Polymeric materials for use as photoablatable inlays

Description

FIELD OF THE INVENTION

[0001] The present invention relates to novel polymeric materials and a method for making and using the same as photoablatable inlays (PAIs). More particularly, the present invention relates to soft, optically transparent, hydrogel materials particularly suited for use in the production of PAIs, and a method for manufacturing and using the same.

BACKGROUND OF THE INVENTION

[0002] Laser-assisted in situ keratomileusis (LASIK) surgery is a surgical refractive vision correction procedure that is extremely popular due in part to the relative lack of pain immediately following surgery and in part to the excellent vision usually achieved by the very next day, if not before. In LASIK surgery, a microkeratome is used to create a thin, circular flap in the cornea tissue of an eye. The surgeon folds the tissue flap out of the way, then removes corneal tissue and reshapes the cornea underneath the flap using an excimer laser. The tissue flap is then laid back in place, covering the area where the corneal tissue was shaped and removed. The major drawback of LASIK surgery is that the procedure is not reversible and additional surgeries are limited by the residual corneal thickness. Additional stromal material must be ablated for additional correction in the likely event a patient's vision deteriorates with time following LASIK surgery. Additional stromal material may not be present to accommodate such additional correction. Accordingly, a surgical refractive vision correction procedure, which is reversible and allows for additional surgeries over time as a patient's vision naturally deteriorates over time, is desired.

SUMMARY OF THE INVENTION

[0003] Soft, foldable, hydrogel polymeric materials having relatively high water contents particularly suited for use as photoablatable inlays (PAIs), corneal inlays, corneal onlays or like ophthalmic devices have now been discovered. The subject hydrogel polymeric materials are suitable for manufacture in the form of a disc or lenticule for placement in the corneal bed of an eye following surgical formation of a flap therein. The hydrogel polymeric material disc or lenticule is then precisely custom ablated in situ to the desired shape using an excimer laser. A surgical procedure using a PAI of the present invention is advantageous in that the number of corrective procedures is not limited by the thickness of the cornea. Likewise, a surgical procedure using a PAI of the present invention is reversible and repeatable to correct hyperopia, astigmatism, and mild to moderate myopia simply by ablating the PAI or replacing a former PAI with a new one that is then ablated to conform to the patient's specific needs.

[0004] Accordingly, it is an object of the present invention to provide a biocompatible polymeric material.

[0005] Another object of the present invention is to provide a hydrogel polymeric material having a high water content similar to that of the cornea.

[0006] Another object of the present invention is to provide a hydrogel polymeric material that is colorless.

[0007] Another object of the present invention is to provide a hydrogel polymeric material that is transparent.

[0008] Another object of the present invention is to provide a polymeric material that is suitable for in situ photoablation.

[0009] Still another object of the present invention is to provide a biocompatible polymeric material that is relatively simple to manufacture.

[0010] These and other objectives and advantages of the present invention, some of which are specifically described and others that are not, will become apparent from the detailed description and claims that follow.

DETAILED DESCRIPTION OF THE INVENTION

[0011] The following detailed description is provided to enable any person skilled in the art to which the present invention pertains to make and use the same, and sets forth the best mode contemplated by the inventors of carrying out the subject invention.

[0012] The present invention relates to soft, optically transparent, hydrogel polymeric materials particularly suited for use in the production of PAIs, and a method for manufacturing and using the same. The hydrogel polymeric materials of the present invention maximize water content for use in the manufacture of ophthalmic devices such as photoablatable inlays (PAIs) and the like. The preferred water content of subject hydrogel polymeric materials for improved biocompatability is approximately 78 percent, which is the reported water content of the human cornea. The subject hydrogel polymeric materials are manufactured in the form of a disc or lenticule for placement in the corneal bed of an eye following surgical formation of a flap therein. The hydrogel polymeric material disc or lenticule is suitable for precise custom ablation in situ to the desired shape using an excimer laser. A surgical procedure using a PAI of the present invention is advantageous in that the number of corrective procedures is not limited by the thickness of the particular patient's cornea as is true of LASIK surgical visual correction. Likewise, a surgical procedure using a PAI of the present invention is reversible and repeatable to correct hyperopia, astigmatism, and mild to moderate myopia simply by ablating the PAI or replacing a former PAI with a new one that is then ablated to meet the patient's specific needs.

