PHOTOSTABLE AND THERMALLY STABLE COLORING COMPOUNDS FOR SELECTIVE FILTERED OPTICS FOR BLUE LIGHT

专利摘要:
photostable and thermally stable dye compounds for selective filtered optics for blue light. a system comprising an optical filter is provided. the optical filter comprises a coloring compound of cuporphyrin. the transmission spectrum of the system has an average transmission over the 460 nm-700 nm wavelength range of at least 80%. the transmission spectrum of the system has an average transmission over the 400 nm-460 nm wavelength range which is less than 75%.
公开号:BR112016025859B1
申请号:R112016025859-2
申请日:2015-05-04
公开日:2021-08-24
发明作者:Dustin Robert Cefalo；Jerry Charles Bommer；Anita TRAJKOVSKA-BROACH；Ronald David Blum；Andrew Ishak；Sean McGinnis
申请人:Frontier Scientific, Inc；
IPC主号:

专利说明:

TECHNICAL FIELD
[001] This disclosure is generally related to coatings comprising a dye or dye mixture that provide selective high energy visible light (HEVL) filtration, particularly filtration of one or more wavelengths in the 400-500 nm spectral range. FUNDAMENTALS
[002] Electromagnetic radiation from the sun continuously bombards the Earth's atmosphere. Light is made up of electromagnetic radiation that travels in waves. The electromagnetic spectrum includes radio waves, millimeter waves, microwaves, infrared, visible light, ultraviolet (UVA and UVB), X-rays and gamma rays. The visible light spectrum includes the longest visible light wavelength of approximately 700 nm and the shortest of approximately 400 nm (nanometers or 10-9 meters). The wavelengths of blue light fall in the approximate range of 400 nm to 500 nm. For the ultraviolet bands, UVB wavelengths are 290 nm to 320 nm, and UVA wavelengths are 320 nm to 400 nm. Gamma and X rays constitute the highest frequencies in this spectrum and are absorbed by the atmosphere. The wavelength spectrum of ultraviolet radiation (UVR) is 100-400 nm. Most UVR wavelengths are absorbed by the atmosphere, except when there are areas of stratospheric ozone depletion. Over the past 20 years, ozone layer depletion has been documented primarily as a result of industrial pollution. Increased exposure to UVR has wide implications for public health, for example, an increased burden of ocular UVR and skin diseases is expected.
[003] The ozone layer absorbs wavelengths of up to 286 nm, thus shielding living beings from exposure to radiation with the highest energy. However, we are exposed to wavelengths above 286 nm, most of which fall within the human visual spectrum (400-700 nm). The human retina responds only to the visible light portion of the electromagnetic spectrum. The shorter wavelengths pose the greatest danger, as they inversely contain more energy. Blue light has been shown to be the portion of the visible spectrum that produces the most important photochemical damage to animal retinal pigment epithelium (RPE) cells. Exposure to these wavelengths has been termed the blue light hazard because these wavelengths are perceived as blue by the human eye. SUMMARY
[004] In one embodiment, a first system comprises an optical filter comprising a Cuporphyrin compound. In one embodiment, the Cu-porphyrin compound has a structure in accordance with Formula I: (Formula I)
or a salt, or a tautomeric form thereof, wherein X is carbon or nitrogen and each of R1 through R8 is independently H, Cl, Br, F, I, Me, a straight chain alkyl having 2-20 atoms of carbon, a branched alkyl having 2-20 carbons, or a moiety represented by -LP; each of R9 through R28 is independently H, F, Br, Cl, I, CH3, a straight chain alkyl having 2-20 carbon atoms, a branched alkyl having 2-20 carbon atoms, nitro, sulfonic acid , carboxylic acid, a carboxylic ester, -R100-OH, -O-R200, -R100-N(R110R111), -R100-N+(R110R111R112), an aryl, a heteroaryl, acrylate, acryloyl, acrylamide, methacrylate, methacrylamide, thiol, amide, or a moiety represented by -LP; or two of adjacent R9 to R28 form an aromatic or non-aromatic ring structure; wherein R100 is a bond, -(CH2)n-, or a branched alkyl having 2-20 carbon atoms, wherein n is 1-20; R110, R111, R112 and R200 are each independently H, Me, a straight chain alkyl having 2-20 carbon atoms, a branched alkyl having 2-20 carbon atoms, or a moiety represented by -LP; where P is a polymer moiety or a polymerizable group and L is null or a linker; provided that when X is nitrogen, then R11, R16, R21 and R26 are each independently an isolated pair or as defined above.
[005] In one embodiment, the Cu-porphyrin compound of the first system is selected from the group consisting of compounds having structures according to Formula II through Formula I-16, described in the detailed description.
[006] In one embodiment, each of R1 through R28, R110-R112, R120, R121, R200-R203, R300-R315, R400-R411, R500-R515 in Formula I and Formulas I-1 through I-16 is H, since in Formula I, when X is nitrogen, then R11, R16, R21, and R26 are each an isolated pair.
[007] In one embodiment, in Formula I and Formulas I-1 through I-16, each of R1 through R8 is independently H, Cl, Br, F, I, CH3, a straight-chain alkyl having 2-20 carbon atoms or a branched alkyl having 2-20 carbons; and each of R9 through R28 is independently H, F, Br, Cl, I, CH3, a straight chain alkyl having 2-20 carbon atoms, a branched alkyl having 2-20 carbon atoms, nitro, acid sulfonic, carboxylic acid, a carboxylic ester, -R100-OH, -O-R200, -R100-N(R110R111), -R100-N+(R110R111R112), an aryl, a heteroaryl, acrylate, acryloyl, acrylamide, methacrylate, methacrylamide , thiol or amide; wherein R100 is a bond, -(CH2)n-, or a branched alkyl having 2-20 carbon atoms, wherein n is 1-20; and R110, R111, R112 and R200 are each independently H, Me, a straight chain alkyl having 2-20 carbon atoms or a branched alkyl having 2-20 carbon atoms. In some embodiments, two of adjacent R9 through R28 in Formula I and Formulas I-1 through I-16 form an aromatic or non-aromatic ring structure, for example, as described herein.
[008] In one embodiment, at least one of R1 to R28, R110-R112, R120, R121, R200-R203, R300-R315, R400-R411, R500-R515 in Formula I and Formulas I-1 through I-16 is -LP, where when there is more than one -LP, each -LP is the same or different.
[009] In one embodiment, 1-8 of R1 to R28, R110-R112, R120, R121, R200-R203, R300-R315, R400-R411, R500-R515 in Formula I and Formulas I-1 through I-16 are -LP, where each -LP is the same or different.
[0010] In one embodiment, P is a polymerizable group. In one embodiment, the polymerizable group is selected from the group consisting of acrylates, acryloyl, acrylamides, methacrylates, methacrylamides, carboxylic acids, thiols, amides, terminal or internal alkynyl groups, terminal or internal alkenyl groups, iodides, bromides, chlorides, azides, carboxylic esters, amines, alcohols, epoxides, isocyanates, aldehydes, acid chlorides, siloxanes, boronic acids, stannanes and benzylic halides.
[0011] In one embodiment, P is a polymer moiety. In one embodiment, the Cu-porphyrin compound is a homopolymer or a copolymer characterized by having a
or a tautomeric form thereof, wherein: X is carbon or nitrogen, each of R1 through R8 is independently H, Cl, Br, F, I, CH3, a straight chain alkyl having 2-20 carbon atoms, an alkyl branched having 2-20 carbons, or a portion represented by -Lm-Pm; and each of R9 through R28 is independently H, F, Br, Cl, I, CH3, a straight chain alkyl having 2-20 carbon atoms, a branched alkyl having 2-20 carbon atoms, nitro, acid sulfonic, carboxylic acid, a carboxylic ester, -R100-OH, -O-R200, -R100-N(R110R111), -R100-N+(R110R111R112), an aryl, a heteroaryl, acrylate, acryloyl, acrylamide, methacrylate, methacrylamide , thiol or amide, or a moiety represented by -Lm-Pm; or two of adjacent R9 to R28 form an aromatic or non-aromatic ring structure; wherein R100 is a bond, -(CH2)n-, or a branched alkyl having 2-20 carbon atoms, wherein n is 1-20; R110, R111, R112 and R200 are each independently H, Me, a straight-chain alkyl having 2-20 carbon atoms, a branched alkyl having 2-20 carbon atoms, or a moiety represented by -Lm -Pm; where Pm is a polymerizable group and Lm is null or a linker; provided that when X is nitrogen, then R11, R16, R21 and R26 are each independently an isolated pair or as defined above; and provided that there is 1-8 -Lm-Pm in Formula I(m), where each -Lm-Pm is the same or different.
[0012] In one embodiment, the polymer portion is selected from the group consisting of biopolymers, polyvinyl alcohol, polyacrylates, polyamides, polyamines, polyepoxides, polyolefins, polyanhydrides, polyesters and polyethylene glycols.
[0013] In an embodiment, L is a linker. In one modality, the linker is -C(O)-, -O-, -OC(O)O-, -C(O)CH2CH2C(O)-, -SS-, -NR130-, -NR130C(O) O-, - OC(O)NR130-, -NR130C(O)-, -C(O)NR130-, -NR130C(O)NR130-, -alkylene-NR130C(O)O-, -alkylene-NR130C(O )NR130-, -alkylene-OC(O)NR130- , -alkylene-NR130-, -alkylene-O-, -alkylene-NR130C(O)-, - alkylene-C(O)NR130-, -NR130C(O) O-alkylene-, -NR130C(O)NR130-alkylene-, - OC(O)NR130-alkylene, -NR130-alkylene-, -O-alkylene-, -NR130C(O)-alkylene-, -C(O) NR130-alkylene-, - alkylene-NR130C(O)O-alkylene-, -alkylene-NR130C(O)NR130-alkylene-, -alkylene-OC(O)NR130-alkylene-, -alkylene- NR130-alkylene-, - alkylene-O-alkylene-, -alkylene-NR130C(O)-alkylene-, -C(O)NR130-alkylene-, where R130 is hydrogen, or optionally substituted alkyl.
