Radiation blockers for contact lenses

Abstract

A hydrogel contact lens formulation for forming a polymeric bulk of a hydrogel contact lens, comprising: a first high energy visible light (HEVL) absorbent comprising a benzotriazole moiety, and a second, different high energy visible light (HEVL) absorbent 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 blocking agents for use in contact lenses and contact lenses comprising the compositions of radiation blocking agents. In particular, the present invention relates to compositions of radiation blocking agents that have been found to impart advantageous properties to hydrogel contact lenses including advantageous light transmission properties. Background Art

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

[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 components of polymeric materials used to make eyeglasses (including contact lenses). UV absorbers are typically compounds that include chromophores that absorb light in the UV spectrum (i.e., 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 eyeglasses also block blue light. Yellow dyes including polymerizable yellow dyes have been added to contact lenses to absorb harmful blue light radiation, such as described in US 5,470,932. These lenses block both UV and HEVL by using two chromophores (UV absorbers and yellow dyes). Many yellow dyes absorb blue light over a wide wavelength range and reduce the transmission of blue light across the range of 380 nm to 500 nm.

[0004] If a sharper cutoff of the transmission spectrum in the high-energy blue-violet region is required, a selective blue light blocker can be used, as described in US2005 / 0243272 and WO 2008 / 048880. Such blue light blockers selectively filter wavelengths in the range of 380nm to 455nm, often absorbing little or no wavelengths above 450nm. Benzotriazole blue light blockers that selectively absorb light in the range of 380nm to 455nm have been developed. However, it has been found that a large amount of known benzotriazole blue light blockers may be required to substantially reduce the transmission level of light in the range of 380nm to 455nm, and / or the known benzotriazole blue light blockers may cause undesirable yellowing of the resulting contact lenses. Including a large amount of benzotriazole blue light blockers in contact lens formulations, such as 2% or more by weight of the entire lens composition, can adversely affect the properties of contact lens materials and / or hinder the processing of contact lens formulations. For example, including high levels of radiation absorbing compounds in hydrogel contact lens formulations can reduce the wettability of the resulting hydrogel contact lenses, leading to a higher incidence of lens defects, and / or hindering the release of the hydrogel lens body from the mold after casting. Including blue light blockers in lens formulations, especially in high amounts, can also result in imparting a yellow tint to the lens. Imparting a yellow tint to a contact lens gives the wearer's eye an undesirable yellow tint that is less acceptable to consumers than a lens that leaves the eye's natural tint 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 contact lenses.

[0006] It is also known to include tinting agents in contact lenses to change the tint of the contact lens for aesthetic purposes or to make the lens more visible when in solution. While tinting agents can be used to counteract the yellowing effects of blue light blockers, there is a need for a radiation absorber package for use in formulating hydrogel contact lenses, particularly silicone hydrogel contact lenses, that can substantially reduce the amount of transmission of harmful wavelengths of light when included in a lens formulation in low amounts (e.g., 3% by weight or less). Ideally, hydrogel contact lenses produced using such formulations would also be non-yellowing. Summary of the invention

[0007] In a first aspect, the present invention provides a radiation absorber package for use in formulating hydrogel contact lenses, 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 containing a benzophenone moiety.

[0008] In a second aspect, the present invention provides a hydrogel contact lens formulation, particularly 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 containing a benzophenone moiety. In addition to the radiation absorbing compound, 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, particularly 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 containing a benzophenone moiety.

[0010] In a fourth aspect, the present invention provides a method of making a hydrogel contact lens, particularly a silicone hydrogel contact lens, comprising the step of polymerizing the formulation of the second aspect of the present invention to form a polymerized contact lens body. Thus, the method of making the hydrogel contact lens of the fourth aspect of the present invention comprises the step of polymerizing a 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 to form a polymerized contact lens body. The formulation polymerized in the method of the fourth aspect of the present invention optionally further comprises a polymerizable UV absorber containing a benzophenone moiety.

[0011] It has been discovered 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 contact lenses having improved properties compared to contact lenses that can be produced using a single type of benzotriazole HEVL light absorber. In particular, it has been discovered that contact lenses produced from formulations containing a combination of two different benzotriazole HEVL absorbers provide a desired reduction in the level of light transmitted by the contact lens in the range of 380 nm to 455 nm when a lower total amount of the benzotriazole high energy short wavelength visible light absorber is included in the formulation. Additionally, it has been discovered that contact lenses produced from formulations containing a combination of two different benzotriazole high energy short wavelength visible light absorbers of the present invention provide a desired reduction in the level of light transmitted by the contact lens in the range of 380 nm to 455 nm without substantial yellowing of the bulk of the contact lens. In particular, it has been found that the formulations of the present invention provide hydrogel contact lenses that block 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 blockers. Advantageously, a 0.003 wt % solution of the second HEVL absorber in ethyl acetate (≥99.8%, HPLC grade) has a highest wavelength of absorbance at 0.1 that is at least 10 nm lower than a 0.003 wt % solution of the first HEVL absorber in ethyl acetate having a highest wavelength of absorbance at 0.1, 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 THE DRAWINGS

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

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

[0014] When referring to the following detailed description of the embodiments of the present disclosure, the present disclosure will be more fully understood and other advantages will become apparent. The present invention will be described in further detail with particular reference to the formulation of the second aspect of the present invention, i.e., the formulation used in the method of the fourth aspect of the present invention (hereinafter referred to as "the formulation of the present invention"). However, it should be understood that since the contact lens of the third aspect of the present invention can be obtained by polymerizing the formulation of the second aspect of the present invention, for example, according to the method of the fourth aspect of the present invention, the ingredients of the formulation of the second aspect of the present invention will be present in the polymerized lens material of the contact lens of the third aspect of the present invention in a polymerized form. Similarly, it should be understood that the radiation absorber package of the first aspect of the present invention is a component of the formulation of the second aspect of the present invention, and the component includes a chromophore that absorbs light across the UV and visible light spectrum. Unless a specific combination of features is mutually exclusive, or otherwise indicated by the context, the features of the radiation absorber package, formulation or glasses, or components thereof, or methods of making glasses (depending on the context) mentioned herein can be combined with any combination of features previously described or subsequently described. In addition, as used in this specification, the singular forms "a," "an," and "the" include plural references (e.g., at least one or more) unless the context clearly dictates otherwise. Thus, for example, reference to "a contact lens" includes a single lens as well as two or more of the same 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 for producing a contact lens, it is possible to more effectively provide a contact lens having blue light blocking properties that prevents transmission of a large amount of HEVL. This combination balances the undesirable yellow coloration of the lens having blue light blocking properties by including a second HEVL absorber that absorbs at a shorter wavelength than the first HEVL absorber. This combination also absorbs a greater proportion of light spanning wavelengths from 380 nm to 455 nm than can be obtained using a single benzotriazole HEVL absorber. Optionally, a third radiation absorbing compound that is a benzophenone UV absorber is included to enhance the absorbance 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 "polymerized contact lens material" of the contact lens of the third aspect of the invention refers to materials that are bonded into the contact lens bulk, whether by covalent bonds, physical entanglements, or otherwise. Materials that can be removed from the lens bulk by extraction with water, ethanol, isopropanol, or mixtures thereof do not constitute part of the polymerized contact lens material, nor do they constitute solvents, such as water, that can be removed from the contact lens bulk by drying. The polymerizable ingredients of the formulation of the second aspect of the invention are typically incorporated into the polymerized contact lens material of the third aspect of the invention.

[0017] The term "radiation absorber package" refers collectively 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, particularly in the range of 350 nm to 400 nm. The term "high energy visible light (HEVL) absorber" as used herein may be defined as a compound having an absorbance of at least 0.5 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 from 250 nm to 800 nm is measured using a PerkinElmer Lambda 365). HEVL absorbers may additionally absorb light of shorter wavelengths (e.g., in the range of 250 nm to 350 nm), and thus act as both HEVL absorbers and UV absorbers, as discussed below. Unless otherwise stated, all absorbance spectra mentioned herein were measured using a PerkinElmer Lambda 365 spectrometer in a 10 mm path length quartz cell as 0.003 wt % solutions in ≥ 99.8 % HPLC grade ethyl acetate.

[0019] Advantageously, the HEVL absorber used in contact lens formulations, including the contact lens formulations of the present invention, has a polymerizable portion in its 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 absorber used in the present invention is generally soluble in the contact lens formulation and is polymerizable so that it forms part of the polymeric matrix of the lens and is retained in the lens during autoclaving and storage.

