number 109-16-0) BVE: 1,4-butanediolvinyl ether (CAS number 17832-28-9) DEGVE: diethylene glycolinyl ether (CAS number 929-37-3) EGVE: ethylene glycolinyl ether (CAS number 764-48-7) TEGDVE: triethylene glycolvinyl ether (CAS number 765-12-8) AE: 2-allyloxyethanol (CAS number 111-45-5) V-64: 2,2'-azobis-2-methylpropanonitrile (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-hydroxyphenyl) ethyl methacrylate ( CAS number 96478-09-0) RBT1: 1,4-bis [4- (2-methacryloxyethyl) phenylamino] anthraquinone (CAS number 121888-69-5) RBT2: 1,4-bis [(2-hydroxyethyl) amino] -9,10-antacenedione bis (2-propenoic) ester (CAS Registry No. 109561071) TPP: Triphenylphosphine (CAS number 603-35-0) pTPP: Polymerizable TPP: diphenyl (P-vinylphenyl) phosphine (CAS number 40538-112) Silicone-hydrogel contact lens fabrication and testing procedure
[0158] [00158] The chemical compounds defined in Examples C1 and 1-25 were, for each example, weighed in amounts that correspond to the described unit parts, and combined to form a mixture. The mixture was filtered through a 0.2 to 5.0 micron syringe filter into a bottle. The mixtures were stored for up to about 2 weeks. Polymerizable silicone-hydrogel contact lens precursor compositions are understood as mixtures, or as used herein, polymerizable compositions. In Examples C1 and 1-25, the listed amounts of ingredients are provided in unit parts of the polymerizable composition by weight.
[0159] [00159] A volume of the polymerizable composition was cast by casting the composition in contact with a lens-defining surface of a female mold member. In all the following examples C1 and 1-25, the mold surface of the female mold member was formed from a non-polar resin, specifically from polypropylene. A male mold member was placed in contact with the female mold member to form a contact lens mold assembly comprising a contact lens shaped cavity containing the polymerizable composition. In Examples C1 and 1-25 below, the molding surface of the male mold member was formed from a non-polar resin, specifically from polypropylene.
[0160] [00160] The contact lens mold assemblies were placed in a greenhouse flushed with nitrogen to allow the polymerizable composition to be thermally cured. For all examples C1 and 1-25, the contact lens mold assemblies were exposed to temperatures of at least about 55 ° C for about 2 hours. Examples of the curing profiles that can be used to cure the silicone hydrogel contact lenses described in the present invention include exposing the contact lens mold assemblies to temperatures of 55 ° C for 40 minutes, 80 ° C for 40 minutes and 100 ° C for 40 minutes. Other contact lenses can be made with the same curing profile, but instead of the first temperature being 55 ° C, it can be 65 ° C.
[0161] [00161] After polymerizing the polymerizable composition to form a polymeric lens body contained in the mold assembly, the contact lens mold assemblies are removed from the mold to separate the male and female mold members. The polymeric lens body remained adhered to the male or female mold. A dry demoulding process where the mold assembly does not come into contact with a liquid medium can be used, or a wet demoulding process where the mold assembly comes into contact with a liquid medium such as, for example, water or solution watery, can be used. A mechanical dry release process may involve applying mechanical force to a portion of one or both of the mold members in order to separate the mold members. In all of the following Examples C1 and 1-25, a dry release procedure was used.
[0162] [00162] The polymeric lens body was then removed from the male or female mold to produce a removed polymeric lens body. In an example of the removal method, the polymeric lens body can be removed from the male mold member using a dry removal process, such as by manually removing the lens from the male mold member or by compressing the male mold member and directing a gas to the male mold member and the polymeric lens body, and lifting the dry polymeric lens body with a vacuum device from the male mold member, which is discarded. In other methods, the polymeric lens body can be removed using a wet removal process by contacting the dry polymeric lens body with a liquid release medium, such as water or an aqueous solution. For example, a male mold member with the polymeric lens body attached may be immersed in a container containing a liquid until the polymeric lens body separates from the male mold member. Or a volume of the liquid release medium can be added to the female mold to soak the polymeric lens body in the liquid and to separate the lens body from the female mold member. In the following Examples C1 and 1-25, a dry lens and removal process was used. After separation, the lens body can be lifted from the mold member manually using forceps or using a vacuum device, and placed on a tray.
[0163] [00163] The removed lens product was then washed to remove extractable materials from the polymeric lens body, and hydrated. Extractable materials included 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 polymer lens body in a form that does has reacted, in a form that has reacted partially or in a non-crosslinked form, or any combination thereof, followed by polymerization of the lens body and before extraction of the lens body. The extractable materials may also have included any non-polymerizable ingredients present in the polymerizable composition, for example, any optional non-polymerizable dyeing agents, UV blockers, diluents or chain transfer agent, or any combination thereof, remaining present in the body. polymeric lens after polymerization of the polymeric lens body, but before extraction of the polymeric lens body.
[0164] [00164] In another method, as in a method that involves removing the lens by compression of the male mold member and directing gas flow to the male mold member, the removed polymerized contact lens bodies can be placed in the carrier cavities or lens trays, where the polymeric lens bodies 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 either 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.
[0165] [00165] In other methods, such as those that involve removing the lens wetly by contacting the mold and the lens with a liquid release medium, the bodies of the removed polymerized conato lens can be washed to remove extractable components from the lens bodies using a washing liquid that is free of a volatile organic solvent, such as a lower alcohol, for example, methanol, ethanol or any combination of these components. For example, the removed polymerized contact lens bodies can be washed to remove extractable components from the lens bodies by contacting the lens bodies with an aqueous washing liquid free of a volatile organic solvent, such as deionized water, or a surfactant solution, a saline solution, a buffer solution or any combination thereof. Washing can take place in the final contact lens package, or it can take place in a washing tray or washing tank.
[0166] [00166] In Examples C1 and 1-25 below, after the dry demoulding and dry lens removal steps, the removed lens bodies were placed in tray wells, and the removed polymeric lens bodies were extracted and hydrated by contact of polymeric lens bodies with one or more volumes of an extraction liquid. The extraction and hydration liquid used in the extraction and hydration process consisted of a) a combination of a volatile organic solvent-based extraction liquid and a volatile organic solvent-free hydration liquid, or b) an extraction and hydration liquid free of volatile organic solvent, that is, a water-based extraction and hydration liquid. Specifically, in Examples C1 and 1-5 below, the extraction and hydration process comprised at least two extraction steps in separate portions of ethanol, followed by at least one extraction step in one portion of an ethanol: water solution of 50 : 50 w / w of Tween 80, followed by at least three extraction and hydration steps in separate portions of a Tween 80 solution in deionized water, where each extraction or extraction and hydration step lasted from about 5 minutes to 3 hours. In Examples 6 to 25 below, the extraction and hydration process used comprised at least three extraction and hydration steps in separate portions of a Tween 80 solution in deionized water, where the temperature of the Tween 80 solution of the portions varied from room temperature at about 90 degrees C, and in which each of the extraction and hydration steps lasted from about 15 minutes to about 3 hours.
[0167] [00167] The washed, extracted and hydrated lenses were then individually placed in contact lens blister packs with a phosphate buffered saline packaging solution. The blister packs were sealed and sterilized by autoclaving.
[0168] [00168] After sterilization, the properties of the lens as contact angle, including dynamic and static contact angle, oxygen permeability, ionic flux, modulus, elongation, tensile strength, water content and the like were determined, as described in this document.
