Radiation blocking agent for contact lenses

Abstract

A hydrogel contact lens formulation for forming a polymeric body of a hydrogel contact lens, comprising: a first high-energy visible light (HEVL) absorber comprising a benzotriazole moiety, and a second different high-energy visible light (HEVL) absorber comprising a benzotriazole moiety; and a hydrogel contact lens obtained from polymerization of the formulation.

Description

TECHNICAL FIELD

[0001] The present invention relates to compositions of radiation blockers for use in contact lenses and contact lenses comprising the compositions of radiation blockers. In particular, the present invention relates to compositions of radiation blockers that have been found to impart advantageous properties to hydrogel contact lenses that include advantageous light transmission properties. BACKGROUND

[0002] The eye is at potential risk of injury when exposed to light in the ultraviolet (UV), visible, and infrared (IR) bands of the electromagnetic spectrum. UV light has the highest energy and greatest potential to cause injury, followed by the violet-blue component of the visible light spectrum, i.e., high-energy visible light (HEVL) at wavelengths of 380 nm to 455 nm.

[0003] Compounds that absorb light at wavelengths that are harmful to the human eye have previously been included in contact lens formulations. Many UV absorbers are known as ingredients for polymeric materials used in the manufacture of ophthalmic lenses, including contact lenses. UV absorbers are typically compounds that include a chromophore that absorbs light in the UV spectrum, i.e., at wavelengths in the range of 100 nm to 380 nm. Compounds containing benzotriazoles, benzophenones, and triazines are known to absorb UV light, and such compounds can be added to contact lens materials to provide protection against UV radiation. In addition to blocking UV light, some ophthalmic lenses also block blue light. Yellow dyes, including polymerizable yellow dyes, have been added to contact lenses to absorb harmful blue light radiation, for example as described in US 5,470,932. These lenses block both UV and HEVL by using two chromophores, a UV absorber and a yellow dye. Many yellow dyes absorb blue light over a wide range of wavelengths and reduce transmission of blue light across the range of 380 nm to 500 nm.

[0004] If a sharper cut-off of the transmission spectrum in the high energy blue-violet region is desired, a selective blue light blocker can be used, described in US2005 / 0243272 and WO 2008 / 048880. Such blue light blockers selectively filter wavelengths in the range of 380 nm to 455 nm, often absorbing little or no wavelengths above 450 nm. Benzotriazole blue light blockers have been developed that selectively absorb light in the range of 380 nm to 455 nm. However, it has been found that large amounts of known benzotriazole blue light blockers can be needed in order to substantially reduce the transmission level of light in the range of 380 nm to 455 nm, and / or the known benzotriazole blue light blockers can cause undesirable yellowing of the resulting contact lens. Including large amounts of benzotriazole blue light blockers, such as in an amount of 2% or more by weight of the entire lens composition, in a contact lens formulation can adversely affect the properties of the contact lens material and / or hinder the handling of the contact lens formulation. For example, including high levels of radiation absorbing compounds in a hydrogel contact lens formulation can reduce the wettability of the resulting hydrogel contact lens, cause a higher incidence of lens defects, and / or hinder the lens body from being de-molded after casting. Including blue light blockers, especially in high amounts, in a lens formulation can also cause the lens to be imparted with a yellow coloration. Imparting a yellow coloration to a contact lens imparts an undesirable yellow tint to the wearer’s eye that is less acceptable to the consumer than a lens that leaves the natural coloration of the eye unchanged.

[0005] US2021 / 0181379 describes lens formulations that include a benzotriazole UV absorber, such as Norbloc, and a benzotriazole HEVL absorber to reduce the transmission of both UV and violet light through the contact lens.

[0006] It is also known to include colorants in contact lenses to change the color of the contact lens for aesthetic purposes or to make the lens more visible when in solution. While colorants can be used to offset the yellowing effect of blue light blockers, there is a need for a radiation absorber package for use in formulating hydrogel contact lenses, especially silicone hydrogel contact lenses, that can substantially reduce the transmission of harmful wavelengths of light when included in a lens formulation in low amounts, such as 3% by weight or less. Ideally, the hydrogel contact lenses produced using such formulations would also be non-yellowing. SUMMARY

[0007] In a first aspect, the present invention provides a radiation absorber package for use in formulating a hydrogel contact lens, comprising: a first high-energy short-wavelength visible light absorber comprising a benzotriazole moiety, and a second different high-energy short-wavelength visible light absorber comprising a benzotriazole moiety. The radiation absorber package of the first aspect of the present invention optionally further comprises a polymerizable UV absorber comprising a benzophenone moiety.

[0008] In a second aspect, the present invention provides a hydrogel contact lens formulation, in particular a silicone hydrogel contact lens formulation, comprising the radiation absorber package of the first aspect of the present invention. The hydrogel contact lens formulation is a polymerizable formulation for forming the body of a hydrogel contact lens. Thus, the hydrogel contact lens formulation of the second aspect of the present invention comprises: a first high-energy short-wavelength visible light absorber comprising a benzotriazole moiety, and a second different high-energy short-wavelength visible light absorber comprising a benzotriazole moiety. The hydrogel contact lens formulation of the second aspect of the present invention optionally further comprises a polymerizable UV absorber comprising a benzophenone moiety. In addition to the radiation absorbing compounds, the hydrogel contact lens formulation of the second aspect of the present invention typically contains polymerizable monomers, oligomers and / or prepolymers, one or more crosslinking agents and one or more polymerization initiators.

[0009] In a third aspect, the present invention provides a hydrogel contact lens, in particular a silicone hydrogel contact lens formed by polymerization of the formulation of the second aspect of the present invention. Thus, the polymeric lens material of the hydrogel contact lens of the third aspect of the present invention comprises: a first high-energy short-wavelength visible light absorbing unit comprising a benzotriazole moiety, and a second different high-energy short-wavelength visible light absorbing unit comprising a benzotriazole moiety. The polymeric lens material of the hydrogel contact lens of the third aspect of the present invention optionally further comprises a UV light absorbing unit comprising a benzophenone moiety.

[0010] In a fourth aspect, the present invention provides a method of manufacturing a hydrogel contact lens, in particular a silicone hydrogel contact lens, comprising the step of polymerizing the formulation of the second aspect of the present invention to form a polymeric contact lens body. Thus, the method of manufacturing a hydrogel contact lens of the fourth aspect of the present invention comprises the step of polymerizing a formulation to form a polymeric contact lens body, the formulation comprising: a first high-energy short-wavelength visible light absorber comprising a benzotriazole moiety, and a second different high-energy short-wavelength visible light absorber comprising a benzotriazole moiety. The formulation polymerized in the method of the fourth aspect of the present invention optionally further comprises a polymerizable UV absorber comprising a benzophenone moiety.

[0011] It has been found that by including a combination of two different benzotriazole HEVL absorbers in a contact lens formulation each having different absorption properties, it is possible to obtain a contact lens having improved properties compared to a contact lens that could be produced using a single type of benzotriazole HEVL light absorber. In particular, it has been found that when a lower total amount of benzotriazole high energy short wavelength visible light absorber is included in the formulation, a contact lens produced from a formulation containing a combination of two different benzotriazole HEVL absorbers provides a desirable reduction in the level of light in the range of 380 nm to 455 nm transmitted by the contact lens. In addition, it has been found that a contact lens produced from a formulation of the present invention containing a combination of two different benzotriazole high energy short wavelength visible light absorbers provides a desirable reduction in the level of light in the range of 380 nm to 455 nm transmitted by the contact lens without substantial yellowing of the contact lens body. In particular, it has been found that the formulations of the present invention provide a hydrogel contact lens that blocks at least 40%, especially at least 50% of blue light in the range of 380 nm to 455 nm without excessive yellowing or the need for large amounts of blue light blocking agents. Advantageously, a 0.003 wt% solution of the second HEVL absorber in ethyl acetate (>99.8%, HPLC grade) has a maximum wavelength of 0.1 absorbance that is at least 10 nm lower than the maximum wavelength of a 0.003 wt% solution of the first HEVL absorber in ethyl acetate having a 0.1 absorbance, wherein the absorbance of the solutions is measured using a Perkin Elmer Lambda 365 spectrometer in a 10 mm path length quartz cell. BRIEF DESCRIPTION OF DRAWINGS

[0012] Figure 1 Light absorption spectra of 0.003 wt% solutions of Norbloc, UV416, UV13 and UV28 in ethyl acetate are shown, where absorbance is on the y-axis and wavelength in nm is on the x-axis.

[0013] Figure 2 Light absorption spectra of 0.003 wt% solutions of UV1, UV5 (UVAM), UV13, UV15 and UV28 in ethyl acetate (>99.8%, HPLC grade) are shown, where absorbance is on the y-axis and wavelength in nm is on the x-axis. DETAILED DESCRIPTION

[0014] The present disclosure and further advantages thereof will become more fully apparent from the following detailed description, when considered in connection with the following drawings. The present application will be further described with particular reference to the formulations of the second aspect of the present application, i.e. the formulations used in the methods of the fourth aspect of the present application (hereinafter referred to as "the formulations of the present application"). However, it will be appreciated that since the contact lenses of the third aspect of the present application can be obtained from polymerization of the formulations of the second aspect of the present application, e.g. according to the methods of the fourth aspect of the present application, the ingredients of the formulations of the second aspect of the present application will be present in the polymerized lens material of the contact lenses of the third aspect of the present application in polymerized form. Likewise, it will be appreciated that the radiation absorber packages of the first aspect of the present application are ingredients of the formulations of the second aspect of the present application, said ingredients comprising chromophores that absorb light across the UV and visible light spectrum. Unless particular combinations of features are mutually exclusive, or otherwise indicated by context, features mentioned herein of the radiation absorber packages, formulations or lenses, or components thereof, or methods of making lenses (depending on context), can be combined with any combination of previously described or subsequently described features. Furthermore, as used in the specification, unless the context clearly dictates otherwise, the singular forms "a," "an," and "the" include plural referents (e.g., at least one or more). Thus, for example, reference to "a contact lens" includes a single lens as well as two or more identical or different lenses.

[0015] The present disclosure is based on the discovery that by including a combination of at least two different benzotriazole HEVL absorbers in a polymerizable formulation from which contact lenses are produced, it is possible to more effectively provide contact lenses having blue light blocking properties that prevent transmission of a substantial amount of HEVL. This combination balances the undesirable yellow coloration of lenses having blue light blocking properties by including a second HEVL absorber that absorbs at shorter wavelengths than the first HEVL absorber. This combination also absorbs a greater proportion of light across the 380 nm to 455 nm wavelengths than can be obtained using a single benzotriazole HEVL absorber. Optionally, a third radiation absorbing compound is included as a benzophenone UV absorber to enhance the absorption of UV light below 380 nm. It has been found that benzophenone UV absorbers are particularly suitable for inclusion in combination with benzotriazole HEVL absorbers because they have significantly different absorption curves.

[0016] The "polymeric contact lens material" of the third aspect of the present invention refers to the material that is bound, whether by covalent bonds, physical entanglements, or otherwise, into the contact lens body. Material that can be removed from the lens body by extraction with water, ethanol, isopropanol, or mixtures thereof, does not constitute part of the polymeric contact lens material, nor does solvent, such as water, that can be removed from the contact lens body by drying. The polymerizable component of the formulation of the second aspect of the present invention is typically incorporated into the polymeric contact lens material of the third aspect of the present invention.

[0017] The term "radiation absorber package" collectively refers to UV blockers, high energy short wavelength visible light absorbers, and colored colorants that absorb light in the wavelength range of 100 nm to 700 nm.

[0018] High energy visible light (HEVL) absorbers are compounds that include a chromophore that absorbs visible light in the violet-blue range of 350 nm to 455 nm. Typically, HEVL absorbers have an absorption maximum (λmax) in the range of 350 nm to 455 nm, especially in the range of 350 nm to 400 nm. The term "high energy visible light (HEVL) absorber" as used herein can be defined as a compound that has at least 0.5 absorbance in the range of 375 nm to 450 nm as a 0.003 wt% solution in ethyl acetate (> 99.8%, HPLC grade) (the solution is measured in a 10 mm path length quartz cell, and the absorbance of the solution is measured using a Perkin Elmer Lambda 365 from 250 nm to 800 nm). HEVL absorbers can additionally absorb light at shorter wavelengths (e.g., in the range of 250 nm to 350 nm) and thus act as both a HEVL absorber and a UV absorber, as discussed below. Unless otherwise stated, all absorption spectra mentioned herein are measured using a Perkin Elmer Lambda 365 spectrometer in a 10 mm path length quartz cell with a 0.003 wt% solution in > 99.8% HPLC grade ethyl acetate.

[0019] Advantageously, the HEVL absorbers used in contact lens formulations, including the contact lens formulations of the present invention, have a polymerizable moiety in their chemical structure, such as a vinyl, acrylate, or methacrylate functional group, for covalent incorporation into the contact lens material during polymerization. Once incorporated into the polymeric contact lens material, the HEVL absorber imparts HEVL absorption properties to the polymeric contact lens material. The HEVL absorbers used in the present invention are typically soluble in the contact lens formulation and are polymerizable such that they form part of the polymeric matrix of the lens and remain in the lens during autoclaving and storage.

[0020] References herein to the amount of an ingredient or component present in a formulation expressed as a weight percent (i.e., % (wt / wt)) are based on the amount of all formulation ingredients excluding diluents and / or solvents that are not incorporated into the final polymeric contact lens material. Thus, for example, the amount of radiation absorbing agent package present in a formulation made by mixing together 1.5 parts of a radiation absorbing agent package, one or more 65 parts of a monomer, 3.5 parts of other active ingredients (e.g., polymerization initiators, colorants, oxygen scavengers, etc.), and 30 parts of an organic solvent and / or water (for a total of 100 parts) is 2.1 % (wt / wt). As used herein, a "component" of a formulation is the collective of all ingredients of a particular type. For example, if a formulation contains 20 % (wt / wt) of a first siloxane monomer and 15 % of a second siloxane monomer and no other siloxanes, the formulation can be described as containing 35 % (wt / wt) of a siloxane component.

[0021] Advantageously, the benzotriazole HEVL absorber component of the formulation used in the method of the second aspect of the invention or the fourth aspect of the invention is no more than 2.7 % (wt / wt), and preferably no more than 2.0 % (wt / wt). Advantageously, the total amount of all HEVL absorbers present in the formulation of the second aspect or fourth aspect of the invention is no more than 2.7 % (wt / wt), and preferably no more than 2.0 % (wt / wt). Alternatively or additionally, the total amount of benzotriazole compounds present in the formulation of the second aspect or fourth aspect of the invention is optionally no more than 2.7 % (wt / wt), and preferably no more than 2.0 % (wt / wt). Advantageously, the total amount of benzotriazole HEVL absorbers incorporated into the polymeric lens material of the third aspect of the invention is no more than 2.7 % (wt / wt) of the total polymeric lens material, and preferably no more than 2.0 % (wt / wt) of the total polymeric lens material. Advantageously, the total amount of all HEVL absorbers incorporated into the polymeric lens material of the third aspect of the invention is no more than 2.7 % (wt / wt) of the total polymeric lens material, and preferably no more than 2.0 % (wt / wt) of the total polymeric lens material. Alternatively or additionally, the total amount of benzotriazole compounds present in the polymeric lens material of the third aspect of the invention is optionally no more than 2.7 % (wt / wt) of the total polymeric lens material, and preferably no more than 2.0 % (wt / wt) of the total polymeric lens material.