[0020] References herein to the amount of ingredients or components present in a formulation expressed as a weight percent (i.e., % (wt / wt)) are based on the amounts of all formulation ingredients excluding diluents and / or solvents that are not incorporated into the final polymerized contact lens material. Thus, for example, the amount of radiation absorber package in a formulation made by mixing together 1.5 parts of radiation absorber package, one or more 65 parts of monomer, 3.5 parts of other active ingredients (e.g., polymerization initiator, colorant, deoxidizer, etc.), and 30 parts of organic solvent and / or water (100 parts total) is 2.1% (wt / wt). As used herein, the "components" of a formulation collectively refer to all ingredients of a particular type. For example, if a formulation comprises 20% (wt / wt) of a first siloxane monomer and 15% of a second siloxane monomer and no other siloxanes, the formulation may be described as comprising 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 does not exceed 2.7% (wt / wt), and preferably does not exceed 2.0% (wt / wt). Advantageously, the total amount of all HEVL absorbers present in the formulation of the second aspect or the fourth aspect of the invention does not exceed 2.7% (wt / wt), and preferably does not exceed 2.0% (wt / wt). Alternatively or in addition, the total amount of benzotriazole compounds present in the formulation of the second aspect or the fourth aspect of the invention optionally does not exceed 2.7% (wt / wt), and preferably does not exceed 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 does not exceed 2.7% (wt / wt), and preferably does not exceed 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 does not exceed 2.7% (wt / wt), and preferably does not exceed 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 optionally does not exceed 2.7% (wt / wt), and preferably does not exceed 2.0% (wt / wt) of the total polymeric lens material.

[0022] The first HEVL absorbent may 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 may 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 may 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 may 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 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 (1):

[0024]

[0025] in:

[0026] ●R 1 Halogen, OH, C 1-12 Alkoxy, -AR 9 -Y, optionally substituted C 1-12 alkyl, optionally substituted phenoxy or optionally substituted naphthoxy, wherein the optional substituent is 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);

[0027] ●R 6 and R 7 One of them is H or C optionally substituted by halogen 1-12 alkyl; and

[0028] ●R 6 and R 7 The other one is:

[0029] OR 8 ;

[0030] in:

[0031] ○R 2 is a bond, optionally substituted by -OH and / or optionally mixed with an ester group1-12 Alkylene, (CH2CH2O) n or (CH2CH(CH3)O) n ;

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

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

[0034] ○Each R 4 are independently H or methyl;

[0035] ○R 5 H, C 1-6 Alkyl or phenyl;

[0036] ○m is 0 to 9;

[0037] ○n is 2 to 10;

[0038] ○j is 1 to 6;

[0039] ○A is -S- or -SO2-;

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

[0041] ○Each R 9 is independently C optionally substituted by -OH and / or impregnated with an ester group 1-12 Alkylene;

[0042] ○ Each of Y and Z is -OH, -OC(O)R 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] ○R 12 C 1-10 Alkylene or 1,2-phenylene.

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

[0048] ●R 1 Halogen, OH, C 1-12 Alkoxy, optionally substituted C 1-12 alkyl, optionally substituted phenoxy or optionally substituted naphthoxy, wherein the optional substituent is 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] ●R 6 and R 7 One of them is H or C optionally substituted by halogen 1-12 alkyl; and

[0050] ●R 6 and R 7 The other one is:

[0051]

[0052] in:

[0053] ○R 2 C is a bond, optionally substituted by -OH and / or mixed with an ester group 1-12 Alkylene, (CH2CH2O) n or (CH2CH(CH3)O) n ;

[0054] ○R 3 is a bond, C(O), C(O)C j H 2j , C 1-6 Alkylene, phenyl or C 1-6 Alkylphenyl;

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

[0056] ○Each R 4 are independently H or methyl;

[0057] ○R 5 H, C 1-6 Alkyl or phenyl;

[0058] ○m is 0 to 9;

[0059] ○n is 2 to 10; and

[0060] ○j is 1 to 6.

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

[0062] ●R 1 H, Cl, Br, OH, C 1-4 Alkoxy, optionally substituted by halogen, C 1-4 Alkyl or phenoxy;

[0063] ●R 6 and R 7 One of them is H or C optionally substituted by 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 is a bond, O, Si(CH3)2 or NR 4 ;

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

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

[0071] ○R 5 For H.

[0072] In yet other aspects of the present 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 them is H, C 1-4 alkyl or trifluoromethyl; and

[0075] ●R 6 and R 7 The other one is:

[0076]

[0077] in:

[0078] ○R 2 C 1-6 alkyl;

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

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

[0081] ○Each R 4 are independently H or methyl; and

[0082] ○R 5 For 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] in:

[0086] R 1 Halogen, OH, C 1-12 Alkoxy, optionally substituted C 1-12 alkyl, optionally substituted phenoxy or optionally substituted naphthoxy, wherein the optional substituent is 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 is C optionally substituted by OH and / or impregnated with ester groups 1-12 Alkylene, (CH2CH2O) n or (CH2CH(CH3)O) n ;

[0088] If R 2 =(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 are independently H or methyl;

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

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

[0093] m is 0 to 9;

[0094] n is 2 to 10; and

[0095] j is 1 to 6.

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

[0097] For the avoidance of doubt, when two or more of adjacent R2, X and R3 are each a bond as in the compounds of formula (1) and (1a) above, then the two or more adjacent groups together form a single bond.

[0098] Unless otherwise stated, the term "alkyl" as used herein refers to straight and branched alkyl. Therefore, for example, reference to C4 alkyl refers to any one 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 alkanediyl and branched divalent saturated alkanediyl. Therefore, for example, reference to C3 alkylene refers to 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 contact lens of the third aspect of the invention comprises two different units derived from polymerisation of a compound of formula (1) above.

[0100] 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 (2):

[0101]

[0102] in:

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

[0104] R 1 is C optionally substituted by -OH and / or impregnated with an ester group 1-12 Alkylene;

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

[0106] R 3 is C optionally substituted by -OH and / or impregnated with an ester group 1-12 Alkylene;

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

[0108]

[0109] R 4 Each of which 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 having formula (2) can be found in US 2021 / 0214321 A1, the contents of which are incorporated herein by reference. Specific examples of HEVL absorbers having formula (2) that may be included in the formulations of the present invention are those having formulas (I-1) to (I-13) of US 2021 / 0214321 A1.

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

[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-methylacrylamidephenyl)-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 ester 2-methyl-2-propenoic 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 ester 2-methyl-2-propenoic acid (UV29, CAS No. 2254219-66-2):

[0137]

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

[0139] The first HEVL absorber advantageously has an absorption cutoff 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 may be at a wavelength that is 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 absorbance level than the second HEVL absorber in the range of 380 nm to 425 nm, for example as a 0.003 wt % solution in ethyl acetate. The second HEVL absorber advantageously has a greater absorbance level than the first HEVL absorber in the range of 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 of HEVL absorbers UV13 and UV28 in ethyl acetate are shown in FIG. UV28 has an absorption cutoff at a higher wavelength than UV13. The highest wavelength with 0.1 absorbance of a 0.003 wt% solution of UV28 in ethyl acetate is 420 nm, while the highest wavelength with 0.1 absorbance of a 0.003 wt% solution of UV13 in ethyl acetate is 406 nm. UV28 has a greater absorbance level than UV13 in the range of 380 nm to 425 nm, and the UV13 has a greater absorbance level than UV28 in the range of 350 nm to 375 nm.

[0141] The first HEVL absorber and the second HEVL absorber may be characterized in that, in the absorption spectrum of a 0.003 wt % solution of the first HEVL absorber and the second HEVL absorber in ethyl acetate, the tangent of the curve at the point defined by the highest wavelength with an absorbance of 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 longer, in particular at least 10 nm longer, than the wavelength at which the tangent of the curve at the point defined by the highest wavelength with an absorbance of 0.5 passes through the 0.0 absorbance axis of the absorption spectrum of the second HEVL absorber. The first HEVL absorber may be characterized in that, in the absorption spectrum of a 0.003 wt % solution of the first HEVL absorber in ethyl acetate, the tangent of the curve at the point defined by the highest wavelength with an absorbance of 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 may 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 a point defined by the highest wavelength with an absorbance of 0.5 passes through the 0.0 absorbance axis at a shorter wavelength (e.g., at least 5 nm shorter, particularly at least 10 nm shorter) than the wavelength at which the tangent to the curve at a point defined by the highest wavelength with an absorbance of 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. Alternatively or in addition, the second HEVL absorber may 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 a point defined by the highest wavelength with an absorbance of 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 line (A) defined by the point with the highest wavelength of 0.5 absorbance on the absorption spectrum of a 0.003 wt% solution of UV28 in ethyl acetate crosses the 0.0 absorbance axis at 422 nm. The tangent line (B) defined by the point with the highest wavelength of 0.5 absorbance on the absorption spectrum of a 0.003 wt% solution of UV13 in ethyl acetate crosses the 0.0 absorbance axis at 407 nm.