[0169] [00169] For the present contact lenses, the contact angles, including the dynamic and static contact angles, can be determined using routine methods known to people normally skilled in the art. For example, the forward and reverse contact angle of the contact lenses presented here can be measured using the conventional drop shape method, such as the sessile drop method or the trapped bubble method.
[0170] [00170] In Examples C1 and 1-25 below, the forward and reverse contact angle of the silicone hydrogel contact lenses was determined using a Kruss DSA 100 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, pages 205-212 and R. Knapikowski, M. Kudra: Kontaktwinkelmessungen nach dem Wilhelmy-Prinzip-Ein statistischer Ansatz zur Fehierbeurteilung ", Chem. Technik, vol. 45, 1993, pages 179-185, and United States Patent No. 6,436,481, all of which are incorporated by reference into the present invention.
[0171] [00171] As an example, the forward contact angle and the recoil contact angle could be determined using a trapped 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 syringe system. The size of the air bubble increased and decreased to obtain the recoil angle (the plateau obtained by increasing the bubble size) and the advance angle (the plateau obtained by decreasing the bubble size).
[0172] [00172] The values of the modulus, elongation and tensile strength of the present lenses can be determined using routine methods known to those normally 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 Instron Model 3342 or 3343 mechanical test system (Instron Corporation, Norwood, MA, USA) and Bluehill materials testing software, using a cutting mold custom rectangular contact lens to prepare the rectangular sample strip. The modulus, elongation and tensile strength were determined inside a chamber with a relative humidity of at least 70%. The lenses to be tested were soaked in phosphate buffer solution (PBS) for at least 10 minutes before testing. By keeping the concave side of the lens upwards, a central strip of the lens was cut using the cutting template. 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 loaded onto the support jaws of the calibrated Instron device, with the strip fitting over at least 75% of the grip surface of each jaw. A test method designed to determine the maximum load (N), the tensile strength (MPa), the stress at maximum load (% elongation) and the mean and standard deviation of the modulus of elasticity (MPa) was performed, and the results were recorded.
[0173] [00173] The percentage energy loss of the present silicone-hydrogel contact lenses can be determined using routine methods known to people normally skilled in the art. For examples C1 and 1-25 below, the percentage of energy loss was determined using an Instron Model 3343 mechanical test system (Instron Corporation, Norwood, MA, USA) with a 10N force transducer (model Instron No 2519-101) and Bluehill material 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 phosphate buffer solution (PBS) for at least 10 minutes. Using forceps, the lens was loaded into the jaws of the calibrated Instron device, with the lens loaded vertically between the jaws as symmetrically as possible, so that the lens fits over at least 75% of the jaw surface of each jaw. A test designed to determine the energy required to stretch the lens to 100% stretch and then return to 0% stretch 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 finished, the energy loss was calculated using the following equation: Energy loss (%) = (Energy up to 100% stretching - Energy to return up to 0% stretching) / Energy up to 100% stretching x 100 %.
[0174] [00174] The ion flow of the present lenses can be determined using routine methods known to those normally skilled in the art. For the lenses in Examples 1-25 below, the ion flow was measured using a technique substantially similar to the "Ion Flow Technique" described in U.S. Patent No. 5,849,811, which is incorporated by reference into the present invention. of measurement, a hydrated lens was equilibrated in deionized water for at least 10 minutes. The lens to be measured was placed in a lens holding device between the male and female portions. The male and female portions included flexible sealing rings that were positioned between the lens and the respective male or female part. After positioning the lens in the lens retainer, the lens retainer was then placed in a screw cap. The cap was screwed into a glass tube to define a donor chamber. The donor chamber was filled with 16 mL of 0.1 molar NaCl solution. A recipient chamber was filled with 80 mL of deionized water. The conductivity meter guides were i immersed in deionized water from 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 recipient chamber, so that the NaCl solution inside the donor chamber was flushed with water inside the recipient chamber. Since the temperature inside the receiving chamber was balanced to 35 degrees C, conductivity measurements were made every 2 minutes for at least 10 minutes. The conductivity versus time data were substantially linear and were used to calculate the ionic flux value for the tested lenses.
[0175] [00175] The oxygen permeability (Dk) of the present lenses can be determined using routine methods known to people normally skilled in the art. For example, the Dk value can be determined using a commercially available instrument under the MOCON® Ox-Tran System model designation (Mocon Inc., Minneapolis, MN, USA), for example, using the Mocon Method, as described in the North Patent -American No. 5,817,924, which is incorporated by reference into the present invention. The Dk values of the lenses of examples 1-25 below were determined using the method described by Chhabra et al. (2007), A single-lens polarographic measurement of oxygen permeability (Dk) for hypertransmissible soft contact lenses. Biomaterials 28: 43314342, which is incorporated by reference into the present invention.
[0176] [00176] The water content in balance (EWC) of the present lenses can be determined using routine methods known to those normally skilled in the art. For the lenses of Examples C1 and 1-25 below, a hydrated silicone-hydrogel contact lens was removed from an aqueous liquid, cleaned to remove excess surface and heavy water. The heavy lens was then dried in an oven at 80 degrees C, under 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.
[0177] [00177] The percentage of wet extractable component or dry extractable component in a lens can be determined by extracting the lenses in an organic solvent in which the polymeric lens body is not soluble according to the methods known to those normally skilled in the art . For the lenses of examples C1 and 1-25 below, a methanol extraction using a Sohxlet extraction process was used. To determine the wet extractable component, a sample (for example, at least 5 lenses per batch) of fully hydrated and sterilized contact lenses was prepared by removing the excess packaging solution from each lens and drying them, overnight. another, in a vacuum oven at 80 ° C. To determine the dry extractable component, a sample of 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. When dry and cooled, 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 to a round bottom flask containing 70-80 ml of methanol. Water was circulated through the condenser and the methanol was heated until it boiled slightly. The lenses were extracted for at least 4 hours from the time it was observed that methanol first condensed. The extracted lenses were again dried overnight at 80 ° C in a vacuum oven. When dry and cooled, each lens was weighed to obtain the dry weight of the extracted lens (W2), and the following calculation was done for each lens, to determine the percentage of the wet extractable component: [(W1-W2) / W1] x 100. COMPARATIVE EXAMPLE C1
[0178] [00178] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified quantities, using the procedures described in the Silicone-Hydrogel Contact Lens Fabrication and Test Procedure, provided above.
[0179] [00179] 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 Silicone-Hydrogel Contact Lens Fabrication and Test Procedure, using a dry demoulding process, dry lens removal process and a washing process that used washing liquids comprising extraction liquids based on volatile organic solvent and hydration liquids consisting of liquids free of volatile organic solvent. These contact lenses contained units derived from just one siloxane monomer, Si1. The lot of contact lenses showed unacceptable average dimensional stability.
[0180] [00180] For example, a sample of 20 of the contact lenses were tested and found to have an average initial chord diameter of 14.63 mm, and the average chord diameter decreased to 14.18 mm under life test conditions accelerated useful equivalent to storage for seven years at room temperature. This change corresponds to an average dimensional stability variance of -3.1%, reflecting that, on average, contact lenses have shrunk by more than ± 3.0% in diameter during the accelerated life test. In more detail, initially, after storage for 0 days at 95 degrees C (equivalent to 0 years at room temperature), the average chord diameter was 14.63 mm; after storage for 6 days at 95 degrees C (equivalent to 2 years of aging at room temperature), the average chord diameter decreased to 14.23 mm; after storage for 12 days at 95 degrees C (equivalent to 4 years of aging at room temperature), the average chord diameter reduced to 14.20 mm; after storage for 20 days at 95 degrees C (equivalent to 7 years of aging at room temperature), the average chord diameter reduced to 14.18 mm.
