Contact lens compounds and contact lenses

Abstract

Silicone hydrogel contact lens formulations are described. The formulations contain silicone components and silicone-free components. The silicone components include two or three compounds represented by formulas 1, 2, or 3. The silicone-free components include methacrylate components and N-vinylamide components. The methacrylate components include hydroxybutyl methacrylate (HOB) and isobornyl methacrylate (IBM). The N-vinylamide components include N-vinyl N-methylacetamide. When the compounds of formulas 1 and 2 are present in the formulation in specified ratios, a desirable silicone hydrogel contact lens can be obtained by preparing HOB and IBM in specific amounts to obtain the specified ratio. Silicone hydrogel contact lenses are also described.

Description

[Technical Field]

[0001] The present invention relates to novel silicone hydrogel contact lens formulations and ophthalmic lenses, particularly contact lenses, and more particularly to silicone hydrogel contact lenses comprising reaction products of polymerizable compositions. [Background technology]

[0002] Silicone hydrogel contact lenses have been found to be an acceptable alternative to hydrogel contact lenses. Contact lens manufacturers are often presented with the introduction of new contact lenses to meet market demand. Therefore, the continuous development of new silicone hydrogel contact lenses to address this demand is necessary. In the development of silicone hydrogel contact lenses, it is difficult to predict whether a new silicone hydrogel contact lens formulation will result in a clinically acceptable silicone hydrogel contact lens. Achieving a good fit, an acceptable level of comfort, an acceptable handling experience, and an acceptable improvement in vision is influenced by various changes in lens chemistry, lens design, and manufacturing processes. For example, changes in the formulation of a silicone hydrogel contact lens can alter oxygen permeability, water content, lens surface wettability, and mechanical properties such as elastic modulus, tensile strength, and resilience. Therefore, it is unpredictable which combination of chemicals in the formulation will produce the desired lens properties. [Overview of the Initiative]

[0003] This invention addresses this ongoing need. The inventors have found that when certain combinations of polysiloxane compounds are used in silicone hydrogel contact lens formulations, it is necessary to adjust other monomers in the formulation in ways previously unknown in order to achieve certain desirable contact lens properties. The disclosure herein describes the invention in more detail. The applicant has revealed that suitable silicone hydrogel contact lens formulations can be formed using a reaction mixture containing a silicone component and a silicone-free component. The silicone component is Formula 1: [ka] (wherein R1 is selected from hydrogen or a methyl group; R2 is hydrogen or C 1-4 Selected from hydrocarbon groups; m represents an integer from 0 to 10; n represents an integer from 4 to 100; a and b represent integers greater than or equal to 1; a+b is from 20 to 500; b / (a+b) is from 0.01 to 0.22, and the arrangement of siloxane units includes random arrangements); and Formula 2: [ka] (In the formula, n is an integer between 10 and 25.) It contains two compounds, preferably essentially consisting of two compounds of formula 1 and formula 2.

[0004] It is important that the compound of formula 1 and the compound of formula 2 are present in a ratio of 50:50 to 77:23, and together in an amount of 45 to 55 mass percent. Preferably, the ratio of the compound of formula 1 to the compound of formula 2 is 53:47 to 77:23. In one embodiment, in the compound of formula 1, R1 is selected from hydrogen or a methyl group; R2 is hydrogen or C 1-4 A hydrocarbon group is selected; m is 0; n represents an integer from 4 to 15; a represents an integer from 50 to 250; b represents an integer from 5 to 50; the arrangement of the siloxane units includes random arrangements, and the a:b ratio is 5:1 to 30:1, preferably 10:1 to 20:1. In further embodiments, the silicone component is a further silicone compound of formula 3: [ka] Furthermore, the formula includes, where m represents an integer from 3 to 12, and n represents an integer from 1 to 10, R 1 R is selected from alkyl groups having 1 to 4 carbon atoms.2 R is a hydrogen atom or a methyl group, 3 This is either a hydrogen atom or a methyl group.

[0005] In some embodiments, in the compound of formula 3, m is 4, n is 1, and R 1 is a butyl group, R 2 H is R 3 It is a methyl group. If the compound of formula 3 is present, it is used in an amount of less than 1% of the total contact lens formulation. In a preferred embodiment of the formulation of the present invention, the silicone component essentially consists of formulas 1, 2, and 3. The combination of compounds in formulas 1 and 2 advantageously allows for the use of smaller amounts of silicone component while still resulting in contact lenses with good oxygen permeability. This also allows for high water content, which is advantageous in terms of wettability. However, when contact lens formulations are manufactured using even small amounts of the compounds of Formulas 1 and 2, the tensile strength and Young's modulus may be increased, as seen in Examples 15-17 of U.S. Patent No. 8,129,442. The applicant demonstrated that by focusing on and selecting the ratios and / or amounts of certain other monomers, it is possible to manufacture lenses having a tensile strength significantly lower than that found in formulations containing the compounds of Formulas 1 and 2. The silicone-free ingredients include N-vinylamide and methacrylate components.

[0006] The methacrylate component comprises hydroxybutyl methacrylate (HOB) and isobornyl methacrylate (IBM), and in some embodiments, essentially consists of or comprises these. It is important that HOB and IBM are present in amounts of 8.5 to 16 mass percent, and that the total amount of IBM is less than 5 mass percent. HOB and IBM are preferably present in the formulation in a ratio of 70:30 to 90:10. Preferably, the mass ratio of HOB to IBM is 85:15 to 90:10, and more preferably the ratio is about 88:12.