[0014] In one embodiment, the Cu-porphyrin compound of the first system is a homopolymer or a copolymer characterized by having a monomeric structure of Formula I (m) I
or a salt, or a tautomeric form thereof, wherein: X is carbon or nitrogen, each of R1 through R8 is independently H, Cl, Br, F, I, CH3, a straight-chain alkyl having 2-20 atoms carbon or a branched alkyl having 2-20 carbons; and each of R9 through R28 is independently H, F, Br, Cl, I, CH3, a straight chain alkyl having 2-20 carbon atoms, a branched alkyl having 2-20 carbon atoms, nitro, acid sulfonic, carboxylic acid, a carboxylic ester, -R100-OH, -O-R200, -R100-N(R110R111), -R100- +(R110R111R112), umaryl, a heteroaryl, acrylate, acryloyl, acrylamide, methacrylate, methacrylamide, thiol or amide; wherein R100 is a bond, -(CH2)n-, or a branched alkyl having 2-20 carbon atoms, wherein n is 1-20; R110, R111, R112 and R200 are each independently H, Me, a straight chain alkyl having 2-20 carbon atoms or a branched alkyl having 2-20 carbon atoms; provided that when X is nitrogen, then R11, R16, R21 and R26 are each independently an isolated pair or as defined above. In some embodiments, two of adjacent R9 through R28 form an aromatic or non-aromatic ring structure, for example, as described herein.
[0015] In one embodiment, the Cu-porphyrin compound is a homopolymer or a copolymer characterized by having a monomeric structure of Formula
or a salt, or a tautomeric form thereof, wherein: X is carbon or nitrogen, each of R1 through R8 is independently H, Cl, Br, F, I, CH3, a straight-chain alkyl having 2-20 carbon atoms. carbon, a branched alkyl having 2-20 carbons, or a moiety represented by -Lm-Pm; and each of R9 through R28 is independently H, F, Br, Cl, I, CH3, a straight chain alkyl having 2-20 carbon atoms, a branched alkyl having 2-20 carbon atoms, nitro, acid sulfonic, carboxylic acid, a carboxylic ester, -R100-OH, -O-R200, -R100-N(R110R111), -R100-N+(R110R111R112), an aryl, a heteroaryl, acrylate, acryloyl, acrylamide, methacrylate, methacrylamide , thiol, amide, or a moiety represented by -Lm-Pm; wherein R100 is a bond, -(CH2)n-, or a branched alkyl having 2-20 carbon atoms, wherein n is 120; R110, R111, R112 and R200 are each independently H, Me, a straight-chain alkyl having 2-20 carbon atoms, a branched alkyl having 2-20 carbon atoms, or a moiety represented by -Lm -Pm; provided that when X is nitrogen, then R11, R16, R21 and R26 are each independently an isolated pair or as defined above; wherein there is 1-4 -Lm-Pm in Formula I(m), wherein Lm is nil, and each Pm is the same polymerizable group or a different polymerizable group, wherein the polymerizable group is selected from the group consisting of acrylates , acryloyl, acrylamides, methacrylates, methacrylamides, carboxylic acids, thiols, amides, terminal or internal alkynyl groups having 2 to 20 carbons, terminal or internal alkenyl groups having 2 to 20 carbons, iodides, bromides, chlorides, azides, carboxylic esters , amines, alcohols, epoxides, isocyanates, aldehydes, acid chlorides, siloxanes, boronic acids, stannanes, and benzyl halides. In some embodiments, two of adjacent R9 through R28 form an aromatic or non-aromatic ring structure, for example, as described herein.
[0016] In one embodiment, the first system further comprises a surface, wherein the optical filter is a coating disposed on the surface, and the coating includes the Cu-porphyrin compound.
[0017] In one embodiment, the first system further comprises a substrate, wherein the optical filter is the Cu-porphyrin compound, and wherein the Cu-porphyrin compound is dispersed throughout the substrate.
[0018] In one embodiment, the first system is an ophthalmic system. In one modality, the ophthalmic system is selected from a group consisting of: an eyeglass lens, a contact lens, an intraocular lens, an intracorneal implant ("corneal inlay"), and an extracorneal implant ("corneal onlay") ”).
[0019] In one embodiment, the first system is a non-ophthalmic ocular system. In one embodiment, the non-ophthalmic eye system is selected from the group consisting of: a window, an automotive windshield, an automotive side window, an automotive rear window, a sunroof window, commercial glass, residential glass, skylights, a camera flash bulb and lens, an artificial lighting device, a fluorescent light or diffuser, a medical instrument, a surgical instrument, a rifle sight, a binocular, a computer monitor, a television screen, an illuminated sign , an electronic device screen, and a patio lamp.
[0020] In one embodiment, the first system further comprises: a first surface, wherein the filter is disposed on the first surface.
[0021] In one embodiment, the first system is a dermatological lotion.
[0022] In one embodiment, the first system further comprises: a second surface, wherein the filter is disposed between the first surface and the second surface. In an embodiment, where the first and second surfaces are glass.
[0023] In one embodiment, the optical filter is embedded in a layer of polyvinyl butyral (PVB), polyvinyl alcohol (PVA), ethylene vinyl acetate (EVA), or polyurethane (PU).
[0024] In one modality, TSRG is the average transmission of the first system over the wavelength range 460 nm-700 nm. TSBlue is the first system's average transmission over the 400-460 nm wavelength range. TSRG > 80% and TSBiue < TSRG - 5%.
[0025] In one embodiment, the first system transmits at least 80% of light at each wavelength across the 460 nm-700 nm range.
[0026] In one modality, the filter of the first system has a transmission spectrum that is different from the transmission spectrum of the first system.
[0027] In one embodiment, TFRG is the average transmission of the filter over the wavelength range 460 nm-700 nm. TFBlue is the average transmission of the filter over the 400-460 nm wavelength range. TFRG >80% and TFBlue < TFRG -5%. The filter has a first local minimum in transmission at a first wavelength within the wavelength range 400-460 nm.
[0028] In one embodiment, the filter transmits less than TFBlue - 5% light at the first wavelength.
[0029] In one embodiment, the first wavelength is within 2 nm of 420 nm. In one embodiment, the first wavelength is within 2 nm of 409 nm. In one embodiment, the first wavelength is within 10 nm of 425 nm. In one embodiment, the first wavelength is within 5 nm of 425 nm. In one embodiment, the first wavelength is within 30 nm of 430 nm.
[0030] In one mode, the filter transmits a maximum of 60% light in the first wavelength.
[0031] In one embodiment, T5 is the average transmission of the filter over a wavelength range from 5 nm below the first wavelength to 5 nm above the first wavelength. T6 is the average transmission of the filter over a wavelength range from 400 nm to 460 nm, excluding the wavelength range from 5 nm below the first wavelength to 5 nm above the first wavelength. T5 is at least 5% smaller than T6.
[0032] In one embodiment, T7 is the average transmission of the filter over a wavelength range from 10 nm below the first wavelength to 10 nm above the first wavelength. T8 is the average transmission of the transmission spectrum over a wavelength range from 400 nm to 460 nm, excluding the wavelength range from 10 nm below the first wavelength to 10 nm above the first wavelength. T7 is at least 5% smaller than T8.
[0033] In one embodiment, the filter has a local second minimum in transmission at a second wavelength within the wavelength range of 460 nm-700 nm.
[0034] In one modality, "CIE Standard Illuminant D65" light that has the CIE LAB coordinates (a*1, b*1, L*1), when transmitted through the first system, results in transmitted light that has the CIE coordinates LAB (a*2, b*2, L*2) . A total color difference ΔE between (a*1, b*1, L*1) and (a*2, b*2, L*2) is less than 5.0.
[0035] In one modality, "CIE Standard Illuminant D65" light that has the CIE LAB coordinates (a*1, b*1, L*1), when transmitted through the first system, results in transmitted light that has the CIE coordinates LAB (a*2, b*2, L*2). “CIE Standard Illuminant D65” light that has the CIE LAB coordinates (a*1 sb*1, L*1), when transmitted through a second system, results in transmitted light that has the CIE LAB coordinates (a*3, b *3, L*3). The second system does not include the optical filter, but otherwise it is identical to the first system, and a total color difference ΔE between (a*2, b*2, L*2) and (a*3, b*3, L *3) is less than 5.0.
[0036] In one modality, "CIE Standard Illuminant D65" light that has the CIE LAB coordinates (a*1, b*1, L*1), when transmitted through the first system, results in transmitted light that has the CIE coordinates LAB (a*2, b*2, L*2). A total saturation difference between (a*1, b*1, L*1) and (a*2, b*2, L*2) is less than 5.0.
[0037] In one modality, "CIE Standard Illuminant D65" light that has the CIE LAB coordinates (a*1, b*1, L*1), when transmitted through the first system, results in transmitted light that has the CIE coordinates LAB (a*2, b*2, L*2). “CIE Standard Illuminant D65” light that has CIE LAB coordinates (a*1, b*1, L*1), when transmitted through a second system, results in transmitted light that has CIE LAB coordinates (a*3, b*3, L*3). The second system does not include the optical filter, but otherwise it is identical to the first system, and a total saturation difference between (a*2, b*2, L*2) and (a*3, b*3, L* 3) is less than 5.0.
[0038] In one modality, "CIE Standard Illuminant D65" light that has the CIE LAB coordinates (a*1, b*1, L*1), when reflected by the first system, results in reflected light that has the CIE LAB coordinates (a*2, b*2, L*2), and a total color difference ΔE between (a*1, b*1, L*1) and (a*2, b*2, L*2) is less than 5.0.
[0039] In one modality, "CIE Standard Illuminant D65" light that has the CIE LAB coordinates (a*1, b*1, L*1), when reflected by the first system, results in reflected light that has the CIE LAB coordinates (a*2, b*2, L*2). “CIE Standard Illuminant D65” light that has the CIE LAB coordinates (a*1, b*1, L*1), when reflected by a second system, results in reflected light that has the CIE LAB coordinates (a*3, b *3, L*3). The second system does not include the optical filter, but otherwise it is identical to the first system. A total color difference ΔE between (a*2, b*2, L*2) and (a*3, b*3, L*3) is less than 5.0.
[0040] In one modality, "CIE Standard Illuminant D65" light that has the CIE LAB coordinates (a*1, b*1, L*1), when reflected by the first system, results in reflected light that has the CIE LAB coordinates (a*2, b*2, L*2), and a total saturation difference between (a*1, b*1, L*1) and (a*2, b*2, L*2) is smaller than 5.0.
[0041] In one modality, "CIE Standard Illuminant D65" light that has the CIE LAB coordinates (a*1, b*1, L*1), when reflected by the first system, results in reflected light that has the CIE LAB coordinates (a*2, b*2, L*2). “CIE Standard Illuminant D65” light that has the CIE LAB coordinates (a*1, b*1, L*1), when reflected by a second system, results in reflected light that has the CIE LAB coordinates (a*3, b *3, L*3). The second system does not include the optical filter, but otherwise it is identical to the first system. A total saturation difference between (a*2, b*2, L*2) and (a*3, b*3, L*3) is less than 5.0.
[0042] In one modality, a total color difference ΔE between (a*2, b*2, L*2) and (a*3, b*3, L*3) is less than 6.0. In one modality, a total color difference ΔE between (a*2, b*2, L*2) and (a*3, b*3, L*3) is less than 5.0.
