Visible light absorbers for ophthalmic devices

Abstract

A visible light-absorbing azo compound having the structure of Formula (I), wherein X1, X2, X3, Y, and Z are as defined herein, and ophthalmic devices formed therefrom. (I)

Description

[0001] Priority requirements

[0002] This application claims priority to U.S. Provisional Patent Application Serial No. 63 / 546,988, filed November 2, 2023, entitled “Visible Light Absorbers for Ophthalmic Devices,” the contents of which are incorporated herein by reference in their entirety. Background Technology

[0003] Ultraviolet (UV) light absorbers are known components of polymeric materials used in the manufacture of ophthalmic lenses, particularly intraocular lenses. UV light absorbers are preferably polymerizable so as to covalently bind to the polymeric network of the lens material, rather than simply being physically embedded in the material, thereby preventing their migration, phase separation, or leaching from the lens material. This stability is particularly important for implantable ophthalmic lenses, where leaching of UV light absorbers can pose both toxicological problems and lead to the loss of UV-blocking activity in the implant. Short-wavelength visible light (violet and blue light) has been shown to be damaging to cells both in vitro and in vivo. Summary of the Invention

[0004] According to one illustrative embodiment, an azo compound that absorbs visible light has the structure of formula I:

[0005] (I)

[0006] X1, X2, and X3 are independently hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a vinyl group, or an allyl group; Y is hydrogen, a substituted or unsubstituted alkyl group, or a vinyl group or an allyl group; and Z is hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a vinyl group, or an allyl group, wherein at least one of X1, X2, X3, Y, and Z is a vinyl group or an allyl group.

[0007] According to another illustrative embodiment, an ophthalmic device is a polymer product of a monomer mixture comprising:

[0008] (a) Azo compounds having the structure of Formula I that absorb visible light:

[0009] (I)

[0010] Where X1, X2, X3, Y, and Z are as defined in this paper, and

[0011] (b) One or more monomers that form ophthalmic devices.

[0012] According to yet another illustrative embodiment, a method for manufacturing an ophthalmic device includes:

[0013] (a) Providing a monomer mixture comprising (i) an azo compound having the structure of Formula I that absorbs visible light:

[0014] (I)

[0015] Wherein X1, X2, X3, Y, and Z are as defined herein, and (ii) one or more monomers forming an ophthalmic device, and

[0016] (b) subjecting a mixture of monomers to polymerization conditions to provide an ophthalmic device. Attached Figure Description

[0017] The features, advantages, and other aspects of the embodiments of this disclosure will become more apparent from the accompanying drawings and the following detailed description, and several embodiments of this disclosure are illustrated herein by way of example rather than limitation. In the drawings:

[0018] Figure 1 The UV / Vis transmission spectra of the intraocular lenses used in Examples 6A and 6B are shown.

[0019] Figure 2 The UV / Vis transmission spectra of the intraocular lenses used in Examples 6A and 6C are shown.

[0020] Figure 3 The UV / Vis transmission spectra of the intraocular lenses used in Examples 6A and 6D are shown.

[0021] Figure 4 The UV / Vis transmission spectra of the intraocular lenses used in Examples 6A and 7A-7D are shown. Detailed Implementation

[0022] The various illustrative embodiments described herein relate to visible light absorbers and ophthalmic devices containing visible light absorbers, such as eye implants, contact lenses, and intraocular lenses.

[0023] definition

[0024] To more clearly define the terms used herein, the following definitions are provided. Unless otherwise stated, the following definitions apply to this disclosure. If a term is used in this disclosure but is not specifically defined herein, the definition in the IUPAC Compendium of Chemical Terminology may apply, provided that the definition does not conflict with any other disclosure or definition applied herein or any claim to which the definition applies is ambiguous or unenabled. If any definition or usage provided by any document incorporated herein by reference conflicts with the definition or usage provided herein, the definition or usage provided herein shall prevail.

[0025] Unless otherwise stated, although compositions and processes are described in accordance with the principle of “comprising” various components or steps, compositions and processes may also be “substantially composed of various components or steps” or “composed of various components or steps”.

[0026] The terms “a / an” and “the” are intended to include plural alternatives, such as at least one. Unless otherwise specified, the terms “including,” “with,” and “having” as used herein are defined as encompassing (i.e., open language).

[0027] This document discloses various numerical ranges. Unless otherwise stated, when an applicant discloses or claims protection for any type of range, the applicant's intent is to individually disclose or claim protection for every possible number that such range can reasonably cover, including the endpoints of the range and any subranges and combinations thereof covered therein. For example, unless otherwise specified, all numerical endpoints of the ranges disclosed herein are approximate values.

[0028] In this document, a value or range may be expressed as “about”, from “about” a specific value and / or to “about” another specific value. When such a value or range is expressed, other disclosed embodiments include the listed specific value, from one specific value and / or to another specific value. Similarly, when a value is expressed as an approximation using the antecedent “about”, it should be understood that the specific value forms another embodiment. It will be further understood that multiple values ​​are disclosed, and each value is also disclosed herein as “about” that specific value in addition to the value itself. On the other hand, the use of the term “about” means ±20% of the value, ±15% of the value, ±10% of the value, ±5% of the value, ±3% of the value, or ±1% of the value.

[0029] The terms "weight%", "volume%", or "molar%" refer to the percentage by weight, volume, or mole of a component based on the total weight, volume, or number of moles of the material containing the component, respectively. In a non-limiting example, if 100 moles of material contain 10 moles of a component, then that component is 10 moles.

[0030] The term "substituted" means that the hydrogen atoms in the parent moiety are optionally substituted by a substituent. Any substituent can be used where steric hindrance at the substitution site is feasible and synthetically possible. The identification of suitable optional substituents is entirely within the capabilities of a person skilled in the art.

[0031] If the applicant chooses to claim a measure smaller than the full scope of this disclosure for any reason, such as taking into account references that the applicant may not have been aware of at the time of filing this application, the applicant reserves the right to exclude or not include any individual member (including any sub-scopes or combinations of sub-scopes) of any stated value or range group that can be claimed under scope or in any similar manner. Furthermore, the applicant reserves the right to exclude or not include any member of the claimed group.

[0032] As mentioned above, short-wavelength visible light (violet and blue light) has been shown to be damaging to cells both in vitro and in vivo. Polymerizable benzotriazole, benzophenone, and triazine absorbers are known. Most of these compounds are referred to as UV absorbers, although some are known to also absorb some visible light. Many absorbers contain olefinically unsaturated groups, such as methacrylate, acrylate, methacrylamide, acrylamide, or styrene groups. Copolymerization with other components in the lens material incorporates the absorber into the resulting polymer chain.

[0033] Benzotriazole vinyl monomers are generally light-stable and can absorb large amounts of visible and UV light, but their manufacture can be difficult and costly. Furthermore, they may be insoluble in lens formulations. If the absorber does not have sufficient solubility in the lens formulation, it may aggregate into micro-regions that can interact with light, leading to reduced optical transparency of the lens. Therefore, there is a need for a visible-light-absorbing vinyl monomer that absorbs light wavelengths between approximately 380 and approximately 500 nanometers (nm), exhibits good solubility in lens articles, is light-stable, and can be manufactured in a cost-effective manner.

[0034] The visible light absorber described herein overcomes the aforementioned problems and advantageously provides an ophthalmic device that exhibits sufficient blocking of visible light at wavelengths between about 380 and about 500 nm. In a non-limiting illustrative embodiment, the visible light absorber is represented by an azo compound having the structure of Formula I:

[0035] (I)

[0036] X1, X2, and X3 are independently hydrogen, a substituted or unsubstituted straight-chain or branched alkyl group, a substituted or unsubstituted alkoxy group, a vinyl group, or an allyl group; Y is hydrogen, a substituted or unsubstituted straight-chain or branched alkyl group, or a vinyl group or an allyl group; and Z is hydrogen, a substituted or unsubstituted straight-chain or branched alkyl group, a substituted or unsubstituted alkoxy group, a vinyl group, or an allyl group, wherein at least one of X1, X2, X3, Y, and Z is a vinyl group or an allyl group.

[0037] Representative examples of substituted or unsubstituted alkyl groups used for the purposes of this document include, by way of example, unsaturated or saturated straight-chain or branched hydrocarbon chain radicals containing carbon and hydrogen atoms having 1 to 18 carbon atoms or 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, 1-methylethyl (isopropyl), n-butyl, n-pentyl, etc.

[0038] Representative examples of substituted or unsubstituted alkoxy groups used for the purposes of this document include, by way of example, alkyl groups attached to the remainder of the molecule via an oxygen bond as defined herein (i.e., having the general formula -OR). 4 ), where R 4 It is an alkyl, cycloalkyl, or aromatic group as defined herein, such as -OCH3, -OC2H5, or -OC6H5, which may be substituted or unsubstituted, etc.

[0039] Representative examples of cycloalkyl groups used for purposes herein include, by way of example, substituted or unsubstituted non-aromatic monocyclic or polycyclic systems having about 3 to about 30 carbon atoms, or 3 to about 12 carbon atoms, or 3 to about 6 carbon atoms, such as, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, perhydronaphthyl, adamantyl and norbornel groups, bridging cyclic groups, or spirobicyclic groups, such as spiro-(4,4)-non-2-yl, etc., optionally containing one or more heteroatoms, such as O and N, to form a heterocyclic alkyl group.

[0040] In a non-limiting illustrative embodiment, X1 and X2 are hydrogen, X3 is a vinyl group, Y is a C1 to C6 alkyl group, and Z is hydrogen.

[0041] In a non-limiting illustrative embodiment, X1 and X2 are hydrogen, X3 is a C1 to C6 alkyl group, Y is a C1 to C6 alkyl group, and Z is an allyl group.

[0042] In a non-limiting illustrative embodiment, each of X1, X2, and X3 is independently a C1 to C6 alkyl group, Y is a vinyl group, and Z is a substituted or unsubstituted alkoxy group.

[0043] In a non-limiting illustrative embodiment, X1 and X2 are hydrogen, X3 is a C1 to C6 alkyl group, Y is a vinyl group or an allyl group, and Z is a C1 to C6 alkoxy group.

[0044] In a non-limiting illustrative embodiment, each of X1, X2, and X3 is independently a C1 to C6 alkyl group, Y is a vinyl group or an allyl group, and Z is hydrogen.

[0045] In a non-limiting illustrative embodiment, one of X1, X2, and X3 is a vinyl group or an allyl group, and the remaining one of X1, X2, and X3 is hydrogen, Y is a vinyl group or an allyl group, and Z is hydrogen, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkoxy group.

[0046] In some embodiments, a suitable vinyl group can be represented by the following general formula:

[0047]

[0048] Where R 1 Independently hydrogen or an alkyl radical having 1 to 6 carbon atoms, and R 2 It is a hydrogen radical or an alkyl radical having 1 to 6 carbon atoms. In some embodiments, a suitable vinyl group is represented by the formula: H₂C═CH-.

[0049] In some embodiments, a suitable allyl group can be represented by the following general formula:

[0050]

[0051] Where R 1 Independently hydrogen or an alkyl radical having 1 to 6 carbon atoms, and R 2 It is a hydrogen radical or an alkyl radical having 1 to 6 carbon atoms. In some embodiments, a suitable vinyl group is represented by the formula: H₂C═CHCH₂-.

[0052] Representative examples of azo compounds having the structure of Formula I include the following:

[0053] ,

[0054] ,

[0055] ,

[0056] ,

[0057] ,

[0058]

[0059] (E)-2-trimethyldiazenyl)-6-methoxy-4-vinylphenol.

[0060]

[0061] (E)-2-methoxy-4-vinyl-6-((4-vinylphenyl)diazepine)phenol.

[0062] Azo compounds having the structure of Formula I that absorb visible light can be prepared using methods known in the art, as illustrated in the examples. For instance, as described in Scheme I below, a reactive diazonium salt of a substituted aniline derivative can be prepared in step 1, and then in step 2, the reactive diazonium salt of the substituted aniline derivative can be azo coupled with a phenolic compound to form an azo compound having the structure of Formula I that absorbs visible light.

