US20060050228A1 - Method for stabilizing refractive index profiles using polymer mixtures - Google Patents

Method for stabilizing refractive index profiles using polymer mixtures Download PDF

Info

Publication number
US20060050228A1
US20060050228A1 US10/935,799 US93579904A US2006050228A1 US 20060050228 A1 US20060050228 A1 US 20060050228A1 US 93579904 A US93579904 A US 93579904A US 2006050228 A1 US2006050228 A1 US 2006050228A1
Authority
US
United States
Prior art keywords
polymer
monomer
refractive index
polymerizing
optical
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US10/935,799
Inventor
Shui Lai
Donald Bruns
Lawrence Sverdrup
Gomaa Abdel-Sadek
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ophthonix Inc
Original Assignee
Ophthonix Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ophthonix Inc filed Critical Ophthonix Inc
Priority to US10/935,799 priority Critical patent/US20060050228A1/en
Assigned to OPHTHONIX, INC. reassignment OPHTHONIX, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ABDEL-SADEK, GOMAA G., BRUNS, DONALD G., SVERDRUP, LAWRENCE H., LAI, SHUI T.
Priority to AU2005282382A priority patent/AU2005282382A1/en
Priority to KR1020077007484A priority patent/KR20070057905A/en
Priority to EP05798022A priority patent/EP1792226A2/en
Priority to JP2007530496A priority patent/JP2008512704A/en
Priority to PCT/US2005/031973 priority patent/WO2006029260A2/en
Publication of US20060050228A1 publication Critical patent/US20060050228A1/en
Priority to IL181309A priority patent/IL181309A0/en
Assigned to COMERICA BANK reassignment COMERICA BANK SECURITY AGREEMENT Assignors: OPHTHONIX, INC.
Priority to US12/361,498 priority patent/US7772297B2/en
Priority to US12/854,061 priority patent/US8034262B2/en
Assigned to COMERICA BANK reassignment COMERICA BANK SECURITY AGREEMENT Assignors: OPHTHONIX, INC.
Abandoned legal-status Critical Current

Links

Images

Classifications

    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/041Lenses
    • GPHYSICS
    • G02OPTICS
    • G02CSPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
    • G02C7/00Optical parts
    • G02C7/02Lenses; Lens systems ; Methods of designing lenses
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29DPRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00Producing optical elements, e.g. lenses or prisms
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29DPRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00Producing optical elements, e.g. lenses or prisms
    • B29D11/00009Production of simple or compound lenses