[0022] The first HEVL absorbent can be present in the formulation in an amount of 0.3% to 0.9% (wt / wt), preferably 0.4% to 0.7% (wt / wt). The second HEVL absorbent can be present in the formulation in an amount of 0.5% to 2.2% (wt / wt), preferably 0.7% to 1.6% (wt / wt). Optionally, the first HEVL absorbent can be present in the formulation in an amount of 0.3% to 0.9% (wt / wt), preferably 0.4% to 0.7% (wt / wt), and the second HEVL absorbent can be present in an amount of 0.5% to 2.2% (wt / wt), preferably 0.7% to 1.6% (wt / wt).

[0023] The first HEVL absorbent and the second HEVL absorbent in the formulation used in the method of the second aspect of the application or the fourth aspect of the application each optionally have formula (1):

[0024]

[0025] wherein:

[0026] • R 1 is halogen, OH, C 1-12 alkyl, -A-R 9 -Y, optionally substituted C 1-12 alkyl, optionally substituted phenoxy or optionally substituted naphthoxy, wherein the optional substituents are halogen, C 1-6 alkyl, C 1-6 alkyl, OH, -(CH2CH2O) n H, -(CH2CH2O) n CH2CH3, -(CH2CH(CH3)O) n H or -(CH2CH(CH3)O) n CH2CH2(CH3);

[0027] • R 6 and R 7 one of R 1-12 and R

[0028] • R 6 and R 7 the other of R

[0029] or -OR 8 ;

[0030] wherein:

[0031] o R 2 is a bond, C1-12 Alkylene, (CH2CH2O) n Or (CH2CH(CH3)O) n ;

[0032] ○X represents bond, O, NR 4 S or (Si(CH3)2O) m Si(CH3)2;

[0033] ○R 3 For bond, C(O), C(O)C j H 2j C 1-6 alkylene, phenyl or C 1-6 Alkylphenyl;

[0034] ○ Each R 4 Independently, it is either H or methyl;

[0035] ○R 5 For H, C 1-6 Alkyl or phenyl;

[0036] ○m ranges from 0 to 9;

[0037] ○n ranges from 2 to 10;

[0038] ○j ranges from 1 to 6;

[0039] ○A is -S- or -SO2-;

[0040] ○R 8 For H, C 1-12 Alkyl, C 6-15 Aryl or -R 9 -Z;

[0041] ○ Each R 9 Independently, C is optionally substituted with -OH and / or heteroester. 1-12 Alkylene;

[0042] Each of ○Y and Z represents -OH and -OC(O)R, respectively. 10 -NH2, -NC(O)R 10 -NCO, -CO2H, -CO2R 10 ,

[0043]

[0044] ○ Each R 10 Independently for C 1-10 Alkyl or C 3-10 alkenyl;

[0045] ○R 11 C 3-10cycloalkenylene; and

[0046] o R 12 is C 1-10 alkylene or 1,2-phenylene.

[0047] In some aspects of the application, the first and second HEVL absorbers each optionally have the above formula (1), wherein:

[0048] o R 1 is halogen, OH, C 1-12 alkoxy, optionally substituted C 1-12 alkyl, optionally substituted phenoxy or optionally substituted naphthoxy, wherein the optional substituents are halogen, C 1-6 alkyl, C 1-6 alkoxy, OH, -(CH2CH2O) n H, -(CH2CH2O) n CH2CH3, -(CH2CH(CH3)O) n H or -(CH2CH(CH3)O) n CH2CH2(CH3);

[0049] o R 6 and R 7 one of R 1-12 is H or C

[0050] o R 6 and R 7 the other of R

[0051]

[0052] wherein:

[0053] o R 2 is a bond, C 1-12 alkylene, (CH2CH2O) n or (CH2CH(CH3)O) n ;

[0054] o R 3 is a bond, C(O), C(O)C j H 2j , C 1-6 alkylene, phenyl or C 1-6 alkylphenyl;

[0055] o X is a bond, O, NR 4 , S or (Si(CH3)2O) m Si(CH3)2;

[0056] ○ Each R 4 Independently, it is either H or methyl;

[0057] ○R 5 For H, C 1-6 Alkyl or phenyl;

[0058] ○m ranges from 0 to 9;

[0059] ○n is between 2 and 10; and

[0060] ○j ranges from 1 to 6.

[0061] In some other aspects of the invention, the first HEVL absorbent and the second HEVL absorbent each optionally have the above formula (1), wherein:

[0062] ●R 1 For H, Cl, Br, OH, C 1-4 Alkyl groups, C groups optionally substituted with halogens 1-4 Alkyl or phenoxy;

[0063] ●R 6 and R 7 One of them is H or C that is optionally substituted with halogen. 1-4 Alkyl; and

[0064] ●R 6 and R 7 The other one is:

[0065]

[0066] in:

[0067] ○R 2 For key or C 1-6 alkyl;

[0068] ○X represents bond, O, Si(CH3)2, or NR. 4 ;

[0069] ○R 3 For bond, C(O) or C 1-6 Alkylphenyl;

[0070] ○ Each R 4 Independently H or methyl; and

[0071] ○R 5 For H.

[0072] In yet another aspect of the invention, the first HEVL absorbent and the second HEVL absorbent each optionally have the above formula (1), wherein:

[0073] ●R 1H, Cl, methoxy, C 1-4 alkyl or trifluoromethyl;

[0074] • R 6 and R 7 one of which is H, C 1-4 alkyl or trifluoromethyl; and

[0075] • R 6 and R 7 the other of which is:

[0076]

[0077] wherein:

[0078] o R 2 is C 1-6 alkyl;

[0079] o X is a bond, O, Si(CH3)2, or NR 4 ;

[0080] o R 3 is a bond, C(O), or C 1-6 alkylphenyl;

[0081] o each R 4 is independently H or methyl; and

[0082] o R 5 is H.

[0083] The first HEVL absorber and the second HEVL absorber in the formulation used in the method of the second aspect of the invention or the fourth aspect of the invention each optionally have formula (1a):

[0084]

[0085] wherein:

[0086] R 1 is halogen, OH, C 1-12 alkoxy, optionally substituted C 1-12 alkyl, optionally substituted phenoxy, or optionally substituted naphthoxy, wherein the optional substituents are halogen, C 1-6 alkyl, C 1-6 alkoxy, OH, -(CH2CH2O) n H, -(CH2CH2O) n CH2CH3, -(CH2CH(CH3)O) n H, or -(CH2CH(CH3)O) n CH2CH2(CH3);

[0087] R2 C1-C6alkylene, (CH2CH2O) 1-12 C1-C6alkylene, (CH2CH2O) n or (CH2CH(CH3)O) n ;

[0088] If R 2 is (CH2CH2O) n or (CH2CH(CH3)O) n , then X is a bond, otherwise X is O, NR 4 , S or (Si(CH3)2O) m Si(CH3)2.

[0089] R 3 is a bond, C(O), C(O)C j H 2j , C 1-6 alkylene, phenyl or C 1-6 alkylphenyl;

[0090] each R 4 is independently H or methyl;

[0091] R 5 is H, C 1-6 alkyl or phenyl;

[0092] R 6 is H or C 1-12 alkyl optionally substituted with halo;

[0093] m is 0 to 9;

[0094] n is 2 to 10; and

[0095] j is 1 to 6.

[0096] When R 2 is (CH2CH2O) n or (CH2CH(CH3)O) n in the above compounds of formula (1) and formula (1a), X is typically not O, for example, when R 2 is (CH2CH2O) n or (CH2CH(CH3)O) n , X can be a bond.

[0097] For the avoidance of doubt, when two or more of adjacent R2, X and R3in the above compounds of formula (1) and formula (1a) are each a bond, then the two or more adjacent groups together form a single bond.

[0098] Unless otherwise stated, the term "alkyl" as used herein refers to both straight-chain and branched alkyl groups. Thus, for example, a reference to C4 alkyl means any or all of n-butyl, isobutyl, sec-butyl, and tert-butyl. Unless otherwise stated, the term "alkylene" as used herein refers to both straight-chain divalent saturated alkyl and branched divalent saturated alkyl groups. Thus, for example, a reference to C3 alkylene means any or all -CH2-CH2-CH2-, -CH(CH3)-CH2-, -CH2-CH(CH3)-, -C(CH3)2-, and -CH(CH2CH3)- groups.

[0099] Optionally, the polymeric contact lens material of the third aspect of the present invention comprises two different units derived from the polymerization of the compound of formula (1) above.

[0100] The first HEVL absorbent and the second HEVL absorbent in the formulation used in the method of the second aspect or the fourth aspect of the present invention optionally each have formula (2):

[0101]

[0102] in:

[0103] A is -S- or -SO2-;

[0104] R 1 C-type carbon atoms optionally substituted with -OH and / or heteroester groups 1-12 Alkylene;

[0105] R 2 For H, C 1-12 Alkyl or C 6-15 Aryl or -R 3 Y;

[0106] R 3 C-type carbon atoms optionally substituted with -OH and / or heteroester groups 1-12 Alkylene;

[0107] Each of X and Y represents -OH and -OC(O)R, respectively. 4 -NH2, -NC(O)R 4 -NCO, -CO2H, -CO2R 4 ,

[0108]

[0109] R 4 Each of them is independently C 1-12 Alkyl or C 3-10 alkenyl;

[0110] R5 C 3-10 cycloalkenylene; and

[0111] R 6 C 1-10 alkylene or 1,2-phenylene.

[0112] Examples of HEVL absorbers of formula (2) can be found in US 2021 / 0214321 Al, incorporated herein by reference. Particular examples of HEVL absorbers of formula (2) that can be included in the formulations of the present application are those absorbers of formulae (1-1) to (1-13) of US 2021 / 0214321 Al.

[0113] It has been found that the presence of a sulfur-containing group at the 5-position of the benzotriazole ring in HEVL absorbers of formula (2) provides a red shift of the main absorption peak of the benzotriazole compound compared to those absorbers lacking a sulfur-containing group, for example in the above-mentioned compounds of formula (1) or formula (1a). Thus, the compounds of formula (2) can be used, inter alia, as second HEVL absorbers in the formulations of the present application. The formulations of the present application can for example include as first HEVL absorber UV28 and as second HEVL absorber a compound of formula (2). It has also been found that the presence of a sulfur-containing group at the 5-position of the benzotriazole ring in HEVL absorbers of formula (2) extends the absorption range of the benzotriazole compound upwards and provides greater absorption level in the range of 400 nm to 450 nm compared to those absorbers lacking a sulfur-containing group, for example in the above-mentioned compounds of formula (1) or formula (1a). Thus, some compounds of formula (2) can also be used as first HEVL absorbers in the formulations of the present application.

[0114] Examples of benzotriazole HEVL absorbers include:

[0115] 2-(1,1-dimethylethyl)-4-[3-[(4-vinylphenyl)methoxy]propoxy]-6-(5-methoxy-2H- benzotriazol-2-yl)-phenol (UV1, CAS No. 159732-06-6):

[0116]

[0117] 2-(5-chloro-2H-benzotriazol-2-yl)-6-(1,1-dimethylethyl)-4-vinyl-phenol (UV5 / UVAM, CAS No. 124883-10-9):

[0118]

[0119] 2-(2-hydroxy-5-methacrylamidophenyl)-5-methoxy-2H-benzotriazole (UV6, CAS No. 110927-08-7):

[0120]

[0121] 2-(3-Allyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole (UV9, CAS No. 2170-39-0):

[0122]

[0123] 1-Methylallyl-2-(2-hydroxy-5-methylphenyl)benzotriazole (UV12, CAS No. 98809-58-6):

[0124]

[0125] 2-[2'-hydroxy-3'-tert-butyl-5'-(3"-methacryloyloxypropoxy)phenyl]-5-methoxy-2H-benzotriazole (UV13, CAS No. 114166-71-1):

[0126]

[0127] 2-3'-tert-butyl-2'-hydroxy-5'-(3'-dimethylvinylsilylpropoxy)-2'-hydroxy-phenyl)-5-methoxybenzotriazole (UV15, CAS No. 122430-79-9):

[0128]

[0129] 2-(2'-hydroxy-5'-methacryloylpropyl-3'-tert-butyl-phenyl)-5-methoxy-2H-benzotriazole (UV16, CAS No. 1245624-41-2):

[0130]

[0131] 3-[3-(1,1-dimethylethyl)-4-hydroxy-5-[5-(trifluoromethyl)-2H-benzotriazol-2-yl]phenoxy]propyl 2-methyl-2-acrylic acid (UV23, CAS No. 2050905-16-1):

[0132]

[0133] 2-[2'-hydroxy-3'-tert-butyl-5'-(3"-methacryloyloxypropoxy)phenyl]-5-chloro-2H-benzotriazole (UV28, CAS No. 275371-71-6):

[0134]

[0135] and

[0136] 3-[3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenoxy]propyl 2-methyl-2-propenoate (UV29, CAS No. 2254219-66-2):

[0137]

[0138] All of the above HEVL absorbers are commercially available from LYNN Laboratories, Inc., 2797 Irving Blvd STE 110, Dallas, TX 75207.

[0139] The first HEVL absorber advantageously has an absorption cut-off at a higher wavelength than the second HEVL absorber. For example, the highest wavelength at which a 0.003 wt% solution of the first HEVL absorber in ethyl acetate has an absorbance of 0.1 can be at a wavelength at least 5 nm, in particular at least 10 nm, higher than the highest wavelength at which a 0.003 wt% solution of the second HEVL absorber in ethyl acetate has an absorbance of 0.1. The first HEVL absorber advantageously has a greater level of absorbance than the second HEVL absorber in the range 380 nm to 425 nm, for example as a 0.003 wt% solution in ethyl acetate. The second HEVL absorber advantageously has a greater level of absorbance than the first HEVL absorber in the range 350 nm to 375 nm, for example as a 0.003 wt% solution in ethyl acetate.

[0140] Figure 1 The absorption spectra of 0.003 wt% solutions in ethyl acetate of HEVL absorbers UV13 and UV28 are shown in Figure 2. UV28 has an absorption cut-off at a higher wavelength than UV13. The highest wavelength at which a 0.003 wt% solution of UV28 in ethyl acetate has an absorbance of 0.1 is 420 nm, whereas the highest wavelength at which a 0.003 wt% solution of UV13 in ethyl acetate has an absorbance of 0.1 is 406 nm. UV28 has a greater level of absorbance than UV13 in the range 380 nm to 425 nm, and the UV13 has a greater level of absorbance than UV28 in the range 350 nm to 375 nm.