[0007] The N-vinylamide component includes N-vinyl N-methylacetamide (VMA). In some embodiments, the N-vinylamide component also includes N-vinylpyrrolidone (NVP). When the N-vinylamide component includes NVP and VMA, the ratio of NVP to VMA is preferably 70:30 to 30:70. In preferred embodiments, the N-vinylamide component consists essentially of NVP and VMA, and preferably consists of NVP and VMA. Preferably, the N-vinylamide component is present in an amount of 33 to 37 mass percent. Surprisingly, it was found that a specific ratio of HOB to IBM, along with the optional inclusion of VMA and NVP, resulted in lenses with desirable properties, particularly lenses with lower tensile strength and lower Young's modulus compared to past lenses formed using combinations of polysiloxane compounds of formulas 1 and 2. The N-vinylamide component essentially consists of N-vinylpyrrolidone (NVP) and N-vinyl N-methylacetamide (VMA), and in some embodiments, it comprises these two components.

[0008] In some embodiments, the total amount of the compound of formula 2, VMA, and HOB exceeds 28 mass percent. In a first particular preferred embodiment, the contact lens formulation comprises a silicone component essentially consisting of formulas 1 and 2, with a ratio of formula 1 to formula 2 of 53:47 to 57:43. The N-vinylamide component essentially consists of NVP and VMA, with an NVP:VMA ratio of 68:32 to 72:28. The methacrylate component essentially consists of HOB and IBM, with an HOB to IBM ratio of 85:15 to 90:10. The silicone component is preferably 45 to 55 mass percent of the formulation. The methacrylate component is more preferably 10 to 20 mass percent of the formulation. The N-vinylamide component is even more preferably 30 to 40 mass percent of the formulation. In a second particularly preferred embodiment, the contact lens formulation comprises a silicone component essentially consisting of formulas 1 and 2, with a ratio of formula 1 to formula 2 of 73:27 to 77:23. The N-vinylamide component essentially consists of NVP and VMA, with a ratio of NVP:VMA of 32:68 to 28:72. The methacrylate component essentially consists of HOB and IBM, with a ratio of HOB to IBM of 85:15 to 90:10. The silicone component is preferably 45 to 55 mass percent of the formulation. The methacrylate component is more preferably 10 to 20 mass percent of the formulation. The N-vinylamide component is even more preferably 30 to 40 mass percent of the formulation.

[0009] In a third particularly preferred embodiment, the contact lens formulation comprises a silicone component essentially consisting of formulas 1, 2, and 3, wherein formula 3 is present in an amount of less than 0.6 mass percent of the formulation, and the ratio of formula 1 to formula 2 is 60:40 to 65:35. The N-vinylamide component essentially consists of VMA. The methacrylate component essentially consists of HOB and IBM, with a ratio of HOB to IBM of 75:25 to 80:20. The silicone component is preferably 45 to 55 mass percent of the formulation. The methacrylate component is more preferably 5 to 15 mass percent of the formulation. The N-vinylamide component is even more preferably 30 to 40 mass percent of the formulation. Preferably, the formulation further comprises at least one of the following: a photoinitiator, a thermal initiator; a crosslinking monomer; a UV blocking agent; and a colorant. In another embodiment of the present invention, a silicone hydrogel contact lens comprising polymerization reaction products of any of the formulations described above is disclosed. Silicone hydrogel contact lenses can have a tensile strength of 0.4 MPa to 1.0 MPa. Silicone hydrogel contact lenses typically have a tensile strength of 1.0 MPa or less, preferably 0.9 MPa or less. Silicone hydrogel contact lenses typically have a tensile strength of at least 0.4 MPa, more preferably at least 0.5 MPa. In at least some preferred embodiments, silicone hydrogel contact lenses have a tensile strength of 0.5 MPa to 0.9 MPa.

[0010] Silicone hydrogel contact lenses can have a droplet contact angle of less than 30 degrees, more preferably less than 25 degrees. Silicone hydrogel contact lenses can have an equilibrium moisture content of 45 to 55% by mass. Silicone hydrogel contact lenses can have an oxygen permeability of greater than 100 barrers, preferably greater than 110 barrers, more preferably greater than 120 barrers, particularly 110 to 140 barrers. Silicone hydrogel contact lenses can have a Young's modulus of 1.1 MPa or less, preferably 1.0 MPa or less. The Young's modulus is preferably at least 0.3 MPa, more preferably at least 0.5 MPa. The preferred range is 0.5 MPa to 0.95 MPa. Silicone hydrogel contact lenses can have a chord diameter of 13.5 to 15.5 mm and a base curve of 7.5 to 9.5 mm. Those skilled in the art recognize other suitable chord diameters and base curves.

[0011] By using the above amounts of these components, it is possible to obtain lenses having a good balance of properties, particularly a good balance of a moderately low elastic modulus and tensile strength. When using certain selected silicone components, the applicant has confirmed that the balance of the silicone-free methacrylate components is important for achieving good properties of the resulting lenses. One way to demonstrate whether a lens has good properties is to examine whether it meets the product of relative methacrylate - flexibility. The applicant has confirmed that a good lens has a value of this product exceeding 1.25. A good lens preferably has a value exceeding 2.5, more preferably exceeding 5. A lens having a product that meets this value exhibits a good balance of physical properties and particularly has a good level of flexibility. The product of relative methacrylate - flexibility is (mass% of HOB / mass% of IBM) * (tensile strength / modulus of elasticity) measured as This dimensionless parameter may enable a person skilled in the art to quickly evaluate whether a lens made of the above - specified main monomers will have good properties.

