Colored contact lenses

Abstract

The present invention provides a contact lens comprising a first colorant having an absorption maximum (λ max ) of a blue light blocking colorant; and a second colorant, wherein the second colorant has an absorption maximum (λ max ) of the polymerizable dye; and optionally further comprising a third colorant, the third colorant being a colorant having an absorption maximum in the range of greater than 600nm to 800nm. The present invention also provides a method for manufacturing the lens.

Description

Technical Field

[0001] The present invention relates to contact lenses, in particular contact lenses comprising a colorant for blocking blue light. More particularly (but not exclusively), the present invention relates to contact lenses comprising such a first colorant for blocking blue light and a separate second colorant for color balancing for the first colorant, and methods for making such contact lenses. Background Art

[0002] Over the years, the development of contact lenses has led to the addition of new features in addition to refractive correction. One desired feature is the blocking of potentially harmful blue light. The human eye responds to light in the visible spectrum (380-780nm). However, the shorter the wavelength, the more energy it contains, and therefore the greatest harm to human health. The wavelength of this so-called high-energy visible light is between 380-500nm. However, blue light is essential for visual processes including color perception and in recent years it has been shown that blue light between 465-495nm plays an important role in the human circadian rhythm. It has also been shown (Blue Light Hazard: New Knowledge, New Approaches to Maintaining Ocular Health, Report of a Roundtable, March 16, 2013) that blue light with a wavelength between 415-455nm produces the greatest phototoxic damage. Thus, in an ideal example, the contact lens would reduce the level of harmful high energy blue light (415-455 nm) passing through the contact lens while allowing blue light (465-495 nm) that is beneficial to non-visual functions to pass through.

[0003] Blue light blocking can be achieved by adding a colorant that absorbs in the blue region of the spectrum, typically a yellow pigment or dye. Such dyes are mentioned, for example, in US 5,470,932, and ideally absorb primarily blue light in the harmful 415-455 nm region of the spectrum. The addition of such yellow colorants has been found to be effective in reducing the harmful effects of blue light, however, the resulting contact lens is tinted by the introduced colorant, typically resulting in a noticeable yellow tint that may affect the user's color perception and may be aesthetically undesirable to some users.

[0004] Contact lenses may also include a treatment colorant and a UV blocker. Treatment colorants are colorants that provide a dull coloration (usually blue), which makes it easier for the user to see and handle the contact lenses. Treatment colorants are usually added to formulations at relatively low levels to produce only a dull coloration, and are therefore usually present at a concentration lower than the blue light blocking component. Therefore, including a blue light blocking colorant can mask or otherwise change the color of the treatment colorant.

[0005] UV blockers are compounds that absorb UV light and have also been found to be harmful to the eyes.

[0006] Additionally, it has been found that some lens tinting agents can discolor or leach out during manufacturing or storage of the lens, thereby causing undesirable changes in the tint of the final lens. Pigments, which are insoluble colorants, have also been found to be less desirable than dyes due to problems such as difficulty in uniformly dispersing the pigment in a contact lens.

[0007] The present invention seeks to alleviate the above problems. Alternatively or additionally, the present invention seeks to provide an improved contact lens. Summary of the invention

[0008] According to a first aspect, the present invention provides a contact lens comprising a polymeric matrix formed by polymerization of a polymerizable composition comprising: one or more monomers; a first colorant having an absorption maximum (λ) in the range of 415 nm to 455 nm; max ) of a blue light blocking colorant; and a second colorant, wherein the second colorant is an absorption maximum (λ max ) of a polymerizable dye; and optionally further comprising a third colorant, which is a colorant having an absorption maximum in the range of greater than 600nm to 800nm.

[0009] The secondary colorant and the tertiary colorant, if present, balance the hue of the primary colorant, thereby rendering the contact lens colorless, gray, or blue.

[0010] Typically, the first colorant is yellow, the second colorant is red or violet, and the third colorant is blue.

[0011] In a preferred aspect, the present invention provides a contact lens comprising a polymeric matrix formed by polymerization of a polymerizable composition comprising: one or more monomers; a first colorant having an absorption maximum (λ) in the range of 415 nm to 455 nm; max ) of a yellow blue light blocking colorant; and a second colorant, wherein the second colorant has an absorption maximum (λ in the range of 470nm to 600nm max ) of a violet or red polymerizable dye; and optionally further comprising a third colorant, which is a blue colorant having an absorption maximum in the range of greater than 600 nm to 800 nm, wherein the second colorant and the third colorant (if present) balance the yellow color of the first colorant, thereby making the contact lens colorless, gray or blue.

[0012] The second colorant absorbs at a longer wavelength than the blue-blocking colorant, at least partially balancing the yellow tint of the blue-blocking colorant and thus shifting the overall color of the lens toward colorless or gray. The second colorant is polymerizable and is present as part of the polymeric matrix of the contact lens, and therefore it cannot leach out of the lens during autoclaving or storage.

[0013] According to another aspect of the present invention, there is also provided a contact lens comprising: a polymer matrix; a first colorant having an absorption maximum (λ) in the range of 415 nm to 455 nm; max ) of a blue light blocking colorant; and a second colorant, wherein the second colorant is as described herein having an absorption maximum (λ) in the range of 470 nm to 600 nm max ) of polymerizable anthraquinone dyes.

[0014] According to another aspect of the present invention, there is also provided a method for manufacturing a contact lens, comprising the step of polymerizing a polymerizable composition in a mold to form a lens-shaped polymerized product comprising a polymer matrix, wherein the polymerizable composition comprises: one or more monomers; a first colorant having an absorption maximum (λ) in the range of 415 nm to 455 nm; max ) of a blue light blocking colorant; and a second colorant, wherein the second colorant is an absorption maximum (λ max ) of a polymerizable dye; and optionally further comprising a third colorant, which is a colorant having an absorption maximum in the range of greater than 600 nm to 800 nm, wherein the second colorant and the third colorant (if present) balance the color of the first colorant, thereby making the contact lens colorless, gray or blue.

[0015] According to a preferred aspect, the present invention provides a method for manufacturing a contact lens, comprising the step of polymerizing a polymerizable composition in a mold to form a lens-shaped polymerized product comprising a polymer matrix, the polymerizable composition comprising: one or more monomers; a first colorant having an absorption maximum (λ) in the range of 415 nm to 455 nm; max ) of a yellow blue light blocking colorant; and a second colorant, wherein the second colorant has an absorption maximum (λ in the range of 470nm to 600nm max ) of a violet or red polymerizable dye; and optionally further comprising a third colorant, which is a blue colorant having an absorption maximum in the range of greater than 600 nm to 800 nm, wherein the second colorant and the third colorant (if present) balance the yellow color of the first colorant, thereby making the contact lens colorless, gray or blue.

[0016] According to another aspect of the present invention, there is also provided a packaged contact lens comprising a sealed package containing a packaging solution and a contact lens as described herein or made by a method as described herein.

[0017] Optional but preferred features are set out in the dependent claims.

[0018] Of course, it should be understood that features described with respect to one aspect of the invention may be incorporated into other aspects of the invention. For example, the method of the invention may incorporate any features described with reference to the contact lens of the invention, and vice versa. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Embodiments of the present invention will now be described, by way of example only, with reference to the accompanying drawings.

[0020] Figure 1 is a graph of a* and b* values ​​from CIELab L*a*b* color measurements of various contact lenses.

[0021] Figure 2 Shown are the UV-vis absorption spectra of RY86-HEMA, RB246, and two dyes (a red dye (Dye 1) and a violet dye (Dye 2)) produced in the dye synthesis examples below. DETAILED DESCRIPTION

[0022] The invention will be more fully understood and other advantages will become apparent when reference is made to the following detailed description of embodiments of the invention.

[0023] The present invention is based on the discovery that it is possible to effectively balance the undesirable yellow tint of a lens having a blue-blocking tint by including a second tint that absorbs at a longer wavelength (typically a red dye or a violet dye) that is soluble in the contact lens formulation and is polymerizable so that it forms part of the polymeric matrix of the lens and remains in the lens during autoclaving and storage. Optionally, the contact lens also includes a third tint to help provide the desired tint.

[0024] As used herein, the term "lens" means an eyeglass that can be placed on a person's eyeball. The term "contact lens" is commonly used in the art to encompass such lenses. It should be understood that such contact lenses will provide clinically acceptable supraorbital movement and will not bind to a person's eyeball. The contact lens may be in the form of a corneal lens (e.g., a lens placed on the cornea of ​​the eye).

[0025] As used herein, percentages and ppm values ​​are understood to be by weight. Unless the context requires a different meaning, percentages and ppm values ​​with respect to contact lenses are understood to be by dry weight. The term "by dry weight" and similar terms are understood to refer to the weight of the dry contact lens, i.e., excluding the presence of any water or other solvents and diluents.

[0026] As used herein, the terms "absorption maximum" and "λ" in relation to a colorant are max ” have the same meaning and refer to the wavelength at which the colorant has the strongest absorbance in methanol solution as measured by UV-vis absorption spectroscopy.

[0027] As used herein, the terms "first colorant", "second colorant" and "third colorant" are understood to refer to a colorant having an absorption maximum (λ) within the specified range. max ) is labeled as a colorant. It should not be considered to imply a limit to the number of such colorants present in the contact lens or polymerizable composition, and thus within the scope of the present invention, the contact lens comprises one or more first colorants, one or more second colorants, and optionally one or more third colorants. Thus, for example, the second colorants may actually each have an absorption maximum (λ) in the range of 470 nm to 600 nm. max ) is a mixture of two or more polymerizable dyes of the type described. The concentration of the colorant mentioned herein is to be understood as the total concentration of all colorants of the type described.

[0028] It will thus be appreciated that the present invention provides contact lenses comprising a polymeric matrix formed by polymerization of a polymerizable composition comprising: one or more monomers; one or more first colorants, each of which has an absorption maximum (λ) in the range of 415 nm to 455 nm; max ) of a blue light blocking colorant; and one or more second colorants, wherein the second colorant or each second colorant has an absorption maximum (λ) in the range of 470nm to 600nm max ) of a polymerizable dye; and optionally further comprising one or more third colorants, each of which is a colorant having an absorption maximum in the range of greater than 600nm to 800nm, wherein the one or more second colorants and the one or more third colorants (if present) balance the color of the one or more first colorants, thereby making the contact lens colorless, gray or blue. It should also be understood that the present invention also provides a method for making a contact lens, comprising the steps of polymerizing a polymerizable composition in a mold to form a lens-shaped polymerized product comprising a polymeric matrix, the polymerizable composition comprising: one or more monomers; one or more first colorants, each of which is a colorant having an absorption maximum (λ) in the range of 415nm to 455nm; max) of a blue light blocking colorant; and one or more second colorants, wherein the second colorant or each second colorant has an absorption maximum (λ) in the range of 470nm to 600nm max ); and optionally further comprising one or more third colorants, each of which is a colorant having an absorption maximum in the range of greater than 600 nm to 800 nm, wherein the one or more second colorants and the one or more third colorants (if present) balance the color of the one or more first colorants to make the contact lens colorless, gray or blue.

[0029] Optionally, there is only one first colorant, only one second colorant, and if a third colorant is present, only one third colorant.