[0043] In a modality, the first system has a YI of a maximum of 35. In a modality, the first system has a YI of a maximum of 30. In a modality, the first system has a YI of a maximum of 27.5. In one modality, the first system has a YI of at most 25. In one modality, the first system has a YI of at most 22.5. In one modality, the first system has a YI of at most 20. In one modality, the first system has a YI of at most 17.5. In one modality, the first system has a YI of maximum 15. In one modality, the first system has a YI of maximum 12.5. In one modality, the first system has a YI of at most 10. In one modality, the first system has a YI of at most 9. In one modality, the first system has a YI of at most 8. In one modality, the first system has a YI of maximum 7. In one mode, the first system has a YI of maximum 6. In one mode, the first system has a YI of maximum 5. In one mode, the first system has a YI of maximum 4. In one mode, the first system has a YI of maximum 3. In one mode, the first system has a YI of maximum 2. In one mode, the first system has a YI of maximum 1.
[0044] In one mode, the filter has a YI of maximum 35. In one mode, the filter has a YI of maximum 30. In one mode, the filter has a YI of maximum 27.5. In one modality, the filter has a YI of maximum 25. In one modality, the filter has a YI of maximum 22.5. In one modality, the filter has a YI of maximum 20. In one modality, the filter has a YI of maximum 17.5. In one modality, the filter has a YI of maximum 15. In one modality, the filter has a YI of maximum 12.5. In one modality, the filter has a YI of maximum 10. In one modality, the filter has a YI of maximum 9. In one modality, the filter has a YI of maximum 8. In one modality, the filter has a YI of maximum 7. In one modality, the filter has a YI of maximum 6. In one modality, the filter has a YI of maximum 5. In one modality, the filter has a YI of maximum 4. In one modality, the filter has a YI of maximum 3. In one modality, the filter has a YI of maximum 2. In one modality, the filter has a YI of maximum 1.
[0045] In one modality, the first system has a YI of maximum 15 if the first system is an ophthalmic system. In one modality, the filter has a maximum YI of 15 if the first system is an ophthalmic system.
[0046] In one modality, the first system has a YI of maximum 35 if the first system is a non-ophthalmic system. In one modality, the filter has a maximum YI of 35 if the first system is a non-ophthalmic system.
[0047] In one embodiment, the slope of the first system's transmission spectrum for at least one wavelength within 10 nm of the first wavelength on the negative side has an absolute value that is less than the absolute value of the slope of the transmission spectrum at a third wavelength. The third wavelength is more than 10 nm from the first wavelength on the negative side.
[0048] In one embodiment, the first system further comprises a UV blocking element. In one embodiment, the UV blocking element is disposed on the filter.
[0049] In one embodiment, the optical filter is a Cu-porphyrin compound, the Cu-porphyrin compound is incorporated into a coating, and the UV blocking element is incorporated into the coating.
[0050] In one embodiment, the first system further comprises an IR blocking element.
[0051] In one embodiment, a method comprises dissolving a Cu-porphyrin compound in a solvent to produce a solution, diluting the solution with a base, filtering the solution, and applying the solution to form an optical filter.
[0052] In one embodiment, wherein application to the solution comprises coating a surface with the solution, wherein the coating is by dip coating, spray coating or spin coating.
[0053] In one embodiment, an ophthalmic system comprising a filter: whereby said ophthalmic system selectively filters 5.0-50% of a wavelength of light within the range of 400-460 nm and transmits at least 80% of light across the visible spectrum; wherein the yellowing index is at most 15.0, and wherein said filter incorporates Cu(II)meso-Tetra(2-naphthyl)porphine.
[0054] In another embodiment, a non-ophthalmic system comprising a selective light wavelength filter that blocks 5-50% of light in the 400-460 nm range and transmits at least 80% of light across the visible spectrum, wherein the yellowing index is at most 35.0, and wherein said filter incorporates Cu(II)meso-Tetra(2-naphthyl)porphine.
[0055] In one embodiment, the optical filter may comprise a mixture of Cuporphyrin coloring compounds.
[0056] In one embodiment, the dye or dye mixture has an absorption spectrum with at least one absorption peak in the range of 400 nm to 500 nm.
[0057] In one embodiment, the (at least one) absorption peak is in the range of 400 nm to 500 nm.
[0058] In one embodiment, the (at least one) absorption peak has a half-maximum full width (FWHM) of less than 60 nm in the 400 nm to 500 nm range.
[0059] In one embodiment, the dye or dye mixture, when incorporated into the optical path of the device, absorbs at least 5% of the (at least one) wavelength of light in the range of 400 nm to 500 nm.
[0060] In one embodiment, the dye or dye mixture aggregates have an average size less than 5 micrometers.
[0061] In one embodiment, the dye or dye mixture aggregates have an average size less than 1 micrometer.
[0062] In one embodiment, providing the solution comprises ultrasonifying the solution to reduce the average aggregate size of the dye or dye mixture contained in the solution.
[0063] In one modality, ultrasonicification is performed in a temperature-controlled environment.
[0064] In one modality, the aggregates have an average size greater than 10 micrometers before the ultrasonification of the solution.
[0065] In one mode, the temperature controlled environment is set to a temperature equal to or less than 50 degrees C.
[0066] In one embodiment, incorporation comprises loading the solution into a resin to form a coating formulation.
[0067] In one embodiment, the coating formulation is subjected to additional ultrasonicification in a temperature-controlled environment for a certain period of time.
[0068] In one embodiment, incorporation further comprises applying the coating formulation on one or both surfaces of the device.
[0069] In one embodiment, the method comprises applying a coating formulation comprising the dye or dye mixture on the first surface to form a coating, the coating selectively inhibiting visible light in a selected range of visible wavelengths. Furthermore, the embedding step comprises air drying or brief thermal baking of the coating or brief UV exposure of the coating.
[0070] In one embodiment, the application of the coating formulation comprises determining an amount of the dye or dye mixture, the amount corresponding to a predetermined percentage of light blocking in the selected range.
[0071] In one embodiment, the dye is one of the group consisting of Cu(II) meso-Tetraphenylporphine or FS-201; Cu(II) meso-Tetra(4-chlorophenyl)porphine or FS-202; Cu(II) meso-Tetra(4-methoxyphenyl)porphine or FS-203; Cu(II) meso-Tetra(4-tert-butylphenyl)porphine or FS-204; Cu(II) meso-Tetra(3,5-di-tert-butylphenyl)porphine or FS-205; Cu(II) meso-Tetra(2-naphthyl)porphine or FS-206; Cu(II) meso-Tetra(N-methyl-4-pyridyl)porphine tetrachloride or FS-207; Cu(II) meso-Tetra(N-Methyl-6-quinolinyl)porphine tetrachloride or FS-208; Cu(II) meso-Tetra(1-naphthyl)porphine or FS-209; Cu(II) meso-Tetra(4-bromophenyl)porphine or FS-210; Cu(II) meso-Tetra(pentafluorophenyl)porphine or Cu1; Cu(II) meso-Tetra(4-sulfonatophenyl)porphine or Cu2; Cu(II) meso-Tetra(N-methyl-4-pyridyl)porphine earth acetate or Cu3; Cu(II) meso-Tetra(4-pyridyl)porphine or Cu4; Cu(II) meso-Tetra(4-carboxyphenyl)porphine or Cu5.
[0072] In one embodiment, the dye is Cu(II) meso-Tetra(2-naphthyl)porphine (FS-206).
[0073] In one embodiment, the dye is Cu(II) meso-Tetra(1-naphthyl)porphine (FS-209).
[0074] In one embodiment, the dye is Cu(II) meso-Tetra(pentafluorophenyl)porphine (Cu1).
[0075] In one embodiment, the dye is Cu(II) meso-Tetra(4-sulfonatophenyl)porphine (Cu2).
[0076] In one embodiment, the dye is Cu(II) meso-Tetra(4-carboxyphenyl)porphine (Cu5).
[0077] In one embodiment, the solution includes a chlorinated solvent.
[0078] In one embodiment, the solution includes a solvent that has a polarity index of 3.0 or greater.
[0079] In one embodiment, the solution comprises a solvent selected from the group consisting of cyclopentanone, cyclohexanone, methyl ethyl ketone, DMSO, DMF, THF, chloroform, methylene chloride, acetonitrile, carbon tetrachloride, dichloroethane, dichloroethylene, dichloropropane, trichloroethane , trichlorethylene, tetrachloroethane, tetrachlorethylene, chlorobenzene, dichlorobenzene, and combinations thereof.
[0080] In one embodiment, the solvent in the solution is chloroform.
[0081] In one embodiment, the solution solvent consists primarily of chloroform.
[0082] In one embodiment, the solvent is a chlorinated solvent.
[0083] In one embodiment, the (at least one) wavelength of light is within the range of 430 nm ± 20 nm.
[0084] In one embodiment, the (at least one) wavelength of light is within the range of 430 nm ± 30 nm.
[0085] In one embodiment, the (at least one) wavelength of light is within the range of 420 nm ± 20 nm.
[0086] In one embodiment, the coating is a base coat.
[0087] In one embodiment, the device selectively filters the (at least one) wavelength in the range 400 nm to 500 nm using at least one of a reflective coating and a multilayer interference coating.
[0088] In one embodiment, the dye or dye mixture, when incorporated into the optical path of the device, absorbs 5-50% light in the range of 400 nm to 500 nm.
[0089] In one embodiment, the dye or dye mixture, when incorporated into the optical path of the device, absorbs 20-40% of light in the range of 400 nm to 500 nm.
[0090] In one modality, the device blocks 5-50% of light in the range from 400 nm to 500 nm.
[0091] In one modality, the device blocks 20-40% of light in the range of 400 nm to 500 nm.
[0092] In one mode, the temperature controlled environment is set at a temperature equal to or less than 50 degrees C and the time period is between 1 hour and 5 hours.
[0093] In one embodiment, the dye or dye mixture has a Soret peak within the range of 400 nm to 500 nm.
[0094] In one embodiment, the (at least one) absorption peak has a half-maximum full width (FWHM) of less than 40 nm in the 400 nm to 500 nm range.
[0095] In one embodiment, the (at least one) wavelength is 430 nm.
[0096] In one embodiment, the peak wavelength filtering is 420 ± 5 nm.
[0097] In one embodiment, the peak wavelength filtering is 420 ± 10 nm.
[0098] In one embodiment, the dye or dye mixture, when incorporated into the optical path of the device, absorbs 5-50% light in the range of 410 nm to 450 nm.
[0099] In one embodiment, the dye or dye mixture, when incorporated into the optical path of the device, absorbs 20-40% of light in the range of 410 nm to 450 nm.
[00100] In one modality, the device blocks 5-50% of light in the range of 410 nm to 450 nm.