Definitions

  • This invention relates generally to optical elements, such as corrective lenses, and to methods for making them. More particularly, this invention relates to optical elements containing two or more polymers.
  • corrections to an optical system to minimize one type of aberration may result in the increase in one of the other aberrations.
  • decreasing coma can result in increasing spherical aberrations.
  • U.S. patent application Ser. No. 09/875,447, filed Jun. 4, 2001, entitled “Wavefront Aberrator and Method of Manufacturing,” discloses, inter alia, a method for making a wavefront aberrator by using a photopolymerization method to change the refractive index of a polymer.
  • a refractive index profile may be formed by selectively curing the polymer on a region-by-region basis by exposure to radiation (e.g., UV light). The refractive index of the exposed polymer in the selected regions increases, but the resulting refractive index profile is not permanent, and over time, the refractive index profile changes and the amplitude of the induced refractive index change tends to decrease over time.
  • a preferred embodiment provides an optical element comprising a first optical cover, a second optical cover, and a layer of polymeric material sandwiched between the first optical cover and the second optical cover, wherein the polymeric material comprises a mixture of a first polymer and a second polymer, the first polymer having a spatially varying degree of cure that provides a predetermined refractive index profile, and the second polymer being cured to thereby stabilize the refractive index profile.
  • Another preferred embodiment provides a method for making an optical element, comprising:
  • Another preferred embodiment provides a method for making an ophthalmic lens, comprising:
  • FIGS. 1A and 1B are cross-sectional views schematically illustrating a preferred optical element.
  • FIG. 1C is a cross-section view schematically illustrating selective polymerization to form a polymer having a spatially varying degree of cure that provides a predetermined refractive index profile.
  • FIG. 1D is a plot schematically illustrating the refractive index profile resulting from the selective polymerization illustrated in FIG. 1C .
  • FIG. 2 is a flow chart illustrating a preferred method for making an optical element.
  • FIG. 3 is a schematic diagram illustrating aberrations in a wavefront.
  • FIG. 4 is a schematic diagram illustrating an index of refraction profile for a preferred lens that compensates for the aberrations shown in FIG. 3 .
  • FIG. 1 illustrates a preferred optical element 10 .
  • the optical element 10 includes a first rigid or flexible optical cover 12 which may be a transparent plate, a second rigid or flexible optical cover 14 which may be a transparent plate, and a layer of polymeric material 16 sandwiched between the first and second optical covers 12 , 14 .
  • a barrier 18 may be used to contain the polymeric material 16 between the first and second plates 12 , 14 prior to, and following, the curing described below.
  • one or both of the first and second covers 12 , 14 may comprise a curved surface which may exhibit a pre-existing refractive power.
  • first and second covers 12 , 14 may each individually be ophthalmic lenses, e.g., a single vision lens, bifocal lens, or progressive addition lens, all of which may or may not include prism power.
  • both of the first and second plates 12 , 14 may be planar lenses having curved surfaces and without refractive power.
  • the polymeric material 16 is preferably made by polymerizing at least two curable constituents such as two monomers 20 , 22 with respective polymerization initiators as illustrated in FIG. 1B .
  • the refractive index of each of the two monomers 20 , 22 changes during polymerization (“curing”) to form the polymeric material 16 .
  • Curing is preferably conducted by exposing the two monomers 20 , 22 to a radiation source, such that the degree of curing varies between locations within the polymeric material 16 , as described in greater detail below.
  • the index of refraction profile is determined by the degree of curing or polymerization of the two monomers.
  • the first monomer 20 is preferably polymerized to form a first polymer having a spatially varying degree of cure that provides a predetermined refractive index profile
  • the second monomer 22 is preferably uniformly polymerized or cured to form a second polymer, thereby stabilizing the first polymer and the refractive index profile.
  • the polymeric material 16 thus comprises a mixture of the first polymer and the second polymer.
  • the two monomers 20 , 22 each cure by exposure to different wavelengths of light.
  • the first monomer 20 can cure by exposure to relatively long ultraviolet wavelength light (e.g., “UVA”) and the second monomer 22 can cure by exposure to relatively short ultraviolet wavelength light (e.g., “UVB”).
  • the first monomer 20 can be, e.g., an acrylate or vinyl ether
  • the second monomer 22 can be, e.g., a vinyl ether or an epoxy.
  • Combinations of first and second monomers can include acrylates and epoxies, thiol-enes and esters, thiol-enes and epoxies, acrylates and vinyl ethers, and vinyl ethers and epoxies.
  • Suitable monomers include, for example, urethanes, thiol-enes, cellulose esters, mercapto-esters, and epoxies.
  • the first monomer and/or the second monomer can be a monomer system that contains two or more monomers that react with one another.
  • thiol-ene is a preferred first monomer that comprises thiol monomers and ene monomers.
  • a wide variety of thiol-ene monomers and polymers are known to those skilled in the art, see, e.g., Jacobine, A. T. in “Radiation Curing in Polymer Science and Technology: Photopolymerization Mechanisms,” Eds. J. P.
  • the first and/or second monomers are photopolymers.
  • the monomer may polymerize spontaneously upon irradiation, or, preferably, a photoinitiator may be used.
  • Suitable photoinitiators include alpha cleavage photoinitiators such as the benzoin ethers, benzil ketals, acetophenones, and phosphine oxides; hydrogen abstraction photoinitiators such as the benzophenones, thioxanthones, camphorquinones and bisimidazole; and cationic photoinitiators such as aryldiazonium salts, arylsulfonium and aryliodonium salts, and ferrocenium salts.
  • other photoinitiators such as the phenylphosphonium benzophene salts, aryl tert-butyl peresters, titanocene, or N-methylmaleimide may be used.
  • the polymerization process is controlled by the duration and intensity of the UV light exposure. More preferably, the polymerization should be substantially stopped when the UV light source is turned off. Thiol-ene polymerization systems, for example, exhibit this “step growth” characteristic.
  • FIG. 2 is a flow chart illustrating a preferred method for making the optical element 10 .
  • a light source selectively polymerizes the first monomer 20 to create a polymeric material 16 having a spatially varying degree of cure that provides a refractive index profile that approximates the refractive index profile desired for the resulting optical element 10 .
  • FIG. 1C schematically illustrates how such selective polymerization may be carried out.
  • a polymer having a spatially varying degree of cure may be formed that provides a predetermined refractive index profile as illustrated in the plot shown in FIG. 1D .
  • Suitable selective polymerization methods are disclosed in U.S. Patent Application Publication No. 2002/0080464 A1 and 2003/0143391 A1, which are hereby incorporated by reference in their entireties and particularly for the purpose of describing such methods.
  • the refractive index in a particular region can be controlled by controlling the degree of polymerization or cure in that region by selective irradiation.
  • Monomer 20 is preferably polymerized using a photoinitiator that responds to a first wavelength of light.
  • the second monomer 22 may be present during the polymerization of the first monomer 20 or may be diffused into polymeric material 16 after polymerization of the first monomer 20 . If present during the polymerization of the first monomer 20 , second monomer 22 preferably undergoes little or no polymerization during the polymerization of the first monomer 20 .
  • the exposure to the first wavelength of light is terminated, ceasing the curing of the first monomer 20 , thereby ceasing the change of the index of refraction.
  • the refractive index profile of the optical element 10 at this stage approximates the desired refractive index profile. For example, as shown in FIG. 1C , the amount of first polymer 40 in the region of optical element 10 exposed to lower amounts of radiation 35 is less than in the regions exposed to greater amounts of radiation 30 , 38 .
  • the spatially varying refractive index profile illustrated in the plot shown in FIG. 1D reflects the respective amounts of first polymer 40 in each region.
  • the refractive index profile at various points 42 , 44 , 46 generally corresponds with the intensity of incident radiation 35 , 30 , 38 (respectively).
  • a light source is activated to irradiate the material 16 with a second wavelength of light that, preferably, substantially completely and uniformly cures the second monomer 22 .
  • An excess of light may be used in block 28 to ensure complete polymerization.
  • less than 100% curing of the second monomer can also be effective to stabilize the index profile.
  • the polymeric material 16 has a viscosity value of greater than about 20,000 centipoise prior to polymerization of the second monomer 22 , a degree of cure of about 40% for the second monomer may be sufficient.
  • the higher the viscosity of the polymeric material 16 the lower the degree of curing of the second monomer 22 required to stabilize the refractive index profile.
  • the amount of the second monomer is about 15% or more by weight in relation to the first monomer, so that when the second polymer component is substantially completely cured, it forms a locking network throughout the entire polymer mixture and renders the first monomer/polymer component substantially immobile.
  • a preferred embodiment for making the polymer mixture 16 involves the use of a relatively low molecular weight first monomer that contains relatively few (preferably three or four) polymerizable functional groups per monomer molecule.
  • a preferred first monomer mixture may comprise thiol-ene, more preferably a thiol-ene comprising a thiol that contains three or four-SH groupss per molecule, and an ene that contains three or four carbon-carbon double bonds per molecule.
  • monomers are preferably chosen to increase the dynamic range of the index of refraction change, or the delta-N value.
  • the second monomer (which may be a mixture of monomers) may comprise a macromer, e.g., a relatively low or intermediate molecular weight polymer that contains reactive groups such as an unsaturated bisphenol-A fumarate polyester (e.g., ATLAC, available commercially from Reichhold, Inc. Research Triangular Park, NC).
  • ATLAC contains approximately 40 ene groups and is soluble in acetone and in various thiol-ene mixtures.