[0030] First colorant

[0031] The first colorant is a blue light blocking pigment or dye, i.e., it absorbs at least a portion of the blue light passing through the contact lens, in particular blue light having a wavelength of 415 to 455 nm. The first colorant is preferably a dye. The first colorant is typically a yellow colorant, preferably a yellow dye. The first colorant has an absorption maximum (λ) in the range of 415 nm to 455 nm, optionally in the range of 415 nm to 445 nm. max ).

[0032] The first colorant may be of any suitable type, for example, the first colorant may be a dye, such as an anthraquinone or azo dye, optionally comprising one or more polymerizable groups, such as acrylate, methacrylate, vinyl, allyl, methacrylamide and acrylamide.

[0033] Those skilled in the art know various blue-blocking dyes suitable for contact lenses. The first colorant can be polymerizable or non-polymerizable. For example, US 5,470,932 describes blue-blocking dyes having a yellow color and containing polymerizable groups such as acrylates and methacrylates. Other yellow dyes suitable for use as blue-blocking dyes include Disperse Orange 3 methacrylamide (2-methyl-N-{4-[(Z)-(4-nitrophenyl)diazenyl]phenyl}prop-2-enamide; CAS Reg. No. 58142-15-7), and based on Reactive Yellow 15 (Reactive Yellow 15). 15)(4-(4,5-dihydro-4-((2-methoxy-5-methyl-4-((2-(sulfonyloxy)ethyl)sulfonyl)phenyl)azo)-3-methyl-5-oxo-1H-pyrazol-1-yl)-]-benzenesulfonic acid; CAS Reg. No. 60958-41-0) and Reactive Yellow 86(4-((5-aminocarbonyl-1-ethyl-1,6-dihydro-2-hydroxy-4-methyl-6-oxo-3-pyridyl)azo)-6-(4,6-dichloro-1,3,5-triazin-2-yl)amino)-1,3-benzenedisulfonic acid, disodium salt; CAS Reg. No. 61951-86-8).

[0034] The first colorant is preferably stable to autoclaving and storage of the contact lenses in the packaging solution so that the tint of the contact lenses remains unchanged during manufacture and storage of the contact lenses.

[0035] If the first colorant is polymerizable, it will also polymerize into the polymeric matrix, so that both the first and second dyes are covalently bonded into the polymeric matrix, and the dyes will not leach out during subsequent handling and storage of the contact lens. The first colorant is preferably a dye that is soluble in the polymerizable composition, so that dissolving the dye in the polymerizable composition produces a uniform distribution of the dye throughout the polymerizable composition. Preferably, after polymerization, the concentration of the first colorant per unit volume of the polymeric matrix does not vary by more than ±5% compared to the average concentration in the entire volume of the polymeric matrix.

[0036] The concentration of the first colorant in the contact lens will be selected based on the desired level of blue light blocking. Preferably, the transmittance in the range of 415nm-455nm is less than 90%, preferably less than 80%, as measured according to Section 4.8 of BS EN ISO 18369-3-2017 as described below. Based on dry weight, the concentration of the first colorant in the contact lens is optionally in the range of 20ppm to 1000ppm, optionally 40ppm to 1000ppm, optionally 100ppm to 1000ppm, optionally 300ppm to 1000ppm, for example 350ppm to 900ppm.

[0037] Second colorant

[0038] The purpose of the second colorant is to at least partially balance the color of the first colorant, which is typically yellow in color and may undesirably affect the vision of the contact lens wearer. The term "color balancing" should be understood to mean counteracting the yellow color of the first colorant. The color balancing colorant (i.e., the second colorant) is used in the proper concentration to make the overall color of the contact lens more similar to colorless, gray, or blue.

[0039] The second colorant has an absorption maximum (λ) in the range of 470 nm to 600 nm, optionally 470 nm to 599 nm, optionally 500 nm to 590 nm. max Typically, the second colorant is a red or violet dye, preferably a violet dye. Optionally, the second colorant is a dye having an absorption maximum (λ) in the range of, for example, 510 nm to 540 nm. max Optionally, the second colorant is a red dye having an absorption maximum (λ) in the range of, for example, 550 nm to 570 nm. max ) violet dye. The inventors have found that in the case where the second colorant is a violet dye, it is generally possible to balance the color of the first colorant using only the second colorant, i.e., without including a third colorant. Optionally, the second colorant is violet, and the contact lens is gray or colorless and does not include a third colorant as defined herein. However, if the second colorant is red, it may be necessary to include a third colorant to achieve the desired degree of color balance. In addition, in some cases, it may be necessary to include a third colorant as a processing colorant to give the contact lens a dull blue coloration. Optionally, the second colorant is red, and the contact lens is gray, colorless or blue and does not include a third colorant as defined herein.

[0040] The second colorant is soluble in the polymerizable composition such that dissolving the second colorant in the polymerizable composition produces a uniform distribution of the second colorant throughout the polymerizable composition. Preferably, after polymerization, the concentration of the second colorant per unit volume of the polymeric matrix does not vary by more than ±5% compared to the average concentration in the volume of the entire polymeric matrix.

[0041] The second colorant can be any suitable type of dye, such as an azo or anthraquinone dye. The inventors have found that anthraquinone dyes exhibit excellent color fastness and stability during the manufacturing process of contact lenses and during the storage of contact lenses, thereby keeping the color of the contact lenses stable. Preferably, the second colorant is an anthraquinone dye, more preferably a violet anthraquinone dye.

[0042] Preferably, the second colorant contains a chromophore and at least one polymerizable group, wherein each polymerizable group is linked to the chromophore via a divalent linking group.

[0043] The chromophore may be any suitable chromophore having an absorption maximum (λ) in the range of 470 nm to 600 nm, optionally 500 nm to 600 nm. max ). Advantageously, the chromophore is an anthraquinone chromophore. The anthraquinone chromophore may be substituted with at least one electron-pushing or electron-withdrawing group. Such electron-pushing or electron-withdrawing groups may affect the absorption spectrum of the chromophore, thereby producing the desired color. Optionally, the anthraquinone chromophore comprises 1 to 3 substituents selected from: -F, -Cl, -Br, -I, -OR 2 、-SR 2 , -R 2 , -NO2, -CN, -NCO, -NCS, -C(=O)R 2 、-C(=O)OR 2 、-NR 2 2. -C(=O)NHR 2 、-C(=O)N(R 2 )2, where each R 2 are independently H or a C1 to C20 hydrocarbon group, preferably a straight or branched chain alkyl group.

[0044] Optionally, the second colorant is a dye comprising 1 to 3, more preferably 1 or 2, and most preferably 2 polymerizable groups. One or more polymerizable groups are optionally each independently selected from acrylate, methacrylate, acrylamide, methacrylamide, allyl and vinyl. Preferably, the polymerizable group is acrylate or methacrylate.

[0045] Each of the polymerizable groups is linked to the chromophore via a linking group.

[0046] Each linking group optionally comprises 2 to 50 atoms selected from C, H, O, Si, N, P, S, F, Cl, Br and I. The linking group is a divalent group. Each linking group may comprise a divalent C1 to C50, optionally a C1 to C20 divalent hydrocarbylene group, which may be substituted or unsubstituted with one or more heteroatoms optionally selected from O, S, N, P, Si, F, Cl, Br and I. Optionally, each linking group is optionally connected to a chromophore via an oxygen, sulfur or nitrogen atom, the chromophore being preferably anthraquinone (for the purposes of the present invention, oxygen, sulfur or nitrogen atoms are considered to be part of the linking group).

[0047] In the case where the chromophore is anthraquinone, the second colorant preferably comprises 1 to 3 polymerizable groups, more preferably 1 or 2 polymerizable groups. In the case where there are two polymerizable groups, the linking group is preferably connected to the anthraquinone at the 1,2-position, 1,3-position, 1,4-position, 1,5-position, 2,6-position, 2,7-position, 1,8-position or 2,8-position of the anthraquinone, and more preferably at the 1,2-position, 1,3-position, 1,4-position or 1,5-position of the anthraquinone. Optionally, when there are two polymerizable groups, the linking group is preferably connected to the anthraquinone at the 1,2-position, 1,3-position, 1,4-position, 1,5-position, 2,6-position, 2,7-position, 1,8-position or 2,8-position of the anthraquinone, and more preferably at the 1,2-position, 1,3-position or 1,5-position of the anthraquinone.

[0048] The second colorant preferably has the formula (1),

[0049] Ch-(LX m ) n (1)

[0050] wherein Ch is a chromophore, L is a linking group or a heteroatom, preferably a linking group, X is a polymerizable group, m is 1 to 3 and n is 1 to 3. Preferably, m=1.

[0051] The second colorant preferably has formula (1a),

[0052] Ch-(LX) n (1a)

[0053] wherein Ch is a chromophore, L is a divalent linking group or a divalent heteroatom, X is a polymerizable group, and n is 1 to 3.

[0054] Optionally, the chromophore Ch is an anthraquinone chromophore, which preferably comprises 1 to 3 substituents selected from: -F, -Cl, -Br, -I, -OR 2 、-SR 2 , -R 2 , -NO2, -CN, -NCO, -NCS, -C(=O)R 2 、-C(=O)OR 2 、-NH2、-C(=O)NHR 2 、-C(=O)N(R 2 )2, where each R 2 are independently H or a C1 to C20 hydrocarbon group.

[0055] Optionally, L is a divalent linking group. Optionally, the linking group L is -N(H)-R 1 -、-SR 1 OR 1, where R 1 is a divalent hydrocarbylene group, optionally C1 to C50, optionally C1 to C20 divalent hydrocarbylene group, which may be substituted or unsubstituted by one or more heteroatoms, wherein the one or more heteroatoms are optionally selected from O, S, N, P, Si, F, Cl, Br and I. R 1 It may, for example, comprise an aryl group, a linear or branched alkylene group or an aryl-alkylene group, said group optionally comprising one or more heteroatoms selected from F, Cl, Br, I, O, N, P and S. Optionally, R 1 Yes -(1,4-Ph)-(CH2) e -, wherein e = 1 to 16. Optionally, R 1 =-(1,4-Ph)-CH2-CH2-.

[0056] Optionally, the linking group L comprises a C6 to C14 aryl group, a C1 to C20 alkyl group, or a C7 to C20 aryl-alkyl group.

[0057] Optionally, each polymerizable group X is independently selected from acrylate, methacrylate, acrylamide, methacrylamide, allyl and vinyl. Preferably, one or more polymerizable groups X are each acrylate or methacrylate.

[0058] Optionally, the or each -LX substituent is according to formula (1c) or formula (1d) below.

[0059]

[0060] Where R 3 It is -H or -CH3.

[0061]

[0062] Optionally, each polymerizable group X is independently selected from acrylate, methacrylate, acrylamide, methacrylamide, allyl and vinyl. Preferably, one or more polymerizable groups X are each acrylate or methacrylate.

[0063] Optionally, the second colorant is according to formula (2)

[0064]

[0065] Wherein a and b can be 0 to 3, with the restriction that 0≤(a+b)≤3; each A is independently selected from -F, -Cl, -Br, -I, -OR 2 、-SR 2 , -R 2 , -NO2, -CN, -NCO, -NCS, -C(=O)R 2 、-C(=O)OR 2、-NR 2 2. -C(=O)NHR 2 、-C(=O)N(R 2 )2, where each R 2 As defined above; c and d may each be 0 to 3, with the proviso that 1≤(c+d)≤3; and L and X are as defined above. Optionally, the anthraquinone has no -LX group at the 1st and 4th positions. Optionally, when (a+b)=0, (c+d)=2 and L=-NHR a -(where -R a - is a divalent group having 1 to 12 carbon atoms), the (LX) group is not in the 1,4-position.