[0181] [00181] In addition, these lenses, when fully hydrated, had an EWC of 61% w / w 66% w / w, a module of 0.14 MPa, an ion flux of 11.60 (x 10-3 mm2 / min x 10-3) and an elongation of about 326% when tested at the start of the shelf life study. EXAMPLE 1
[0182] [00182] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified quantities, using the procedures described in the Silicone-Hydrogel Contact Lens Manufacturing and Test Procedure, provided above.
[0183] [00183] 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 Silicone-Hydrogel Contact Lens Manufacturing and Test Procedure, using a dry demoulding process, dry lens removal process and a washing process that used washing liquids comprising extraction liquids based on volatile organic solvent and hydration liquids consisting of liquids free of volatile organic solvent. These contact lenses contained units derived from two siloxane monomers, Si1 and Si3. This batch of contact lenses had an acceptable average dimensional stability variance.
[0184] [00184] For example, a sample of 20 of the contact lenses had an initial average chord diameter of 13.98 mm, and the average chord diameter decreased to 13.70 mm under accelerated life test conditions representative of seven years of aging at room temperature. This change corresponds to an average dimensional stability variance of -2.0%, reflecting that the contact lenses shrunk the diameter, on average, by less than ± 3.0% during the accelerated stability test. In more detail, initially, after storage for 0 days at 95 degrees C (equivalent to 0 years at room temperature), the average chord diameter was 13.98 mm; after storage for 7 days at 95 degrees C (equivalent to 2.4 years of aging at room temperature), the average chord diameter decreased to 13.90 mm; after storage for 14 days at 95 degrees C (equivalent to 5 years of aging at room temperature), the average chord diameter reduced to 13.82 mm; after storage for 22 days at 95 degrees C (equivalent to 7.8 years of aging at room temperature), the average chord diameter reduced to 13.70 mm.
[0185] [00185] 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 study. EXAMPLE 2
[0186] [00186] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified quantities, using the procedures described in the Silicone-Hydrogel Contact Lens Fabrication and Test Procedure, provided above.
[0187] [00187] 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 Silicone-Hydrogel Contact Lens Fabrication and Test Procedure, using a dry demoulding process, dry lens removal process and a washing process that used washing liquids comprising extraction liquids based on volatile organic solvent and hydration liquids consisting of liquids free of volatile organic solvent. These contact lenses contained units derived from two siloxane monomers, Si1 and Si3. This batch of contact lenses had an acceptable average dimensional stability variance.
[0188] [00188] For example, contact lenses had an initial average chord diameter of 14.54 ± 0.03 mm and the average chord diameter decreased to 14.24 ± 0.03 mm under accelerated life test conditions equivalent to aging for seven years at room temperature. This change corresponds to an average dimensional stability variance of -2.1%, reflecting that, on average, the lot of contact lens decreased in diameter by less than ± 3.0%. In more detail, after storage for 0 days at 95 degrees C (equivalent to 0 years of aging at room temperature), the average chord diameter was 14.54 mm ± 0.03 mm; after storage for 6 days at 95 degrees C (equivalent to 2 years of aging at room temperature), the mean chord diameter was 14.39 ± 0.02 mm; after storage for 12 days at 95 degrees C (equivalent to 4 years of aging at room temperature), the average chord diameter was 14.32 0.03 mm; after storage for 20 days at 95 degrees C (equivalent to 7 years of aging at room temperature), the mean chord diameter was 14.24 ± 0.03 mm.
[0189] [00189] Furthermore, these lenses, when fully hydrated, had an EWC of 52% w / w, a module of 0.63 MPa and an ion flux of 3.62 (x 10-3 mm2 / min), when tested at the beginning of the storage time study. EXAMPLE 3
[0190] [00190] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified quantities, using the procedures described in the Silicone-Hydrogel Contact Lens Manufacturing and Test Procedure, provided above.
[0191] [00191] 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 Silicone-Hydrogel Contact Lens Fabrication and Test Procedure, using a dry demoulding process, dry lens removal process and a washing process that used washing liquids comprising extraction liquids based on volatile organic solvent and hydration liquids consisting of liquids free of volatile organic solvent. These contact lenses contained units derived from two siloxane monomers, Si1 and Si3. This batch of contact lenses had an acceptable average dimensional stability variance.
[0192] [00192] For example, a sample of 20 of the contact lenses had an initial mean chord diameter of 14.03 ± 0.03 mm and the mean chord diameter decreased to 13.81 ± 0.03 mm under life test conditions accelerated useful equivalent to seven years at room temperature. This change corresponds to an average dimensional stability variance of -1.6%, reflecting that, on average, contact lenses decreased in diameter by less than ± 3.0%. In more detail, initially, after storage for 0 days at 95 degrees C (equivalent to 0 years of aging at room temperature), the average chord diameter was 14.03 ± 0.03 mm; after 6 days of storage at 95 degrees C (equivalent to 2 years of aging at room temperature), the average chord diameter was 13.93 ± 0.03 mm; after 12 days of storage at 95 degrees C (equivalent to 4 years of aging at room temperature), the average chord diameter was 13.87 ± 0.03 mm; after 20 days of storage at 95 degrees C (equivalent to 7 years of aging at room temperature), the average chord diameter was 13.81 ± 0.02 mm.
[0193] [00193] Furthermore, these silicone hydrogel contact lenses, when fully hydrated, had an EWC of about 52% w / w, a modulus of about 0.58 MPa, a content of wet extractables of about 0 , 67%, a static bubble contact angle of about 30 degrees; and a dynamic bubble forward conato angle of about 50.1 degrees when tested at the start of the storage time study. EXAMPLE 4
[0194] [00194] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified quantities, using the procedures described in the Silicone-Hydrogel Contact Lens Fabrication and Test Procedure, provided above.
[0195] [00195] 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 Silicone-Hydrogel Contact Lens Fabrication and Test Procedure, using a dry demoulding process, dry lens removal process and a washing process that used washing liquids comprising extraction liquids based on volatile organic solvent and hydration liquids consisting of liquids free of volatile organic solvent. These contact lenses contained units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had an acceptable average dimensional stability variance.
[0196] [00196] For example, contact lenses had an average initial rope diameter of 14.06 ± 0.04 mm and the average rope diameter decreased to 13.98 ± 0.03 mm under accelerated life test conditions equivalent to seven years of aging at room temperature. This change corresponds to an average dimensional stability variance of -0.6%, reflecting that, on average, contact lenses decreased in diameter by less than ± 3.0%. In more detail, initially after storage for 0 days at 95 degrees C (equivalent to 0 years of aging at room temperature), the average chord diameter was 14.06 ± 0.04 mm; after storage for 6 days at 95 degrees C (equivalent to 2 years of aging at room temperature), the average chord diameter was 13.98 ± 0.04 mm; after 12 days of storage at 95 degrees C (equivalent to 4 years of aging at room temperature), the average chord diameter was 13.97 ± 0.04 mm; after 20 days of storage at 95 degrees C (equivalent to 7 years of aging at room temperature), the average chord diameter was 13.98 ± 0.03 mm.
[0197] [00197] Furthermore, these silicone-hydrogel contact lenses, when fully hydrated, had an EWC of 53% w / w 54% w / w, a modulus of about 0.43 MPa, a content of wet extractables of about 1.23% w / w, a static bubble contact angle of about 38 degrees, a dynamic bubble advance conato angle of about 50.0 degrees, an ion flow of 2.5 to 3.0 (x10-3 mm2 / min), a Dk of 70 barrers, an elongation of about 450%, a tensile strength of 1.40 MPa, a percentage transmittance of 98%, an energy loss of 36% and a swelling factor of about 21% when tested at the start of the storage time study. When tested prior to extraction and hydration, the polymeric lens bodies had a dry extractable content of about 17% w / w. EXAMPLE 5