[00101] In one modality, the device blocks 20-40% of light in the range of 410 nm to 450 nm.
[00102] In one embodiment, the dye or dye mixture, when incorporated into the optical path of the device, absorbs 5-50% light in the range of 400 nm to 460 nm.
[00103] In one embodiment, the dye or dye mixture, when incorporated into the optical path of the device, absorbs 20-40% of light in the range of 400 nm to 460 nm.
[00104] In one modality, the device blocks 5-50% of light in the range from 400 nm to 460 nm.
[00105] In one modality, the device blocks 20-40% of light in the range of 400 nm to 460 nm.
[00106] In one embodiment, the dye or dye mixture, when incorporated into the optical path of the device, absorbs 5-50% of light in the range of 400 nm to 440 nm.
[00107] In one embodiment, the dye or dye mixture, when incorporated into the optical path of the device, absorbs 20-40% of light in the range of 400 nm to 440 nm.
[00108] In one modality, the device blocks 5-50% of light in the range of 400 nm to 440 nm.
[00109] In one modality, the device blocks 20-40% of light in the range of 400 nm to 440 nm.
[00110] In one modality, the opacity level of the device that has the dye or dye mixture incorporated in it is less than 0.6%.
[00111] In one modality, filtering is achieved through absorption, reflection, interference, or any combination of these.
[00112] In one embodiment, an ophthalmic system is provided comprising an ophthalmic lens selected from the group consisting of an eyeglass lens (prescription or over-the-counter), sunglasses (prescription or over-the-counter), a lens photochromic, a contact lens (prescription or over-the-counter), colored cosmetic contact lens, the visibility tinting of a contact lens, intraocular lens, intracorneal implant, extracorneal implant, corneal graft and corneal tissue, electronic lens , over-the-counter reading glasses or loupes, safety glasses, safety goggles, safety vests, visual rehabilitation devices, and a selective light wavelength filter that blocks 5-50% of light that has a wavelength in the range between 400-500 nm and transmits at least 80% of light across the visible spectrum. In addition, the wavelength selective filter comprises a dye or dye mixture that has an average aggregate size of less than 1 micrometer. In one modality, the range is 400-460 nm.
[00113] In order to provide such an optimal ophthalmic system it is desirable to include standardized yellowness index ranges, wherein the upper end of said range closely approximates a cosmetically unacceptable yellow color. The coating can be applied to any ophthalmic system, just as an example: an eyeglass lens, a sunglasses lens, a contact lens, intraocular lens, intracorneal implant, extracorneal implant, corneal graft, electroactive ophthalmic system or any other type of lens or non-ophthalmic system. It is preferred that the yellowness index (YI) be 15.0 or less for ophthalmic systems, or YI is 35.0 or less for non-ophthalmic systems.
[00114] A coating as described above is also provided, wherein the coating is applied to an eyeglass lens, sunglasses lens, contact lens, intraocular lens, intracorneal implant, extracorneal implant, corneal graft, corneal tissue , electroactive ophthalmic system or a non-ophthalmic system and selectively inhibits visible light between 430 ± 20 nm, and wherein the coating blocks a maximum of 30% light within the range of 430 ± 20 nm with a yellowing index of 15.0 or less. In one embodiment, the lens made with the process discussed above may have a yellowness index (YI) of 15.0 or less. In other embodiments, a YI of 12.5 or less, or 10.0 or less, or 9.0 or less, or 8.0 or less, or 7.0 or less, or 6.0 or less, or 5 .0 or less, or 4.0 or less, or 3.0 or less is preferred to reduce the blue light dose to the retina and allow for the best possible cosmetic of the intended application. YI varies based on specific filter application
[00115] In one modality, the system has an opacity level of less than 0.6%.
[00116] In one embodiment, a method is provided which comprises providing a solution containing a dye or a dye mixture, ultrasonicating the solution to reduce the average size of dye aggregates or dye mixture contained in the solution, and incorporating the dye or dye mixture in the optical path of a device that transmits light.
[00117] In one embodiment, an ophthalmic system is provided prepared by a process comprising the provision of a solution containing a dye or dye mixture, the dye or dye mixture forming aggregates of average size smaller than 10 micrometers, incorporation of the dye or dye mixture in the optical path of the ophthalmic lens, and the dye or dye mixture selectively filters out at least one wavelength of light within the range of 400 nm to 500 nm. Furthermore, the system having the dye or dye mixture incorporated therein has an average transmission of at least 80% across the visible spectrum.
[00118] In one embodiment, the ophthalmic system comprises an ophthalmic lens, the ophthalmic lens selected from the group consisting of an eyeglass lens (prescription or over-the-counter), sunglasses (prescription or over-the-counter), a photochromic lens, a contact lens (prescription or over-the-counter), colored cosmetic contact lens, the visibility tinting of a contact lens, intraocular lens, intracorneal implant, extracorneal implant, corneal graft, and corneal tissue, electronic lens, over-the-counter reading glasses or loupes, safety glasses, safety goggles, safety vests, and devices for visual rehabilitation. In addition, the ophthalmic system comprises a selective light wavelength filter that blocks 5-50% of light that has a wavelength in the range 400-500 nm and transmits at least 80% of light across the visible spectrum, the wavelength selective filter comprising the dye or dye mixture.
[00119] In one mode, the system displays a yellowing index of at most 15.
[00120] In one modality, the opacity level of the ophthalmic system is less than 0.6%.
[00121] In one embodiment, the system is a non-ophthalmic system.
[00122] Modalities could include non-ophthalmic systems, just for example: any type of windows, or glass sheet, laminate, or any transparent material, automotive windshield or automotive windows, aircraft windows, agricultural equipment such as, for example, windows and windshield in the cabin of a farm tractor, windshields or windows on buses or trucks, sunroofs, skylights, bulbs and camera flash lenses, any type of artificial lighting device (the light fixture or the filament or both), any type of light bulb, fluorescent lighting, LED lighting or any type of diffuser, medical instruments, surgical instruments, rifle sights, binoculars, computer monitors, television screens, any electronic device that emits portable light or non-portable, illuminated signs or any other item or system by which light is emitted or transmitted or passes through filtered or unfiltered.
[00123] The modalities disclosed in this descriptive report may include non-ophthalmic systems. Any non-ophthalmic system in which light is transmitted through or by the non-ophthalmic system is also envisioned. Just as an example, a non-ophthalmic system could include: automobile windows and windshields, aircraft windows and windshields, any type of window, computer monitors, televisions, medical instruments, diagnostic instruments, lighting products, fluorescent lighting , or any type of lighting product or light diffuser. Additionally, military and space applications apply, as acute or chronic exposure to high-energy visible light wavelengths can have a deleterious effect on soldiers and astronauts. Any type of product other than those described as ophthalmic is considered a non-ophthalmic product. Thus, any type of product or device by which visible light is emitted or travels through said product or device in which light from that product or device enters the human eye is provided.
[00124] Also provided is a coating as described above, where the coating is applied to a non-ophthalmic system and selectively inhibits visible light between 430 ± 20 nm or, in other embodiments, 430 ± 30 nm, and where the coating blocks 5% to 70% light within the range of 430 ± 20 nm or 430 ± 30 nm with a yellowness index of 35.0 or less. In other embodiments, a YI of 30 or less, or 25.0 or less, or 20.0 or less, or 17.5 or less, or 15.0 or less, or 12.5 or less, or 10.0 or less, or 9.0 or less, or 8.0 or less, 7.0 or less, 6.0 or less, 5.0 or less, 4.0 or less, 3.0 or less, is preferred for reduce the dose of blue light to the retina and allow the best possible cosmetic for the intended application. YI varies based on specific filter application.
[00125] In one embodiment, the coating is applied by any of: spin coating, dip coating, spray coating, evaporation, sputtering, chemical vapor deposition or any combination thereof, or by other methods known in the art of application of coatings.
[00126] A coating as described above is also provided, where the coating is applied to a non-ophthalmic system and selectively inhibits visible light between 430 ± 20 nm or, in other embodiments, 430 ± 30 nm, and where the coating blocks 5% to 60% light within the range of 430 ± 20 nm or 430 ± 30 nm with a yellowing index of 35.0 or less. In other embodiments, a YI of 30 or less, or 25.0 or less, or 20.0 or less, or 17.5 or less, or 15.0 or less, or 12.5 or less, or 10.0 or less, or 9.0 or less, or 8.0 or less, 7.0 or less, 6.0 or less, 5.0 or less, 4.0 or less, 3.0 or less, is preferred for reduce the dose of blue light to the retina and allow the best possible cosmetic for the intended application. YI varies based on specific filter application.
[00127] Also provided is a coating as described above, where the coating is applied to a non-ophthalmic system and selectively inhibits visible light between 430 ± 20 nm or, in other embodiments, 430 ± 30 nm, and where the coating blocks 5% to 50% light within the range of 430 ± 20 nm or 430 ± 30 nm with a yellowing index of 35.0 or less. In other embodiments, a YI of 30 or less, or 25.0 or less, or 20.0 or less, or 17.5 or less, or 15.0 or less, or 12.5 or less, or 10.0 or less, or 9.0 or less, or 8.0 or less, 7.0 or less, 6.0 or less, 5.0 or less, 4.0 or less, 3.0 or less, is preferred for reduce the dose of blue light to the retina and allow the best possible cosmetic for the intended application. YI varies based on specific filter application.
[00128] Also provided is a coating as described above, where the coating is applied to a non-ophthalmic system and selectively inhibits visible light between 430 ± 20 nm or, in other embodiments, 430 ± 30 nm, and where the coating blocks 5% to 40% light within the range of 430 ± 20 nm or 430 ± 30 nm with a yellowing index of 35.0 or less. In other embodiments, a YI of 30 or less, or 25.0 or less, or 20.0 or less, or 17.5 or less, or 15.0 or less, or 12.5 or less, or 10.0 or less, or 9.0 or less, or 8.0 or less, 7.0 or less, 6.0 or less, 5.0 or less, 4.0 or less, 3.0 or less, is preferred for reduce the dose of blue light to the retina and allow the best possible cosmetic for the intended application. YI varies based on specific filter application.
[00129] In some embodiments, selective blue light filtration coatings comprising porphyrin dyes exhibit tunable filtration with: - less color or Chroma C - Delta E* lower (full color) and - lower YI values when compared to chroma blockers blue broadband or other coatings. Particularly, in one modality, the coatings disclosed in this descriptive report, which can provide up to 40% blue light blocking, have:- Chroma C < 5,0,- |a*| and |b*| < 2 and 4, respectively, - YI < 8.0, - delta E* < 5.0 and - JND < 2 units, - at high transmittance level.