[0141] The first and second HEVL absorbers can be characterized in that, in the absorption spectrum of a 0.003 wt% solution of the first and second HEVL absorbers in ethyl acetate, a tangent to the curve at the point defined by the highest wavelength at which the absorbance is 0.5 passes through the 0.0 absorbance axis of the absorption spectrum of the first HEVL absorber at a wavelength that is at least 5 nm, especially at least 10 nm, longer than the wavelength at which the tangent to the curve at the point defined by the highest wavelength at which the absorbance is 0.5 passes through the 0.0 absorbance axis of the absorption spectrum of the second HEVL absorber. The first HEVL absorber can be characterized in that, in the absorption spectrum of a 0.003 wt% solution of the first HEVL absorber in ethyl acetate, a tangent to the curve at the point defined by the highest wavelength at which the absorbance is 0.5 passes through the 0.0 absorbance axis between 412 nm and 440 nm, between 415 nm and 435 nm, and preferably between 415 nm and 430 nm. The second HEVL absorber can be characterized in that, in the absorption spectrum of a 0.003 wt% solution of the second HEVL absorber in ethyl acetate, a tangent to the curve at the point defined by the highest wavelength at which the absorbance is 0.5 passes through the 0.0 absorbance axis at a wavelength that is shorter than the wavelength at which the tangent to the curve at the point defined by the highest wavelength at which the absorbance is 0.5 passes through the 0.0 absorbance axis of the absorption spectrum of the 0.003 wt% solution of the first HEVL absorber in ethyl acetate (e.g., a wavelength that is at least 5 nm shorter, especially at least 10 nm shorter). Alternatively or additionally, the second HEVL absorber can be characterized in that, in the absorption spectrum of a 0.003 wt% solution of the second HEVL absorber in ethyl acetate, a tangent to the curve at the point defined by the highest wavelength at which the absorbance is 0.5 passes through the 0.0 absorbance axis between 385 nm and 415 nm, preferably between 390 nm and 412 nm.

[0142] From Figure 1 It can be seen that the tangent (A) to the point defined by the highest wavelength at which the absorbance is 0.5 on the absorption spectrum of a 0.003 wt% solution of UV28 in ethyl acetate passes through the 0.0 absorbance axis at 422 nm. The tangent (B) to the point defined by the highest wavelength at which the absorbance is 0.5 on the absorption spectrum of a 0.003 wt% solution of UV13 in ethyl acetate passes through the 0.0 absorbance axis at 407 nm.

[0143] The first HEVL absorbent is characterized in that the highest wavelength of absorbance of 0.1 in the absorption spectrum of a 0.003 wt% solution of the first HEVL absorbent in ethyl acetate is between 412 nm and 440 nm, between 415 nm and 435 nm, and preferably between 415 nm and 430 nm. The second HEVL absorbent is characterized in that the highest wavelength of absorbance of 0.1 in the absorption spectrum of a 0.003 wt% solution of the second HEVL absorbent in ethyl acetate is at a wavelength shorter than the highest wavelength of absorbance of 0.1 in the absorption spectrum of a 0.003 wt% solution of the first HEVL absorbent in ethyl acetate (e.g., at least 5 nm shorter, especially at least 8 nm shorter). Alternatively or additionally, the second HEVL absorbent is characterized in that the highest wavelength of absorbance of 0.1 in the absorption spectrum of a 0.003 wt% solution of the second HEVL absorbent in ethyl acetate is between 385 nm and 412 nm, preferably between 390 nm and 410 nm.

[0144] from Figure 2 As can be seen, the highest wavelength with an absorbance of 0.1 in a 0.003 wt% solution of UV28 in ethyl acetate is 420 nm. The highest wavelength with an absorbance of 0.1 in a 0.003 wt% solution of UV13 in ethyl acetate is 406 nm, which is >8 nm shorter than the highest wavelength with an absorbance of 0.1 in a 0.003 wt% solution of UV28 in ethyl acetate.

[0145] Advantageously, a 0.003 wt% solution of the first HEVL absorber in ethyl acetate has an absorbance peak in the range of 360 nm to 410 nm, for example, 360 nm to 400 nm, and especially 360 nm to 390 nm. Advantageously, a 0.003 wt% solution of the second HEVL absorber in ethyl acetate has an absorbance peak at a wavelength at least 5 nm shorter than the absorbance peak of the 0.003 wt% solution of the first HEVL absorber in ethyl acetate falling in the range of 360 nm to 410 nm (e.g., between 5 nm and 25 nm, especially between 5 nm and 15 nm). Alternatively or additionally, a 0.003 wt% solution of the first HEVL absorber in ethyl acetate has an absorbance of at least 0.35 at a wavelength of 400 nm, and / or at least 0.55, especially at least 0.57, at a wavelength of 390 nm. Alternatively or additionally, a 0.003 wt% solution of the first HEVL absorber in ethyl acetate has an absorbance of at least 0.15, particularly at least 0.20, at a wavelength of 410 nm. A 0.003 wt% solution of the second HEVL absorber in ethyl acetate advantageously has an absorbance of less than 0.30 at a wavelength of 400 nm, and / or less than 0.55, particularly less than 0.53, at a wavelength of 390 nm. Alternatively or additionally, a 0.003 wt% solution of the second HEVL absorber in ethyl acetate has an absorbance of less than 0.12, particularly less than 0.10, at a wavelength of 410 nm. Advantageously, a 0.003 wt% solution of the second HEVL absorber in ethyl acetate has an absorbance of 0.1 at a wavelength at least 8 nm lower than that of the first HEVL absorber, particularly at least 10 nm.

[0146] from Figure 1 As can be seen, UV28 has an absorbance peak at 368 nm in a 0.003 wt% solution in ethyl acetate, and UV13 has an absorbance peak at 359 nm in a 0.003 wt% solution of the second HEVL absorber in ethyl acetate. Figure 2 As can be seen, a 0.003 wt% solution of UV28 in ethyl acetate has an absorbance of approximately 0.43 for light at a wavelength of 400 nm and approximately 0.63 for light at a wavelength of 390 nm. 0.003 wt% solutions of UV1, UV5 (UVAM), UV13, and UV15 each have an absorbance of less than 0.30 for light at a wavelength of 400 nm and an absorbance of 0.60 or lower for light at a wavelength of 390 nm. A 0.003 wt% solution of UV1, UV5 (UVAM), UV13, or UV15 in ethyl acetate has an absorbance at a wavelength at least 10 nm lower than that of UV28.

[0147] It has been found that the inclusion of a combination of two HEVL absorbers meeting the above criteria in a contact lens formulation results in a lens that is particularly effective in providing a high level of absorption of violet-blue light in the range of 380 nm to 455 nm. Furthermore, this combination provides a lens with a desirable color without imparting an undesirable yellowing to the wearer's eye. For example, if the first HEVL absorber has a higher absorption cutoff, for example, a HEVL absorber characterized by a tangent to the curve at the point defined by the highest wavelength at which the absorbance is 0.5 in the absorbance spectrum of a 0.003 wt% solution of the HEVL absorber in ethyl acetate passes above 440 nm through the 0.0 absorbance axis, and / or the HEVL absorber can be characterized by the highest wavelength at which the absorbance is 0.1 on the absorbance spectrum of a 0.003 wt% solution of the HEVL absorber in ethyl acetate being higher than 430 nm, then the resulting lens can have a greater yellowing effect, and / or a greater amount of blue colorant can be needed in the lens formulation to offset the yellowing effect of the first HEVL absorber. An example of a benzotriazole HEVL meeting the above stated absorbance requirements is UV28. An example of a less desirable HEVL absorber with a higher absorption cutoff is UV23.

[0148] Optionally, at least one of the first HEVL absorber and the second HEVL absorber, especially the first HEVL absorber, is 2-[2'-hydroxy-3'-tert-butyl-5'-(3"- methacryloyloxypropoxy)phenyl]-5-chloro-2H-benzotriazole (UV28). UV28 can be present in the formulation in an amount of 0.3% to 0.9% (wt / wt), preferably 0.4% to 0.7% (wt / wt).

[0149] Optionally, the first HEVL absorber is UV28, and the second HEVL absorber is characterized by a 0.003 wt% solution of the second HEVL absorber in ethyl acetate having a highest wavelength of 0.1 absorbance of no more than 415 nm, especially no more than 410 nm. UV28 advantageously has a greater level of absorbance in the range of 380 nm to 425 nm, for example as a 0.003 wt% solution in ethyl acetate, than the second HEVL absorber. The second HEVL absorber advantageously has a greater level of absorbance in the range of 350 nm to 375 nm, for example as a 0.003 wt% solution in ethyl acetate, than UV28.

[0150] Optionally, the first HEVL absorber is UV28 and the second HEVL absorber is characterized in that the wavelength at which the tangent to the absorption spectrum of a 0.003 wt% solution of the second HEVL absorber in ethyl acetate at an absorbance of 0.5 crosses the 0.0 absorbance axis is shorter (e.g., at least 5 nm shorter, especially at least 10 nm shorter) than the wavelength at which the tangent to the absorption spectrum of a 0.003 wt% solution of UV28 in ethyl acetate at an absorbance of 0.5 crosses the 0.0 absorbance axis. Optionally, the first HEVL absorber is UV28 and the second HEVL absorber is characterized in that the longest wavelength at which the absorbance of a 0.003 wt% solution of the second HEVL absorber in ethyl acetate is 0.1 is shorter (e.g., at least 5 nm shorter, especially at least 8 nm shorter) than the longest wavelength at which the absorbance of a 0.003 wt% solution of UV28 in ethyl acetate is 0.1. Optionally, a 0.003 wt% solution of the second HEVL absorber in ethyl acetate has an absorbance peak at a wavelength that is at least 5 nm, preferably at least 7 nm, optionally at least 8 nm, shorter than an absorbance peak of a 0.003 wt% solution of UV28 in ethyl acetate that falls within the range of 360 nm to 380 nm.

[0151] Optionally, at least one of the first HEVL absorber and the second HEVL absorber, especially the second HEVL absorber, is selected from 2-(1,1 -dimethylethyl)-4-[3-[(4- vinylphenyl)methoxy]propoxy]-6-(5-methoxy-2H-benzotriazol-2-yl)-phenol (UV1), 2-(5- chloro-2H-benzotriazol-2-yl)-6-(1,1 -dimethylethyl)-4-vinyl-phenol (UV5 / UVAM), 2-[2'- hydroxy-3'-tert-butyl-5'-(3"-methacryloyloxypropoxy)phenyl]-5-methoxy-2H- benzotriazole (UV13), and 2-3'-tert-butyl-2'-hydroxy-5'-(3"-dimethylethylsilanylpropoxy)-2'- hydroxy-phenyl)-5-methoxybenzotriazole (UV15). One of UV1, UV5, UV13, or UV15 or a combination of any of UV1, UV5, UV13, and UV15 can be present in an amount of 0.5% to 2.2% (wt / wt) and preferably 0.7% to 1.6% (wt / wt). The second HEVL absorber can be UV13. UV13 can be present in an amount of 0.5% to 2.2% (wt / wt) and preferably 0.7% to 1.6% (wt / wt).

[0152] The absorption spectrum of each of UV1 and UV15 is very similar to that of UV13 (shown in Figure 1 UV5 (UVAM) has a similar absorption curve to UV13 at wavelengths higher than 330 nm (e.g., between 330 nm and 500 nm), and also has a second peak of absorbance at about 310 nm, and thus the absorption curve below 330 nm is similar to that of UV28 (shown in Figure 1 Thus, in some embodiments of the application, UV5 (UVAM) can be a particularly advantageous second HEVL absorber, e.g., in formulations where enhanced levels of UV absorbance in the range of 300 nm to 320 nm are desired, in preference to UV1, UV15, or UV13.

[0153] Optionally, the first HEVL absorber is UV28, and the second HEVL light absorber is one of UV1, UV5, UV13, or UV15, or a combination of any of UV1, UV5, UV13, and UV15. The one of UV1, UV5, UV13, or UV15, or the combination of any of UV1, UV5, UV13, and UV15 can be present in an amount of 0.5% to 2.2% (wt / wt), and preferably 0.7% to 1.6% (wt / wt); and the UV28 can be present in an amount of 0.3% to 0.9% (wt / wt), and preferably 0.4% to 0.7% (wt / wt). Optionally, the first HEVL absorber is UV28, and the second HEVL light absorber is UV13. The UV13 can be present in an amount of 0.5% to 2.2% (wt / wt), and preferably 0.7% to 1.6% (wt / wt); and the UV28 can be present in an amount of 0.3% to 0.9% (wt / wt), and preferably 0.4% to 0.7% (wt / wt).

[0154] Optionally, the total amount of HEVL absorbers having formula (1) present in the formulations of the application does not exceed 2.7% (wt / wt), and preferably does not exceed 2.0% (wt / wt). Optionally, the formulations of the application comprise one of UV1, UV5, UV13, or UV15, or a combination of any of UV1, UV5, UV13, and UV15, especially UV13, in an amount of 0.5% to 2.2% (wt / wt), and preferably 0.7% to 1.6% (wt / wt); and comprise UV28 in an amount of 0.3% to 0.9% (wt / wt), and preferably 0.4% to 0.7% (wt / wt), wherein the total amount of HEVL absorbers having formula (1) present in the formulation does not exceed 2.7% (wt / wt), and preferably does not exceed 2.0% (wt / wt).

[0155] Optionally, the total amount of units of HEVL absorber having formula (1) present in the polymeric lens material of the contact lens derived from the third aspect of the application is in the range of 0.1 to 3.0 wt / wt of the polymeric lens material, preferably in the range of 0.2 to 2.5 wt / wt of the polymeric lens material, and more preferably in the range of 0.3 to 2.0 wt / wt of the polymeric lens material. For example, the total amount of units of high energy short wavelength visible light absorber having formula (1) present in the polymeric lens material of the contact lens derived from the third aspect of the application is optionally no more than 2.7 wt / wt of the polymeric lens material, and preferably no more than 2.0 wt / wt of the polymeric lens material.

[0156] The term "UV absorber" refers to a compound comprising a chromophore that absorbs light in the UV spectrum, i.e. at wavelengths in the range of 100 nm to 400 nm. In particular, a 0.003 wt% solution of the UV absorber in ethyl acetate has an absorption maximum (λmax) in the range of 220 nm to 350 nm, especially in the range of 250 nm to 350 nm. The UV absorber present in the formulations and lenses of the present application advantageously has a maximum absorbance (λmax) in the range of 250 nm to 350 nm, between 260 nm and 320 nm, especially between 270 nm and 310 nm, as a 0.003 wt% solution in ethyl acetate.

[0157] A compound can act as both a HEVL absorber and a UV absorber. For example, UV28 has an absorption maximum (λmax) at about 308 nm in the range of 220 nm to 350 nm, an absorbance higher than 0.5 in the range of about 288 nm to about 330 nm and about 337 nm to about 397 nm, and an absorption maximum (λmax) at about 369 nm in the range of 350 nm to 455 nm, as a 0.003 wt% solution in ethyl acetate. The term "HEVL absorber" used herein encompasses compounds that act as HEVL absorbers only, and compounds that act as both HEVL absorbers and UV absorbers. The UV absorber included in the formulations of the present application is advantageously not a bifunctional HEVL absorber and UV absorber. The UV absorber can have an absorbance cutoff in the visible range, i.e. does not absorb a substantial amount of light above 380 nm. For example, a 0.003 wt% solution of the UV absorber in ethyl acetate does not have an absorbance of at least 0.5 in the range of 375 nm to 450 nm. Both the first HEVL absorber and / or the second HEVL absorber present in the formulations of the present application have an absorbance higher than 0.5 in the range of 375 nm to 450 nm, as a 0.003 wt% solution in ethyl acetate, and can also optionally have an absorption maximum (λmax) in the range of 220 nm to 350 nm, especially in the range of 250 nm to 350 nm.