[0198] [00198] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified quantities, using the procedures described in the Silicone-Hydrogel Contact Lens Fabrication and Test Procedure, provided above.
[0199] [00199] 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 Silicone-Hydrogel Contact Lens Manufacturing and Test Procedure, using a dry demoulding process, dry lens removal process and a washing process that used washing liquids comprising extraction liquids based on volatile organic solvent and hydration liquids consisting of liquids free of volatile organic solvent. These contact lenses contained units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had acceptable average dimensional stability, and had an acceptable average dimensional stability variance.
[0200] [00200] In addition, these silicone-hydrogel contact lenses had, when fully hydrated, an oxygen permeability greater than 60 barrers, an EWC of about 53% w / w, an ion flow of about 2.90 ( x10-3 mm2 / mm), a modulus of about 0.40 MPa, an elongation of about 425%, a tensile strength of about 1.4 MPa, a static bubble contact angle of about 37 degrees, a dynamic bubble advance contact angle of about 48 to 52 degrees, a light transmittance of about 98%, a moisture extractable content of about 1.30% w / w, an energy loss of about 35% to about 36% and a swelling factor of about 21%, when tested at the start of the shelf life study and had an average dimensional stability variance less than plus or minus 3.0% after storage for at least 2 weeks at 80 degrees C. EXAMPLE 6
[0201] [00201] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified quantities, using the procedures described in the Silicone-Hydrogel Contact Lens Fabrication and Test Procedure, provided above.
[0202] [00202] 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 Silicone-Hydrogel Contact Lens Manufacturing and Test Procedure, using a dry demoulding process, dry lens removal process and a washing process that used extraction and hydration liquids consisting of extraction liquids free of volatile organic solvent. The lenses in this batch were not exposed to a volatile organic solvent during their manufacture. These contact lenses contained units derived from two siloxane monomers, Si1 and Si3. This batch of contact lenses had an acceptable average dimensional stability variance.
[0203] [00203] 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), an 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 break time in water greater than 20 seconds, a component wet extractable of about 3.9% w / w and an energy loss of about 40%, when tested at the beginning of the storage time study, and had an average dimensional stability variance less than plus or minus 3.0% after storage for more than 2 weeks at 80 degrees C. When tested prior to extraction and hydration, the polymeric lens bodies had a dry extractable component at about 11% w / w.
[0204] [00204] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified quantities, using the procedures described in the Silicone-Hydrogel Contact Lens Manufacturing and Test Procedure, provided above.
[0205] [00205] 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 Silicone Hydrogel Contact Lens Fabrication and Test Procedure, using a dry demoulding process, dry lens removal process and a washing process that used extraction and hydration liquids consisting of extraction liquids free of volatile organic solvent. The lenses in this batch were not exposed to a volatile organic solvent during their manufacture. These contact lenses contained units derived from two siloxane monomers, Si1 and Si3. This batch of contact lenses had an acceptable average dimensional stability variance.
[0206] [00206] Furthermore, these silicone-hydrogel 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 about 0.77 MPa, an elongation of about 349%, a tensile strength of about 1.75 MPa, a break time in water greater than 20 seconds, a content of wet extractables of about 4.42 % w / w and an energy loss of about 41%, when tested at the start of the storage time study, and had an average dimensional stability variance of less than plus or minus 3.0% after storage for at least 2 weeks at 80 degrees C. EXAMPLE 8
[0207] [00207] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified quantities, using the procedures described in the Silicone-Hydrogel Contact Lens Fabrication and Test Procedure, provided above.
[0208] [00208] 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 Silicone-Hydrogel Contact Lens Manufacturing and Test Procedure, using a dry demoulding process, dry lens removal process and a washing process that used extraction and hydration liquids consisting of extraction liquids free of volatile organic solvent. The lenses in this batch were not exposed to a volatile organic solvent during their manufacture. These contact lenses contained units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had an acceptable average dimensional stability variance.
[0209] [00209] Furthermore, these silicone-hydrogel 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 modulus of about 0.61 MPa, an elongation of about 275%, a tensile strength of about 1.51 MPa, a break time in water greater than 20 seconds and a wet extractable component of about 4.10% w / w, when tested at the start of the shelf life study, and had an average dimensional stability variance of less than plus or minus 3.0% for more than 2 weeks at 80 degrees C. EXAMPLE 9
[0210] [00210] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified quantities, using the procedures described in the Silicone-Hydrogel Contact Lens Fabrication and Test Procedure, provided above.
[0211] [00211] 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 Silicone-Hydrogel Contact Lens Fabrication and Test Procedure, using a dry demoulding process, dry lens removal process and a washing process that used extraction and hydration liquids consisting of extraction liquids free of volatile organic solvent. The lenses in this batch were not exposed to a volatile organic solvent during their manufacture. These contact lenses contained units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had an acceptable average dimensional stability variance.
[0212] [00212] Furthermore, these silicone-hydrogel contact lenses, when fully hydrated, had an EWC of about 58% w / w, an ion flow of about 2.75 (x10-3 mm2 / min), a modulus of about 0.66 MPa, an elongation of about 216%, a tensile strength of about 0.87 MPa, a break time in water greater than 20 seconds and a wet extractable component of about 4.56% w / w, when tested at the beginning of the storage time study, and had an average dimensional stability variance less than plus or minus 3.0% after storage for 6 days at 95 degrees C. EXAMPLE 10
[0213] [00213] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified quantities, using the procedures described in the Silicone-Hydrogel Contact Lens Fabrication and Test Procedure, provided above.
[0214] [00214] 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 Silicone-Hydrogel Contact Lens Manufacturing and Test Procedure, using a dry demoulding process, dry lens removal process and a washing process that used extraction and hydration liquids consisting of extraction liquids free of volatile organic solvent. The lenses in this batch were not exposed to a volatile organic solvent during their manufacture. These contact lenses contained units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had an acceptable average dimensional stability variance.
[0215] [00215] Furthermore, these silicone-hydrogel 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 modulus of about 0.57 MPa, an elongation of about 310%, a tensile strength of about 1.90 MPa, a break time in water greater than 20 seconds, a wet extractable component of about 4.74% w / w and an energy loss of about 34 to 36%, when tested at the beginning of the storage time study, and had an average dimensional stability variance less than plus or minus 3.0% after storage for 7 days at 80 degrees C. When tested before extraction and hydration, the polymeric lens bodies had a dry extractable component at about 14.39% w / w. EXAMPLE 11
[0216] [00216] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified quantities, using the procedures described in the Silicone-Hydrogel Contact Lens Manufacturing and Test Procedure, provided above.
[0217] [00217] 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 Silicone-Hydrogel Contact Lens Fabrication and Test Procedure, using a dry demoulding process, dry lens removal process and a washing process that used extraction and hydration liquids consisting of extraction liquids free of volatile organic solvent. The lenses in this batch were not exposed to a volatile organic solvent during their manufacture. These contact lenses contained units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had an acceptable average dimensional stability variance.