  • the second monomer has a relatively high viscosity, as compared to the first monomer, to thereby slow the diffusion of the low molecular weight components of the first polymer.
  • use of the relatively high viscosity ATLAC as the second monomer preferably slows the diffusion of portions of the thiol-ene monomer/polymer mixture (prepared by prior polymerization of the first thiol-ene monomer) that are uncured or cured to a relatively low degree.
  • Similar macromers containing reactive functional groups can be used as a component of the second monomer.
  • Subsequent polymerization of the second monomer preferably forms a very high viscosity matrix that stabilizes the first polymer (and thereby stabilizing the refractive index profile) by slowing or preventing diffusion of the components of the first polymer, and particularly the lower molecular weight components of the first polymer (such as first monomer and oligomers thereof).
  • the degree of curing of the second monomer to form the second polymer is substantially uniform in a spatial sense, such that the degree of cure of the second polymer does not undesirably affect the intended refractive index profile.
  • the second polymer may also stabilize the first polymer by the formation of covalent bonding between them.
  • the low molecular weight thiol and ene monomers polymerize to form a denser and more compact polymer, resulting in an increase in the index of refraction.
  • the low molecular weight thiol and/or ene monomers, and/or the growing thiol-ene polymer also preferably react with the ATLAC.
  • the higher index regions formed by the thiol-ene polymerization are thus stabilized by the covalent bonding of such units to the ATLAC.
  • the low molecular weight thiol-ene units are relatively free to migrate by diffusion; hence the desired higher index of refraction regions tend to diffuse away over time, resulting in the stability problems discussed above.
  • Another method of stabilizing the refractive index profile formed by the spatially varying degree of cure is to use an entirely different type of polymer as the second component to stabilize the index profile. For example, one may first use a photo-polymerization process as described above to generate the desired index of refraction profile, then instead of using a second monomer that is cured by UV light to form a second polymer that provides increased stability, one can use a second monomer that is cured by heating as illustrated in block 28 in FIG. 2 .
  • One such example is an epoxy which is thermally curable, e.g., instead of ATLAC in the embodiment discussed above, a thermally curable epoxy is used instead.
  • the steps used to form the desired index of refraction profile remain essentially the same, then heat is applied to cure the epoxy, thereby stabilizing the first polymer in an epoxy matrix.
  • One embodiment is to choose an epoxy that cures at relatively low (e.g., below 80° C.) or close to room temperature.
  • the thiol, ene, and epoxy is then kept near or below room temperature to prevent the curing of the epoxy.
  • the index profile may then be created by activating the photo-initiator that induces the thiol-ene polymerization.
  • the system is warmed up slightly to reach the epoxy curing temperature, polymerizing the epoxy turns and freezing-in the thiol-ene polymer to thereby stabilize the index of refraction profile.
  • Another embodiment is a method of stabilizing the index of refraction profile by curing thermally. Once the index of refraction profile is written in the polymer mixture, it is preferable to avoid degrading the index profile. Heating the epoxy could potentially degrade the profile.
  • One method of minimizing that risk is to perform the epoxy curing in two steps: First, the second polymer in the mixture is allowed to gel (partially polymerize) at room temperature after the writing of the index profile in the polymer, and then the temperature is raised, e.g., to about 60° C. to 85° C., to complete the full curing process.
  • the gel state provides a high viscosity environment around the index profile and thereby decreases the diffusion rate of the first polymer, e.g., the photo-polymerized thiol-ene polymer.
  • the complete curing at elevated temperature stabilizes the index profile.
  • FIG. 3 illustrate how the desired refractive index profile can be determined.
  • the first monomer 20 (which may be a mixture of monomers) is partially cured in a manner that varies spatially to achieve the desired refractive index profile, and that the curing of the second monomer 22 (which may also be a mixture of monomers) may change the refractivity somewhat.
  • an overall profile is obtained that is the combination of the desired refractivity index distribution resulting from selective polymerization of the first monomer 20 and the added change in refractivity over the entire material 16 that results from the curing of the second monomer 22 .
  • FIG. 3 A schematic illustration of a wavefront 30 is shown in FIG. 3 , showing a divergent wave which may consist of spherical, astigmatism and high order aberrations.
  • the higher order aberrations are typically describable by third and higher order terms of Zernicke polynomials.
  • the wavefront has intersections located at points 34 , 36 , 38 , 40 .
  • the peak of the wavefront is indicated at 42 , which is traveling ahead of the intersections 34 , 36 , 38 , 40 .
  • the distance between the peak 42 and the intersections is typically expressed in the units of physical distance in space.
  • the peak 42 has a projected point 44 on the plane 32 .
  • the desired refractive index profile for a portion of the material 16 is one that exhibits, after curing, an index of refraction that results in the conjugate of the wavefront 30 such that a plane wave exits the optical element 10 .
  • An illustrative curing profile is shown in FIG. 4 , which has a three dimensional distribution profile 46 that is essentially identical to that of the profile of the wave 30 shown in FIG. 3 .
  • the retardation required for compensation can be calculated as follows.
  • the difference of the index of refraction, ⁇ n between cured and uncured material 16 is typically in the range of 0.001 to 0.05 and may be determined by routine experimentation.
  • the retardation is the physical distance “d” between the wave peak 42 , and its projection point 44 on the plane 32 .
  • the thickness of the material 16 consequently is at least d/ ⁇ n.
  • the scale of the magnitude of the retardation is such that the magnitude of thickness of the cured material or the integrated index difference at a profile peak 46 to its projection 48 on a cross-sectional plane 50 is d/ ⁇ n.
  • the effect of such a refractive index profile is that the peak 42 of the wave 30 will experience the most retardation, and the wave at the intersections 34 , 36 , 38 , 40 experiences no retardation at corresponding locations 52 , 54 , 56 , 58 of the refractive index profile in the uncured portion of the material 16 .
  • the desired refractive index profile of the material 16 after curing is such that its index of refraction establishes a profile that matches the profile of the wave for which compensation is desired.
  • the curing can be undertaken using a light source in combination with a beam shaping unit.
  • the light source with beam shaping unit creates a light beam that is substantially collimated.
  • a non-collimated beam may also be used if desired.
  • the light beam may pass through a focusing lens to form a converging, or focusing, light beam that is directed toward the optical element 10 , where the light beam passes through the first transparent plate 12 to focus on a desired volume in the material 16 .
  • This irradiates the monomer at that location, preferably activating the photoinitiator and beginning the curing process within the material 16 .
  • the curing process results in a corresponding change of the index of refraction within the material. Terminating the exposure to the light ceases the curing, thereby ceasing the change of the index of refraction.
  • the activation and power level of the light source and its position are preferably controlled by a controller which is electrically connected to the light source and to shuttling components on which the source may be mounted.
  • the converging light beam passes through the transparent plate 12 and converges within the material 16 . Specifically, the light ray edges of the beam converge at the desired focal point to cure the material 16 at the focal point. Then, the light beam is moved to another point adjacent to the just-cured point to cure the next point, and so on.
  • the details of various methods of light energy delivery by beam scanning have been disclosed in U.S. Patent Application Publication No. 2003/0143391 A1, which is hereby incorporated by reference in its entirety and particularly for the purpose of describing such methods.
  • focal point is used herein, it is to be understood that the light beam at its point of focus is not at a true “point”, which in mathematics has no volume, but rather is focused in a volume referred to as a “beam waist” which represents the region in the material 16 undergoing by exposure to the converging light beam.
  • beam waist represents the region in the material 16 undergoing by exposure to the converging light beam.
  • a beam with a cone angle that is in the range of 0.002 radians to 1.5 radians may be used.
  • the distance between curing volumes should be less than the beam waist of the light beam, creating an overlap region.
  • the size of the beam overlap region can vary in the range of about ten to about seventy five percent (10%-75%) of the size of the beam waist.
  • the size of the beam overlap region can vary in the range of about forty to about sixty percent (40%-60%) of the size of the beam waist.
  • the beam waist is in the range of twenty microns (20 ⁇ m) or less.
  • beam waists in the range of about 0.1 micron to about two hundred microns may be used. It is to be understood that the curing volumes can be sequential and contiguous to each other, or the scan sequence may be randomly accessed, such that the new curing location can be isolated from the previous location, with no overlap of the beam waists.
  • Preferred optical elements may be used to correct aberrations in optical components such as telescopes, microscopes, ophthalmic diagnostic instruments including confocal scanning ophthalmoscopes, and fundus cameras.
  • the viewing instrument generally includes refractive elements such lenses, reflective elements such as mirrors and beam splitters, and diffractive elements such as gratings and acousto- and electro-optical crystals.
  • Preferred embodiments may be used to eliminate costly manufacturing of such apparatus by using less costly optics and by compensating for the attendant residual aberrations with correcting elements such as are described above.
  • the optical element 10 shown in FIG. 1 is a correcting element configured as, for example, an ophthalmic lens, to correct aberrations caused by imperfections in a patient's eye.