[0066] Optionally, the second colorant is according to formula (3) or formula (4):

[0067]

[0068] Optionally, the second colorant is one of Compounds 1 to 7 set forth in the Prophetic Examples below.

[0069] The concentration of the second colorant in the contact lens will be selected based on the color intensity required to balance the color of the first colorant. Based on dry weight, the concentration of the second colorant in the contact lens is optionally in the range of 20 ppm to 1000 ppm, optionally 40 ppm to 1000 ppm, optionally 100 ppm to 1000 ppm, optionally 300 ppm to 1000 ppm, for example 350 ppm to 900 ppm.

[0070] Third colorant

[0071] Optionally, the contact lens comprises a third colorant having an absorption maximum (λ) in the range of greater than 600 nm to 800 nm, optionally 610 nm to 780 nm. max ) colorant. The absorption maximum of the third colorant is located at a higher wavelength than the absorption maximum of the second colorant. The third colorant can be a pigment or a dye. Typically, the third colorant is blue. Preferably, the third colorant is a blue dye. The third colorant can be a process dye. Such process dyes are well known to those skilled in the art. The third colorant can be a blue polymerizable dye. Polymerizable dyes suitable for use as process dyes are disclosed in, for example, US 5,055,602. The third colorant is optionally an anthraquinone dye, preferably a polymerizable anthraquinone dye, such as RB246: 1,4-bis(4-(2-methacryloyloxyethyl)phenylamino)anthraquinone (CAS No. 121888-69-5).

[0072] The third colorant is included in the polymerizable composition prior to polymerization.The third colorant is preferably soluble in the polymerizable composition and is uniformly distributed throughout the polymerizable composition and the final contact lens.

[0073] The concentration of the third colorant in the contact lens is optionally in the range of 20 ppm to 1000 ppm, optionally 20 ppm to 800 ppm, such as 40 ppm to 300 ppm, based on dry weight.

[0074] UV absorbing compounds

[0075] The contact lens optionally also includes at least one compound that absorbs UV light. Such UV absorbing compounds are also known as UV blocking compounds and are well known to those skilled in the art. They are typically added to contact lens formulations to protect the eyes from the harmful effects of UV light. UV absorbing compounds are typically colorless and are therefore not considered as first, second or third colorants as in the present invention.

[0076] The concentration of the UV absorbing compound in the contact lens optionally ranges from 0.5 wt% to 2.0 wt%, optionally from 0.7 wt% to 1.5 wt%.

[0077] If present, at least one UV blocking compound is preferably included in the polymerizable composition prior to polymerization.The at least one UV blocking compound is preferably soluble in the polymerizable composition and uniformly distributed throughout the polymerizable composition and the final contact lens.

[0078] Polymeric Matrix

[0079] Contact lenses are generally formed by polymerizing a polymerizable composition comprising one or more monomers to produce a polymeric matrix having the desired properties. The polymeric matrix can be formed, for example, by dispensing the polymerizable composition into a mold having the desired shape and then sealing the mold prior to polymerization. After polymerization, the polymeric matrix is ​​formed to have the desired shape and is then subjected to processing steps such as washing, packaging, and autoclaving.

[0080] The second colorant is a polymerizable dye and will become an integral part of the polymer matrix during polymerization. Thus, the polymer matrix includes side chains derived from the second colorant. These side chains may be in the form of -L-C, wherein L is a linking group as defined above, and C is a chromophore as defined above.

[0081] Similarly, if the first and / or third colorant is also a polymerizable dye, the first and / or third colorant will also become a major part of the polymer matrix. Therefore, in this case, the first and / or third colorant will also generate corresponding side chains in the polymer matrix.

[0082] The polymer matrix forms the material of the contact lens. The polymer matrix can be of any type suitable for contact lenses, and the polymerizable composition can therefore include any monomer suitable for making contact lenses. Preferably, the contact lens is a hydrogel contact lens. A hydrogel is a polymeric material that can maintain water in a state of equilibrium at room temperature and has an equilibrium moisture content of at least 10% by weight. Optionally, the equilibrium moisture content of the hydrogel does not exceed 95% by weight, optionally does not exceed 90% by weight.

[0083] Optionally, the contact lens is a conventional hydrogel material, i.e., a hydrogel material that does not contain silicone. For example, the contact lens may be a conventional hydrogel of Group 1, Group 2, Group 3 and Group 4 as defined in Part 1, Chapter 4 of BS EN ISO 13369 2017. The materials so defined include both ionic and non-ionic materials, as well as both low-water and high-water content materials using the definitions in the reference standard. These types of hydrophilic materials are typically prepared using a polymerizable composition comprising at least one monomer suitable for making a lens device, preferably hydroxyethyl methacrylate, N-vinyl pyrrolidone, alkyl methacrylate (e.g., methyl methacrylate, methacrylic acid, aryl methacrylate, glyceryl methacrylate, fluorinated methacrylate, alkyl-substituted acrylate or methacrylate) or a combination thereof in the case of contact lenses. Of course, other monomers and additives for making lenses may also be used. Optionally, the hydrogel has an equilibrium moisture content of at least 10% by weight at 25°C, optionally at least 20% by weight. Optionally, the hydrogel has an equilibrium moisture content of no more than 90 wt%, optionally no more than 80 wt% at 25°C.

[0084] Suitable lens materials include, but are not limited to, bufilcon A, etafilcon A, methafilcon A, ocufilcon C, perfilcon A, phemfilcon A and vifilcon A, methafilcon B, occufilcon D, etafilcon A, lidofilcon A or lidofilcon B, alphafilcon A, tetrafilcon A, surfilcon A, vasurilcon A, hioxifilcon A.

[0085] The contact lens can be a silicone hydrogel contact lens. The silicone hydrogel material is usually formed by curing a polymerizable composition (i.e., a monomer mixture) comprising the following: at least one siloxane monomer or macromer, and at least one hydrophilic monomer or at least one hydrophilic polymer, or a combination thereof. As used herein, the term "monomer" refers to a molecule comprising a polymerizable carbon-carbon double bond (i.e., a polymerizable group) that can react with the same or different other molecules containing polymerizable groups to form a polymer or copolymer. The term monomer encompasses polymerizable prepolymers and macromers, and unless otherwise specified, there is no size restriction on the monomer. The monomer may contain a single polymerizable carbon-carbon double bond or more than one polymerizable group, and therefore has cross-linking functionality. "Siloxane monomer" is a molecule containing at least one Si-O group and at least one polymerizable group. Siloxane monomers suitable for contact lens compositions are well known in the art (see, for example, U.S. Patent No. 8,658,747 and U.S. Patent No. 6,867,245). (All patents and publications mentioned herein and throughout are incorporated herein by reference in their entirety.) Siloxane macromers are siloxane monomers that contain one or more polymerized segments. In some examples, the polymerizable composition contains a total amount of siloxane monomers of at least 10%, 20%, or 30% by weight to about 40%, 50%, 60%, or 70% by weight. Unless otherwise indicated, as used herein, a given weight percentage (wt%) or ppm of a component in a polymerizable composition is relative to the total weight of all polymerizable ingredients, which, for purposes of the present invention, also includes any interpenetrating polymer network (IPN) polymers in the polymerizable composition (as further described below). The weight of the polymerizable composition contributed by components (e.g., diluents) that are not incorporated into the final contact lens product is not included in the wt% or ppm calculation.

[0086] Optionally, the polymerizable composition includes a hydrophilic vinyl monomer. As used herein, a "hydrophilic vinyl monomer" is any hydrophilic monomer that does not contain siloxane (i.e., does not contain Si-O groups) and has a polymerizable vinyl group present in its molecular structure. As used herein, the term "acrylic" refers to a polymerizable group present in acrylates, methacrylates, acrylamides, methacrylamides, etc. Therefore, as used herein, although there are carbon-carbon double bonds in acrylate and methacrylate groups, such polymerizable groups are not considered to be vinyl groups. In addition, as used herein, if at least 50 grams of monomers are completely soluble in 1 liter of water (i.e., about 5% water-soluble) at 20°C as determined visually using a standard shake bottle method, the monomer has "hydrophilicity". In various examples, the hydrophilic vinyl monomer is N-vinyl-N-methylacetamide (VMA) or N-vinyl pyrrolidone (NVP) or any combination thereof. In one example, the polymerizable composition comprises at least 10 wt%, 15 wt%, 20 wt%, or 25 wt% to about 45 wt%, 60 wt%, or 75 wt% hydrophilic vinyl monomers. As used herein, a given weight percentage of a particular class of components (e.g., hydrophilic vinyl monomers, siloxane monomers, or the like) in a polymerizable composition is equal to the sum of the weight % of each ingredient in the composition belonging to that class. Thus, for example, a polymerizable composition comprising 5 wt% VMA and 25 wt% NVP and no other hydrophilic vinyl monomers is referred to as comprising 30 wt% hydrophilic vinyl monomers. In another specific example, the polymerizable composition comprises about 25 wt% to about 75 wt% VMA or NVP or a combination thereof.

[0087] Examples of other suitable hydrophilic monomers are N,N-dimethylacrylamide (DMA), 2-hydroxyethyl methacrylate (HEMA), ethoxyethyl methacrylamide (EOEMA), ethylene glycol methyl ether methacrylate (EGMA), hydroxy-substituted C1-6 alkyl acrylates and methacrylates, such as 2-hydroxyethyl methacrylate, (meth)acrylamide, (C1-6 alkyl)acrylamide and (C1-6 alkyl)methacrylamide, ethoxylated acrylates and methacrylates, hydroxy-substituted (C1-6 alkyl)acrylamide and (C1-6 alkyl)methacrylamide, hydroxy-substituted C1-6 alkyl vinyl ethers), vinyl sulfonic acids. sodium, sodium styrene sulfonate, vinyl-containing monomers (e.g., N-vinylpyrrole, 2-vinyloxazoline, 2-vinyl-4,4'-dialkyloxazolin-5-one, 2-vinylpyridine and 4-vinylpyridine, vinyl unsaturated carboxylic acids having a total of 3 to 5 carbon atoms, such as methacrylic acid, amino(C1-C6 alkyl)- (wherein the term "amino" also includes quaternary ammonium)), dimethylaminoethyl methacrylate (DMAEMA), mono(C1-C6 alkylamino)(C1-C6 alkyl) and di(C1-C6 alkylamino)(C1-C6 alkyl) acrylates and methacrylates, allyl alcohol, and zwitterionic monomers including sulfobetaines and carboxybetaines, and combinations thereof.