[0158] Optionally, the hydrogel contact lens formulations of the present application can include one or more UV absorbers, i.e., the contact lens formulation can include a UV absorber, or can include a UV absorber component that includes two or more UV absorbers. UV absorbers that can be included in the formulations of the present application include, for example, benzophenone, or benzotriazole, or any combination thereof.

[0159] The UV absorbers are advantageously covalently bonded to the polymeric matrix of the lens material, rather than simply physically entrapped in the material, to prevent migration, phase separation, or leaching of the absorber from the lens material. This stability is advantageous because leaching of the UV absorber can present toxicological problems and / or result in loss of UV blocking activity of the contact lens. The UV absorbers used in the present application are generally soluble in the contact lens formulation, and are polymerizable, such that they form part of the polymeric matrix of the lens and remain in the lens during autoclaving and storage. The UV absorbers are advantageously polymerizable UV absorbers that include one or more reactive groups capable of participating in a curing reaction by which the polymeric matrix of the polymeric lens material is formed, such that the polymerizable UV absorber is covalently bonded into the polymeric lens material. Polymerizable UV absorbers generally include ethylenically unsaturated groups capable of participating in a free radical polymerization reaction, such as vinyl or (meth)acrylate, (meth)acrylamide, or styryl groups. Many copolymerizable benzotriazole, benzophenone, methyl salicylate, acrylonitrile, and triazine UV absorbers are known. Many of these UV absorbers contain ethylenically unsaturated polymerizable groups. Copolymerization with other ingredients of the lens formulation, typically with a free radical initiator, incorporates the UV absorber into the resulting contact lens material. Incorporation of additional functional groups on the UV absorber can affect one or more of the UV absorption properties, solubility, or reactivity of the UV absorber. Suitable polymerizable UV absorbers include 2-(4-benzoyl-3-hydroxyphenoxy)ethyl acrylate (CAS No. 16432-81-8, UV416) and “Norbloc,” 2-(3-(2H-benzotriazol-2-yl)-4-hydroxy-phenyl)ethyl methacrylate (CAS No. 96478-09-0, NORBLOC 7966, from Noramco, Athens, GA., USA). The UV absorber or UV absorber component can be present in the formulations of the present application in an amount of up to about 5.0% (wt / wt), typically in an amount of about 0.1% (wt / wt) to about 2.0% (wt / wt), or about 0.2% (wt / wt) to about 1.5% (wt / wt), for example 0.3% (wt / wt) to 1.0% (wt / wt).

[0160] The hydrogel contact lens formulation used in the method of the second aspect of the invention or the fourth aspect of the invention optionally further comprises a polymerizable UV absorber having an absorbance maximum (λmax) in the range from 250 nm to 380 nm, between 260 nm and 320 nm, especially between 270 nm and 310 nm, as a 0.003 wt% solution in ethyl acetate. The UV light absorbing units present in the polymeric lens material of the hydrogel contact lens of the third aspect of the invention can be derived from the polymerizable UV absorbers described herein with reference to the formulations of the invention. Thus, the polymeric lens material of the hydrogel contact lens of the third aspect of the invention optionally comprises UV light absorbing units derived from a polymerizable UV absorber having an absorbance maximum (λmax) in the range from 250 nm to 380 nm, between 260 nm and 320 nm, especially between 270 nm and 310 nm, as a 0.003 wt% solution in ethyl acetate.

[0161] The hydrogel contact lens formulation used in the method of the second aspect of the invention or the fourth aspect of the invention optionally further comprises a polymerizable UV absorber comprising a benzophenone moiety. Likewise, the polymeric lens material of the hydrogel contact lens of the third aspect of the invention optionally further comprises UV light absorbing units comprising a benzophenone moiety. The UV light absorbing units comprising a benzophenone moiety present in the polymeric lens material of the third aspect of the invention can be derived from the polymerizable UV absorbers described herein with reference to the formulations of the invention.

[0162] The hydrogel contact lens formulation used in the method of the second aspect of the invention or the fourth aspect of the invention optionally comprises a polymerizable UV absorber comprising a benzophenone moiety having an absorbance maximum (Amax) in the range from 250 nm to 380 nm, between 260 nm and 320 nm, especially between 270 nm and 310 nm, as a 0.003 wt% solution in ethyl acetate. The UV light absorbing units present in the polymeric lens material of the third aspect of the invention can be derived from the polymerizable UV absorbers described herein with reference to the formulations of the invention. Thus, the polymeric lens material of the hydrogel contact lens of the third aspect of the invention optionally comprises UV light absorbing units derived from a polymerizable UV absorber comprising a benzophenone moiety having an absorbance maximum (Amax) in the range from 250 nm to 380 nm, between 260 nm and 320 nm, especially between 270 nm and 310 nm, as a 0.003 wt% solution in ethyl acetate. The benzophenone UV absorbers included in the formulations of the invention are advantageously not bifunctional HEVL absorbers and UV absorbers. The benzophenone UV absorbers can have an absorbance cut-off in the visible range, i.e. the benzophenone UV absorbers do not absorb a substantial amount of light above 380 nm. For example, a 0.003 wt% solution of the benzophenone UV absorber in ethyl acetate does not have an absorbance of at least 0.5 in the range from 375 nm to 450 nm.

[0163] It has been found that the inclusion of a UV absorber in the formulation used in the method of the second aspect of the application or the fourth aspect of the application, which has an absorbance maximum (Amax) in the range from 250 nm to 380 nm, between 260 nm and 320 nm, especially between 270 nm and 310 nm, as a 0.003 wt% solution in ethyl acetate, and / or comprises a benzophenone moiety, enables the resulting eyewear to have a high level of absorption across the range from 250 nm to 455 nm at a lower overall level of UV blocker than when including a UV absorber which has an absorbance maximum (Amax) in the range from 250 nm to 380 nm, above 320 nm, as a 0.003 wt% solution in ethyl acetate, and / or comprises a benzotriazole or triazine moiety, especially a benzotriazole moiety. Without wishing to be bound by any theory, it is hypothesised that, due to the significant difference in absorption between the benzophenone UV absorber, which has an absorbance maximum (Amax) in the range from 250 nm to 380 nm, between 260 nm and 320 nm, as a 0.003 wt% solution in ethyl acetate, and two different HEVL absorbers each comprising a benzotriazole moiety, the combination of the benzophenone UV absorber and the two different HEVL absorbers is more effective at providing light blocking across the range from 260 nm to 440 nm than the combination of a UV absorber which has an absorbance maximum (Amax) in the range from 250 nm to 380 nm, above 320 nm, and / or a benzotriazole moiety, such as Norbloc.

[0164] Optionally, the formulation of the application comprises one or more polymerisable UV absorbers comprising a benzophenone moiety in an amount of no more than 1.5% (wt / wt), preferably no more than 1.0% (wt / wt). The polymerisable UV absorber is optionally 2-(4-benzoyl-3-hydroxyphenoxy)ethyl acrylate (UV416).

[0165] The formulations of the present application can also optionally include at least one colorant, i.e., a colorant or a colorant component comprising two or more colorants. In one example, the colorant can be a reactive dye or a pigment effective to provide color to the resulting contact lenses or effective to reduce the amount of tinting of the resulting contact lenses. The colorant or colorant component of the polymerizable formulation can comprise a polymerizable colorant, or can comprise a non-polymerizable colorant, or any combination thereof. The polymerizable colorant can be a colorant whose molecular structure comprises a polymerizable functional group, or can be a colorant whose molecular structure includes both a monomer moiety and a dye moiety, i.e., the colorant can be a monomer-dye compound. The molecular structure of the colorant may, for example, comprise a beta sulfone functional group, a triazine functional group, or an anthraquinone moiety. Suitable colorants include, for example, vat blue 6 (7, 16-dichloro-6, 15-dihydroanthracene azine-5, 9, 14, 18-tetraone), 1-amino-4-[3-(beta-sulfatoethylsulfonyl)anilino]-2-anthraquinone sulfonic acid (C.I. Reactive Blue 19, RB-19), or a monomer-dye compound of reactive blue 19 with hydroxyethyl methacrylate (RB-19 HEMA), 1,4-bis[4-[(2-methacryloyl-oxyethyl)anilino]anthraquinone (Reactive Blue 246, RB-246, CAS No. 121888-69-5, available from Arran Chemical Company, Athlone, Ireland), 1,4-bis[(2-hydroxyethyl)amino]-9,10-anthracenedione bis(2-propenyl) ester (Reactive Blue 247, RB-247, CAS No. 109561-07-1, also available from Arran Chemical Company), or reactive blue 4 (RB-4, CAS No. 13324-20-4, available from ThermoFisher), or a monomer-dye compound of reactive blue 4 with hydroxyethyl methacrylate (RB-4 HEMA or “blue HEMA”). Additional examples of suitable monomer-dye compounds are described in US 5,944,853 and US 7,216,975, both of which are incorporated herein by reference in their entirety. Other exemplary colorants are disclosed, for example, in US 2008 / 0048350 and US 4,997,897, the disclosures of which are incorporated herein by reference in their entirety. The formulations of the present application advantageously comprise a blue or blue-green colorant comprising an anthraquinone moiety, particularly a polymerizable blue or blue-green colorant comprising an anthraquinone moiety. The polymeric lens material of the contact lenses of the present application can further comprise units derived from a polymerizable blue or blue-green colorant comprising an anthraquinone moiety. The polymerizable blue or blue-green colorant is optionally selected from 1,4-bis[4-(2-methacryloyloxyethyl)anilino]-9,10-anthraquinone (RB246) or 1,4-bis[(2-methacryloyloxyethyl)amino]-9,10-anthraquinone (RB247).

[0166] The radiation-absorber package of HEVL-absorbing agents and optionally UV-absorbing agents and optionally colouring agents can be selected so that the light transmission properties of the contact lens produced from the contact lens formulation comprising the radiation-absorber package meet the required specifications. For example, the hydrogel contact lens formulation of the second aspect of the application can comprise a radiation-absorber package which produces a contact lens meeting the requirements of Class 1 UV blocking (defined in BS EN ISO 18369-2:2017, Table 4) (i.e. a contact lens capable of blocking >90% of UVA rays and >99% of UVB rays) or Class 2 UV blocking (i.e. a contact lens blocking >50% of UV-A rays and >95% of UV-B rays). Advantageous formulations of the application provide a contact lens which blocks at least 30% of HEVL light, in particular at least 40% of HEVL light, preferably at least 45% of HEVL light, in addition to providing UV blocking. The formulation can also provide a contact lens which blocks at least 35% of violet light, in particular at least 45% of violet light, preferably at least 50% of violet light. The contact lens of the third aspect of the application advantageously meets the requirements of Class 1 UV blocking (defined in BS EN ISO 18369-2:2017, Table 4) (i.e. capable of blocking >90% of UVA rays and >99% of UVB rays) or Class 2 UV blocking (i.e. blocking >50% of UV-A rays and >95% of UV-B rays). Advantageous contact lenses of the application block at least 30% of HEVL light, in particular at least 40% of HEVL light, preferably at least 45% of HEVL light, in addition to providing UV blocking. The contact lenses of the application can block at least 35% of violet light, in particular at least 45% of violet light, preferably at least 50% of violet light. “UVA” refers to radiation occurring at wavelengths between 315 nanometres and 400 nanometres (nm); “UVB” refers to radiation occurring between 280 nm and 315 nm; “violet light” refers to radiation occurring at wavelengths between 380 nm and 440 nm, and “high energy visible light” (HEVL) refers to radiation occurring at wavelengths between 380 nm and 455 nm.

[0167] The polymeric material of the contact lens of the third aspect of the application can have the following light transmission properties, and / or the hydrogel contact lens formulation of the second aspect of the application can produce a contact lens of material meeting the following light transmission properties:

[0168]

[0169] The transmission properties of the eyewear material were measured on 1 mm thick 1 x 2 cm rectangular cast films. The films were analyzed by UV-visible transmission spectroscopy from 300 nm to 800 nm using a Perkin Elmer Lambda 35 instrument equipped with a LabSphere RSA-PE-20 integrating sphere.

[0170] The contact lenses of the third aspect of the application optionally have a yellowness index of less than 8.0, preferably less than 6.0, especially less than 5.0, as determined by the ASTM E313-05 method. The hydrogel contact lens formulations of the second aspect of the application optionally produce hydrogel contact lenses having a yellowness index of less than 8.0, preferably less than 6.0, especially less than 5.0, as determined by the ASTM E313-05 method.

[0171] The contact lenses of the third aspect of the application are hydrogel contact lenses, including conventional (i.e., non-silicone hydrogel contact lenses) and silicone hydrogel contact lenses. "Hydrogel" refers to a crosslinked polymeric material having a three-dimensional polymeric network (i.e., a polymeric matrix) that is insoluble in water, but contains at least 10% by weight of water in its polymeric matrix when it is fully hydrated. "Silicone hydrogel" refers to a hydrogel obtained by polymerization of a hydrogel contact lens formulation that includes at least one silicone-containing monomer. The term "non-silicone hydrogel" refers to a hydrogel that does not contain silicone.

[0172] Polymerizable formulations suitable for making conventional hydrogel and silicone hydrogel contact lenses are well known in the art. The radiation absorber packages of the first aspect of the application are suitable for incorporation into a wide range of polymerizable formulations used to form hydrogel (including silicone hydrogel) contact lenses. In addition to the radiation absorbing compounds, the hydrogel contact lens formulations of the second aspect of the application include monomers and other components suitable for forming the hydrogel contact lenses described below.

[0173] Generally, hydrogel contact lenses are formed by free radical propagation reactions involving polymerization of terminal ethylenically unsaturated groups (also referred to herein as "polymerizable groups"). Exemplary polymerizable groups include (meth)acryloyl, (meth)acrylamide, allyl, and vinyl and styryl. As used herein, a "vinyl-containing monomer" is any non-silicone monomer having a single polymerizable carbon-carbon double bond (i.e., a vinyl group) present in the molecular structure, wherein the carbon-carbon double bond of the vinyl group is attached to an sp3 hybridized carbon atom. The reactivity of a vinyl group under free radical polymerization is lower than the carbon-carbon double bond present in a (meth)acrylate or methacrylate polymerizable group. The term "(meth)acrylamide" means methacrylamide and / or acrylamide. The term "(meth)acrylate" means methacrylate and / or acrylate. The term "terminal (meth)acryloyl" means one (meth)acryloyl group at one of the two ends of a main chain (or backbone) of an organic compound. An "N-vinyl amide monomer" means an amide compound having a vinyl group CH=CH2 directly attached to the nitrogen atom of the amide group.

[0174] A "monomer" is a molecule having one or more polymerizable groups that can react with other monomers, the same or different, to form larger polymer or copolymer chains or three-dimensional polymeric matrices in the polymerization process. A monomer having two or more polymerizable groups can be referred to as a "crosslinker," described further below. The term "monomer" encompasses macromonomers and polymerizable oligomers, i.e., polymerizable molecules containing one or more repeating unit chains, such as polymerizable siloxanes; thus, monomers are not size limited (i.e., maximum molecular weight) unless otherwise indicated. As used in this application, unless otherwise specified, the term "molecular weight" of a polymeric material refers to the absolute number average molecular weight (in Daltons), as determined, for example, with 1H NMR end group analysis or with GPC using polystyrene standards. The term "polymer" refers to a material formed by polymerization and / or crosslinking of one or more monomers.