Best Mode for Carrying Out the Invention

[0012] A silicone hydrogel contact lens is described herein that has good dimensional stability, is ophthalmically acceptable, and can be manufactured without using volatile organic solvents or diluents in the formulation. The silicone hydrogel contact lens includes a polymeric lens body that is a reaction product of a polymerizable composition or a silicone hydrogel contact lens formulation containing a silicone component and a silicone - free component. The silicone component includes or consists essentially of two compounds of Formula 1 and Formula 2. It is important that the compounds of Formula 1 and the compounds of Formula 2 are in a ratio of 50:50 to 77:23 and together in an amount of 45 to 55 mass percent. References herein to "at least one" of an element type refer to both a) a single element and b) combinations of two or more elements of the same type. Throughout this disclosure, references to the "total amount" of a particular component (i.e., a combination of two or more components of the same type) in a polymerizable composition refer to the sum of the amounts of all components of the same type. The following definitions of the cited terms shown below are applicable herein unless otherwise indicated by context.

[0013] A "monomer" refers to any molecule that can react with other molecules, whether identical or different, to form a polymer or copolymer. Therefore, this term encompasses polymerizable prepolymers and macromers, and there are no size restrictions on monomers unless otherwise specified. A "siloxane monomer" contains at least one Si-O group and is typically either "monofunctional" or "polyfunctional," meaning each group has either one or more polymerizable groups. A "non-siloxane monomer" is a monomer that does not contain a Si-O group. "Silicone components" are components or parts of silicone hydrogel contact lens formulations that consist entirely of siloxane monomers. "Silicone-free ingredients" are ingredients or parts of silicone hydrogel contact lens formulations that consist entirely of non-siloxane monomers. "N-vinylamide component" is a component or part of a silicone-free component of a silicone hydrogel contact lens formulation, consisting of at least one nonsiloxane monomer having a vinyl group directly bonded to a nitrogen atom. "Methacrylate component" is a component or part of a silicone-free component of a silicone hydrogel contact lens formulation, consisting of at least one nonsiloxane monomer having one polymerizable methacrylate group.

[0014] "(meth)acrylate-containing monomer" refers to any non-siloxane monomer (e.g., methyl methacrylate) having one polymerizable (meth)acrylate group. Siloxane monomers having at least one polymerizable (meth)acrylate group are referred to herein as "(meth)acrylate-containing siloxane monomers." "(meth)acrylate" refers to both methacrylate and acrylate groups. When referring to methacrylate or acrylate alone, it is explicitly mentioned. "Consists of" means a formulation or component that contains only the listed components, compounds, or monomers. "Consisting essentially of" means that the formulation or component contains the described compound or monomer, but may also contain other monomers or compounds within the scope of the definition of the formulation or component, such as dimer or polymer impurities. These additional monomers or compounds may be present in amounts that do not affect the final lens formulation. The additional monomers or reactive elements may be present in amounts less than 5%, less than 2%, less than 1%, less than 0.5%, or less than 0.1% based on the total amount of a particular formulation or component. A "polymeric composition" is a composition containing polymeric elements, and the composition has not yet been exposed to conditions that cause polymerization of the polymeric elements. Therefore, the silicone hydrogel contact lens formulations of the present invention are considered polymeric compositions.

[0015] In the case of polyorganosiloxane prepolymers and other polydisperse monomers, the term "molecular weight" as used herein refers to the absolute number average molecular weight M n (in units of Daltons (Da) or g / mol). The number average molecular weight is typically measured using GPC with polystyrene standards. Additionally, the number average molecular weight may be determined by checking the number average molecular weight in the technical data sheets or specifications provided by chemical suppliers to contact lens manufacturers. In the present disclosure, when a value is given for a repeating group in a structural formula such as Formula 1, Formula 2, or Formula 3, this is an average value. One of ordinary skill in the art will understand that such complex molecules contain a mixture of components. As used herein, the term "total formulation" or "total contact lens formulation" refers to all elements of the formulation excluding diluents and / or solvents that are not incorporated into the final polymeric contact lens material. It can be understood that when the mass percentage of an element in the total formulation is indicated, it refers to the mass percentage of the element based on the total mass of the formulation. Throughout this disclosure, any reference to “examples,” “specific examples,” or similar phrases is intended to describe one or more features of a contact lens, polymerizable composition, or method of manufacture (as contextually indicated), which may be combined with any combination of the aforementioned or subsequent examples (i.e., features), provided that no particular combination of features contradicts each other or unless otherwise indicated in the context.

[0016] Throughout this disclosure, where a set of lower and upper limits are presented, all possible combinations of the ranges are conceivable, as if each combination were specifically described. Furthermore, throughout this disclosure, where a set of values ​​is presented with a modifier placed before the first value, unless otherwise indicated by context, that modifier is implicitly intended to precede each value in the series. For example, with respect to the values ​​listed above, the modifier "approximately (number) ~" is implicitly intended to precede the 50:50 ratio, and the modifier "~approximately (number)" is implicitly intended to precede the 80:20 ratio. As used herein, unless otherwise specified, a ratio refers to a mass ratio. As used herein, a mass ratio refers to the ratio of the mass of the first component in the formulation to the mass of the second component. Silicone hydrogel contact lens formulations containing silicone components and silicone-free components are disclosed herein. The silicone component comprises, or essentially consists of, a bifunctional (meth)acrylate-containing siloxane monomer and a monofunctional methacrylate-containing siloxane monomer, or in some embodiments consists of them.