[0088] The polymerizable composition may also include a hydrophobic monomer that does not contain silicon. Examples of suitable hydrophobic auxiliary monomers include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl acrylate, 2-hydroxybutyl methacrylate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, styrene, chloroprene, vinyl chloride, vinylidene chloride, acrylonitrile, 1-butene, butadiene, methacrylonitrile, vinyl toluene, vinyl ethyl ether, methacrylate perfluorohexyl ethylthiocarbonylamine ethyl ester, methacrylate isobornyl, methacrylate trifluoroethyl, methacrylate hexafluoroisopropyl, methacrylate tetrafluoropropyl, methacrylate hexafluorobutyl. In addition, as used herein, if less than 50 grams of monomer can be completely dissolved in 1 liter of water at 20° C. (i.e., about 5% water-soluble), the monomer has "hydrophobicity", as determined visually using the standard shake bottle method.

[0089] In addition, or as an alternative to hydrophilic monomers, the polymerizable composition may include a non-polymerizable hydrophilic polymer, which produces a polymerized lens body comprising an interpenetrating polymer network (IPN), wherein the non-polymerizable hydrophilic polymer and the silicone hydrogel polymer matrix interpenetrate. In this example, the non-polymerizable hydrophilic polymer is referred to as an IPN polymer, which acts as an internal wetting agent in a contact lens. In contrast, the polymer chains formed by the polymerization of the monomers present in the polymerizable composition in the silicone hydrogel network are not considered to be IPN polymers. IPN polymers can be high molecular weight hydrophilic polymers, such as about 50,000 to about 500,000 daltons. In a particular example, the IPN polymer is polyvinyl pyrrolidone (PVP). In other examples, the polymerizable composition is substantially free of polyvinyl pyrrolidone or other IPN polymers.

[0090] The polymerizable composition may additionally include at least one crosslinking agent. As used herein, a "crosslinking agent" is a molecule having at least two polymerizable groups. Thus, a crosslinking agent may react with functional groups on two or more polymer chains to bridge one polymer to another polymer. The crosslinking agent may include an acryloyl or vinyl group, or both an acryloyl and vinyl group. In certain embodiments, the crosslinking agent does not contain a siloxane moiety, i.e., the crosslinking agent is a non-siloxane crosslinking agent. A variety of crosslinking agents suitable for silicone hydrogel polymerizable compositions are known in the art (see, e.g., U.S. Pat. No. 8,231,218, which is incorporated herein by reference). Examples of suitable crosslinking agents include, but are not limited to, lower alkylene glycol di(meth)acrylates, such as triethylene glycol dimethacrylate and diethylene glycol dimethacrylate; poly(lower alkylene) glycol di(meth)acrylates; lower alkylene di(meth)acrylates; allyl methacrylates; divinyl ethers, such as triethylene glycol divinyl ether, diethylene glycol divinyl ether, 1,4-butanediol divinyl ether, and 1,4-cyclohexanedimethanol divinyl ether; divinyl sulfone; divinylbenzene and trivinylbenzene; trimethylolpropane tri(meth)acrylate; pentaerythritol tetra(meth)acrylate; bisphenol A di(meth)acrylate; methylenebis(meth)acrylamide; triallyl phthalate; 1,3-bis(3-methacryloxypropyl)tetramethyldisiloxane; diallyl phthalate; triallyl isocyanate, and combinations thereof.

[0091] As will be appreciated by those skilled in the art, the polymerizable composition may include other polymerizable or non-polymerizable components conventionally used in contact lens formulations, such as one or more of a polymerization initiator, an oxygen scavenger, a chain transfer agent, a diluent, or the like. In some examples, the polymerizable composition may include an amount of an organic diluent to prevent or minimize the phase separation between the hydrophilic component and the hydrophobic component of the polymerizable composition, thereby obtaining an optically clear lens. Diluents commonly used in contact lens formulations include hexanol, ethanol, and / or other primary, secondary, or tertiary alcohols. In other examples, the polymerizable composition does not contain or is substantially free of (e.g., less than 500ppm) organic diluents. In such examples, the use of siloxane monomers containing hydrophilic portions such as polyethylene oxide groups, hydroxyl side groups, or other hydrophilic groups may make it unnecessary to include a diluent in the polymerizable composition. Non-limiting examples of these and other ingredients that may be included in the polymerizable composition are provided in U.S. Pat. No. 8,231,218.

[0092] Non-limiting examples of silicone hydrogels that can be used include comfilcon A, fanfilcon A, stenfilcon A, senofilcon A, senofilcon C, somofilcon A, narafilcon A, delefilcon A, narafilcon B, lotrafilcon A, lotrafilcon B, balafilcon A, samfilcon A, galyfilcon A, asmofilcon A, riofilcon A, kalifilcon A, olifilcon A, senofilcon B, and enfilcon A.

[0093] In a specific embodiment, the polymerizable composition comprises 25 wt % to 55 wt % of one or more siloxane monomers; 30 wt % to 55 wt % of a vinyl monomer selected from NVP and VMA and combinations thereof; and optionally about 1 wt % to about 20 wt % of a hydrophilic monomer selected from the following: N,N-dimethylacrylamide (DMA), 2-hydroxyethyl methacrylate (HEMA), ethoxyethyl methacrylamide (EOEMA) and ethylene glycol methyl ether methacrylate (EGMA) and combinations thereof; and optionally about 1 wt % to about 20 wt % of a hydrophobic monomer selected from the following: methyl methacrylate (MMA), isobornyl methacrylate (IBM) and 2-hydroxybutyl methacrylate (HOB). The silicone hydrogel materials prepared from this specific embodiment of the polymerizable composition include Stanfikon A, Conocofikon A, Somofikon A, Fanfikon A and Enfikon A.

[0094] As noted above, in preferred embodiments, the contact lenses of the present invention may be considered soft contact lenses and, in particular, soft silicone hydrogel contact lenses.

[0095] Contact lenses can have any lens wearing form. The lens wearing form refers to the number of days that the lens can be worn continuously without removal. In one example, the contact lens is a daily disposable lens. Daily disposable lenses are suitable for single use, can be worn continuously for up to about 12 or 16 hours, and should be discarded after a single use. In another example, the contact lens is a daily wear lens. Daily wear lenses are worn during waking hours, usually up to about 12 to 16 hours, and are removed before going to bed. Daily wear lenses are usually stored in a contact lens case containing a contact lens care solution, which is used to clean and sterilize the lenses when not in use. Daily wear lenses are usually discarded after up to 30 days of wearing. In another example, the contact lens is an extended wear lens. Extended wear lenses are usually worn continuously for up to 6, 14 or 30 consecutive days and nights.

[0096] As part of the present invention, contact lenses can be sealed in contact lens packaging. The packaging solution sealed in the contact lens packaging can be any conventional contact lens compatible solution. In one example, the packaging solution comprises an aqueous solution of a buffer and / or a tension agent, is composed of it or is essentially composed of it. In another example, the packaging solution contains additional agents, such as one or more additional antibacterial agents and / or comfort agents and / or hydrophilic polymers, and / or surfactants and / or other beneficial agents. In some examples, the packaging solution may include polysaccharides (e.g., hyaluronic acid, hydroxypropyl methylcellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, etc.) or other high molecular weight polymers, such as polyvinyl pyrrolidone, which is commonly used as a comfort polymer or thickener in ophthalmic solutions and contact lens packaging solutions. In other examples, the packaging solution may include ophthalmic drugs. The pH value of the packaging solution can be in the range of about 6.8 or 7.0 to about 7.8 or 8.0. In one example, the packaging solution includes a phosphate buffer or a borate buffer. In another example, the packaging solution comprises a tonicity agent selected from sodium chloride or sorbitol in an amount to maintain osmotic pressure within the range of about 200 to 400 mOsm / kg, and typically about 270 mOsm / kg to about 310 mOsm / kg.

[0097] Regarding contact lens packaging, this packaging may include or comprise a plastic base member, the plastic base member comprising a cavity configured to accommodate a contact lens and a packaging solution and a flange area extending outwardly around the cavity. A removable foil is adhered to the flange area to provide a sealed contact lens packaging. Such contact lens packaging, commonly referred to as a "blister pack", is well known in the art (see, e.g., U.S. Patent No. 7,426,993). The packaging may also include two foil members bonded together, the two foil members may be flat, or one or both foil members may be formed into an appropriate geometric shape to accommodate the lens and the packaging solution.

[0098] It should be understood that sealed contact lens packages can be manufactured using conventional manufacturing methods. In the method for manufacturing contact lens packages, the method may include the following steps: placing unworn contact lenses and contact lens packaging solutions in a receptacle, placing a cover on the receptacle, and sealing the cover on the receptacle. Generally speaking, the receptacle is configured to accommodate a single pair of contact lenses and a packaging solution sufficient to completely cover the contact lenses, typically about 0.5 to 1.5 ml. The receptacle can be made of any suitable material, such as glass or plastic or foil. In one example, the receptacle includes a plastic base member, which includes: a cavity, which is configured to accommodate contact lenses and packaging solutions; and a flange area, which extends outward around the cavity, and the cover includes a removable foil adhered to the flange area to provide a sealed contact lens package. The removable foil can be sealed by any conventional means such as heat sealing or gluing. In another example, the receptacle is in the form of a plastic base member including a plurality of threads and the cover includes a plastic cap member including a compatible set of threads for engaging with the threads of the base member, thereby providing a resealable cover. It should be understood that other types of packaging can also be used to provide a resealable package. For example, a contact lens package may include a plastic cover that includes a compatible part that engages with the receptacle to form a tight fit. The method of manufacturing a sealed contact lens package may further include sterilizing unworn contact lenses by autoclaving the sealed contact lens package. Autoclaving typically involves subjecting the sealed contact lens package to a temperature of at least 121° C. for at least 20 minutes. Preferably, the contact lenses of the present invention do not significantly change color after autoclaving at 121° C. in a sealed package containing a packaging solution for 20 minutes.

[0099] The contact lens can be provided unworn (i.e., a new contact lens, not yet used by a patient), immersed in a packaging solution and sealed in a package. The package can be a blister pack, a glass bottle, a foil to foil package, or other suitable container. The package comprises a base member having a cavity for accommodating the packaging solution and the unworn contact lens. The sealed package can be sterilized by a sterilizing amount of radiation (including heat or steam), for example, by autoclaving or by gamma radiation, electron beam radiation, ultraviolet radiation, etc.

[0100] In certain examples, the packaged contact lenses are sterilized by autoclaving.

[0101] The final product may be a packaged sterile contact lens (e.g., a silicone hydrogel contact lens) that is ophthalmically compatible. "Ophthalmically compatible" refers to a material that can be placed in direct contact with the ocular environment without causing significant changes to the ocular environment, is toxicologically inert, and does not cause discomfort to the user both during contact and after removal. The term also refers to the properties of the lens material such that the deposition of proteins, lipids, or other biomolecules inherent to the ocular environment is limited to a level such that the performance of the device is not compromised and the device can be easily removed after the contact period.

[0102] Contact lenses

[0103] The contact lenses can have any suitable design and thickness, and many such designs are known to those skilled in the art.

[0104] As mentioned above, the contact lens can be a soft contact lens, optionally a hydrogel contact lens, such as a silicone hydrogel contact lens.

[0105] The contact lenses are colorless, gray, or blue. Optionally, the lenses are gray or blue. Various color space-based systems are known for defining colors and allow the color of an object to be defined using specific symbols. For example, the International Commission on Illumination (Commission Internationale de l'Eclairage; CIE) has defined color spaces (including CIE XYZ, CIEL*a*b*, and CIE L*C*h) for communicating and representing colors.