[0175] The formulations of the present application generally comprise hydrophilic monomers, and can also comprise hydrophobic monomers. As used herein, a "hydrophilic monomer" means a monomer that does not contain silicone, wherein at least 50 grams of the monomer is completely soluble in 1 liter of water at 20°C (i.e., about 5% soluble in water), as visibly determined using the standard shake flask method.

[0176] The hydrogel contact lens formulations of the present application generally comprise at least one hydrophilic monomer, optionally in an amount of at least 25% (wt / wt), such as in an amount of at least 30% (wt / wt), especially in an amount of at least 35% (wt / wt).

[0177] Suitable hydrophilic monomers include hydrophilic vinylamide-containing monomers and hydrophilic vinyl ether-containing monomers. In some examples, the hydrophilic vinylamide-containing monomers can be selected from N-vinyl-N-methyl acetamide (VMA), or N-vinyl pyrrolidone (NVP), or N-vinyl formamide, or N-vinyl acetamide, or N-vinyl-N-ethyl acetamide, or N-vinyl isopropylamide, or N-vinyl caprolactam, or N-vinyl-N-ethyl formamide, or any combination thereof. In some examples, the hydrophilic vinylamide-containing monomers consist of VMA or NVP, or a combination of VMA and NVP. The vinyl ether-containing monomers can be selected from 1,4-butanediol vinyl ether (BVE), or ethylene glycol vinyl ether (EGVE), or diethylene glycol vinyl ether (DEGVE), or 1,4-cyclohexanedimethanol vinyl ether (CHDMVE), or poly(ethylene glycol) vinyl ether having 4 to 10 ethylene glycol units, or poly(ethylene glycol) vinyl ether having more than 10 ethylene glycol units, or any combination thereof. In some examples, the vinyl ether-containing monomers can be poly(ethylene glycol) vinyl ether having at least 1, 2, or 3 ethylene glycol units and at most 4, 6, 8, or 10 ethylene glycol units. In addition to the hydrophilic vinylamide-containing monomers and the hydrophilic vinyl ether-containing monomers, one or more vinyl-containing monomers can also be included in the formulations of the present application. For example, in addition to the vinylamide-containing monomers and the vinyl ether-containing monomers, vinyl monomers having vinyl ester or allyl ester polymerizable groups can be included in the formulations of the present application. The hydrophilic monomers can be hydrophilic monomers containing (meth)acrylate or (meth)acrylamide groups, examples of which include 2-hydroxyethyl methacrylate (HEMA), 4-hydroxybutyl acrylate glyceryl methacrylate, 2-hydroxyethyl methacrylamide, ethoxyethyl methacrylamide (EOEMA), polyethylene glycol monomethacrylate, methacrylic acid (MA), and acrylic acid.

[0178] The formulations of the second aspect of the present application can include at least one hydrophilic N-vinylamide monomer, optionally in an amount of at least 20% (wt / wt), for example in an amount of at least 30% (wt / wt), especially in an amount of at least 35% (wt / wt). The formulations of the second aspect of the present application can include at least one hydrophilic N-vinylamide monomer in an amount of 25% to 55% (wt / wt), especially 30% to 50% (wt / wt). The formulations of the second aspect of the present application can include N-methyl N-vinyl acetamide in an amount of 25% to 55% (wt / wt), especially 30% to 50% (wt / wt).

[0179] The polymerizable monomers can optionally include hydrophobic monomers. As used herein, the term "hydrophobic monomer" refers to monomers that lack siloxane groups and are less than 5% soluble in water at 20°C as determined using standard shake flask methods.

[0180] The hydrophobic monomer lacking a siloxane group can be a (meth)acrylate group-containing hydrophobic monomer. As used herein, a "hydrophobic acrylate-containing monomer" is any non-siloxane monomer having a single polymerizable acrylate group (e.g., methyl methacrylate, acrylamide, etc.). In a particular example, the hydrophobic acrylate-containing monomer has a polymerizable methacrylate group. Many suitable acrylate-containing monomers are known in the art. Exemplary hydrophobic acrylate-containing monomers include methyl acrylate, isopropyl acrylate, cyclohexyl acrylate, methyl methacrylate (MMA), butyl acrylate, t-butyl methacrylate (tBMA), perfluorohexylethylthiocarbonylaminoethyl methacrylate, isobornyl methacrylate (IBM), trifluoroethyl methacrylate, hexafluoroisopropyl methacrylate, hexafluorobutyl methacrylate, 2-hydroxybutyl methacrylate (HOB), 2-hydroxypropyl methacrylate (HPMA), and ethylene glycol methyl ether methacrylate (EGMA). Advantageous non-siloxane hydrophobic monomers include hydroxybutyl methacrylate, isobornyl methacrylate, or a combination of hydroxybutyl methacrylate and isobornyl methacrylate. The hydrogel contact lens formulation can include an acrylate-containing hydrophobic monomer to further enhance the mechanical strength and / or stiffness of the lens, or to impart other desired properties.

[0181] The hydrophobic monomer lacking a siloxane group is not limited to (meth)acrylate group-containing monomers, and can include vinyl or other ethylenically unsaturated reactive groups. Other examples of hydrophobic monomers include vinyl acetate, vinyl propionate, vinyl butyrate, styrene, chlorobutadiene, chloroethylene, vinylidene chloride, acrylonitrile, and methacrylonitrile.

[0182] The formulation can include about 2% to about 20% (wt / wt), e.g., 4% to 16% (wt / wt), especially 6% to 12% (wt / wt), of the non-siloxane hydrophobic monomer component. 2 to 20% (wt / wt), especially 5 to 15% (wt / wt), of the formulation can be hydroxybutyl methacrylate, isobornyl methacrylate, or a combination of hydroxybutyl methacrylate and isobornyl methacrylate.

[0183] The hydrogel contact lens formulations used in the methods of the second and / or fourth aspects of the present application can be silicone hydrogel contact lens formulations comprising a siloxane-containing monomer in addition to the hydrophilic monomer and optional hydrophobic monomer lacking a siloxane group. The hydrogel contact lenses of the third aspect of the present application can be silicone hydrogel contact lenses comprising a siloxane group in the matrix of the polymeric lens material. As used herein, "siloxane monomer" refers to a monomer having at least one siloxane group. The siloxane monomer can comprise a terminal acrylate or methacrylate group. The (meth)acrylate-containing siloxane monomers that can be used in the formulations of the present application described herein are well known in the art. The siloxane monomer can be a mono-functional (meth)acrylate-containing siloxane, a di-functional (meth)acrylate-containing siloxane, or comprise a combination of mono-functional (meth)acrylate-containing siloxane monomers and di-functional (meth)acrylate-containing siloxane monomers. In examples where the (meth)acrylate-containing siloxane monomer consists of one or more mono-functional (meth)acrylate-containing siloxane monomers (i.e., it does not contain any multi-functional (meth)acrylate-containing siloxane monomers), the silicone hydrogel contact lens formulation will typically further comprise a (meth)acrylate-containing crosslinker, described further below. In a particular example, the (meth)acrylate-containing siloxane monomer has one or more polymerizable methacrylate groups. Various non-limiting examples of suitable acrylate-containing siloxane monomers include 3-[tris(trimethylsilyloxy)silyl]propyl methacrylate ("TRIS"), 3-methacryloyloxy-2-hydroxypropyloxy)propyl bis(trimethylsilyloxy)methylsilane ("SiGMA"), methacrylic acid methyl di(triethylsilyloxy)silyl glycerol ethyl ester ("SiGEMA"), and monomethacryloxypropyl functional polydimethylsiloxanes such as MCR-M07 and MCS-M11, all of which are available from Gelest (Morrisville, PA, USA).

[0184] The hydrogel contact lens formulations of the second aspect of the present application are optionally silicone hydrogel contact lens formulations comprising at least one polymerizable siloxane monomer, optionally in an amount of at least 25% (wt / wt), such as in an amount of at least 35% (wt / wt), especially in an amount of at least 40% (wt / wt).

[0185] The silicone hydrogel contact lens formulation can include at least one difunctional siloxane having a molecular weight of at least 5,000 Daltons, especially at least one difunctional siloxane having a molecular weight of at least 8,000 Daltons. The difunctional siloxane typically has a molecular weight of less than 25,000 Daltons, for example a molecular weight of less than 20,000 Daltons, especially a molecular weight of less than 15,000 Daltons. It has been found that including siloxanes having higher molecular weights can result in formulations having unacceptably high viscosities. The silicone hydrogel contact lens formulation can include at least one difunctional siloxane having a molecular weight of 5,000 to 25,000 Daltons, for example at least one difunctional siloxane having a molecular weight of 6,500 to 20,000 Daltons, especially at least one difunctional siloxane having a molecular weight of at least 8,000 to 15,000 Daltons. Advantageously, at least 30% (wt / wt) of the siloxane content can be difunctional siloxanes having a molecular weight of at least 5,000 Daltons or at least 8,000 Daltons, for example 8,000 to 20,000 Daltons. Advantageously, at least 40% (wt / wt) of the siloxane content is difunctional having a molecular weight of at least 5,000 Daltons or at least 8,000 Daltons, for example 8,000 to 20,000 Daltons. The formulation advantageously comprises between 15 and 45 wt% of difunctional siloxanes, for example between 20 and 40 wt% of difunctional siloxanes having a molecular weight of at least 5,000 Daltons or at least 8,000 Daltons, for example 8,000 to 20,000 Daltons. In some embodiments, the silicone hydrogel contact lens formulation can include at least one difunctional siloxane having a molecular weight of at least 10,000 Daltons. At least 30% (wt / wt) of the siloxane content can be difunctional siloxanes having a molecular weight of at least 10,000 Daltons, or at least 40% (wt / wt) of the siloxane content is difunctional having a molecular weight of at least 10,000 Daltons. The formulation can comprise between 15 and 45 wt% of difunctional siloxanes, for example between 20 and 40 wt% of difunctional siloxanes having a molecular weight of at least 10,000 Daltons. The silicone hydrogel contact lens formulation can include at least one monofunctional siloxane monomer, for example having a molecular weight of less than 3,000 Daltons. At least 20% (wt / wt) of the siloxane content can be monofunctional siloxanes having a molecular weight of less than 3,000 Daltons. Advantageously, at least 30% (wt / wt) of the siloxane content is monofunctional having a molecular weight of less than 3,000 Daltons. The formulation can comprise one or more monofunctional siloxane monomers between 10 and 30 wt%, for example one or more monofunctional siloxane monomers between 10 and 30 wt% having a molecular weight of less than 3,000 Daltons. The monofunctional siloxane typically has a molecular weight of at least 200 Daltons.

[0186] In one example, the monofunctional siloxane monomer can comprise a (meth)acrylate-containing siloxane monomer represented by formula (I), (I)

[0187]

[0188] wherein m is an integer from 3 to 10, n is an integer from 0 to 10, R 1 is an alkyl group having 1 to 4 carbon atoms, R 2 is hydrogen or methyl, and R 3 is hydrogen or methyl. In another particular example, the acrylate-containing siloxane monomer is represented by Formula I, wherein R 1 is butyl, R 2 is hydrogen, R 3 is methyl, m is 4, and n is 1. Methods of making siloxane monomers represented by Formula (I) are described in U.S. Publication No. 20090299022, incorporated herein by reference.

[0189] In another example, the monofunctional siloxane monomer can comprise an (meth)acrylate-containing siloxane monomer represented by Formula (II),

[0190]

[0191] wherein n is an integer from about 10 to 15. Formula II siloxane monomers and other suitable monomers are described in U.S. Patent No. 6,867,245 and U.S. Patent No. 6,310,169, both incorporated herein by reference.

[0192] Examples of suitable commercially available monofunctional siloxane monomers include 2-methyl-2-[3-(9-butyl-1,1,3,3,5,5,7,7,9,9- decamethylpentasiloxane-1 -yl)propoxy]ethyl 2-propenoate, which is X-22-1622 (also known as KF1622) available from Shin-Etsu Chemical Co., Ltd., Tokyo, Japan (CAS No. 1052075-57-6), methacryloyloxypropyl terminated poly(dimethyl)siloxane FMM (Shin-Etsu Silicones of America, Akron, Ohio, USA) (CAS No. 697234-76-7), and 3-methacryloyloxy-2-hydroxypropyloxy)propyl bis(trimethylsiloxy)methylsilane SiGMA.

[0193]

[0194] Silicone hydrogel contact lens formulations can include, for example, at least one difunctional siloxane monomer having a molecular weight of at least 8,000 Daltons. The formulation can include one or more difunctional siloxane monomers between 10 and 45 wt%, especially one or more difunctional siloxane monomers between 20 and 40 wt%. The formulation advantageously includes one or more difunctional siloxane monomers having a molecular weight of at least 8,000 Daltons between 10 and 45 wt% or between 20 and 40 wt%. The formulation can include one or more difunctional siloxane monomers having a molecular weight of at least 10,000 Daltons between 10 and 45 wt% or between 20 and 40 wt%.

[0195] In one example, the difunctional siloxane monomer can include a (meth)acrylate-containing siloxane monomer represented by formula (III),

[0196]

[0197] wherein R1is selected from hydrogen or methyl; R2is selected from hydrogen or C 1-4 hydrocarbyl; m represents an integer from 0 to 10; n represents an integer from 4 to about 15, 25, or 100; a and b represent integers of 1 or greater; a + b equals 20 to 500; b / (a + b) equals 0.01 to 0.22; and the configuration of siloxane units includes a random configuration. In a more particular example, the acrylate-containing siloxane monomer is represented by formula II, wherein R1and R2are methyl, m is 0, n represents an integer from about 5 to about 10, a represents an integer from about 70 to about 90, and b represents an integer from 1 to about 10; such siloxane monomer has a molecular weight of about 8,000 to about 10,000 Daltons. Methods of making the compound of formula III are described in US 2009 / 0234089, which is incorporated herein by reference. A particularly suitable difunctional siloxane monomer is PEG-functionalized poly(dimethyl)siloxane dimethacrylate monomer M5A (CAS No. 1216820-69-7), which is macromer A described in Example 2 of US 2009 / 0234089.

[0198] Other suitable difunctional siloxane monomers are represented by formula (IV):

[0199]

[0200] wherein R 3 is selected from hydrogen or methyl, m represents an integer from 0 to 10, and n represents an integer from 1 to 500. In a particular example, the difunctional siloxane monomer is a methacryloyloxypropyl-terminated polydimethylsiloxane having a molecular weight of 4500 to 5500 represented by formula IV, wherein R 3DMS-R18, which is commercially available from Gelest, Inc. (Morrisville, PA, USA) and is referred to as "DMS-R18" from the manufacturer. Additional suitable methylpropenoyloxypropyl terminated polydimethylsiloxanes include DMS-R22 and DMS-R31, which are also commercially available from Gelest, Inc.

[0201] Yet another suitable difunctional siloxane monomer is represented by formula (V),

[0202]

[0203] where n is an integer of about 100 to 150, m and p are each an integer of about 5 to 10, and h is an integer of about 2 to 8. Methods of preparing compounds of formula V are described in U.S. Patent No. 6,867,245, which is incorporated herein by reference. Additional (meth)acrylate-containing siloxane monomers that can be used in the formulations of the present application described herein are known in the art (see, for example, U.S. Patent No. 7,572,841, U.S. Patent Publication No. 2006 / 0063852, and U.S. Patent No. 5,998,498, each of which is incorporated herein by reference).