[0017] The bifunctional (meth)acrylate-containing siloxane monomer is given by formula 1: [ka] Represented by the formula, where R1 is selected from hydrogen or a methyl group; R2 is hydrogen or C 1-4Selected from hydrocarbon groups; m represents an integer from 0 to 10; n represents an integer from 4 to 100; a and b represent integers greater than or equal to 1; a+b is from 20 to 500; b / (a+b) is from 0.01 to 0.22, and the arrangement of siloxane units includes random arrangements. The difunctional (meth)acrylate-containing siloxane monomer of formula 1 may have an average molecular weight Mw of at least 8,000, 10,000, 12,000, or 15,000 Da. The difunctional (meth)acrylate-containing siloxane monomer of formula 1 may have an average molecular weight Mw of less than 25,000 Da, less than 20,000 Da, less than 12,000 Da, less than 11,000 Da, less than 10,000 Da, or less than 9,000 Da. Preferably, the difunctional (meth)acrylate-containing siloxane monomer has an average molecular weight Mw of 8,000 to 20,000 Da. In one preferred embodiment, the difunctional (meth)acrylate-containing siloxane monomer of formula 1 has an average molecular weight Mw of 8,000 to 11,000 Da. In another preferred embodiment, the bifunctional (meth)acrylate-containing siloxane monomer of formula 1 has an average molecular weight Mw of 15,000 to 20,000 Da.

[0018] In one embodiment, in the compound of formula 1, R1 is selected from hydrogen or a methyl group; R2 is hydrogen or C 1-4 A hydrocarbon group is selected; m is 0; n represents an integer from 4 to 15; a represents an integer from 50 to 250; b represents an integer from 5 to 50; the arrangement of the siloxane units includes random arrangements; and the a:b ratio is 5:1 to 30:1, preferably 10:1 to 20:1. R1 is preferably a methyl group. R2 is preferably H or a methyl group, or more preferably a methyl group. m is even more preferably 0. n is preferably 6 to 9. In a preferred embodiment, a is 60-100, more preferably 70-80, and b is 4-8, more preferably 5-8. It is even more preferable that R1 is methyl, R2 is methyl, m is 0, and n is 7-8. A particularly preferred bifunctional (meth)acrylate-containing siloxane monomer has CAS registry number 1216820-69-7.

[0019] In another preferred embodiment, a is 140-220, more preferably 150-200, and b is 8-15, more preferably 9-13. It is even more preferable that R1 is methyl, R2 is methyl, m is 0, and n is 7-8. A method for preparing the compound of Formula 1 is described in U.S. Patent No. 8,129,442 (incorporated herein by reference). Monofunctional methacrylate-containing siloxane monomers are given by formula 2: [ka] It is expressed as follows, where n is an integer between approximately 10 and 25, preferably between 13 and 18.

[0020] The monofunctional methacrylate-containing siloxane monomer of formula 2 has an average molecular weight of less than 2,000 Da, preferably less than 1,800 Da, and greater than 800 Da, preferably greater than 1,000 Da. In further specific examples, the monofunctional methacrylate-containing siloxane monomer may have an average molecular weight of 1,000 to 1,800 Da. Preferably, the monofunctional methacrylate-containing siloxane monomer has CAS registry number 697234-76-7. The siloxane monomer of Formula 2 is described in U.S. Patent No. 6,310,169 (incorporated herein by reference). The mass ratio of the compound of formula 1 to the compound of formula 2 is 50:50 to 77:23. In one preferred embodiment, the mass ratio of the compound of formula 1 to the compound of formula 2 is 53:47 to 77:23. In some specific embodiments, the mass ratio is 52:48 to 58:42. In some specific embodiments, the mass ratio is 60:40 to 65:35. In some specific embodiments, the mass ratio is 70:30 to 77:23. In some specific embodiments, the mass ratio is about 55:45, about 63:37, or about 75:25.

[0021] The compounds of formula 1 and formula 2 together are present in an amount of 45 to 55 percent by mass. In a further embodiment, the silicone component is a monofunctional (meth)acrylate-containing siloxane monomer of formula 3: [ka] The formula further comprises a silicone compound, where m represents an integer from 3 to 12, n represents an integer from 1 to 10, and R 1 R is selected from alkyl groups having 1 to 4 carbon atoms, and R in formula 3 2 and R 3 Each of these is independently selected from either a hydrogen atom or a methyl group.

[0022] In some embodiments, in the compound of formula 3, m is 4 and n is 1. 1 is a butyl group, R 2 H is R 3 It is even more preferable that it be a methyl group. If the compound of formula 3 is present, it is used in an amount of less than 1 mass percent, preferably less than 0.8 mass percent, and more preferably less than 0.6 mass percent of the total contact lens formulation. In a preferred embodiment of the formulation of the present invention, the silicone component essentially consists of formulas 1, 2, and 3, and preferably consists of formulas 1, 2, and 3. In some embodiments, the mass percentage of the silicone component is greater than 48%, greater than 48.5%, or greater than 49%. In some embodiments, the mass percentage of the silicone component is less than 53%, less than 52.5%, less than 52%, less than 51.5%, less than 51%, or less than 50.5%. In some embodiments, any lower limit of the mass percentage of the silicone component is combined with any upper limit of the mass percentage of the silicone component. For example, the silicone component may be present in the formulation at 48% (mass / mass) to 53% (mass / mass), preferably 48% to 51%.

