Irradiation blocker for contact lenses

Abstract

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

Description

Technical Field

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

Background Art

[0002] The eye is at 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 is most likely to cause damage, followed by the violet-blue component of the visible spectrum, i.e., high-energy visible light (HEVL) at wavelengths of 380 - 455 nm. Compounds that absorb light of wavelengths harmful to the human eye are already included in contact lens formulations. Many UV absorbers are known as components of the polymeric materials used to make ophthalmic lenses, including contact lenses. UV absorbers are typically compounds that contain chromophores that absorb light in the UV spectrum, i.e., wavelengths in the range of 100 - 380 nm. Benzotriazole, benzophenone, and triazine-containing compounds are known to absorb UV light, and such compounds can be added to contact lens materials to provide protection from UV irradiation. In addition to blocking UV light, some ophthalmic lenses also block blue light. For example, as described in US 5,470,932, yellow dyes containing polymerizable yellow dyes have been added to contact lenses to absorb harmful blue light irradiation. These lenses block both UV and HEVL by using two chromophores: a UV absorber and a yellow dye. Many yellow dyes absorb blue light over a wide wavelength range and reduce the transmission of blue light over the range of 380 - 500 nm.

[0003] When a sharper cut-off of the transmission spectrum in the high-energy blue-violet range is desired, a selective blue light blocker can be used as described in US Patent Application Publication No. 2005 / 0243272 and WO2008 / 048880. Such blue light blockers selectively filter wavelengths in the range of 380 to 455 nm and, in many cases, have little or no absorption of wavelengths above 450 nm. Benzotriazole blue light blockers were developed to selectively absorb light having wavelengths in the range of 380 to 455 nm. However, it has been found that known benzotriazole blue light blockers may need to be included in large amounts to substantially reduce the transmission level of light in the 380 to 455 nm range and / or may lead to undesirable yellowing of the resulting contact lens. Inclusion of a large amount, for example, 2% by mass or more of the benzotriazole blue light blocker in the contact lens formulation throughout the lens composition can adversely affect the properties of the contact lens material and / or prevent the processing of the contact lens formulation. For example, inclusion of a high level of irradiation-absorbing compounds in a hydrogel contact lens formulation can reduce the wettability of the resulting hydrogel contact lens, increase the incidence of lens defects, and / or prevent the demolding of the hydrogel lens body from the mold after casting. Inclusion of a blue light blocker, especially in large amounts, in the lens formulation can also lead to the possibility that a yellowish colouration is imparted to the lens. The imparting of a yellow colouration to the contact lens gives an undesirable yellow tint to the wearer's eye, which is less acceptable to consumers than a lens that leaves the natural colour of the eye unchanged.

[0004] US Patent Application Publication No. 2021 / 0181379 describes a lens formulation that includes a benzotriazole UV absorber, such as Norbloc, together with a benzotriazole HEVL absorber to reduce the transmittance of both UV and violet light through the contact lens. It is also known to include a tinting agent in a contact lens to change the tint for aesthetic purposes or to make it more visible when the lens is in solution. Although the tinting agent can be used to neutralize the yellowing effect of a blue light blocker, there is a need for an irradiation absorber package for use in the formulation of hydrogel contact lenses, especially silicone hydrogel contact lenses, which can substantially reduce the transmission of harmful wavelengths of light when included in the lens formulation in low amounts such as 3% by weight or less. Ideally, hydrogel contact lenses manufactured using such formulations also do not yellow. SUMMARY OF THE INVENTION

[0005] In a first aspect, the present invention provides an irradiation absorber package for use in the formulation of a hydrogel contact lens comprising a first high energy short wavelength visible light absorber comprising a benzotriazole moiety and a second different high energy short wavelength visible light absorber comprising a benzotriazole moiety. The irradiation absorber package of the first aspect of the present invention may further comprise a polymerizable UV absorber comprising a benzophenone moiety. In a second aspect, the present invention provides a hydrogel contact lens formulation, especially a silicone hydrogel contact lens formulation, comprising the irradiation absorber package of the first aspect of the present invention. The hydrogel contact lens formulation is a polymerizable formulation for forming a hydrogel contact lens body. 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 may further comprise a polymerizable UV absorber comprising a benzophenone moiety. In addition to the irradiation absorbing compound, the hydrogel contact lens formulation of the second aspect of the present invention typically contains a polymerizable monomer, oligomer and / or prepolymer, one or more crosslinking agents, and one or more polymerization initiators.

[0006] In a third aspect, the present invention provides a hydrogel contact lens formed from the polymerization of the formulation of the second aspect of the present invention, particularly a silicone hydrogel contact lens. Accordingly, the polymeric lens material of the hydrogel contact lens of the third aspect of the present invention includes a first high-energy short-wavelength visible light absorbing unit containing a benzotriazole moiety and a second different high-energy short-wavelength visible light absorbing unit containing a benzotriazole moiety. The polymeric lens material of the hydrogel contact lens of the third aspect of the present invention may further include a UV light absorbing unit containing a benzophenone moiety. In a fourth aspect, the present invention provides a method for manufacturing a hydrogel contact lens, particularly a silicone hydrogel contact lens, the method comprising the step of polymerizing the formulation of the second aspect of the present invention to form a polymeric contact lens body. Accordingly, the method for manufacturing a hydrogel contact lens of the fourth aspect of the present invention includes the step of polymerizing a formulation containing a first high-energy short-wavelength visible light absorber containing a benzotriazole moiety and a second different high-energy short-wavelength visible light absorber containing a benzotriazole moiety to form a polymeric contact lens body. The formulation polymerized by the method of the fourth aspect of the present invention may further include a polymerizable UV absorber containing a benzophenone moiety.

[0007] It has been found that by including in a contact lens formulation a combination of two different benzotriazole HEVL absorbers having different absorption characteristics, it is possible to obtain a contact lens having improved properties that can be manufactured using a single type of benzotriazole HEVL light absorber. In particular, contact lenses manufactured from a formulation containing a combination of two different benzotriazole HEVL absorbers have been found to provide a desirable reduction in the transmission level of light in the 380 - 455 nm range when the total amount of benzotriazole high energy short wavelength visible light absorber contained in the formulation is lower. In addition, contact lenses manufactured from the formulations of the present invention containing a combination of two different benzotriazole high energy short wavelength visible light absorbers have been found to provide a desirable reduction in the transmission level of light in the 380 - 455 nm range without substantial yellowing of the contact lens body. In particular, the formulations of the present invention have been found to provide hydrogel contact lenses that block at least 40%, especially at least 50%, of blue light in the 380 - 455 nm range without excessive yellowing or the need for large amounts of blue light blockers. Advantageously, the maximum wavelength at which a 0.003 mass% solution of the second HEVL absorber in ethyl acetate (≥99.8%, HPLC grade) has an absorbance of 0.1 is at least 10 nm lower than the maximum wavelength at which a 0.003 mass% solution of the first HEVL absorber in ethyl acetate has an absorbance of 0.1, where the absorbance of the solution is measured in a quartz cell with a 10 mm path length using a Perkin Elmer Lambda 365 spectrometer.

Brief Description of the Drawings

[0008]

Figure 1

Figure 2

DETAILED DESCRIPTION OF THE INVENTION

[0009] This disclosure will be more fully understood and further advantages will become apparent when reference is made to the following detailed description of embodiments of the disclosure. The present invention is described in more detail by specific reference to the formulation of the second aspect of the present invention, hereinafter referred to as "the formulation of the present invention" herein, i.e., the formulation used in the method of the fourth aspect of the present invention. However, the contact lens of the third aspect of the present invention can be obtained, for example, by polymerizing the formulation of the second aspect of the present invention according to the method of the fourth aspect of the present invention, and it is understood that the components of the formulation of the second aspect of the present invention are present in the polymerized form of the polymer lens material of the contact lens of the third aspect of the present invention. Similarly, it is understood that the irradiation absorber package of the first aspect of the present invention is a component of the formulation of the second aspect of the present invention that includes a chromophore that absorbs light over the UV and visible spectra. The features of the irradiation absorber package, formulation or lens or its components, or the method of manufacturing a lens (depending on the context) referred to herein can be combined in any combination of the features described above or hereinafter described, unless the context indicates that a particular combination of features is mutually exclusive. Further, as used herein, 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, a reference to "a contact lens" includes a single lens and two or more of the same or different lenses.

[0010] The present disclosure is based on the discovery that a contact lens having blue light blocking properties can be more effectively provided by including a combination of at least two different benzotriazole HEVL absorbers in a polymerizable formulation in which the contact lens is manufactured. Such a combination takes the undesirable yellowish color balance of the lens having blue blocking properties by including a second HEVL absorber that absorbs at a shorter wavelength than the first HEVL absorber. Such a combination also absorbs light over the 380 - 455 nm wavelength at a higher rate than can be obtained using a single benzotriazole HEVL absorber. Optionally, a third irradiation absorbing compound that is a benzophenone UV absorber is included to enhance the absorbance of UV light below 380 nm. The benzophenone UV absorber has been found to be particularly suitable for inclusion in combination with benzotriazole HEVL absorbers due to having significantly different absorption profiles. The "polymeric contact lens material" of the contact lens of the third aspect of the present invention refers to a material bonded to the contact lens body, whether by covalent bond, physical engagement or otherwise. A material that can be removed from the lens body by extraction with water, ethanol, isopropanol or a mixture thereof is not a component of the polymeric contact lens material, nor is it a solvent such as water that can be removed from the contact lens body by drying. The polymerizable components of the formulation of the second aspect of the present invention are typically incorporated into the polymeric contact lens material of the third aspect of the present invention.

[0011] The term "irradiation absorber package" collectively refers to a UV blocker, a high energy short wavelength visible light absorber, and a colored tint that absorbs light having a wavelength in the range of 100 - 700 nm. A high-energy visible light (HEVL) absorber is a compound containing a chromophore that absorbs visible light in the violet-blue range of 350 - 455 nm. Typically, the HEVL absorber has an absorption maximum (λmax) in the range of 350 - 455 nm, especially in the range of 350 - 400 nm. As used herein, the term "high-energy visible light (HEVL) absorber" can be defined as a compound having an absorbance of at least 0.5 in the range of 375 nm - 450 nm as a 0.003 mass% solution in ethyl acetate (≥99.8%, HPLC grade) (the solution is measured by the absorbance of the solution in the range of 250 - 800 nm using a quartz cell with a path length of 10 mm and Perkin Elmer Lambda 365). The HEVL absorber can further absorb light at shorter wavelengths, for example, in the range of 250 - 350 nm, and thus can function as both an HEVL absorber and a UV absorber as discussed below. Unless otherwise stated, all absorbance spectra referred to herein are measured as a 0.003 mass% solution in ethyl acetate (≥99.8%, HPLC grade) in a quartz cell with a path length of 10 mm using a Perkin Elmer Lambda 365 spectrometer.

[0012] Advantageously, the HEVL absorbers used in contact lens formulations containing the contact lens formulations of the present invention have polymerizable moieties such as vinyl, acrylate, or methacrylate functional groups in their chemical structures for incorporation by covalent bonding into the contact lens material during polymerization. Once incorporated into the polymeric contact lens material, the HEVL absorbers impart HEVL absorption characteristics to the polymeric contact lens material. The HEVL absorbers used in the present invention are typically soluble and polymerizable in the contact lens formulation, so they form part of the polymeric matrix of the lens and are retained in the lens during autoclaving and storage.