Abstract

A method for making an optical element comprises polymerizing a first monomer to form a first polymer, the first polymer having a spatially varying degree of cure that provides a predetermined refractive index profile; and polymerizing a second monomer in the presence of the first polymer to form a second polymer intermixed with the first polymer, the second polymer stabilizing the first polymer and the refractive index profile.

Description

    BACKGROUND OF THE INVENTION
  • 1. Field of the Invention
  • This invention relates generally to optical elements, such as corrective lenses, and to methods for making them. More particularly, this invention relates to optical elements containing two or more polymers.
  • 2. Description of the Related Art
  • Many optical systems such as the human eye contain aberrations. In attempting to correct for such aberrations, it is common to assume that the light passing through the system is limited to paraxial rays, specifically, rays that are near the optical axis and that are contained within small angles. Corrective optics produced according to this assumption generally have only spherical surfaces. For example, it is typically assumed that ocular imperfections in the human eye are limited to lower order imperfections, including the imperfections commonly called “astigmatism” and “defocus”, that can be corrected by lenses having spherical surfaces. However, higher order imperfections can exist, including but not limited to imperfections known as “coma” and “trefoil.” These imperfections unfortunately cannot be corrected by conventional glasses or contact lenses, leaving patients with less than optimum vision even after the best available corrective lenses have been prescribed.
  • Moreover, it is often difficult to simultaneously minimize all aberrations. Indeed, corrections to an optical system to minimize one type of aberration may result in the increase in one of the other aberrations. For example, decreasing coma can result in increasing spherical aberrations. Furthermore, it is often necessary to correct aberrations in an optical system that are introduced during manufacturing. This process can be iterative and time consuming, requiring, as it does, assembly, alignment, and performance evaluation to identify aberrations, followed by disassembly, polishing or grinding to correct the aberrations, and then reassembling and retest. Several iterations might be needed before a suitable system is developed.
  • U.S. patent application Ser. No. 09/875,447, filed Jun. 4, 2001, entitled “Wavefront Aberrator and Method of Manufacturing,” discloses, inter alia, a method for making a wavefront aberrator by using a photopolymerization method to change the refractive index of a polymer. A refractive index profile may be formed by selectively curing the polymer on a region-by-region basis by exposure to radiation (e.g., UV light). The refractive index of the exposed polymer in the selected regions increases, but the resulting refractive index profile is not permanent, and over time, the refractive index profile changes and the amplitude of the induced refractive index change tends to decrease over time.
  • SUMMARY OF THE INVENTION
  • A preferred embodiment provides an optical element comprising a first optical cover, a second optical cover, and a layer of polymeric material sandwiched between the first optical cover and the second optical cover, wherein the polymeric material comprises a mixture of a first polymer and a second polymer, the first polymer having a spatially varying degree of cure that provides a predetermined refractive index profile, and the second polymer being cured to thereby stabilize the refractive index profile.
  • Another preferred embodiment provides a method for making an optical element, comprising:
  • polymerizing a first monomer to form a first polymer, the first polymer having a spatially varying degree of cure that provides a predetermined refractive index profile; and
  • polymerizing a second monomer in the presence of the first polymer to form a second polymer intermixed with the first polymer, the second polymer stabilizing the refractive index profile.
  • Another preferred embodiment provides a method for making an ophthalmic lens, comprising:
  • forming a mixture comprising a first monomer, a second monomer, a first photoinitiator, and a second photoinitiator;
  • placing the mixture between a first optical cover and a second optical cover;
  • exposing the mixture to a first radiation source, thereby polymerizing the first monomer to form a first polymer, the first polymer having a spatially varying degree of cure that provides a predetermined refractive index profile; and
  • exposing the second monomer to a second radiation source, thereby polymerizing the second monomer to form a second polymer intermixed with the first polymer
  • These and other embodiments are described in greater detail below.
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • These and other aspects of the invention will be readily apparent from the following description and from the appended drawings (not to scale), which are meant to illustrate and not to limit the invention, and wherein:
  • FIGS. 1A and 1B are cross-sectional views schematically illustrating a preferred optical element. FIG. 1C is a cross-section view schematically illustrating selective polymerization to form a polymer having a spatially varying degree of cure that provides a predetermined refractive index profile. FIG. 1D is a plot schematically illustrating the refractive index profile resulting from the selective polymerization illustrated in FIG. 1C.
  • FIG. 2 is a flow chart illustrating a preferred method for making an optical element.
  • FIG. 3 is a schematic diagram illustrating aberrations in a wavefront.
  • FIG. 4 is a schematic diagram illustrating an index of refraction profile for a preferred lens that compensates for the aberrations shown in FIG. 3.
  • DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
  • FIG. 1 illustrates a preferred optical element 10. In FIG. 1A, the optical element 10 includes a first rigid or flexible optical cover 12 which may be a transparent plate, a second rigid or flexible optical cover 14 which may be a transparent plate, and a layer of polymeric material 16 sandwiched between the first and second optical covers 12, 14. If desired, a barrier 18 may be used to contain the polymeric material 16 between the first and second plates 12, 14 prior to, and following, the curing described below. If desired, one or both of the first and second covers 12, 14 may comprise a curved surface which may exhibit a pre-existing refractive power. Thus, the first and second covers 12, 14 may each individually be ophthalmic lenses, e.g., a single vision lens, bifocal lens, or progressive addition lens, all of which may or may not include prism power. Alternatively, both of the first and second plates 12, 14 may be planar lenses having curved surfaces and without refractive power.
  • The polymeric material 16 is preferably made by polymerizing at least two curable constituents such as two monomers 20, 22 with respective polymerization initiators as illustrated in FIG. 1B. The refractive index of each of the two monomers 20, 22 changes during polymerization (“curing”) to form the polymeric material 16. Curing is preferably conducted by exposing the two monomers 20, 22 to a radiation source, such that the degree of curing varies between locations within the polymeric material 16, as described in greater detail below. The index of refraction profile is determined by the degree of curing or polymerization of the two monomers. The first monomer 20 is preferably polymerized to form a first polymer having a spatially varying degree of cure that provides a predetermined refractive index profile, and the second monomer 22 is preferably uniformly polymerized or cured to form a second polymer, thereby stabilizing the first polymer and the refractive index profile. The polymeric material 16 thus comprises a mixture of the first polymer and the second polymer. Those skilled in the art will understand that the term “polymeric material” as used herein is a broad term that encompasses various monomers and polymers, as well as monomer/monomer, monomer/polymer, and polymer/polymer mixtures.
  • In the illustrated embodiment, the two monomers 20, 22 each cure by exposure to different wavelengths of light. By way of non-limiting example, the first monomer 20 can cure by exposure to relatively long ultraviolet wavelength light (e.g., “UVA”) and the second monomer 22 can cure by exposure to relatively short ultraviolet wavelength light (e.g., “UVB”). The first monomer 20 can be, e.g., an acrylate or vinyl ether, and the second monomer 22 can be, e.g., a vinyl ether or an epoxy. Combinations of first and second monomers can include acrylates and epoxies, thiol-enes and esters, thiol-enes and epoxies, acrylates and vinyl ethers, and vinyl ethers and epoxies.