[0063] Option I

[0064]

[0065] This method is illustrative only, and other methods for preparing visible-light-absorbing azo compounds having the structure of Formula I are considered herein. For example, as those skilled in the art will understand, other azo compounds having the structure of Formula I can be prepared using similar reaction sequences and corresponding starting materials. Typically, azo compounds having the structure of Formula I can be prepared by azo coupling of aniline (optionally substituted) with a variety of phenolic compounds.

[0066] In a non-limiting illustrative embodiment, as can be combined with one or more of the preceding paragraphs, the visible light absorber described herein can be incorporated into a variety of materials in applications where it is desirable to block visible light (such as blue light, i.e., light with wavelengths between about 380 and about 500 nm). In a non-limiting illustrative embodiment, one application includes incorporating a visible light absorber as described herein into an ophthalmic device.

[0067] The ophthalmic devices described herein are intended for direct contact with body tissues or fluids. As used herein, the term "ophthalmic device" refers to a device that resides within or on the eye. These devices may provide optical correction, wound care, drug delivery, diagnostic functionality, or cosmetic enhancement or effects, or a combination of these properties. Suitable ophthalmic devices include, for example, ophthalmic lenses, such as soft contact lenses (e.g., soft hydrogel lenses, soft non-hydrogel lenses), rigid contact lenses (e.g., rigid gas-permeable lens materials), intraocular lenses, overlapping lenses, ocular inserts, optical inserts, eyeglasses, sunglasses, etc. As will be understood by those skilled in the art, a lens is considered "soft" if it can fold back on itself without breaking.

[0068] In an illustrative embodiment, the ophthalmic device includes a lens, inlay, external body, or insert selected from intraocular implants or intraocular lenses, contact lenses, corneal inlays, corneal external bodies, and corneal inserts.

[0069] In some illustrative embodiments, the ophthalmic device is an intraocular implant or an intraocular lens. Specifically, the ophthalmic devices described herein include intraocular implants and / or intraocular lenses made at least partially or entirely of the polymeric monomer mixtures described herein. Such intraocular implants or intraocular lenses may include an optical portion and one or more tactile portions. For example, the polymeric monomer mixtures described herein may constitute part or all of the optical portion of the intraocular implant or intraocular lens. In some embodiments, the optical portion of the implant or lens will have a core made of one of the polymeric monomer mixtures described herein, which is surrounded by a different polymer or material. Implants or lenses in which the optical portion is at least partially made of one of the polymeric monomer mixtures described herein will generally also have a tactile portion. The tactile portion may also be made of the polymeric monomer mixtures described herein, or may be made of a different material, such as another polymer.

[0070] In some embodiments, the intraocular implant or intraocular lens is an integral lens having a soft, foldable central optical zone and a peripheral zone (tactile zone), both zones being made of the same polymer. In other embodiments, the optical zone and tactile zone may be formed of different types of polymers or materials, if desired. Some implants or lenses may also have tactile portions made of different materials, for example, one or more tactile portions may be made of the same material as the optical portion, and other tactile portions may be made of materials other than the polymeric monomer mixtures described herein. Multicomponent implants or lenses can be manufactured by embedding one material within another while performing an extrusion process to solidify a rigid material around a soft material, or by forming an interpenetrating network of rigid components as a pre-formed hydrophobic core. Where one or more tactile portions are made of a material different from the optical portion of the lens, the tactile portions can be attached to the optical portion in any manner known in the art, such as by drilling one or more holes in the optical portion and inserting the tactile portion.

[0071] The polymeric monomer mixtures described herein have been designed to be foldable so that an intraocular lens can be inserted into an individual's eye through a small incision. In the illustrative embodiments, the incision will be less than 2.5 mm. In other illustrative embodiments, the incision will be less than 2 mm. The tactile portion of the lens provides the necessary support for the implant or lens in the eye after insertion and unfolding, and helps stabilize the position of the lens after insertion and closure of the incision. The shape of the tactile portion design is not particularly limited and can be any desired configuration, such as a plate-like or gradient-thickness spiral wire, also known as a C-ring design.

[0072] Before hydration, the diameter of the optic portion of an intraocular lens can be approximately 2 to 6 mm. A diameter of approximately 2 to 6 mm is fairly standard in the art and is generally chosen to cover the pupil in its fully dilated state under natural conditions. However, this size is not limited to any particular diameter or size of the intraocular lens, and other sizes can be considered. Furthermore, the optic portion of the lens does not have to be circular; it can also be elliptical, square, or any other shape, as desired.

[0073] The intraocular lens may further include one or more non-optical tactile components extending from the outermost peripheral surface of the optical portion. The tactile components can be of any desired shape, such as a gradient spiral filament or a flat section, and serve to support the lens within the posterior chamber of the eye. Lenses can be manufactured with any desired design configuration. If the intraocular lens includes components other than the optical and tactile portions, such other portions may be made of polymers (as in the tactile and optical portions) or, if desired, of another material.

[0074] Intraocular lenses (IOLs) can be inserted into the eye in any manner known in the art. For example, in one embodiment, the IOL can be folded before insertion into the eye using an IOL inserter or by small, thin forceps typically used by ophthalmologists. Once the implant or lens reaches the target location, it is released to unfold. As is well known in the art, the lens to be replaced is typically removed before the IOL is inserted. The IOLs described herein can be made of soft polymer materials that are generally physiologically inert and capable of providing a clear, transparent refractive lens body even after folding and unfolding. In some embodiments, foldable IOLs can be inserted into any eye by injection, whereby the mechanically compliant material is folded and forced through a cannula, such as a cannula with an inner diameter of 1 mm to 3 mm.

[0075] In a non-limiting illustrative embodiment, as may be combined with one or more of the preceding paragraphs, the ophthalmic device may be obtained from a polymer of a monomer mixture comprising (a) one or more visible light absorbers comprising an azo compound having the structure of Formula I, and (b) one or more monomers forming the ophthalmic device.

[0076] In some embodiments, the one or more visible light absorbers comprising an azo compound having the structure of Formula I may be present in the monomer mixture in an amount of about 0.005 wt% to about 0.5 wt%, based on the total weight of the monomer mixture. In some embodiments, the one or more visible light absorbers comprising an azo compound having the structure of Formula I may be present in the monomer mixture in an amount of about 0.005 wt% to about 0.2 wt%, based on the total weight of the monomer mixture. In some embodiments, the one or more visible light absorbers comprising an azo compound having the structure of Formula I may be present in the monomer mixture in an amount of about 0.005 wt% to about 0.1 wt%, based on the total weight of the monomer mixture. In some embodiments, the one or more visible light absorbers comprising an azo compound having the structure of Formula I may be present in the monomer mixture in an amount of about 0.01 wt% to about 0.04 wt%, based on the total weight of the monomer mixture.

[0077] In some embodiments, the one or more monomers forming an ophthalmic device may be present in the monomer mixture in an amount ranging from about 50% to about 98% by weight, based on the total weight of the monomer mixture. In some embodiments, the one or more monomers forming an ophthalmic device may be present in the monomer mixture in an amount ranging from about 90% to about 96% by weight, based on the total weight of the monomer mixture.

[0078] In a non-limiting illustrative embodiment, as can be combined with one or more of the preceding paragraphs, the monomers used in the monomer mixture for forming an ophthalmic device may be one or more hydrophilic monomers. Suitable hydrophilic monomers include, for example, unsaturated carboxylic acids, acrylamides, vinyl lactams, hydroxyl-containing (meth)acrylates, hydrophilic ethylene carbonates, hydrophilic urethanes, hydrophilic oxazolones, and poly(olefin glycol) functionalized with polymerizable groups, as well as mixtures thereof. Representative examples of unsaturated carboxylic acids include methacrylic acid, acrylic acid, and mixtures thereof. Representative examples of amides include alkylamides, such as N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, and mixtures thereof. Representative examples of cyclic lactams include N-vinyl-2-pyrrolidone, N-vinylcaprolactam, N-vinyl-2-piperidinone, and mixtures thereof. Representative examples of hydroxyl-containing (meth)acrylates include 2-hydroxyethyl methacrylate (HEMA), glyceryl methacrylate, and mixtures thereof. Further examples include the hydrophilic ethylene carbonate or urethane monomers disclosed in U.S. Patent No. 5,070,215 and the hydrophilic oxazolone monomers disclosed in U.S. Patent No. 4,910,277. Other suitable hydrophilic monomers will be apparent to those skilled in the art. Mixtures of the aforementioned hydrophilic monomers may also be used in the monomer mixtures described herein.

[0079] In one illustrative embodiment, the hydrophilic monomer is one or more of acrylamide and hydroxyl-containing (meth)acrylate as defined above.

[0080] In a non-limiting illustrative embodiment, the hydrophilic monomer used herein may be a high glass transition temperature (Tg) hydrophilic monomer or homopolymer. "High glass transition temperature hydrophilic monomer or homopolymer" is a hydrophilic monomer or homopolymer that, when incorporated into a polymer with one or more other monomers and a crosslinking agent, increases the glass transition temperature of the resulting polymer compared to a polymer formed without a high glass transition temperature hydrophilic monomer or homopolymer. In an illustrative embodiment, the hydrophilic monomer and / or its corresponding homopolymer may have a Tg value greater than 50°C, for example, a Tg value between about 60 and about 100°C. For example, a hydrophilic monomer (such as HEMA) has no Tg value; however, when it polymerizes into a corresponding homopolymer (polyHEMA), the corresponding homopolymer may have a Tg value of about 60°C. Increasing the Tg value brings the additional benefit of reduced surface tack, which is beneficial for manufacturing IOLs with minimal particle size and other appearance defects.

[0081] In some embodiments, the hydrophilic monomer may be present in the monomer mixture in an amount ranging from about 15% to about 40% by weight, based on the total weight of the monomer mixture. In some embodiments, the hydrophilic monomer may be present in the monomer mixture in an amount ranging from about 25% to about 35% by weight, based on the total weight of the monomer mixture.

[0082] In non-limiting illustrative embodiments, as can be combined with one or more of the preceding paragraphs, the one or more monomers used in the monomer mixture to form an ophthalmic device can be one or more polyethylene glycol (meth)acrylate monomers. In some embodiments, the one or more polyethylene glycol (meth)acrylate monomers can be represented by the structure of Formula II:

[0083] (II)

[0084] in:

[0085] R 1 Z is a hydrogen atom or a methyl radical; Z is a divalent group selected from the following groups: —COO—, —CONH—, —CONCH3—, —OCO—, —O—, —SO2—, —CO—O—CO— and —CO—CH2—CO—; x is 0 or 1; R 2 It is a straight-chain, branched, cyclic, or aromatic, saturated or unsaturated divalent carbon radical with 1 to 30 carbon atoms; m is 0 or 1; n is an integer between 3 and 300, including the end values; and R 3 A carbon-based free radical consisting of a hydrogen atom or 1 to 30 carbon atoms, either straight-chain, branched, cyclic, aromatic, saturated, or unsaturated.

[0086] In some implementation schemes, R 2 It can be an alkylene radical containing 1 to 20 carbon atoms, such as methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, tert-butylene, pentylene, isopentylene, n-hexylene, isohexylene, heptylene, isohexylene, n-octylene, isooctylene, nonylene, isononylene, decylene, isodecanylene, n-dodecylene, isododecylene, tridecylene, n-tetradecylene, hexadecylene, n-octadecylene, dodecylene, or arachidylene; a substituted or unsubstituted cycloalkylene radical containing 5 to 10 carbon atoms, such as cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene, cyclononylene, or cyclodecylene; or a phenylene radical —C6H4— (ortho, meta, or para), which optionally contains 1 to 18 heteroatoms selected from O, N, S, F, Si, and P. 12Alkyl radical substitution; benzylidene radical —C6H4—CH2—; radicals of the following formulas: —CH2—O—CO—O—, CH2—CH2—O—CO—O—, —CH2—CO—O—, —CH2—CH2—CO—O—, —CH2—O—CO—NH—, —CH2—CH2—O—CO—NH—; —CH2—NH—CO—NH—, —CH2—CH2—NH—CO—NH—; —CH2—CHOH—, —CH2—CH2—CHO H—、—CH2—CH2—CH(NH2)—、—CH2—CH(NH2)—、—CH2—CH2—CH(NHR')—、—CH2—CH(NHR')—、—CH2—CH2—CH(NR'R'')—、—CH2—CH(NR'R'')—、—CH2—CH2—CH2—NR'—、—CH2—CH2—CH2—O—;—CH2—CH2—CHR'—O—, where R' and R'' represent straight-chain or branched C1-C 22 Alkyl groups; or mixtures of these free radicals.