[00130] In addition, in one modality, the coatings revealed in this descriptive report, which block 20% of blue light, have:- Chroma C = 2-3,- YI = 3 -4,- delta E* < 2.0 e- JND < 1 unit, - at transmittance level >90%. BRIEF DESCRIPTION OF THE DRAWINGS / FIGURES
[00131] Embodiments of the invention will now be described, by way of example only, with reference to the accompanying schematic drawings. The accompanying drawings, which are incorporated in this descriptive report and form part of the descriptive report, illustrate the present disclosure and further serve to explain the disclosed principles.
[00132] FIG. 1A shows decorative chemical structures of Cu-porphyrin in the FS dye series.
[00133] FIG. 1B shows more chemical structures of Cu-porphyrin dyes in the FS dye series.
[00134] FIG. 1C shows more chemical structures of Cu-porphyrin dyes in the FS dye series.
[00135] FIG. 1D shows more chemical structures of Cu-porphyrin dyes Cu dye series.
[00136] FIG. 2A shows chemical structures of porphyrin dyes in the TPP dye series.
[00137] FIG. 2B shows further chemical structures of porphyrin dyes in the TPP and FS-201 dye series.
[00138] FIG. 3A shows chemical structures of Cu-porphyrin dyes in the PF dye series.
[00139] FIG. 3B shows more chemical structures of Cu-porphyrin dyes in the PF dyes and Cu1 dye series.
[00140] FIG. 4 shows a schematic representation of the calculation of X, Y, and Z tristimulus values.
[00141] FIG. 5A shows the CIE LAB color system.
[00142] FIG. 5B shows another representation of the CIE LAB color system.
[00143] FIG. 6 shows the CIE LCH color system.
[00144] FIG. 7 shows the CIE 1931 color space.
[00145] FIG. 8 shows 1976 CIE color space.
[00146] FIG. 9A shows full color difference, delta E*, in CIE LAB color space.
[00147] FIG. 9B shows total color difference, delta E*, in CIE LCH color space.
[00148] FIG. 10 shows the a* and b* coordinates (CIE LAB color system) for blue selective blocking coatings comprising FS-206 dye with blue light blocking ranging from 10% to 40%.
[00149] FIG. 11 shows the delta a* and delta b* coordinates (CIE LAB color system) for blue selective blocking coatings comprising FS-206 dye with blue light blocking ranging from 10% to 40%.
[00150] FIG. 12 shows a YI vs. Exemplary Delta E for blue selective blocking coatings comprising FS-206 dye. Each symbol represents the measured coating; all coatings shown provide blue light blocking in the 10-40% range and exhibited YI between 2 and 8. The color difference in this FIG. (Delta E) was calculated as: La*b* (SAMPLE) - La*b* (STANDARD) with the polycarbonate lens with the worked surface used as the STANDARD.
[00151] FIG. 13 o shows the yellowing index vs. Chroma for blue interlocking finishes. The symbols represent coatings with about 20% blue light blocking, while the broken ellipsoid gives the range for coatings with 10-40% blue light blocking.
[00152] FIG. 14 shows Hue vs. Chroma for blue interlocking finishes. The symbols represent coatings with about 20% blue light blocking, while the broken ellipsoid gives the range for coatings with 10-40% blue light blocking.
[00153] FIG. 15 shows transmission spectra of selective filtration coatings on glass substrates comprising Cu(II) meso-Tetra(2-naphthyl)porphine (FS-206) dye at different concentrations. The ability to fine-adjust the % blue light blocking and YI can be obtained by adjusting the dye concentration in the coating. Table 7 provides examples of the relationship between dye concentration, YI, and % blue light blocking for coatings containing FS-206 dye.
[00154] FIG. 16 shows transmission spectra of selective filtration coating on glass substrates comprising FS-207 dye at different concentrations. Table 8 provides examples of the relationship between dye concentration, YI, and % blue block. Note: The glass substrate does not contribute to the YI shown in the Figure (in other words, the YI of the glass substrate is 0).
[00155] FIG. 17A shows the yellowing index (YI) vs. % blue light blocking, calculated for a different spectral range for coatings on glass substrates comprising FS-206 dye at different concentrations. Note: The glass substrate does not contribute to the YI shown in the Figure, (in other words, the YI of the glass substrate is 0).
[00156] FIG. 17B shows the yellowing index (YI) vs. % blue light blocking, calculated for a different spectral range for coatings on glass substrates comprising FS-206 dye at different concentrations.
[00157] FIG. 17C shows the yellowing index (YI) vs. % blue light blocking, calculated for a spectral range other than FIG. 17B for coatings on glass substrates comprising FS-206 dye at different concentrations.
[00158] FIG. 17D shows the yellowing index (YI) vs. % blue light blocking, calculated for a different spectral range for coatings on glass substrates comprising FS-206 dye at different concentrations.
[00159] FIG. 17E shows the yellowing index (YI) vs. % blue light blocking, calculated for a different spectral range for coatings on glass substrates comprising FS-206 dye at different concentrations.
[00160] FIG. 17F shows the yellowing index (YI) vs. % blue light blocking, calculated for a different spectral range for coatings on glass substrates comprising FS-206 dye at different concentrations.
[00161] FIG. 18A shows dye transmission spectra of the TPP dye series before, during and after laboratory exposure testing to visible UV light under ambient conditions. Samples of blue blocking coatings comprising the individual dyes were exposed to Dymax Blue Wave 200 light for 30, 60 and 90 min, with the most stable dyes (determined after exposure to visible UV light for 90 min) exposed for up to 120 min. This set of dyes was selected in order to determine the most stable central metal within the porphyrin ring, while the pendants in all cases were phenyl.
[00162] FIG. 18B shows transmission spectra of more dyes from the TPP and FS-201 dye series before, during and after laboratory exposure testing to visible UV light under ambient conditions. Samples of blue blocking coatings comprising the individual dyes were exposed to Dymax Blue Wave 200 light for 30, 60 and 90 min, with the most stable dyes (determined after exposure to visible UV light for 90 min) exposed for up to 120 min. This set of dyes was selected in order to determine the most stable central metal within the porphyrin ring, while the pendants in all cases were phenyl.
[00163] FIG. 19A shows transmission spectra of the FS dye series before, during and after laboratory exposure testing to visible UV light under ambient conditions. Samples of blue blocking coatings comprising the individual dyes were exposed to Dymax Blue Wave 200 light for 30, 60 and 90 min, with the most stable dyes (determined after exposure to visible UV light for 90 min) exposed for up to 120 min. These dye sets were selected for testing in this category to determine the most stable pendant attached to a porphyrin with copper (Cu) as a central metal.
[00164] FIG. 19B shows transmission spectra of most FS series dyes before, during and after laboratory exposure testing to visible UV light under ambient conditions. Samples of blue blocking coatings comprising the individual dyes were exposed to Dymax Blue Wave 200 light for 30, 60 and 90 min, with the most stable dyes (determined after exposure to visible UV light for 90 min) exposed for up to 120 min. These dye sets were selected for testing in this category to determine the most stable pendant attached to a porphyrin with copper (Cu) as a central metal.
[00165] FIG. 19C shows transmission spectra of most FS-series and CU-series dyes before, during and after laboratory exposure testing to visible UV light under ambient conditions. Samples of blue blocking coatings comprising the individual dyes were exposed to Dymax Blue Wave 200 light for 30, 60 and 90 min, with the most stable dyes (determined after exposure to visible UV light for 90 min) exposed for up to 120 min. These dye sets were selected for testing in this category to determine the most stable pendant attached to a porphyrin with copper (Cu) as a central metal.
[00166] FIG. 19D shows serial transmission spectra of CU dyes before, during and after laboratory exposure testing to visible UV light under ambient conditions. Samples of blue blocking coatings comprising the individual dyes were exposed to Dymax Blue Wave 200 light for 30, 60 and 90 min, with the most stable dyes (determined after exposure to visible UV light for 90 min) exposed for up to 120 min. These dye sets were selected for testing in this category to determine the most stable pendant attached to a porphyrin with copper (Cu) as a central metal.
[00167] FIG. 20A shows transmission spectra of the TPP dye series before and during outdoor weathering test. Blue blocking coating samples comprising the individual dyes were exposed to the external environment for 24 hours/day for 1, 3 and 5 days. Outdoor testing continued for the most stable dyes. This set of dyes was selected in order to determine the most stable central metal within the porphyrin ring, while the pendants in all cases were phenyl.
[00168] FIG. 20B shows transmission spectra of more dyes from the TPP and FS-201 dye series before and during the outdoor weathering test. Blue blocking coating samples comprising the individual dyes were exposed to the external environment for 24 hours/day for 1, 3 and 5 days. Outdoor testing continued for the most stable dyes. This set of dyes was selected in order to determine the most stable central metal within the porphyrin ring, while the pendants in all cases were phenyl.
[00169] FIG. 21A shows transmission spectra of F-series and PF-series dyes before and during outdoor weathering testing. Blue blocking coating samples comprising the individual dyes were exposed to the external environment for 24 hours/day for 1 and 3 days. Outdoor testing continued for the most stable dyes. This set of dyes was selected in order to determine the most stable central metal within the porphyrin ring, while the pendants in all cases were penta-fluorophenyl.
[00170] FIG. 21B shows transmission spectra of most PF series dyes before and during outdoor weathering testing. Blue blocking coating samples comprising the individual dyes were exposed to the external environment for 24 hours/day for 1 and 3 days. Outdoor testing continued for the most stable dyes. This set of dyes was selected in order to determine the most stable central metal within the porphyrin ring, while the pendants in all cases were penta-fluor-phenyl.
[00171] FIG. 21C shows transmission spectra of most PF series dyes before and during outdoor weathering test. Blue blocking coating samples comprising the individual dyes were exposed to the external environment for 24 hours/day for 1 and 3 days. Outdoor testing continued for the most stable dyes. This set of dyes was selected in order to determine the most stable central metal within the porphyrin ring, while the pendants in all cases were penta-fluor-phenyl.
[00172] FIG. 21D shows transmission spectra of most F-series and PF-series dyes before and during outdoor weathering testing. Blue blocking coating samples comprising the individual dyes were exposed to the external environment for 24 hours/day for 1 and 3 days. Outdoor testing continued for the most stable dyes. This set of dyes was selected in order to determine the most stable central metal within the porphyrin ring, while the pendants in all cases were penta-fluorophenyl.
[00173] FIG. 22A shows transmission spectra of the FS dye series before and during outdoor weathering test. Blue blocking coating samples comprising the individual dyes were exposed to the external environment for 24 hours/day for 1, 3 and 5 days. Outdoor testing continued for the most stable dyes. These dye sets were selected for testing in this category to determine the most stable pendant attached to a porphyrin with copper (Cu) as a central metal.