[0143] The first HEVL absorber may be characterized in that the highest wavelength with an absorbance of 0.1 on the absorption spectrum of a 0.003 wt % solution of the first HEVL absorber 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 absorber may be characterized in that the highest wavelength with an absorbance of 0.1 on the absorption spectrum of a 0.003 wt % solution of the second HEVL absorber in ethyl acetate is at a shorter wavelength (e.g., at least 5 nm shorter, particularly at least 8 nm shorter) than the wavelength at which the highest wavelength with an absorbance of 0.1 on the absorption spectrum of a 0.003 wt % solution of the first HEVL absorber in ethyl acetate is at. Alternatively or in addition, the second HEVL absorber may be characterized in that the highest wavelength with an absorbance of 0.1 on the absorption spectrum of a 0.003 wt % solution of the second HEVL absorber 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 in the figure, the highest wavelength with an absorbance of 0.1 on the absorption spectrum of a 0.003 wt% solution of UV28 in ethyl acetate is 420 nm. The highest wavelength with an absorbance of 0.1 on the absorption spectrum of a 0.003 wt% solution of UV13 in ethyl acetate is 406 nm, i.e., shorter than the highest wavelength with an absorbance of 0.1 on the absorption spectrum of a 0.003 wt% solution of UV28 in ethyl acetate by >8 nm.

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

[0146] from Figure 1 As can be seen, a 0.003 wt % solution of UV28 in ethyl acetate has an absorbance peak at 368 nm, and a 0.003 wt % solution of UV13 in ethyl acetate of the second HEVL absorber has an absorbance peak at 359 nm. Figure 2 As can be seen in the figure, a 0.003wt% solution of UV28 in ethyl acetate has an absorbance of about 0.43 for light at a wavelength of 400nm, and an absorbance of about 0.63 for light at a wavelength of 390nm. A 0.003wt% solution of UV1, UV5 (UVAM), UV13, and UV15 each has an absorbance of less than 0.30 for light at a wavelength of 400nm, and an absorbance of 0.60 or less for light at a wavelength of 390nm. A 0.003wt% solution of UV1, UV5 (UVAM), UV13, or UV15 in ethyl acetate has an absorbance of 0.1 at a wavelength that is at least 10nm lower than the wavelength of UV28.

[0147] It has been found that including a combination of two HEVL absorbers that meet the above criteria in a contact lens formulation produces a lens that is particularly effective in providing a high level of absorbance of violet-blue light in the range of 380 nm to 455 nm. In addition, this combination provides a lens with a desired tint without imparting undesirable yellowing to the wearer's eyes. For example, if the first HEVL absorber has a higher absorbance cutoff, such as a HEVL absorber characterized by a tangent to the curve at a point defined by the highest wavelength with an absorbance of 0.5 in the absorbance spectrum of a 0.003 wt % solution of the HEVL absorber in ethyl acetate crossing the 0.0 absorbance axis above 440 nm, and / or the HEVL absorber may be characterized by a highest wavelength with an absorbance of 0.1 above 430 nm on the absorbance spectrum of a 0.003 wt % solution of the HEVL absorber in ethyl acetate, then the resulting lens may have a greater yellowing effect, and / or a greater amount of blue colorant may be required in the lens formulation to offset the yellowing effect of the first HEVL absorber. An example of a benzotriazole HEVL that meets the absorbance requirements set out above is UV28. An example of a less desirable HEVL absorber with a higher absorbance cutoff is UV23.

[0148] Optionally, at least one of the first HEVL absorber and the second HEVL absorber, in particular the first HEVL absorber, is 2-[2'-hydroxy-3'-tert-butyl-5'-(3"-methacryloxypropoxy)phenyl]-5-chloro-2H-benzotriazole (UV28). UV28 may 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 in that a 0.003 wt% solution of the second HEVL absorber in ethyl acetate has a maximum wavelength of 0.1 absorbance of no more than 415 nm, in particular no more than 410 nm. UV28 advantageously has a greater absorbance level than the second HEVL absorber in the range of 380 nm to 425 nm, for example as a 0.003 wt% solution in ethyl acetate. The second HEVL absorber advantageously has a greater absorbance level than UV28 in the range of 350 nm to 375 nm, for example as a 0.003 wt% solution in ethyl acetate.

[0150] Optionally, the first HEVL absorber is UV28, and the second HEVL absorber is characterized in that the tangent line of the highest wavelength with an absorbance of 0.5 on the absorption spectrum of a 0.003 wt % solution of the second HEVL absorber in ethyl acetate passes through the 0.0 absorbance axis at a shorter wavelength (e.g., at least 5 nm shorter, particularly at least 10 nm shorter) than the wavelength at which the tangent line of the highest wavelength with an absorbance of 0.5 on the absorption spectrum of a 0.003 wt % solution of UV28 in ethyl acetate passes through the 0.0 absorbance axis. Optionally, the first HEVL absorber is UV28, and the second HEVL absorber is characterized in that the highest wavelength with an absorbance of 0.1 on the absorption spectrum of a 0.003 wt % solution of the second HEVL absorber in ethyl acetate is at a shorter wavelength (e.g., at least 5 nm shorter, particularly at least 8 nm shorter) than the wavelength at which the tangent line of the highest wavelength with an absorbance of 0.1 on the absorption spectrum of a 0.003 wt % solution of UV28 in ethyl acetate is. Optionally, the first HEVL absorber is UV28 and a 0.003 wt % solution of the second HEVL absorber in ethyl acetate has a peak absorbance at a wavelength at least 5 nm shorter, preferably at least 7 nm shorter, optionally at least 8 nm shorter than the absorption peak of a 0.003 wt % solution of UV28 in ethyl acetate falling 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"-dimethylvinylsilylpropoxy)-2'-hydroxy-phenyl)-5-methoxybenzotriazole (UV15). One of UV1, UV5, UV13 or UV15 or a combination of any one of UV1, UV5, UV13 and UV15 may 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 may be UV13. UV13 may 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 having a maximum at about 360 nm to 365 nm ( Figure 1 ). UV5 (UVAM) has an absorption curve similar to that of UV13 at wavelengths above 330 nm (e.g., between 330 nm and 500 nm), and also has a second absorbance peak at about 310 nm, and thus the absorption curve below 330 nm is similar to that of UV28 ( Figure 1 ). Thus, in some embodiments of the present invention, UV5 (UVAM) may be a particularly advantageous second HEVL absorber in preference to UV1, UV15 or UV13, for example in formulations where enhanced UV absorbance levels in the 300-320 nm range are desired.

[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 one of UV1, UV5, UV13, and UV15. One of UV1, UV5, UV13, or UV15, or a combination of any one of UV1, UV5, UV13, and UV15 may be present in an amount of 0.5% to 2.2% (wt / wt), and preferably 0.7% to 1.6% (wt / wt); and UV28 may 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. UV13 may be present in an amount of 0.5% to 2.2% (wt / wt) and preferably 0.7% to 1.6% (wt / wt); and UV28 may 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 of formula (1) present in the formulation of the present invention does not exceed 2.7% (wt / wt), and preferably does not exceed 2.0% (wt / wt). Optionally, the formulation of the present invention comprises one of UV1, UV5, UV13 or UV15 in an amount of 0.5% to 2.2% (wt / wt), preferably 0.7% to 1.6% (wt / wt), or a combination of any of UV1, UV5, UV13 and UV15, especially UV13; and comprises UV28 in an amount of 0.3% to 0.9% (wt / wt), preferably 0.4% to 0.7% (wt / wt), wherein the total amount of HEVL absorbers of 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, by weight percentage, of units of the HEVL absorber of formula (1) present in the polymeric lens material derived from the contact lens of the third aspect of the invention is as described above for the formulation of the second aspect of the invention. For example, the total amount of units of the high energy short wavelength visible light absorber of formula (1) present in the polymeric lens material derived from the contact lens of the third aspect of the invention optionally does not exceed 2.7% (wt / wt) of the polymeric lens material, and preferably does not exceed 2.0% (wt / wt).

[0156] The term "UV absorber" refers to a compound comprising a chromophore that absorbs light in the UV spectrum (i.e., 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 invention advantageously has an absorbance maximum (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] Compounds can act as both HEVL absorbers and UV absorbers. For example, a 0.003 wt % solution of UV28 in ethyl acetate has an absorption maximum (λmax) at about 308 nm in the range of 220 nm to 350 nm, an absorption greater 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. The term "HEVL absorber" as used herein encompasses compounds that act only as HEVL absorbers, and compounds that act as both HEVL absorbers and UV absorbers. The UV absorber included in the formulation of the present invention is advantageously not a bifunctional HEVL absorber and a UV absorber. The UV absorber may have an absorbance cutoff in the visible light range, i.e., does not absorb a significant amount of light above 380 nm. For example, a 0.003 wt % solution of a UV absorber in ethyl acetate does not have an absorbance of at least 0.5 in the range of 375 nm to 450 nm. The first HEVL absorber and / or the second HEVL absorber present in the formulation of the present invention both have an absorption higher than 0.5 in the range of 375 nm to 450 nm as a 0.003 wt % solution in ethyl acetate, and may optionally also have an absorption maximum (λmax) in the range of 220 nm to 350 nm, in particular in the range of 250 nm to 350 nm.

[0158] Optionally, the hydrogel contact lens formulations of the present invention may include one or more UV absorbers, that is, the contact lens formulations may include a UV absorber, or may include a UV absorber component containing two or more UV absorbers. UV absorbers that may be included in the formulations of the present invention include, for example, benzophenone, or benzotriazole, or any combination thereof.