[0204] In one example, the siloxane monomer can comprise a combination of monofunctional (meth)acrylate-containing siloxane monomers and difunctional (meth)acrylate-containing siloxane monomers. In one such example, the monofunctional (meth)acrylate-containing siloxane monomers have a molecular weight of less than 2,000, 1,000, or 750 Daltons, and the difunctional (meth)acrylate-containing siloxane monomers have a molecular weight of at least 3,000, 5,000, or 8,000 Daltons. In the case of polyorganosiloxane monomers (such as those represented by formula II, formula IV, and formula V above) and other polydisperse monomers, the molecular weight can be determined with 1H NMR end group analysis. In a particular example, the monofunctional (meth)acrylate-containing siloxane monomers have a molecular weight of about 250 to about 1000, and the difunctional (meth)acrylate-containing siloxane monomers have a molecular weight of about 5,000 to about 16,000 Daltons. In another particular example, the monofunctional (meth)acrylate-containing siloxane monomers have a molecular weight of about 500 to about 1,000 Daltons, and the difunctional (meth)acrylate-containing siloxane monomers have a molecular weight of about 5,000 to about 12,000 Daltons.

[0205] The formulations of the present invention generally comprise one or more polymerization initiators, that is, the hydrogel contact lens formulations can comprise an initiator, or can comprise an initiator component comprising two or more polymerization initiators or a combination of a polymerization initiator, a synergist, and an activator. The term "initiator" refers to a chemical that initiates a cross-linking / polymerization reaction. The initiator is typically a free radical initiator that forms free radicals that initiate the propagation of the polymerization reaction. Polymerization initiators that can be included in the formulations of the present invention include, for example, an azo compound or an organic peroxide or both. The initiator can be a photoinitiator that is activated upon exposure to actinic radiation, such as UV light, or a thermal initiator that is activated upon exposure to heat. Initiators that can be present in the hydrogel contact lens formulations include, for example, benzoin ethyl ether, or benzyl dimethyl ketal, or a,a-diethoxyacetophenone, or 2,4,6-trimethylbenzoyldiphenylphosphine oxide, or benzoin peroxide, or t-butyl peroxide, or azobisisobutyronitrile, or azobisdimethylvaleronitrile, or any combination thereof. UV photoinitiators can include, for example, a phosphine oxide (e.g., diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide), or benzoin methyl ether, or 1-hydroxycyclohexyl phenyl ketone, or Darocur (available from BASF, Florham Park, N.J., USA), or Irgacur (also available from BASF), or any combination thereof. Advantageously, the polymerization initiator is a thermal initiator. Examples of suitable thermal initiators include 2,2'-azobis-2-methylpropionitrile (Vazo-64, from E.I. DuPont de Nemours & Co., Wilmington, Del., USA, CAS number 78-67-1), also known as 2,2'-azobis(isobutyronitrile) (AIBN), 2,2'-azobis(2,4-dimethylvaleronitrile) (VAZO-52, also from DuPont, CAS number 4419-11-8), also known as 2,2'-azobis(dimethylvaleronitrile), and 1, 1 '-azobis(cyanocyclohexane) (VAZO-88, also from DuPont, CAS number 2094-98-6), also known as 1, 1 '-azobis(cyclohexanecarbonitrile). The polymerization initiator or initiator component can be present in the hydrogel contact lens formulation in an amount of from about 0.1% (wt / wt) to about 1.5% (wt / wt), or from about 0.2% (wt / wt) to about 1.0% (wt / wt), especially from about 0.2% (wt / wt) to about 0.8% (wt / wt). The hydrogel contact lens formulations of the second aspect of the present invention are optionally thermal curing formulations comprising at least one thermal initiator. The method of the fourth aspect of the present invention optionally comprises thermal curing the formulation. Thermal curing or actinic curing methods are well known to those skilled in the art.

[0206] The hydrogel contact lens formulations of the present invention can further comprise a crosslinking agent. A crosslinking agent can react with functional groups on two or more polymer chains in order to bridge one polymer to another. As used herein, a "crosslinking agent" is any compound having two or more polymerizable groups with a molecular weight of less than about 2,000 Daltons, typically less than 700 Daltons. As used herein, an "acrylate-containing crosslinking agent" has at least two polymerizable acrylate groups and no other type of polymerizable group. A "vinyl-containing crosslinking agent" has at least two polymerizable vinyl groups and no other type of polymerizable group. Vinyl-containing crosslinking agents, as well as acrylate-containing crosslinking agents, can generally have a molecular weight of less than 1500, 1000, 500, or 250. Examples of vinyl-containing crosslinking agents that can be used in the formulations of the present invention include, but are not limited to, a divinyl ether, or a divinyl sulfone, or triallyl isocyanurate, and any combination thereof. Exemplary divinyl ethers include diethylene glycol divinyl ether, or triethylene glycol divinyl ether, or 1,4-butanediol divinyl ether, or 1,4-cyclohexanedimethanol divinyl ether, or any combination thereof. Generally, a vinyl-containing crosslinking agent can have two or three polymerizable vinyl groups. When present, the total amount of vinyl-containing crosslinking agent in the hydrogel contact lens formulation is generally from about 0.02, 0.04, or 0.06 mol. % to about 0.10, 0.15, or 0.20 mol. %. Examples of acrylate-containing crosslinking agents that can be used in the formulations of the present invention include, but are not limited to, lower alkylene glycol di(meth)acrylate, poly(lower alkylene) glycol di(meth)acrylate, lower alkylene di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, bisphenol A di(meth)acrylate, methylene bis(meth)acrylamide, and 1,3-bis(3-methacryloyloxypropyl)tetramethyldisiloxane. In certain examples, the acrylate-containing crosslinking agent is a non-silicone crosslinking agent. When present, the total amount of acrylate-containing crosslinking agent in the hydrogel contact lens formulation is generally from about 0.20, 0.25, 0.30, or 0.35 mol. % to about 0.50, 0.60, 0.70, 0.80, or 1.0 mol. %. For the avoidance of doubt, multifunctional polymerizable compounds having a molecular weight greater than 2,000 Daltons are not considered to be crosslinking agents. Thus, bifunctional siloxanes described herein having a molecular weight greater than 2,000 Daltons are not considered to be crosslinking agents.

[0207] The formulations of the present invention can optionally further comprise a chain transfer agent. Chain transfer is a polymerization reaction in which the activity of a growing polymer chain is transferred to another molecule, thereby reducing the average molecular weight of the final polymer. Examples of chain transfer agents include, for example, a thiol compound, a halocarbon compound, or a C3-C5 hydrocarbon, such as allyloxyethanol.

[0208] In addition to the polymerizable components, the hydrogel contact lens formulation can include non-polymerizable components conventionally used in contact lens formulations. Additional components such as organic diluents or oxygen scavengers can also be included. Non-limiting examples of these and additional components that can be included in the formulations of the present invention are provided in US 2007 / 0296914.

[0209] Advantageous formulations of the second aspect of the invention include at least one hydrophilic monomer, optionally in an amount of at least 25% (wt / wt). Advantageous formulations optionally include at least one N-vinyl amide hydrophilic monomer, optionally in an amount of at least 15% (wt / wt). Advantageous formulations are optionally silicone hydrogel contact lens formulations including at least one polymerizable siloxane monomer, optionally in an amount of at least 25% (wt / wt). Advantageous formulations are optionally silicone hydrogel contact lens formulations including: a siloxane component present in an amount of at least 35% (wt / wt), wherein at least 40% of the siloxane content is a difunctional siloxane having a molecular weight of at least 8,000 Daltons; and an N-vinyl amide monomer component present in an amount of at least 37% (wt / wt).

[0210] Advantageous formulations of the second aspect of the invention include: 25 wt% to 55 wt% of a siloxane monomer or a combination of siloxane monomers; 30 wt% to 55 wt% of a vinyl monomer selected from NVP, VMA, or a combination thereof; and optionally about 1 wt% to about 20 wt% of a hydrophilic monomer selected from N,N-dimethylacrylamide (DMA), 2-hydroxyethyl methacrylate (HEMA), ethoxyethyl methacrylamide (EOEMA), or ethylene glycol methylether methacrylate (EGMA), or any combination thereof; and optionally about 1 wt% to about 20 wt% of a hydrophobic monomer selected from methyl methacrylate (MMA), isobornyl methacrylate (IBM), or 2-hydroxybutyl methacrylate (HOB), or any combination thereof. Contact lens materials made from such formulations include stenfilcon A, comfilcon A, somofilcon A, fanfilcon A, and enfilcon A.

[0211] The contact lenses of the third aspect of the present invention advantageously comprise a polymeric lens material derived from the second aspect of the present invention, comprising an advantageous polymerizable formulation containing the monomers and siloxane components described above. The monomers and siloxane components described above may be incorporated into the polymeric lens material in the amounts described above; for example, at least 25% (wt / wt) of the polymeric material may be units derived from hydrophilic monomers having terminal olefinic unsaturated polymerizable groups. The advantageous formulations described above have been found particularly suitable for use in combination with the radiation absorber packaging of the first aspect of the present invention, i.e., suitable for combination with a first HEVL absorber comprising a benzotriazole moiety, a second different HEVL absorber comprising a benzotriazole moiety, and optionally a polymerizable UV absorber comprising a benzophenone moiety.

[0212] Example

[0213] The following examples illustrate certain aspects and advantages of the invention, and should therefore be understood as not being limiting.

[0214] Surface wettability

[0215] The water contact angle on a contact lens is a measure of the wettability of the lens surface. In this paper, the contact angle of the lens-forming surface is measured using the droplet method and data from Krüz. The DSA-100 droplet shape analysis system or equivalent analyzer was used to determine the droplet shape using 3 μl of PBS dropped onto the center of the eyeglass surface.

[0216] Equilibrium water content

[0217] The balanced water content (EWC) of contact lenses is measured as follows:

[0218] The amount of water (expressed as a weight percentage) present in a fully hydrated hydrogel contact lens in saline solution was determined at room temperature (i.e., 20°C). After the lenses were blotted dry with a cloth, five lenses were stacked on a pan of an analytical balance, and the hydrated weight of the lenses was measured. The lenses were then placed in a laboratory oven at 100 ± 2°C for 16 to 18 hours, removed from the oven, and cooled to room temperature in a desiccator for at least 30 minutes. The mass of the dried lenses was then measured, and the water content was calculated by subtracting the mass of the dried lens from the weight of the hydrated lenses.

[0219] Yellowness index (YI)

[0220] The "Yellowness Index" (YI) is a quantifiable and standardized method of measuring the perceived yellowness of a sample from spectral data from the observer's perspective. The YI of a sample describes the color change from colorless to yellow. Higher YI values indicate stronger yellow coloration. The YI of a contact lens can be determined using the protocol of ASTM E313-05, using the CIE-D65 illuminant and the 1931 (2° viewing angle) standard illuminant factor.

[0221] The following example illustrates the effect of varying the amount of high-energy, short- wavelength visible light absorbers and colorants present in the lens formulation while keeping the amount of polymerizable monomers constant.

[0222] Cast molding of contact lenses

[0223] The hydrogel contact lens formulations described below were cast molded by placing a volume of the composition on a concave mold member and fitting a convex mold member thereon to form a contact lens mold assembly. The concave and convex mold members were made of non-polar resin, e.g., polypropylene. The formulations were heat cured to form the polymeric lens body by placing the mold assembly in a nitrogen oven under the following cycle: 30 min. N2purge at room temperature, 40 min at 55°C or 65°C, 40 min at 80°C, and 40 min at 100°C.

[0224] After curing, the convex and concave mold members were dried demolded, and the polymeric lens body was dried demolded from the convex mold member. The demolded polymeric lens body was exposed to an extraction and hydration process consisting of soaking the lens body in denatured ethanol (Special Commercial Use Denatured Ethanol (TSDA) 7 containing 5.0% vol. isopropyl alcohol) twice, then in a mixture of 50% denatured ethanol (TSDA 7) and 50% deionized water, and then in deionized water three times.

[0225] The resulting contact lens had an average center thickness of 0.097 mm, a diameter of 14 mm, and a base curve of 8.3.

[0226] Base lens formulation

[0227] A base polymerizable silicone hydrogel contact lens formulation was prepared containing 10 parts of hydrophobic monomers (consisting of 2.31 parts of isobornyl methacrylate (IBM) and 7.69 parts of hydroxybutyl methacrylate (HOB)), 43 parts of hydrophilic monomers (consisting of 43 parts of N-vinyl N-methylacetamide (VMA)), 54 parts of polymerizable siloxanes (consisting of 19.98 parts of FMM, 33.48 parts of M5A, and 0.54 parts of KF1622), and 1.7 parts of other reagents including thermal initiator (AIBN) and crosslinker (triallyl isocyanurate). The same base formulation was used in all examples.

[0228] The lenses prepared from the base formulation without the addition of the radiation absorber package were optically clear, meaning that the transmittance between 381 nm and 780 nm was at least 97% (measured according to ISO 18369).

[0229] Other suitable base formulations are described in EP 3 634 733 B1, for example, the contents of which are incorporated herein by reference, including the formulations listed in Examples 4 to 24.

[0230] Formulation including only UV13

[0231] The radiation absorber package of each of Examples 1 to 13 was added to the base formulation and cast molded into lenses of the size described above. The lenses of each of Examples 1 to 13 had an eye-acceptable surface wettability and a water content of 50 to 51 wt%.

[0232] The effect of adding different amounts of UV13 to the base formulation was explored in Comparative Examples 1 to 5, as shown in Table 1:

[0233] Table 1

[0234]

[0235] To achieve a blockage of 50% of the light with wavelengths between 380 nm and 455 nm, it is necessary to include a high content of UV13, i.e. greater than 2.5 wt%.

[0236] The yellowness index of the lenses prepared from the formulations of Comparative Examples 2 and 5 indicates that increasing the amount of UV13 in the formulation increases the yellowness of the lenses.

[0237] Formulation including only UV28

[0238] The effect of adding different amounts of UV28 to the base formulation was explored in Comparative Examples 6 and 7, as shown in Table 2:

[0239] Table 2

[0240]

[0241]

[0242] Incorporation of 0.5 wt% UV28 into the base formulation resulted in eyewear that blocked 37% of light in the range of 380 nm to 455 nm. While increasing the amount of UV28 incorporated into the base formulation to 0.90 wt% resulted in eyewear that blocked 51% of light in the range of 380 nm to 455 nm, it was found difficult to remove the eyewear from the mold and obtain an acceptable eyewear at this UV28 loading.

[0243] For comparison purposes, Comparative Example 8 incorporated the radiation absorber package of Example 2, Formulation IV of US2021 / 0181379 into an eyewear formulation having the base formulation described above. This resulted in eyewear that blocked only 35% of light in the range of 380 nm to 455 nm.

[0244] The yellowness index (YI) of the eyewear prepared from the formulations of Comparative Examples 6 and 7 indicates that increasing the amount of UV28 in the formulation increases the yellowness of the eyewear.