[00174] FIG. 22B shows transmission spectra of most FS series dyes before and during outdoor weathering test. Blue blocking coating samples comprising the individual dyes were exposed to the external environment for 24 hours/day for 1, 3 and 5 days. Outdoor testing continued for the most stable dyes. These dye sets were selected for testing in this category to determine the most stable pendant attached to a porphyrin with copper (Cu) as a central metal.
[00175] FIG. 22C shows transmission spectra of most FS-series and Cu-series dyes before and during outdoor weathering test. Blue blocking coating samples comprising the individual dyes were exposed to the external environment for 24 hours/day for 1, 3 and 5 days. Outdoor testing continued for the most stable dyes. These dye sets were selected for testing in this category to determine the most stable pendant attached to a porphyrin with copper (Cu) as a central metal.
[00176] FIG. 22D shows transmission spectra of most Cu series dyes before and during outdoor weathering test. Blue blocking coating samples comprising the individual dyes were exposed to the external environment for 24 hours/day for 1, 3 and 5 days. Outdoor testing continued for the most stable dyes. These dye sets were selected for testing in this category to determine the most stable pendant attached to a porphyrin with copper (Cu) as a central metal.
[00177] FIG. 22E shows transmission spectra of the most stable FS dye series before and during the 60-day outdoor weathering test. These dye sets were selected for testing in this category to determine the most stable pendant attached to a porphyrin with copper (Cu) as a central metal.
[00178] FIG. 22F shows more transmission spectra of more stable FS dye series before and during outdoor weathering test performed for 60 days. These dye sets were selected for testing in this category to determine the most stable pendant attached to a porphyrin with copper (Cu) as a central metal.
[00179] FIG. 22G shows transmission spectra of the most stable Cu dye series before and during the 60-day outdoor weathering test. These dye sets were selected for testing in this category to determine the most stable pendant attached to a porphyrin with copper (Cu) as a central metal.
[00180] FIG. 23 shows the order of central metals of porphyrins with phenyl pendants according to their photostability. Photostability decreases moving from dye #1 towards a larger #. The ordering of the photostability of the dye was done according to the results of the laboratory exposure test to visible UV light and the outdoor weathering test for the TPP dye series. A similar trend was observed when the PF dye series was tested.
[00181] FIG. 24 shows the order of pendants according to their photostability as evaluated in porphyrin dyes with copper (Cu) as a central metal. Photostability decreases going from slope #1 toward a larger slope #. The ordering of the photostability of the pendant was done according to the results of the laboratory exposure test to visible UV light and the outdoor weathering test for the FS dye series and the Cu dye series.
[00182] FIG. 25 shows a schematic representation of laminated glass consisting of two glass substrates and a polymer interlayer.
[00183] FIG. 26 shows polymer interlayer structures that can be used in laminated glass applications.
[00184] FIG. 27A shows a schematic representation of blue selective blocking coatings further protected with UV blockers/stabilizers, where the UV blocking layer is added on top of the blue blocking coating.
[00185] FIG. 27B shows another schematic representation of selective blue blocking coatings further protected with UV blockers/stabilizers, in which the blue blocking coating is exposed to coloration in the UV blocking bath and the UV blocking diffuses into the coating.
[00186] FIG. 27C shows another schematic representation of selective blue blocking coatings further protected with UV blockers/stabilizers, where UV blocker and/or UV stabilizer is added to the blue blocking coating.
[00187] FIG. 27D shows a schematic representation of selective blue blocking coatings further protected with UV blockers/stabilizers, where the UV blocker is chemically attached to the dye molecule in the blue blocking coating.
[00188] FIG. 28A shows examples of reactive groups that can be attached to existing porphyrin pendants or directly to the porphyrin ring.
[00189] FIG. 28B shows an example of different possible reactive groups that can be attached to a specific Cu-porphyrin compound, porphyrin pendant or porphyrin ring.
[00190] FIG. 28C shows another example of different possible reactive groups that can be attached to a specific Cu-porphyrin compound, porphyrin pendant or porphyrin ring.
[00191] FIG. 28D shows another example of different possible reactive groups that can be attached to a specific Cu-porphyrin compound, porphyrin pendant, or porphyrin ring.
[00192] FIG. 29A shows an embodiment of manufacturing steps for CR-39 lenses.
[00193] FIG. 29B shows another embodiment of CR-39 lens fabrication.
[00194] FIG. 29C shows yet another embodiment of CR-39 lens fabrication.
[00195] FIG. 30 shows an embodiment of manufacturing steps for PC lenses.
[00196] FIG. 31 shows an embodiment of manufacturing steps for MR-8 lenses.
[00197] FIG. 32A shows an MR-8 lens fabrication modality.
[00198] FIG. 32B shows another MR-8 lens manufacturing modality.
[00199] FIG. 32C shows yet another MR-8 lens manufacturing modality.
[00200] FIG. 33 shows manufacturing steps for MR-7 lenses.
[00201] FIG. 34 shows manufacturing steps for MR-10 lenses.
[00202] FIG. 35 shows an embodiment in which a removable protective layer is used during the manufacture of a lens.
[00203] FIG. 36 shows an example of both HPO-based coated surfaces on inherently non-UV blocking lens substrates.
[00204] FIG. 37 shows an example of both HPO-based coated surfaces on inherently UV-blocking lens substrates.
[00205] FIG. 38 shows transmission spectra of (a) glass substrate coated on both surfaces with HPO base comprising FS-206-porphyrin dye (solid line), (b) glass substrate coated on both surfaces with the same base as in (a), but the coating was pulled from a surface (dotted line), and (c) glass substrate of which a surface was covered with protective tape before dip coating with the same HPO base as in (a) (broken line).
[00206] FIG. 39 shows a schematic cross-sectional representation of (a) semi-finished block (SFB), (b) finished thick lens blocks, and (c) finished lens blocks with the surface worked. Semi-finished blocks (a) and thick lens blocks with surface worked (b) are capable of being surface worked into finished lens blocks (c).
[00207] FIG. 40 shows the CIE Standard D65 Illuminant transmission spectrum.
[00208] FIG. 41 shows an exemplary transmission spectrum of systems comprising an optical filter.
[00209] FIG. 42 shows additional exemplary transmission spectra of systems comprising an optical filter.
[00210] FIG. 43 shows additional exemplary transmission spectra of systems comprising an optical filter.
FIG. 44 shows additional exemplary transmission spectra of systems comprising an optical filter.
[00212] FIG. 45 shows additional exemplary transmission spectra of systems comprising an optical filter.
[00213] FIG. 46 shows additional exemplary transmission spectra of systems comprising an optical filter.
[00214] FIG. 47 shows additional exemplary transmission spectra of systems comprising an optical filter.
[00215] FIG. 48 shows additional exemplary transmission spectra of systems comprising an optical filter.
[00216] FIG. 49 shows the percent reduction in cell death as a function of percent selective blue light blocking (430 ± 20 nm).
[00217] FIG. 50A shows FS-206 dye transmission spectra before and after thermal testing.
[00218] FIG. 50B shows FS-209 dye transmission spectra before and after thermal testing.
[00219] FIG. 50C shows Cu1 dye transmission spectra before and after thermal testing.
[00220] FIG. 50D shows Cu1 dye transmission spectra before and after thermal testing.
[00221] FIG. 51 shows an exemplary transmission spectrum of a glass slide.
[00222] FIG. 52 shows exemplary transmission spectra of a glass slide of FIG. 51 which is coated with base and a hard coating.
[00223] FIG. 53 shows the transmission spectra of a system comprising the glass slide of FIG. 51. The glass slide is coated with an optical filter that has about 20% blue light blocking and the hard coating used in FIG. 52. The optical filter used in FIG. 53 comprises the base used in FIG. 52.
[00224] FIG. 54 shows the transmission spectra of a system comprising the glass slide of FIG. 51. The glass slide is coated with an optical filter that has about 30% blue light blocking and the hard coating used in FIG. 52. The optical filter used in FIG. 54 comprises the base used in FIG. 52.
[00225] FIG. 55 shows the transmission spectra of a system comprising the glass slide of FIG. 51. The glass slide is coated with an optical filter that has about 40% blue light blocking and the hard coating used in FIG. 52. The optical filter used in FIG. 55 comprises the base used in FIG. 52. DETAILED DESCRIPTION GLOSSARY
[00226] Across wavelength range or across range: Includes the start point and end point of the wavelength range, and each wavelength in the range. For example, across the wavelength range 460 -700 nm includes the wavelengths 460 nm, 700 nm, and each wavelength between 460 nm and 700 nm.
[00227] Alkoxy groups: Alkoxy groups include, without limitation, methoxy, ethoxy, propoxy, isopropoxy, butoxy and isobutoxy.
[00228] At least 5% less than X%: Means 5% is subtracted from X%. So, for example, if X% is 80%, then “at least 5% less than X%” would be less than 75%. The percentage should not be calculated by multiplying - that is, 5% less than 80% is not 80% (0.95) = 76%, but 80% - 5% = 75%.
[00229] Average transmission: The “average transmission” for a wavelength band or bands is the average value of the transmission spectra across the band(s). Mathematically, the average transmission is: A / W, where W is the length of the wavelength band(s) along the X axis of the transmission spectrum, and A is the area under the transmission spectrum in the length band wave. This is to say that the "average transmission" of a spectrum over a wavelength band is calculated by integrating the spectrum to determine the area under the transmittance curve across the band, and dividing by the length of the wavelength band. .
[00230] So, for example, a spectrum that has 90% transmission at most wavelengths in a wavelength range, but 50% transmission only at some wavelengths in the wavelength range would have an “average transmission” above 80% across the wavelength range, as the calculation described above would result in a number close to 90%, despite the fact that transmission at a few points is well below 80%.
[00231] An application of "average transmission" is in calculating T5 and T6. The filter has an average transmission (T5) over a wavelength range that is 5 nm below a first wavelength up to 5 nm above the first wavelength. If the first wavelength is 420 nm, the range (W) for T5 is 10 nm (415 nm-425 nm, inclusive). The area (A) under the transmission spectrum of the filter between 415 nm and 425 nm is determined. That area (A) is divided by the wavelength range (W).
[00232] The transmission spectrum of the filter also has a transmission average (T6) in a wavelength range from 400 nm to 460 nm. However, that range excludes a range that is 5 nm below to 5 nm above the first wavelength. Thus, if the first wavelength is 420 nm, the range (W) for T6 is 48 nm (400 nm to 414 nm, inclusive, and 426 nm to 460 nm, inclusive). The area (A) under the transmission spectrum of the filter between 400 nm to 414 nm and 426 nm to 460 nm is determined. The area (A) is then divided by the wavelength range (W) to obtain an average transmission. The comparison of T5 with T6 aims to describe the magnitude of a slope in the filter's transmission spectrum around the first wavelength. T5 is at least 5% smaller than T6.