[0013] References in this specification to the amount of an ingredient or component present in a formulation expressed as a mass percentage (i.e., % (mass / mass)) are to the amount of all formulation components except diluents and / or solvents that are not incorporated into the final polymeric contact lens material. Thus, for example, the amount of the radiation absorber package in a formulation made by mixing together 1.5 parts of a radiation absorber package, 65 parts of a monomer, 3.5 parts of other active components (e.g., polymerization initiators, colorants, oxygen scavengers, etc.), and 30 parts of an organic solvent and / or water (to total 100 parts) is 2.1% (mass / mass). As used herein, "component" of a formulation refers collectively to all components of a particular type. For example, if a formulation contains 20% (mass / mass) of a first siloxane monomer and 15% of a second siloxane monomer and no other siloxanes, the formulation can be described as containing 35% (mass / mass) of a siloxane component. Advantageously, the benzotriazole HEVL absorbent component of the formulation of the second aspect of the present invention or the benzotriazole HEVL absorbent component of the formulation used in the method of the fourth aspect of the present invention does not exceed 2.7% (mass / mass), preferably does not exceed 2.0% (mass / mass). Advantageously, the total amount of all HEVL absorbents present in the formulation of the second or fourth aspect of the present invention does not exceed 2.7% (mass / mass), preferably does not exceed 2.0% (mass / mass). Alternatively or in addition, the total amount of benzotriazole compounds present in the formulation of the second or fourth aspect of the present invention may not exceed 2.7% (mass / mass), preferably does not exceed 2.0% (mass / mass). Advantageously, the total amount of benzotriazole HEVL absorbent incorporated into the polymeric lens material of the third aspect of the present invention does not exceed 2.7% (mass / mass) of the total polymeric lens material, preferably does not exceed 2.0% (mass / mass). Advantageously, the total amount of all HEVL absorbents incorporated into the polymeric lens material of the third aspect of the present invention does not exceed 2.7% (mass / mass) of the total polymeric lens material, preferably does not exceed 2.0% (mass / mass). Alternatively or in addition, the total amount of benzotriazole compounds present in the polymeric lens material of the third aspect of the present invention may not exceed 2.7% (mass / mass) of the total polymeric lens material, preferably does not exceed 2.0% (mass / mass).

[0014] The first HEVL absorbent may be present in the formulation in an amount of 0.3% to 0.9% (mass / mass), preferably 0.4% to 0.7% (mass / mass). The second HEVL absorbent may be present in the formulation in an amount of 0.5% to 2.2% (mass / mass), preferably 0.7% to 1.6% (mass / mass). Optionally, the first HEVL absorbent may be present in the formulation in an amount of 0.3% to 0.9% (mass / mass), preferably 0.4% to 0.7% (mass / mass), and the second HEVEL absorbent may be present in an amount of 0.5% to 2.2% (mass / mass), preferably 0.7% to 1.6% (mass / mass).

[0015] In the formulation of the second aspect of the present invention or the formulation used in the method of the fourth aspect of the present invention, the first and second HEVL absorbents may each be of the formula (1). [Chemical formula] (In the formula, · R 1 is halogen, OH, C 1-12 alkyloxy, -A-R 9 -Y, optionally substituted C 1-12 alkyl, optionally substituted phenoxy, or optionally substituted naphthyloxy, and any 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 optionally halogen-substituted C 1-12 alkyl; · R 6 and R 7 The other is

[0016] [Chemical formula] or -OR 8 ; ○ R 2 is a bond, optionally substituted with -OH and / or interrupted by an ester group, C 1-12 alkylene, (CH2CH2O) n or (CH2CH(CH3)O) n ; ○ X is a bond, O, NR 4 S, or (Si(CH3)2O) m Si(CH3)2; ○ R 3is a bond, C(O), C(O)C j H 2j , C 1-6 alkylene, phenyl, or C 1-6 alkylphenyl; ○ Each R 4 is independently H or methyl; ○ R 5 is H, C 1-6 alkyl, or phenyl; ○ m is from 0 to 9; ○ n is from 2 to 10; ○ j is from 1 to 6; ○ A is -S- or -SO2-; ○ R 8 is H, C 1-12 alkyl, C 6-15 arylalkyl, or -R 9 -Z; ○ Each R 9 is independently C 1-12 alkylene which may be substituted by -OH and / or interrupted by an ester group; ○ Each of Y and Z is independently -OH, -OC(O)R 10 , -NH2, -NC(O)R 10 , -NCO, -CO2H, -CO2R 10 ,

[0017]

Chemical formula

[0018] In some aspects of the present invention, the first and second HEVL absorbents may each be of the above formula (1). (Wherein, · R 1 is halogen, OH, C 1-12 alkyloxy, optionally substituted C 1-12 alkyl, optionally substituted phenoxy, or optionally substituted naphthyloxy, and any 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 which is H, or optionally substituted C 1-12 alkyl; · R 6 and R 7 the other is

[0019]

Chemical formula

[0020] In some further aspects of the present invention, the first and second HEVL absorbents may each be of the above formula (1). (wherein, · R 1 is H, Cl, Br, OH, C 1-4 alkoxy, C optionally substituted with halogen 1-4 alkyl, or phenoxy; · R 6 and R 7 one of which is H or C optionally substituted with halogen 1-4 alkyl; · R 6 and R 7 the other is

[0021]

Chemical formula

[0022]

Chemical formula

[0023] In the formulation of the second aspect of the present invention or the formulation used in the method of the fourth aspect of the present invention, the first and second HEVL absorbents may each be of formula (1a).

Chemical formula

[0024] In the compounds of the above formulas (1) and (1a), when R 2 is (CH2CH2O) n or (CH2CH(CH3)O) n , X is typically other than O; for example, when R 2 is (CH2CH2O) n or (CH2CH(CH3)O) n , X may be a bond. To avoid ambiguity, when two or more of the adjacent R2, X, and R3 are each a bond in the compounds of the above formulas (1) and (1a), the two or more adjacent groups together form a single bond. As used herein, the term "alkyl" refers to both straight-chain and branched-chain alkyl groups unless otherwise specified. Thus, for example, a reference to a C4 alkyl group refers to any or all of the n-butyl, isobutyl, s-butyl, and t-butyl groups. As used herein, the term "alkylene" refers to both straight-chain and branched-chain divalent saturated alkanediyl groups unless otherwise specified. Thus, for example, a reference to a C3 alkylene refers to any or all of the -CH2-CH2-CH2-, -CH(CH3)-CH2-, -CH2-CH(CH3)-, -C(CH3)2-, and -CH(CH2CH3)- groups.

[0025] Optionally, the polymeric contact lens material of the contact lens of the third aspect of the present invention contains two different units derived from the polymerization of the compound of the above formula (1). The first and second HEVL absorbents of the formulation of the second aspect of the present invention or the formulation used in the method of the fourth aspect of the present invention may each be of formula (2). [Chemical formula] (In the formula, A is -S- or -SO2-; R 1 is C alkylene which may be substituted with -OH and / or interrupted by an ester group; 1-12 is alkylene; R 2 is H, C 1-12 alkyl, C 6-15 arylalkyl, or -R 3 Y; R 3 is C alkylene which may be substituted with -OH and / or interrupted by an ester group; 1-12 is alkylene; Each of X and Y is independently -OH, -OC(O)R4 、 -NH2, -NC(O)R 4 、 -NCO, -CO2H, -CO2R 4 、

[0026]

Chem.

[0027] Examples of the HEVL absorbent of formula (2) can be found in U.S. Patent Application Publication No. 2021 / 0214321, the content of which is incorporated herein by reference. Specific examples of the HEVL absorbent of formula (2) that can be included in the formulations of the present invention are those of formulas (I-1) to (I-13) of U.S. Patent Application Publication No. 2021 / 0214321. Due to the presence of a sulfur-containing group at the 5-position of the benzotriazole ring of the HEVL absorbent of formula (2), for example, compared with a compound of the above formula (1) or (1a) that does not contain a sulfur-containing group, a red shift of the basic absorption peak of the benzotriazole compound is brought about. Therefore, the compound of formula (2) can be particularly useful as the second HEVL absorbent of the formulation of the present invention. The formulation of the present invention may contain, for example, UV28 as the first HEVL absorbent and a compound of formula (2) as the second HEVL absorbent. Due to the presence of a sulfur-containing group at the 5-position of the benzotriazole ring of the HEVL absorbent of formula (2), for example, compared with a compound of the above formula (1) or (1a) that does not contain a sulfur-containing group, the absorption range of the benzotriazole compound expands upward, and a higher level of absorbance is brought about in the range of 400 to 450 nm. Therefore, some compounds of formula (2) can also be useful as the first HEVL absorbent of the formulation of the present invention.

[0028] Examples of benzotriazole HEVL absorbents include 2-(1,1-Dimethylethyl)-4-[3-[(4-ethenylphenyl)methoxy]propoxy]-6-(5-methoxy-2H-benzotriazol-2-yl)-phenol (UV1, CAS No. 159732-06-6):

Chemical formula

[0029]

Chemical formula

Chemical formula

[0030]

Chem.

[0031]

Chem.

[0032]

Chem.

[0033]

Chem.

[0034]

Chem.

[0035]

Chem.

[0036]

Chem.

[0037]

Chem.

[0038] All of the above HEVL absorbers are available from LYNN Laboratories, Inc., 2797 Irving Blvd STE 110, Dallas, TX 75207. The first HEVL absorbent preferably has an absorption cut-off at a higher wavelength than the second HEVL absorbent. For example, the maximum wavelength at which a 0.003 mass% solution of the first HEVL absorbent in ethyl acetate has an absorbance of 0.1 can be at least 5 nm, particularly at least 10 nm higher than the maximum wavelength at which a 0.003 mass% solution of the second HEVL absorbent in ethyl acetate has an absorbance of 0.1. The first HEVL absorbent preferably has a higher level of absorbance than the second HEVL absorbent in the range of 380 to 425 nm, for example, as a 0.003 mass% solution in ethyl acetate. The second HEVL absorbent preferably has a higher level of absorbance than the first HEVL absorbent in the range of 350 to 375 nm, for example, as a 0.003 mass% solution in ethyl acetate.

[0039] Absorption spectra for 0.003 mass% solutions of HEVL absorbents UV13 and UV28 in ethyl acetate are shown in Figure 1. UV28 has an absorption cut-off at a higher wavelength than UV13. The maximum wavelength at which a 0.003 mass% solution of UV28 in ethyl acetate has an absorbance of 0.1 is 420 nm, while the maximum wavelength at which a 0.003 mass% solution of UV13 in ethyl acetate has an absorbance of 0.1 is 406 nm. UV28 has a higher level of absorbance than UV13 in the range of 380 to 425 nm, and UV13 has a higher level of absorbance than UV28 in the range of 350 to 375 nm.

[0040] The first and second HEVL absorbents are such that, in the absorption spectra of 0.003 mass% solutions of the first and second HEVL absorbents in ethyl acetate, the tangent to the curve at the point defined by the maximum wavelength at which the absorbance of the absorption spectrum of the first HEVL absorbent is 0.5 intersects the 0.0 absorbance axis at a wavelength that is at least 5 nm longer, particularly at least 10 nm longer, than the wavelength at which the tangent to the curve at the point defined by the maximum wavelength at which the absorbance of the absorption spectrum of the second HEVL absorbent is 0.5 intersects the 0.0 absorbance axis. The first HEVL absorbent may be characterized in that, in the absorption spectrum of a 0.003 mass% solution of the first HEVL absorbent in ethyl acetate, the tangent to the curve at the point defined by the maximum wavelength at which the absorbance is 0.5 intersects the 0.0 absorbance axis at 412 to 440 nm, 415 to 435 nm, preferably 415 to 430 nm. The second HEVL absorbent may be characterized in that, in the absorption spectrum of a 0.003 mass% solution of the second HEVL absorbent in ethyl acetate, the tangent to the curve at the point defined by the maximum wavelength at which the absorbance is 0.5 intersects the 0.0 absorbance axis at a wavelength shorter than the wavelength at which the tangent to the curve at the point defined by the maximum wavelength at which the absorbance of the absorption spectrum of the 0.003 mass% solution of the first HEVL absorbent in ethyl acetate intersects the 0.0 absorbance axis, for example, at least 5 nm shorter, particularly at least 10 nm shorter. Alternatively or in addition, the second HEVL absorbent may be characterized in that, in the absorption spectrum of a 0.003 mass% solution of the second HEVL absorbent in ethyl acetate, the tangent to the curve at the point defined by the maximum wavelength at which the absorbance is 0.5 intersects the 0.0 absorbance axis at 385 to 415 nm, preferably 390 to 412 nm.