[0159] The UV absorber is advantageously covalently bonded to the polymeric matrix of the lens material, rather than simply physically embedded in the material, to prevent the absorber from migrating, phase separating, or leaching out of the lens material. This stability is advantageous because leaching of the UV absorber may present toxicological problems and / or result in loss of UV blocking activity of the contact lens. The UV absorber used in the present invention is generally soluble in the contact lens formulation and is polymerizable so that it forms part of the polymeric matrix of the lens and remains in the lens during autoclaving and storage. The UV absorber is advantageously a polymerizable UV absorber that includes one or more reactive groups capable of participating in a curing reaction by which the polymeric matrix of the polymerized lens material is formed, such that the polymerizable UV absorber is covalently bonded to the polymerized lens material. The polymerizable UV absorber typically includes an ethylenically unsaturated group capable of participating in a free radical polymerization reaction, such as a vinyl group or a (meth)acrylate, (meth)acrylamide, or styryl group. 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 may affect one or more of the UV absorbing 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 may be present in the formulations of the invention in an amount up to about 5.0% (wt / wt), typically in an amount from about 0.1% (wt / wt) to about 2.0% (wt / wt) or from 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 a maximum absorbance (λmax) as a 0.003 wt% solution in ethyl acetate in the range of 250 nm to 380 nm, between 260 nm and 320 nm, particularly between 270 nm and 310 nm. The UV light absorbing unit present in the polymerized lens material of the hydrogel contact lens of the third aspect of the invention may be derived from the polymerizable UV absorber described herein with reference to the formulation of the invention. Therefore, the polymerized lens material of the hydrogel contact lens of the third aspect of the invention optionally comprises a UV light absorbing unit derived from a polymerizable UV absorber having a maximum absorbance (λmax) as a 0.003 wt% solution in ethyl acetate in the range of 250 nm to 380 nm, between 260 nm and 320 nm, particularly between 270 nm and 310 nm.

[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 containing a benzophenone moiety. Likewise, the polymerized lens material of the hydrogel contact lens of the third aspect of the invention optionally further comprises a UV light absorbing unit containing a benzophenone moiety. The UV light absorbing unit containing a benzophenone moiety present in the polymerized lens material of the third aspect of the invention may be derived from the polymerizable UV absorber described herein with reference to the formulation 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 containing a benzophenone moiety, the polymerizable UV absorber having a maximum absorbance (λmax) as a 0.003 wt% solution in ethyl acetate in the range of 250 nm to 380 nm, between 260 nm and 320 nm, particularly between 270 nm and 310 nm. The UV light absorbing unit present in the polymerized lens material of the third aspect of the invention may be derived from the polymerizable UV absorber described herein with reference to the formulation of the invention. Thus, the polymerized lens material of the hydrogel contact lens of the third aspect of the invention optionally comprises a UV light absorbing unit derived from a polymerizable UV absorber containing a benzophenone moiety, the polymerizable UV absorber having a maximum absorbance (λmax) as a 0.003 wt% solution in ethyl acetate in the range of 250 nm to 380 nm, between 260 nm and 320 nm, particularly between 270 nm and 310 nm. The benzophenone UV absorber included in the formulation of the present invention is advantageously not a difunctional HEVL absorber and a UV absorber. The benzophenone UV absorber may have an absorbance cutoff in the visible light range, i.e., the benzophenone UV absorber does not absorb a significant amount of light above 380 nm. For example, a 0.003 wt % solution of a benzophenone UV absorber in ethyl acetate does not have an absorbance of at least 0.5 in the range of 375 nm to 450 nm.

[0163] It has been found that including a UV absorber having a maximum absorbance (λmax) in the range of 250nm to 380nm, between 260nm and 320nm, especially between 270nm and 310nm, and / or comprising a benzophenone moiety as a 0.003wt% solution in ethyl acetate enables the resulting lenses to have high absorption levels across the range of 250nm to 455nm at lower overall levels of UV blockers than when including a UV absorber having a maximum absorbance (λmax) in the range of 250nm to 380nm, above 320nm, and / or comprising a benzotriazole or triazine moiety, especially a benzotriazole moiety, as a 0.003wt% solution in ethyl acetate. Without wishing to be bound by any theory, it is hypothesized that, due to the significant absorption difference between benzophenone UV absorbers and benzotriazole HEVL absorbers, a combination of a benzophenone UV absorber (which has a maximum absorbance (λmax) between 260 nm and 320 nm in the range of 250 nm to 380 nm as a 0.003 wt % solution in ethyl acetate) and two different HEVL absorbers, each comprising a benzotriazole moiety, is more effective in providing light blocking across the range of 260 nm to 440 nm than a combination comprising a UV absorber (which has a maximum absorbance (λmax) above 320 nm in the range of 250 nm to 380 nm) and / or a benzotriazole moiety (e.g., Norbloc).

[0164] Optionally, the formulations of the present invention comprise one or more polymerizable 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 polymerizable UV absorber is optionally 2-(4-benzoyl-3-hydroxyphenoxy)ethyl acrylate (UV416).

[0165] The formulations of the present invention may also optionally include at least one colorant, i.e., one colorant or a colorant component comprising two or more colorants. In one example, the colorant may be a reactive dye or pigment that is effective to provide color to the resulting lenses or to effectively reduce the amount of tinting of the resulting lenses. The colorant or colorant component of the polymerizable formulation may include a polymerizable colorant, or may include a non-polymerizable colorant, or any combination thereof. The polymerizable colorant may be a colorant whose molecular structure includes a polymerizable functional group, or may be a colorant whose molecular structure includes both a monomer portion and a dye portion, i.e., the colorant may be a monomer-dye compound. The molecular structure of the colorant may, for example, include a beta sulfone functional group, a triazine functional group, or an anthraquinone portion. Suitable colorants include, for example, vat blue (VAT Blue) 6 (7,16-dichloro-6,15-dihydroanthrazine-5,9,14,18-tetraone), 1-amino-4-[3-(β-sulfoethylsulfonyl)phenylamino]-2-anthraquinonesulfonic acid (CI Reactive Blue 19, RB-19) or a monomer-dye compound of Reactive Blue 19 and hydroxyethyl methacrylate (RB-19HEMA), 1,4-bis[4-[(2-methacryloyl-oxyethyl)phenylamino]anthraquinone (Reactive Blue 246, RB-246, CAS No. 121888-69-5, available from Arran Chemical Co., Athlone, Ireland). Company, Athlone, Ireland)), 1,4-bis[(2-hydroxyethyl)amino]-9,10-anthracene dione bis(2-propylene) ester (Reactive Blue 247, RB-247, CAS No. 109561-07-1, also available from Allen Chemical Company) or Reactive Blue 4 (RB-4, CAS No. 13324-20-4, available from Thermo Fisher Scientific (ThermoFisher)), or a monomer-dye compound of Reactive Blue 4 and hydroxyethyl methacrylate (RB-4HEMA 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 invention advantageously comprise a blue or cyan colorant containing an anthraquinone moiety, in particular a polymerizable blue or cyan colorant comprising an anthraquinone moiety. The polymerized lens material of the contact lenses of the present invention may further comprise units derived from a polymerizable blue or cyan colorant comprising an anthraquinone moiety. The polymerizable blue or cyan colorant is optionally selected from 1,4-bis[4-(2-methacryloyloxyethyl)phenylamino]-9,10-anthraquinone (RB246) or 1,4-bis[(2-methacryloyloxyethyl)amino]-9,10-anthraquinone (RB247).

[0166] The radiation absorber package of the HEVL absorber and optional UV absorber and optional colorant can be selected so that the light transmission characteristics of the contact lens produced by the contact lens formulation containing the radiation absorber package meet the required specifications. For example, the hydrogel contact lens formulation of the second aspect of the present invention may include a radiation absorber package that produces a contact lens that meets 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 light and >99% of UVB light) or Class 2 UV blocking (i.e., a contact lens that blocks >50% of UV-A light and >95% of UV-B light). The advantageous formulation of the present invention provides a contact lens that blocks at least 30% of HEVL light, especially at least 40% of HEVL light, preferably at least 45% of HEVL light in addition to providing UV blocking. The formulation may also provide a contact lens that blocks at least 35% of violet light, especially at least 45% of violet light, preferably at least 50% of violet light. The contact lenses of the third aspect of the invention advantageously meet 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 light and >99% of UVB light) or Class 2 UV blocking (i.e., blocking >50% of UV-A light and >95% of UV-B light). Advantageous contact lenses of the present invention block at least 30% of HEVL light, especially at least 40% of HEVL light, preferably at least 45% of HEVL light in addition to providing UV blocking. The contact lenses of the present invention can block at least 35% of violet light, especially at least 45% of violet light, preferably at least 50% of violet light. “UVA” refers to radiation occurring at wavelengths between 315 and 400 nanometers (nm); “UVB” refers to radiation occurring between 280 and 315 nm; “violet” refers to radiation occurring at wavelengths between 380 and 440 nm, and “high energy visible light” (HEVL) refers to radiation occurring at wavelengths between 380 and 455 nm.