[0023] In another preferred embodiment, the amount of compound of formula 2 is preferably more than 12 mass percent of the total composition. More preferably, the amount of compound of formula 2 is less than 25 mass percent. For example, the compound of formula 2 may be present in the formulation at 12 to 25% (mass / mass). In another preferred embodiment, the amount of compound of formula 1 is preferably less than 38 mass percent. More preferably, the amount of compound of formula 1 is greater than 26 mass percent. For example, compound of formula 1 may be present in the formulation at 26-38% (mass / mass). It is particularly preferable that the amount of compound in formula 2 exceeds 12 mass percent, and the amount of compound in formula 1 is less than 38 mass percent. Furthermore, it can be understood that the silicone component of the formulation of the present invention does not contain hydroxy-functionalized siloxane compounds, or does not contain TRIS, or neither. The silicone-free components include N-vinylamide component (c) and methacrylate component (d). The N-vinylamide component includes N-vinyl N-methylacetamide (VMA) vinegar. The N-vinylamide component may further contain N-vinylpyrrolidone (NVP). The N-vinylamide component is essentially composed of NVP and VMA, and more preferably consists of NVP and VMA.

[0024] In one preferred embodiment, when the N-vinylamide component contains both NVP and VMA, the ratio of NVP to VMA is 70:30 to 30:70. In some embodiments, the ratio is about 70:30. In some embodiments, the ratio is about 30:70. In further specific examples, the polymerizable composition has a mass ratio of about 40:60 to 45:55 for the total amount of N-vinylamide component to the total amount of (meth)acrylate-containing siloxane monomers (i.e., monofunctional and bifunctional (meth)acrylate-containing siloxane monomers). A ratio of 41:59 to 42:58 is even more preferred. In some embodiments, the mass percentage of the N-vinylamide component is greater than 34% or greater than 34.5%. In some embodiments, the mass percentage of the N-vinylamide component is less than 40%, less than 39%, less than 37%, less than 36%, or less than 35.5%. In some embodiments, the lower limit of the mass percentage of the N-vinylamide component is combined with any of the upper limits of the mass percentage of the N-vinylamide component. In some embodiments, the mass percentage of the N-vinylamide component is between 34.5% and 35.5%.

[0025] In one preferred embodiment, the N-vinylamide component essentially consists of VMA, and preferably consists of VMA. In further specific examples, the polymerizable composition has a mass ratio of approximately 40:60 to 45:55 between the total amount of N-vinylamide component and the total amount of (meth)acrylate-containing siloxane monomers (i.e., monofunctional and bifunctional (meth)acrylate-containing siloxane monomers). A ratio of 44:56 to 45:55 is more preferable. If the N-vinylamide component consists essentially of VMA, or consists of VMA, the mass percentage of the N-vinylamide component is greater than 35% or greater than 38%. The mass percentage of the N-vinylamide component is less than 40% or less than 39%. In some embodiments, the lower limit of the mass percentage of the N-vinylamide component is combined with any of the upper limits of the mass percentage of the N-vinylamide component. In some embodiments, the mass percentage of the N-vinylamide component is between 38% and 39%. In another specific example, the total amount of the compound of formula 2 and the N-vinylamide component is at least 47 mass percent, preferably at least 50 mass percent. The total amount of the compound of formula 2 and the N-vinylamide component is less than 70 mass percent, preferably less than 60 mass percent.

[0026] The methacrylate components include hydroxybutyl methacrylate (HOB) and isobornyl methacrylate (IBM). It is important that HOB and IBM are present in the formulation in amounts of 8.5 to 16 mass percent, and that the total amount of IBM is less than 5 mass percent. Preferably, HOB and IBM are present in the formulation in a ratio of 70:30 to 90:10. The methacrylate component (d) comprises hydroxybutyl methacrylate (HOB) and isobornyl methacrylate (IBM), and in some embodiments consists essentially of them. In some embodiments, the HOB to IBM ratio is greater than 60:40, greater than 65:35, greater than 70:30, greater than 75:25, greater than 80:20, greater than 85:15, or greater than 87:13. In some embodiments, the HOB to IBM ratio is less than 90:10, less than 89.5:10.5, less than 89:11, or less than 88.5:11.5. In some embodiments, any lower limit of the HOB to IBM ratio is combined with any upper limit of the HOB to IBM ratio. In some embodiments, the HOB to IBM ratio is 85:15 to 90:10 or about 88:12. In some embodiments, hydroxybutyl methacrylate and isobornyl methacrylate are present in the formulation in a mass percentage greater than 11, greater than 12, or greater than 13 mass percent. In some embodiments, hydroxybutyl methacrylate and isobornyl methacrylate are present in the formulation in a mass percentage less than 16. In some embodiments, the lower limits of HOB and IBM are combined with either the upper limit of HOB and IBM. Preferably, the total amount of HOB and IBM is 13.6 to 16 mass percent.

[0027] In one alternative embodiment, the mass ratio of HOB to IBM is preferably 75:25 to 80:20, more preferably about 77:23. In this embodiment, the total amount of HOB and IBM is preferably less than 10% by mass. Other silicone-free methacrylate-containing monomers are known in this field and may be present in contact lens formulations. Exemplary silicone-free methacrylate-containing monomers include methyl methacrylate (MMA), tert-butyl methacrylate (tBMA), 2-hydroxyethyl methacrylate (HEMA), ethylene glycol methyl ether methacrylate (EGMA), and combinations thereof. A preferred further silicone-free methacrylate-containing monomer is methyl methacrylate (MMA).

[0028] These additional methacrylate-containing monomers are preferably present in a total amount of less than 5%, more preferably less than 3% by mass, and even more preferably less than 1% by mass of the contact lens formulation, and the methacrylate component essentially consists of HOB and IBM. It is particularly preferable that no other methacrylate-containing monomers are present. In one specific example, the polymerizable composition may have a mass ratio of the compound of formula 2 to the total amount of nonsiloxane methacrylate-containing monomer that exceeds 0.9:1, preferably exceeding 1:1. In another specific example, the total amount of non-silicone and siloxane monomers containing monofunctional methacrylate is greater than 26 mass percent, preferably greater than 30 mass percent. Typically, the formulation further includes one or more additional ingredients common in contact lens formulations. Suitable additional ingredients include photoinitiators, thermal initiators, crosslinkers, UV blockers, and colorants.