[0106] One such system suitable for defining the color of contact lenses is the CIELab L*a*b* color space. It is a three-dimensional representation of color, where L* is the lightness-darkness coordinate, and a* and b* coordinates define red / green and blue / yellow. A related system uses the same color space, with CIELab L*C*h* coordinates defining color. This is generally the same L (brightness) axis, but C (chromaticity) and h (hue) are different from a* and b*. C (chromaticity) is the distance from the L axis and h, and hue is defined as the angle starting at the +a* axis and expressed in degrees (e.g., 0° is +a* or red, and 90° is +b or yellow). CIELab L*, a*, and b* values ​​can be converted to CIELab L*, C*, and h* values ​​by methods known to those skilled in the art, and vice versa.

[0107] Chroma is a measure of the degree of coloration, where zero chroma corresponds to a neutral or gray hue. Optionally, the contact lens is gray, where gray is optionally defined as having a chroma (C*) value of 5.0 or less, and a hue (h*) value of 166 degrees or less or greater than or equal to 275 degrees. Hue (h*) is a measure of what color is present, such as green, blue, etc. Optionally, the contact lens is blue, where blue is optionally defined as having a hue (h*) value greater than 166 degrees and less than 275 degrees. Optionally, the contact lens is gray or blue and has at least one of the following: a) a chroma (C*) value of 5.0 or less, and b) a hue (h*) value greater than 166 degrees and less than 275 degrees.

[0108] The concentration of the colorant will be selected so that the portion of visible light transmitted through the contact lens is not reduced to an undesirable degree that would hamper the user's ability to see, especially in low light conditions. Reference herein to light transmittance in a certain wavelength range should be taken to mean the transmittance measured at 1 nm intervals in the wavelength range as per section 4.8 of BS EN ISO 18369-3-2017, with the results averaged to obtain an average value. Typically, the transmittance of the contact lens in the visible light range of 380 nm to 780 nm is at least 80%, optionally at least 90%, as measured in accordance with section 4.8 of BS EN ISO 18369-3-2017.

[0109] Method for manufacturing contact lenses

[0110] The present invention provides a method for manufacturing a contact lens, comprising the steps of polymerizing a polymerizable composition in a mold to form a lens-shaped polymerized product comprising a polymer matrix, the polymerizable composition comprising: one or more monomers; a first colorant having an absorption maximum (λ) in the range of 415 nm to 455 nm; max ) of a yellow blue light blocking colorant; and a second colorant, wherein the second colorant has an absorption maximum (λ in the range of 470nm to 600nm max ) of a violet or red polymerizable dye; and optionally further comprising a third colorant, which is a blue colorant having an absorption maximum in the range of greater than 600 nm to 800 nm, wherein the second colorant and the third colorant (if present) balance the yellow color of the first colorant, thereby making the contact lens colorless, gray or blue.

[0111] Optionally, the polymerizable composition comprises 20 ppm to 1000 ppm, optionally 40 ppm to 1000 ppm, optionally 100 ppm to 1000 ppm, optionally 300 ppm to 1000 ppm, for example 350 ppm to 900 ppm of the first colorant, based on the total weight of all polymerizable components in the polymerizable composition.

[0112] Optionally, the first colorant is also polymerizable.

[0113] Optionally, the polymerizable composition comprises a second colorant in a range of 20 ppm to 1000 ppm, optionally 40 ppm to 1000 ppm, optionally 100 ppm to 1000 ppm, optionally 300 ppm to 1000 ppm, for example 350 ppm to 900 ppm, based on the total weight of all polymerizable components in the polymerizable composition.

[0114] Optionally, the polymerizable composition comprises a third colorant in a range from 20 ppm to 1000 ppm, optionally from 20 ppm to 800 ppm, such as from 40 ppm to 300 ppm, based on the total weight of all polymerizable components in the polymerizable composition.

[0115] Optionally, the third colorant is also polymerizable.

[0116] Optionally, the polymerizable composition further comprises 0.5 wt% to 2.0 wt%, optionally 0.7 wt% to 1.5 wt% of a UV absorbing compound, based on the total weight of all polymerizable components in the polymerizable composition.

[0117] The polymerizable composition can be dispensed into a contact lens mold and cured (i.e., polymerized) using any suitable curing method. Typically, the polymerizable composition is exposed to a polymerizing amount of heat or ultraviolet light (UV). In the case of UV curing (also referred to as photopolymerization), the polymerizable composition typically includes a photoinitiator, such as benzoin methyl ether, 1-hydroxycyclohexyl phenyl ketone, DAROCUR or IRGACUR (available from Ciba Specialty Chemicals). Photopolymerization methods for contact lenses are described, for example, in U.S. Pat. No. 5,760,100. In the case of thermal curing (also referred to as thermal curing), the polymerizable composition typically includes a thermal initiator. Exemplary thermal initiators or catalysts well known in the art include azo or peroxide containing compounds such as 2,2'-azobis(2,4-dimethylvaleronitrile) (VAZO-52), 2,2'-azobis(2-methylpropionitrile) (VAZO-64) and 1,1'-azobis(cyanocyclohexane) (VAZO-88); benzoyl peroxide, lauroyl peroxide, di-isopropyl peroxydicarbonate, azobis(2,4-dimethylvaleronitrile), azobis(isobutyronitrile); redox systems such as ammonium persulfate; and photoinitiators effective in the UV spectrum or visible spectrum or a combination of these spectra, including, for example, benzoin methyl ether or phosphine oxides, such as diphenyl(2,4-trimethylbenzoyl)phosphine oxide. Preferably, thermal curing is carried out in an atmosphere containing less than 150 ppm oxygen and more preferably less than 100 ppm oxygen. More preferably, thermal curing is carried out in an inert atmosphere, such as nitrogen or an inert gas containing less than 50 ppm oxygen. Thermal polymerization methods for contact lenses are described, for example, in US Pat. Nos. 8,231,218 and 7,854,866, which are incorporated herein by reference.

[0118] After polymerization, the resulting lens-shaped polymer product is removed from the mold (lens demolded) and washed to extract any unreacted or partially reacted components and to hydrate the lens. The washing step involves contacting the polymerized lens with one or more volumes of one or more washing liquids. In some examples, a first volume of washing liquid is used to "wet" demold the lens from the mold. In other examples, a mechanical method is used to "dry demold" the lens from the mold. The method of the present invention preferably includes a step of hydrating the lens-shaped polymer product to form a hydrogel contact lens. In some examples, the washing liquid used to wash and hydrate the lens may include one or more volatile organic solvents (e.g., methanol, ethanol, a mixture of lower alcohols such as industrial methanolic alcohol, chloroform or the like). In other examples, only a washing liquid that does not contain volatile organic solvents (e.g., deionized water) is used to wash and hydrate the lens.

[0119] After the polymerization step or the washing step, the polymerized lens may be subjected to a surface modification treatment to increase the wettability of the contact lens. A variety of surface modification methods for increasing the wettability of the contact lens surface are known in the art. Examples include plasma treatment, attaching a hydrophilic polymer to the polymerized lens (e.g., by a layer-by-layer technique), and adding a hydrophilic polymer to the contact lens packaging solution. These and other surface modification methods are known in the art (see, e.g., U.S. Pat. Nos. 4,143,949, 7,582,327, 7,841,716).

[0120] Preferably, the method of the present invention further comprises the steps of immersing the polymerized product or hydrogel contact lens in a package containing a packaging solution, sealing the package, and optionally sterilizing the sealed package. For example, after washing and any optional method steps (such as surface modification), the hydrated polymerized lens is placed in a blister pack, a glass bottle or other suitable container, which is collectively referred to herein as a "package". Typically, a packaging solution is also added to the container. Suitable packaging solutions include phosphate buffered saline or borate buffered saline, and any optional additional ingredients, such as comfort agents, drugs, surfactants to prevent the lens from adhering to its packaging, or the like. The package is sealed, and the sealed polymerized lens is sterilized by radiation, heat or steam (such as autoclaving), gamma radiation, electron beam radiation or the like. In some examples, the lens can be packaged under sterile conditions, so that a post-packaging sterilization step is not required. In some examples, the polymerized lens can be demolded by dry lens, placed directly in its final package together with the packaging solution, sealed and optionally sterilized. Therefore, the washing step can be performed simultaneously with the packaging and sterilization steps. Preferably, the contact lenses are sterilized by autoclaving.

[0121] Synthesis of Example Dyes

[0122] 4-Bromophenethyl methacrylate

[0123]

[0124] At 0°C, 2-(4-bromophenyl)ethanol (25 g, 124 mmol) was dissolved in dichloromethane (250 cm 3 ) was slowly added with triethylamine (35 cm 3 Then methacryloyl chloride (13 cm 3, 131mmol) to maintain the temperature below 5°C. After the addition, the reaction mixture was stirred at 0-5°C for 1 hour, and then at 23°C for 17 hours. The suspension was collected by filtration and washed with dichloromethane. The combined filtrate was washed with distilled water, 2N aqueous hydrochloric acid solution and distilled water in sequence. The organic layer was dehydrated over anhydrous magnesium sulfate, filtered and the solvent was removed in vacuo. The crude material was purified by a silica gel plug (heptane: ethyl acetate; 9: 1) to give 4-bromophenethyl methacrylate (29.4g, 88%) as a colorless oil. 1 H NMR (CDCl3) 7.42-7.46 (2H, m), 7.12 (2H, d), 6.07 (1H, s), 5.54-5.57 (1H, m), 4.34 (2H, t), 2.95 (2H, t), 1.93 (3H, s).

[0125] Dye 1

[0126]

[0127] N,N-dimethylformamide (80 cm 3 ), 4-bromophenethyl methacrylate (16.9 g, 63 mmol), 1,5-diaminoanthraquinone (5.0 g, 21 mmol), copper (I) iodide (800 mg, 4.2 mmol), copper (800 mg, 12.6 mmol), potassium carbonate (880 mg, 6.3 mmol) and sodium acetate (5.86 g, 71.4 mmol) were heated at 150 ° C for 45 hours. The reactants were cooled to about 100 ° C, and 4-bromophenethyl methacrylate (2.3 g, 8.6 mmol), copper (I) iodide (800 mg, 4.2 mmol) and copper (800 mg, 12.6 mmol) were added. The reaction mixture was then heated at 150 ° C for another 24 hours and then cooled. The mixture was poured into distilled water (250 cm 3 ) and stirred for 30 min, then filtered. The residue was purified by repeated column chromatography (heptane:ethyl acetate; gradient 1:0 to 9:1) followed by recrystallization (heptane / ethyl acetate) to give dye 1 (390 mg, <1%) as a dark purple solid. 1 H NMR (CDCl3) 11.35 (2H, s), 7.69-7.74 (2H, m), 7.42-7.53 (4H, m), 7.26-7.31 (6H, m), 6.10-6.13 (2H, m), 5.56-5.60 (2H, m), 4.39 (4H, t), 3.02 (4H, t), 1.96 (6H, s). UV-vis(λ max , dichloromethane) 537nm.