[0041] As can be seen from Fig. 1, for the absorption spectrum of a 0.003 mass% solution of UV28 in ethyl acetate, the tangent line (A) to the point defined by the maximum wavelength at an absorbance of 0.5 intersects the 0.0 absorbance axis at 422 nm. For the absorption spectrum of a 0.003 mass% solution of UV13 in ethyl acetate, the tangent line (B) to the point defined by the maximum wavelength at an absorbance of 0.5 intersects the 0.0 absorbance axis at 407 nm. The first HEVL absorbent may be characterized in that, for the absorption spectrum of a 0.003 mass% solution of the first HEVL absorbent in ethyl acetate, the maximum wavelength at an absorbance of 0.1 is 412 - 440 nm, 415 - 435 nm, preferably 415 - 430 nm. The second HEVL absorbent may be characterized in that, for the absorption spectrum of a 0.003 mass% solution of the second HEVL absorbent in ethyl acetate, the maximum wavelength at an absorbance of 0.1 is a wavelength shorter than the wavelength at the maximum wavelength at an absorbance of 0.1 for the absorption spectrum of a 0.003 mass% solution of the first HEVL absorbent in ethyl acetate, for example, at least 5 nm shorter, especially at least 8 nm shorter. Alternatively or in addition, the second HEVL absorbent may be characterized in that, for the absorption spectrum of a 0.003 mass% solution of the second HEVL absorbent in ethyl acetate, the maximum wavelength at an absorbance of 0.1 is 385 - 412 nm, preferably 390 - 410 nm. As can be seen from Fig. 2, for the absorption spectrum of a 0.003 mass% solution of UV28 in ethyl acetate, the maximum wavelength at an absorbance of 0.1 is 420 nm. For the absorption spectrum of a 0.003 mass% solution of UV13 in ethyl acetate, the maximum wavelength at an absorbance of 0.1 is 406 nm, that is, more than 8 nm shorter than the maximum wavelength at an absorbance of 0.1 for the absorption spectrum of a 0.003 mass% solution of UV28 in ethyl acetate.

[0042] Advantageously, a 0.003% by mass solution of the first HEVL absorbent in ethyl acetate has an absorbance peak in the range of 360 to 410 nm, for example, 360 to 400 nm, especially 360 to 390 nm. Advantageously, a 0.003% by mass solution of the second HEVL absorbent in ethyl acetate has a peak absorbance at a wavelength that is at least 5 nm shorter, for example, 5 to 25 nm shorter, especially 5 to 15 nm shorter than the absorbance peak of a 0.003% by mass solution of the first HEVL absorbent in ethyl acetate that falls within the range of 360 to 410 nm. Alternatively or in addition, a 0.003% by mass solution of the first HEVL absorbent in ethyl acetate has an absorbance of at least 0.35 for light at a wavelength of 400 nm and / or at least 0.55, especially at least 0.57, for light at a wavelength of 390 nm. Alternatively or in addition, a 0.003% by mass solution of the first HEVL absorbent in ethyl acetate has an absorbance of at least 0.15, especially at least 0.20, for light at a wavelength of 410 nm. A 0.003% by mass solution of the second HEVL absorbent in ethyl acetate advantageously has an absorbance of less than 0.30 for light at a wavelength of 400 nm and / or less than 0.55, especially less than 0.53, for light at a wavelength of 390 nm. Alternatively or in addition, a 0.003% by mass solution of the second HEVL absorbent in ethyl acetate has an absorbance of less than 0.12, especially less than 0.10, for light at a wavelength of 410 nm. Advantageously, the wavelength at which a 0.003% by mass solution of the second HEVL absorbent has an absorbance of 0.1 is at least 8 nm, especially at least 10 nm, below the wavelength of the first HEVL absorbent.

[0043] As can be seen from Fig. 1, the 0.003 mass% solution of UV28 in ethyl acetate has an absorbance peak at 368 nm, and the 0.003 mass% solution of UV13 of the second HEVL absorber in ethyl acetate has an absorbance peak at 359 nm. As can be seen from Fig. 2, the 0.003 mass% solution of UV28 in ethyl acetate has an absorbance of about 0.43 for light with a wavelength of 400 nm and an absorbance of about 0.63 for light with a wavelength of 390 nm. The 0.003 mass% solutions of UV1, UV5 (UVAM), UV13 and UV15 each have an absorbance of less than 0.30 for light with a wavelength of 400 nm and an absorbance of less than 0.60 for light with a wavelength of 390 nm. The wavelength at which the 0.003 mass% solution of UV1, UV5 (UVAM), UV13 or UV15 in ethyl acetate has an absorbance of 0.1 is at least 10 nm below the wavelength of UV28.

[0044] It has been found that by including in the contact lens formulation a combination of two HEVL absorbers that meet the above criteria, a lens can be obtained that particularly effectively provides a high level of absorbance of violet-blue light in the range of 380 - 455 nm. Furthermore, such a combination provides a lens having a desirable color without imparting an undesirable yellowing to the wearer's eye. For example, when the first HEVL absorber has a higher absorbance cut-off, e.g., in the absorption spectrum of the 0.003 mass% solution of the HEVL absorber in ethyl acetate, the tangent to the curve at the point defined by the highest wavelength at which the absorbance is 0.5 intersects the 0.0 absorbance axis above 440 nm, and / or the HEVL absorber may be characterized in that the highest wavelength at which the absorbance is 0.1 with respect to the absorption spectrum of the 0.003 mass% solution of the HEVL absorber in ethyl acetate is above 430 nm, the resulting lens may have a higher yellowing effect and / or may require a larger amount of blue colorant in the lens formulation to counteract the yellowing effect of the first HEVL absorber. An example of a benzotriazole HEVL that meets the absorbance requirements shown above is UV28. An example of a less desirable HEVL absorber with a higher absorbance cut-off is UV23.

[0045] Optionally, at least one of the first and second HEVL absorbents, especially the first HEVL absorbent, is 2-[2'-hydroxy-3'-tert-butyl-5'-(3''-methacryloyloxypropoxy)phenyl]-5-chloro-2H-benzotriazole (UV28). UV28 may be present in the formulation in an amount of 0.3% to 0.9% (mass / mass), preferably 0.4% to 0.7% (mass / mass). Optionally, the first HEVL absorbent is UV28, and the second HEVL absorbent is characterized in that the maximum wavelength at which a 0.003 mass% solution of the second HEVL absorbent in ethyl acetate has an absorbance of 0.1 is 415 nm or less, especially 410 nm or less. UV28 preferably has a higher level of absorbance than the second HEVL absorbent in the range of 380 to 425 nm, for example as a 0.003 mass% solution in ethyl acetate. The second HEVL absorbent preferably has a higher level of absorbance than UV28 in the range of 350 to 375 nm, for example as a 0.003 mass% solution in ethyl acetate.

[0046] Optionally, the first HEVL absorbent is UV28, and the second HEVL absorbent is such that the tangent line at the maximum wavelength with an absorbance of 0.5 with respect to the absorption spectrum of a 0.003 mass% solution of the second HEVL absorbent in ethyl acetate intersects the 0.0 absorbance axis at a wavelength shorter than the wavelength at which the tangent line at the maximum wavelength with an absorbance of 0.5 with respect to the absorption spectrum of a 0.003 mass% solution of UV28 in ethyl acetate intersects the 0.0 absorbance axis, for example, at least 5 nm shorter, especially at least 10 nm shorter. Optionally, the first HEVL absorbent is UV28, and the second HEVL absorbent is such that the maximum wavelength with an absorbance of 0.1 with respect to the absorption spectrum of the second HEVL absorbent in ethyl acetate is at a wavelength shorter than the wavelength at the maximum wavelength with an absorbance of 0.1 with respect to the absorption spectrum of a 0.003 mass% solution of UV28 in ethyl acetate, for example, at least 5 nm shorter, especially at least 8 nm shorter. Optionally, the first HEVL absorbent is UV28, and the 0.003 mass% solution of the second HEVL absorbent 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 the 0.003 mass% solution of UV28 in ethyl acetate falling within the range of 360 to 380 nm.

[0047] Optionally, at least one of the first and second HEVL absorbents, especially the second HEVL absorbent, is selected from 2-(1,1-dimethylethyl)-4-[3-[(4-ethenylphenyl)methoxy]propoxy]-6-(5-methoxy-2H-benzotriazol-2-yl)-phenol (UV1), 2-(5-chloro-2H-benzotriazol-2-yl)-6-(1,1-dimethylethyl)-4-ethenyl-phenol (UV5 / UVAM), 2-[2'-hydroxy-3'-tert-butyl-5'-(3''-methacryloyloxypropoxy)phenyl]-5-methoxy-2H-benzotriazol (UV13), and 2-3'-t-butyl-2'-hydroxy-5'-(3''-dimethylvinylsilylpropoxy)-2'-hydroxy-phenyl)-5-methoxybenzotriazole (UV15). One of UV1, UV5, UV13 or UV15, or any combination of UV1, UV5, UV13 and UV15 may be present in an amount of 0.5% to 2.2% (mass / mass), preferably 0.7% to 1.6% (mass / mass). The second HEVL absorbent may be UV13. UV13 may be present in an amount of 0.5% to 2.2% (mass / mass), preferably 0.7% to 1.6% (mass / mass). The absorbance spectra of each of UV1 and UV15 are all very similar to the absorbance spectrum of UV13 having a maximum at about 360 - 365 nm (as shown in Figure 1). UV5 (UVAM) has an absorption profile similar to that of UV13 at wavelengths above 330 nm (e.g., 330 - 500 nm), and also has a second absorbance peak at about 310 nm and thus an absorption profile below 330 nm similar to that of UV28 (as shown in Figure 1). Thus, in some embodiments of the present invention, UV5 (UVAM) can be a particularly advantageous second HEVL absorbent that is preferred over UV1, UV15 or UV13, for example, in formulations where an enhanced level of UV absorbance in the range of 300 - 320 nm is required.

[0048] Optionally, the first HEVL absorbent is UV28, and the second HEVL light absorbent is one of UV1, UV5, UV13 or UV15, or any combination of UV1, UV5, UV13 and UV15. One of UV1, UV5, UV13 or UV15, or any combination of UV1, UV5, UV13 and UV15 may be present in an amount of 0.5% to 2.2% (mass / mass), preferably 0.7% to 1.6% (mass / mass); UV28 may be present in an amount of 0.3% to 0.9% (mass / mass), preferably 0.4% to 0.7% (mass / mass). Optionally, the first HEVL absorbent is UV28 and the second HEVL light absorbent is UV13. UV13 may be present in an amount of 0.5% to 2.2% (mass / mass), preferably 0.7% to 1.6% (mass / mass); UV28 may be present in an amount of 0.3% to 0.9% (mass / mass), preferably 0.4% to 0.7% (mass / mass). Optionally, the total amount of the HEVL absorbent of formula (1) present in the formulation of the present invention does not exceed 2.7% (mass / mass), preferably does not exceed 2.0% (mass / mass). Optionally, the formulation of the present invention contains one of UV1, UV5, UV13 or UV15, or any combination of UV1, UV5, UV13 and UV15, especially UV13 in an amount of 0.5% to 2.2% (mass / mass), preferably 0.7% to 1.6% (mass / mass); contains UV28 in an amount of 0.3% to 0.9% (mass / mass), preferably 0.4% to 0.7% (mass / mass), and the total amount of the HEVL absorbent of formula (1) present in the formulation does not exceed 2.7% (mass / mass), preferably does not exceed 2.0% (mass / mass).

[0049] Optionally, the total amount in mass percentage of the units derived from the HEVL absorber of formula (1) present in the polymer lens material of the contact lens of the third aspect of the present invention is as described above for the formulation of the second aspect of the present invention. For example, the total amount of the units derived from the high-energy short-wavelength visible light absorber of formula (1) present in the polymer lens material of the contact lens of the third aspect of the present invention may not exceed 2.7% (mass / mass) of the polymer lens material, preferably not exceed 2.0% (mass / mass). The term "UV absorber" refers to a compound containing a chromophore that absorbs light in the UV spectrum, i.e., wavelengths in the range of 100 to 400 nm. In particular, a 0.003 mass% solution of the UV absorber in ethyl acetate has absorption maxima (λmax) in the range of 220 to 350 nm, especially in the range of 250 to 350 nm. The UV absorber present in the formulation and the lens of the present invention preferably has a maximum absorbance (λmax) in the range of 250 to 350 nm, 260 to 320 nm, especially 270 to 310 nm, as a 0.003 mass% solution in ethyl acetate.