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

[0168]

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

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

[0171] The contact lens of the third aspect of the present invention is a hydrogel contact lens, including conventional (i.e., non-silicone hydrogel contact lenses) and silicone hydrogel contact lenses. "Hydrogel" refers to a cross-linked polymeric material having a three-dimensional polymer network structure (i.e., polymer matrix), which is insoluble in water but contains at least 10% by weight of water in its polymer matrix when fully hydrated. "Silicone hydrogel" refers to a hydrogel obtained by polymerization of a hydrogel contact lens formulation comprising 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 preparing conventional hydrogel and silicone hydrogel contact lenses are well known in the art. The radiation absorber package of the first aspect of the present invention is suitable for incorporation into a wide range of polymerizable formulations for forming hydrogel (including silicone hydrogel) contact lenses. In addition to the radiation absorbing compound, the hydrogel contact lens formulation of the second aspect of the present invention also includes monomers and other components suitable for forming the hydrogel contact lenses described below.

[0173] Typically, hydrogel contact lenses are formed by a free radical propagation reaction involving the 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 groups. 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 mixed carbon atom. The reactivity of the vinyl group under free radical polymerization is lower than the carbon-carbon double bond present in an acrylate or methacrylate polymerizable group. The term "(meth)acrylamide" refers to methacrylamide and / or acrylamide. The term "(meth)acrylate" refers to methacrylate and / or acrylate. The term "terminal (meth)acryloyl" refers to one (meth)acryloyl group at one of the two ends of the main chain (or backbone) of an organic compound. "N-vinylamide monomer" refers to an amide compound having a vinyl group CH=CH2 directly attached to the nitrogen atom of the amide group.

[0174] "Monomer" is a molecule having one or more polymerizable groups, which can react with the same or different other monomers to form a larger polymer or copolymer chain or a three-dimensional polymer matrix during polymerization. A monomer having two or more polymerizable groups may be referred to as a "crosslinker", which is further described below. The term "monomer" encompasses macromolecular monomers and polymerizable oligomers, i.e., polymerizable molecules containing one or more repeating unit chains, such as polymerizable silicones; therefore, unless otherwise indicated, there is no size limit (i.e., maximum molecular weight) for monomers. As used in this application, unless otherwise specified, the term "molecular weight" of a polymeric material refers to an absolute number average molecular weight (in Daltons), such as determined by 1H NMR end group analysis or by GPC using a polystyrene standard. The term "polymer" refers to a material formed by polymerization and / or crosslinking of one or more monomers.

[0175] The formulations of the present invention typically comprise hydrophilic monomers, and may also comprise hydrophobic monomers. As used herein, "hydrophilic monomers" refers to silicone-free monomers, 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 determined visually using a standard shake bottle method.

[0176] The hydrogel contact lens formulations of the present invention typically 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 vinyl amide monomers and hydrophilic vinyl ether monomers. In some examples, the hydrophilic vinyl amide monomer can be selected from N-vinyl-N-methylacetamide (VMA), or N-vinyl pyrrolidone (NVP), or N-vinyl formamide, or N-vinyl acetamide, or N-vinyl-N-ethylacetamide, or N-vinyl isopropylamide, or N-vinyl caprolactam, or N-vinyl-N-ethylformamide, or any combination thereof. In some examples, the hydrophilic vinyl amide monomer consists of VMA or NVP, or a combination of VMA and NVP. The vinyl ether-containing monomer may 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 monomer may be a 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 vinyl amide-containing monomer and the hydrophilic vinyl ether-containing monomer, one or more vinyl-containing monomers may also be included in the formulations of the present invention. For example, in addition to the vinyl amide-containing monomer and the vinyl ether-containing monomer, a vinyl monomer having a vinyl ester or allyl ester polymerizable group may be included in the formulations of the present invention. The hydrophilic monomer may be a hydrophilic monomer containing a (meth)acrylate or (meth)acrylamide group, examples of which include 2-hydroxyethyl methacrylate (HEMA), 4-hydroxybutyl acrylate glycerol methacrylate, 2-hydroxyethyl methacrylamide, ethoxyethyl methacrylamide (EOEMA), polyethylene glycol monomethacrylate, methacrylic acid (MA) and acrylic acid.

[0178] The formulation of the second aspect of the invention may 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 formulation of the second aspect of the invention may include at least one hydrophilic N-vinylamide monomer in an amount of 25% to 55% (wt / wt), especially 30% to 50% (wt / wt). The formulation of the second aspect of the invention may include N-methyl N-vinylacetamide in an amount of 25% to 55% (wt / wt), especially 30% to 50% (wt / wt).

[0179] The polymerizable monomers may optionally include a hydrophobic monomer. As used herein, the term "hydrophobic monomer" refers to a monomer that lacks a siloxane group and is less than 5% soluble in water at 20°C as determined using a standard shake flask method.

[0180] The hydrophobic monomer lacking a siloxane group may be a hydrophobic monomer containing a (meth)acrylate group. 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 specific 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, tert-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-silicone hydrophobic monomers include hydroxybutyl methacrylate, isobornyl methacrylate, or a combination of hydroxybutyl methacrylate and isobornyl methacrylate. Hydrogel contact lens formulations may include acrylate-containing hydrophobic monomers to further enhance the mechanical strength and / or hardness of the lens, or to impart other desired properties.

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

[0182] The formulation may comprise from about 2% to about 20% (wt / wt), for example 4% to 16% (wt / wt), especially 6% to 12% (wt / wt) of a non-silicone hydrophobic monomer component. From 2 to 20% (wt / wt), especially 5 to 15% (wt / wt) of the formulation may be hydroxybutyl methacrylate, isobornyl methacrylate, or a combination of hydroxybutyl methacrylate and isobornyl methacrylate.

[0183] The hydrogel contact lens formulation used in the method of the second aspect and / or the fourth aspect of the present invention may be a silicone hydrogel contact lens formulation comprising a siloxane-containing monomer in addition to a hydrophilic monomer and an optional hydrophobic monomer lacking a siloxane group. The hydrogel contact lens of the third aspect of the present invention may be a silicone hydrogel contact lens comprising a siloxane group in the matrix of a polymerized lens material. As used herein, "siloxane monomer" refers to a monomer having at least one siloxane group. The siloxane monomer may include a terminal acrylate or methacrylate group. The (meth) acrylate-containing siloxane monomers that can be used in the formulations of the present invention described herein are well known in the art. The siloxane monomer may be a monofunctional (meth) acrylate-containing siloxane, a difunctional (meth) acrylate-containing siloxane, or a combination of a monofunctional (meth) acrylate-containing siloxane monomer and a difunctional (meth) acrylate-containing siloxane monomer. In examples where the (meth)acrylate-containing siloxane monomer consists of one or more monofunctional (meth)acrylate-containing siloxane monomers (i.e., it does not contain any multifunctional (meth)acrylate-containing siloxane monomers), the silicone hydrogel contact lens formulation will typically further comprise a (meth)acrylate-containing cross-linker, further described below. In a specific 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(trimethylsiloxy)silyl]propyl methacrylate ("TRIS"), 3-methacryloyloxy-2-hydroxypropyloxy)propyl bis(trimethylsiloxy)methylsilane ("SiGMA"), methylbis(trimethylsiloxy)silylglycerolethyl methacrylate ("SiGEMA"), and monomethacryloyloxypropyl functional polydimethylsiloxanes such as MCR-M07 and MCS-M11, all of which are commercially available from Gelest (Morrisville, PA, USA).

[0184] The hydrogel contact lens formulation of the second aspect of the invention is optionally a silicone hydrogel contact lens formulation comprising at least one polymerizable siloxane monomer, optionally in an amount of at least 25% (wt / wt), for example in an amount of at least 35% (wt / wt), in particular in an amount of at least 40% (wt / wt).

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

[0186] In one example, the monofunctional siloxane monomer may include a (meth)acrylate-containing siloxane monomer represented by formula (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 In another specific 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 for preparing siloxane monomers represented by formula (I) are described in US Publication No. 20090299022, which is incorporated herein by reference.

[0189] In another example, the monofunctional siloxane monomer may include a (meth)acrylate-containing siloxane monomer represented by formula (II),

[0190]

[0191] wherein n is an integer from about 10 to 15. Siloxane monomers of Formula II and other suitable monomers are described in US Pat. Nos. 6,867,245 and 6,310,169, both of which are 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-acrylate (which is available from Shin-Etsu Chemical Co., Ltd., Tokyo, Japan (CAS No. 1052075-57-6) as X-22-1622 (also known as KF1622)), methacryloxypropyl-terminated poly(dimethyl)siloxane FMM (Shin-Etsu Silicones of America, Akron, Ohio, USA) (CAS No. 697234-76-7), and 3-methacryloxy-2-hydroxypropoxy)propylbis(trimethylsiloxy)methylsilane SiGMA.