[0087] In some implementations, n is between 5 and 200, inclusive; or between 6 and 120, inclusive; or between 7 and 50, inclusive.

[0088] In some implementation schemes, R 3 It is a hydrogen atom; optionally bonded by C1-C 12 Alkyl radical-substituted phenyl radical; C1-C 30 Or C1-C 22 Or C2-C 16 Alkyl radicals; or C3-C 12 Or C4-C8 or C5-C6 cycloalkyl radicals. In some embodiments, R 3 It can be methyl, ethyl, propyl, benzyl, ethylhexyl, lauryl, stearyl, and behenyl (—(CH2)). 21 —CH3) chain.

[0089] In some embodiments, suitable polyethylene glycol (meth)acrylate monomers are poly(ethylene glycol) phenyl ether acrylates with an average molecular weight of 236, 280 or 324, purchased from Aldrich.

[0090] In some embodiments, polyethylene glycol (meth)acrylate may be present in the monomer mixture in an amount ranging from about 35% to about 60% by weight, based on the total weight of the monomer mixture. In some embodiments, polyethylene glycol (meth)acrylate may be present in the monomer mixture in an amount ranging from about 40% to about 50% by weight, based on the total weight of the monomer mixture.

[0091] In a non-limiting illustrative embodiment, as can be combined with one or more of the preceding paragraphs, the monomers used in the monomer mixture for forming ophthalmic devices can be one or more heterocyclic monomers having olefinically unsaturated reactive end groups. olefinically unsaturated reactive end groups are well known to those skilled in the art. Suitable olefinically unsaturated polymerizable groups include, for example, (meth)acrylates, vinyl carbonates, urethane O-vinyl esters, urethane N-vinyl esters, styrene-containing radicals, and (meth)acrylamide. As used herein, the term "(meth)" indicates an optional methyl substituent. Thus, terms such as "(meth)acrylate" indicate methacrylates or acrylates, and "(meth)acrylamide" indicates methacrylamide or acrylamide. In one embodiment, the olefinically unsaturated reactive end group can be represented by the following general formula:

[0092]

[0093] Where R 1 Independently hydrogen, fluorine, or methyl; R 2 Independently hydrogen, fluorine, alkyl radicals having 1 to 6 carbon atoms, or -CO-YR 3 Free radicals, where Y is -O-, -S-, or -NH-, and R 3 It is a divalent alkylene radical having 1 to approximately 10 carbon atoms.

[0094] In another illustrative embodiment, the (meth)acrylate group of the heterocyclic (meth)acrylate monomer is a reactive end group containing a (meth)acrylate. Suitable reactive end groups containing (meth)acrylate can be those represented by the following structures:

[0095]

[0096] Where R is hydrogen or methyl; L is O, NR 1 Or S, where R 1 The symbol is H, CH3, CH2CH3, or CH(CH3)2; m is an integer from 0 to 4, and R* is a linking group or bond. Suitable linking groups include, for example, any divalent hydrocarbon radical or moiety, such as independently straight-chain or branched, substituted or unsubstituted C1-C6 alkyl groups, or -OR. 2 Group, wherein R 2 Alkyl groups having 1 to 6 carbon atoms.

[0097] The term "heterocyclic," either alone or in combination with other terms, means, unless otherwise specified, the non-aromatic cyclic version of "alkyl" and "heteroalkyl," wherein the carbon atoms constituting one or more rings do not necessarily need to be bonded to hydrogen atoms because all carbon valences are involved in bonding with non-hydrogen atoms. Representative examples of heterocyclic groups of heterocyclic monomers with olefinically unsaturated reactive end groups for the purposes of this document include, by way of example, substituted or unsubstituted stable 3- to 15-membered ring radicals containing carbon atoms and one to five heteroatoms, such as nitrogen, phosphorus, oxygen, sulfur, and mixtures thereof. Suitable heterocyclic radicals of heterocyclic monomers with olefinically unsaturated reactive end groups for the purposes of this document can be monocyclic, bicyclic, or tricyclic systems, which may include fused ring systems, bridging ring systems, or spirocyclic systems, and the nitrogen, phosphorus, carbon, oxygen, or sulfur atoms in the heterocyclic radical may optionally be oxidized to various oxidation states. Examples of such heterocyclic radicals include, but are not limited to, azacyclic butyl, carbazolyl, dioxopranyl, piperidinyl, piperazine, pyrrolyl, 2-oxopraninyl, 2-oxopraninyl, 2-oxopraninyl, morpholinyl, and mixtures thereof.

[0098] In an illustrative embodiment, the heterocyclic moiety may include a single cyclic heteroatom (e.g., O, N, S, or P). In an illustrative embodiment, the heterocyclic alkyl moiety may include two optionally different cyclic heteroatoms (e.g., O, N, S, Si, or P).

[0099] Heterocyclic monomers having olefinically unsaturated reactive end groups can be unsubstituted or substituted. In illustrative embodiments, substituted heterocyclic monomers having olefinically unsaturated reactive end groups include heterocyclic moieties of heterocyclic monomers substituted with one or more of the following: hydroxyl groups, halogen groups, carboxyl groups, cyano groups, nitro groups, oxo (=O) groups, thio (=S) groups, substituted or unsubstituted alkyl groups, or substituted or unsubstituted alkoxy groups.

[0100] In a non-limiting illustrative embodiment, the heterocyclic (meth)acrylic acid monomer can be represented by the structure of Formula III:

[0101] (III)

[0102] Where x is an integer from 1 to 6, or 1 to 5, or 1 to 4, or 1 to 2; y is an integer from 0 to 3, or 1 to 3; R 3R is a hydrogen, hydroxyl group, halogen group, carboxyl group, cyano group, nitro group, oxo (=O) group, thio (=S) group, substituted or unsubstituted alkyl group or substituted or unsubstituted alkoxy group; X is a heteroatom, such as O, N, S or P; B is O, NR or S, wherein R is H, CH3, CH2CH3 or CH(CH3)2; D is O, S or bond; A is H or CH3; and z is 0 to 4, provided that if D is a bond, then at least one of y and z is 0.

[0103] In the illustrative embodiment, the one or more heterocyclic (meth)acrylic acid monomers are represented by the structure of Formula III, where x is an integer from 1 to 4; y is 0; R 3 X is an oxo group; D is O; z is an integer from 1 to 4; B is O; and A is H or CH3.

[0104] In the illustrative embodiment, the one or more heterocyclic (meth)acrylic acid monomers are represented by the structure of Formula III, where x is an integer from 1 to 3; y is 0; R 3 X is an oxo group; D is O; z is an integer from 2 to 3; B is O; and A is H or CH3.

[0105] In the illustrative embodiment, the one or more heterocyclic (meth)acrylic acid monomers are represented by the structure of Formula III, wherein x is an integer of 1 or 2; y is an integer from 1 to 4; R 3 X is an oxo group, D is a bond; z is 0; B is O; and A is H or CH3.

[0106] In illustrative embodiments, suitable one or more heterocyclic (meth)acrylic acid monomers include, for example, 3-(2-oxopyrrolidone-1-yl)propyl acrylate, 2-(2-oxopyrrolidone-1-yl)ethyl acrylate, 3-(2-oxopyrrolidone-1-yl)propyl methacrylate, 2-(2-oxopyrrolidone-1-yl)ethyl methacrylate, (2-oxopyrrolidone-1-yl)methyl methacrylate, 4-(2-oxopyrrolidone-1-yl)butyl methacrylate, (2-oxopyrrolidone-1-yl)methacrylate, 4-(2-oxopyrrolidone-1-yl)butyl acrylate, 3-(1H-pyrrolo-1-yl)propyl acrylate, 3-(1H-pyrrolo-1-yl)propyl methacrylate, and mixtures thereof.

[0107] In some embodiments, heterocyclic monomers having olefinically unsaturated reactive end groups may be present in the monomer mixture in an amount ranging from about 15% to about 50% by weight, based on the total weight of the monomer mixture. In some embodiments, heterocyclic monomers having olefinically unsaturated reactive end groups may be present in the monomer mixture in an amount ranging from about 25% to about 40% by weight, based on the total weight of the monomer mixture.

[0108] In a non-limiting illustrative embodiment, as can be combined with one or more of the preceding paragraphs, the monomers used in the monomer mixture for forming ophthalmic devices can be one or more aromatic monomers having olefinically unsaturated reactive end groups. As used herein, the term "aromatic" refers to a conjugated cyclic unsaturated hydrocarbon in a molecule, represented by a benzene skeleton, a naphthyl skeleton, etc. Representative examples of aromatic groups of aromatic monomers having olefinically unsaturated reactive end groups used herein include, by way of example, substituted or unsubstituted monocyclic or polycyclic aromatic radicals containing about 5 to about 25 carbon atoms, or 6 to 12 carbon atoms, or 6 to 10 carbon atoms, such as, for example, phenyl, naphthyl, tetrahydronaphthyl, indene, biphenyl, etc., optionally containing one or more heteroatoms, such as O and N, etc.

[0109] In a non-limiting illustrative embodiment, an aromatic monomer having an olefinically unsaturated reactive end group can be represented by the structure of Formula IV:

[0110] (IV)

[0111] Where A is H, CH3, CH2CH3 or CH2OH;

[0112] B is (CH2) m Or [0(CH2)2] z ;

[0113] C is (CH2) W ;

[0114] m is 2-6;

[0115] z is 1-10;

[0116] Y can be non-existent, O, S, or NR, provided that if Y is O, S, or NR, then B is (CH2). m ;

[0117] R' represents H, CH3, and C. n 'H2n'+1 (n'=1-10), iso-OC3H7, C6H5, or CH2C6H5; w is 0-6, provided that m + w≤8; and

[0118] D can be H, C1-C4 alkyl, C1-C4 alkoxy, C6H5, CH2C6H5, or halogen.

[0119] In a non-limiting illustrative embodiment, as can be combined with one or more of the preceding paragraphs, the aromatic monomer having an olefinically unsaturated reactive end group can be one or more arylalkyl monomers having an olefinically unsaturated reactive end group.

[0120] Representative examples of arylalkyl groups used for purposes herein include, by way of example, substituted or unsubstituted aromatic groups as defined above that are directly bonded to an alkyl group, such as -CH2C6H5, -C2H5C6H5, etc.

[0121] The olefinically unsaturated reactive end group of an aromatic monomer having an olefinically unsaturated reactive end group can be any of those discussed above. In the illustrative embodiment, the olefinically unsaturated reactive end group is a (meth)acrylate end group.

[0122] Specific examples of aromatic (meth)acrylic acid monomers include 2-phenylethyl acrylate, 2-phenylethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, 3-phenylpropyl acrylate, 3-phenylpropyl methacrylate, and mixtures thereof.

[0123] In some embodiments, based on the total weight of the monomer mixture, aromatic monomers having olefinically unsaturated reactive end groups may be present in the monomer mixture in an amount ranging from about 40% to about 80% by weight. In some embodiments, based on the total weight of the monomer mixture, aromatic monomers having olefinically unsaturated reactive end groups may be present in the monomer mixture in an amount ranging from about 50% to about 70% by weight.