[0050] The compound can function as both a HEVL absorber and a UV absorber. For example, a 0.003% by mass solution of UV28 in ethyl acetate has an absorption maximum (λmax) at about 308 nm in the range of 220 - 350 nm, has an absorption greater than 0.5 in the ranges of about 288 - about 330 nm and about 337 - about 397 nm, and has an absorption maximum (λmax) at about 369 nm in the range of 350 - 455 nm. As used herein, the term "HEVL absorber" includes compounds that function only as HEVL absorbers, as well as compounds that function as both HEVL absorbers and UV absorbers. The UV absorber contained in the formulation of the present invention is preferably not a dual - function HEVL absorber and UV absorber. The UV absorber can have an absorbance cut - off below the visible range, that is, it does not absorb light above 380 nm in a significant amount. For example, a 0.003% by mass solution of the UV absorber in ethyl acetate does not have an absorbance of at least 0.5 in the range of 375 nm - 450 nm. Each of the first and / or second HEVL absorbers present in the formulation of the present invention, as a 0.003% by mass solution in ethyl acetate, has an absorption greater than 0.5 in the range of 375 nm - 450 nm, and optionally also has an absorption maximum (λmax) in the range of 220 - 350 nm, especially in the range of 250 - 350 nm. Optionally, the hydrogel contact lens formulation of the present invention can include one or more UV absorbers, that is, the contact lens formulation can include a UV absorber or can include a UV absorber component that includes two or more UV absorbers. The UV absorbers that can be included in the formulation of the present invention include, for example, benzophenone or benzotriazole, or any combination thereof.

[0051] The UV absorber is preferably covalently bonded to the polymer matrix of the lens material, rather than simply physically encapsulated in the material, to prevent the absorber from migrating, phase separating, or leaking from the lens material. Such stability is advantageous because leakage of the UV absorber can present toxicological problems and / or lead to loss of the UV blocking activity of the contact lens. The UV absorbers used in the present invention are typically soluble and polymerizable in contact lens formulations, so that they form part of the polymer matrix of the lens and are retained in the lens during autoclaving and storage. The UV absorber is preferably a polymerizable UV absorber containing one or more reactive groups capable of participating in the curing reaction, whereby the polymer matrix of the polymeric lens material is formed and the polymerizable UV absorber covalently bonds to the polymeric lens material. The polymerizable UV absorber typically contains ethylenically unsaturated groups capable of participating in a radical polymerization reaction, such as vinyl or (meth)acrylate, (meth)acrylamide, or styrene groups. A number of copolymerizable benzotriazoles, benzophenones, methyl salicylates, acrylonitriles, and triazine UV absorbers are known. Many of these UV absorbers contain ethylenically unsaturated polymerizable groups. The UV absorber is incorporated into the contact lens material from which it is obtained by copolymerization with other components of the lens formulation, typically with a radical initiator. Incorporation of additional functional groups into the UV absorber can affect one or more of the UV absorption characteristics, 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, manufactured by Noramco, Athens, GA., USA).The UV absorber or UV absorber component may be present in the formulations of the present invention in an amount of up to about 5.0% (mass / mass), typically from about 0.1% (mass / mass) to about 2.0% (mass / mass), or from about 0.2% (mass / mass) to about 1.5% (mass / mass), for example, from 0.3% (mass / mass) to 1.0% (mass / mass).

[0052] The hydrogel contact lens formulation of the second aspect of the present invention or the hydrogel contact lens formulation used in the method of the fourth aspect of the present invention may further contain a polymerizable UV absorber having a maximum absorbance (λmax) in the range of 250 to 380 nm, 260 to 320 nm, particularly 270 to 310 nm, as a 0.003% by mass solution in ethyl acetate. The UV light absorbing unit present in the polymer lens material of the hydrogel contact lens of the third aspect of the present invention may be derived from the polymerizable UV absorber described herein with reference to the formulations of the present invention. Accordingly, the polymer lens material of the hydrogel contact lens of the third aspect of the present invention may contain a UV light absorbing unit derived from a polymerizable UV absorber having a maximum absorbance (λmax) in the range of 250 to 380 nm, 260 to 320 nm, particularly 270 to 310 nm, as a 0.003% by mass solution in ethyl acetate.

[0053] The hydrogel contact lens formulation of the second aspect of the present invention or the hydrogel contact lens formulation used in the method of the fourth aspect of the present invention may further contain a polymerizable UV absorber containing a benzophenone moiety. Similarly, the polymer lens material of the hydrogel contact lens of the third aspect of the present invention may further contain a UV light absorbing unit containing a benzophenone moiety. The UV light absorbing unit containing a benzophenone moiety present in the polymer lens material of the third aspect of the present invention may be derived from the polymerizable UV absorber described herein with reference to the formulations of the present invention.

[0054] The hydrogel contact lens formulation of the second aspect of the present invention or the hydrogel contact lens formulation used in the method of the fourth aspect of the present invention may contain a polymerizable UV absorber containing a benzophenone moiety as a 0.003 mass% solution in ethyl acetate, and has a maximum absorbance (λmax) in the range of 250 to 380 nm, 260 to 320 nm, particularly 270 to 310 nm. The UV light absorbing unit present in the polymer lens material of the third aspect of the present invention may be derived from the polymerizable UV absorber described herein with reference to the formulation of the present invention. Accordingly, the polymer lens material of the hydrogel contact lens of the third aspect of the present invention may contain a UV light absorbing unit derived from a polymerizable UV absorber containing a benzophenone moiety, which has a maximum absorbance (λmax) in the range of 250 to 380 nm, 260 to 320 nm, particularly 270 to 310 nm, as a 0.003 mass% solution in ethyl acetate. The benzophenone UV absorber contained in the formulation of the present invention is preferably not a dual-functional HEVL absorber and a UV absorber. The benzophenone UV absorber may have an absorbance cut-off below the visible range, that is, the benzophenone UV absorber does not absorb light above 380 nm in a significant amount. For example, a 0.003 mass% solution of the 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.

[0055] In the formulation of the second aspect of the present invention or the formulation used in the method of the fourth aspect of the present invention, by including a UV absorber having a maximum absorbance (λmax) in the range of 250 to 380 nm, 260 to 320 nm, particularly 270 to 310 nm, as a 0.003% by mass solution in ethyl acetate, and / or containing a benzophenone moiety, the resulting lens has a higher absorbance over the range of 250 to 455 nm at a lower overall level of the UV blocker than when a UV absorber having a maximum absorbance (λmax) in the range of 250 to 380 nm and above 320 nm, as a 0.003% by mass solution in ethyl acetate, and / or containing a benzotriazole or triazine moiety, particularly a benzotriazole moiety, is included. Without wishing to be bound by any theory, due to the significant difference in absorption between the benzophenone UV absorber and the benzotriazole HEVL absorber, a combination of a benzophenone UV absorber having a maximum absorbance (λmax) in the range of 250 to 380 nm, 260 to 320 nm as a 0.003% by mass solution in ethyl acetate, and two different HEVL absorbers each containing a benzotriazole moiety is hypothesized to provide more effective light blocking over the range of 260 to 440 nm than a combination containing a UV absorber having a maximum absorbance (λmax) in the range of 250 to 380 nm and above 320 nm and / or a benzotriazole moiety, such as Norbloc. Optionally, the formulation of the present invention includes one or more polymerizable UV absorbers containing a benzophenone moiety in an amount not exceeding 1.5% (mass / mass), preferably not exceeding 1.0% (mass / mass). The polymerizable UV absorber may be 2-(4-benzoyl-3-hydroxyphenoxy)ethyl acrylate (UV416).

[0056] The formulations of the present invention may also contain at least one flavoring agent, i.e., a flavoring agent component containing one flavoring agent or two or more flavoring agents. In one example, the flavoring agent can be a reactive dye or pigment that effectively imparts color to the resulting lens or effectively reduces the amount of color tone of the resulting lens. The flavoring agent or flavoring agent component of the polymerizable formulation can include a polymerizable flavoring agent, or a non-polymerizable flavoring agent, or any combination thereof. A polymerizable flavoring agent can be a flavoring agent that contains a polymerizable functional group in its molecular structure, or a flavoring agent that contains both a monomer moiety and a dye moiety in its molecular structure, i.e., the flavoring agent can be a monomer dye compound. The molecular structure of the flavoring agent may include, for example, a beta-sulfone functional group, a triazine functional group, or an anthraquinone moiety. Suitable flavoring agents include, for example, VAT Blue 6 (7,16-dichloro-6,15-dihydroanthrazine-5,9,14,18-tetrone), 1-amino-4-[3-(beta-sulphatoethylsulphonyl)anilino]-2-anthraquinonesulphonic acid (C.I. Reactive Blue 19, RB-19) or the monomer dye compound of Reactive Blue 19 and hydroxyethyl methacrylate (RB-19 HEMA), 1,4-bis[4-[(2-methacryloxyethyl)phenylamino]anthraquinone (Reactive Blue 246, RB-246, CAS number 121888-69-5, available from Arran Chemical Company, Athlone, Ireland), 1,4-bis[(2-hydroxyethyl)amino]-9,10-anthracenedione bis(2-propene) ester (Reactive Blue 247, RB-247, CAS number 109561-07-1, also available from Arran Chemical Company), or Reactive Blue 4 (RB-4, CAS number 13324-20-4, available from ThermoFisher) or the monomer dye compound of Reactive Blue 4 and hydroxyethyl methacrylate (RB-4 HEMA or "Blue HEMA").Further examples of suitable monomeric dye compounds are described in US5,944,853 and US7,216,975, both of which are incorporated herein by reference in their entirety. Other exemplary colorants are disclosed, for example, in US Patent Publication No. US2008 / 0048350, and US4,997,897, the disclosures of which are incorporated herein by reference in their entirety. The formulations of the present invention advantageously include a blue or blue - green colorant comprising an anthraquinone moiety, particularly a polymerizable blue or blue - green colorant comprising an anthraquinone moiety. The polymeric lens material of the contact lenses of the present invention may further comprise units derived from a polymerizable blue or blue - green colorant comprising an anthraquinone moiety. The polymerizable blue or blue - green colorant may be selected from 1,4 - bis[4-(2 - methacryloxyethyl)phenylamino]-9,10 - anthraquinone (RB246) or 1,4 - bis[(2 - methacryloxyethyl)amino]-9,10 - anthraquinone (RB247).

[0057] The irradiation absorber packaging of the HEVL absorber can be selected, together with any UV absorber and any flavoring agent, such that the light transmission characteristics of the contact lens produced from the contact lens formulation containing the irradiation absorber packaging meet the required specifications. For example, the hydrogel contact lens formulation of the second aspect of the present invention provides a contact lens that meets the requirements of Class 1 UV blocking (defined in Table 4 of BS EN ISO 18369-2:2017), i.e., a contact lens capable of blocking >90% of UVA rays and >99% of UVB rays, or a contact lens that meets the requirements of Class 2 UV blocking, i.e., a contact lens that blocks >50% of UV-A rays and >95% of UV-B rays. The preferred formulation of the present invention, in addition to providing UV blocking, provides a contact lens that blocks at least 30% of HEVL, particularly at least 40% of HEVL, preferably at least 45% of HEVL light. The formulation may also provide a contact lens that blocks at least 35% of violet light, particularly at least 45% of violet, preferably at least 50% of violet light. The contact lens of the third aspect of the present invention advantageously meets the requirements of Class 1 UV blocking (defined in Table 4 of BS EN ISO 18369-2:2017), i.e., it can block >90% of UVA rays and >99% of UVB rays, or meets the requirements of Class 2 UV blocking, i.e., it can block >50% of UV-A rays and >95% of UV-B rays. The preferred contact lens of the present invention, in addition to providing UV blocking, blocks at least 30% of HEVL, particularly at least 40% of HEVL, preferably at least 45% of HEVL light. The contact lens of the present invention can block at least 35% of violet light, particularly at least 45% of violet, preferably at least 50% of violet light. "UVA" refers to irradiation occurring at wavelengths of 315 - 400 nanometers (nm); "UVB" refers to irradiation occurring at 280 - 315 nm; "violet" refers to irradiation occurring at wavelengths of 380 - 440 nm, and "high energy visible light" (HEVL) refers to irradiation occurring at wavelengths of 380 - 455 nm.