  • Other monomers that polymerize by photoinitiation may also be used. Suitable monomers include, for example, urethanes, thiol-enes, cellulose esters, mercapto-esters, and epoxies. The first monomer and/or the second monomer can be a monomer system that contains two or more monomers that react with one another. For example, thiol-ene is a preferred first monomer that comprises thiol monomers and ene monomers. A wide variety of thiol-ene monomers and polymers are known to those skilled in the art, see, e.g., Jacobine, A. T. in “Radiation Curing in Polymer Science and Technology: Photopolymerization Mechanisms,” Eds. J. P. Fouassier and J. F. Rabek, Elsevier Applied Science: London, pp. 219-268 (1993). Preferably, the first and/or second monomers are photopolymers. The monomer may polymerize spontaneously upon irradiation, or, preferably, a photoinitiator may be used. Suitable photoinitiators include alpha cleavage photoinitiators such as the benzoin ethers, benzil ketals, acetophenones, and phosphine oxides; hydrogen abstraction photoinitiators such as the benzophenones, thioxanthones, camphorquinones and bisimidazole; and cationic photoinitiators such as aryldiazonium salts, arylsulfonium and aryliodonium salts, and ferrocenium salts. Alternatively, other photoinitiators such as the phenylphosphonium benzophene salts, aryl tert-butyl peresters, titanocene, or N-methylmaleimide may be used.
  • In a preferred embodiment, the polymerization process is controlled by the duration and intensity of the UV light exposure. More preferably, the polymerization should be substantially stopped when the UV light source is turned off. Thiol-ene polymerization systems, for example, exhibit this “step growth” characteristic. FIG. 2 is a flow chart illustrating a preferred method for making the optical element 10. At block 24 a light source selectively polymerizes the first monomer 20 to create a polymeric material 16 having a spatially varying degree of cure that provides a refractive index profile that approximates the refractive index profile desired for the resulting optical element 10. FIG. 1C schematically illustrates how such selective polymerization may be carried out. By subjecting areas in which a greater degree of polymerization is desired to higher levels of irradiation (indicated by multiple arrows 30 in FIG. 1C), and subjecting areas in which a lower degree of polymerization is desired to lower and intermediate levels of irradiation (indicated by a single arrow 35 and a double arrow 38, respectively), a polymer having a spatially varying degree of cure may be formed that provides a predetermined refractive index profile as illustrated in the plot shown in FIG. 1D. Suitable selective polymerization methods are disclosed in U.S. Patent Application Publication No. 2002/0080464 A1 and 2003/0143391 A1, which are hereby incorporated by reference in their entireties and particularly for the purpose of describing such methods. Since the monomer 20 has an index of refraction that changes upon polymerization, the refractive index in a particular region can be controlled by controlling the degree of polymerization or cure in that region by selective irradiation. Monomer 20 is preferably polymerized using a photoinitiator that responds to a first wavelength of light. The second monomer 22 may be present during the polymerization of the first monomer 20 or may be diffused into polymeric material 16 after polymerization of the first monomer 20. If present during the polymerization of the first monomer 20, second monomer 22 preferably undergoes little or no polymerization during the polymerization of the first monomer 20.
  • At block 26, the exposure to the first wavelength of light is terminated, ceasing the curing of the first monomer 20, thereby ceasing the change of the index of refraction. The refractive index profile of the optical element 10 at this stage approximates the desired refractive index profile. For example, as shown in FIG. 1C, the amount of first polymer 40 in the region of optical element 10 exposed to lower amounts of radiation 35 is less than in the regions exposed to greater amounts of radiation 30, 38. The spatially varying refractive index profile illustrated in the plot shown in FIG. 1D reflects the respective amounts of first polymer 40 in each region. Thus, by spatially varying the degree of cure of the first polymer 40, the refractive index profile at various points 42, 44, 46 generally corresponds with the intensity of incident radiation 35, 30, 38 (respectively). Then, at block 28 a light source is activated to irradiate the material 16 with a second wavelength of light that, preferably, substantially completely and uniformly cures the second monomer 22. An excess of light may be used in block 28 to ensure complete polymerization. However, less than 100% curing of the second monomer can also be effective to stabilize the index profile. For example, when the polymeric material 16 has a viscosity value of greater than about 20,000 centipoise prior to polymerization of the second monomer 22, a degree of cure of about 40% for the second monomer may be sufficient. In general, the higher the viscosity of the polymeric material 16, the lower the degree of curing of the second monomer 22 required to stabilize the refractive index profile. Preferably, the amount of the second monomer is about 15% or more by weight in relation to the first monomer, so that when the second polymer component is substantially completely cured, it forms a locking network throughout the entire polymer mixture and renders the first monomer/polymer component substantially immobile.
  • A preferred embodiment for making the polymer mixture 16 involves the use of a relatively low molecular weight first monomer that contains relatively few (preferably three or four) polymerizable functional groups per monomer molecule. For example, a preferred first monomer mixture may comprise thiol-ene, more preferably a thiol-ene comprising a thiol that contains three or four-SH groupss per molecule, and an ene that contains three or four carbon-carbon double bonds per molecule. Those skilled in the art are aware of additional examples, see Jacobine, A. T., in “Radiation Curing in Polymer Science and Technology: Photopolymerization Mechanisms,” Eds. J. P. Fouassier and J. F. Rabek, Elsevier Applied Science: London, pp. 219-268 (1993). By using relatively low molecular weight first monomers, the magnitude of the refractive index change due to volume shrinkage or densification is maximized. Thus, monomers are preferably chosen to increase the dynamic range of the index of refraction change, or the delta-N value.
  • The second monomer (which may be a mixture of monomers) may comprise a macromer, e.g., a relatively low or intermediate molecular weight polymer that contains reactive groups such as an unsaturated bisphenol-A fumarate polyester (e.g., ATLAC, available commercially from Reichhold, Inc. Research Triangular Park, NC). A preferred ATLAC contains approximately 40 ene groups and is soluble in acetone and in various thiol-ene mixtures. Preferably, the second monomer has a relatively high viscosity, as compared to the first monomer, to thereby slow the diffusion of the low molecular weight components of the first polymer. For example, in a preferred thiol-ene/ATLAC combination, use of the relatively high viscosity ATLAC as the second monomer preferably slows the diffusion of portions of the thiol-ene monomer/polymer mixture (prepared by prior polymerization of the first thiol-ene monomer) that are uncured or cured to a relatively low degree. Similar macromers containing reactive functional groups can be used as a component of the second monomer. Subsequent polymerization of the second monomer preferably forms a very high viscosity matrix that stabilizes the first polymer (and thereby stabilizing the refractive index profile) by slowing or preventing diffusion of the components of the first polymer, and particularly the lower molecular weight components of the first polymer (such as first monomer and oligomers thereof). Preferably, the degree of curing of the second monomer to form the second polymer is substantially uniform in a spatial sense, such that the degree of cure of the second polymer does not undesirably affect the intended refractive index profile.
  • The second polymer may also stabilize the first polymer by the formation of covalent bonding between them. For example, in preferred thiol-ene/ATLAC systems, upon photo-polymerization, the low molecular weight thiol and ene monomers polymerize to form a denser and more compact polymer, resulting in an increase in the index of refraction. The low molecular weight thiol and/or ene monomers, and/or the growing thiol-ene polymer, also preferably react with the ATLAC. The higher index regions formed by the thiol-ene polymerization are thus stabilized by the covalent bonding of such units to the ATLAC. Without the ATLAC, the low molecular weight thiol-ene units are relatively free to migrate by diffusion; hence the desired higher index of refraction regions tend to diffuse away over time, resulting in the stability problems discussed above.
  • Another method of stabilizing the refractive index profile formed by the spatially varying degree of cure is to use an entirely different type of polymer as the second component to stabilize the index profile. For example, one may first use a photo-polymerization process as described above to generate the desired index of refraction profile, then instead of using a second monomer that is cured by UV light to form a second polymer that provides increased stability, one can use a second monomer that is cured by heating as illustrated in block 28 in FIG. 2. One such example is an epoxy which is thermally curable, e.g., instead of ATLAC in the embodiment discussed above, a thermally curable epoxy is used instead. The steps used to form the desired index of refraction profile remain essentially the same, then heat is applied to cure the epoxy, thereby stabilizing the first polymer in an epoxy matrix.