[0013] The preferred hydrogel polymeric materials of the present invention are copolymers of hydrophilic monomers. Suitable hydrophilic monomers for use in the present invention include for example but are not limited to 2-hydroxyethyl methacrylate, hydroxyethoxyethyl methacrylate, hydroxydiethoxyethyl methacrylate, methoxyethyl methacrylate, methoxyethoxyethyl methacrylate, methoxydiethoxyethyl methacrylate, poly(ethylene glycol) methacrylate, methoxy-poly(ethylene glycol) methacrylate, methacrylic acid, sodium methacrylate, glycerol methacrylate, hydroxypropyl methacrylate, N-vinylpyrrolidione, hydroxypropyl methacrylamide, N,N-dimethylacrylamide, N-methylacrylamide and hydroxybutyl methacrylate. Preferred hydrophilic monomers are 2-hydroxyethyl methacrylate (HEMA) and methacrylic acid (MAA) to maximize water content.

[0014] Hydrogel polymeric materials of the present invention include for example but are not limited to poly(2-hydroxyethyl methacrylate-co-methacrylic acid), poly(2-hydroxyethyl methacrylate-co-N-vinylpyrrolidinone), poly(2-hydroxyethyl methacrylate-co-dimethylacrylamide), poly(N-vinylpyrrolidinone-co-2-methacrylic acid), poly(2-hydroxyethyl methacrylate-co-4-t-butyl-2-hydroxyethyl methacrylate) and poly(N-vinylpyrrolidinone-co-4-t-butyl-2-hydroxyethyl methacrylate).

[0015] The subject hydrogel polymeric materials are synthesized by polymerizing one or more of the above-described hydrophilic monomers in the presence of optionally 0.01 but more preferably 0.01 to 3.0 weight percent crosslinker and at least 0.01 but more preferably 0.02 to 2.0 weight percent initiator. Optionally, an ultraviolet light absorber may also be added.

[0016] Suitable crosslinkers include for example but are not limited to ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate and poly(ethylene glycol) dimethacrylate wherein ethylene glycol dimethacrylate is preferred.

[0017] The hydrophilic monomers of the present invention may be readily cured in cast shapes by one or more conventional methods. Such methods include for example but are not limited to ultraviolet light (UV) polymerization, visible light polymerization, microwave polymerization, thermal polymerization, free radical polymerization, living radical polymerization or combinations thereof. Metallocene catalysts may also be used in certain instances.

[0018] Suitable free radical thermal polymerization initiators include for example but are not limited to organic peroxides, such as acetyl peroxide, lauroyl peroxide, decanoyl peroxide, stearoyl peroxide, benzoyl peroxide, t-butyl peroxypivalate, peroxydicarbonate, and the like.

[0019] Representative UV initiators include those known in the field such as for example but not limited to benzoin methyl ether, benzoin ethyl ether, Darocur™ 1173, 1164, 2273, 1116, 2959 and 3331 (EM Industries, Inc., Hawthorne, N. Y.) and Irgacur™651 and 184 (Ciba-Geigy, Basel, Switzerland).

[0020] Other suitable initiators include for example but are not limited to azobis(isobutyronitrile), 2,2′-azobis(2,4-dimethylvaleronitrile), 2,2′-azobis(methylbutyronitrile), 1,1′-azobis(cyanocyclohexane), di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-bis(2-ethylhexanoyl peroxy)hexane, t-butyl peroxyneodecanote, t-butyl peroxy 2-ethylhexanoate, di(4-t-butyl cyclohexyl) peroxydicarbonate, t-butyl peroxypivalate, decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, 2,4-pentanedione peroxide, di(n-propyl) peroxydicarbonate, t-amyl peroxyneodecanoate and t-butyl peroxyacetate wherein 2,2′-azobis(isobutyronitrile) is preferred.

[0021] Suitable ultraviolet light absorbers include for example but are not limited to beta-(4-benzotriazoyl-3-hydroxyphenoxy)ethyl acrylate, 4-(2-acryloxyethoxy)-2-hydroxybenzophenone, 4-methacryloxy-2-hydroxybenzophenone, 2-(2′-methacryloxy-5′-methylphenyl)benzotriazole, 2-(2′-hydroxy-5′-methacryoxyethylphenyl)-2H-benzotriazole, 2-[3′-tert-butyl-2′-hydroxy-5′-(3″-methacryloyloxypropyl)phenyl]-5-chlorobenzotriazole, 2-(3′-tert-butyl-5′-(3″-dimethylvinylsilylpropoxy)-2′-hydroxyphenyl]-5-methoxybenzotriazole, 2-(3′-allyl-2′-hydroxy-5′-methylphenyl)benzotriazole, 2-[3′-tert-butyl-2′-hydroxy-5′-(3″methacryloyloxypropoxy)phenyl]-5-methoxybenzotriazole, and 2-[3′-tert-butyl-2′-hydroxy-5′-(3″-methacryloyloxypropoxy)phenyl]-5-chlorobenzotriazole wherein beta-(4-benzotriazoyl-3-hydroxyphenoxy)ethyl acrylate is the preferred ultraviolet light absorber.