[0058] The polymer material of the contact lens according to the third aspect of the present invention may have the following light transmission characteristics, and / or the hydrogel contact lens preparation according to the second aspect of the present invention may result in a contact lens of a material that satisfies the following light transmission characteristics. [Table 1]

[0059] The transmission characteristics of the lens material were measured with a 1×2 cm rectangular cast film 1 mm thick. The film was analyzed by UV-visible transmission spectroscopy from 300 to 800 nm using a Perkin-Elmer Lambda 35 instrument equipped with a Lab Sphere RSA-PE-20 integrating sphere. The contact lens according to the third aspect of the present invention may have a yellowness of less than 8.0, preferably less than 6.0, and particularly less than 5.0, as determined by the ASTM E313-05 method. The hydrogel contact lens preparation according to the second aspect of the present invention may result in a hydrogel contact having a yellowness of less than 8.0, preferably less than 6.0, and particularly less than 5.0, as determined by the ASTM E313-05 method.

[0060] The contact lens according to 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 polymer material having a three-dimensional polymer network (i.e., a polymer matrix) that is insoluble in water but contains at least 10 mass percent water in its polymer matrix when fully hydrated. "Silicone hydrogel" refers to a hydrogel obtained by the polymerization of a hydrogel contact lens preparation containing at least one silicone-containing monomer. The term "non-silicone hydrogel" refers to a hydrogel that does not contain silicone. Suitable polymerizable formulations for use in the preparation of conventional hydrogels and silicone hydrogel contact lenses are well known in the art. The irradiation absorber packaging of the first aspect of the present invention is suitable for incorporation into a wide range of polymerizable formulations for forming hydrogel contact lenses containing silicone hydrogels. In addition to the irradiation absorbing compound, the hydrogel contact lens formulation of the second aspect of the present invention contains monomers and other components suitable for forming hydrogel contact lenses as described below.

[0061] 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)acrylic, (meth)acrylamide, allyl, and vinyl, and styrenyl groups. As used herein, a "vinyl-containing monomer" is any non-siloxane monomer (i.e., a vinyl group) having a single polymerizable carbon-carbon double bond present in its molecular structure, and the carbon-carbon double bond of the vinyl group is bonded to an sp3 hybridized carbon atom. The vinyl group is less reactive than the carbon-carbon double bond present in acrylate or methacrylate polymerizable groups under free radical polymerization. The term "(meth)acrylamide" refers to methacrylamide and / or acrylamide. The term "(meth)acrylate" refers to methacrylate and / or acrylate. The term "terminal (meth)acrylic group" refers to one (meth)acrylic group at one of the two ends of the main chain (or backbone) of an organic compound. An "N-vinylamide monomer" refers to an amide compound having a vinyl group CH=CH2 directly bonded to the nitrogen atom of the amide group.

[0062] A "monomer" is a molecule having one or more polymerizable groups that can react with the same or different other monomers in a polymerization process to form a larger polymer or copolymer chain or a three-dimensional polymer matrix. Monomers having two or more polymerizable groups can be referred to as "crosslinking agents", as further described below. The term "monomer" includes macromonomers and polymerizable oligomers, i.e., polymerizable molecules containing one or more chains of repeating units, such as polymerizable polysiloxanes; thus, there are no restrictions (i.e., maximum molecular weight) on the size of the monomer, unless otherwise indicated. As used in this application, the term "molecular weight" of a polymeric material refers to the absolute number average molecular weight (in daltons), determined, for example, by 1H NMR end group analysis or by GPC using polystyrene standards, unless otherwise specified. The term "polymer" refers to a material formed by polymerizing and / or crosslinking one or more monomers. The formulations of the present invention typically contain hydrophilic monomers and may also contain hydrophobic monomers. As used herein, a "hydrophilic monomer" refers to a silicone-free monomer in which at least 50 grams of the monomer is completely soluble in 1 liter of water at 20 °C (i.e., approximately 5% water-soluble), as determined visually using the standard shaking flask method.

[0063] The hydrogel contact lens formulations of the present invention typically contain at least one hydrophilic monomer, optionally in an amount of at least 25% (mass / mass), for example, in an amount of at least 30% (mass / mass), especially in an amount of at least 35% (mass / mass). Suitable hydrophilic monomers include hydrophilic vinylamide-containing monomers and hydrophilic vinyl ether-containing monomers. In some examples, the hydrophilic vinylamide-containing monomer can be selected from N-vinyl-N-methylacetamide (VMA), or N-vinylpyrrolidone (NVP), or N-vinylformamide, or N-vinylacetamide, or N-vinyl-N-ethylacetamide, or N-vinylisopropylamide, or N-vinylcaprolactam, or N-vinyl-N-ethylformamide, or any combination thereof. In some examples, the hydrophilic vinylamide-containing monomer consists of VMA or NVP, or a combination of VMA and NVP. The vinyl ether-containing monomer can be selected from 1,4-butanediol vinyl ether (BVE), or ethylene glycol vinyl ether (EGVE), or diethylene glycol vinyl ether (DEGVE), or 1,4-cyclohexanedimethanol vinyl ether (CHDMVE), or poly(ethylene glycol) vinyl ether having 4 to 10 ethylene glycol units, or poly(ethylene glycol) vinyl ether having more than 10 ethylene glycol units, or any combination thereof. In some examples, the vinyl ether-containing monomer can be poly(ethylene glycol) vinyl ether having at least 1, 2, or 3 ethylene glycol units to 4, 6, 8, or 10 ethylene glycol units. One or more vinyl-containing monomers may be included in the formulations of the present invention in addition to the hydrophilic vinylamide-containing monomers and hydrophilic vinyl ether-containing monomers. For example, a vinyl monomer having a vinyl ester or allyl ester polymerizable group may be included in the formulations of the present invention in addition to the vinylamide-containing monomer and vinyl ether-containing monomer.The hydrophilic monomer may be a (meth)acrylate or a (meth)acrylamide group-containing hydrophilic monomer, 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.

[0064] The formulation of the second aspect of the present invention may contain at least one hydrophilic N-vinylamide monomer, optionally in an amount of at least 20 percent (mass / mass), for example, in an amount of at least 30% (mass / mass), especially in an amount of at least 35 percent (mass / mass). The formulation of the second aspect of the present invention may contain at least one hydrophilic N-vinylamide monomer in an amount of 25% to 55% (mass / mass), especially in an amount of 30% to 50% (mass / mass). The formulation of the second aspect of the present invention may contain N-methyl N-vinylacetamide in an amount of 25% to 55% (mass / mass), especially in an amount of 30% to 50% (mass / mass). The polymerizable monomer may include a hydrophobic monomer. As used herein, the term "hydrophobic monomer" refers to a monomer that does not contain a siloxane group and has a water solubility of less than 5% at 20 °C as determined using the standard shaking flask method.

[0065] The hydrophobic monomer that does not contain a siloxane group may be a (meth)acrylate group-containing hydrophobic monomer. As used herein, a "hydrophobic acrylate-containing monomer" is any non-siloxane monomer that has 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).Preferred non-siloxane 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 stiffness of the lens, or to impart other desirable properties.

[0066] The hydrophobic monomers that do not contain siloxane groups are not limited to (meth)acrylate group-containing monomers, but may contain vinyl or other ethylenically unsaturated reactive groups. Further examples of hydrophobic monomers include vinyl acetate, vinyl propionate, vinyl butyrate, styrene, chloroprene, vinyl chloride, vinylidene chloride, acrylonitrile, and methacrylonitrile. The formulation may contain from about 2% to about 20% (mass / mass), for example, from 4% to 16% (mass / mass), especially from 6% to 12% (mass / mass) of a non-siloxane hydrophobic monomer component. 2 to 20% (mass / mass) of the formulation, especially 5 to 15% (mass / mass), may be hydroxybutyl methacrylate, isobornyl methacrylate, or a combination of hydroxybutyl methacrylate and isobornyl methacrylate.

[0067] The hydrogel contact lens formulation of the second aspect of the present invention and / or the hydrogel contact lens formulation used in the method of the fourth aspect of the present invention may be a silicone hydrogel contact lens formulation containing a siloxane-containing monomer in addition to a hydrophilic monomer and any hydrophobic monomer not containing a siloxane group. The hydrogel contact lens of the third aspect of the present invention may be a silicone hydrogel contact lens containing a siloxane group in the matrix of the polymeric lens material. As used herein, "siloxane monomer" refers to a monomer having at least one siloxane group. The siloxane monomer may contain 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 may include a combination of monofunctional and difunctional (meth)acrylate-containing siloxane monomers. In the example 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 polyfunctional (meth)acrylate-containing siloxane monomers), the silicone hydrogel contact lens formulation typically further includes a (meth)acrylate-containing crosslinking agent 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-hydroxypropyl)propyldi(trimethylsiloxy)methylsilane ("SiGMA"), methyldi(trimethylsiloxy)silylpropyl glycerol ethyl methacrylate ("SiGEMA"), and monomethacryloyloxypropyl-functional polydimethylsiloxane, for example, MCR-M07 and MCS-M11, all available from Gelest (Morrisville, PA, USA).

[0068] The hydrogel contact lens formulation of the second aspect of the present invention may be a formulation containing at least one polymerizable siloxane monomer, optionally in an amount of at least 25% (mass / mass), for example, in an amount of at least 35% (mass / mass), especially in an amount of at least 40% (mass / mass).

[0069] The silicone hydrogel contact lens formulation may include at least one bifunctional siloxane having a molecular weight of at least 5,000 Daltons, especially at least one bifunctional siloxane having a molecular weight of at least 8,000 Daltons. The bifunctional siloxane typically has a molecular weight of less than 25,000 Daltons, for example, less than 20,000 Daltons, especially less than 15,000 Daltons. It has been found that including siloxanes with higher molecular weights can result in formulations having unacceptably high viscosities. The silicone hydrogel contact lens formulation may include at least one bifunctional siloxane having a molecular weight of 5,000 to 25,000 Daltons, for example, at least one bifunctional siloxane having a molecular weight of 6,500 to 20,000 Daltons, especially at least one bifunctional siloxane having a molecular weight of at least 8,000 to 15,000 Daltons. Advantageously, at least 30% (mass / mass) of the siloxane content may be a bifunctional siloxane having a molecular weight of at least 5,000 Daltons, or at least 8,000 Daltons, for example, 8,000 to 20,000 Daltons. Preferably, at least 40% (mass / mass) of the siloxane content is bifunctional and has a molecular weight of at least 5,000 Daltons, or at least 8,000 Daltons, for example, 8,000 to 20,000 Daltons. The formulation advantageously includes 15 to 45% by weight of a bifunctional siloxane, for example, 20 to 40% by weight of a bifunctional siloxane having a molecular weight of at least 5,000 Daltons, or at least 8,000 Daltons, for example, 8,000 to 20,000 Daltons. In some embodiments, the silicone hydrogel contact lens formulation may include at least one bifunctional siloxane having a molecular weight of at least 10,000 Daltons. At least 30% (mass / mass) of the siloxane content may be a bifunctional siloxane having a molecular weight of at least 10,000 Daltons, or at least 40% (mass / mass) of the siloxane content is bifunctional and has a molecular weight of at least 10,000 Daltons.The formulation may contain 15 to 45% by weight of a bifunctional siloxane, for example, 20 to 40% by weight of a bifunctional siloxane having a molecular weight of at least 10,000 Daltons. The silicone hydrogel contact lens formulation may contain at least one monofunctional siloxane monomer having a molecular weight of less than 3000 Daltons, for example. At least 20% (weight / weight) of the siloxane content may be a monofunctional siloxane having a molecular weight of less than 3000 Daltons. Advantageously, at least 30% (weight / weight) of the siloxane content is monofunctional and has a molecular weight of less than 3000 Daltons. The formulation may contain 10 to 30% by weight of a monofunctional siloxane monomer, for example, 10 to 30% by weight of a monofunctional siloxane monomer having a molecular weight of less than 3000 Daltons. The monofunctional siloxane typically has a molecular weight of at least 200 Daltons.

[0070] In one example, the monofunctional siloxane monomer may include a (meth)acrylate-containing siloxane monomer represented by formula (I). [Chemical formula] (In the formula, 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 a methyl group, R 3 is hydrogen or a methyl group). In a further specific example, the acrylate-containing siloxane monomer is such that R 1 is a butyl group, R 2 is hydrogen, R 3 is a methyl group, m is 4, and n is 1, and is represented by formula I. The method for preparing the siloxane monomer represented by formula (I) is described in US Patent Publication No. 20090299022, which is incorporated herein by reference.