[0124] In a non-limiting illustrative embodiment, representative examples of monomers for forming one or more ophthalmic devices in a monomer mixture, such as those that can be combined with one or more of the preceding paragraphs, include methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, n-vinylpyrrolidone, styrene, eugenol (4-hydroxyvinylbenzene), and α-methylstyrene. Furthermore, for applications involving high-refractive-index foldable lenses, suitable monomers include, but are not limited to, 2-ethylphenoxymethacrylate, 2-ethylphenoxyacrylate, 2-ethylthiophenylmethacrylate, 2-ethylthiophenylmethacrylate, 2-ethylaminophenylmethacrylate, phenylmethacrylate, benzylmethacrylate, 2-phenylethylmethacrylate (PEMA), 2-phenylethylmethacrylate (PEA), 3-phenylpropylmethacrylate, 4-phenylbutylmethacrylate, 4-methylphenylmethacrylate, 4-methylbenzylmethacrylate, 2-2-methylphenylethylmethacrylate, 2-3-methylphenylethylmethacrylate, 2-4-methyl... Phenyl ethyl methacrylate, 2-(4-propylphenyl)ethyl methacrylate, 2-(4-(1-methylethyl)phenyl)ethyl methacrylate, 2-(4-methoxyphenyl)ethyl methacrylate, 2-(4-cyclohexylphenyl)ethyl methacrylate, 2-(2-chlorophenyl)ethyl methacrylate, 2-(3-chlorophenyl)ethyl methacrylate, 2-(4-chlorophenyl)ethyl methacrylate, 2-(4-bromophenyl)ethyl methacrylate, 2-(3-phenylphenyl)ethyl methacrylate, 2-(4-phenylphenyl)ethyl methacrylate), 2-(4-benzylphenyl)ethyl methacrylate, etc., including the corresponding methacrylates and acrylates. N-vinylpyrrolidone, styrene, eugenol, and α-methylstyrene can also be used in high-refractive-index foldable lens applications.

[0125] In non-limiting illustrative embodiments, the monomer mixture may further comprise one or more crosslinking agents, as it can be combined with one or more of the preceding paragraphs. Crosslinking agents suitable for use herein are known in the art. For example, in non-limiting illustrative embodiments, suitable one or more crosslinking agents comprise one or more crosslinking agents containing at least two olefinically unsaturated reactive end groups. In one embodiment, the olefinically unsaturated reactive end group is a (meth)acrylate-containing reactive end group. In another embodiment, the olefinically unsaturated reactive end group is a non-(meth)acrylate reactive end group. In one embodiment, the olefinically unsaturated reactive end group is a combination of one or more (meth)acrylate-containing reactive end groups and one or more non-(meth)acrylate reactive end groups.

[0126] In one illustrative embodiment, suitable crosslinking agents containing at least two olefinically unsaturated reactive end groups include, for example, one or more crosslinking agents containing di(meth)acrylate, tri(meth)acrylate, or tetra(meth)acrylate. In one illustrative embodiment, suitable crosslinking agents containing one or more di(meth)acrylates, tri(meth)acrylates, or tetra(meth)acrylates include, for example, crosslinking agents containing alkyl polyol di(meth)acrylates, tri(meth)acrylates, or tetra(meth)acrylates, such as, for example, one or more alkylene glycol di(meth)acrylate crosslinking agents, one or more alkylene glycol tri(meth)acrylate crosslinking agents, one or more alkylene glycol tetra(meth)acrylate crosslinking agents, one or more alkylene glycol di(meth)acrylate crosslinking agents, alkylene glycol tri(meth)acrylate crosslinking agents, alkylene glycol tetra(meth)acrylate crosslinking agents, pharmaceuticals, one or more alkyltriol di(meth)acrylate crosslinking agents, alkyltriol tri(meth)acrylate crosslinking agents, alkyltriol tetra(meth)acrylate crosslinking agents, pharmaceuticals, one or more alkyltetraol di(meth)acrylate crosslinking agents, alkyltetraol tri(meth)acrylate crosslinking agents, alkyltetraol tetra(meth)acrylate crosslinking agents, and mixtures thereof.

[0127] In illustrative embodiments, one or more alkylene glycol di(meth)acrylate crosslinking agents include tetraethylene glycol dimethacrylate, ethylene glycol di(meth)acrylate having up to about 10 ethylene glycol repeating units, butanediol di(meth)acrylate, etc. In one embodiment, one or more alkylene glycol di(meth)acrylate crosslinking agents include butanediol di(meth)acrylate crosslinking agents, hexanediol di(meth)acrylate, etc. In one embodiment, one or more alkyltriol tri(meth)acrylate crosslinking agents are trimethylolpropane trimethacrylate crosslinking agents. In one embodiment, one or more alkyltetraol tetra(meth)acrylate crosslinking agents are pentaerythritol tetramethacrylate crosslinking agents.

[0128] In a non-limiting illustrative embodiment, suitable crosslinking agents include, for example, ethylene glycol diacrylate, diethylene glycol diacrylate, allyl acrylate, 1,3-propanediol diacrylate, 2,3-propanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol diacrylate, triethylene glycol diacrylate, cyclohexane-1,1-dimethyldimethyl diacrylate, 1,4-cyclohexanediol diacrylate, 1,3-adamantanediol diacrylate, 1,3-adamantanedimethyl diacrylate, 2,2-diethyl-1,3-propanediol diacrylate, 2,2-diisobutyl-1,3-propanediol diacrylate, 1,3-cyclohexanedimethyl diacrylate, 1,4-cyclohexanedimethyl diacrylate; neopentyl glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate; and their corresponding methacrylates.

[0129] In a non-limiting illustrative embodiment, suitable crosslinking agents include, for example, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, 1,3-propanediol diacrylate, 1,3-propanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, poly(ethylene glycol) diacrylate (Mn = 700 Daltons), poly(ethylene glycol) dimethacrylate (Mn = 700 Daltons), and poly(ethylene glycol) dimethacrylate (Mn = 1000 Daltons).

[0130] In non-limiting illustrative embodiments, such as those that can be combined with one or more of the preceding paragraphs, the one or more crosslinking agents may be present in the monomer mixture in an amount sufficient to form an ophthalmic device. In some embodiments, the one or more crosslinking agents are present in the monomer mixture in an amount of about 1% to about 10% by weight, based on the total weight of the monomer mixture. In some embodiments, the one or more crosslinking agents may be present in the monomer mixture in an amount of about 3% to about 5% by weight, based on the total weight of the monomer mixture.

[0131] In a non-limiting illustrative embodiment, as can be combined with one or more of the preceding paragraphs, the monomer mixture may further contain a reactive (polymerizable) ultraviolet (UV) absorber so that the ophthalmic device, such as a lens, can have an ultraviolet absorbance substantially equal to that of the natural lens of the eye. The UV-absorbing material can be any compound that absorbs ultraviolet light (i.e., light with wavelengths shorter than about 400 nm) but does not absorb any significant amount of visible light. It is preferable to use a reactive (polymerizable) ultraviolet (UV) absorber such that the UV absorber can be copolymerized with one or more monomers forming the ophthalmic device, thereby covalently bonding with the polymer matrix. In this way, any possibility of the UV absorber leaching from the lens and entering the interior of the eye is minimized. A suitable reactive UV absorber can be any known reactive UV absorber. In a non-limiting illustrative embodiment, suitable reactive UV absorbers include, for example, 2-(2'-hydroxy-3'-methylallyl-5'-methylphenyl)benzotriazole (tradely known as o-methylallyl Tinuvin P (“oMTP”), commercially available from Polysciences, Inc., Warrington, Pa.), 3-(2H-benzo[d][1,2,3]triazol-2-yl)-4-hydroxyphenyl ethyl methacrylate and 2-(3-(tert-butyl)-4-hydroxy-5-(5-methoxy-2H-benzo[d][1,2,3]triazol-2-yl)phenoxy)ethyl methacrylate.

[0132] In some illustrative embodiments, suitable reactive UV absorbers include, for example, UV absorbers having the structure shown in Formula V.

[0133] (V)

[0134] in:

[0135] R 1 C1 to C 12 Alkylene, (CH2CH2O) n (CH2CH(CH3)O) n or CH2CH2CH2(Si(CH3)2O) b Si(CH3)2CH2CH2CH2;

[0136] If R 1 (CH2CH) 2O ) n Or (CH2CH(CH3)O) n , or if R 2 If the value is Si(CH3)2, then X is a bond; otherwise, X is O, NR, or S.

[0137] R is H, CH2Si(CH3)3, C1 to C6 alkyl or phenyl;

[0138] R 2 For key, C (=O), C (=O)C j H 2j C1 to C6 alkylene, phenyl, C1 to C6 alkylphenyl or Si(CH3)2;

[0139] R 3 It is H or CH3;

[0140] R 4 It is H, C1 to C6 alkyl or phenyl;

[0141] R 5 = C4 to C 12 tertiary alkyl groups;

[0142] b is 1 to 9;

[0143] n is between 1 and 10; and

[0144] j ranges from 1 to 6.

[0145] In some illustrative embodiments, suitable reactive UV absorbers include one or more compounds of, for example, the following formula:

[0146] ,

[0147] ,

[0148] ,

[0149] ,

[0150] and

[0151] .

[0152] These reactive UV compounds are illustrative only and are not intended to be limiting. Any known or subsequently developed reactive UV absorbers are considered for use herein.

[0153] In some embodiments, the reactive UV absorber may be present in the monomer mixture in an amount ranging from about 0.1 wt% to about 5 wt%, based on the total weight of the monomer mixture. In some embodiments, the reactive UV absorber may be present in the monomer mixture in an amount ranging from about 1.5 wt% to about 2.5 wt%, based on the total weight of the monomer mixture. In some embodiments, the reactive UV absorber may be present in the monomer mixture in an amount ranging from about 1.5 wt% to about 2 wt%, based on the total weight of the monomer mixture.

[0154] The ophthalmic device (e.g., an intraocular lens) of the illustrative embodiments described herein can be prepared by polymerizing the aforementioned monomer mixture to form a product, which can then be shaped into a suitable form by, for example, turning, injection molding, compression molding, cutting, etc. For example, the ophthalmic device described herein can be prepared by combining one or more alicyclic (meth)acrylic acid monomers, one or more hydrophilic monomers, and one or more crosslinking agents, and polymerizing the resulting mixture.

[0155] Polymerization can be promoted by exposing the mixture to heat and / or radiation (such as ultraviolet light, visible light, or high-energy radiation). A polymerization initiator can be included in the mixture to promote the polymerization step. Suitable polymerization initiators include thermal initiators and photoinitiators. Representative examples of suitable free radical thermal polymerization initiators include, for example, organic peroxides such as acetyl peroxide, lauroyl peroxide, decanoyl peroxide, stearyl peroxide, benzoyl peroxide, tert-butyl peroxypentanoate, dicarbonate peroxide, etc. Suitable free radical thermal polymerization initiators also include, for example, 2,2'-azobis(4-methoxy-2,4-dimethylpentanonitrile) (VAZO 33), 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride (VAZO 44), 2,2'-azobis(2-amidinylpropane) dihydrochloride (VAZO 50), 2,2'-azobis(2,4-dimethylpentanonitrile) (VAZO 52), 2,2'-azobis(isobutyronitrile) (VAZO 64 or AIBN), 2,2'-azobis-2-methylbutyronitrile (VAZO 67), and 1,1-azobis(1-cyclohexanenitrile) (VAZO 33), 2,2'-azobis(2-(2-imidazolin-2-yl)propane) dihydrochloride (VAZO 64), 2,2'-azobis(1-cyclohexanenitrile) ... 88); 2,2'-azobis(2-cyclopropylpropionitrile), 2,2'-azobis(methyl isobutyrate), 4,4'-azobis(4-cyanovaleric acid), and combinations thereof. In one embodiment, the thermal initiator is 2,2'-azobis(isobutyronitrile) (VAZO 64 or AIBN).

[0156] Representative UV initiators are those known in the art, and include benzoin methyl ether, benzoin ethyl ether, and Darocure. ®1173, 1164, 2273, 1116, 2959, 3331 (EM Industries) and Irgacure ® 184, 651 and 819 (Ciba-Geigy), etc.

[0157] In illustrative embodiments, the initiator is used in the monomer mixture at a concentration of about 0.01 wt% to about 5 wt% based on the total weight of the monomer mixture. In other illustrative embodiments, the initiator is used in the monomer mixture at a concentration of about 0.01 wt% to about 3 wt% based on the total weight of the monomer mixture. In other illustrative embodiments, the initiator is used in the monomer mixture at a concentration of about 0.01 wt% to about 1.5 wt% based on the total weight of the monomer mixture.