  • One embodiment is to choose an epoxy that cures at relatively low (e.g., below 80° C.) or close to room temperature. The thiol, ene, and epoxy is then kept near or below room temperature to prevent the curing of the epoxy. The index profile may then be created by activating the photo-initiator that induces the thiol-ene polymerization. When the desired index of refraction profile is reached, the system is warmed up slightly to reach the epoxy curing temperature, polymerizing the epoxy turns and freezing-in the thiol-ene polymer to thereby stabilize the index of refraction profile.
  • Another embodiment is a method of stabilizing the index of refraction profile by curing thermally. Once the index of refraction profile is written in the polymer mixture, it is preferable to avoid degrading the index profile. Heating the epoxy could potentially degrade the profile. One method of minimizing that risk is to perform the epoxy curing in two steps: First, the second polymer in the mixture is allowed to gel (partially polymerize) at room temperature after the writing of the index profile in the polymer, and then the temperature is raised, e.g., to about 60° C. to 85° C., to complete the full curing process. The gel state provides a high viscosity environment around the index profile and thereby decreases the diffusion rate of the first polymer, e.g., the photo-polymerized thiol-ene polymer. The complete curing at elevated temperature stabilizes the index profile.
  • The patent application entitled “Apparatus and Method for Curing of UV-Protected UV-Curable Monomer and Polymer Mixtures,” Ser. No. 10/848,942, filed May 18, 2004, and the application to which it claims priority, U.S. Provisional Application No. 60/472,669, filed on May 21, 2003, are hereby incorporated by reference in their entireties, and particularly for the purpose of describing preferred methods for making the polymeric material 16.
  • Reference is made to FIG. 3 to illustrate how the desired refractive index profile can be determined. Those skilled in the art will understand from the discussion above that the first monomer 20 (which may be a mixture of monomers) is partially cured in a manner that varies spatially to achieve the desired refractive index profile, and that the curing of the second monomer 22 (which may also be a mixture of monomers) may change the refractivity somewhat. Preferably, an overall profile is obtained that is the combination of the desired refractivity index distribution resulting from selective polymerization of the first monomer 20 and the added change in refractivity over the entire material 16 that results from the curing of the second monomer 22.
  • A schematic illustration of a wavefront 30 is shown in FIG. 3, showing a divergent wave which may consist of spherical, astigmatism and high order aberrations. The higher order aberrations are typically describable by third and higher order terms of Zernicke polynomials. At an imaginary cross sectional plane 32, the wavefront has intersections located at points 34, 36, 38, 40. The peak of the wavefront is indicated at 42, which is traveling ahead of the intersections 34, 36, 38, 40. The distance between the peak 42 and the intersections is typically expressed in the units of physical distance in space. The peak 42 has a projected point 44 on the plane 32.
  • To correct the aberrations in this wavefront, a refractive index profile is created in the material 16 that will slow down the peak 42. Accordingly, the desired refractive index profile for a portion of the material 16 is one that exhibits, after curing, an index of refraction that results in the conjugate of the wavefront 30 such that a plane wave exits the optical element 10. An illustrative curing profile is shown in FIG. 4, which has a three dimensional distribution profile 46 that is essentially identical to that of the profile of the wave 30 shown in FIG. 3.
  • Specifically, in one preferred, non-limiting embodiment, the retardation required for compensation can be calculated as follows. The difference of the index of refraction, Δn between cured and uncured material 16 is typically in the range of 0.001 to 0.05 and may be determined by routine experimentation. The retardation is the physical distance “d” between the wave peak 42, and its projection point 44 on the plane 32. The thickness of the material 16 consequently is at least d/Δn. In the curing profile for the material 16, the scale of the magnitude of the retardation is such that the magnitude of thickness of the cured material or the integrated index difference at a profile peak 46 to its projection 48 on a cross-sectional plane 50 is d/Δn. The effect of such a refractive index profile is that the peak 42 of the wave 30 will experience the most retardation, and the wave at the intersections 34, 36, 38, 40 experiences no retardation at corresponding locations 52, 54, 56, 58 of the refractive index profile in the uncured portion of the material 16. Accordingly, the desired refractive index profile of the material 16 after curing is such that its index of refraction establishes a profile that matches the profile of the wave for which compensation is desired.
  • The curing can be undertaken using a light source in combination with a beam shaping unit. Preferably, the light source with beam shaping unit creates a light beam that is substantially collimated. It should be appreciated, however, that a non-collimated beam may also be used if desired. In one exemplary, non-limiting embodiment, the light beam may pass through a focusing lens to form a converging, or focusing, light beam that is directed toward the optical element 10, where the light beam passes through the first transparent plate 12 to focus on a desired volume in the material 16. This irradiates the monomer at that location, preferably activating the photoinitiator and beginning the curing process within the material 16. The curing process results in a corresponding change of the index of refraction within the material. Terminating the exposure to the light ceases the curing, thereby ceasing the change of the index of refraction.
  • The activation and power level of the light source and its position are preferably controlled by a controller which is electrically connected to the light source and to shuttling components on which the source may be mounted. In a preferred embodiment, the converging light beam passes through the transparent plate 12 and converges within the material 16. Specifically, the light ray edges of the beam converge at the desired focal point to cure the material 16 at the focal point. Then, the light beam is moved to another point adjacent to the just-cured point to cure the next point, and so on. The details of various methods of light energy delivery by beam scanning have been disclosed in U.S. Patent Application Publication No. 2003/0143391 A1, which is hereby incorporated by reference in its entirety and particularly for the purpose of describing such methods.
  • While the term “focal point” is used herein, it is to be understood that the light beam at its point of focus is not at a true “point”, which in mathematics has no volume, but rather is focused in a volume referred to as a “beam waist” which represents the region in the material 16 undergoing by exposure to the converging light beam. Generally speaking and without limitation, a beam with a cone angle that is in the range of 0.002 radians to 1.5 radians may be used.
  • Preferably, the distance between curing volumes should be less than the beam waist of the light beam, creating an overlap region. In a preferred embodiment, the size of the beam overlap region can vary in the range of about ten to about seventy five percent (10%-75%) of the size of the beam waist. In a particularly preferred, non-limiting embodiment, the size of the beam overlap region can vary in the range of about forty to about sixty percent (40%-60%) of the size of the beam waist. In one embodiment in which a tightly focused beam is preferred, the beam waist is in the range of twenty microns (20 μm) or less. However, beam waists in the range of about 0.1 micron to about two hundred microns may be used. It is to be understood that the curing volumes can be sequential and contiguous to each other, or the scan sequence may be randomly accessed, such that the new curing location can be isolated from the previous location, with no overlap of the beam waists.
  • Other methods for selectively curing the monomers (e.g., a photomask) may also be used. Suitable selective polymerization methods are disclosed in U.S. Patent Application Publication No. 2002/0080464 A1, which is hereby incorporated by reference in its entirety and particularly for the purpose of describing such methods.
  • Preferred optical elements may be used to correct aberrations in optical components such as telescopes, microscopes, ophthalmic diagnostic instruments including confocal scanning ophthalmoscopes, and fundus cameras. In such cases, the viewing instrument generally includes refractive elements such lenses, reflective elements such as mirrors and beam splitters, and diffractive elements such as gratings and acousto- and electro-optical crystals. Preferred embodiments may be used to eliminate costly manufacturing of such apparatus by using less costly optics and by compensating for the attendant residual aberrations with correcting elements such as are described above. In a preferred embodiment, the optical element 10 shown in FIG. 1 is a correcting element configured as, for example, an ophthalmic lens, to correct aberrations caused by imperfections in a patient's eye.
  • It will be appreciated by those skilled in the art that various omissions, additions and modifications may be made to the processes described above without departing from the scope of the invention, and all such modifications and changes are intended to fall within the scope of the invention, as defined by the appended claims.