[0022] The subject hydrogel polymeric materials having a refractive index of approximately 1.30 or greater in the hydrated state as measured by an Abbe refractometer at 589 nm and 37 degrees Celsius with a sodium light source, and approximately 60 percent or greater, but preferably 65 to 90 percent and most preferably 70 to 80 percent water content by weight are described in still greater detail in the examples that follow.

EXAMPLE 1

Preparation of Acrylic-based Cast Molded Film (Sample 1)

[0023] HEMA (98 weight percent) and methacrylic acid (MM) (2 weight percent) were combined in flasks. Enough EGDMA crosslinker was added to comprise 0.16 weight percent of total weight of HEMA and MM. Darocur™ 1173 initiator was added to equal 0.5 weight percent of the total weight of monomers. The solution was cast in films by pouring the solution onto plates and exposing the same to ultraviolet radiation for two hours under nitrogen. Following ultraviolet radiation exposure, the films were annealed at 115° Celsius for fifteen minutes and then slowly cooled. Films having a thickness of approximately 560 μm were obtained. Discs or lenticules were then cut from the films for study.

EXAMPLE 2

Preparation of Acrylic-based Cast Molded Film (Sample 2)

[0024] HEMA (96 weight percent) and methacrylic acid (MM) (4 weight percent) were combined in flasks. Darocur™ 1173 initiator was added to equal 0.5 weight percent of the total weight of monomers. The solution was cast in films by pouring the solution onto plates and exposing the same to ultraviolet radiation for two hours under nitrogen. Following ultraviolet radiation exposure, the films were annealed at 115° Celsius for fifteen minutes and then slowly cooled. Films having a thickness of approximately 560 μm were obtained. Discs or lenticules were then cut from the films for study.

EXAMPLE 3

Ablation Study of Acrylic-based Cast Molded Films

[0025] A Visx™ excimer laser (Visx, Incorporated, Santa Clara, Calif.) was used to do three phototherapeutic keratectomy (PTK) ablations of 25, 50 and 100 μm depths at usual clinical settings of 160 mJ and 10 Hz on sample discs or lenticules from Example 1 and Example 2 above, hereinafter referred to as Sample 1 and Sample 2, respectively. Prior to ablating the hydrated samples, Samples 1 and 2 were blotted to remove any excess surface moisture present from storage. Following ablation, Samples 1 and 2 were packaged in 5 ml vials with borate buffer and observed on a Nikon™ stereomicroscope (Nikon, Corporation, Japan) with a Nikon™ 950 digital camera and a SmartScope™/ROI microscope (Optical Gaging Products, Inc., Rochester, N. Y.). Pictures and dimensions were taken. The ablation depths were measured on the SmartScope™/ROI microscope at ×132 magnification under bright field conditions.

[0026] Ablation rates as a ratio of the measured ablation depth versus the intended ablation depth were measured for Samples 1 and 2. The ablation data is summarized in Table 1 below.

1TABLE 1Ablation Data SummarySampleWater ContentMeasured vs.Avg. Depth PTK @Number(%)Intended Depth25 μm50 μm100 μm173.14.01/1121 ± 5224 ± 5422 ± 10282.34.62/1141 ± 5256 ± 5488 ± 10

[0027] The ablation data of Table 1 is likewise depicted in the graphs of Charts 1 and 2 below.

[0028] Upon observation of Samples 1 and 2, the ablation areas were clear with no signs of cracks or haze in both dark and bright field conditions. The unablated material however showed some haze when observed under dark field conditions. The ablation areas featured some striae and scattered vacuole-like features at 50 μm, and more noticeably at 100 μm, but not to a degree to cause a deleterious effect on vision. The cross-sectioned surfaces were rough at 100 μm but remained smooth at 25 and 50 μm when observed at ×20 magnification. The cross-sectioned surface of Sample 2 looked slightly smoother with less striation and deeper ablation than that of Sample 1 at 100 μm of intended ablation, possibly due to its higher water content.