[0128] 4-Iodophenethyl methacrylate

[0129]

[0130] At 0°C, 2-(4-iodophenyl)ethanol (20 g, 81 mmol) was dissolved in dichloromethane (200 cm 3 ) was slowly added with triethylamine (22.5 cm 3 Then methacryloyl chloride (8.7 cm 3 , 89 mmol) to maintain the temperature below 5 ° C. After the addition, the reaction mixture was stirred at 0-5 ° C for 1 hour and at 23 ° C for 150 minutes. The solid was collected by filtration and washed with dichloromethane. The combined filtrate was washed with distilled water, 2N aqueous hydrochloric acid solution and distilled water. The organic layer was dried over anhydrous magnesium sulfate, filtered and the solvent was removed in vacuo. The residue was purified by silica gel plug (heptane: ethyl acetate; 95: 5) to give 4-iodophenylethyl methacrylate (22.9 g, 90%) as a colorless oil. 1 HNMR (CDCl3) 7.61-7.67 (2H, m), 6.97-7.03 (2H, m), 6.07 (1H, s), 5.53-5.58 (1H, m), 4.33 (2H, t), 2.93 (2H, t), 1.93 (3H, s).

[0131] The absorption maximum (λ max ) is 541nm.

[0132] Dye 2

[0133]

[0134] N,N-dimethylformamide (28 cm 3 A mixture of 4-iodophenethyl methacrylate (5.0 g, 15.8 mmol), 1-amino-4-methoxyanthraquinone (1.9 g, 7.9 mmol), copper (I) iodide (150 mg, 0.79 mmol), copper (150 mg, 2.4 mmol), potassium carbonate (160 mg, 1.2 mmol) and sodium acetate (1.10 g, 13.4 mmol) was heated at 150° C. for 60 hours. After being allowed to cool, the reaction mixture was poured into distilled water (150 cm 3 ) and the solid was collected by filtration. The residue was purified by column chromatography (heptane:ethyl acetate; 9:1) to give dye 2 (300 mg, 9%) as a dark blue solid. 1H NMR (CDCl3) 13.73 (1H, s), 11.79 (1H, s), 8.34-8.42 (2H, m), 7.80-7.87 (2H, m), 7.54-7.60 ( 1H, m), 7.13-7.31 (5H, m), 6.11 (1H, s), 5.58 (1H, s), 4.39 (2H, t), 3.02 (2H, t), 1.96 (3H, s). UV-vis(λ max , ethanol) 570nm.

[0135] The absorption maximum (λ max ) is 585nm.

[0136] Dyes 1 and 2 were used in the following lens making examples.

[0137] The UV-vis absorption spectra of the four dyes (Dye 1, Dye 2, RY86-HEMA and RB246) used in the following contact lens examples were measured using a Perkin Elmer Lambda 35 UV / Vis spectrophotometer. A 5 ppm solution of each dye was prepared in methanol. The spectra were operated in a 1 cm plastic optical cell. Methanol was used to automatically zero the baseline. The scan range was between 780 nm and 270 nm, with a data interval of 1 nm and a slit width of 1 nm. The absorbance maxima of each dye are reported in Table 1 below, and the spectra are shown in Figure 2 middle.

[0138] dye λmax(nm) RY-86-HEMA 422 Red Dye(Dye 1) 531 Purple Dye(Dye 2) 560 Blue Dye(RB246) 634

[0139] Table 1: Lambda of four dyes max value

[0140] Examples of Predictive Dye Synthesis

[0141] Intermediate 1

[0142]

[0143] 1,2-Dibromo-9,10-anthracenedione (5 g) and dimethyl sulfoxide (25 cm 3 ) was added to the suspension of 2-(4-aminophenyl)ethanol (25 g). The mixture was then heated under reflux for 4 hours, allowed to cool to 23°C and poured into stirred water (200 cm 3 The solid was collected by filtration and subsequently recrystallized from ethanol to afford Intermediate 1.

[0144] Intermediate 2

[0145]

[0146] Intermediate 2 was prepared in a similar manner to Intermediate 1 except 2,6-dibromo-9,10-anthracenedione was used as the starting material.

[0147] Intermediate 3

[0148]

[0149] Intermediate 3 was prepared in a similar manner to Intermediate 1, except 1-bromo-9,10-anthracenedione was used as the starting material.

[0150] Intermediate 4

[0151]

[0152] Intermediate 4 was prepared in a similar manner to Intermediate 1, except 1-bromo-4-methoxy-9,10-anthracenedione was used as the starting material.

[0153] Intermediate 5

[0154]

[0155] Intermediate 5 was prepared in a similar manner to Intermediate 1, except 1,8-dibromo-9,10-anthracenedione was used as the starting material.

[0156] Intermediate 6

[0157]

[0158] Intermediate 6 was prepared in a similar manner to Intermediate 1 except 1,3-dibromo-9,10-anthracenedione was used as the starting material.

[0159] Intermediate 7

[0160]

[0161] Intermediate 7 was prepared in a similar manner to Intermediate 1 except 2,7-dibromo-9,10-anthracenedione was used as the starting material.

[0162] Compound 1

[0163] Pathway A

[0164]

[0165] Compound 1 was prepared in a similar manner to dye 1, except that 1,2-diaminoanthraquinone was used as the starting material.

[0166] Pathway B

[0167]

[0168] To intermediate 1 (1 g), anhydrous acetonitrile (15 cm 3 ) and triethanolamine (2 g) were dropwise added with methacryloyl chloride (1 cm 3 The mixture was then stirred at 23°C for 5 hours. Ethylene glycol (20 cm 3 ), followed by addition of water to give a precipitate. The crude material was collected by filtration and then purified by column chromatography to give Compound 1.

[0169] Compound 2

[0170] Route A

[0171]

[0172] Compound 2 was prepared in a similar manner to Compound 1 (Route A), except that 2,6-diaminoanthraquinone was used as the starting material.

[0173] Route B

[0174]

[0175] Compound 2 was prepared in a similar manner to compound 1 (Route B), except that intermediate 2 was used as the starting material.

[0176] Compound 3

[0177] Route A

[0178]

[0179] Compound 3 was prepared in a similar manner to Compound 1 (Route A), except that 1,8-diaminoanthraquinone was used as the starting material.

[0180] Route B

[0181]

[0182] Compound 3 was prepared in a similar manner to compound 1 (Route B), except that intermediate 5 was used as starting material.

[0183] Compound 4

[0184] Route A

[0185]

[0186] Compound 4 was prepared in a similar manner to compound 1 (Route A), except that 1,3-diaminoanthraquinone was used as the starting material.

[0187] Route B

[0188]

[0189] Compound 4 was prepared in a similar manner to compound 1 (Route B), except that intermediate 6 was used as the starting material.

[0190] Compound 5

[0191] Route A

[0192]

[0193] Compound 5 was prepared in a similar manner to Compound 1 (Route A), except that 2,7-diaminoanthraquinone was used as the starting material.

[0194] Route B

[0195]

[0196] Compound 5 was prepared in a similar manner to compound 1 (Route B), except that intermediate 7 was used as the starting material.

[0197] Compound 6

[0198] Route A

[0199]

[0200] Compound 6 was prepared in a manner similar to compound 1 (Route A), except that 1-aminoanthraquinone was used as the starting material and only 1 equivalent of 4-bromophenethyl methacrylate was used.

[0201] Route B

[0202]

[0203] Compound 6 was prepared in a similar manner to compound 1 (Route B), except that intermediate 3 was used as the starting material.

[0204] Compound 7

[0205] Route B

[0206]

[0207] Compound 7 was prepared in a similar manner to compound 1 (Route B), except that intermediate 4 was used as the starting material.

[0208] Example - Lens Manufacturing

[0209] The following chemical substances are referred to herein and may be referred to by their abbreviations.

[0210] RB246: 1,4-bis(4-(2-methacryloyloxyethyl)phenylamino)anthraquinone (CAS No. 121888-69-5)

[0211] RY86-HEMA: 2-Propenoic acid, 2-methyl-, 2-[[4-[[5-[2-[5-(aminocarbonyl)-1-ethyl-1,6-dihydro-2-hydroxy-4-methyl-6-oxo-3-pyridinyl]-2,4-disulfonylphenyl]amino]-6-chloro-1,3,5-triazin-2-yl]oxy]ethyl ester, sodium salt (1:2) (CAS No. 2254162-81-5).

[0212] Silicone Hydrogel Contact Lens Manufacturing and Inspection Procedures

[0213] For each example, the compounds described in the example were weighed out in amounts corresponding to the described unit parts and combined to form a mixture. The mixture was filtered through a 0.2-5.0 micron syringe filter into a bottle. The mixture was stored for up to 2 weeks. The mixture should be understood as a polymerizable silicone hydrogel contact lens precursor composition, or as used herein, a polymerizable composition. In the examples, the amounts of the listed ingredients are provided in the form of unit parts of the polymerizable composition by weight.

[0214] A volume of the polymerizable composition is cast into shape by placing the composition in contact with a lens-defining surface of a female mold part. In all of the following examples, the molding surface of the female mold part is formed of a non-polar resin, specifically polypropylene, although polar resins such as polybutylene terephthalate (PBT) may also be used. A male mold part is placed in contact with the female mold part to form a contact lens mold assembly containing a contact lens-shaped cavity containing the polymerizable composition. In the following examples, the molding surface of the male mold part is formed of a non-polar resin, specifically polypropylene.

[0215] The contact lens mold assemblies were placed in a nitrogen flushed oven to thermally cure the precursor composition into a lens-shaped polymerized product. For all examples, the contact lens mold assemblies were exposed to a temperature of at least about 55° C. for about 2 hours. Examples of curing profiles that can be used to cure the silicone hydrogel contact lenses described herein include exposing the contact lens mold assemblies to the following temperatures: 65° C. for 40 minutes, 80° C. for 40 minutes, and 100° C. for 40 minutes. Other contact lenses can be made by the same curing profile, but instead of the first temperature being 65° C., it can be 55° C.

[0216] In another method, the contact lens mold assembly can be exposed to UV light (eg, UVA or UVA+) for at least 30 minutes to UV cure the precursor composition into a lens-shaped polymerized product.

[0217] After the polymerizable composition is polymerized, the contact lens mold assembly is demolded to separate the male and female mold parts. The lens-shaped polymerized product remains adhered to the male or female mold. A dry demolding process in which the mold assembly is not in contact with a liquid medium may be used, or a wet demolding process in which the mold assembly is in contact with a liquid medium (e.g., water or an aqueous solution) may be used. A mechanical dry demolding process may involve applying a mechanical force to a portion of one or both mold parts to separate the mold parts. In all of the following examples, a dry demolding process is used.

[0218] The polymerized contact lens body is then demolded from the male or female mold to produce a demolded polymerized contact lens body. In one example of a lens demolding method, a dry lens demolding process can be used to demold the polymerized contact lens body from the male mold part, such as by manually peeling the lens from the male mold part, or by compressing the male mold part and directing gas to the male mold part and the polymerized contact lens body, and the dry polymerized contact lens body is lifted from the male mold part with a vacuum device, and the male mold part is discarded. In other methods, a wet lens demolding process can be used to demold the polymerized contact lens body by contacting the dry polymerized contact lens body with a liquid release medium (such as water or an aqueous solution). For example, the male mold part with the adhered polymerized contact lens body can be immersed in a receptacle containing a liquid until the polymerized contact lens body separates from the male mold part. Alternatively, a volume of liquid release medium can be added to the female mold to soak the polymerized contact lens body in the liquid and separate the lens body from the female mold part. In the following examples, a dry lens demolding process is used. After separation, the lens body can be lifted from the mold part manually using tweezers or using a vacuum device and placed in a tray.