[0218] [00218] 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 modulus of about 0.69 MPa, an elongation of about 314%, a tensile strength of about 1.30 MPa, a break time in water greater than 20 seconds, a wet extractable component of about 1.81% w / w an energy loss of about 34%, when tested at the start of the storage time study, and had an average dimensional stability variance less than plus or minus 3.0% after storage for 14 days at 80 degrees C . EXAMPLE 12
[0219] [00219] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified quantities, using the procedures described in the Silicone-Hydrogel Contact Lens Manufacturing and Test Procedure, provided above.
[0220] [00220] 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 Silicone-Hydrogel Contact Lens Manufacturing and Test Procedure, using a dry demoulding process, dry lens removal process and a washing process that used extraction and hydration liquids consisting of extraction liquids free of volatile organic solvent. The lenses in this batch were not exposed to a volatile organic solvent during their manufacture. These contact lenses contained units derived from three siloxane monomers, Si1, Si2 and Si3. This batch of contact lenses had an acceptable average dimensional stability variance.
[0221] [00221] 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 modulus of about 0.85 MPa, an elongation of about 284%, a tensile strength of about 1.88 MPa, a break time in water greater than 20 seconds, a wet extractable component of about 2.38% w / w an energy loss of about 36%, when tested at the start of the storage time study, and had an average dimensional stability variance less than plus or minus 3.0% after storage for 14 days at 80 degrees C . EXAMPLE 13
[0222] [00222] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified quantities, using the procedures described in the Silicone-Hydrogel Contact Lens Fabrication and Test Procedure, provided above.
[0223] [00223] 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 Silicone-Hydrogel Contact Lens Fabrication and Test Procedure, using a dry demoulding process, dry lens removal process and a washing process that used extraction and hydration liquids consisting of extraction liquids free of volatile organic solvent. The lenses in this batch were not exposed to a volatile organic solvent during their manufacture. These contact lenses contained units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had an acceptable average dimensional stability variance.
[0224] [00224] Furthermore, these silicone-hydrogel 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 modulus of about 0.66 MPa, an elongation of about 274%, a tensile strength of about 1.40 MPa and a content of wet extractables of about 3.8% w / w when tested at the start of the study of storage time, and had an average dimensional stability variance less than plus or minus 3.0% after storage for 7 days at 80 degrees C. EXAMPLE 14
[0225] [00225] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified quantities, using the procedures described in the Silicone-Hydrogel Contact Lens Manufacturing and Test Procedure, provided above.
[0226] [00226] 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 Silicone-Hydrogel Contact Lens Manufacturing and Test Procedure, using a dry demoulding process, dry lens removal process and a washing process that used extraction and hydration liquids consisting of extraction liquids free of volatile organic solvent. The lenses in this batch were not exposed to a volatile organic solvent during their manufacture. These contact lenses contained units derived from three siloxane monomers, Si1, Si2 and Si3. This batch of contact lenses had an acceptable average dimensional stability variance.
[0227] [00227] Furthermore, these silicone-hydrogel contact lenses, when fully hydrated, had a modulus of about 0.81 MPa, an elongation of about 351%, a tensile strength of about 1.61 MPa and a EWC of 30% w / w and 70% w / w, when tested at the beginning of the shelf life study, and had an average dimensional stability variance less than plus or minus 3.0% for 14 days at 80 degrees C. EXAMPLE 15
[0228] [00228] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified quantities, using the procedures described in the Silicone-Hydrogel Contact Lens Fabrication and Test Procedure, provided above.
[0229] [00229] 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 Silicone-Hydrogel Contact Lens Manufacturing and Test Procedure, using a dry demoulding process, dry lens removal process and a washing process that used extraction and hydration liquids consisting of extraction liquids free of volatile organic solvent. The lenses in this batch were not exposed to a volatile organic solvent during their manufacture. These contact lenses contained units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had an acceptable average dimensional stability variance.
[0230] [00230] In addition, these silicone-hydrogel contact lenses, when fully hydrated, had an ion flux of about 3.33 (x10-3 mm2 / min), a modulus of about 0.74 MPa and an elongation of about 222%, when tested at the beginning of the shelf life study, and had an average dimensional stability variance less than plus or minus 3.0% for 14 days at 80 degrees C. EXAMPLE 16
[0231] [00231] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified quantities, using the procedures described in the Silicone-Hydrogel Contact Lens Manufacturing and Test Procedure, provided above.
[0232] [00232] 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 Silicone-Hydrogel Contact Lens Manufacturing and Test Procedure, using a dry demoulding process, dry lens removal process and a washing process that used extraction and hydration liquids consisting of extraction liquids free of volatile organic solvent. The lenses in this batch were not exposed to a volatile organic solvent during their manufacture. These contact lenses contained units derived from two siloxane monomers, Si1 and Si3. This batch of contact lenses had an acceptable average dimensional stability variance.
[0233] [00233] Furthermore, these silicone-hydrogel contact lenses, when fully hydrated, had an EWC of about 57% w / w, a modulus of about 0.70 MPa, an energy loss of about 40% and a dynamic bubble advance contact angle of about 50 to about 60 degrees when tested at the start of the storage time study, and had a mean dimensional stability variance of less than plus or minus 3.0% over 14 days at 80 degrees C. EXAMPLE 17
[0234] [00234] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified quantities, using the procedures described in the Silicone-Hydrogel Contact Lens Fabrication and Test Procedure, provided above.
[0235] [00235] 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 Silicone-Hydrogel Contact Lens Manufacturing and Test Procedure, using a dry demoulding process, dry lens removal process and a washing process that used extraction and hydration liquids consisting of extraction liquids free of volatile organic solvent. The lenses in this batch were not exposed to a volatile organic solvent during their manufacture. These contact lenses contained units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had an acceptable average dimensional stability variance.
[0236] [00236] Furthermore, these silicone-hydrogel contact lenses, when fully hydrated, had an EWC of about 56% w / w, a module of about 0.50 MPa and a dynamic bubble advance contact angle about 47 to about 51 degrees, when tested at the start of the shelf life study, and had an average dimensional stability variance of less than plus or minus 3.0% for 4.4 weeks at 80 degrees C. EXAMPLE 18
[0237] [00237] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified quantities, using the procedures described in the Silicone-Hydrogel Contact Lens Fabrication and Test Procedure, provided above.
[0238] [00238] 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 Silicone-Hydrogel Contact Lens Fabrication and Test Procedure, using a dry demoulding process, dry lens removal process and a washing process that used extraction and hydration liquids consisting of extraction liquids free of volatile organic solvent. The lenses in this batch were not exposed to a volatile organic solvent during their manufacture. These contact lenses contained units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had an acceptable average dimensional stability variance.
[0239] [00239] Furthermore, these silicone-hydrogel contact lenses, when fully hydrated, had an EWC of about 55% w / w, a module of about 0.60 MPa and a dynamic bubble advance contact angle about 47 to about 55 degrees when tested at the start of the storage time study, and had an average dimensional stability variance of less than plus or minus 3.0% during 2 weeks of storage at 80 degrees C. EXAMPLE 19
[0240] [00240] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified quantities, using the procedures described in the Silicone-Hydrogel Contact Lens Manufacturing and Test Procedure, provided above.
[0241] [00241] 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 Silicone-Hydrogel Contact Lens Manufacturing and Test Procedure, using a dry demoulding process, dry lens removal process and a washing process that used extraction and hydration liquids consisting of extraction liquids free of volatile organic solvent. The lenses in this batch were not exposed to a volatile organic solvent during their manufacture. These contact lenses contained units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had an acceptable average dimensional stability variance.