Claims (20)

1. An optical element comprising:
a first optical cover, a second optical cover, and a layer of polymeric material sandwiched between the first optical cover and the second optical cover;
wherein the polymeric material comprises a mixture of a first polymer and a second polymer, the first polymer having a spatially varying degree of cure that provides a predetermined refractive index profile, and the second polymer being cured to thereby stabilize the refractive index profile.
2. The optical element of claim 1, in which the first and second optical covers are transparent plates.
3. The optical element of claim 1 in which the first and the second optical covers are ophthalmic lenses.
4. The optical element of claim 2 in which the first polymer and the second polymer form a pair selected from the group consisting of polyacrylate/epoxy, polyacrylate/polyvinyl ether, thiol-ene polymer/polyester, thiol-ene polymer/epoxy, and polyvinyl ether/epoxy.
5. The optical element of claim 1 in which the first polymer is selected from the group consisting of thiol-ene polymer, epoxy, polyacrylate and polyvinyl ether.
6. The optical element of claim 1 in which the second polymer is selected from the group consisting of epoxy, polyester, polyacrylate and polyvinyl ether.
7. A method for making an optical element, comprising:
polymerizing a first monomer to form a first polymer, the first polymer having a spatially varying degree of cure that provides a predetermined refractive index profile; and
polymerizing a second monomer in the presence of the first polymer to form a second polymer intermixed with the first polymer, the second polymer stabilizing the refractive index profile.
8. The method of claim 7 in which the second monomer and first polymer are sandwiched between first and second cover plates during the polymerizing of the second monomer.
9. The method of claim 8 in which the first and second cover plates are ophthalmic lenses.
10. The method of claim 7 in which the polymerizing of the first monomer is conducted by exposing the first monomer to a first radiation source.
11. The method of claim 10 in which the first monomer comprises a photoinitiator.
12. The method of claim 10 in which the polymerizing of the second monomer is conducted by exposing the second monomer to a second radiation source different from the first radiation source.
13. The method of claim 7 in which the first monomer is selected from the group consisting of epoxy, thiol, ene, acrylate, vinyl ether, and mixtures thereof.
14. The method of claim 7 in which the second monomer is selected from the group consisting of epoxy, acrylate, ester and vinyl ether.
15. The method of claim 7 comprising intermixing the first monomer and the second monomer prior to the polymerizing of the first monomer.
16. The method of claim 7 in which the first polymer is a thiol-ene polymer and the second polymer is selected from the group consisting of epoxy polymer and unsaturated polyester.
17. A method for making an ophthalmic lens, comprising:
forming a mixture comprising a first monomer, a second monomer, a first photoinitiator, and a second photoinitiator;
placing the mixture between a first optical cover and a second optical cover;
exposing the mixture to a first radiation source, thereby polymerizing the first monomer to form a first polymer, the first polymer having a spatially varying degree of cure that provides a predetermined refractive index profile; and
exposing the second monomer to a second radiation source, thereby polymerizing the second monomer to form a second polymer intermixed with the first polymer.
18. The method of claim 17 in which substantially all of the second monomer is consumed by the polymerizing of the second monomer.
19. The method of claim 17 in which the second polymer is partially cured.
20. The method of claim 17 in which the first and the second optical covers are selected from the group consisting of transparent plate, plano ophthalmic lens, single vision ophthalmic lens, bifocal ophthalmic lens, and progressive addition ophthalmic lens.
US10/935,799 2004-09-07 2004-09-07 Method for stabilizing refractive index profiles using polymer mixtures Abandoned US20060050228A1 (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
US10/935,799 US20060050228A1 (en) 2004-09-07 2004-09-07 Method for stabilizing refractive index profiles using polymer mixtures
PCT/US2005/031973 WO2006029260A2 (en) 2004-09-07 2005-09-07 Method for stabilizing refractive index profiles using polymer mixtures
JP2007530496A JP2008512704A (en) 2004-09-07 2005-09-07 Method for producing optical element with stabilized refractive index profile using polymer mixture
KR1020077007484A KR20070057905A (en) 2004-09-07 2005-09-07 Method for stabilizing refractive index profiles using polymer mixtures
EP05798022A EP1792226A2 (en) 2004-09-07 2005-09-07 Method for stabilizing refractive index profiles using polymer mixtures
AU2005282382A AU2005282382A1 (en) 2004-09-07 2005-09-07 Method for stabilizing refractive index profiles using polymer mixtures
IL181309A IL181309A0 (en) 2004-09-07 2007-02-13 Method for stabilizing refractive index profiles using polymer mixtures
US12/361,498 US7772297B2 (en) 2004-09-07 2009-01-28 Method for stabilizing refractive index profiles using polymer mixtures
US12/854,061 US8034262B2 (en) 2004-09-07 2010-08-10 Optical element for stabilizing refractive index profiles using polymer mixtures

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US10/935,799 US20060050228A1 (en) 2004-09-07 2004-09-07 Method for stabilizing refractive index profiles using polymer mixtures

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US12/361,498 Division US7772297B2 (en) 2004-09-07 2009-01-28 Method for stabilizing refractive index profiles using polymer mixtures

Publications (1)

Publication Number Publication Date
US20060050228A1 true US20060050228A1 (en) 2006-03-09

Family

ID=35995820

Family Applications (3)

Application Number Title Priority Date Filing Date
US10/935,799 Abandoned US20060050228A1 (en) 2004-09-07 2004-09-07 Method for stabilizing refractive index profiles using polymer mixtures
US12/361,498 Active US7772297B2 (en) 2004-09-07 2009-01-28 Method for stabilizing refractive index profiles using polymer mixtures
US12/854,061 Active US8034262B2 (en) 2004-09-07 2010-08-10 Optical element for stabilizing refractive index profiles using polymer mixtures

Family Applications After (2)

Application Number Title Priority Date Filing Date
US12/361,498 Active US7772297B2 (en) 2004-09-07 2009-01-28 Method for stabilizing refractive index profiles using polymer mixtures
US12/854,061 Active US8034262B2 (en) 2004-09-07 2010-08-10 Optical element for stabilizing refractive index profiles using polymer mixtures

Country Status (7)

Country Link
US (3) US20060050228A1 (en)
EP (1) EP1792226A2 (en)
JP (1) JP2008512704A (en)
KR (1) KR20070057905A (en)
AU (1) AU2005282382A1 (en)
IL (1) IL181309A0 (en)
WO (1) WO2006029260A2 (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070195264A1 (en) * 2006-02-14 2007-08-23 Lai Shui T Subjective Refraction Method and Device for Correcting Low and Higher Order Aberrations
US20070258046A1 (en) * 2006-02-14 2007-11-08 Lai Shui T Subjective Wavefront Refraction Using Continuously Adjustable Wave Plates of Zernike Function
US20070285799A1 (en) * 2006-03-20 2007-12-13 Dreher Andreas W Materials and methods for producing lenses
US20080037135A1 (en) * 2006-07-25 2008-02-14 Lai Shui T Method of Making High Precision Optics Having a Wavefront Profile
US20080137032A1 (en) * 2006-12-06 2008-06-12 General Electric Company Optical lens and method of manufacturing
AU2014200799B2 (en) * 2006-03-20 2015-08-06 Essilor International (Compagnie Générale d'Optique) Materials and methods for producing lenses
US9758615B2 (en) 2012-12-21 2017-09-12 Dow Global Technologies Llc Phase-segmented non-isocyanate elastomers

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2773523T5 (en) * 2016-10-21 2023-05-10 Zeiss Carl Vision Int Gmbh Spectacle glass and 3D printing process for its manufacture
US11678975B2 (en) 2019-04-05 2023-06-20 Amo Groningen B.V. Systems and methods for treating ocular disease with an intraocular lens and refractive index writing
US11583388B2 (en) 2019-04-05 2023-02-21 Amo Groningen B.V. Systems and methods for spectacle independence using refractive index writing with an intraocular lens
US11564839B2 (en) 2019-04-05 2023-01-31 Amo Groningen B.V. Systems and methods for vergence matching of an intraocular lens with refractive index writing
US11583389B2 (en) 2019-04-05 2023-02-21 Amo Groningen B.V. Systems and methods for correcting photic phenomenon from an intraocular lens and using refractive index writing
US11944574B2 (en) 2019-04-05 2024-04-02 Amo Groningen B.V. Systems and methods for multiple layer intraocular lens and using refractive index writing
US11529230B2 (en) 2019-04-05 2022-12-20 Amo Groningen B.V. Systems and methods for correcting power of an intraocular lens using refractive index writing
WO2021131348A1 (en) * 2019-12-27 2021-07-01 富士フイルム株式会社 Bonding-type optical element and method for manufacturing bonding-type optical element