[0193]

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

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

[0196]

[0197] wherein R1 is selected from hydrogen or methyl; R2 is selected from hydrogen or C 1-4 A hydrocarbon group; 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 is equal to 20 to 500; b / (a+b) is equal to 0.01 to 0.22; and the configuration of the siloxane unit includes a random configuration. In a more specific example, the acrylate-containing siloxane monomer is represented by Formula II, wherein R1 and R2 are 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; this siloxane monomer has a molecular weight of about 8,000 to about 10,000 Daltons. Methods for preparing compounds 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 macromonomer A described in Example 2 of US 2009 / 0234089.

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

[0199]

[0200] Where R 3 is selected from hydrogen or methyl, m represents an integer of 0 to 10, and n represents an integer of 1 to 500. In a specific example, the bifunctional siloxane monomer is a methacryloxypropyl-terminated polydimethylsiloxane having a molecular weight of 4500 to 5500 represented by Formula IV, wherein R 3is methyl, m is 0, and n is an integer from 40 to 60, which is commercially available from Gallester Corporation (Morrisville, Pennsylvania, USA) and is referred to as "DMS-R18" by the manufacturer. Additional suitable methacryloxypropyl-terminated polydimethylsiloxanes include DMS-R22 and DMS-R31, also available from Gallester Corporation.

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

[0202]

[0203] wherein n is an integer from about 100 to 150, m and p are both integers from about 5 to 10, and h is an integer from about 2 to 8. Methods for preparing compounds of Formula V are described in U.S. Pat. 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 invention described herein are known in the art (see, e.g., U.S. Pat. No. 7,572,841, U.S. Pat. No. 2006 / 0063852, and U.S. Pat. No. 5,998,498, each of which is incorporated herein by reference).

[0204] In one example, the siloxane monomer may include a combination of a monofunctional (meth)acrylate-containing siloxane monomer and a difunctional (meth)acrylate-containing siloxane monomer. In one such example, the monofunctional (meth)acrylate-containing siloxane monomer has a molecular weight of less than 2,000, 1,000, or 750 Daltons, and the difunctional acrylate-containing siloxane monomer has 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 by 1H NMR end group analysis. In a specific example, the monofunctional (meth)acrylate-containing siloxane monomer has a molecular weight of about 250 to about 1000, and the difunctional acrylate-containing siloxane monomer has a molecular weight of about 5,000 to about 16,000 Daltons. In another specific example, the monofunctional (meth)acrylate-containing siloxane monomer has a molecular weight of about 500 to about 1,000 Daltons, and the difunctional (meth)acrylate-containing siloxane monomer has a molecular weight of about 5,000 to about 12,000 Daltons.

[0205] The formulations of the present invention typically include one or more polymerization initiators, that is, the hydrogel contact lens formulations may include an initiator, or may include an initiator component that includes two or more polymerization initiators or a combination of polymerization initiators, synergists, and activators. The term "initiator" refers to a chemical substance that initiates a crosslinking / polymerization reaction. The initiator is typically a free radical initiator that forms free radicals that initiate a polymerization reaction that propagates free radicals. Polymerization initiators that may be included in the formulations of the present invention include, for example, azo compounds or organic peroxides or both. The initiator may be a photoinitiator that is activated when exposed to actinic radiation such as UV light, or a thermal initiator that is activated when exposed to heat. Initiators that may be present in the hydrogel contact lens formulation include, for example, benzoin ethyl ether, or benzyl dimethyl ketal, or α, α-diethoxyacetophenone, or 2,4,6-trimethylbenzoyldiphenylphosphine oxide, or benzoin peroxide, or tert-butyl peroxide, or azobisisobutyronitrile, or azobisdimethylvaleronitrile, or any combination thereof. The UV photoinitiator may 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, NJ, 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 EI DuPont de Nemours & Co., Wilmington, Del., USA, CAS No. 78-67-1), also known as 2,2'-azobis(isobutyronitrile) (AIBN), 2,2'-azobis(2,4-dimethylvaleronitrile) (VAZO-52, also from EI DuPont, CAS No. 4419-11-8), also known as 2,2'-azobis(dimethylvaleronitrile), and 1,1'-azobis(cyanocyclohexane) (VAZO-88, also from EI DuPont, CAS No. 2094-98-6), also known as 1,1'-azobis(cyclohexanecarbonitrile). The polymerization initiator or initiator component may be present in the hydrogel contact lens formulation in an amount of about 0.1% (wt / wt) to about 1.5% (wt / wt), or about 0.2% (wt / wt) to about 1.0% (wt / wt), particularly about 0.2% (wt / wt) to about 0.8% (wt / wt). The hydrogel contact lens formulation of the second aspect of the invention is optionally a thermally cured formulation comprising at least one thermal initiator. The method of the fourth aspect of the invention optionally comprises thermally curing the formulation. Thermal or actinic curing methods are well known to those skilled in the art.

[0206] The hydrogel contact lens formulations of the present invention may further include a crosslinking agent. The crosslinking agent can react with functional groups on two or more polymer chains so as to bridge one polymer to another polymer. 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 types of polymerizable groups. A "vinyl-containing crosslinking agent" has at least two polymerizable vinyl groups and no other types of polymerizable groups. Vinyl-containing crosslinking agents and acrylate-containing crosslinking agents can typically 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, divinyl ether, or 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. Typically, the vinyl-containing crosslinking agent may have two or three polymerizable vinyl groups. When present, the total amount of vinyl-containing crosslinking agent in the hydrogel contact lens formulation is typically 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)acrylates, poly(lower alkylene) glycol di(meth)acrylates, lower alkylene di(meth)acrylates, trimethylolpropane tri(meth)acrylates, pentaerythritol tetra(meth)acrylates, bisphenol A di(meth)acrylates, methylenebis(meth)acrylamide, and 1,3-bis(3-methacryloxypropyl)tetramethyldisiloxane. In certain instances, the acrylate-containing crosslinker is a non-silicone crosslinker. When present, the total amount of acrylate-containing crosslinkers in the hydrogel contact lens formulation is typically 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 crosslinkers. Thus, bifunctional siloxanes having a molecular weight greater than 2,000 Daltons described herein are not considered crosslinkers.

[0207] The formulation of the present invention may 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, thiol compounds, halocarbon compounds or C3-C5 hydrocarbons, such as allyloxyethanol.

[0208] In addition to polymerizable ingredients, hydrogel contact lens formulations may contain non-polymerizable ingredients conventionally used in contact lens formulations. Additional ingredients such as organic diluents or deoxidizers may also be included. Non-limiting examples of these and additional ingredients that may be included in the formulations of the present invention are provided in US2007 / 0296914.

[0209] Advantageous formulations of the second aspect of the invention comprise at least one hydrophilic monomer, optionally in an amount of at least 25% (wt / wt). Advantageous formulations optionally include at least one N-vinylamide hydrophilic monomer, optionally in an amount of at least 15% (wt / wt). Advantageous formulations are optionally silicone hydrogel contact lens formulations comprising 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 comprising: 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-vinylamide monomer component present in an amount of at least 37% (wt / wt).

[0210] Advantageous formulations of the second aspect of the invention comprise: 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 methyl ether 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 lens of the third aspect of the invention advantageously comprises a polymerized lens material derived from the advantageous polymerizable formulation of the second aspect of the invention comprising the monomers and siloxane components described above. The monomers and siloxane components described above may be incorporated into the polymerized lens material in the amounts described above, for example, at least 25% (wt / wt) of the polymerized material may be units derived from a hydrophilic monomer having a terminal ethylenically unsaturated polymerizable group. It has been found that the advantageous formulation described above is particularly suitable for use in combination with the radiation absorber package of the first aspect of the 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] Examples

[0213] The following examples illustrate certain aspects and advantages of the present invention, which should be construed as not limiting thereby.

[0214] Surface wettability

[0215] The water contact angle on a contact lens is a measure of the surface wettability of the contact lens. As used herein, the contact angle of the lens-forming surface of a contact lens is measured by the sessile drop method using the PTFE® from Kruess. The measurements were performed using a 3 μl drop of PBS placed on the center of the lens surface using a DSA-100 Drop Shape Analysis System or equivalent analyzer.

[0216] Balanced water content

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

[0218] The amount of water (expressed as a weight percentage) present in a fully hydrated hydrogel contact lens equilibrated in saline solution was determined at room temperature (i.e., 20° C.). After blotting the lenses with a cloth, a stack of 5 lenses was placed in a pan on an analytical balance, and the hydrated weight of the lenses was determined. The lenses were then placed in a laboratory oven at 100±2° C. to dry for 16 to 18 hours, then removed from the oven and cooled to room temperature in a desiccator for at least 30 minutes. The mass of the dried lens was then determined, and the mass of the dried lens was subtracted from the weight of the hydrated lens to calculate the water content.

[0219] Yellowness Index (YI)

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

[0221] The following examples illustrate the effect of varying the amount of high energy, short wavelength visible light absorber and tint present in a lens formulation while keeping the amount of polymerizable monomer constant.