[0029] The polymerizable composition may further contain at least one nonsiloxane crosslinking agent. As used herein, “crosslinking agent” is any compound having a molecular weight of less than about 2,000 Da together with two or more ethylenically unsaturated groups. Therefore, the crosslinking agent can react with functional groups on two or more polymer chains to crosslink one polymer to another. TAIC is particularly preferred as a crosslinking agent in the formulations of the present invention. The crosslinking agent is preferably used in an amount of 0.03 to 0.2 mass percent of the contact lens formulation. The composition may further contain one or more colorants. Preferred colorants are reactive colorants, particularly those identified as "reactive blue" dyes. The composition may further contain one or more UV-blocking agents. Contact lenses can be made from the polymerizable compositions described herein by curing and other processing methods known in the art, such as casting, spin casting, injection molding, forming a polymerized rod and then turning it. In one specific example, the polymerizable composition is cast between molds formed of thermoplastic polymers. The thermoplastic polymer is typically a non-polar material such as polypropylene, but polar mold materials such as ethylene vinyl alcohol are also used in this art. Simply put, a first mold member, called the "female mold member," which defines the front surface of the contact lens, is filled with a certain amount of polymerizable composition sufficient to form one polymer lens body. A second mold member, called the "male mold member," which defines the rear surface of the contact lens (i.e., the surface that contacts the eye), is paired with the female mold member to form a mold assembly having a lens-shaped cavity with a certain amount of polymerizable composition in between.

[0030] Polymerize the polymerizable composition inside the contact lens mold assembly using one of the following appropriate curing methods. Typically, the polymerizable composition is exposed to an amount of heat or ultraviolet (UV) light required for polymerization. In the case of UV curing, also known as photopolymerization, the polymerizable composition typically contains a photoinitiator such as benzoin methyl ether, 1-hydroxycyclohexyl phenyl ketone, Darocur, or Irgacur (available from Ciba Specialty Chemicals). A method for photopolymerization of contact lenses is described in U.S. Patent No. 5,760100, which is incorporated herein by reference. In the case of thermal curing, also known as heat curing, the polymerizable composition typically contains a thermal initiator. Exemplary thermal initiators include 2,2'-azobis(2,4-dimethylpentanenitrile) (VAZO-52), 2,2'-azobis(2-methylpropanenitrile) (VAZO-64), and 1,1'-azobis(cyanocyclohexane) (VAZO-88). The contact lens mold assembly containing the contact lens compound is cured by exposing it to heat or ultraviolet light for a period of time ranging from approximately 1 to 5 hours. Further thermal polymerization methods for contact lenses are described in U.S. Patent Publication No. 2007 / 0296914 and U.S. Patent No. 7854866, which are incorporated herein by reference.

[0031] Upon completion of curing, the polymerized material between the mold members of the mold assembly has the shape of a contact lens, which is referred to herein as a “polymer lens.” The male and female mold members are demolded, i.e., separated, and the polymer lens is removed, i.e., delendised, from the mold members to which it is attached. These processes are called demolding and delenduction, respectively, and various such methods are known to those skilled in the art. In some methods, the demolding and delenduction processes may include one process step, such as separating the mold using a liquid that removes the polymer lens from the mold. In other methods, such as when using a dry demolding process, the polymer lens typically remains on one of the mold members and is delendised in a subsequent process step. Delenduction may be a wet or dry process. In one example, delenduction is performed by a “float-off” method, in which the mold member to which the polymer lens is attached is immersed in water. The water may be heated (e.g., up to about 100°C). Typically, the polymer lens floats away from the mold member in about 10 minutes. Dry lens removal may be performed manually, for example, using tweezers to remove the polymer lens from the mold material, or the polymer lens may be removed using an automated mechanical process, such as that described in U.S. Patent No. 7,811,483 (incorporated herein by reference). Further methods for demolding and lens removal of silicone hydrogel contact lenses are described in U.S. Patent Publication No. 2007 / 0035049 (incorporated herein by reference).

[0032] After lens removal, the polymer lens body is washed to remove unreacted or partially reacted components and to hydrate the polymer lens body. For example, the contact lens may be exposed to an organic solvent such as ethanol, isopropyl alcohol, industrial methanol-modified alcohol, or water, or a mixture thereof. An exemplary washing method is described in U.S. Patent Publication No. 2007 / 0296914 (incorporated herein by reference) and in Example 1 below. After washing, the hydrated polymer lens bodies are typically housed in blister packaging, glass vials, or other suitable containers, all of which are referred to herein as “packages.” A packaging solution is also added to the container, which is typically a buffered saline solution such as phosphate-buffered saline or borate-buffered saline. The packaging solution may contain additional components such as comfort agents, hydrophilic polymers, surfactants, or other additives to prevent the lenses from sticking to the container. The packages are sealed, and the sealed polymer lens bodies are sterilized by autoclaving. The final product is a sterile, packaged, ophthalmologically acceptable contact lens.