[0158] Typically, polymerization can be carried out in an inert atmosphere, such as nitrogen or argon, for about 15 minutes to about 72 hours. If thermoplastic molds made of various types of polymer resins are used, the molds can be treated with an inert gas such as nitrogen or argon before use. The resulting crude polymer product can be extracted using organic solvents (e.g., acetone or isopropanol) to remove unreacted components or byproducts that typically form during free radical polymerization. If desired, the resulting polymer product can be dried under vacuum, for example, for about 5 hours to about 72 hours, to remove residual solvents. The final product can be packaged into dry lenses or left in an aqueous solution in the final packaging configuration.

[0159] If necessary, it may be desirable to remove residual diluent from the lens prior to edge finishing operations, which can be performed by evaporation at or near ambient pressure or under vacuum. Increased temperatures can be used to shorten the time required for diluent evaporation. As will be readily apparent to those skilled in the art, the time, temperature, and pressure conditions for the solvent removal step will vary depending on factors such as the volatility of the diluent and specific monomer components. If desired, the mixture used to produce the hydrogel lens may also contain crosslinking agents and wetting agents known in the art for preparing hydrogel materials.

[0160] The ophthalmic devices (such as intraocular lenses) described herein can undergo optional machining operations. For example, optional machining steps may include grinding or polishing the lens edges and / or surfaces. Typically, such machining processes can be performed before or after the product is released from the mold part, for example, by removing the lens from the mold using vacuum tweezers to dry release the lens from the mold, and then transferring the lens to a second set of vacuum tweezers using mechanical tweezers and placing it against a rotating surface to smooth the surface or edges. The lens can then be flipped over to machine the other side of the lens.

[0161] The lenses can then be transferred to individual lens packages containing a buffered saline solution. The saline solution can be added to the package before or after lens transfer. Suitable packaging designs and materials are known in the art. The plastic package is releasably sealed with a film. Suitable sealing films are known in the art and include foils, polymer films, and mixtures thereof. The sealed package containing the lenses is then sterilized to ensure a sterile product. Suitable sterilization methods and conditions are known in the art and include, for example, autoclaving.

[0162] As will be readily understood by those skilled in the art, other steps may be included in the molding and packaging process described above. Such other steps may include, for example, coating the formed lens, surface treating the lens during formation (e.g., by mold transfer), inspecting the lens, discarding defective lenses, cleaning the half-mold, reusing the half-mold, and combinations thereof.

[0163] The following examples are provided to enable those skilled in the art to practice the invention, and are merely illustrative. The examples should not be construed as limiting the scope of the invention as defined in the claims.

[0164] The following describes the formation of various polymerization products and their characterization using standard testing procedures, such as:

[0165] Water %: Extract both sets of lenses or films with solvent and vacuum dry at 70-90 °C for at least 16 hours, then weigh to determine the dry weight. Subsequently, equilibrate the samples in deionized water at ambient temperature (20-25 °C) for at least 16 hours. Then blot the samples dry on a piece of lens paper to remove excess water, and weigh to determine the wet weight. Calculate the water percentage from the wet and dry weights as follows: Water % = 100 * [(wet weight) – (dry weight)] / (wet weight).

[0166] Extractable weight % — After polymerization, six lenses or films from each of the two groups are weighed separately to determine the "unextracted weight". The samples are then solvent-extracted for at least 16 hours to remove residual monomers, oligomers, and other impurities. The samples are then vacuum-dried at 70–90 °C for at least 16 hours and weighed to determine the dry weight ("extracted weight"). Extractable weight % = 100 * [(unextracted weight) – (extracted weight)] / (unextracted weight)

[0167] In the embodiments, the following abbreviations are used.

[0168] PEG-PEA: Poly(ethylene glycol) phenyl ether acrylate (average Mn = 324).

[0169] HEMA: 2-hydroxyethyl methacrylate.

[0170] EGDMA: Ethylene glycol dimethacrylate.

[0171] X-monomer: 3-(3-(tert-butyl)-5-(5-chloro-2H-benzo[d][1,2,3]triazol-2-yl)-4-hydroxyphenoxy)propyl methacrylate.

[0172] Example 1

[0173] Preparation of (E)-4-allyl-2-methoxy-6-(p-tolyldiazelinyl)phenol represented by the following structure.

[0174]

[0175] In a 500 ml round-bottom flask equipped with a magnetic stirrer, add 25.0 g (234 mmol) of p-toluidine (Oakwood Chemical), 100 ml of concentrated HCl (37-38%, Oakwood Chemical), 150 ml of anhydrous ethanol, and 100 ml of deionized water. Add a solution of sodium nitrite (17.1 g, 247 mmol, EMD) in 100 ml of water dropwise over 30 minutes, while maintaining the reaction mixture at -10°C. Stir the reaction mixture for another hour. Add sulfamic acid (1.7 g, Oakwood Chemical) and stir the mixture for another 20 minutes. Filter the solids and set the cooled filtrate aside. In a 1 L round-bottom flask equipped with a magnetic stirrer, add 38.3 g (233 mmol) of 4-allyl-2-methoxyphenol (Oakwood Chemical), 100 ml of deionized water, and 100 ml of anhydrous ethanol. Approximately 1 / 4 volume of a solution consisting of 56.0 g (1.40 mol) of aqueous NaOH was added to a solution of 4-allyl-2-methoxyphenol, and the mixture was cooled to 0 °C. The diazo mixture and the remaining NaOH solution were simultaneously added dropwise to the 4-allyl-2-methoxyphenol mixture over 30 to 60 minutes, and the mixture was stirred at 0 °C for 1 hour and then at ambient temperature for 20 hours. The mixture was poured into 3 L of deionized water and acidified to pH 4 with 1 N HCl. The solid was filtered, washed with several liters of water, and dried under vacuum at 50 °C to give 39 g (59%) of a deep red solid.

[0176] Example 2

[0177] Preparation of (E)-2-(p-Tolyldiazelinyl)-4-vinylphenol represented by the following structure.

[0178]

[0179] Add 2.23 g (20.8 mmol) p-toluidine (Oakwood), 9.0 mL concentrated HCl (aqueous solution) (37-38%, Oakwood), 100 mL anhydrous ethanol, and 100 mL deionized water to a 500 mL round-bottom flask equipped with a magnetic stirrer. Add a solution of sodium nitrite (1.53 g, 22.2 mmol, EMD) in 30 mL of water dropwise over 30 minutes, while maintaining the reaction mixture at -10°C. Stir the reaction mixture for another hour. Add sulfamic acid (315 mg, Oakwood), and stir for another 20 minutes. Filter out the solids and set aside the cold diazo solution. Add 26.2 g (21.8 mmol) 4-vinylphenol (10% propylene glycol solution, Oakwood), 100 mL 2-propanol, and 100 mL deionized water to a 1 L round-bottom flask equipped with a magnetic stirrer. Approximately 1 / 4 volume of a solution consisting of 5.06 g (127 mmol) of NaOH in 50 mL of deionized water was added to the 4-vinylphenol solution, and the reaction mixture was cooled to 0 °C. The diazo mixture and the remaining NaOH solution were simultaneously added to the 4-vinylphenol mixture over 30 to 60 minutes, followed by stirring at 0 °C for an additional 1 hour and then at ambient temperature for 20 hours. The mixture was poured into 3 L of deionized water and acidified to pH 4 with 1 N HCl. The solid was filtered, washed with several liters of water, and dried under vacuum at 50 °C to give 3.1 g (63%) of orange solid.

[0180] Example 3

[0181] Preparation of (E)-4-methyl-2-((4-vinylphenyl)diazepine)phenol represented by the following structure.

[0182]

[0183] Add 6.35 g (53.3 mmol) of 4-vinylaniline (containing 0.5% KOH granules, Oakwood), 18 ml of concentrated HCl (37-38%, Oakwood), 100 ml of anhydrous ethanol, and 100 ml of deionized water to a 500 ml round-bottom flask equipped with a magnetic stirrer. Add a solution of sodium nitrite (3.91 g, 56.7 mmol, EMD) in 50 ml of water dropwise over 30 minutes, while maintaining the reaction mixture at -10°C. Stir the reaction mixture for another hour. Add sulfamic acid (430 mg, Oakwood) and stir for another 20 minutes. Filter out the solids and set aside the cold diazo solution. Add 5.48 g (50.7 mmol) of p-cresol (Sigma-Aldrich), 100 ml of 2-propanol, and 100 mL of deionized water to a 1 L round-bottom flask equipped with a magnetic stirrer. Approximately 1 / 4 volume of a solution consisting of 12.8 g (320 mmol) of NaOH in 80 ml of deionized water was added to the p-cresol solution, and the reaction mixture was cooled to 0°C. The diazo mixture and the remaining NaOH solution were simultaneously added to the p-cresol mixture over 30 to 60 minutes, followed by stirring at 0°C for an additional 1 hour and then at ambient temperature for 20 hours. The mixture was poured into 3 L of deionized water and acidified to pH 4 with 1 NHCl. The solid was filtered, washed with several liters of water, and dried under vacuum at 50°C to give 6 g (50%) of orange solid.

[0184] Example 4

[0185] Preparation of (E)-2-allyl-4-(tert-butyl)-6-(p-tolyldiazelinyl)phenol represented by the following structure.

[0186]

[0187] Add 63.9 mg (0.596 mmol) p-toluidine (Oakwood Chemical Company), 0.25 mL concentrated HCl (aqueous solution) (37-38%, Oakwood Chemical Company), 50 mL anhydrous ethanol, and 50 mL deionized water to a 250 mL round-bottom flask equipped with a magnetic stirrer. Add a solution of sodium nitrite (40.6 mg, 0.588 mmol, EMD) in 10 mL of water dropwise over 30 minutes, while maintaining the reaction mixture at -10°C. Stir the reaction mixture for another hour. Add sulfamic acid (53 mg, Oakwood Chemical Company) and stir for another 20 minutes. Filter out the solids and set aside the cold diazo solution. Add 94 mg (490 mmol), 2-allyl-4-tert-butylphenol (Sigma-Aldrich), 50 mL 2-propanol, and 50 mL deionized water to a 250 mL round-bottom flask equipped with a magnetic stirrer. Approximately 1 / 4 volume of a solution consisting of 265 mg (6.63 mmol) NaOH in 40 mL of deionized water was added to the 2-allyl-4-tert-butylphenol solution, and the reaction mixture was cooled to 0 °C. The diazo mixture and the remaining NaOH solution were simultaneously added to the 2-allyl-4-tert-butylphenol mixture over 30 to 60 minutes, and then stirred for an additional hour at 0 °C and then at ambient temperature for 20 hours. The mixture was poured into 2 L of deionized water and acidified to pH 4 with 1 N HCl. The solid was filtered, washed with several liters of water, and dried under vacuum at 50 °C to give 100 mg (66%) of a deep red solid.

[0188] Example 5

[0189] Preparation of (E)-4-allyl-2-(trimethylmethyldiazelenyl)phenol represented by the following structure.

[0190]

[0191] In a 250 mL round-bottom flask equipped with a magnetic stirrer, add 1.01 g (7.47 mmol) of 2,4,6-trimethylaniline (Oakwood), 3 mL of concentrated HCl (aqueous solution) (37-38%, Oakwood), 70 mL of anhydrous ethanol, and 70 mL of deionized water. Add a solution of sodium nitrite (0.55 g, 8.0 mmol, EMD) in 50 mL of water dropwise over 30 minutes, while maintaining the reaction mixture at -10°C. Stir the reaction mixture for another hour. Add sulfamic acid (183 mg, Oakwood) and stir for another 20 minutes. Filter out the solids and set aside the cold diazo solution. In a 500 mL round-bottom flask equipped with a magnetic stirrer, add 1.00 g (7.45 mmol) of 4-allylphenol (Ambeed), 80 mL of 2-propanol, and 80 mL of deionized water. Approximately 1 / 4 volume of a solution consisting of 1.78 g (44.5 mmol) of NaOH in 80 mL of deionized water was added to the 4-allylphenol solution, and the reaction mixture was cooled to 0 °C. The diazo mixture and the remaining NaOH solution were simultaneously added to the 4-allylphenol mixture over 30 to 60 minutes, and the mixture was stirred for an additional 1 hour at 0 °C and then stirred at ambient temperature for 20 hours. The mixture was poured into 4 L of deionized water and acidified to pH 4 with 1 N HCl. The solid was filtered, washed with several liters of water, and dried under vacuum at 50 °C to give 1.2 g (57%) of red solid.