[00233] Blue light: Light in the wavelength range from 400 nm to 500 nm.
[00234] CIE LAB: A quantified color space adopted by the “International Commission on Illumination”, alternatively known as the “Commission Internationale de l'Eclairage” or CIE. This system is based on the scientific understanding that vision is based on light vs. distinctions. dark, red vs. green and blue vs. yellow. This three-dimensional color space has a vertical axis that represents lightness (L*) from black to white, and 2 horizontal color axes that represent green - red (a* negative to a* positive) and blue-yellow (b* negative up to positive b*). Any perceived color can be represented as a point in color space with coordinates (L*, a*, b*). The coordinates (a*, b*) define the color, while the L* define the lightness of that color. In this system, color can alternatively be defined by saturation and hue.
[00235] As used herein, CIE LAB refers to the 1976 CIE LAB color space.
[00236] “CIE Standard Illuminant D65”: A specific spectrum of light defined by an international organization and widely known to the relevant scientific community. According to the International Organization for Standardization (ISO): “[D65] is intended to represent average daylight and has a correlated color temperature of approximately 6500 K. “CIE Standard Illuminant D65” should be used in all colorimetric calculations that require representative daylight unless there are specific reasons for using a different illuminant”. ISO 10526: 1999/CIE S005/E-1998. “CIE” is an abbreviation for “Commission Internationale de l’Eclairage”, or “International Commission on Illumination”, an international authority on light, illumination, color and color spaces.
[00237] Figure 49 illustrates the spectrum for “CIE Standard Illuminant D65”.
[00238] The CIE LAB color coordinates for D65 light were calculated to be (see Method for calculating CIE LAB color coordinates below for color calculation method):L* = 100.00a* = -0.013b* = -0.097
[00239] Chroma: a measurement of color saturation in the CIE LAB space. Chroma takes into account differences in a* and b*, but not L*. For a certain set of coordinates (a*1, b*1, L*1), the “chroma” is (a*1)2 + (b*1)2)1/2e is a measure of how far the point is of the neutral axis of color which has coordinates (0, 0, L*1). But, the difference in saturation between two points in color space, where the two points have coordinates (a*1, b*1, L*1) and (a*2, b*2, L*2), is ((a*2 - a*1)2 + (b*2-b*1)2)1/2
[00240] Copper-porphyrin compound: A compound that has the following chemical structure:
wherein R1 through R12 can each independently be H or any possible substituent.
[00241] Cu(II): copper(II); Cu2+.
[00242] Delta E or ΔE: In CIE LAB space, ΔE is the distance between two points, and is a measure of the perceived color difference. When the two points have CIE LAB coordinates (a*1, b*1, L*1) and (a*2, b*2, L*2),ΔE = ( (a*2 - a*1) 2 + (b*2 - b*1) + (L*2 - L*1) 2) ^/2
[00243] Laid on: A layer is “laid on” a surface as long as it is attached to the surface. The layer can be above or below the surface. There may be intervening layers.
[00244] Dispersed through: A compound is dispersed through a substrate if the molecules of the compound are located throughout the structure of the substrate.
[00245] Spectacle lens: An spectacle lens includes any lens worn over the eye. Eyeglass lenses are often supported by a frame. Eyeglass lenses can be supported in other ways, for example by an adjustable band worn around the head that can also function as a safety shield or water barrier. Examples of eyeglass lenses include prescription lenses, over-the-counter lenses, multifocal lenses, safety lenses, over-the-counter reading glasses, goggles, and sunglasses lenses. Eyeglass lenses can be made of glass, but they can also be made of other materials. Common eyeglass materials include polycarbonate (e.g., MR-10), allyl diglycol carbonate (also known as CR-39), and others known in the art.
[00246] Filter: A molecular compound or physical structure that attenuates light transmitted through an object or reflected by the object to which the filter is applied. Filters can work through reflection, absorption or interference.
[00247] Hue: A color tint measurement in the CIE LAB system. For a certain set of coordinates (a*1, b*1, L*1), the “hue” angle is Arctangent (b*/a*)
[00248] This can be viewed as the angle between the positive axis a* and the line drawn to the point (a*1, b*1). The angle is measured by convention in the counterclockwise direction; for example, shades of red along the positive a* axis have a hue angle of 0°, shades of yellow along the positive b* axis have a hue angle of 90°, shades of green along the negative a axis * have a hue angle of 180°, and shades of blue along the negative b axis* have a hue angle of 270°.
[00249] Negative side of a wavelength: The negative side of a wavelength means on the left side of where the wavelength is located on the X axis of a transmission spectrum, when the wavelengths increase from left to the right along the X axis. For example, if the current wavelength is 420 nm, a wavelength that is “on the negative side of” 420 nm is 410 nm.
[00250] Non-Ocular System: A system that does not pass light through a wearer's eye. A non-limiting example is a skin or dermatological lotion.
[00251] Non-ophthalmic ocular system: A non-ophthalmic ocular system is any system through which light passes on its way to the eye of a user that is not an ophthalmic system. Together, ophthalmic and non-ophthalmic eye systems include all systems through which light passes on its way to a wearer's eye. Light sources such as light bulbs or video screens can be considered non-ophthalmic systems as light passes through several layers of the light source on its way to a user's eye. Non-limiting examples of non-ophthalmic systems include a window, an automotive windshield, an automotive side window, an automotive rear window, a sunroof window, commercial glass, residential glass, skylights, a bulb and camera flash lens, an artificial lighting device, a magnifying glass, a fluorescent light or diffuser, a medical instrument, a surgical instrument, a rifle sight, a binocular, a computer monitor, a television screen, an illuminated sign, and a light fixture of patios.
[00252] Eye: Visual; observed by the eye.
[00253] Eye system: Any system through which light passes on its way to a wearer's eye.
[00254] Ophthalmic: From the eye or belonging to the eye. As used herein, the term "ophthalmic" is a subset of "ocular".
[00255] Ophthalmic system: An ophthalmic system is worn by a wearer, and modifies the light to which the wearer's eye is exposed. Ophthalmic systems are a subset of ocular systems. Common ophthalmic systems include an eyeglass lens, a sunglasses lens, a contact lens, an intraocular lens, an intracorneal implant, safety glasses, and an extracorneal implant. These systems can be used to correct vision, to protect the eye from physical harm, to protect the eye from harmful radiation, and/or for cosmetic purposes. Systems through which a user looks only occasionally and which are typically not used, for example a magnifying glass, rifle sight, camera lens, binoculars or telescope, are not considered “ophthalmic” systems.
[00256] Optical filter: A filter that has a light transmission spectrum that attenuates certain wavelengths of light as they pass through the optical filter.
[00257] Phototic light transmission: Phototic light transmission is a quantitative measurement of light transmission through a lens. It differs from average transmission in that the transmission values at each wavelength are weighted using the spectral sensitivity of the human eye. In this sense, it is often considered more relevant for visual applications than the average transmission that weights all wavelengths equally and therefore does not take into account the physics of human vision. There are different technical terms for this metric and photooptics is included in this definition to explicitly indicate which color matching functions are used for photooptic vision.
[00258] Phototic light transmission can be calculated using various colorimetric systems of the CIE (“Commission Internationale de l'Eclairage”). In general, the light transmission is the transmission integral, TÀ, multiplied by the light source intensity, SÀ, multiplied by the color combination function yÀ, as shown in the equation:

[00259] This equation can be found in [3(3.3.8)] in “Color Science: Concepts and Methods, Quantitative Data and Formulae”, G. Wyszecki and W. Stiles, 1982, page 157 (“Wyszecki”). The value is calculated over the wavelength range of 400-700 nm using a 1 nm wavelength increment, the SÀ values of the D65 1971 illuminant, and the CIE 1931 color matching functions. The SÀ values of the illuminant and the yÀ values of the color matching function were obtained from Wyszecki, pages 156, 725-735. The constant k in this equation is given by the equation:

[00260] As the data are available in different values in 1 nm wavelength increments, the calculation is done by summing the data in a spreadsheet to approximate the integral, as shown in the equation below:

[00261] Reflected by: In the context of an ophthalmic system, light on its way to the user's eye is “reflected by” the system and can be observed by those looking at the user.
[00262] Similarly, in the context of a non-ophthalmic system, light on its way to the user's eye is “reflected” by the system, and then potentially to an observer. For example, the measurement of light “reflected by” a car windshield should be light coming from outside the car and reflecting off the windshield.
[00263] Reflection spectrum: A spectrum that shows, for each wavelength, the percentage of light reflected at that wavelength by the object that has the transmission spectrum. Since it is based on percentages at each wavelength, a reflection spectrum is independent of the light source used to measure the spectrum.
[00264] Slope: In the context of a broadcast spectrum curve or similar, the “slope” at a point is the slope of the line tangent to the curve at that point. When data is distinct, for example when a transmission spectrum is defined by a value at each integer value wavelength, the “slope” at a point can be calculated using data from adjacent points. For example, the slope of a transmission curve at 440 nm is the slope of the line connecting the transmission value at 439 nm to the transmission value at 441 nm.
[00265] Substrate: In a structure that has multiple layers created by deposition of some layers on others, the substrate is the initial layer on which the other layers are deposited. The substrate is often, but not always, the thickest layer in a structure. For example, in an eyeglass lens, the finished lens block is the substrate. Any coatings deposited on the block are not the substrate.
[00266] A structure can have multiple substrates if the existing structures are attached to each other. For example, a shatterproof windshield can be manufactured by attaching two layers of glass using PVB as an adhesive. Each glass layer can be considered a substrate, as each glass layer was, at some point, an initial layer with nothing deposited on it or affixed to it. Chemical compounds can be dispersed across a substrate.
[00267] Surface: Any face of a layer of material on which other material can be placed. For example, in a semi-finished CR-39 lens block, the finished face is a surface. Additionally, the unfinished face is also a surface.
[00268] Transmission: The fraction of light that is transmitted through a system. Transmission is measured by a spectrometer that can detect the amount of light at specific wavelengths. These measurements are usually made by measuring the amount of light from a light source at a specific wavelength in the air (no system) and then measuring under the same conditions with the system between the light source and the detector. Transmission is the proportion, or percentage, of light that is transmitted through the system at each wavelength. Light not transmitted through the system is reflected, scattered, or absorbed. The transmission range is 0-1 or 0-100%. These measurements are generally independent of the measurement system's light source.
[00269] Transmission spectrum: A spectrum that shows, for each wavelength, the percentage of light transmitted at that wavelength by the object that has the transmission spectrum. Since it is based on percentages at each wavelength, a transmission spectrum is independent of the light source used to measure the spectrum.