[0071] In another example, the monofunctional siloxane monomer may include a (meth)acrylate-containing siloxane monomer represented by formula (II). [Chemical] (wherein n is an integer of about 10 to 15). The siloxane monomer of Formula II and other suitable monomers are all described in U.S. Patent No. 6,867,245 and U.S. Patent No. 6,310,169, which are incorporated herein by reference. Examples of suitable commercially available monofunctional siloxane monomers include 2-propenoic acid, 2-methyl-, 2-[3-(9-butyl-1,1,3,3,5,5,7,7,9,9-decamethylpentasiloxan-1-yl)propoxy]ethyl ester, available from Shin-Etsu Chemical Co., Ltd., Tokyo, Japan, X-22-1622 (also called KF1622) (CAS No. 1052075-57-6), methacryloxypropyl-terminated poly(dimethyl)siloxane FMM from Shin-Etsu Silicones of America, Akron, Ohio, USA (CAS No. 697234-76-7), and 3-methacryloxy-2-hydroxypropyl)propyldi(trimethylsiloxy)methylsilane SiGMA.

[0072] [Chemical]

[0073] The silicone hydrogel contact lens formulation may include, for example, at least one bifunctional siloxane monomer having a molecular weight of at least 8,000 daltons. The formulation may contain 10 to 45% by weight of the bifunctional siloxane monomer, especially 20 to 40% by weight of the bifunctional siloxane monomer. Advantageously, the formulation contains 10 to 45% or 20 to 40% by weight of a bifunctional siloxane monomer having a molecular weight of at least 8,000 daltons. The formulation may contain 10 to 45% or 20 to 40% by weight of a bifunctional siloxane monomer having a molecular weight of at least 10,000 daltons.

[0074] In one example, the difunctional siloxane monomer may include a (meth)acrylate-containing siloxane monomer represented by formula (III).

Chemical formula

[0075] Another preferred difunctional siloxane monomer is represented by formula (IV).

Chemical formula

[0076] Another suitable difunctional siloxane monomer is represented by formula (V).

Chemical formula

[0077] 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 such an 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. For polyorganosiloxane monomers such as those represented by the above formulas II, IV, and V, 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 Daltons, and the difunctional acrylate-containing siloxane monomer has a molecular weight of about 5,000 to about 16,000 Daltons. In a further specific example, the monofunctional (meth)acrylate-containing siloxane monomer has a molecular weight of about 500 to about 1000 Daltons, and the difunctional (meth)acrylate-containing siloxane monomer has a molecular weight of about 5,000 to about 12,000 Daltons.

[0078] The formulations of the present invention typically include one or more polymerization initiators, i.e., the hydrogel contact lens formulations may include an initiator, or may include an initiator component including two or more polymerization initiators, or a combination of a polymerization initiator, a synergist, and an activator. The term "initiator" refers to a chemical substance that initiates a crosslinking / polymerization reaction. The initiator is typically a free radical initiator that forms radicals that initiate a radical propagation polymerization reaction. Examples of 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 upon exposure to actinic radiation such as UV light, or a thermal initiator that is activated upon exposure to heat. Examples of initiators that may be present in the hydrogel contact lens formulations include, for example, benzoin ethyl ether, or benzyl dimethyl ketal, or alpha,alpha-diethoxyacetophenone, or 2,4,6-trimethylbenzoyl diphenylphosphine oxide, or benzoyl peroxide, or t-butyl peroxide, or azobisisobutyronitrile, or azobisdimethylvaleronitrile, or any combination thereof. Examples of UV photoinitiators include, for example, phosphine oxides, such as diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, or benzoin methyl ether, or 1-hydroxycyclohexyl phenyl ketone, or Darocur (also available from BASF, Florham Park, N.J., USA), or Irgacur (also available from BASF), or any combination thereof. Advantageously, the polymerization initiator is a thermal initiator.Examples of suitable thermal initiators include 2,2'-azobis(2-methylpropanenitrile), also known as 2,2'-azobis(isobutyronitrile) (AIBN) (VAZO-64, manufactured by E.I. DuPont de Nemours & Co., Wilmington, Del., USA, CAS number 78-67-1), 2,2'-azobis(2,4-dimethylpentanenitrile), also known as 2,2'-azobis(dimethylvaleronitrile) (VAZO-52, also manufactured by E.I. DuPont, CAS number 4419-11-8), and 1,1'-azobis(cyanocyclohexane), also known as 1,1'-azobis(cyclohexanecarbonitrile) (VAZO-88, also manufactured by E.I. DuPont, CAS number 2094-98-6). The polymerization initiator or initiator component may be present in the hydrogel contact lens formulation in an amount of from about 0.1% (mass / mass) to about 1.5% (mass / mass), or from about 0.2% (mass / mass) to about 1.0% (mass / mass), particularly from about 0.2% (mass / mass) to about 0.8% (mass / mass). The hydrogel contact lens formulation of the second aspect of the present invention may be a thermosetting formulation containing at least one thermal initiator. The method of the fourth aspect of the present invention may include thermosetting the formulation. Thermosetting or chemical curing methods are well known to those skilled in the art.

[0079] The hydrogel contact lens formulation of the present invention may further contain a crosslinking agent. The crosslinking agent can react with the functional groups of two or more polymer chains to crosslink one polymer with another. As used herein, a "crosslinking agent" is any compound having two or more polymerizable groups with a molecular weight of less than about 2000 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, without limitation, divinyl ether, or divinyl sulfone, or triallyl isocyanurate, and any combination thereof. Exemplary divinyl ethers include diethylene glycol divinyl ether, or triethylene glycol divinyl, or 1,4-butanediol divinyl ether, or 1,4-cyclohexanedimethanol divinyl ether, or any combination thereof. Typically, a vinyl-containing crosslinking agent can have two or three polymerizable vinyl groups. When present, the total amount of vinyl-containing crosslinking agent in the hydrogel contact lens formulation is 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, without limitation, lower alkylene glycol di(meth)acrylate, poly(lower alkylene) glycol di(meth)acrylate, lower alkylene di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, bisphenol A di(meth)acrylate, methylenebis(meth)acrylamide, and 1,3-bis(3-methacryloxypropyl)tetramethyldisiloxane. In certain examples, the acrylate-containing crosslinking agent is a non-siloxane crosslinking agent.When present, the total amount of acrylate-containing crosslinking agent 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%. To avoid doubt, polyfunctional polymerizable compounds having a molecular weight greater than 2000 Daltons are not considered crosslinking agents. Thus, the difunctional siloxanes as described herein having a molecular weight greater than 2000 Daltons are not considered crosslinking agents.

[0080] The formulations of the present invention may further contain a chain transfer agent. Chain transfer is a polymerization reaction in which the activity of a growing polymer chain moves to another molecule and the average molecular weight of the final polymer decreases. Examples of chain transfer agents include, for example, thiol compounds, halogenated carbon compounds, or C3-C5 hydrocarbons, such as allyloxyethanol. The hydrogel contact lens formulation may contain non-polymerizable components in addition to the polymerizable components conventionally used in contact lens formulations. Additional components, such as organic diluents or oxygen scavengers, may also be included. Non-limiting examples of these and additional components that may be included in the formulations of the present invention are provided in U.S. Patent Publication No. 2007 / 0296914.

[0081] Preferred formulations of the second aspect of the present invention contain at least one hydrophilic monomer, optionally in an amount of at least 25% (mass / mass). Preferred formulations may contain at least one N-vinylamide hydrophilic monomer, optionally in an amount of at least 15% (mass / mass). Preferred formulations may be silicone hydrogel contact lens formulations containing at least one polymerizable siloxane monomer, optionally in an amount of at least 25% (mass / mass). Preferred formulations may be silicone hydrogel contact lens formulations containing a siloxane component present in an amount of at least 35% (mass / mass), wherein at least 40% of the siloxane component 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% (mass / mass).

[0082] A preferred formulation of the second aspect of the present invention comprises 25% to 55% by mass of a siloxane monomer or a combination of siloxane monomers, 30% to 55% by mass of a vinyl monomer selected from NVP, VMA or a combination thereof, and optionally about 1% to about 20% by mass 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% to about 20% by mass 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. The contact lens of the third aspect of the present invention preferably comprises a polymeric lens material derived from a preferred polymerizable formulation of the second aspect of the present invention containing the monomers and siloxane components described above. The monomers and siloxane components described above may be incorporated into the polymeric lens material in the amounts described above. For example, at least 25% (mass / mass) of the polymeric material may be derived from a hydrophilic monomer having a terminal ethylenically unsaturated polymerizable group. The preferred formulation described above has been found to be particularly suitable for use in combination with the irradiation absorber packaging of the first aspect of the present invention, i.e., in combination with a first HEVL absorber containing a benzotriazole moiety, a second different HEVL absorber containing a benzotriazole moiety, and a polymerizable UV absorber optionally containing a benzophenone moiety.

Examples

[0083] The following examples illustrate certain aspects and advantages of the present invention, and it should be understood that the present invention is not limited by the examples. Wettability of the surface The water contact angle for a contact lens is a measure of the wettability of the surface of the contact lens. As used herein, the contact angle of the lens-forming surface of the contact lens is determined by the sessile drop method using a Kruss DSA-100 Drop Shape Analysis System or equivalent analyzer, with 3 μl of PBS dropped onto the center of the lens surface. Equilibrium water content The equilibrium water content (EWC) of the contact lens is determined as follows: The amount of water (expressed as a mass percentage) present in a hydrated hydrogel contact lens that has been completely equilibrated in saline is determined at room temperature (i.e., 20 °C). After blotting the lens with a cloth, a stack of 5 lenses is placed on the pan of an analytical balance to determine the hydrated mass of the lens. The lens is then placed in a laboratory oven at 100 ± 2 °C and dried for 16 - 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 is then determined, and the water content is calculated by subtracting the mass of the dried lens from the mass of the hydrated lens.

[0084] Yellowness index (YI) "Yellowness index" (YI) is a quantifiable and standardized method for measuring the yellowness of a sample as perceived from the observer's perspective, calculated from spectroscopic data. The YI of a sample describes the color change from colorless to yellow. The higher the YI value, the stronger the yellow tint. The YI of a contact lens can be determined using the ASTM E313-05 protocol with a CIE-D65 light source and a 1931 (2° field of view) standard illuminant factor. The following examples illustrate the effect of varying the amounts of high-energy short-wavelength visible light absorbers and colorants present in the lens formulation while maintaining the amount of polymerizable monomer constant.

[0085] Cast molding of contact lenses The hydrogel contact lens formulation described below was cast by placing a certain volume of the composition into a female member, fitting a male member thereon to form a contact lens mold assembly. The female and male members were made of a non-polar resin (e.g., polypropylene). The formulation was thermally cured to form a polymer lens body by placing the mold assembly in a nitrogen oven in the following cycle: N2 purge for 30 minutes at room temperature, 40 minutes at 55 °C or 65 °C, 40 minutes at 80 °C, and 40 minutes at 100 °C. After curing, the male and female members were dried and demolded, and the polymer lens body was dried and lens-removed from the male member. The lens-removed polymer lens body was exposed to an extraction and hydration process consisting of immersing the lens body twice in denatured ethanol (Trade Specific Denatured Alcohol (TSDA) 7 containing 5.0% by volume isopropanol), followed by immersion in a mixture of 50% denatured ethanol (TSDA 7) and 50% deionized water, and then immersion three times in deionized water. The resulting contact lens had an average center thickness of 0.097 mm, a diameter of 14 mm, and a base curve of 8.3.

[0086] Base lens formulation A base polymerizable silicone hydrogel contact lens formulation 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 part of KF1622), and 1.7 parts of other agents including a thermal initiator (AIBN) and a crosslinking agent (triallyl isocyanurate) was prepared. The same base formulation was used in all examples. Lenses prepared from the base formulation without the addition of an irradiation absorber package were optically transparent, meaning that the light transmittance was at least 97% in the range of 381 nm to 780 nm (measured according to ISO 18369). Other suitable base formulations include, for example, the formulations listed in Examples 4 to 24, which are described in EP3634733B1, the content of which is incorporated herein by reference.