[0192] Examples 6A-6D

[0193] IOL formulations are prepared from monomer mixtures made by mixing the following components listed in Table 1 in amounts of % by weight, based on the total weight of the monomer mixture.

[0194] Table 1

[0195]

[0196] The components in Table 1 were vortexed together in a 40 ml glass vial, purged with nitrogen, and then filtered through a syringe using a series of 1.0 μm and 0.2 μm Acrodisc PTFE filters. The formulation was poured into a polypropylene half-mold to prepare a +34 diopter lens or a 0.5 mm thick disc. An irradiance of ~10⁻¹¹ mW / cm² was used. 2 The samples were photocured for 2 to 6 hours using a superluminescent fluorescent lamp (~420 nm λ Max). The test specimens were extracted in acetone for 20 hours, air-dried for 6 to 20 hours, and then vacuum-dried at 80°C for at least 16 hours. The UV / Vis transmission spectra of the lenses obtained in Examples 6A-6D are visible in […]. Figure 1-3 middle.

[0197] Examples 7A-7D

[0198] Based on the total weight of the monomer mixture, the IOL formulation prepared using the stock solutions of Examples 6A and 6B without the initiator was mixed with the Irgacure 819 photoinitiator as shown in Table 2 below in amounts per % by weight.

[0199] Table 2

[0200]

[0201] The components in Table 2 were vortexed together in a 40 ml glass vial, purged with nitrogen, and then filtered through a syringe using a series of 1.0 μm and 0.2 μm Acrodisc PTFE filters. The formulation was poured into a polypropylene half-mold to prepare a +34 diopter lens or a 0.5 mm thick disc. An irradiance of ~10⁻¹¹ mW / cm² was used. 2 The samples were photocured for 2 to 6 hours using a superluminescent fluorescent lamp (~420 nm λ Max). The test specimens were extracted in acetone for 20 hours, air-dried for 6 to 20 hours, and then vacuum-dried at 80°C for at least 16 hours. The UV / Vis transmission spectra of the lenses obtained in Examples 7A-7D can be seen in... Figure 4 middle.

[0202] As shown in Table 3, the extractable percentage and equilibrium water content (EWC) of the lenses prepared in Examples 7A-7D were tested at ambient temperature.

[0203] Table 3

[0204]

[0205] 1 The extracted sample was equilibrated in deionized water at ambient temperature for at least 20 hours.

[0206] According to one aspect of this disclosure, an azo compound that absorbs visible light has the structure of formula I:

[0207] (I)

[0208] X1, X2, and X3 are independently hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a vinyl group, or an allyl group; Y is hydrogen, a substituted or unsubstituted alkyl group, or a vinyl group or an allyl group; and Z is hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a vinyl group, or an allyl group, wherein at least one of X1, X2, X3, Y, and Z is a vinyl group or an allyl group.

[0209] In a non-limiting illustrative embodiment, as may be combined with one or more of the preceding paragraphs, X1 and X2 are hydrogen, X3 is a vinyl group, Y is a C1 to C6 alkyl group, and Z is hydrogen.

[0210] In a non-limiting illustrative embodiment, as may be combined with one or more of the preceding paragraphs, X1 and X2 are hydrogen, X3 is a C1 to C6 alkyl group, Y is a C1 to C6 alkyl group, and Z is an allyl group.

[0211] In a non-limiting illustrative embodiment, each of X1, X2, and X3 is independently a C1 to C6 alkyl group, Y is a vinyl group, and Z is a substituted or unsubstituted alkoxy group, as may be combined with one or more of the preceding paragraphs.

[0212] In a non-limiting illustrative embodiment, as may be combined with one or more of the preceding paragraphs, X1 and X2 are hydrogen, X3 is a C1 to C6 alkyl group, Y is a vinyl group or an allyl group, and Z is a C1 to C6 alkoxy group.

[0213] In a non-limiting illustrative embodiment, as may be combined with one or more of the preceding paragraphs, each of X1, X2, and X3 is independently a C1 to C6 alkyl group, Y is a vinyl group or an allyl group, and Z is hydrogen.

[0214] In a non-limiting illustrative embodiment, as may be combined with one or more of the preceding paragraphs, one of X1, X2, and X3 is a vinyl group or an allyl group, and the remainder of X1, X2, and X3 is hydrogen, Y is a vinyl group or an allyl group, and Z is hydrogen, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkoxy group.

[0215] According to another aspect of this disclosure, an ophthalmic device is a polymer product of a monomer mixture comprising:

[0216] (a) Azo compounds having the structure of Formula I that absorb visible light:

[0217] (I)

[0218] Wherein X1, X2, and X3 are independently hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a vinyl group, or an allyl group; Y is hydrogen, a substituted or unsubstituted alkyl group, or a vinyl group or an allyl group; and Z is hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a vinyl group, or an allyl group, wherein at least one of X1, X2, X3, Y, and Z is a vinyl group or an allyl group, and

[0219] (b) One or more monomers that form ophthalmic devices.

[0220] In a non-limiting illustrative embodiment, as may be combined with one or more of the preceding paragraphs, X1 and X2 are hydrogen, X3 is a vinyl group, Y is a C1 to C6 alkyl group, and Z is hydrogen.

[0221] In a non-limiting illustrative embodiment, as may be combined with one or more of the preceding paragraphs, in the azo compound that absorbs visible light, X1 and X2 are hydrogen, X3 is a C1 to C6 alkyl group, Y is a C1 to C6 alkyl group, and Z is an allyl group.

[0222] In a non-limiting illustrative embodiment, as may be combined with one or more of the preceding paragraphs, in the azo compound that absorbs visible light, each of X1, X2, and X3 is independently a C1 to C6 alkyl group, Y is a vinyl group, and Z is a substituted or unsubstituted alkoxy group.

[0223] In a non-limiting illustrative embodiment, as may be combined with one or more of the preceding paragraphs, in the azo compound that absorbs visible light, X1 and X2 are hydrogen, X3 is a C1 to C6 alkyl group, Y is a vinyl group or an allyl group, and Z is a C1 to C6 alkoxy group.

[0224] In a non-limiting illustrative embodiment, as may be combined with one or more of the preceding paragraphs, in the azo compound that absorbs visible light, each of X1, X2, and X3 is independently a C1 to C6 alkyl group, Y is a vinyl group or an allyl group, and Z is hydrogen.

[0225] In a non-limiting illustrative embodiment, as may be combined with one or more of the preceding paragraphs, in the azo compound that absorbs visible light, one of X1, X2, and X3 is a vinyl group or an allyl group, and the remainder of X1, X2, and X3 is hydrogen, Y is a vinyl group or an allyl group, and Z is hydrogen, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkoxy group.

[0226] In a non-limiting illustrative embodiment, as may be combined with one or more of the preceding paragraphs, the monomer mixture contains about 0.005% by weight to about 0.5% by weight of the one or more visible light absorbers based on the total weight of the monomer mixture.

[0227] In a non-limiting illustrative embodiment, as may be combined with one or more of the preceding paragraphs, the monomer mixture contains about 0.005% by weight to about 0.2% by weight of the one or more visible light absorbers based on the total weight of the monomer mixture.

[0228] In a non-limiting illustrative embodiment, as may be combined with one or more of the preceding paragraphs, the monomer mixture contains about 0.005% by weight to about 0.1% by weight of the one or more visible light absorbers based on the total weight of the monomer mixture.

[0229] In a non-limiting illustrative embodiment, such as that which may be combined with one or more of the preceding paragraphs, the one or more monomers forming the ophthalmic device include styrene.

[0230] In a non-limiting illustrative embodiment, such as that which may be combined with one or more of the preceding paragraphs, the one or more monomers forming an ophthalmic device include one or more hydrophilic monomers.

[0231] In a non-limiting illustrative embodiment, as may be combined with one or more of the preceding paragraphs, the one or more hydrophilic monomers are selected from the group consisting of: unsaturated carboxylic acids, acrylamide, vinyl lactam, hydroxyl-containing (meth)acrylates, hydrophilic ethylene carbonate, hydrophilic urethane, hydrophilic oxazolone, and poly(olefin glycol) functionalized with polymerizable groups, as well as mixtures thereof.

[0232] In a non-limiting illustrative embodiment, such as that which may be combined with one or more of the preceding paragraphs, the one or more monomers forming an ophthalmic device include one or more polyethylene glycol (meth)acrylate monomers.

[0233] In a non-limiting illustrative embodiment, such as that which can be combined with one or more of the preceding paragraphs, the one or more polyethylene glycol (meth)acrylate monomers are represented by the structure of Formula II:

[0234] (II)

[0235] Where R 1Z is a hydrogen atom or a methyl radical; Z is a divalent group selected from the following groups: —COO—, —CONH—, —CONCH3—, —OCO—, —O—, —SO2—, —CO—O—CO— and —CO—CH2—CO—; x is 0 or 1; R 2 It is a straight-chain, branched, cyclic, or aromatic, saturated or unsaturated divalent carbon radical with 1 to 30 carbon atoms; m is 0 or 1; n is an integer between 3 and 300, including the end values; and R 3 A carbon-based free radical consisting of a hydrogen atom or 1 to 30 carbon atoms, either straight-chain, branched, cyclic, aromatic, saturated, or unsaturated.

[0236] In a non-limiting illustrative embodiment, as can be combined with one or more of the preceding paragraphs, the one or more monomers forming the ophthalmic device include one or more heterocyclic monomers having olefinically unsaturated reactive end groups.

[0237] In a non-limiting illustrative embodiment, as can be combined with one or more of the preceding paragraphs, the one or more heterocyclic monomers having olefinically unsaturated reactive end groups include one or more monocyclic heterocyclic monomers having olefinically unsaturated reactive end groups.

[0238] In a non-limiting illustrative embodiment, as can be combined with one or more of the preceding paragraphs, the one or more monocyclic heterocyclic monomers having olefinically unsaturated reactive end groups include C3-C8 heterocyclic monomers having olefinically unsaturated reactive end groups.

[0239] In a non-limiting illustrative embodiment, the one or more heterocyclic monomers having olefinically unsaturated reactive end groups, as can be combined with one or more of the preceding paragraphs, include one or more heterocyclic (meth)acrylic acid monomers.

[0240] In a non-limiting illustrative embodiment, as can be combined with one or more of the preceding paragraphs, the one or more heterocyclic monomers having olefinically unsaturated reactive end groups include one or more heterocyclic (meth)acrylic acid monomers represented by the structure of Formula III:

[0241] (III)

[0242] Where x is an integer from 1 to 6, or 1 to 5, or 1 to 4, or 1 to 2; y is an integer from 0 to 3, or 1 to 3; R 3R is a hydrogen, hydroxyl group, halogen group, carboxyl group, cyano group, nitro group, oxo (=O) group, thio (=S) group, substituted or unsubstituted alkyl group or substituted or unsubstituted alkoxy group; X is a heteroatom, such as O, N, S or P; B is O, NR or S, wherein R is H, CH3, CH2CH3 or CH(CH3)2; D is O, S or bond; A is H or CH3; and z is 0 to 4, provided that if D is a bond, then at least one of y and z is 0.

[0243] In a non-limiting illustrative embodiment, as can be combined with one or more of the preceding paragraphs, x is an integer from 1 to 4; y is 0; R 3 X is an oxo group; D is O; z is an integer from 1 to 4; B is O; and A is H or CH3.