[0222] Cast molding of contact lenses

[0223] The hydrogel contact lens formulations described below are 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 are made of a non-polar resin (e.g., polypropylene). The formulations are thermally cured to form a polymerized lens body by placing the mold assembly in a nitrogen oven under the following cycle: 30 min. N2 purge 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 male and female mold members are dry demolded, and the polymerized lens body is dry delensed from the male mold member. The delensed polymerized lens body is exposed to an extraction and hydration process consisting of soaking the lens body twice in denatured ethanol (special commercial denatured ethanol (TSDA) 7 containing 5.0% vol. isopropyl alcohol), followed by soaking in a mixture of 50% denatured ethanol (TSDA 7) and 50% deionized water, and then soaking in deionized water three times.

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

[0226] Basic eyeglass preparations

[0227] A base polymerizable silicone hydrogel contact lens formulation was prepared containing 10 parts of a hydrophobic monomer (consisting of 2.31 parts of isobornyl methacrylate (IBM) and 7.69 parts of hydroxybutyl methacrylate (HOB)), 43 parts of a hydrophilic monomer (consisting of 43 parts of N-vinyl N-methylacetamide (VMA)), 54 parts of a polymerizable siloxane (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 a thermal initiator (AIBN) and a crosslinker (triallyl isocyanate). The same base formulation was used in all examples.

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

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

[0230] UV13 only formulation

[0231] The radiation absorber package of each of Examples 1-13 was added to the base formulation and cast molded into lenses of the dimensions described above. The lenses of each of Examples 1-13 had an ocularly 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] In order to achieve 50% blocking of light of wavelengths between 380 nm and 455 nm, it is necessary to include a high content of UV13, ie greater than 2.5 wt%.

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

[0237] UV28 only formulation

[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] Incorporating 0.5 wt% UV28 into the base formulation produced lenses that blocked 37% of light in the range of 380-455 nm. Although increasing the amount of UV28 incorporated into the base formulation to 0.90 wt% resulted in blocking 51% of light in the range of 380-455 nm, at this UV28 loading it was found difficult to remove the lenses from the molds and a low yield of acceptable lenses was obtained.

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

[0244] The Yellowness Index (YI) of the lenses prepared from the formulations of Comparative Examples 6 and 7 indicated that increasing the amount of UV28 in the formulation increased the yellowness of the lenses.

[0245] Formulations comprising a combination of UV13 and UV28

[0246] In Examples 9-13, radiation absorber packages including both UV13 and UV28 were added to the same base silicone hydrogel contact lens formulation, and the formulation was cast into the 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 includes UV28, the resulting formulation provides enhanced blocking of transmission in the range of 380nm to 455nm. The glasses formed from the formulation of Example 10 including 1.08wt% UV13 and 0.49wt% UV28 block 50% of the transmission in the range of 380nm to 455nm, i.e., provide the same level of HEVL blocking as Comparative Example 5, even though only 60% of the total amount of benzotriazole HEVL blocker is included, 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 the HEVL in the range of 380 nm to 455 nm while keeping the total amount of HEVL absorber below 2 wt % of the total lens formulation. Increasing the amount of HEVL absorber in Examples 11, 12, and 13 results in an increase in the amount of HEVL blocked by the lens by up to another 5%. However, the wettability (as indicated by the pedestal water drop contact angle) of lenses cast from the formulations of Examples 11 to 13 is lower than the wettability of lenses cast from the formulations of Examples 9 and 10.

[0251] Changing UV absorbers

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

[0253] Table 4

[0254]

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

[0256] Tinting of glasses

[0257] The effect of including different radiation absorber packages in the polymerizable lens formulation was explored by placing lenses cast from the formulations on glass eyes with blue irises. It was found that the tinting imparted by lenses cast from the formulations of Comparative Examples 1, 6 and 10 of the present invention produced natural looking eyes and outperformed the commercially available Oasys MAX™ lenses containing a tricyclic HEVL absorber, which imparted a significant undesirable yellow / green halo at the edge of the iris of the glass eye and on its sclera. The YI of the Acuvue Oasys Max™ lenses was determined to be 6.95 and is therefore 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, an observation consistent with the YI values ​​reported above in Table 3. Thus, it has been found that glasses with a YI less than 6.0, especially less than 5.0, give the eye a more natural appearance than glasses with a YI greater than 6.0.

[0259] Absorption spectrum

[0260] Solutions of Norbloc, UV416, UV13 and UV28 in ethyl acetate were measured for light absorption in the range of 250 nm to 500 nm. Figure 1 The absorption spectra of each compound are shown in . All solutions were 0.003 wt % solutions prepared in ≥ 99.8 %, HPLC grade ethyl acetate, and the absorbance of the solutions was measured from 250 mm to 800 mm using a PerkinElmer Lambda 365 spectrometer.

[0261] The light absorption of solutions of UV1, UV5 (UVAM), UV13, UV15 and UV28 in ethyl acetate was measured in the range of 380 nm to 460 nm. Figure 2 The absorption spectra of each compound are shown in . All solutions were 0.003 wt % solutions prepared in ≥ 99.8 %, HPLC grade ethyl acetate, and the absorbance of the solutions was measured from 250 mm to 800 mm using a PerkinElmer 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, is more effective in absorbing 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 in the range of 350 nm to 455 nm was found to be 359 nm, and the peak absorbance of a solution of UV28 in the range of 350 nm to 455 nm was found to be 369 nm. UV13 was found to be more effective in absorbing light in the range of 340 nm to 375 nm, while UV28 was found to be more effective in 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 containing a benzotriazole moiety, is more effective in providing light blocking across the 260 nm to 440 nm range than a combination containing a benzotriazole UV absorber due to the significant absorption differences between benzophenone and benzotriazole compounds. Figure 1 It can be seen that 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 that of UV13 and UV28, thereby providing enhanced absorbance across a wider wavelength range.

[0264] The disclosure herein refers to certain illustrated examples, which should be understood to be presented as examples rather than as limitations. Although exemplary examples are discussed, the foregoing detailed description is intended to be interpreted as covering all modifications, alternatives, and equivalents of the examples that may be within the spirit and scope of the invention as defined by the additional disclosure.

[0265] The present invention includes the following aspects / embodiments / features in any order and / or in 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 comprises a benzotriazole moiety.

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

[0270] 3. The formulation according to 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 a wavelength at least 10 nm lower 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 a wavelength at least 10 nm lower.

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

[0272] a. The first HEVL absorber is characterized in that a tangent to a point on the curve defined by the highest wavelength at which the absorbance is 0.5 passes through a 0.0 absorbance axis on the absorption 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 in that a tangent to a point on the curve defined by the highest wavelength at which the absorbance is 0.5 passes through a 0.0 absorbance axis on the absorption spectrum of a 0.003 wt % solution of the first HEVL absorber in ethyl acetate at a wavelength shorter than the wavelength at which the tangent to a point on the curve defined by the highest wavelength at which the absorbance is 0.5 passes through a 0.0 absorbance axis on the absorption spectrum of a 0.003 wt % solution of the first HEVL absorber in ethyl acetate (e.g., a wavelength at least 5 nm shorter, in particular at least 10 nm shorter);

[0273] and / or

[0274] b. The second HEVL absorber is characterized in that a tangent to a point on the curve defined by the highest wavelength at which absorbance is 0.5 passes through the 0.0 absorbance axis on the absorption spectrum of a 0.003 wt % solution of the first HEVL absorber in ethyl acetate 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 a point on the curve defined by the highest wavelength at which absorbance is 0.5 passes through the 0.0 absorbance axis on the absorption spectrum of a 0.003 wt % solution of the first HEVL absorber in ethyl acetate at a wavelength shorter than the wavelength at the highest wavelength at which absorbance is 0.5 on the absorption spectrum of a 0.003 wt % solution of the first HEVL absorber in ethyl acetate (e.g., a wavelength at least 5 nm shorter, particularly at least 8 nm shorter);

[0275] and / or

[0276] c. The first HEVL absorber is characterized in that the highest wavelength with an absorbance of 0.1 on the absorption 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 the highest wavelength with an absorbance of 0.1 on the absorption spectrum of a 0.003 wt % solution of the second HEVL absorber in ethyl acetate is between 385 nm and 412 nm, preferably between 390 nm and 410 nm;

[0277] and / or

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

[0279] and / or

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

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

[0282]

[0283] in:

[0284] R 1 Halogen, OH, C 1-12 Alkoxy, -A-R9-Y, optionally substituted C 1-12 alkyl, optionally substituted phenoxy or optionally substituted naphthoxy, wherein the optional substituent is 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);

[0285] R 6 and R 7 One of them is H or C optionally substituted by halogen 1-12 alkyl; and

[0286] R 6 and R 7 The other one is:

[0287] OR 8 ,in:

[0288] R 2 C is a bond, optionally substituted by -OH and / or mixed with an ester group 1-12 Alkylene, (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, or NR 4 、S or (Si(CH3)2O) m Si(CH3)2;

[0291] Each R 4 are independently H or methyl;

[0292] R 5 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 H, C 1-12 Alkyl, C 6-15 Aralkyl or -R 9 -Z;

[0298] Each R9 is independently C optionally substituted by -OH and / or impregnated with an ester group 1-12 Alkylene;

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

[0300]

[0301] Each R 10 Independently for C 1-10 Alkyl or C 3-10 alkenyl;

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

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

[0304] 6. The formulation according to 5, wherein the total amount of the HEVL absorber of formula (1) present does not exceed 2.7% (wt / wt), preferably does not exceed 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"-methacryloxypropoxy)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: 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"-dimethylvinylsilylpropoxy)-2'-hydroxy-phenyl)-5-methoxybenzotriazole (UV15), especially 2-[2'-hydroxy-3'-tert-butyl-5'-(3"-methacryloyloxypropoxy)phenyl]-5-methoxy-2H-benzotriazole (UV13).