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5064712A (en) * 1989-03-20 1991-11-12 Corning Incorporated Laminated lens structure
US5236970A (en) * 1987-02-05 1993-08-17 Allergan, Inc. Optically clear reinforced silicone elastomers of high optical refractive index and improved mechanical properties for use in intraocular lenses
US5807906A (en) * 1995-02-27 1998-09-15 Essilor International-Compagnie Generale D'optique Process for obtaining a transparent article with a refractive index gradient
US6391983B1 (en) * 1997-02-14 2002-05-21 Sola International Holdings, Ltd. Casting composition of aromatic polyvinyl monomer, polythiol and epoxy strain reducer
US20020080464A1 (en) * 2000-11-27 2002-06-27 Bruns Donald G. Wavefront aberrator and method of manufacturing
US6450642B1 (en) * 1999-01-12 2002-09-17 California Institute Of Technology Lenses capable of post-fabrication power modification
US20030143391A1 (en) * 2001-06-04 2003-07-31 Lai Shui T. Apparatus and method of fabricating a compensating element for wavefront correction using spatially localized curing of resin mixtures
US6630083B1 (en) * 1999-12-21 2003-10-07 Johnson & Johnson Vision Care, Inc. Methods and compositions for the manufacture of ophthalmic lenses
US20040008319A1 (en) * 2002-07-11 2004-01-15 Lai Shui T. Optical elements and methods for making thereof
US6712466B2 (en) * 2001-10-25 2004-03-30 Ophthonix, Inc. Eyeglass manufacturing method using variable index layer
US6786602B2 (en) * 2001-05-31 2004-09-07 Marc Abitbol Aberration correction spectacle lens

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US143391A (en) 1873-09-30 Improvement in harvester-droppers
US80464A (en) 1868-07-28 dqolittle
US8319A (en) 1851-08-26 Limekiln

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5236970A (en) * 1987-02-05 1993-08-17 Allergan, Inc. Optically clear reinforced silicone elastomers of high optical refractive index and improved mechanical properties for use in intraocular lenses
US5064712A (en) * 1989-03-20 1991-11-12 Corning Incorporated Laminated lens structure
US5807906A (en) * 1995-02-27 1998-09-15 Essilor International-Compagnie Generale D'optique Process for obtaining a transparent article with a refractive index gradient
US6391983B1 (en) * 1997-02-14 2002-05-21 Sola International Holdings, Ltd. Casting composition of aromatic polyvinyl monomer, polythiol and epoxy strain reducer
US6450642B1 (en) * 1999-01-12 2002-09-17 California Institute Of Technology Lenses capable of post-fabrication power modification
US6630083B1 (en) * 1999-12-21 2003-10-07 Johnson & Johnson Vision Care, Inc. Methods and compositions for the manufacture of ophthalmic lenses
US20020080464A1 (en) * 2000-11-27 2002-06-27 Bruns Donald G. Wavefront aberrator and method of manufacturing
US6786602B2 (en) * 2001-05-31 2004-09-07 Marc Abitbol Aberration correction spectacle lens
US20030143391A1 (en) * 2001-06-04 2003-07-31 Lai Shui T. Apparatus and method of fabricating a compensating element for wavefront correction using spatially localized curing of resin mixtures
US6712466B2 (en) * 2001-10-25 2004-03-30 Ophthonix, Inc. Eyeglass manufacturing method using variable index layer
US20040008319A1 (en) * 2002-07-11 2004-01-15 Lai Shui T. Optical elements and methods for making thereof

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7726811B2 (en) 2006-02-14 2010-06-01 Lai Shui T Subjective wavefront refraction using continuously adjustable wave plates of Zernike function
US10383512B2 (en) 2006-02-14 2019-08-20 Shui T. Lai Subjective wavefront refraction using continuously adjustable wave plates of Zernike function
US9320426B2 (en) 2006-02-14 2016-04-26 Shui T. Lai Subjective wavefront refraction using continuously adjustable wave plates of zernike function
US7699471B2 (en) 2006-02-14 2010-04-20 Lai Shui T Subjective refraction method and device for correcting low and higher order aberrations
US20070195264A1 (en) * 2006-02-14 2007-08-23 Lai Shui T Subjective Refraction Method and Device for Correcting Low and Higher Order Aberrations
US20070258046A1 (en) * 2006-02-14 2007-11-08 Lai Shui T Subjective Wavefront Refraction Using Continuously Adjustable Wave Plates of Zernike Function
US20080071002A1 (en) * 2006-03-20 2008-03-20 Jagdish Jethmalani Custom monomers and polymers for spectacle lenses
US7701641B2 (en) * 2006-03-20 2010-04-20 Ophthonix, Inc. Materials and methods for producing lenses
US20100265457A1 (en) * 2006-03-20 2010-10-21 Chomyn Jeffrey S Materials and methods for producing lenses
AU2014200799B2 (en) * 2006-03-20 2015-08-06 Essilor International (Compagnie Générale d'Optique) Materials and methods for producing lenses
US20070285617A1 (en) * 2006-03-20 2007-12-13 Mills Gary D Optical elements with a gap between two lens materials
US7950799B2 (en) 2006-03-20 2011-05-31 Ophthonix, Inc. Optical elements with a gap between two lens materials
US20070285799A1 (en) * 2006-03-20 2007-12-13 Dreher Andreas W Materials and methods for producing lenses
US7969660B2 (en) * 2006-03-20 2011-06-28 Opthonix, Inc. Materials and methods for producing lenses
US20080037135A1 (en) * 2006-07-25 2008-02-14 Lai Shui T Method of Making High Precision Optics Having a Wavefront Profile
US7959284B2 (en) 2006-07-25 2011-06-14 Lai Shui T Method of making high precision optics having a wavefront profile
US20080137032A1 (en) * 2006-12-06 2008-06-12 General Electric Company Optical lens and method of manufacturing
US9758615B2 (en) 2012-12-21 2017-09-12 Dow Global Technologies Llc Phase-segmented non-isocyanate elastomers

Also Published As

Publication number Publication date
AU2005282382A1 (en) 2006-03-16
US20090137696A1 (en) 2009-05-28
EP1792226A2 (en) 2007-06-06
JP2008512704A (en) 2008-04-24
US20100302504A1 (en) 2010-12-02
WO2006029260A3 (en) 2008-04-03
KR20070057905A (en) 2007-06-07
WO2006029260A2 (en) 2006-03-16
US8034262B2 (en) 2011-10-11
US7772297B2 (en) 2010-08-10
IL181309A0 (en) 2007-07-04

Similar Documents

Publication Publication Date Title
US7772297B2 (en) Method for stabilizing refractive index profiles using polymer mixtures
US20080123197A1 (en) Apparatus and method of fabricating an ophthalmic lens for wavefront correction using spatially localized curing of photo-polymerization materials
AU2003265955B2 (en) Apparatus and method of fabricating a compensating element for wavefront correction using spatially localized curing of resin mixtures
US7969660B2 (en) Materials and methods for producing lenses
EP1535104B1 (en) Apparatus and method of correcting higher-order aberrations of the human eye
US6989938B2 (en) Wavefront aberrator and method of manufacturing
US20110255156A1 (en) Monomers and polymers for optical elements
AU2014200799B2 (en) Materials and methods for producing lenses
JP2001526980A (en) Holographic ophthalmic lens
Sverdrup et al. Programmable Wavefront Control with Photopolymers

Legal Events

Date Code Title Description
AS Assignment

Owner name: OPHTHONIX, INC., CALIFORNIA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:LAI, SHUI T.;BRUNS, DONALD G.;SVERDRUP, LAWRENCE H.;AND OTHERS;REEL/FRAME:015627/0427;SIGNING DATES FROM 20041117 TO 20050125

AS Assignment

Owner name: COMERICA BANK, CALIFORNIA

Free format text: SECURITY AGREEMENT;ASSIGNOR:OPHTHONIX, INC.;REEL/FRAME:021096/0573

Effective date: 20080530

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION

AS Assignment

Owner name: COMERICA BANK, CALIFORNIA

Free format text: SECURITY AGREEMENT;ASSIGNOR:OPHTHONIX, INC.;REEL/FRAME:026412/0706

Effective date: 20110526