[0219] In the following examples, after the dry demolding and dry lens demolding steps, the dry lens-shaped polymerized product is placed in the cavities of a tray, and then the lens-shaped polymerized product is washed to remove extractable materials from the polymerized contact lens body and hydrated.

[0220] The extraction and hydration liquid used in the extraction and hydration process consisted of denatured ethanol, a 50 / 50 mixture of denatured ethanol and deionized water, and deionized water. Specifically, in the following examples, the extraction and hydration process used comprised at least one extraction step sequentially performed in denatured ethanol and a 50:50 mixture of ethanol:water, followed by at least one extraction step performed in deionized water, and wherein each extraction and hydration step lasted from about 15 minutes to about 3 hours at a temperature between 20°C and 30°C.

[0221] The washed, extracted and hydrated lenses are then individually placed in contact lens blister packs with phosphate buffered saline packing solution. The blister packs are sealed and sterilized by autoclaving.

[0222] After sterilization, lens properties such as wet lens diameter, base curve, refractive index, water content, UV-vis spectrum, and the like are measured as described herein.

[0223] The diameter and sag height of each lens were measured using an Optimec in phosphate buffered saline, and the base curve radius was calculated.

[0224] The wet center thickness (CT) of the lens is measured using a Rehder CT measuring instrument. The contact lens is removed from the aqueous solution and any excess solution is removed by lightly touching the lint-free cloth. The lens is centered on the ball holder and the anvil is lowered until it contacts the lens surface. The CT reading is recorded.

[0225] For the lenses of the following examples, the refractive index (RI) was measured using a CLR-12-70 refractometer. The contact lens was removed from the aqueous solution and any excess solution was removed by shaking or gently touching with a dust-free cloth. The contact lens was then placed on the curved surface press and the cover was closed, the latch was engaged and the RI reading was taken after stabilization.

[0226] The UV-vis spectra of the lenses were measured using a Perkin Elmer Lambda 35 UV / Vis spectrophotometer based on the method described in part 3 of ISO 18369. The spectra were operated with the lenses in aqueous solutions in a flat trough unit with a V-shaped insert and holder. The trough opening allowed the lens to maintain its natural shape during the measurement, i.e., its optical path was greater than the sag of the lens, and its height and width were greater than the diameter of the lens. The trough holder had an opening that focused the incident light beam on the optical zone of the lens. The baseline was automatically zeroed using deionized water. The scan range was between 780nm and 270nm, with a data interval of 1nm and a slit width of 1nm. The visible light, blue light, UVA and UVB lens transmittance of each lens was calculated and for each example, the average results of 5-10 lenses were reported.

[0227] Visible light transmittance = average %T between 780nm and 380nm

[0228] Blue light transmittance = average %T between 415nm and 455nm

[0229] UVA = Average T% between 380nm and 315nm

[0230] UVB = Average %T between 315nm and 280nm

[0231] Example 1

[0232] The polymerizable composition of Standfikon A was used as the base formulation. Dyes were added to this base formulation according to the formulation in Table 1, and several batches of silicone hydrogel contact lenses were prepared and tested with these formulations according to the described manufacturing procedures and testing methods, using the dry demolding process, dry lens demolding process, and extraction and hydration, packaging and sterilization processes as described above.

[0233] RY86 is a yellow dye for blocking blue light and is the first colorant according to the present invention.

[0234] The red dye is the second colorant according to the present invention and corresponds to Dye 1 prepared in the above Synthesis Example.

[0235] The violet dye is the second colorant according to the present invention and corresponds to Dye 2 prepared in the above Synthesis Example.

[0236] The blue dye is RB246 and is the third colorant according to the present invention.

[0237] Examples RY86HEMA Red Dye Purple Dye Blue Dye A 350ppm B 350ppm 500ppm C 350ppm 300ppm D 350ppm 300ppm E 350ppm 100ppm F 350ppm 500ppm 290ppm G 350ppm 300ppm 290ppm H 350ppm 300ppm 290ppm I 350ppm 100ppm 290ppm J 350ppm 290ppm K 350ppm 100ppm 90ppm L 350ppm 200ppm

[0238] Table 2: Tintant Content in Example Lens Polymerizable Compositions

[0239] The light transmittance of the lenses was measured as described above and the results are provided in Table 3.

[0240]

[0241]

[0242] Table 3: Light transmittance results of example lenses

[0243] The center thickness, diameter, base curve radius, and refractive index of each example lens were measured, and the results are provided in Table 4.

[0244] A sample of 5 to 10 lenses was measured and the results averaged.

[0245] Examples Average CT(mm) Average diameter(mm) Average BCR(mm) Average RI A 0.109 14.47 8.91 1.398 B 0.095 14.37 8.89 1.399 C 0.106 14.40 8.90 1.398 D 0.094 14.39 8.92 1.399 E 0.098 14.43 8.93 1.399 F 0.094 14.28 8.80 1.401 G 0.088 14.33 8.85 1.398 H 0.095 14.28 8.80 1.399 I 0.094 14.11 8.66 1.401 J 0.093 14.40 8.87 1.399 K 0.097 14.40 8.85 1.398

[0246] Table 4: Center thickness, diameter, base curve radius and refractive index results of the example lenses

[0247] To measure the absorption maximum of each lens, contact lens formulations having the individual dye concentrations shown in Table 5 were prepared.

[0248] RY86-HEMA Red Dye Purple Dye Blue Dye CT(mm) λmax(nm) Max Abs 350 0 0 0 0.109 421 0.0580 0 500 0 0 0.144 541 0.0533 0 0 500 0 0.093 585 0.0560

[0249] Table 5: Absorption maxima (λ) of contact lenses containing a single dye max )

[0250] λ of red dye and violet dye in Table 5 maxThe values ​​differ slightly from those measured in methanol solution (Table 1), but it is believed that the difference is mainly due to the relatively broad shape of these peaks.

[0251] The tint of the example lenses was measured according to the following method.

[0252] The lens color was measured using a Sheen Micromatch 181 / 3 colorimeter. The colorimeter was calibrated using black and white calibration standards, and the calibration was checked using a green calibration disk. The following settings were used for measurement: the selected color system was CIELab, the index was set to ΔE*, the light source was set to D65, and the observer was set to 10°. The hydrogel contact lens to be measured was removed from the packaging solution, and gently wiped to remove surface moisture, and placed on a white plastic spherical bracket to ensure that there were no bubbles trapped under the lens. The bracket with the lens in place was then held against the hole of the colorimeter and measured. This procedure was repeated ten times and the average reading was calculated. A clear lens was used as a control, and the color measurement reading was standardized by specifying that the a* value of the clear lens on a white background was zero and the *b value was zero. Standard commercially available lenses with treatment dyes were also measured for comparison, and the lens types used were Biofinity, MyDay, Acuvue Oasys, B+LUltra, and Alcon Dailies Total 1. CIELab L*C*h* values ​​were calculated from the measured CIELab L*, a*, and b* values ​​using the standard conversion equations, L8=L*, C*=(a2+b2)1 / 2 and h°=arctan(b* / a*).

[0253] The lens color results for lens AL are provided in Table 6 and are plotted in the form of an L*a*b* diagram along with the values ​​for commercial lenses and lenses with different concentrations of red dye (Dye 1) or violet dye (Dye 2). Figure 1 middle.

[0254]

[0255] Table 6: L*a*b* and L*C*h* results for example contact lenses A to L

[0256] since Figure 1 As can be seen from Table 6, the example lens A containing only the yellow blue light blocking dye RY86 (colorant 1) is in Figure 1 The upper left area corresponds to the intense yellow coloration. Figure 1The two arrows shown in FIG. 1 and FIG. 2 show that lenses containing increasing amounts of red dye or violet dye (as the only colorant) generally tend to go in the opposite direction, i.e., further to the lower right region of the color space, indicating that the yellow color of the blue-blocking dye can be balanced by adding appropriate amounts of these red dyes and violet dyes. Lens L, which includes yellow dye RY86 (first colorant) and blue dye RB246 (second colorant), is also in the upper left quadrant, corresponding to intense green coloration. Lenses AJ are generally closer to the origin in the center of the diagram, indicating a relatively low color level. The commercially available lenses all have extremely low color levels and are close to the origin.

[0257] Visual evaluation of lenses AL showed that lenses D, E, F, G, and H were gray or blue and conformed to the present invention, while lenses A, B, C, I, J, K, and L were not gray or blue and did not conform to the present invention. Lenses D, E, F, and G were each gray in appearance, and their chroma (C*) values ​​were less than 5.0 and their hue (h*) values ​​were 166 degrees or less, or greater than or equal to 275 degrees. Lens H was blue, its hue (h*) value was greater than 166 degrees and less than 275 degrees, and its chroma (C*) value was less than 5.0.

[0258] Example:

[0259] Various embodiments of the present invention are described as follows:

[0260] Embodiment 1) A contact lens comprising a polymeric matrix formed by polymerization of a polymerizable composition comprising: one or more monomers; a first colorant having an absorption maximum (λ) in the range of 415 nm to 455 nm; max ) of a blue light blocking colorant; and a second colorant, wherein the second colorant is an absorption maximum (λ max ); and optionally further comprising a third colorant, which is a colorant having an absorption maximum in the range of greater than 600nm to 800nm, wherein the second colorant and the third colorant, if present, balance the color of the first colorant, thereby making the contact lens colorless, gray or blue.

[0261] Embodiment 2) The contact lens of embodiment 1, wherein the first colorant is also polymerizable and the polymeric matrix is ​​formed by polymerization of a polymerizable composition comprising one or more monomers, the first colorant and the second colorant.

[0262] Embodiment 3) The contact lens of embodiment 1 or embodiment 2, wherein the first colorant is non-polymerizable.

[0263] Embodiment 4) The contact lens of any preceding embodiment, wherein the second colorant is an anthraquinone dye.

[0264] Embodiment 5) The contact lens of any preceding embodiment, wherein the second colorant is a dye and contains a chromophore and at least one polymerizable group, wherein each polymerizable group is linked to the chromophore via a linker group.

[0265] Embodiment 6) A contact lens as in any of the preceding embodiments, wherein the second colorant is a dye of formula (1)

[0266] Ch-(LX m ) n (1)

[0267] wherein Ch is a chromophore, L is a linking group or a heteroatom, X is a polymerizable group, m is 1 to 3, and n is 1 to 3.

[0268] Embodiment 7) A contact lens as in embodiment 5 or 6, wherein m=1, and the linking group L is -N(H)-R 1 -、-SR 1 -OR 1 -, where R 1 is a divalent hydrocarbylene group which may be substituted or unsubstituted by one or more heteroatoms.

[0269] Embodiment 8) A contact lens as in any one of embodiments 5 to 7, wherein the linking group L comprises a C6 to C14 aryl group, a C1 to C20 alkyl group or a C7 to C20 aryl-alkyl group.