[0307] 9. The formulation according to 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 according to 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 according to any one of 1 to 10, wherein the polymerizable UV absorber is 2-(4-benzoyl-3-hydroxyphenoxy)ethyl acrylate (UV416).

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

[0311] 13. The formulation according to 12, wherein the polymerizable blue or cyan 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 according to any one of 1 to 13, which is a thermally curable formulation comprising at least one thermal initiator.

[0313] 15. The formulation according to 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 according to 15, comprising at least one hydrophilic N-vinyl amide monomer, optionally in an amount of at least 15% (wt / wt).

[0315] 17. The formulation according to 16, comprising at least 30% (wt / wt) of one or more hydrophilic N-vinylamide monomers.

[0316] 18. The formulation according to 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 the 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 according to any one of 18 to 20, comprising:

[0320] a silicone 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 silicone content is a difunctional silicone having a molecular weight of at least 8,000 Daltons; and

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

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

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

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

[0325] a. one or more hydrophilic N-vinyl amide 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-silicone hydrophobic methacrylate monomer in an amount of at least 5% (wt / wt) based on the total weight of the formulation.

[0328] 25. The formulation according to 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 according to 24 or 25, wherein the difunctional siloxane monomer is a (meth)acrylate-containing siloxane monomer represented by formula (III),

[0334]

[0335] Wherein R1 is selected from hydrogen or methyl; R2 is selected from hydrogen or C 1-4 a hydrocarbon group; m represents an integer from 0 to 10; n represents an integer from 4 to about 15, 25 or 100; a and b represent an integer of 1 or greater; a+b is equal to 20 to 500; b / (a+b) is equal to 0.01 to 0.22; and the configuration of the siloxane unit includes a random configuration.

[0336] 27. The formulation according to 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 of about 10 to 15.

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

[0340] 29. The contact lens according to 28, which has the following light transmission properties:

[0341]

[0342] 30. The contact lens according to 28 or 29, having a yellowness index of less than 6.0 as measured by the ASTM E313-05 method.

[0343] All references cited in this disclosure are hereby incorporated by reference in their entirety to the extent they are not inconsistent with this disclosure.

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

Claims

1. 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, wherein 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, And wherein a 0.003 wt % solution of the second HEVL absorber in ethyl acetate has a peak absorbance at a wavelength between 5 nm and 25 nm shorter than the absorbance peak of the 0.003 wt % solution of the first HEVL absorber in ethyl acetate falling within the range of 360 nm to 410 nm.

2. The formulation of claim 1, wherein the first HEVL absorbent and the second HEVL absorbent each have formula (1): in: R 1 Halogen, OH, C 1-12 Alkoxy, -A-R9-Y, optionally substituted C 1-12 alkyl, optionally substituted phenoxy or optionally substituted naphthoxy, wherein the optional substituent is 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); R 6 and R 7 One of them is H or C optionally substituted by halogen 1-12 alkyl; and R 6 and R 7 The other one is: OR 8 ,in: R 2 C is a bond, optionally substituted by -OH and / or mixed with an ester group 1-12 Alkylene, (CH2CH2O) n or (CH2CH(CH3)O) n ; R 3 is a bond, C(O), C(O)C j H 2j , C 1-6 Alkylene, phenyl or C 1-6 Alkylphenyl; X is a bond, O, or NR 4 、S or (Si(CH3)2O) m Si(CH3)2; Each R 4 are independently H or methyl; R 5 H, C 1-6 Alkyl or phenyl; m is 0 to 9; n is 2 to 10; j is 1 to 6; A is -S- or -SO2-; R 8 H, C 1-12 Alkyl, C 6-15 Aralkyl or -R 9 -Z; Each R 9 is independently C optionally substituted by -OH and / or impregnated with an ester group 1-12 Alkylene; Each of Y and Z is -OH, -OC(O)R 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 cycloalkenylene; and R 12 C 1-10 Alkylene or 1,2-phenylene.

3. A formulation according to claim 2, wherein the total amount of HEVL absorber of formula (1) present does not exceed 2.7% (wt / wt), preferably does not exceed 2.0% (wt / wt).

4. A formulation according to any preceding claim, wherein: The first HEVL absorber is 2-[2'-hydroxy-3'-tert-butyl-5'-(3"-methacryloxypropoxy)phenyl]-5-chloro-2H-benzotriazole (UV28).

5. The formulation according to any preceding claim, wherein 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), 2-3'-tert-butyl-2'-hydroxy-5'-(3"-dimethylvinylsilylpropoxy)-2'-hydroxy-phenyl)-5-methoxybenzotriazole (UV15), especially 2-[2'-hydroxy-3'-tert-butyl-5'-(3"-methacryloyloxypropoxy)phenyl]-5-methoxy-2H-benzotriazole (UV13).

6. The formulation according to any one of claims 1 to 5, 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).

7. A formulation according to any preceding claim comprising a polymerisable UV absorber comprising a benzophenone moiety, optionally in an amount of no more than 1.5% (wt / wt), preferably no more than 1.0% (wt / wt).

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

9. The formulation according to any preceding claim, further comprising a polymerizable blue or cyan colorant containing an anthraquinone moiety.

10. The formulation according to claim 9, wherein the polymerizable blue or cyan 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).

11. The formulation according to any preceding claim, which is a thermally curable formulation comprising at least one thermal initiator.

12. The formulation according to any preceding claim, further comprising at least one hydrophilic monomer, optionally in an amount of at least 25% (wt / wt).

13. The formulation according to claim 12, comprising at least one hydrophilic N-vinyl amide monomer, optionally in an amount of at least 15% (wt / wt).

14. The formulation of claim 13, comprising at least 30% (wt / wt) of one or more hydrophilic N-vinyl amide monomers.

15. The formulation according to any preceding claim, 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).

16. The formulation of claim 15 comprising 30% to 60% (wt / wt) of the polymerizable siloxane component.

17. A formulation according to claim 15 or claim 16, 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.

18. The formulation according to any one of claims 15 to 17, 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% of the siloxane content is a difunctional siloxane having a molecular weight of at least 8,000 Daltons; and The N-vinyl amide monomer component is present in an amount of at least 37% (wt / wt) based on the total weight of the formulation.

19. The formulation according to any preceding claim, comprising at least 5% (wt / wt), based on the total weight of the formulation, of a non-silicone hydrophobic monomer, in particular a hydrophobic methacrylate monomer.

20. The formulation of claim 19, wherein the hydrophobic monomer comprises hydroxybutyl methacrylate, isobornyl methacrylate, or a combination of hydroxybutyl methacrylate and isobornyl methacrylate.

21. The formulation according to any one of claims 1 to 11, comprising: a. one or more hydrophilic N-vinyl amide monomers in an amount of at least 30% (wt / wt), 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 c. a non-silicone hydrophobic methacrylate monomer in an amount of at least 5% (wt / wt) based on the total weight of the formulation.

22. The formulation according to any one of claims 1 to 11, comprising: a. N-methyl N-vinylacetamide in an amount of 30% to 50% (wt / wt) of the total formulation, 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, 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, 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.

23. The formulation of claim 21 or claim 22, wherein the difunctional siloxane monomer is a (meth)acrylate-containing siloxane monomer represented by formula (III), Wherein R1 is selected from hydrogen or methyl; R2 is selected from hydrogen or C 1-4 a hydrocarbon group; m represents an integer from 0 to 10; n represents an integer from 4 to about 15, 25 or 100; a and b represent an integer of 1 or greater; a+b is equal to 20 to 500; b / (a+b) is equal to 0.01 to 0.22; and the configuration of the siloxane unit includes a random configuration.

24. The formulation of claim 21, claim 22 or claim 23, wherein the monofunctional siloxane monomer is a methacrylate-containing siloxane monomer represented by formula (II), wherein n is an integer of about 10 to 15.

25. A hydrogel contact lens obtained from the polymerisation of a formulation according to any preceding claim.

26. The contact lens of claim 25, having the following light transmission properties:

27. A contact lens according to claim 25 or claim 26 having a yellowness index of less than 6.0 as measured by the ASTM E313-05 method.

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