[0242] [00242] In addition, these silicone-hydrogel contact lenses, when fully hydrated, had an EWC of about 55% w / w and about 56% w / w, a module of 0.71 MPa and a contact angle dynamic bubble advance stuck from about 45 to about 47 degrees when tested at the start of the shelf life study, and had a mean dimensional stability variance of less than plus or minus 3.0% for at least 2 weeks at 80 degrees C. EXAMPLE 20
[0243] [00243] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified quantities, using the procedures described in the Silicone-Hydrogel Contact Lens Fabrication and Test Procedure, provided above.
[0244] [00244] 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 Silicone Hydrogel Contact Lens Fabrication and Test Procedure, using a dry demoulding process, dry lens removal process and a washing process that used extraction and hydration liquids consisting of extraction liquids free of volatile organic solvent. The lenses in this batch were not exposed to a volatile organic solvent during their manufacture. These contact lenses contained units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had an acceptable average dimensional stability variance.
[0245] [00245] Furthermore, these silicone-hydrogel 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 start of the shelf life study , and had an average dimensional stability variance of less than plus or minus 3.0% for 2 weeks at 80 degrees C. EXAMPLE 21
[0246] [00246] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified quantities, using the procedures described in the Silicone-Hydrogel Contact Lens Fabrication and Test Procedure, provided above.
[0247] [00247] 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 Silicone-Hydrogel Contact Lens Manufacturing and Test Procedure, using a dry demoulding process, dry lens removal process and a washing process that used extraction and hydration liquids consisting of extraction liquids free of volatile organic solvent. The lenses in this batch were not exposed to a volatile organic solvent during their manufacture. These contact lenses contained units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had an acceptable average dimensional stability variance.
[0248] [00248] In addition, silicone-hydrogel contact lenses, when fully hydrated, had an EWC of about 55% w / w and about 56% w / w, a module of 0.53 MPa, an angle of contact of dynamic bubble advance stuck from about 51 to about 53 degrees and an energy loss of about 34%, when tested at the start of the storage time study, and had an average dimensional stability variance less than more or less 3.0% for 4.4 weeks at 80 degrees C. EXAMPLE 22
[0249] [00249] A polymerizable silicone composition was obtained by mixing and filtering the following chemical compounds in the specified quantities, using the procedures described in the Silicone-Hydrogel Contact Lens Fabrication and Test Procedure, provided above.
[0250] [00250] 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 Silicone-Hydrogel Contact Lens Fabrication and Test Procedure, using a dry demoulding process, dry lens removal process and a washing process that used extraction and hydration liquids consisting of extraction liquids free of volatile organic solvent. The lenses in this batch were not exposed to a volatile organic solvent during their manufacture. These contact lenses contained units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had an acceptable average dimensional stability variance.
[0251] [00251] In addition, these silicone-hydrogel 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 modulus of about 0.7 MPa, an elongation of about 300%, a tensile strength of about 1.5 MPa, a dynamic forward contact angle of trapped bubble of about 44 to about 48 degrees, a wet extractable component of about 5.10% w / w and an energy loss of about 32% to about 33%, when tested at the start of the shelf life study, and had an average dimensional stability variance less than about 3.0% after storage for 4.4 weeks at 80 degrees C. When tested before extraction and hydration, the polymeric lens bodies had a dry extractable component at about 12.2% w / w. EXAMPLE 23
[0252] [00252] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified quantities, using the procedures described in the Silicone-Hydrogel Contact Lens Fabrication and Test Procedure, provided above.
[0253] [00253] 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 Silicone Hydrogel Contact Lens Fabrication and Test Procedure, using a dry demoulding process, dry lens removal process and a washing process that used extraction and hydration liquids consisting of extraction liquids free of volatile organic solvent. The lenses in this batch were not exposed to a volatile organic solvent during their manufacture. These contact lenses contained units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had an acceptable average dimensional stability variance.
[0254] [00254] In addition, these silicone-hydrogel 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, a dynamic bubble contact advance angle of about 55 at about 58 degrees, a wet extractable 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 storage time study, and had an average dimensional stability variance less than plus or minus 3.0% after storage for 4.4 weeks at 80 degrees C. When tested before extraction and hydration, the polymeric lens bodies had a dry extractable component at about 10.6% w / w. EXAMPLE 24
[0255] [00255] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified quantities, using the procedures described in the Silicone-Hydrogel Contact Lens Manufacturing and Test Procedure, provided above.
[0256] [00256] 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 Silicone-Hydrogel Contact Lens Manufacturing and Test Procedure, using a dry demoulding process, dry lens removal process and a washing process that used extraction and hydration liquids consisting of extraction liquids free of volatile organic solvent. The lenses in this batch were not exposed to a volatile organic solvent during their manufacture. These contact lenses contained units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had an acceptable average dimensional stability variance.
[0257] [00257] 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 modulus of about 0.5 MPa, an elongation of about 279%, a tensile strength of about 1.2 MPa, a dynamic bubble contact advance angle of about 45 to about 47 degrees, a wet extractable component at about 4.55% w / w and an energy loss of about 30% to about 33%, when tested at the start of the shelf life study, and had an average dimensional stability variance less than more or less 3.0% after storage for 14 days at 80 degrees C. When tested before extraction and hydration, the polymeric lens bodies had a dry extractable component at about 13.65% w / w. EXAMPLE 25
[0258] [00258] A polymerizable composition was obtained by mixing and filtering the following chemical compounds in the specified quantities, using the procedures described in the Silicone-Hydrogel Contact Lens Manufacturing and Test Procedure, provided above.
[0259] [00259] 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 Silicone-Hydrogel Contact Lens Manufacturing and Test Procedure, using a dry demoulding process, dry lens removal process and a washing process that used extraction and hydration liquids consisting of extraction liquids free of volatile organic solvent. The lenses in this batch were not exposed to a volatile organic solvent during their manufacture. These contact lenses contained units derived from two siloxane monomers, Si1 and Si2. This batch of contact lenses had an acceptable average dimensional stability variance.
[0260] [00260] 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 bubble advance contact angle of about 47 at about 53 degrees, a wet extractable component at about 4.10% w / w and an energy loss of about 34% to about 35%, when tested at the start of the shelf life study, and had a variance of average dimensional stability less than plus or minus 3.0% after storage for 14 days at 80 degrees C. When tested before extraction and hydration, it was found that the polymeric lens bodies had a dry extractable component at about 9, 80% w / w.
[0261] [00261] Although the disclosure in this document refers to certain illustrated modalities, it should be understood that these modalities are presented by way of example, and not for the purpose of limitation. The intention of the detailed description above, while discussing exemplary modalities, is to be interpreted as covering all modifications, alternatives and equivalents of the modalities as they may fit within the spirit and scope of the invention, as defined by the further disclosure.
[0262] [00262] Several publications and patents have been cited above. Each of the publications and patents cited are hereby incorporated by reference in their entirety.