[0245] Formulation including a combination of UV13 and UV28

[0246] In Examples 9 to 13, radiation absorber packages including both UV13 and UV28 were added to the same base silicone hydrogel contact lens formulation and the formulations were cast into contact lenses of Table 3:

[0247] Table 3

[0248]

[0249] Example 9 shows that when UV13 is added to the formulation of Comparative Example 6 that already included UV28, the resulting formulation provides enhanced transmission blocking in the range of 380 nm to 455 nm. The eyewear formed from the formulation of Example 10 that included 1.08 wt% UV13 and 0.49 wt% UV28 blocked 50% of transmission in the range of 380 nm to 455 nm, i.e. provided the same level of HEVL blocking as Comparative Example 5, even though it included only 60% of the total amount of benzotriazole HEVL blocker, thus illustrating that the use of a combination of benzotriazole HEVL blockers enables a greater degree of blocking to be achieved at a lower total loading.

[0250] The formulation of Example 10 provides a good overall balance of properties, blocking 50% of HEVL in the range of 380 nm to 455 nm, while keeping the total amount of HEVL absorbers below 2 wt% of the total spectacle formulation. Increasing the amount of HEVL absorbers in Examples 11, 12, and 13 results in an increase in the amount of HEVL blocked by the spectacles of up to another 5%. However, the wettability (as indicated by the water contact angle of a sessile drop) of the spectacles cast from the formulations of Examples 11 to 13 is lower than the wettability of the spectacles cast from the formulations of Examples 9 and 10.

[0251] Changing UV absorbers

[0252] In Examples 14 to 17, a package of radiation absorbers including HEVL absorbers and either benzophenone UV absorber UV416 or benzotriazole UV absorber Norbloc was added to the same base silicone hydrogel contact lens formulation, and the formulations were cast into contact lenses of Table 4:

[0253] Table 4

[0254]

[0255] The lenses of the UV416-containing formulation of Example 14 exhibit Class 1 UV block and block 50% of transmission in the range of 380 nm to 455 nm. The formulation of Example 17 is the same as the formulation of Example 14, except that the UV absorber is changed from 0.3 parts by weight of UV416 to 0.3 parts by weight of Norbloc. The UV block of Example 17 is not as good as the UV block of Example 14, notably, the UVB block of Example 17 is >40% worse than the UVB block of Example 14. The poorer UV block of the compositions of the present invention containing benzotriazole UV absorbers (e.g., Norbloc) compared to the formulations of the present invention comprising a preferred benzophenone UV absorber (e.g., UV416) means that Class 1 UV block across the entire contact lens range (especially contact lenses with low center thicknesses) can not be consistently achieved at low loadings of benzotriazole UV absorbers. Thus, higher loadings of benzotriazole UV absorbers as in Examples 15 and 16 can be needed to achieve Class 1 UV block across the entire lens range. Conversely, in the lens formulations of the present invention comprising a combination of benzotriazole HEVL absorbers, lower amounts of benzophenone UV absorbers (e.g., UV416) can be needed compared to benzotriazole UV absorbers (e.g., Norbloc) to produce lenses with the desired light blocking properties.

[0256] Coloring of lenses

[0257] The effect of including different radiation absorber packages in polymerizable contact lens formulations was explored by placing contact lenses cast from the formulations on glass eyes with blue irises. It was found that the coloration imparted by contact lenses cast from the formulations of Comparative Example 1, Comparative Example 6, and Example 10 of the present invention produced a natural looking eye and was superior in appearance to commercially available Oasys MAX™ contact lenses containing a tricyclic HEVL absorber, which imparted a significant undesirable yellow / green halo at the edge of the iris and on the sclera of the glass eye. The YI of the Acuvue Oasys Max™ contact lenses was determined to be 6.95 and was thus significantly higher than the YI of Example 10 of the present invention.

[0258] The increased amount of UV28 in the formulations of Examples 11 and 12 compared to Examples 9 and 10 also resulted in a slight undesirable yellowing of the glass eye, which observation is consistent with the YI values reported in Table 3 above. Thus, it was found that contact lenses having a YI of less than 6.0, especially less than 5.0, impart a more natural appearance to the eye than contact lenses having a YI greater than 6.0.

[0259] Absorption spectrum

[0260] The optical absorption of solutions of Norbloc, UV416, UV13, and UV28 in ethyl acetate was determined over the range of 250 nm to 500 nm. Figure 1 The absorption spectra of each compound are shown in Table 3. The solutions were all 0.003 wt% solutions prepared in >99.8%, HPLC grade ethyl acetate, and the absorbance of the solutions was measured from 250 nm to 800 nm using a Perkin Elmer Lambda 365 spectrometer.

[0261] The optical absorption of solutions of UV1, UV5 (UVAM), UV13, UV15, and UV28 in ethyl acetate was determined over the range of 380 nm to 460 nm. Figure 2 The absorption spectra of each compound are shown in Table 3. The solutions were all 0.003 wt% solutions prepared in >99.8%, HPLC grade ethyl acetate, and the absorbance of the solutions was measured from 250 nm to 800 nm using a Perkin Elmer Lambda 365 spectrometer.

[0262] Without wishing to be bound by any theory, it is hypothesized that the use of two different high-energy, short-wavelength visible light absorbers each comprising a benzotriazole moiety can more effectively absorb light in the range of 350 nm to 420 nm due to differences in the absorption maxima of the different compounds. The peak absorbance of a solution of UV13 in ethyl acetate was found to be 359 nm in the range of 350 nm to 455 nm, and the peak absorbance of a UV28 solution was found to be 369 nm in the range of 350 nm to 455 nm. UV13 was found to be more effective at absorbing light in the range of 340 nm to 375 nm, while UV28 was found to be more effective at absorbing light in the range of 380 nm to 440 nm.

[0263] It is also hypothesized that the use of a benzophenone UV absorber in combination with two different HEVL absorbers each comprising a benzotriazole moiety can be more effective at providing light blockage across the range of 260 nm to 440 nm than a combination comprising a benzotriazole UV absorber due to the significant difference in absorption between benzophenone and benzotriazole compounds. From Figure 1 As can be seen, there is significant overlap between the absorption spectra of the benzotriazole UV absorber Norbloc and the benzotriazole HEVL absorbers UV13 and UV28, while the absorption spectrum of the benzophenone UV absorber UV416 is complementary to the absorption spectra of UV13 and UV28, providing enhanced absorbance across a wider range of wavelengths.

[0264] The disclosure herein refers to certain illustrated examples, and it is understood that these examples are presented by way of example and not by way of limitation. Although exemplary examples are discussed, it is to be understood that the foregoing detailed description is to be considered an illustration of the example described herein and is not a limitation.

[0265] The present invention includes the following aspects / embodiments / features in any order and / or any combination:

[0266] 1. A hydrogel contact lens formulation for forming a polymeric body of a hydrogel contact lens, comprising:

[0267] a first high-energy visible light (HEVL) absorber comprising a benzotriazole moiety,

[0268] a second different high-energy visible light (HEVL) absorber comprising a benzotriazole moiety.

[0269] 2. The formulation of 1, further comprising a polymerizable UV absorber comprising a benzophenone moiety.

[0270] 3. The formulation of 1 or 2, wherein the highest wavelength at which a 0.1 absorbance of a 0.003 wt% solution of the second HEVL absorber in ethyl acetate has at least 10 nm less than the highest wavelength at which a 0.1 absorbance of a 0.003 wt% solution of the first HEVL absorber in ethyl acetate has.

[0271] 4. The formulation of any one of 1 to 3, wherein:

[0272] a. the first HEVL absorber is characterized in that a tangent to the point on the curve bounded by the highest wavelength at which an absorbance of 0.5 passes through the 0.0 absorbance axis on the absorbance spectrum of a 0.003 wt% solution of the first HEVL absorber in ethyl acetate is between 412 nm and 440 nm, preferably between 415 nm and 435 nm, especially between 415 nm and 430 nm; and the second HEVL absorber is characterized in that a tangent to the point on the curve bounded by the highest wavelength at which an absorbance of 0.5 passes through the 0.0 absorbance axis on the absorbance spectrum of a 0.003 wt% solution of the second HEVL absorber in ethyl acetate at a wavelength shorter than the wavelength at which the tangent to the point on the curve bounded by the highest wavelength at which an absorbance of 0.5 passes through the 0.0 absorbance axis on the absorbance spectrum of a 0.003 wt% solution of the first HEVL absorber in ethyl acetate (e.g., a wavelength at least 5 nm shorter, especially at least 10 nm shorter);

[0273] and / or

[0274] b. the second HEVL absorber is characterized in that a tangent to the point on the curve bounded by the highest wavelength at which an absorbance of 0.5 passes through the 0.0 absorbance axis on the absorbance spectrum of a 0.003 wt% solution of the first HEVL absorber in ethyl acetate is between 385 nm and 415 nm, preferably between 390 nm and 412 nm; and the second HEVL absorber is characterized in that a tangent to the point on the curve bounded by the highest wavelength at which an absorbance of 0.5 passes through the 0.0 absorbance axis on the absorbance spectrum of a 0.003 wt% solution of the second HEVL absorber in ethyl acetate at a wavelength shorter than the highest wavelength at which an absorbance of 0.5 on the absorbance spectrum of a 0.003 wt% solution of the first HEVL absorber in ethyl acetate (e.g., a wavelength at least 5 nm shorter, especially at least 8 nm shorter);

[0275] and / or

[0276] c. the first HEVL absorber is characterized by a highest wavelength of absorbance of 0.1 on an absorbance spectrum of a 0.003 wt% solution of the first HEVL absorber in ethyl acetate between 412 nm and 440 nm, preferably between 415 nm and 435 nm, in particular between 415 nm and 430 nm; and the second HEVL absorber is characterized by a highest wavelength of absorbance of 0.1 on an absorbance spectrum of a 0.003 wt% solution of the second HEVL absorber in ethyl acetate between 385 nm and 412 nm, preferably between 390 nm and 410 nm;

[0277] and / or

[0278] d. the 0.003 wt% solution of the first HEVL absorber in ethyl acetate has an absorbance peak in the range of 360 nm to 410 nm, and the 0.003 wt% solution of the second HEVL absorber in ethyl acetate has an absorbance peak at a wavelength at least 5 nm shorter (e.g., between 5 nm and 25 nm shorter, in particular between 5 nm and 15 nm shorter) than the absorbance peak of the 0.003 wt% solution of the first HEVL absorber in ethyl acetate that falls in the range of 360 nm to 410 nm;

[0279] and / or

[0280] e. the 0.003 wt% solution of the first HEVL absorber in ethyl acetate has an optical absorbance at a 400 nm wavelength of at least 0.35, and / or an optical absorbance at a 390 nm wavelength of at least 0.55; and the 0.003 wt% solution of the second HEVL absorber in ethyl acetate has an optical absorbance at a 400 nm wavelength of less than 0.30, and / or an optical absorbance at a 390 nm wavelength of less than 0.55.

[0281] 5. The formulation of any one of 1 to 4, wherein the first HEVL absorber and the second HEVL absorber each have the formula (1):

[0282]

[0283] wherein:

[0284] R 1 halogen, OH, C 1-12 alkoxy, -A-R 9 -Y, optionally substituted C 1-12 alkyl, optionally substituted phenoxy, or optionally substituted naphthoxy, wherein optional substituents are halogen, C 1-6 alkyl, C 1-6 alkyl, C nH, -(CH2CH2O) n CH2CH3, -(CH2CH(CH3)O) n H or -(CH2CH(CH3)O) n CH2CH2(CH3);

[0285] R 6 and R 7 one of which is H or C 1-12 alkyl optionally substituted with halo; and

[0286] R 6 and R 7 the other of which is:

[0287] or -OR 8 wherein:

[0288] R 2 is a bond, C 1-12 alkylene optionally substituted with -OH and / or interrupted with an ester group, (CH2CH2O) n or (CH2CH(CH3)O) n ;

[0289] R 3 is a bond, C(O), C(O)C j H 2j , C 1-6 alkylene, phenyl, or C 1-6 alkylphenyl;

[0290] X is a bond, O, NR 4 , S, or (Si(CH3)2O) m Si(CH3)2;

[0291] each R 4 is independently H or methyl;

[0292] R 5 is H, C 1-6 alkyl, or phenyl;

[0293] m is 0 to 9;

[0294] n is 2 to 10;

[0295] j is 1 to 6;

[0296] A is -S- or -SO2-;

[0297] R 8 is H, C 1-12 alkyl, C 6-15 aralkyl, or -R 9 -Z;

[0298] each R 9 independently C 1-12 alkylene;

[0299] each of Y and Z is independently -OH, -OC(O)R 10 , -NH2, -NC(O)R 10 , -NCO, -CO2H, -CO2R 10 ,

[0300]

[0301] each R 10 independently C 1-10 alkyl or C 3-10 alkenyl;

[0302] R 11 is C 3-10 cycloalkenylene; and

[0303] R 12 is C 1-10 alkylene or 1,2-phenylene.

[0304] 6. The formulation according to 5, wherein the total amount of HEVL absorber of formula (1) present is not more than 2.7% (wt / wt), preferably not more than 2.0% (wt / wt).

[0305] 7. The formulation according to any one of 1 to 6, wherein the first HEVL absorber is 2-[2'-hydroxy-3'-tert-butyl-5'-(3"-methacryloyloxypropoxy)phenyl]-5-chloro-2H- benzotriazole (UV28).

[0306] 8. The formulation according to any one of 1 to 7, wherein the second HEVL absorber is selected from the group consisting of 2-(1,1-dimethylethyl)-4-[3-[(4- vinylphenyl)methoxy]propoxy]-6-(5-methoxy-2H-benzotriazol-2-yl)-phenol (UV1), 2-(5-chloro-2H-benzotriazol-2-yl)-6-(1,1-dimethylethyl)-4-vinyl-phenol (UV5 / UVAM), 2-[2'-hydroxy-3'-tert-butyl-5'-(3"-methacryloyloxypropoxy)phenyl]-5-methoxy-2H- benzotriazole (UV13), 2-3'-tert-butyl-2'-hydroxy-5'-(3"-dimethylethylvinylsilylpropoxy)-2'- hydroxy-phenyl)-5-methoxybenzotriazole (UV15), in particular 2-[2'-hydroxy-3'-tert-butyl- 5'-(3"-methacryloyloxypropoxy)phenyl]-5-methoxy-2H-benzotriazole (UV13).

[0307] 9. The formulation of any one of 1 to 8, wherein the first HEVL absorber is present in an amount of 0.3% to 0.9% (wt / wt), preferably 0.4% to 0.7% (wt / wt); and the second HEVL absorber is present in an amount of 0.5% to 2.2% (wt / wt), preferably 0.7% to 1.6% (wt / wt).

[0308] 10. The formulation of any one of 1 to 9, comprising a polymerizable UV absorber comprising a benzophenone moiety in an amount of no more than 1.5% (wt / wt), preferably no more than 1.0% (wt / wt).

[0309] 11. The formulation of any one of 1 to 10, wherein the polymerizable UV absorber is 2-(4-benzoyl-3-hydroxyphenoxy)ethyl acrylate (UV416).

[0310] 12. The formulation of any one of 1 to 11, further comprising a polymerizable blue or blue-green colorant comprising an anthraquinone moiety.

[0311] 13. The formulation of 12, wherein the polymerizable blue or blue-green colorant is selected from 1,4-bis[4-(2-methacryloyloxyethyl)phenylamino]-9,10-anthraquinone (RB246) or 1,4-bis[(2-methacryloyloxyethyl)amino]-9,10-anthraquinone (RB247).