[0029] PAIs manufactured using the hydrogel polymeric materials of the present invention are preferably of a round or oval design capable of being placed on the cornea of an eye under a cornea tissue flap made by a microkeratome or like surgical devices, or by like surgical methods known to those skilled in the art of ophthalmology. PAIs of the present invention are manufactured by selecting the desired hydrogel polymeric material and cast molding the material using techniques known to those skilled in the art or casting the material as a film or rod. If cast as a film or rod, the material film or rod is then lathed or machined into a round or oval PAI. The PAIs once manufactured are cleaned, polished, optionally hydrated, packaged and sterilized by customary methods known to those skilled in the art.

[0030] While there is shown and described herein certain specific compositions useful for purposes of manufacturing PAIs of the present invention it will be manifest to those skilled in the art that various modifications may be made without departing from the spirit and scope of the underlying inventive concept and that the same is not limited to particular compositions and methods herein described except insofar as indicated by the scope of the appended claims.

Claims

1. A hydrogel polymeric material suitable for use as a photoablatable corneal inlay comprising: one or more hydrophilic monomers; an optional crosslinker; and an initiator to form a hydrogel polymeric material with a water content of 60 percent by weight or greater and shows no cracking or haze upon clinical photoablation.
2. The hydrogel polymeric material of claim 1 wherein said material includes an ultraviolet light absorbing material.
3. The hydrogel polymeric material of claim 1 wherein said composition includes an ultraviolet light absorbing material selected from the group consisting of beta-(4-benzotriazoyl-3-hydroxyphenoxy)ethyl acrylate, 4-(2-acryloxyethoxy)-2-hydroxybenzophenone, 4-methacryloxy-2-hydroxybenzophenone, 2-(2′-methacryloxy-5′-methylphenyl)benzotriazole, 2-(2′-hydroxy-5′-methacryoxyethylphenyl)-2H-benzotriazole, 2-[3′-tert-butyl-2′-hydroxy-5′-(3″-methacyloyloxypropyl)phenyl]-5-chlorobenzotriazole, 2-(3′-tert-butyl-5′-(3-dimethylvinylsilylpropoxy)-2′-hydroxyphenyl]-5-methoxybenzotriazole, 2-(3′-allyl-2′-hydroxy-5′-methylphenyl)benzotriazole, 2-[3′-tert-butyl-2′-hydroxy-5′-(3″-methacryloyloxypropoxy)phenyl]-5-methoxybenzotriazole and 2-[3′-tert-butyl-2′-hydroxy-5′-(3″-methacryloyloxypropoxy)phenyl]-5-chlorobenzotriazole.
4. The hydrogel polymeric material of claim 1 wherein said composition includes beta-(4-benzotriazoyl-3-hydroxyphenoxy)-ethyl acrylate as an ultraviolet light absorbing material.
5. The hydrogel polymeric material of claim 1 wherein said initiator is selected from the group consisting of azobis(isobutyronitrile), 2,2′-azobis(2,4-dimethylvaleronitrile), 2,2′-azobis(methylbutyronitrile), 1,1′-azobis(cyanocyclohexane), di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, t-butylperoxyneodecanote, t-butyl peroxy 2-ethylhexanoate, di(4-t-butyl cyclohexyl) peroxydicarbonate, t-butyl peroxypivalate, decanoyl peroxide, lauroyl peroxide, acetyl peroxide, stearoyl peroxide, benzoyl peroxide, 2,4-pentanedione peroxide, di(n-propyl)peroxydicarbonate, peroxydicarbonate, t-amyl peroxyneodecanoate, t-butyl peroxyacetate, benzoin methyl ether, benzoin ethyl ether, Darocur™ 1173, 1164, 2273, 1116, 2959 and 3331 and Irgacur™ 651 and 184.
6. The hydrogel polymeric material of claim 1 wherein said initiator is azobis(isobutyronitrile).
7. The hydrogel polymeric material of claim 1 wherein said crosslinker is selected from the group consisting of ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate and poly(ethylene glycol) dimethacrylate.