[0033] In any of the above examples, the contact lens may be characterized by one or more of the following properties: contact angle, oxygen permeability, tensile strength, Young's modulus, and equilibrium water content, as described in detail below. In any of the examples below, the contact lens may have a contact angle of less than approximately 30° or less than 25°, where the contact angle is the static advancing contact angle measured using the Cecil drop method. To measure the contact angle of the contact lens surface, immerse the contact lens to be tested in phosphate buffer solution (PBS) for at least 12 hours. Using rubber-tipped tweezers, remove the lens from the PBS and shake to remove excess water. Cut each lens into 4 mm diameter pieces with a lens cutter. Place the contact lens piece face down on a microscope lens cleaning paper and wipe and dry the surface of the contact lens piece to be tested by gently dragging the piece across the cleaning paper using rubber-tipped tweezers until no more liquid is seen being absorbed by the cleaning paper. Place the lens piece on a microscope slide, ensuring that the surface is facing upwards and flat. Perform the measurement quickly to ensure that the lens piece does not dry out (as evidenced by deformation of the lens piece). On the Kruss DSA-100, activate the droplet shape analysis program and select the following settings: camera tilt = +2; 100 μl syringe with straight needle; dispensing solution = purified water; dispensing volume = 0.75 μl; dispensing speed = 7.5 μl / min; and dispensing mode = volume, selecting the "Cecil Drop (VCA eq)" method. Place the microscope slide on the sample stage so that the long side of the lens fragment is perpendicular to the camera. Move the syringe to fit within the observation screen and adjust the image until the maximum value reaches the center window. Dispense water into the lens. Take an image of the droplet within 10-15 seconds after dispensing the water. The calculation method is selected according to the contact angle as follows: <30° = circle fitting method, 30°~130° = tangent method 1; >130° = tangent method 2. Measure the average contact angle of five lens fragments to determine the contact angle of a specific surface (i.e., the back or front) of the contact lens.

[0034] Regarding oxygen permeability, the Dk values ​​obtained in the following examples were measured using a Rehder 201T Oxygen Permometer / polarograph cell according to the polarography method described in section 4.4.3 of ISO 18369-4:2017. In any of the following examples, the contact lens may have a Young's modulus (i.e., tensile modulus) of at least 0.3 MPa or 0.5 MPa, and may range from 0.95 MPa, 1.0 MPa, or 1.1 MPa. In a preferred embodiment, the contact lens has a Young's modulus of 0.3 MPa to 1.1 MPa, preferably 0.5 to 0.95 MPa.

[0035] The contact lens has a tensile strength of 1.0 MPa or less, preferably 0.9 MPa or less. Typically, the contact lens has a tensile strength of at least 0.4 MPa, more preferably at least 0.5 MPa. A preferred embodiment of the contact lens of the present invention has a tensile strength of 0.5 MPa to 0.9 MPa. The modulus of elasticity, elongation, and tensile strength values ​​reported herein were measured using an Instron Model 3342, 3343, or 5944 mechanical testing system (Instron Corporation, Norwood, Massachusetts, USA) and Bluehill Materials Testing Software, using a custom-made rectangular contact lens punching die with a 4 mm space for preparing rectangular sample pieces. The modulus of elasticity was measured in a chamber with a minimum relative humidity of 70%. Before testing, the lenses were immersed in phosphate buffer solution (PBS) for at least 10 minutes. A central piece of the lens was cut out using the punching die, keeping the concave side of the lens facing upwards. The thickness of the piece was measured using a calibrated gauge (Rehder electronic thickness gauge, Rehder Development Company, Castro Valley, California, USA). Using tweezers, the piece was mounted on the grip of the calibrated Instron instrument, with the piece mounted on at least 75% of the grip surface of each grip. The specified test methods were used to measure the mean and standard deviation of the maximum load (N), tensile strength (MPa), strain at maximum load (% elongation), and tensile modulus (MPa), and the results were recorded.

[0036] In any of the above examples, the contact lens may have an equilibrium water content (EWC) of at least about 30%, 40%, or 45%, and up to about 50%, 55%, 60%, or 70% by mass. For example, the contact lens may have an EWC of 40-60% by mass. To measure the EWC, excess surface water was wiped off the lens, and the lens was weighed to obtain the post-hydration mass. The lens was dried in an oven at 105°C and weighed. The mass difference was determined by subtracting the mass of the dry lens from the mass of the post-hydration lens. The mass % of the lens EWC = (mass difference / post-hydration mass) × 100. In one specific example, the contact angle is ≤30°, and the equilibrium water content is most preferably at least 45%, and up to 55% by mass.

[0037] As is evident from the overall disclosure of the application, including the claim structure and specific examples, the exemplary components of the polymerizable compositions disclosed herein are typically combined in embodiments of the present invention. For example, a person skilled in the art would recognize that the polymerizable compositions of the present invention advantageously include the exemplary monofunctional (meth)acrylate-containing siloxane monomers disclosed herein in combination with the exemplary difunctional (meth)acrylate-containing siloxane monomers disclosed herein, in combination with the exemplary N-vinylamide components disclosed herein, and in combination with the exemplary (meth)acrylate components disclosed herein. As demonstrated by specific examples, preferred combinations of monofunctional methacrylate-containing siloxane monomers, bifunctional (meth)acrylate-containing siloxane monomers, N-vinylamide components, and methacrylate-containing monomers of the present invention have been found to realize contact lenses of the present invention that have advantageous properties such as reduced tensile strength. [Examples]

[0038] The following examples illustrate specific aspects and advantages of the present invention, and it should be understood that the invention is not limited thereto. The reactants used in the examples are described in detail in Table 1, the specific amounts of each component used are listed in Table 2 as mass percentages of the total composition, the ratios of the components and the combined total amounts are shown in Table 3, and the properties are shown in Table 4. The silicone hydrogel lenses of Examples 1-3 and the Comparative Example were manufactured according to the following method. All the compounds or monomers were mixed and stirred to form a polymerizable composition or a silicone hydrogel contact lens compound. The compound was poured into a contact lens mold. The lenses were cured using ultraviolet light for approximately one hour (Examples 1 and 2 and Comparative Example) or using heat for approximately five hours (Example 3). Those skilled in the art are aware of appropriate methods for curing contact lens formulations. The cured polymers were removed from the contact lens molds, washed with organic solvents, water, or a combination thereof to remove unreacted substances, and then the washed contact lenses were packaged and sterilized in an autoclave to obtain sterilized packaged contact lenses. All contact lenses in the examples and comparative examples were transparent, flexible, and had good wettability.