权利要求:
Claims (18)
[0001]
Silicone-hydrogel contact lens CHARACTERIZED by the fact that it comprises: a polymeric lens body which is the product of the reaction of a polymerizable composition, said polymerizable composition comprising (a) a first siloxane monomer represented by formula (1):
[0002]
Contact lens, according to claim 1, CHARACTERIZED by the fact that it has an oxygen permeability of at least 55 barrers, or an equilibrium water content of 30% w / w 70% w / w, or a module of elasticity of 0.2 MPa to 0.9 MPa, or any combination thereof.
[0003]
Contact lens according to claim 1, CHARACTERIZED by the fact that in the first siloxane monomer, m of the formula (1) is 4, n is 1, R1 of the formula (1) is a butyl group and each R2 of the formula (1) is independently a hydrogen atom or a methyl group.
[0004]
Contact lens, according to claim 1, CHARACTERIZED by the fact that the first siloxane monomer has an average numerical molecular weight of 400 Daltons to 700 Daltons.
[0005]
Contact lens, according to claim 1, CHARACTERIZED by the fact that the second siloxane monomer has an average numerical molecular weight greater than 7,000 Daltons.
[0006]
Contact lens, according to claim 1, 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, a is a integer from 65 to 90, b is an integer from 1 to 10 and R1 from formula (2) is a methyl group.
[0007]
Contact lens according to claim 1, CHARACTERIZED by the fact that the polymerizable composition comprises at least one hydrophilic monomer and at least one hydrophilic monomer comprises at least one vinyl-containing hydrophilic monomer.
[0008]
Contact lens according to claim 7, CHARACTERIZED by the fact that the at least one vinyl-containing monomer comprises at least one amide-containing hydrophilic monomer that has an N-vinyl group.
[0009]
Contact lens according to claim 1, CHARACTERIZED by the fact that the polymerizable composition comprises at least one hydrophilic monomer, and at least one hydrophilic monomer is present in the polymerizable composition in an amount of 30 unit parts to 60 unit parts .
[0010]
Contact lens according to claim 1, CHARACTERIZED by the fact that the polymerizable composition comprises at least one crosslinking agent, and the at least one crosslinking agent comprises at least one vinyl containing crosslinking agent.
[0011]
Method of manufacturing a silicone hydrogel contact lens FEATURED by the fact that it comprises: providing a polymerizable composition, said polymerizable composition comprising (a) a first siloxane monomer represented by formula (1):
[0012]
Method according to claim 11, CHARACTERIZED by the fact that it further comprises repeating the steps to produce a plurality of silicone hydrogel contact lenses having an average dimensional stability variance less than plus or minus three percent (± 3, 0%) over a period of time from two weeks to seven years when stored at room temperature, or when stored under accelerated life test conditions, for a period of time and temperature equivalent to storage from two weeks to seven years at temperature the said average dimensional stability variance being an average of the dimensional stability variance determined for at least 20 individual lenses of the lot by the following equation (A): (Final Diameter - Original Diameter) / Original Diameter) x 100 (A) .
[0013]
Method, according to claim 11, CHARACTERIZED by the fact that, in the first siloxane monomer, m of formula (1) is 4, n of formula (1) is 1, R1 is a butyl group and each R2 of Formula ( 1) it is independently a hydrogen atom or a methyl group.
[0014]
Method according to claim 11, CHARACTERIZED by the fact that the first siloxane monomer has an average numerical molecular weight of 400 Daltons to 700 Daltons.
[0015]
Method according to claim 11, CHARACTERIZED by the fact that the second siloxane monomer has an average numerical molecular weight greater than 7,000 Daltons.
[0016]
Method according to claim 11, 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, a is an integer from 65 to 90, b is an integer from 1 to 10 and R1 of formula (2) is a methyl group.
[0017]
Method according to claim 11, CHARACTERIZED by the fact that the contact step comprises contacting the polymeric lens body with a washing liquid comprising a volatile organic solvent.
[0018]
Method according to claim 11, CHARACTERIZED by the fact that the contact step comprises contacting the polymeric lens body with an aqueous washing liquid that is free of a volatile organic solvent.