8. The hydrogel polymeric material of claim 1 wherein said crosslinker is ethylene glycol dimethacrylate.
9. The hydrogel polymeric material of claim 1 wherein at least one of said hydrophilic monomers is selected from the group consisting of 2-hydroxyethyl methacrylate, hydroxyethoxyethyl methacrylate, hydroxydiethoxyethyl methacrylate, methoxyethyl methacrylate, methoxyethoxyethyl methacrylate, methoxydiethoxyethyl methacrylate, poly(ethylene glycol) methacrylate, methoxy-poly(ethylene glycol) methacrylate, methacrylic acid, sodium methacrylate, glycerol methacrylate, hydroxypropyl methacrylate, N-vinylpyrrolidione, hydroxypropyl methacrylamide, N,N-dimethylacrylamide, N-methylacrylamide and hydroxybutyl methacrylate.
10. The hydrogel polymeric material of claim 1 wherein at least one of said hydrophilic monomers is 2-hydroxyethyl methacrylate or methacrylic acid.
11. A photoablatable cornea inlay manufactured from a composition comprising: one or more hydrophilic monomers; an optional crosslinker; and an initiator to form a composition with a water content of approximately 60 percent or greater by weight that shows no cracking or haze upon clinical photoablation.
12. The inlay of claim 11 wherein said composition includes an ultraviolet light absorbing material.
13. The inlay of claim 11 wherein said composition includes an ultraviolet light absorbing material selected from the group consisting of beta-(4-benzotriazoyl-3-hydroxyphenoxy)ethyl acrylate, 4-(2-acryloxyethoxy)-2-hydroxybenzophenone, 4-methacryloxy-2-hydroxybenzophenone, 2-(2′-methacryloxy-5′-methylphenyl)benzotriazole, 2-(2′-hydroxy-5′-methacryoxyethylphenyl)-2H-benzotriazole, 2-[3′-tert-butyl-2′-hydroxy-5′-(3″-methacyloyloxypropyl)phenyl]-5-chlorobenzotriazole, 2-(3′-tert-butyl-5′-(3-dimethylvinylsilylpropoxy)-2′-hydroxyphenyl]-5-methoxybenzotriazole, 2-(3′-allyl-2′-hydroxy-5′-methylphenyl)benzotriazole, 2-[3′-tert-butyl-2′-hydroxy-5′-(3″-methacryloyloxypropoxy)phenyl]-5-methoxybenzotriazole and 2-[3′-tert-butyl-2′-hydroxy-5′-(3″-methacryloyloxypropoxy)phenyl]-5-chlorobenzotriazole.
14. The inlay of claim 11 wherein said composition includes beta-(4-benzotriazoyl-3-hydroxyphenoxy)-ethyl acrylate as an ultraviolet light absorbing material.
15. The inlay of claim 11 wherein said initiator is selected from the group consisting of azobis(isobutyronitrile), 2,2′-azobis(2,4-dimethylvaleronitrile), 2,2′-azobis(methylbutyronitrile), 1,1′-azobis(cyanocyclohexane), di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 2, 5-dimethyl-2, 5-bis(2-ethylhexanoylperoxy)hexane, t-butylperoxyneodecanote, t-butyl peroxy 2-ethylhexanoate, di(4-t-butyl cyclohexyl) peroxydicarbonate, t-butyl peroxypivalate, decanoyl peroxide, lauroyl peroxide, acetyl peroxide, stearoyl peroxide, benzoyl peroxide, 2,4-pentanedione peroxide, di(n-propyl)peroxydicarbonate, peroxydicarbonate, t-amyl peroxyneodecanoate, t-butyl peroxyacetate, benzoin methyl ether, benzoin ethyl ether, Darocur™ 1173, 1164, 2273, 1116, 2959 and 3331 and Irgacur™ 651 and 184.
16. The inlay of claim 11 wherein said initiator is azobis(isobutyronitrile).
17. The inlay of claim 11 wherein said crosslinker is selected from the group consisting of ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate and poly(ethylene glycol) dimethacrylate.
18. The inlay of claim 11 wherein said crosslinker is ethylene glycol dimethacrylate.
19 The inlay of claim 11 wherein at least one of said hydrophilic monomers is selected from the group consisting of 2-hydroxyethyl methacrylate, hydroxyethoxyethyl methacrylate, hydroxydiethoxyethyl methacrylate, methoxyethyl methacrylate, methoxyethoxyethyl methacrylate, methoxydiethoxyethyl methacrylate, poly(ethylene glycol) methacrylate, methoxy-poly(ethylene glycol) methacrylate, methacrylic acid, sodium methacrylate, glycerol methacrylate, hydroxypropyl methacrylate, N-vinylpyrrolidione, hydroxypropyl methacrylamide, N,N-dimethylacrylamide, N-methylacrylamide and hydroxybutyl methacrylate.