[0087] Formulations containing only UV13 The irradiation absorbent packaging of each of Examples 1 to 13 was added to the base formulation and cast into lenses of the dimensions described above. All of the lenses of Examples 1 to 13 had ophthalmically acceptable surface wettability and a water content of 50 - 51% by mass. The effects of adding various amounts of UV13 to the base formulation were investigated in Comparative Examples 1 to 5 shown in Table 1. [Table 2] To achieve 50% blocking of light having a wavelength of 380 - 455 nm, it was necessary to include a high level of UV13, i.e., more than 2.5% by mass of UV13. The yellowness of the lenses prepared from the formulations of Comparative Examples 2 and 5 demonstrates that increasing the amount of UV13 in the formulation increases the yellowing of the lenses.

[0088] Formulations containing only UV28 The effects of adding various amounts of UV28 to the base formulation were investigated in Comparative Examples 6 and 7 shown in Table 2. [Table 3]

[0089] Incorporation of 0.5% by mass of UV28 into the base formulation yielded lenses that blocked 37% of the light in the 380 - 455 nm range. Increasing the amount of UV28 incorporated into the base formulation to 0.90% by mass resulted in 51% blocking of the light in the 380 - 455 nm range, while at such a UV28 loading, it was found that it was difficult to remove the lenses from the mold and a low yield of acceptable lenses was obtained. Comparative Example 8 incorporates the irradiation absorber package of Example 2 and Formulation IV of US Patent Publication No. 2021 / 0181379 for comparison purposes into a lens formulation having the base formulation described above. As a result, a lens that blocks only 35% of the light in the range of 380 to 455 nm was obtained. The yellowness index (YI) of the lenses prepared from the formulations of Comparative Examples 6 and 7 demonstrates that increasing the amount of UV28 in the formulation increases the yellowness of the lens.

[0090] Formulations containing a combination of UV13 and UV28 In Examples 9 to 13, an irradiation absorber package containing both UV13 and UV28 was added to the same base silicone hydrogel contact lens formulation, and the formulation was cast into the contact lenses in Table 3.

Table 4

[0091] Example 9 shows that when UV13 is added to the formulation of Comparative Example 6 which already contains UV28, the resulting formulation provides enhanced blocking of transmission in the range of 380 to 455 nm. The lens formed from the formulation of Example 10 containing 1.08% by mass of UV13 and 0.49% by mass of UV28 blocks 50% of the transmission in the range of 380 to 455 nm, that is, it provides the same level of HEVL blocking as Comparative Example 5 despite containing only 60% of the total amount of benzotriazole HEVL blocking agent. Thus, it is shown that by using a combination of benzotriazole HEVL blocking agents, it is possible to achieve a higher degree of blocking at a lower total loading. The formulation of Example 10 maintained the total amount of the HEVL absorbent at less than 2% by mass of the total lens formulation while blocking 50% of the HEVL in the range of 380 to 455 nm, resulting in a good overall balance of properties. By increasing the amount of the HEVL absorbent in Examples 11, 12, and 13, the amount of HEVL blocked by the lens increased by up to 5% at most. However, the wettability of the lenses cast from the formulations of Examples 11 to 13 was lower than that of the lenses cast from the formulations of Examples 9 and 10, as indicated by the water contact angle of the static droplets.

[0092] Various UV absorbers In Examples 14 to 17, an irradiation absorbent package containing either the HEVL absorbent and the benzophenone UV absorber UV416 or the benzotriazole UV absorber Norbloc was added to the same base silicone hydrogel contact lens formulation, and the formulation was cast into the contact lenses in Table 4.

[0093] [Table 5]

[0094] The lens of the formulation of Example 14 containing UV416 exhibited Class 1 UV blocking and blocked 50% of the transmission in the range of 380 - 455 nm. The formulation of Example 17 was identical to the formulation of Example 14 except that the UV absorber was changed from 0.3 parts by mass of UV416 to 0.3 parts by mass of Norbloc. The UV blocking of Example 17 was inferior to that of Example 14. In particular, the UVB blocking of Example 17 was >40% inferior to that of Example 14. The inferior UV blocking in the compositions of the present invention containing benzotriazole UV absorbers such as Norbloc, compared to the formulations of the present invention containing preferred benzophenone UV absorbers such as UV416, means that Class 1 UV blocking across the full range of contact lenses, especially in contact lenses with a low center thickness, may not be consistently achieved with low-loading benzotriazole UV absorbers. Thus, as in Examples 15 and 16, a higher-loading benzotriazole UV absorber may be necessary to achieve Class 1 UV blocking across the full range of lenses. Conversely, in the case of the lens formulations of the present invention containing a combination of benzotriazole HEVL absorbers, a lower amount of benzophenone UV absorbers such as UV416 may be required compared to benzotriazole UV absorbers such as Norbloc to produce lenses with desirable light-blocking characteristics.

[0095] Color of the lens The effect of including different irradiation absorber packages in the polymerizable lens formulation was investigated by placing a lens cast from the formulation on a glass prosthetic eye with a blue iris. The color imparted by the lenses cast from the formulations of Comparative Example 1, Comparative Example 6, and Example 10 of the present invention resulted in a natural-looking eye and had a superior appearance compared to the commercially available Oasys MAX (trademark) lens containing a tricyclic HEVL absorber that imparted a prominent undesirable yellow / green halo on the edge of the iris and the sclera of the glass prosthetic eye. The YI of the Acuvue Oasys Max (trademark) lens was 6.95 and was thus found to be significantly higher than that of Example 10 of the present invention. Compared with Examples 9 and 10, the increase in UV28 in the formulations of Examples 11 and 12 also resulted in a slight undesirable yellowing of the glass artificial eye, and this observation is consistent with the YI values reported in Table 3 above. Therefore, it was found that lenses having a YI of less than 6.0, especially less than 5.0, impart a more natural appearance to the eye than lenses having a YI of more than 6.0.

[0096] Absorption spectrum Absorption of light in the range of 250 - 500 nm was determined for solutions of Norbloc, UV416, UV13, and UV28 in ethyl acetate. The absorption spectra for each compound are shown in FIG. 1. All solutions were 0.003% by mass solutions prepared with ≧99.8%, HPLC grade ethyl acetate, and the absorbance of the solutions from 250 - 800 mm was measured using a Perkin Elmer Lambda 365 spectrometer. Absorption of light in the range of 380 - 460 nm was determined for solutions of UV1, UV5 (UVAM), UV13, UV15, and UV28 in ethyl acetate. The absorption spectra for each compound are shown in FIG. 2. All solutions were 0.003% by mass solutions prepared with ≧99.8%, HPLC grade ethyl acetate, and the absorbance of the solutions from 250 - 800 mm was measured using a Perkin Elmer Lambda 365 spectrometer.

[0097] 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 containing a benzotriazole moiety, allows for more effective absorption of light in the 350 - 420 nm range due to the difference in absorption maxima for different compounds. The peak absorbance in the range of 350 - 455 nm for the solution of UV13 in ethyl acetate was found to be 359 nm, and the peak absorbance in the range of 350 - 455 nm for the solution of UV28 was found to be 369 nm. UV13 was found to more effectively absorb light in the range of 340 - 375 nm, while UV28 was found to more effectively absorb light in the range of 380 - 440 nm.

[0098] Also, by using a benzophenone UV absorber in combination with two different HEVL absorbers each containing a benzotriazole moiety, it is hypothesized that due to the significant difference in absorption between the benzophenone and the benzotriazole compound, blocking of light over the range of 260 - 440 nm is achieved more effectively than with combinations containing benzotriazole UV absorbers. As can be seen from Figure 1, while there is significant overlap between the absorption spectra of the benzotriazole UV absorber Norbloc and the benzotriazole HEVL absorbers UV13 and UV28, the absorption spectrum of the benzophenone UV absorber UV416 is complementary to the absorption spectra of UV13 and UV28, providing enhanced absorbance over a broader range of wavelengths. It should be understood that the disclosure herein refers to certain exemplary examples, which are presented by way of illustration and not limitation. The intent of the foregoing detailed description, although discussing exemplary examples, is to be construed as encompassing all variations, alternatives, and equivalents of the examples as may fall within the spirit and scope of the invention as defined by the additional disclosure.

[0099] The present invention includes the following aspects / embodiments / features in any order and / or in any combination. 1. A hydrogel contact lens formulation for forming a polymer body of a hydrogel contact lens, comprising: a first high energy visible light (HEVL) absorber containing a benzotriazole moiety, a second different high energy visible light (HEVL) absorber containing a benzotriazole moiety The formulation. 2. The formulation according to 1, further comprising a polymerizable UV absorber containing a benzophenone moiety. 3. The formulation according to 1 or 2, wherein the maximum wavelength at which a 0.003 wt% solution of the second HEVL absorber in ethyl acetate has an absorbance of 0.1 is at least 10 nm lower than the maximum wavelength at which a 0.003 wt% solution of the first HEVL absorber in ethyl acetate has an absorbance of 0.1. 4. a. The tangent line to the curve defined by the highest wavelength at which the absorbance is 0.5 with respect to the absorption spectrum of a 0.003 mass% solution of the first HEVL absorbent in ethyl acetate intersects the 0.0 absorbance axis at 412 - 440 nm, preferably 415 - 435 nm, particularly 415 - 430 nm for the first HEVL absorbent; for the second HEVL absorbent, the tangent line to the curve defined by the highest wavelength at which the absorbance is 0.5 with respect to the absorption spectrum of a 0.003 mass% solution of the second HEVL absorbent in ethyl acetate intersects the 0.0 absorbance axis at a wavelength shorter than the wavelength at which the tangent line to the curve defined by the highest wavelength at which the absorbance is 0.5 with respect to the absorption spectrum of a 0.003 mass% solution of the first HEVL absorbent in ethyl acetate intersects the 0.0 absorbance axis, for example, at least 5 nm shorter, particularly at least 10 nm shorter; and / or b. The tangent line to the curve defined by the highest wavelength at which the absorbance is 0.5 with respect to the absorption spectrum of a 0.003 mass% solution of the first HEVL absorbent in ethyl acetate intersects the 0.0 absorbance axis at 385 - 415 nm, preferably 390 - 412 nm for the second HEVL absorbent; for the second HEVL absorbent, the tangent line to the curve defined by the highest wavelength at which the absorbance is 0.5 with respect to the absorption spectrum of a 0.003 mass% solution of the second HEVL absorbent in ethyl acetate intersects the 0.0 absorbance axis at a wavelength shorter than the wavelength at the highest wavelength at which the absorbance is 0.5 with respect to the absorption spectrum of a 0.003 mass% solution of the first HEVL absorbent in ethyl acetate, for example, at least 5 nm shorter, particularly at least 8 nm shorter; and / or c. The first HEVL absorbent is characterized in that the maximum wavelength at which the absorbance is 0.1 with respect to the absorption spectrum of a 0.003% by mass solution of the first HEVL absorbent in ethyl acetate is 412 to 440 nm, preferably 415 to 435 nm, particularly 415 to 430 nm; the second HEVL absorbent is characterized in that the maximum wavelength at which the absorbance is 0.1 with respect to the absorption spectrum of a 0.003% by mass solution of the second HEVL absorbent in ethyl acetate is 385 to 412 nm, preferably 390 to 410 nm; and / or d. The 0.003% by mass solution of the first HEVL absorbent in ethyl acetate has an absorbance peak in the range of 360 to 410 nm, and the 0.003% by mass solution of the second HEVL absorbent in ethyl acetate has a peak absorbance at a wavelength that is at least 5 nm shorter, for example, 5 to 25 nm shorter, particularly 5 to 15 nm shorter, than the absorbance peak of the 0.003% by mass solution of the first HEVL absorbent in ethyl acetate that falls within the range of 360 to 410 nm; and / or e. The 0.003% by mass solution of the first HEVL absorbent in ethyl acetate has an absorbance of at least 0.35 for light at a wavelength of 400 nm and / or an absorbance of at least 0.55 for light at a wavelength of 390 nm; the 0.003% by mass solution of the second HEVL absorbent in ethyl acetate has an absorbance of less than 0.30 for light at a wavelength of 400 nm and / or an absorbance of less than 0.55 for light at a wavelength of 390 nm. The preparation according to any one of 1 to 3. 5. The preparation according to any one of 1 to 4, wherein the first and second HEVL absorbents are each of formula (1).