[0039] [Table 1] [Table 2] [Table 3] [Table 4] In Table 3, "(Formula 2)" refers to the general structure of the compound of Formula 2 in this description, and Si-2 is a specific embodiment of Formula 2.

[0040] It is surprising that the specific selection of non-silicone monomers and the HOB to IBM ratio can result in such a significant decrease in the tensile strength of the resulting lens. The lens of the present invention retains other advantageous features found in prior art lenses formed using the same combination of siloxane monomers, such as high Dk and good droplet contact angle. While the disclosures herein refer to specific illustrated examples, it should be understood that these examples are presented as examples and not as limitations. The intent of the foregoing detailed description is to consider exemplary examples, but to be construed as covering any modifications, substitutes, and equivalents of the examples that may fall within the spirit and scope of the invention as defined by further disclosure. Several publications and patents are cited herein above. Each of the cited publications and patents is incorporated herein by reference in its entirety.

Claims

1. (i) Silicone components; (ii) Silicone-free ingredients and A silicone hydrogel contact lens formulation containing, Silicone components, (a) Compound of formula 1 【Chemistry 1】 (In the formula, R 1 R is selected from hydrogen or a methyl group; 2 is hydrogen or C 1-4 Selected from hydrocarbon groups; m represents an integer from 0 to 10; n represents an integer from 4 to 100; a and b represent integers greater than or equal to 1; a + b is from 20 to 500; b / (a + b) is from 0.01 to 0.22, and the arrangement of siloxane units includes random arrangements); (b) Compound of formula 2 【Chemistry 2】 (In the formula, n is between 10 and 25) The compound contains the compound of formula 1 and the compound of formula 2 in a ratio of 50:50 to 77:23, together in a ratio of 45 to 55 mass percent; The silicone-free components are N-vinylamide component (c) and methacrylate component (d). Includes, The N-vinylamide component (c) comprises N-vinyl N-methylacetamide (VMA); The methacrylate component (d) contains hydroxybutyl methacrylate (HOB) and isobornyl methacrylate (IBM), wherein hydroxybutyl methacrylate and isobornyl methacrylate are present in the formulation in amounts of 8.5 to 16 mass percent, and the total amount of IBM is less than 5 mass percent. Silicone hydrogel contact lens compound.

2. The formulation according to claim 1, wherein the total amount of the compound of formula 2, VMA, and HOB exceeds 28 mass percent.

3. The formulation according to claim 1 or claim 2, further comprising at least one of a photoinitiator, a thermal initiator, a crosslinking monomer, a UV blocker, and a colorant.

4. The formulation according to any one of claims 1 to 3, wherein the N-vinylamide component (c) comprises VMA and N-vinylpyrrolidone (NVP).

5. The formulation according to any one of claims 1 to 4, wherein the N-vinylamide component is present in an amount of 33 to 39 mass percent.

6. The formulation according to any one of claims 1 to 5, wherein the ratio of HOB to IBM is 85:15 to 90:

10.

7. The formulation according to any one of claims 1 to 6, wherein the ratio of the compound of formula 1 to the compound of formula 2 is 55:45 to 75:

25.

8. The formulation according to any one of claims 1 to 7, wherein the ratio of HOB to IBM is approximately 88:

12.

9. The ratio of equation 1 to equation 2 is 53:47 to 57:43; The N-vinylamide component essentially consists of NVP and VMA, with an NVP:VMA ratio of 68:32 to 72:28; The methacrylate component essentially consists of HOB and IBM, with a HOB-to-IBM ratio of 85:15 to 90:

10. The compound according to claim 1.

10. The silicone component is given by formulas 1, 2, and 3: 【Transformation 3】 (In the formula, m represents an integer from 3 to 12, n represents an integer from 1 to 10, R 1 R is selected from alkyl groups having 1 to 4 carbon atoms, and R in formula 3 2 and R 3 The composition according to claim 1, which essentially consists of (each of which is independently selected from a hydrogen atom or a methyl group), Formula 3 is present in an amount of less than 0.6 mass percent of the composition; The ratio of equation 1 to equation 2 is 60:40 to 65:35; The N-vinylamide component essentially consists of VMA; The methacrylate component essentially consists of HOB and IBM, with a HOB-to-IBM ratio of 75:25 to 80:

20. compound.

11. A silicone hydrogel contact lens comprising a polymerization reaction product of the formulation according to any one of claims 1 to 10.

12. A silicone hydrogel contact lens according to claim 11, wherein the tensile strength is 0.4 MPa to 1 MPa.

13. A silicone hydrogel contact lens according to claim 11 or claim 12, wherein the droplet contact angle is less than 30°.

14. A silicone hydrogel contact lens according to any one of claims 11 to 13, wherein the equilibrium water content is 45% by mass to 55% by mass.

15. A silicone hydrogel contact lens according to any one of claims 11 to 14, wherein the oxygen permeability is 110 to 140 bars.

16. A silicone hydrogel contact lens according to any one of claims 11 to 15, wherein the Young's modulus is 0.3 MPa to 1.1 MPa.

17. A silicone hydrogel contact lens according to any one of claims 11 to 16, wherein the string diameter is 13.5 to 15.5 mm and the base curve is 7.5 to 9.5 mm.

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