[0312] 14. The formulation of any one of 1 to 13, which is a thermal curing formulation comprising at least one thermal initiator.

[0313] 15. The formulation of any one of 1 to 14, further comprising at least one hydrophilic monomer, optionally in an amount of at least 25% (wt / wt).

[0314] 16. The formulation of 15, comprising at least one hydrophilic N-vinyl amide monomer, optionally in an amount of at least 15% (wt / wt).

[0315] 17. The formulation of 16, comprising one or more hydrophilic N-vinyl amide monomers in an amount of at least 30% (wt / wt).

[0316] 18. The formulation of any one of 1 to 17, wherein the formulation is a silicone hydrogel contact lens formulation comprising a polymerizable siloxane component, optionally in an amount of at least 25% (wt / wt).

[0317] 19. The formulation of 18, comprising 30% to 60% (wt / wt) of a polymerizable siloxane component.

[0318] 20. The formulation of 18 or 19, wherein at least 40% (wt / wt) of the polymerizable siloxane content is a difunctional siloxane having a molecular weight of at least 8,000 Daltons, and wherein at least 25% (wt / wt) of the polymerizable siloxane content is a monofunctional siloxane having a molecular weight of less than 3,000 Daltons.

[0319] 21. The formulation of any one of 18 to 20, comprising:

[0320] a siloxane component present in an amount of at least 35% (wt / wt) based on the total weight of the formulation, wherein at least 40% of the siloxane content is a difunctional siloxane having a molecular weight of at least 8,000 Daltons; and

[0321] an N-vinylamide monomer component present in an amount of at least 37% (wt / wt) based on the total weight of the formulation.

[0322] 22. The formulation of any one of 1 to 21, comprising at least 5% (wt / wt) of a non-siloxane hydrophobic monomer, especially a hydrophobic methacrylate monomer, based on the total weight of the formulation.

[0323] 23. The formulation of 22, wherein the hydrophobic monomer comprises hydroxybutyl methacrylate, isobornyl methacrylate, or a combination of hydroxybutyl methacrylate and isobornyl methacrylate.

[0324] 24. The formulation of any one of 1 to 14, comprising:

[0325] a. one or more hydrophilic N-vinylamide monomers in an amount of at least 30% (wt / wt),

[0326] b. a polymerizable siloxane component in an amount of 35% to 60% (wt / wt) of the total formulation, wherein at least 40% (wt / wt) of the polymerizable siloxane content is a difunctional siloxane having a molecular weight of at least 8,000 Daltons, and wherein at least 25% (wt / wt) of the polymerizable siloxane content is a monofunctional siloxane having a molecular weight of less than 3,000 Daltons, and

[0327] c. a non-siloxane hydrophobic methacrylate monomer in an amount of at least 5% (wt / wt) based on the total weight of the formulation.

[0328] 25. The formulation of any one of 1 to 14, comprising:

[0329] a. N-methyl N-vinylacetamide in an amount of 30% to 50% (wt / wt) of the total formulation,

[0330] b. a difunctional (meth)acrylate-containing siloxane having a molecular weight of at least 8,000 Daltons in an amount of 20% to 40% (wt / wt) of the total formulation,

[0331] c. a monofunctional (meth)acrylate-containing siloxane having a molecular weight of less than 3,000 Daltons in an amount of 10% to 30% (wt / wt) of the total formulation,

[0332] d. hydroxybutyl methacrylate, isobornyl methacrylate, or a combination of hydroxybutyl methacrylate and isobornyl methacrylate in an amount of 5% to 15% (wt / wt) of the total formulation.

[0333] 26. The formulation of 24 or 25, wherein the difunctional siloxane monomer is a (meth)acrylate-containing siloxane monomer represented by formula (III),

[0334]

[0335] wherein R1is selected from hydrogen or methyl; R2is selected from hydrogen or C 1-4 hydrocarbyl; m represents an integer from 0 to 10; n represents an integer from 4 to about 15, 25, or 100; a and b represent integers of 1 or greater; a + b equals 20 to 500; b / (a + b) equals 0.01 to 0.22; and the configuration of siloxane units comprises a random configuration.

[0336] 27. The formulation of any one of 24 to 26, wherein the monofunctional siloxane monomer is a methacrylate-containing siloxane monomer represented by formula (II),

[0337]

[0338] wherein n is an integer from about 10 to 15.

[0339] 28. A hydrogel contact lens obtained from polymerization of the formulation of any one of 1 to 27.

[0340] 29. The contact lens of 28 having the following light transmission properties:

[0341]

[0342] 30. The contact lens of 28 or 29 having a Yellowness Index determined using the method of ASTM E313-05 of less than 6.0.

[0343] The entire contents of all cited references mentioned in the disclosure are incorporated herein by reference to the extent that they provide exemplary procedural or other details consistent with or supplementary to the present disclosure, to the extent that they are not inconsistent with the present disclosure, and to the extent that the present disclosure is not otherwise deficient.

[0344] Other embodiments of the application will be apparent to those skilled in the art from consideration of the specification and practice of the application disclosed herein. It is intended that the specification and examples be considered as exemplary only, with the true scope and spirit of the application being indicated by the following claims and equivalents thereof.

Claims

1. A hydrogel contact lens formulation for forming a polymeric body of a hydrogel contact lens, comprising: A first high-energy visible light absorber comprising a benzotriazole moiety, namely, a first HEVL absorber, wherein a 0.003 wt% ethyl acetate solution of the first HEVL absorber has an absorbance peak in the range of 360 nm to 410 nm. and A second, distinct high-energy visible light absorber comprising a benzotriazole moiety, namely, a second HEVL absorber, wherein a 0.003 wt% ethyl acetate solution of the second HEVL absorber has a peak absorbance at a wavelength between 5 nm and 25 nm shorter than the peak absorbance of a 0.003 wt% ethyl acetate solution of the first HEVL absorber, which falls in the range of 360 nm to 410 nm. The first HEVL absorbent and the second HEVL absorbent each have formula (1): in: R 1 Halogen, OH, C 1-12 Alkoxy, -AR 9 -Y, C which can be arbitrarily replaced 1-12 Alkyl, optionally substituted phenoxy, or optionally substituted naphthoxy, wherein the optional substituent is halogen, C 1-6 Alkyl, C 1-6 Alkyl group, OH group, -(CH2CH2O) n H、-(CH2CH2O) n CH2CH3、-(CH2CH(CH3)O) n H or -(CH2CH(CH3)O) n CH2CH2(CH3); R 6 and R 7 One of them is H or C that is optionally substituted with halogen. 1-12 Alkyl; and R 6 and R 7 The other one is: or -OR 8 ,in: R 2 C bonds that are optionally substituted with -OH and / or heteroester groups 1-12 Alkylene, (CH2CH2O) n Or (CH2CH(CH3)O) n ; R 3 For bond, C(O), C(O)C j H 2j C 1-6 alkylene, phenyl or C 1-6 Alkylphenyl; X represents bond, O, NR 4 S or (Si(CH3)2O) m Si(CH3)2; Each R 4 Independently, it is either H or methyl; R 5 For H, C 1-6 Alkyl or phenyl; m is between 0 and 9; n is between 2 and 10; j is 1 to 6; A is -S- or -SO2-; R 8 For H, C 1-12 Alkyl, C 6-15 Aryl or -R 9 -Z; Each R 9 Independently, C is optionally substituted with -OH and / or heteroester. 1-12 Alkylene; Each of Y and Z represents -OH and -OC(O)R, respectively. 10 -NH2, -NC(O)R 10 -NCO, -CO2H, -CO2R 10 , Each R 10 Independently for C 1-10 Alkyl or C 3-10 alkenyl; R 11 C 3-10 cyclohexene group; and R 12 C 1-10 Alkylene or 1,2-phenylene.

2. The formulation according to claim 1, wherein the total amount of HEVL absorbent of formula (1) present does not exceed 2.7% wt / wt.

3. The formulation according to claim 1, wherein the total amount of HEVL absorbent of formula (1) present does not exceed 2.0% wt / wt.

4. The formulation according to any one of claims 1 to 3, wherein: The first HEVL absorbent is 2-[2'-hydroxy-3'-tert-butyl-5'-(3"-methacryloyloxypropoxy)phenyl]-5-chloro-2H-benzotriazole (UV28).

5. The formulation according to any one of claims 1 to 3, wherein the second HEVL absorbent is selected from: 2-(1,1-dimethylethyl)-4-[3-[(4-vinylphenyl)methoxy]propoxy]-6-(5-methoxy-2H-benzotriazole-2-yl)-phenol (UV1), 2-(5-chloro-2H-benzotriazole-2-yl)-6-(1,1-dimethylethyl)-4-vinyl-phenol (UV5 / UVAM), 2-[2'-hydroxy-3'-tert-butyl-5'-(3"-methacryloyloxypropoxy)phenyl]-5-methoxy-2H-benzotriazole (UV13), 2-3'-tert-butyl-2'-hydroxy-5'-(3"-dimethylvinylsilylpropoxy)-2'-hydroxy-phenyl)-5-methoxybenzotriazole (UV15).

6. The formulation according to any one of claims 1 to 3, wherein the first HEVL absorbent is present in an amount of 0.3% to 0.9% wt / wt; and the second HEVL absorbent is present in an amount of 0.5% to 2.2% wt / wt.

7. The formulation according to claim 6, wherein the first HEVL absorbent is present in an amount of 0.4% to 0.7% wt / wt.

8. The formulation according to any one of claims 1 to 3, wherein the second HEVL absorbent is present in an amount of 0.7% to 1.6% wt / wt.

9. The formulation according to any one of claims 1 to 3, comprising a polymerizable UV absorber containing a benzophenone moiety in an amount not exceeding 1.5% wt / wt.

10. The formulation according to claim 9, wherein the polymerizable UV absorber comprising the benzophenone portion is present in an amount not exceeding 1.0% wt / wt.

11. The formulation according to claim 9, wherein the polymerizable UV absorber is 2-(4-benzoyl-3-hydroxyphenoxy)ethyl acrylate (UV416).

12. The formulation according to any one of claims 1 to 3, further comprising a polymerizable blue or blue-green colorant containing an anthraquinone moiety.

13. The formulation according to claim 12, wherein the polymerizable blue or blue-green colorant is selected from 1,4-bis[4-(2-methacryloyloxyethyl)phenylamino]-9,10-anthraquinone (RB246) or 1,4-bis[(2-methacryloyloxyethyl)amino]-9,10-anthraquinone (RB247).

14. The formulation according to any one of claims 1 to 3, wherein it is a thermosetting formulation comprising at least one thermal initiator.

15. The formulation according to any one of claims 1 to 3, further comprising at least one hydrophilic monomer.

16. The formulation according to claim 15, wherein the at least one hydrophilic monomer is present in an amount of at least 25% wt / wt.

17. The formulation according to claim 15, comprising at least one hydrophilic N-vinylamide monomer.

18. The formulation according to claim 17, wherein the at least one hydrophilic N-vinylamide monomer is present in an amount of at least 15% wt / wt.

19. The formulation according to claim 17, comprising one or more hydrophilic N-vinylamide monomers at least 30% wt / wt.

20. The formulation according to any one of claims 1 to 3, wherein the formulation is a silicone hydrogel contact lens formulation comprising a polymerizable siloxane component.

21. The formulation according to claim 20, wherein the polymerizable siloxane component is present in an amount of at least 25% wt / wt.

22. The formulation according to claim 20, comprising 30% to 60% wt / wt of a polymerizable siloxane component.

23. The formulation of claim 20, wherein at least 40% wt / wt of the polymerizable siloxane component is a bifunctional siloxane with a molecular weight of at least 8,000 Daltons, and wherein at least 25% wt / wt of the polymerizable siloxane component is a monofunctional siloxane with a molecular weight of less than 3,000 Daltons.

24. The formulation according to claim 20, comprising: A siloxane component present in an amount of at least 35% wt / wt based on the total weight of the formulation, wherein at least 40% wt / wt of the siloxane component is a bifunctional siloxane with a molecular weight of at least 8,000 Daltons; and The N-vinylamide monomer component is present in an amount of at least 37% wt / wt based on the total weight of the formulation.

25. The formulation according to any one of claims 1 to 3, comprising at least 5% wt / wt of a nonsiloxane hydrophobic monomer based on the total weight of the formulation.

26. The formulation according to claim 25, wherein the non-siloxane hydrophobic monomer is a hydrophobic methacrylate monomer.

27. The formulation according to claim 25, wherein the hydrophobic monomer comprises hydroxybutyl methacrylate, isoborneol methacrylate, or a combination of hydroxybutyl methacrylate and isoborneol methacrylate.

28. The formulation according to any one of claims 1 to 3, comprising: a. One or more hydrophilic N-vinylamide monomers in an amount of at least 30% wt / wt. b. A polymerizable siloxane component comprising 35% to 60% wt / wt of the total weight of the formulation, wherein at least 40% wt / wt of the polymerizable siloxane component is a bifunctional siloxane with a molecular weight of at least 8,000 Daltons, and wherein at least 25% wt / wt of the polymerizable siloxane component is a monofunctional siloxane with a molecular weight of less than 3,000 Daltons. c. A nonsiloxane hydrophobic methacrylate monomer in an amount of at least 5% wt / wt based on the total weight of the formulation.

29. The formulation according to any one of claims 1 to 3, comprising: a. N-methyl-N-vinylacetamide in an amount of 30% to 50% wt / wt of the total weight of the formulation, b. A bifunctional (meth)acrylate-containing siloxane with a molecular weight of at least 8,000 Daltons, comprising 20% ​​to 40% wt / wt of the total weight of the formulation. c. A monofunctional (meth)acrylate-containing siloxane with a molecular weight of less than 3,000 Daltons, comprising 10% to 30% wt / wt of the total weight of the formulation. d. A 5% to 15% wt / wt amount of hydroxybutyl methacrylate, isoborneol methacrylate, or a combination of hydroxybutyl methacrylate and isoborneol methacrylate, in the total weight of the formulation.

30. The formulation according to claim 28, wherein the bifunctional siloxane is a (meth)acrylate-containing siloxane monomer represented by formula (III), In formula (III), R1 is selected from hydrogen or methyl; R2 is selected from hydrogen or C 1-4 Hydrocarbon group; m represents an integer from 0 to 10; n represents an integer from 4 to 100; a and b represent integers of 1 or greater; a+b equals 20 to 500; b / (a+b) is equal to 0.01 to 0.22; and the configuration of the siloxane unit includes random configuration.

31. The formulation according to claim 30, where n represents an integer from 4 to 25.

32. The formulation according to claim 31, where n represents an integer from 4 to 15.

33. The formulation according to claim 28, wherein the monofunctional siloxane is a methacrylate-containing siloxane monomer represented by formula (II). In equation (II), n is an integer from 10 to 15.

34. A hydrogel contact lens obtained from the polymerization of a formulation according to any one of claims 1 to 33.

35. The contact lens according to claim 34, having the following light transmission characteristics: and The range of the transmission characteristics mentioned therein was determined by measurements of UV and visible light in air.

36. The contact lens according to claim 34 or claim 35, having a yellowness index of less than 6.0 as determined by the ASTM E313-05 method.

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