[0270] Embodiment 9) A contact lens as in any of the preceding embodiments, wherein the chromophore Ch is an anthraquinone chromophore, which preferably comprises 1 to 3 substituents selected from: -F, -Cl, -Br, -I, -OR 2 、-SR 2 , -R 2 , -NO2, -CN, -NCO, -NCS, -C(=O)R 2 、-C(=O)OR 2 、-NH2、-C(=O)NHR 2 、-C(=O)N(R 2 )2, where each R 2 are independently H or a C1 to C20 hydrocarbon group.

[0271] Embodiment 10) A contact lens as in any of the preceding embodiments, wherein the second colorant is a dye of formula (2)

[0272]

[0273] wherein a and b may each be 0 to 3, provided that 0≤(a+b)≤3; each A is independently selected from -F, -Cl, -Br, -I, -OR 2 、-SR2 , -R 2 , -NO2, -CN, -NCO, -NCS, -C(=O)R 2 、-C(=O)OR 2 、-NR 2 2. -C(=O)NHR 2 、-C(=O)N(R 2 )2, where each R 2 are independently H or a C1 to C20 hydrocarbon group; c and d may each be 0 to 3, provided that 1≤(c+d)≤3; L is a divalent linking group; and X is a polymerizable group.

[0274] Embodiment 11) A contact lens as in any of the preceding embodiments, wherein the second colorant is a dye of formula (3) or formula (4):

[0275]

[0276] Embodiment 12) A contact lens as in any of the preceding embodiments, wherein the absorption maximum (λ max ) is in the range of 500nm to 600nm.

[0277] Embodiment 13) A contact lens as in any preceding embodiment, wherein the first colorant is present in an amount of about 20 ppm to about 1000 ppm by dry weight, and / or the second colorant is present in an amount of about 20 ppm to about 1000 ppm by dry weight.

[0278] Embodiment 14) The contact lens of any preceding embodiment, wherein the third colorant is present in an amount of about 20 ppm to about 300 ppm by dry weight.

[0279] Embodiment 15) The contact lens of any preceding embodiment, wherein the polymerizable composition comprises a total amount of siloxane monomers in an amount of about 20 wt% to about 60 wt%, based on the total weight of all polymerizable ingredients in the polymerizable composition.

[0280] Embodiment 16) A contact lens as in any preceding embodiment, wherein the polymerizable composition comprises a total amount of vinyl-containing hydrophilic monomers in an amount of about 20 wt% to about 60 wt%, based on the total weight of all polymerizable ingredients in the polymerizable composition.

[0281] Example 17) A contact lens as in Example 16, wherein the vinyl-containing hydrophilic monomer is N-vinyl-N-methylacetamide (VMA), or N-vinyl pyrrolidone (NVP), or a combination of VMA and NVP.

[0282] Embodiment 18) The contact lens of any preceding embodiment, wherein the polymerizable composition comprises an acrylate-containing hydrophilic monomer in an amount of up to about 20 wt. %, based on the total weight of all polymerizable ingredients in the polymerizable composition.

[0283] Embodiment 19) A contact lens as in any preceding embodiment, which is a hydrogel contact lens.

[0284] Embodiment 20) A contact lens as in any preceding embodiment, which is a silicone hydrogel contact lens.

[0285] Embodiment 21) The contact lens of any preceding embodiment, further comprising 0.5 wt% to 2.0 wt% of a UV absorbing compound on a dry weight basis.

[0286] Embodiment 22) The contact lens of any preceding embodiment, wherein the first colorant, the second colorant, and the third colorant if present, are dyes soluble in the polymerizable composition.

[0287] Embodiment 23) A contact lens as in any preceding embodiment, wherein the first colorant, the second colorant, and the third colorant if present, are autoclave stable such that the colorants do not change color or color intensity when the contact lens is autoclaved.

[0288] Embodiment 24) A contact lens as in any preceding embodiment, which does not substantially change color during autoclaving.

[0289] Embodiment 25) A contact lens as in any preceding embodiment, having a visible light transmittance of at least 80% as measured according to section 4.8 of BS EN ISO 18369-3-2017.

[0290] Embodiment 26) A contact lens comprising: a polymer matrix; a first colorant having an absorption maximum (λ max ) of a blue light blocking colorant; and a second colorant, wherein the second colorant is any one of Examples 5 to 11 having an absorption maximum (λ) in the range of 470 nm to 600 nm max ) of polymerizable anthraquinone dyes.

[0291] Embodiment 27) A method of making a contact lens comprising the steps of polymerizing a polymerizable composition in a mold to form a lens-shaped polymerized product comprising a polymer matrix, the polymerizable composition comprising: one or more monomers; a first colorant having an absorption maximum (λ) in the range of 415 nm to 455 nm; max ) of a blue light blocking colorant; and a second colorant, wherein the second colorant is an absorption maximum (λmax ); and optionally further comprising a third colorant, which is a colorant having an absorption maximum in the range of greater than 600nm to 800nm, wherein the second colorant and the third colorant, if present, balance the color of the first colorant, thereby making the contact lens colorless, gray or blue.

[0292] Embodiment 28) The method of embodiment 27 further comprises the step of hydrating the lens-shaped polymerization product to form a hydrogel contact lens.

[0293] Embodiment 29) A method as in Embodiment 28, wherein the hydrogel contact lens has a visible light transmittance of at least 80% as measured according to section 4.8 of BS EN ISO 18369-3-2017.

[0294] Embodiment 30) The method of any one of embodiments 27 to 29, further comprising the steps of immersing the polymerized product or hydrogel contact lens in a package containing a packaging solution, sealing the package, and optionally sterilizing the sealed package.

[0295] Embodiment 31) A method as in any one of Embodiments 27 to 30, wherein the polymerizable composition comprises 20 ppm to 1000 ppm of a first colorant, based on the total weight of all polymerizable ingredients in the polymerizable composition, and / or 20 ppm to 1000 ppm of a second colorant, based on the total weight of all polymerizable ingredients in the polymerizable composition.

[0296] Embodiment 32) The method of any one of embodiments 27 to 31, wherein the first colorant is also polymerizable.

[0297] Embodiment 33) The method of any one of embodiments 27 to 32, wherein the polymerizable composition further comprises 0.5 wt% to 2.0 wt% of a UV absorbing compound, based on the total weight of all polymerizable ingredients in the polymerizable composition.

[0298] Example 34) A method as in any one of Examples 27 to 33, which is a method for manufacturing a contact lens as in any one of Examples 1 to 26.

[0299] Embodiment 35) A packaged contact lens comprises a sealed package, wherein the sealed package contains a packaging solution and a contact lens as in any one of embodiments 1 to 26 or a contact lens made by the method as in any one of embodiments 27 to 33.

[0300] The present invention has been described above with reference to many optional features and specific embodiments. Many variations will be apparent to those skilled in the art from the above description. All such obvious variations are within the full intended scope of the claims.

Claims

1. A hydrogel contact lens comprising a polymeric matrix formed by polymerization of a polymerizable composition comprising: one or more monomers; a first colorant having an absorption maximum λ in the range of 415 nm to 455 nm; max A blue light blocking colorant; and a second colorant, wherein the second colorant has an absorption maximum λ in the range of 470nm to 600nm max A polymerizable dye; wherein the second colorant balances the color of the first colorant, thereby making the hydrogel contact lens colorless, gray or blue, wherein the second colorant is a dye of formula (2): wherein a and b may each be 0 to 3, provided that 0≤(a+b)≤3; and each A is independently selected from -F, -Cl, - Br、-I、-OR 2 、-SR 2 、-R 2 、-NO2、-CN、-NCO、-NCS、-C(=O)R 2 、-C(=O)OR 2 、-NR 2 2、 -C(=O)NHR 2 、-C(=O)N(R 2 )2, where each R 2 are independently H or a C1 to C20 hydrocarbon group; c and d may each be 0 to 3, provided that 1≤(c+d)≤3; L is a divalent linking group; and X is a polymerizable group.

2. The hydrogel contact lens according to claim 1, wherein the second colorant is a dye of formula (3) or formula (4):

3. The hydrogel contact lens according to claim 1 or 2, wherein the absorption maximum λ of the second coloring agent is max In the range of 500nm to 600nm.

4. The hydrogel contact lens of claim 1 or 2, wherein the first colorant is present in an amount of 20 ppm to 1000 ppm by dry weight, and / or the second colorant is present in an amount of 20 ppm to 1000 ppm by dry weight.

5. The hydrogel contact lens of claim 1 or 2, wherein the hydrogel contact lens further comprises a third colorant having an absorption maximum λ in the range of from greater than 600 nm to less than or equal to 800 nm. max of colorant.

6. The hydrogel contact lens of claim 5, wherein the third colorant is present in an amount of 20 ppm to 300 ppm on a dry weight basis.

7. The hydrogel contact lens of claim 1 or 2, wherein the polymerizable composition comprises a total amount of siloxane monomers in an amount of 20 wt% to 60 wt%, based on the total weight of all polymerizable ingredients in the polymerizable composition.

8. The hydrogel contact lens of claim 1 or 2, wherein the polymerizable composition comprises a total amount of vinyl-containing hydrophilic monomers in an amount of 20 wt% to 60 wt%, based on the total weight of all polymerizable ingredients in the polymerizable composition.

9. The hydrogel contact lens of claim 1 or 2, wherein the first colorant and the second colorant are autoclave stable such that the first colorant and the second colorant do not change color or color intensity when the hydrogel contact lens is autoclaved.

10. The hydrogel contact lens of claim 5, wherein the third colorant is autoclave stable such that the third colorant does not change color or color intensity when the hydrogel contact lens is autoclaved.

11. A method of making a hydrogel contact lens comprising the steps of polymerizing a polymerizable composition in a mold to form a lens-shaped polymerized product comprising a polymer matrix, the polymerizable composition comprising: one or more monomers; a first colorant having an absorption maximum λ in the range of 415 nm to 455 nm; max A blue light blocking colorant; and a second colorant, wherein the second colorant has an absorption maximum λ in the range of 470nm to 600nm max A polymerizable dye; wherein the second colorant balances the color of the first colorant, thereby making the hydrogel contact lens colorless, gray or blue, wherein the second colorant is a dye of formula (2): wherein a and b may each be 0 to 3, provided that 0≤(a+b)≤3; and each A is independently selected from -F, -Cl, - Br、-I、-OR 2 、-SR 2 、-R 2 、-NO2、-CN、-NCO、-NCS、-C(=O)R 2 、-C(=O)OR 2 、-NR 2 2、 -C(=O)NHR 2 、-C(=O)N(R 2 )2, where each R 2 are independently H or a C1 to C20 hydrocarbon group; c and d may each be 0 to 3, provided that 1≤(c+d)≤3; L is a divalent linking group; and X is a polymerizable group.

12. The method of claim 11, wherein the hydrogel contact lens further comprises a third colorant having an absorption maximum λ in the range of from greater than 600 nm to less than or equal to 800 nm. max of colorant.

13. The method of claim 11 or claim 12, further comprising the step of hydrating the lens-shaped polymerization product to form a hydrogel contact lens.

14. The method according to claim 13, further comprising the steps of: The polymerized product or the hydrogel contact lens is immersed in a package containing a packaging solution, and the package is sealed.

15. The method of claim 14, further comprising the step of sterilizing the sealed package.

16. A packaged hydrogel contact lens comprising a sealed package containing a packaging solution and a hydrogel contact lens according to any one of claims 1 to 10 or a hydrogel contact lens made by the method according to any one of claims 11 to 15.

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