[0100]

Chemical formula

[0101]

Chemical formula

[0102]

Chemical formula

[0103] 6. The formulation according to 5, wherein the total amount of the HEVL absorbent of formula (1) present does not exceed 2.7% (mass / mass), preferably does not exceed 2.0% (mass / mass). 7. The preparation according to any one of 1 to 6, wherein the first HEVL absorbent is 2-[2'-hydroxy-3'-tert-butyl-5'-(3''-methacryloyloxypropoxy)phenyl]-5-chloro-2H-benzotriazole (UV28). 8. The second HEVL absorbent is selected from 2-(1,1-dimethylethyl)-4-[3-[(4-ethenylphenyl)methoxy]propoxy]-6-(5-methoxy-2H-benzotriazol-2-yl)-phenol (UV1), 2-(5-chloro-2H-benzotriazol-2-yl)-6-(1,1-dimethylethyl)-4-ethenyl-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), and especially 2-[2'-hydroxy-3'-tert-butyl-5'-(3''-methacryloyloxypropoxy)phenyl]-5-methoxy-2H-benzotriazole (UV13), and is the lumber according to any one of 1 to 7.

[0104] 9. The first HEVL absorbent is present in an amount of 0.3% to 0.9% (mass / mass), preferably 0.4% to 0.7% (mass / mass), and the second HEVL absorbent is present in an amount of 0.5% to 2.2% (mass / mass), preferably 0.7% to 1.6% (mass / mass), and is the preparation according to any one of 1 to 8. 10. The preparation according to any one of 1 to 9, which contains a polymerizable UV absorbent containing a benzophenone moiety in an amount not exceeding 1.5% (mass / mass), preferably not exceeding 1.0% (mass / mass). 11. The preparation according to any one of 1 to 10, wherein the polymerizable UV absorbent is 2-(4-benzoyl-3-hydroxyphenoxy)ethyl acrylate (UV416). 12. The preparation according to any one of 1 to 11, which further contains a polymerizable blue or blue-green colorant containing an anthraquinone moiety. 13. The formulation according to claim 12, wherein the coincident cyan or blue-green colorant is selected from 1,4-bis[4-(2-methacryloyloxyethyl)phenylamino]-9,10-anthraquinone (RB246) or 1,4-bis[(2-methacryloyloxyethyl)amino]-9,10-anthraquinone (RB247).

[0105] 14. The formulation according to any one of claims 1 to 13, which is a thermosetting formulation containing at least one thermal initiator. 15. The formulation according to any one of claims 1 to 14, further containing at least one hydrophilic monomer, optionally in an amount of at least 25% (mass / mass). 16. The formulation according to claim 15, containing at least one hydrophilic N-vinylamide monomer, optionally in an amount of at least 15% (mass / mass). 17. The formulation according to claim 16, containing at least 30% (mass / mass) of a hydrophilic N-vinylamide monomer. 18. The formulation according to any one of claims 1 to 17, which is a silicone hydrogel contact lens formulation containing a polymerizable siloxane component, optionally in an amount of at least 25% (mass / mass). 19. The formulation according to claim 18, containing 30 to 60% (mass / mass) of a polymerizable siloxane component. 20. The formulation according to claim 18 or 19, wherein at least 40% (mass / mass) of the polymerizable siloxane content is a bifunctional siloxane having a molecular weight of at least 8,000 Daltons, and at least 25% (mass / mass) of the polymerizable siloxane content is a monofunctional siloxane having a molecular weight of less than 3,000 Daltons.

[0106] 21. A siloxane component present in an amount of at least 35% (mass / mass) based on the total mass of the formulation, wherein at least 40% of the siloxane content is a bifunctional 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% (mass / mass) based on the total mass of the formulation The formulation according to any one of claims 18 to 20, containing the above. 22. A formulation according to any one of 1 to 21, comprising at least 5% (mass / mass) of a non-siloxane hydrophobic monomer, especially a hydrophobic methacrylate monomer, based on the total mass of the formulation. 23. The formulation according to 22, wherein the hydrophobic monomer comprises hydroxybutyl methacrylate, isobornyl methacrylate, or a combination of hydroxybutyl methacrylate and isobornyl methacrylate.

[0107] 24. a. At least 30% (mass / mass) of a hydrophilic N-vinylamide monomer, and b. A polymerizable siloxane component in an amount of 35 to 60% (mass / mass) of the total formulation, wherein at least 40% (mass / mass) of the polymerizable siloxane content is a bifunctional siloxane having a molecular weight of at least 8,000 daltons, and at least 25% (mass / mass) of the polymerizable siloxane content is a monofunctional siloxane having a molecular weight of less than 3,000 daltons, and c. At least 5% (mass / mass) of a non-siloxane hydrophobic methacrylate monomer based on the total mass of the formulation and being a formulation according to any one of 1 to 14. 25. a. N-methyl N-vinylacetamide in an amount of 30 to 50% (mass / mass) of the total formulation, and b. A bifunctional (meth)acrylate-containing siloxane having a molecular weight of at least 8,000 daltons in an amount of 20 to 40% (mass / mass) of the total formulation, and c. A monofunctional (meth)acrylate-containing siloxane having a molecular weight of less than 3,000 daltons in an amount of 10 to 30 (mass / mass) of the total formulation, and d. Hydroxybutyl methacrylate, isobornyl methacrylate, or a combination of hydroxybutyl methacrylate and isobornyl methacrylate in an amount of 5 to 15% (mass / mass) of the total formulation and being a formulation according to any one of 1 to 14.

[0108] 26. The formulation according to 24 or 25, wherein the difunctional siloxane monomer is a (meth)acrylate-containing siloxane monomer represented by formula (III). [Chemical formula] (In the formula, R1 is selected from either hydrogen or a methyl group; R2 is selected from either hydrogen or a C 1-4 hydrocarbon group; m represents an integer from 0 to 10; n represents an integer from 4 to about 15, 25, or up to 100; a and b represent integers of 1 or more; a + b is equal to 20 to 500; b / (a + b) is equal to 0.01 to 0.22; the configuration of the siloxane units includes a random configuration)

[0109] 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). [Chemical formula] (In the formula, n is an integer of about 10 to 15) 28. A hydrogel contact lens obtained from the polymerization of the formulation according to any one of 1 to 27.

[0110] 29. The contact lens according to 28, having the following light transmission characteristics. [Table 6] 30. The contact lens according to 28 or 29, having a yellowness of less than 6.0 as determined by the ASTM E313-05 method.

[0111] The entire contents of all references cited in this disclosure are incorporated herein by reference to the extent that they do not conflict with this disclosure. Other embodiments of the invention will be apparent to those of ordinary skill in the art from a consideration of this specification and practice of the invention disclosed herein. This specification and the examples are considered exemplary only, and the true scope and spirit of the invention are intended to be indicated by the following claims and their equivalents.

Claims

1. 1. A silicone hydrogel contact lens formulation for forming a polymer body of a hydrogel contact lens, comprising: at least one hydrophilic monomer, at least one hydrophilic N-vinyl amide monomer, and a polymerizable siloxane component; a first high energy visible light (HEVL) absorber comprising a benzotriazole moiety; a second, different high energy visible light (HEVL) absorber comprising a benzotriazole moiety; and Including, a 0.003 wt. % solution of the first HEVL absorber in ethyl acetate has an absorbance peak in the range of 360 to 410 nm; a 0.003 wt. % solution of the second HEVL absorber in ethyl acetate has a peak absorbance at a wavelength 5 to 25 nm shorter than the absorbance peak of a 0.003 wt. % solution of the first HEVL absorber in ethyl acetate falling in the range of 360 to 410 nm; the first HEVL absorber is 2-[2'-hydroxy-3'-tert-butyl-5'-(3''-methacryloyloxypropoxy)phenyl]-5-chloro-2H-benzotriazole (UV28); A formulation wherein the second HEVL absorber is 2-[2'-hydroxy-3'-tert-butyl-5'-(3''-methacryloyloxypropoxy)phenyl]-5-methoxy-2H-benzotriazole (UV13).

2. 2. The formulation of claim 1, wherein the total amount of the first HEVL absorber and the second HEVL absorber present does not exceed 2.7% (wt / wt).

3. The formulation of claim 1, wherein the first HEVL absorber is present in an amount of 0.3% to 0.9% (mass / mass) and the second HEVL absorber is present in an amount of 0.5% to 2.2% (mass / mass).

4. The formulation of claim 1, comprising a polymerizable UV absorber containing a benzophenone moiety in an amount not exceeding 1.5% (wt / wt).

5. The formulation of claim 4, wherein the polymerizable UV absorber is 2-(4-benzoyl-3-hydroxyphenoxy)ethyl acrylate (UV416).

6. 10. The formulation of claim 1, further comprising a polymerizable blue or blue-green tinting agent comprising an anthraquinone moiety.

7. The formulation of claim 6, wherein the polymerizable blue or blue-green tinting agent is selected from 1,4-bis[4-(2-methacryloxyethyl)phenylamino]-9,10-anthraquinone (RB246) or 1,4-bis[(2-methacryloxyethyl)amino]-9,10-anthraquinone (RB247).

8. 10. The formulation of claim 1, which is a heat-cured formulation comprising at least one thermal initiator.

9. The formulation of claim 1, comprising at least one hydrophilic monomer in an amount of at least 25% (mass / mass).

10. The formulation of claim 9, comprising the at least one hydrophilic N-vinylamide monomer in an amount of at least 15% (wt / wt).

11. 11. The formulation of claim 10, comprising at least 30% (w / w) of hydrophilic N-vinylamide monomers.

12. The formulation of claim 1, comprising the polymerizable siloxane component in an amount of at least 25% (wt / wt).

13. 13. The formulation of claim 12, comprising 30-60% (w / w) of the polymerizable siloxane component.

14. The formulation of claim 12 or claim 13, wherein at least 40% (wt / wt) of the polymerizable siloxane content is difunctional siloxanes having a molecular weight of at least 8,000 daltons and at least 25% (wt / wt) of the polymerizable siloxane content is monofunctional siloxanes having a molecular weight of less than 3000 daltons.

15. 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; an N-vinylamide monomer component present in an amount of at least 37% (wt / wt) based on the total weight of the formulation; 13. The formulation of claim 12, comprising:

16. 10. The formulation of claim 1, comprising at least 5% (wt / wt) of non-siloxane hydrophobic monomers, based on the total weight of the formulation.

17. The formulation of claim 16, wherein the hydrophobic monomer comprises hydroxybutyl methacrylate, isobornyl methacrylate, or a combination of hydroxybutyl methacrylate and isobornyl methacrylate.

18. a. a hydrophilic N-vinyl amide monomer in an amount of at least 30% (wt / wt); b. a polymerizable siloxane component in an amount of 35-60% (wt / wt) of the total formulation, wherein at least 40% (wt / wt) of the polymerizable siloxane content is difunctional siloxanes having a molecular weight of at least 8,000 daltons and at least 25% (wt / wt) of the polymerizable siloxane content is monofunctional siloxanes having a molecular weight of less than 3000 daltons; c. a non-siloxane hydrophobic methacrylate monomer in an amount of at least 5% (wt / wt) based on the total weight of the formulation; 2. The formulation of claim 1, comprising:

19. a. N-methyl N-vinylacetamide in an amount of 30-50% (w / w) 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 20-40% (w / w) of the total formulation; c. a monofunctional (meth)acrylate-containing siloxane having a molecular weight less than 3000 Daltons in an amount of 10-30 (wt / wt) of the total formulation; d. Hydroxybutyl methacrylate, isobornyl methacrylate, or a combination of hydroxybutyl methacrylate and isobornyl methacrylate in an amount of 5-15% (w / w) of the total formulation; 2. The formulation of claim 1, comprising:

20. 20. The formulation of claim 18 or claim 19, wherein the difunctional siloxane monomer is a (meth)acrylate-containing siloxane monomer represented by formula (III): 【Chemistry 1】 (III) (In the formula, R 1 is selected from either hydrogen or a methyl group; R 2 is hydrogen or C 1-4 m represents an integer of 0 to 10; n represents an integer of 4 to 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 units includes a random configuration.

21. 20. The formulation of claim 18 or claim 19, wherein the monofunctional siloxane monomer is a methacrylate-containing siloxane monomer represented by formula (II): 【Chemistry 2】 (II) (wherein n is an integer from 10 to 15)

22. A hydrogel contact lens obtained from polymerization of the formulation of claim 1.

23. 23. The contact lens of claim 22 having the following light transmission characteristics: Table 1

24. 24. The contact lens of claim 22 or claim 23, having a yellowness index of less than 6.0 as determined by ASTM E313-05 method.

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