[0244] In a non-limiting illustrative embodiment, as can be combined with one or more of the preceding paragraphs, x is an integer from 1 to 3; y is 0; R 3 X is an oxo group; D is O; z is an integer from 2 to 3; B is O; and A is H or CH3.

[0245] In a non-limiting illustrative embodiment, as can be combined with one or more of the preceding paragraphs, x is an integer of 1 or 2; y is an integer from 1 to 4; R 3 X is an oxo group, D is a bond; z is 0; B is O; and A is H or CH3.

[0246] In a non-limiting illustrative embodiment, such as that which can be combined with one or more of the preceding paragraphs, the one or more monomers forming the ophthalmic device include one or more aromatic monomers having olefinically unsaturated reactive end groups.

[0247] In a non-limiting illustrative embodiment, the one or more aromatic monomers having an olefinic unsaturated reactive end group, as can be combined with one or more of the preceding paragraphs, are substituted or unsubstituted monocyclic or polycyclic aromatic radicals containing about 5 to about 25 carbon atoms.

[0248] In a non-limiting illustrative embodiment, as can be combined with one or more of the preceding paragraphs, the aromatic group of the aromatic monomer having an olefinically unsaturated reactive end group is a substituted or unsubstituted monocyclic or polycyclic aromatic free radical containing about 5 to about 25 carbon atoms.

[0249] In a non-limiting illustrative embodiment, as can be combined with one or more of the preceding paragraphs, the aromatic group of the aromatic monomer having an olefinically unsaturated reactive end group is a substituted or unsubstituted monocyclic aromatic radical containing 6 to 12 carbon atoms that is directly bonded to an alkyl group.

[0250] In a non-limiting illustrative embodiment, the one or more aromatic monomers having olefinically unsaturated reactive end groups, as can be combined with one or more of the preceding paragraphs, include one or more (meth)acrylic acid monomers.

[0251] In a non-limiting illustrative embodiment, as may be combined with one or more of the preceding paragraphs, the (meth)acrylic group of the one or more aromatic (meth)acrylic monomers is a reactive end group containing (meth)acrylic ester.

[0252] In a non-limiting illustrative embodiment, such as that which can be combined with one or more of the preceding paragraphs, the one or more aromatic (meth)acrylic acid monomers are selected from the group consisting of: 2-phenylethyl acrylate, 2-phenylethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, 3-phenylpropyl acrylate, 3-phenylpropyl methacrylate, and mixtures thereof.

[0253] In a non-limiting illustrative embodiment, as may be combined with one or more of the preceding paragraphs, the monomer mixture contains about 50% to about 98% by weight of the one or more monomers forming the ophthalmic device, based on the total weight of the monomer mixture.

[0254] In a non-limiting illustrative embodiment, the monomer mixture may further comprise one or more crosslinking agents, as it may be combined with one or more of the preceding paragraphs.

[0255] In a non-limiting illustrative embodiment, such as that which can be combined with one or more of the preceding paragraphs, the one or more crosslinking agents are selected from the group consisting of: 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, 1,3-propanediol diacrylate, 1,3-propanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, poly(ethylene glycol) diacrylate, poly(ethylene glycol) dimethacrylate and poly(ethylene glycol) dimethacrylate.

[0256] In a non-limiting illustrative embodiment, the monomer mixture may further comprise one or more compounds that absorb ultraviolet light, as may be combined with one or more of the preceding paragraphs.

[0257] In a non-limiting illustrative embodiment, as may be combined with one or more of the preceding paragraphs, the one or more ultraviolet-absorbing compounds include the ultraviolet-absorbing compound benzotriazole.

[0258] In a non-limiting illustrative embodiment, as may be combined with one or more of the preceding paragraphs, the ophthalmic device absorbs light with wavelengths between about 380 and about 500 nanometers (nm).

[0259] In a non-limiting illustrative embodiment, as may be combined with one or more of the preceding paragraphs, the light is blue light.

[0260] According to another aspect of this disclosure, a method for manufacturing an ophthalmic device includes:

[0261] (a) Providing a monomer mixture, the monomer mixture comprising:

[0262] (i) Azo compounds with the structure of Formula I that absorb visible light:

[0263] (I)

[0264] Wherein X1, X2, and X3 are independently hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a vinyl group, or an allyl group; Y is hydrogen, a substituted or unsubstituted alkyl group, or a vinyl group or an allyl group; and Z is hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a vinyl group, or an allyl group, wherein at least one of X1, X2, X3, Y, and Z is a vinyl group or an allyl group, and

[0265] (ii) one or more monomers forming an ophthalmic device; and

[0266] (b) subjecting a mixture of monomers to polymerization conditions to provide an ophthalmic device.

[0267] In a non-limiting illustrative embodiment, as may be combined with one or more of the preceding paragraphs, X1 and X2 are hydrogen, X3 is a vinyl group, Y is a C1 to C6 alkyl group, and Z is hydrogen.

[0268] In a non-limiting illustrative embodiment, as may be combined with one or more of the preceding paragraphs, in the azo compound that absorbs visible light, X1 and X2 are hydrogen, X3 is a C1 to C6 alkyl group, Y is a C1 to C6 alkyl group, and Z is an allyl group.

[0269] In a non-limiting illustrative embodiment, as may be combined with one or more of the preceding paragraphs, in the azo compound that absorbs visible light, each of X1, X2, and X3 is independently a C1 to C6 alkyl group, Y is a vinyl group, and Z is a substituted or unsubstituted alkoxy group.

[0270] In a non-limiting illustrative embodiment, as may be combined with one or more of the preceding paragraphs, in the azo compound that absorbs visible light, X1 and X2 are hydrogen, X3 is a C1 to C6 alkyl group, Y is a vinyl group or an allyl group, and Z is a C1 to C6 alkoxy group.

[0271] In a non-limiting illustrative embodiment, as may be combined with one or more of the preceding paragraphs, in the azo compound that absorbs visible light, each of X1, X2, and X3 is independently a C1 to C6 alkyl group, Y is a vinyl group or an allyl group, and Z is hydrogen.

[0272] In a non-limiting illustrative embodiment, as may be combined with one or more of the preceding paragraphs, in the azo compound that absorbs visible light, one of X1, X2, and X3 is a vinyl group or an allyl group, and the remainder of X1, X2, and X3 is hydrogen, Y is a vinyl group or an allyl group, and Z is hydrogen, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkoxy group.

[0273] In a non-limiting illustrative embodiment, as may be combined with one or more of the preceding paragraphs, the monomer mixture contains about 0.005% by weight to about 0.5% by weight of the one or more visible light absorbers based on the total weight of the monomer mixture.

[0274] In a non-limiting illustrative embodiment, as may be combined with one or more of the preceding paragraphs, the monomer mixture contains about 0.005% by weight to about 0.2% by weight of the one or more visible light absorbers based on the total weight of the monomer mixture.

[0275] In a non-limiting illustrative embodiment, as may be combined with one or more of the preceding paragraphs, the monomer mixture contains about 0.005% by weight to about 0.1% by weight of the one or more visible light absorbers based on the total weight of the monomer mixture.

[0276] In a non-limiting illustrative embodiment, such as that which may be combined with one or more of the preceding paragraphs, the one or more monomers forming the ophthalmic device include styrene.

[0277] In a non-limiting illustrative embodiment, such as that which may be combined with one or more of the preceding paragraphs, the one or more monomers forming an ophthalmic device include one or more hydrophilic monomers.

[0278] In a non-limiting illustrative embodiment, as may be combined with one or more of the preceding paragraphs, the one or more hydrophilic monomers are selected from the group consisting of: unsaturated carboxylic acids, acrylamide, vinyl lactam, hydroxyl-containing (meth)acrylates, hydrophilic ethylene carbonate, hydrophilic urethane, hydrophilic oxazolone, and poly(olefin glycol) functionalized with polymerizable groups, as well as mixtures thereof.

[0279] In a non-limiting illustrative embodiment, such as that which may be combined with one or more of the preceding paragraphs, the one or more monomers forming an ophthalmic device include one or more polyethylene glycol (meth)acrylate monomers.

[0280] In a non-limiting illustrative embodiment, such as that which can be combined with one or more of the preceding paragraphs, the one or more polyethylene glycol (meth)acrylate monomers are represented by the structure of Formula II:

[0281] (II)

[0282] Where R 1 Z is a hydrogen atom or a methyl radical; Z is a divalent group selected from the following groups: —COO—, —CONH—, —CONCH3—, —OCO—, —O—, —SO2—, —CO—O—CO— and —CO—CH2—CO—; x is 0 or 1; R 2 It is a straight-chain, branched, cyclic, or aromatic, saturated or unsaturated divalent carbon radical with 1 to 30 carbon atoms; m is 0 or 1; n is an integer between 3 and 300, including the end values; and R 3 A carbon-based free radical consisting of a hydrogen atom or 1 to 30 carbon atoms, either straight-chain, branched, cyclic, aromatic, saturated, or unsaturated.

[0283] In a non-limiting illustrative embodiment, as can be combined with one or more of the preceding paragraphs, the one or more monomers forming the ophthalmic device include one or more heterocyclic monomers having olefinically unsaturated reactive end groups.

[0284] In a non-limiting illustrative embodiment, as can be combined with one or more of the preceding paragraphs, the one or more heterocyclic monomers having olefinically unsaturated reactive end groups include one or more monocyclic heterocyclic monomers having olefinically unsaturated reactive end groups.

[0285] In a non-limiting illustrative embodiment, as can be combined with one or more of the preceding paragraphs, the one or more monocyclic heterocyclic monomers having olefinically unsaturated reactive end groups include C3-C8 heterocyclic monomers having olefinically unsaturated reactive end groups.

[0286] In a non-limiting illustrative embodiment, the one or more heterocyclic monomers having olefinically unsaturated reactive end groups, as can be combined with one or more of the preceding paragraphs, include one or more heterocyclic (meth)acrylic acid monomers.

[0287] In a non-limiting illustrative embodiment, as can be combined with one or more of the preceding paragraphs, the one or more heterocyclic monomers having olefinically unsaturated reactive end groups include one or more heterocyclic (meth)acrylic acid monomers represented by the structure of Formula III:

[0288] (III)

[0289] Where x is an integer from 1 to 6, or 1 to 5, or 1 to 4, or 1 to 2; y is an integer from 0 to 3, or 1 to 3; R 3 R is a hydrogen, hydroxyl group, halogen group, carboxyl group, cyano group, nitro group, oxo (=O) group, thio (=S) group, substituted or unsubstituted alkyl group or substituted or unsubstituted alkoxy group; X is a heteroatom, such as O, N, S or P; B is O, NR or S, wherein R is H, CH3, CH2CH3 or CH(CH3)2; D is O, S or bond; A is H or CH3; and z is 0 to 4, provided that if D is a bond, then at least one of y and z is 0.

[0290] In a non-limiting illustrative embodiment, as can be combined with one or more of the preceding paragraphs, x is an integer from 1 to 4; y is 0; R 3 X is an oxo group; D is O; z is an integer from 1 to 4; B is O; and A is H or CH3.

[0291] In a non-limiting illustrative embodiment, as can be combined with one or more of the preceding paragraphs, x is an integer from 1 to 3; y is 0; R 3 X is an oxo group; D is O; z is an integer from 2 to 3; B is O; and A is H or CH3.

[0292] In a non-limiting illustrative embodiment, as can be combined with one or more of the preceding paragraphs, x is an integer of 1 or 2; y is an integer from 1 to 4; R 3 X is an oxo group, D is a bond; z is 0; B is O; and A is H or CH3.

[0293] In a non-limiting illustrative embodiment, such as that which can be combined with one or more of the preceding paragraphs, the one or more monomers forming the ophthalmic device include one or more aromatic monomers having olefinically unsaturated reactive end groups.

[0294] In a non-limiting illustrative embodiment, the one or more aromatic monomers having an olefinic unsaturated reactive end group, as can be combined with one or more of the preceding paragraphs, are substituted or unsubstituted monocyclic or polycyclic aromatic radicals containing about 5 to about 25 carbon atoms.