20. The inlay of claim 11 wherein said hydrophilic monomer is 2-hydroxyethyl methacrylate or methacrylic acid.
21. A method of making a photoablatable corneal inlay from a hydrogel polymeric material comprising: lathing or machining a hydrogel polymeric material sheet or rod polymerized from polymerization materials including at least one hydrophilic monomers, an initiator and an optional crosslinker, to form a round or oval inlay with a water content of 60 percent by weight or greater that shows no cracking or haze upon clinical photoablation.
22. A method of making a photoablatable corneal inlay from a hydrogel polymeric material comprising: cast molding in the form of a disc or lenticule a hydrogel polymeric material polymerized from polymerization materials including at least one hydrophilic monomers, an initiator and an optional crosslinker, to form a round or oval inlay with a water content of 60 percent by weight or greater that shows no cracking or haze upon clinical photoablation.
23. The method of claim 21 or 22 wherein said polymerization materials include an ultraviolet light absorbing material.
24. The method of claim 21 or 22 wherein said polymerization materials include an ultraviolet light absorbing material selected from the group consisting of beta-(4-benzotriazoyl-3-hydroxyphenoxy)ethyl acrylate, 4-(2-acryloxyethoxy)-2-hydroxybenzophenone, 4-methacryloxy-2-hydroxybenzophenone, 2-(2′-methacryloxy-5′-methylphenyl)benzotriazole, 2-(2′-hydroxy-5′-methacryoxyethylphenyl)-2H-benzotriazole, 2-[3′-tert-butyl-2′-hydroxy-5′-(3″-methacyloyloxypropyl)phenyl]-5-chlorobenzotriazole, 2-(3′-tert-butyl-5′-(3-dimethylvinylsilylpropoxy)-2′-hydroxyphenyl]-5-methoxybenzotriazole, 2-(3′-allyl-2′-hydroxy-5′-methylphenyl)benzotriazole, 2-[3′-tert-butyl-2′-hydroxy-5′-(3″-methacryloyloxypropoxy)phenyl]-5-methoxybenzotriazole and 2-[3′-tert-butyl-2′-hydroxy-5′-(3″-methacryloyloxypropoxy)phenyl]-5-chlorobenzotriazole.
25. The method of claim 21 or 22 wherein said polymerization materials include beta-(4-benzotriazoyl-3-hydroxyphenoxy)-ethyl acrylate as an ultraviolet light absorbing material.
26. The method of claim 21 or 22 wherein said initiator is selected from the group consisting of azobis(isobutyronitrile), 2,2′-azobis(2,4-dimethylvaleronitrile), 2,2′-azobis(methylbutyronitrile), 1,1′-azobis(cyanocyclohexane), di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, t-butylperoxyneodecanote, t-butyl peroxy 2-ethylhexanoate, di(4-t-butyl cyclohexyl) peroxydicarbonate, t-butyl peroxypivalate, decanoyl peroxide, lauroyl peroxide, acetyl peroxide, stearoyl peroxide, benzoyl peroxide, 2,4-pentanedione peroxide, di(n-propyl)peroxydicarbonate, peroxydicarbonate, t-amyl peroxyneodecanoate, t-butyl peroxyacetate, benzoin methyl ether, benzoin ethyl ether, Darocur™ 1173, 1164, 2273, 1116, 2959 and 3331 and Irgacur™ 651 and 184.
27. The method of claim 21 or 22 wherein said initiator is azobis(isobutyronitrile).
28. The method of claim 21 or 22 wherein said crosslinker is selected from the group consisting of ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate and poly(ethylene glycol) dimethacrylate.
29. The method of claim 21 or 22 wherein said crosslinker is ethylene glycol dimethacrylate.
30. The method of claim 21 or 22 wherein at least one of said hydrophilic monomers is selected from the group consisting of 2-hydroxyethyl methacrylate, hydroxyethoxyethyl methacrylate, hydroxydiethoxyethyl methacrylate, methoxyethyl methacrylate, methoxyethoxyethyl methacrylate, methoxydiethoxyethyl methacrylate, poly(ethylene glycol) methacrylate, methoxy-poly(ethylene glycol) methacrylate, methacrylic acid, sodium methacrylate, glycerol methacrylate, hydroxypropyl methacrylate, N-vinylpyrrolidione, hydroxypropyl methacrylamide, N,N-dimethylacrylamide, N-methylacrylamide and hydroxybutyl methacrylate.