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同族专利:

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公开号 | 公开日

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TW201243428A|2012-11-01|

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GB2502755A|2013-12-04|

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CA2827205A1|2012-09-07|

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GB2502755B|2014-03-26|

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CA2827205C|2014-08-26|

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BR112013022001A2|2017-07-25|

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SG192242A1|2013-09-30|

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CN104011110B|2016-05-04|

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WO2012118673A3|2014-03-13|

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MY151110A|2014-04-15|

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WO2012118673A2|2012-09-07|

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US8445614B2|2013-05-21|

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JP2014515117A|2014-06-26|

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AU2012223584A8|2014-08-14|

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AU2012223584B2|2014-06-05|

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CN104011110A|2014-08-27|

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JP5904603B2|2016-04-13|

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KR20130123457A|2013-11-12|

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AU2012223584B8|2014-08-14|

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US20120220743A1|2012-08-30|

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MX2013009216A|2014-09-08|

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AU2012223584A1|2013-09-12|

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MX354797B|2018-03-21|

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TWI531826B|2016-05-01|

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HK1197078A1|2015-01-02|

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GB201316970D0|2013-11-06|

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KR101528997B1|2015-06-15|

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法律状态:
2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-08-27| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-04-07| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2020-07-21| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-09-08| 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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2021-08-24| B25G| Requested change of headquarter approved|Owner name: COOPERVISION INTERNATIONAL HOLDING COMPANY, LP (BB) |

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2021-09-14| 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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US201161447164P| true| 2011-02-28|2011-02-28|

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US61/447,164|2011-02-28|

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PCT/US2012/026213|WO2012118673A2|2011-02-28|2012-02-23|Dimensionally stable silicone hydrogel contact lenses|

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