[0295] In a non-limiting illustrative embodiment, as can be combined with one or more of the preceding paragraphs, the aromatic group of the aromatic monomer having an olefinically unsaturated reactive end group is a substituted or unsubstituted monocyclic or polycyclic aromatic free radical containing about 5 to about 25 carbon atoms.

[0296] In a non-limiting illustrative embodiment, as can be combined with one or more of the preceding paragraphs, the aromatic group of the aromatic monomer having an olefinically unsaturated reactive end group is a substituted or unsubstituted monocyclic aromatic radical containing 6 to 12 carbon atoms that is directly bonded to an alkyl group.

[0297] In a non-limiting illustrative embodiment, the one or more aromatic monomers having olefinically unsaturated reactive end groups, as can be combined with one or more of the preceding paragraphs, include one or more (meth)acrylic acid monomers.

[0298] In a non-limiting illustrative embodiment, such as that which can be combined with one or more of the preceding paragraphs, the one or more aromatic (meth)acrylate monomers are selected from the group consisting of: 2-phenylethyl acrylate, 2-phenylethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, 3-phenylpropyl acrylate, 3-phenylpropyl methacrylate, and mixtures thereof.

[0299] In a non-limiting illustrative embodiment, as may be combined with one or more of the preceding paragraphs, the monomer mixture contains about 50% to about 98% by weight of the one or more monomers forming the ophthalmic device, based on the total weight of the monomer mixture.

[0300] In a non-limiting illustrative embodiment, the monomer mixture may further comprise one or more crosslinking agents, as it may be combined with one or more of the preceding paragraphs.

[0301] In a non-limiting illustrative embodiment, such as that which can be combined with one or more of the preceding paragraphs, the one or more crosslinking agents are selected from the group consisting of: 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, 1,3-propanediol diacrylate, 1,3-propanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, poly(ethylene glycol) diacrylate, poly(ethylene glycol) dimethacrylate and poly(ethylene glycol) dimethacrylate.

[0302] In a non-limiting illustrative embodiment, the monomer mixture may further comprise one or more compounds that absorb ultraviolet light, as may be combined with one or more of the preceding paragraphs.

[0303] In a non-limiting illustrative embodiment, as may be combined with one or more of the preceding paragraphs, the one or more ultraviolet-absorbing compounds include the ultraviolet-absorbing compound benzotriazole.

[0304] In a non-limiting illustrative embodiment, as may be combined with one or more of the preceding paragraphs, the ophthalmic device absorbs light with wavelengths between about 380 and about 500 nanometers (nm).

[0305] For the sake of brevity, the various features disclosed herein, described in the context of a single embodiment, may also be provided individually or in any suitable sub-combination. All combinations of embodiments are specifically covered by the illustrative embodiments disclosed herein, as if each combination were individually and explicitly disclosed. Furthermore, all sub-combinations listed in embodiments describing such variables are also explicitly covered by the inventive compositions and disclosed herein, as if each such sub-combination were individually and explicitly disclosed herein.

[0306] It will be understood that various modifications can be made to the embodiments disclosed herein. Therefore, the above description should not be construed as limiting, but merely as an example of preferred embodiments. For example, the functions described above and implemented as the best mode for operating the invention are for illustrative purposes only. Other arrangements and methods can be implemented by those skilled in the art without departing from the scope and spirit of the invention. Furthermore, those skilled in the art will contemplate other modifications within the scope and spirit of the appended features and advantages.

Claims

1. An azo compound that absorbs visible light, said azo compound having the structure of Formula I: (I) X1, X2, and X3 are independently hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a vinyl group, or an allyl group; Y is hydrogen, a substituted or unsubstituted alkyl group, or a vinyl group or an allyl group; and Z is hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a vinyl group, or an allyl group, wherein at least one of X1, X2, X3, Y, and Z is a vinyl group or an allyl group.

2. The azo compound that absorbs visible light according to claim 1, wherein X1 and X2 are hydrogen, X3 is a vinyl group, Y is a C1 to C6 alkyl group, and Z is hydrogen.

3. The azo compound that absorbs visible light according to claim 1, wherein X1 and X2 are hydrogen, X3 is a C1 to C6 alkyl group, Y is a C1 to C6 alkyl group, and Z is an allyl group.

4. The azo compound that absorbs visible light according to claim 1, wherein each of X1, X2 and X3 is independently a C1 to C6 alkyl group, Y is a vinyl group, and Z is a substituted or unsubstituted alkoxy group.

5. The azo compound that absorbs visible light according to claim 1, wherein X1 and X2 are hydrogen, X3 is a C1 to C6 alkyl group, Y is a vinyl group or an allyl group, and Z is a C1 to C6 alkoxy group.

6. The azo compound that absorbs visible light according to claim 1, wherein each of X1, X2 and X3 is independently a C1 to C6 alkyl group, Y is a vinyl group or an allyl group, and Z is hydrogen.

7. The azo compound that absorbs visible light according to claim 1, wherein one of X1, X2 and X3 is a vinyl group or an allyl group, and the remaining one of X1, X2 and X3 is hydrogen, Y is a vinyl group or an allyl group, and Z is hydrogen, a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkoxy group.

8. An ophthalmic device, said ophthalmic device being a polymer of a monomer mixture, said monomer mixture comprising: (a) Azo compounds having the structure of Formula I that absorb visible light: (I) Wherein X1, X2, and X3 are independently hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a vinyl group, or an allyl group; Y is hydrogen, a substituted or unsubstituted alkyl group, or a vinyl group or an allyl group; and Z is hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a vinyl group, or an allyl group, wherein at least one of X1, X2, X3, Y, and Z is a vinyl group or an allyl group; and (b) One or more monomers that form ophthalmic devices.

9. The ophthalmic device according to claim 8, wherein in the azo compound that absorbs visible light, X1 and X2 are hydrogen, X3 is a vinyl group, Y is a C1 to C6 alkyl group, and Z is hydrogen.

10. The ophthalmic device according to claim 8, wherein in the azo compound that absorbs visible light, X1 and X2 are hydrogen, X3 is a C1 to C6 alkyl group, Y is a C1 to C6 alkyl group, and Z is an allyl group.

11. The ophthalmic device according to claim 8, wherein in the azo compound that absorbs visible light, each of X1, X2 and X3 is independently a C1 to C6 alkyl group, Y is a vinyl group, and Z is a substituted or unsubstituted alkoxy group.

12. The ophthalmic device according to claim 8, wherein in the azo compound that absorbs visible light, X1 and X2 are hydrogen, X3 is a C1 to C6 alkyl group, Y is a vinyl group or an allyl group, and Z is a C1 to C6 alkoxy group.

13. The ophthalmic device according to claim 8, wherein in the azo compound that absorbs visible light, each of X1, X2 and X3 is independently a C1 to C6 alkyl group, Y is a vinyl group or an allyl group, and Z is hydrogen.

14. The ophthalmic device of claim 8, wherein in the azo compound that absorbs visible light, one of X1, X2 and X3 is a vinyl group or an allyl group, and the remainder of X1, X2 and X3 is hydrogen, Y is a vinyl group or an allyl group, and Z is hydrogen, a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkoxy group.

15. The ophthalmic device of claim 8, wherein, based on the total weight of the monomer mixture, the monomer mixture comprises about 0.005% by weight to about 0.5% by weight of a visible light absorber.

16. The ophthalmic device according to any one of claims 8 to 15, wherein one or more monomers forming the ophthalmic device comprise styrene.

17. The ophthalmic device according to any one of claims 8 to 16, wherein the one or more monomers forming the ophthalmic device comprise one or more hydrophilic monomers.

18. The ophthalmic device according to any one of claims 8 to 17, wherein the one or more monomers forming the ophthalmic device comprise one or more polyethylene glycol methacrylate monomers.

19. The ophthalmic device of claim 18, wherein the one or more polyethylene glycol methacrylate monomers are represented by the structure of formula II: (II) Where R 1 Z is a hydrogen atom or a methyl radical; Z is a divalent group selected from the following groups: —COO—, —CONH—, —CONCH3—, —OCO—, —O—, —SO2—, —CO—O—CO— and —CO—CH2—CO—; x is 0 or 1; R 2 It is a straight-chain, branched, cyclic, or aromatic, saturated or unsaturated divalent carbon radical with 1 to 30 carbon atoms; m is 0 or 1; n is an integer between 3 and 300, including the end values; and R 3 A carbon-based free radical consisting of a hydrogen atom or 1 to 30 carbon atoms, either straight-chain, branched, cyclic, aromatic, saturated, or unsaturated.

20. The ophthalmic device according to any one of claims 8 to 19, wherein the one or more monomers forming the ophthalmic device comprise one or more heterocyclic monomers having olefinically unsaturated reactive end groups.

21. The ophthalmic device of claim 20, wherein the one or more heterocyclic monomers having olefinically unsaturated reactive end groups comprise one or more heterocyclic (meth)acrylic acid monomers represented by the structure of Formula III: (III) Where x is an integer from 1 to 6, or 1 to 5, or 1 to 4, or 1 to 2; y is an integer from 0 to 3, or 1 to 3; R 3 R is a hydrogen, hydroxyl group, halogen group, carboxyl group, cyano group, nitro group, oxo (=O) group, thio (=S) group, substituted or unsubstituted alkyl group or substituted or unsubstituted alkoxy group; X is a heteroatom, such as O, N, S or P; B is O, NR or S, wherein R is H, CH3, CH2CH3 or CH(CH3)2; D is O, S or bond; A is H or CH3; and z is 0 to 4, provided that if D is a bond, then at least one of y and z is 0.

22. The ophthalmic device according to any one of claims 8 to 21, wherein, based on the total weight of the monomer mixture, the monomer mixture comprises about 50% to about 98% by weight of one or more of the monomers forming the ophthalmic device.

23. The ophthalmic device according to any one of claims 8 to 21, wherein, based on the total weight of the monomer mixture, the monomer mixture comprises about 90% to about 96% by weight of the one or more monomers forming the ophthalmic device.

24. The ophthalmic device according to any one of claims 8 to 23, wherein the monomer mixture further comprises one or more crosslinking agents.

25. The ophthalmic device according to any one of claims 8 to 24, wherein the monomer mixture further comprises one or more compounds that absorb ultraviolet light.

26. The ophthalmic device according to any one of claims 8 to 25, wherein the ophthalmic device absorbs light with a wavelength between about 380 and about 500 nanometers (nm).

27. The ophthalmic device of claim 26, wherein the light is blue light.

28. The ophthalmic device according to any one of claims 8 to 27, wherein the ophthalmic device is one of a contact lens or an intraocular lens.

29. A method for manufacturing an ophthalmic device, the method comprising: (a) Providing a monomer mixture, the monomer mixture comprising: (i) Azo compounds with the structure of Formula I that absorb visible light: (I) Wherein X1, X2, and X3 are independently hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a vinyl group, or an allyl group; Y is hydrogen, a substituted or unsubstituted alkyl group, or a vinyl group or an allyl group; and Z is hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a vinyl group, or an allyl group, wherein at least one of X1, X2, X3, Y, and Z is a vinyl group or an allyl group, and (ii) one or more monomers forming an ophthalmic device; and (b) subjecting the monomer mixture to polymerization conditions to provide an ophthalmic device.

30. The method of claim 29, wherein, based on the total weight of the monomer mixture, the monomer mixture contains about 0.005% by weight to about 0.5% by weight of a visible light absorber.

31. The method of claim 29 or 30, wherein, based on the total weight of the monomer mixture, the monomer mixture comprises about 50% to about 98% by weight of the one or more monomers forming the ophthalmic device.

32. The method of claim 29 or 30, wherein, based on the total weight of the monomer mixture, the monomer mixture comprises about 90% to about 96% by weight of the one or more monomers forming the ophthalmic device.

33. The method according to any one of claims 29 to 32, wherein the one or more monomers forming the ophthalmic device comprise one or more of a hydrophilic monomer, a polyethylene glycol methacrylate monomer, and a heterocyclic monomer having an olefinically unsaturated reactive end group.

34. The method according to any one of claims 29 to 33, wherein the ophthalmic device absorbs light with a wavelength between about 380 and about 500 nanometers (nm).

35. The method of claim 34, wherein the light is blue light.

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