31. The method of claim 21 or 22 wherein at least one of said hydrophilic monomers is 2-hydroxyethyl methacrylate or methacrylic acid.
32. A method of using a photoablatable corneal inlay manufactured from a hydrogel polymeric material polymerized from polymerization materials including one or more hydrophilic monomers, an initiator and an optional crosslinker, having a water content of approximately 60 percent by weight or greater, comprising: placing said photoablatable inlay on cornea tissue within an eye under lifted tissue flap; and ablating said photoablatable inlay prior to covering the same with said lifted tissue flap.
33. The method of claim 32 wherein said polymerization materials include an ultraviolet light absorbing material.
34. The method of claim 32 wherein said polymerization materials include an ultraviolet light absorbing material selected from the group consisting of beta-(4-benzotriazoyl-3-hydroxyphenoxy)ethyl acrylate, 4-(2-acryloxyethoxy)-2-hydroxybenzophenone, 4-methacryloxy-2-hydroxybenzophenone, 2-(2′-methacryloxy-5′-methylphenyl)benzotriazole, 2-(2′-hydroxy-5′-methacryoxyethylphenyl)-2H-benzotriazole, 2-[3′-tert-butyl-2′-hydroxy-5′-(3″-methacyloyloxypropyl)phenyl]-5-chlorobenzotriazole, 2-(3′-tert-butyl-5′-(3-dimethylvinylsilylpropoxy)-2′-hydroxyphenyl]-5-methoxybenzotriazole, 2-(3′-allyl-2′-hydroxy-5′-methylphenyl)benzotriazole, 2-[3′-tert-butyl-2′-hydroxy-5′-(3″-methacryloyloxypropoxy)phenyl]-5-methoxybenzotriazole and 2-[3′-tert-butyl-2′-hydroxy-5′-(3″-methacryloyloxypropoxy)phenyl]-5-chlorobenzotriazole.
35. The method of claim 32 wherein said polymerization materials include beta-(4-benzotriazoyl-3-hydroxyphenoxy)-ethyl acrylate as an ultraviolet light absorbing material.
36. The method of claim 32 wherein said initiator is selected from the group consisting of azobis(isobutyronitrile), 2,2′-azobis(2,4-dimethylvaleronitrile), 2,2′-azobis(methylbutyronitrile), 1,1′-azobis(cyanocyclohexane), di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, t-butylperoxyneodecanote, t-butyl peroxy 2-ethylhexanoate, di(4-t-butyl cyclohexyl) peroxydicarbonate, t-butyl peroxypivalate, decanoyl peroxide, lauroyl peroxide, acetyl peroxide, stearoyl peroxide, benzoyl peroxide, 2,4-pentanedione peroxide, di(n-propyl)peroxydicarbonate, peroxydicarbonate, t-amyl peroxyneodecanoate, t-butyl peroxyacetate, benzoin methyl ether, benzoin ethyl ether, Darocur™ 1173, 1164, 2273, 1116, 2959 and 3331 and Irgacur™ 651 and 184.
37. The method of claim 32 wherein said initiator is azobis(isobutyronitrile).
38. The method of claim 32 wherein said crosslinker is selected from the group consisting of ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate and poly(ethylene glycol) dimethacrylate.
39. The method of claim 32 wherein said crosslinker is ethylene glycol dimethacrylate.
40. The method of claim 32 wherein at least one of said hydrophilic monomers is selected from the group consisting of 2-hydroxyethyl methacrylate, hydroxyethoxyethyl methacrylate, hydroxydiethoxyethyl methacrylate, methoxyethyl methacrylate, methoxyethoxyethyl methacrylate, methoxydiethoxyethyl methacrylate, poly(ethylene glycol) methacrylate, methoxy-poly(ethylene glycol) methacrylate, methacrylic acid, sodium methacrylate, glycerol methacrylate, hydroxypropyl methacrylate, N-vinylpyrrolidione, hydroxypropyl methacrylamide, N,N-dimethylacrylamide, N-methylacrylamide and hydroxybutyl methacrylate.
41. The method of claim 32 wherein said hydrophilic monomer is 2-hydroxyethyl methacrylate or methacrylic acid.

Polymeric materials for use as photoablatable inlays

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