[00270] Transmitted through: In the context of an ophthalmic system, light on its way to the user's eye is “transmitted through” the system, and then to the user's eye. Similarly, in the context of a non-ophthalmic system, light on its way to the wearer's eye is “broadcast through” the system, and then to the wearer's eye. For example, the measurement of light “transmitted through” a car windshield should be light coming from outside the car into the car.
[00271] Visible light: Light that has a wavelength in the range of 400 nm to 700 nm.
[00272] Yellowness Index: A measure of how “yellow” light appears after transmission through a system, [needs further description of standard definition]. The yellowing index of a system can be calculated from its transmission spectra, [describe how or provide reference/standard].
[00273] Method for CIE LAB color coordinate and yellowness index calculations: All CIE LAB color coordinates (a*, b*, L*) and yellowness indices (YI) described and claimed in this descriptive report are calculated using standardized colorimetric formulas in an Excel spreadsheet based on spectral transmission data. Calculations are made using 1 nm intervals from 380-780 nm for the CIE 1931 color matching functions. See G. Wyszecki and WS Stiles, "Color Science: Concepts and Methods, Quantitative Data and Formulae", 2nd Edition, 1982, (“Wyszecki”), CIE 1931 color matching functions: x(À), y(A), z(À)- Table 1 (3.3.1), pages 725-735. and the D65 CIE 1971 illuminant. (Wyszecki, D65 CIE 1971 illuminant - Table 1 (3.3.4), pages 754-758). When transmission data was not available in 1 nm wavelength increments, this data was converted to this pattern using linear interpolation of the data. Tristimulus values were calculated using the following distinct sum versions of Wysecki and Styles integral equations:
equation 3 (3.3.8), pages 157.
[00274] The equations and reference values used to convert the tristimulus values to the L*a*b* CIE 1976 color coordinates (Wyszecki, equation 5 (3.3.9), page 167) are shown below along with the values of White reference D65 1931:

[00275] The yellowing index (YI) was calculated using the transmission data, the equation below and the coefficients in ASTM E313 - 05 in the table below. “ASTM E313 - 05, Standard Practice for Calculating Yellowness and Whiteness Indices from Instrumentally Measured Color Coordinates”, “ASTM International”.
[00276] YI was calculated assuming the D65 CIE light source with standard 1931 illuminating factors (2° viewing angle).
where X, Y, and Z are the CIE tristimulus values and the coefficients depend on the illuminant and observer, as indicated in the table below from ASTM standard E313-05.
Equation coefficients for the yellowing index
[00277] The numbering convention for substituents used herein places the substituents R1 through R8 on a pyrrole of the Cu-porphyrin complex, and R groups with higher numbers elsewhere. This allows for an easy distinction between permitted substituents in pyrroles and permitted substituents elsewhere. The inventors believe that certain substituents can degrade molecular stability if placed on the pyrrole (at one or more of the positions of R1 through R8), but may be relatively benign if placed elsewhere. The numbering convention used here allows for the easy description of a narrow group of substituents permitted on pyrrole, and a broader group of substituents permitted elsewhere.
[00278] Cataracts and macular degeneration are believed to result from photochemical damage to the lens and retina, respectively. Exposure to blue light has also been shown to accelerate the proliferation of uveal melanoma cells. The most energetic photons in the visible spectrum have wavelengths between 380 and 500 nm and are perceived as violet or blue. The wavelength dependence of phototoxicity plus all mechanisms is often represented as a spectrum of action, as described in Mainster and Sparrow, "How Much Blue Light Should an IOL Transmit " Br. J. Oftalmol., 2003, v. 87, pages 1523-29 and FIG. 6. In eyes without an intraocular lens (aphakic eyes), light with wavelengths shorter than 400 nm can cause damage. In phakic eyes, this light is absorbed by the intraocular lens and therefore does not contribute to retinal phototoxicity; however, it can cause optical lens degradation or cataracts.
[00279] The pupil of the eye responds to photooptic retinal illuminance, in troland (a unit of conventional retinal illuminance; a method for correcting photometric measurements of luminance values that fall on the human eye by scaling these values by the effective pupil size), which is the product of the incident flux with the wavelength-dependent sensitivity of the retina and the projected area of the pupil. This sensitivity is described in Wyszecki and Stiles, "Color Science: Concepts and Methods, Quantitative Data and Formulae" (Wiley: N.Y.) - 1982, esp. pages 102-107.
[00280] Current research strongly supports the premise that short-wavelength visible light (blue light) having a wavelength of approximately 400-500 nm could be a contributing cause of AMD (age-related macular degeneration). The greatest level of retinal damage from blue light is believed to occur in a region around 430 nm, eg 400-460 nm. Research even suggests that blue light worsens other causative factors in AMD, for example, heredity, smoking, and binge drinking.
[00281] The human retina includes multiple layers. These layers, listed in order from the first exposed to any light entering the eye to the deepest, include: 1) Nerve fiber layer 2) Ganglion cells 3) Inner plexiform layer 4) Bipolar and horizontal cells 5) Plexiform layer external 6) Photoreceptors (cones and rods) 7) Retinal pigment epithelium (RPE) 8) Bruch's membrane 9) Choroid.
[00282] When light is absorbed by the eye's photoreceptor cells (cones and rods), the cells whiten and become unreceptive until they recover. This recovery process is a metabolic process and is called the “visual cycle”. Blue light absorption has been shown to reverse this process prematurely. This premature reversal increases the risk of oxidative damage and is believed to lead to the formation of the pigment lipofuscin in the retina. This formation occurs in the retinal pigment epithelium (RPE) layer. It is believed that aggregates of extracellular materials called drusen are formed as a result of excessive amounts of lipofuscin.
[00283] Current research indicates that over the course of a person's life, starting as an infant, metabolic waste by-products accumulate within the retinal pigment epithelium layer as a function of light interactions with the retina. This metabolic waste product is characterized by certain fluorophores, one of the most prominent being the constituent of lipofuscin A2E. In vitro studies by Sparrow indicate that the lipofuscin A2E chromophore found within the RPE is maximally excited by light at 430 nm. It is theorized that an inflection point is reached when after a formation of this metabolic waste (specifically the lipofuscin fluorophore) has reached a certain level of accumulation, the physiological ability of the human body to metabolize a part of this waste within the retina decreases when people reach certain age threshold, and a blue light stimulus of the proper wavelength causes drusen to form in the RPE layer. Drusen is then believed to still interfere with normal metabolic physiology/activity which allows adequate nutrients to reach photoreceptors, thereby contributing to age-related macular degeneration (AMD). AMD is the leading cause of severe irreversible loss of visual acuity in the United States and the Western world. AMD damage is expected to increase dramatically over the next 20 years as the projected change in population and the global increase in the number of aging individuals is expected.
[00284] The drusen prevent or block the RPE layer from providing adequate nutrients to the photoreceptors, which leads to damage or even death of these cells. To further complicate this process, it appears that when lipofuscin absorbs blue light in high amounts it becomes toxic, causing further damage and/or death to the RPE cells. The lipofuscin A2E constituent is believed to be at least partially responsible for the short wavelength sensitivity of RPE cells. It has been shown that A2E is maximally excited by blue light; the photochemical events that result from this excitation can lead to cell death. See, for example, Janet R. Sparrow et al., "Blue Light-Absorbing Intraocular Lens and Retinal Pigment Epithelium Protection in vitro", J. Cataract Refract. Surg. 2004, vol. 30, pages 873-78. A reduction in short wavelength transmission in an ophthalmic system may be useful in reducing cell death as a consequence of photoelectric effects in the eye, eg excitation of A2E, a lipofuscin fluorophore.
[00285] It has been shown that reducing incident light to 430 ± 30 nm by about 50% can reduce cell death by about 80%. See, for example, Janet R. Sparrow et al., "Blue Light-Absorbing Intraocular Lens and Retinal Pigment Epithelium Protection in vitro", J. Cataract Refract. Surg. 2004, vol. 30, pages 873-78, the disclosure of which is incorporated by reference in its entirety. It is further believed that reducing the amount of blue light, eg light in the 430-460 nm range, by as little as 5% may similarly reduce cell death and/or degeneration and therefore avoid or reduce adverse effects conditions such as atrophic age-related macular degeneration. FIG. 49 shows the percent reduction in cell death as a function of percent selective blue light blocking (430 ± 20 nm).
[00286] Additional laboratory evidence by Sparrow at Columbia University for high-throughput optics has demonstrated that blue light filtering dye concentrations at levels as low as 1.0 ppm and 1.9 ppm can provide retinal benefit in a predominantly colorless system, " Light Filtering in Retinal Pigment Epithelial Cell Culture Model” Optometry and Vision Science 88; 6 (2011): 1-7, referenced in its entirety. As shown in Figures 51 and 52 of the Sparrow report, it is possible to vary the concentration of the filter system up to a level of 1.0 ppm or greater to a level of about 35 ppm, as exemplified with the perylene dye. Any concentration level between about 1.0 ppm or greater to about 35 ppm can be used. Other dyes that exhibit similar blue light blocking function could also be used with similar varying concentration of dye levels.
[00287] Table 1 below demonstrates reduction of RPE cell death as percentages of light blocking increase with the porphyrin dye, MTP.

[00288] From a theoretical perspective, the following seems to occur: 1) The gradual increase in tailings occurs within the level of the pigment epithelium starting in childhood and throughout life. 2) The metabolic activity and ability of the retina to deal with these wastes typically decrease with age. 3) The pigment in the macula typically decreases as the individual ages, thus filtering out less blue light. 4) Blue light causes lipofuscin to become toxic. The resulting toxicity damages pigment epithelial cells.
[00289] The lighting and vision care industries have standards regarding the exposure of human vision to UVA and UVB radiation. There is no such pattern with regard to blue light. For example, in common fluorescent tubes available today, the glass envelope predominantly blocks ultraviolet light, but blue light is transmitted with little attenuation. In some cases, the envelope is designed to have increased transmission of the blue region of the spectrum. This danger from artificial light sources can also cause eye damage. There is also growing concern that exposure to LED lights could impact retinal integrity.
[00290] Conventional methods for reducing exposure to blue light from ocular media typically completely occlude light below a threshold wavelength, while also reducing exposure to light at longer wavelengths. For example, the lenses described in U.S. Patent No. 6,955,430 to Pratt transmit less than 40% of incident light at wavelengths as long as 650 nm, as shown in FIG. 6 of Patent 6,955,430 to Pratt. The blue light blocking lens disclosed by Johansen and Diffendaffer in U.S. Patent No. 5,400,175 similarly attenuates light by more than 60% across the entire visible spectrum, as illustrated in FIG. 3 of the '175 patent.
[00291] Balancing the range and amount of blue light blocked can be difficult, as blocking and/or inhibiting blue light affects color balance, color vision, if an individual looks through the optical device. , and the color in which the optical device is perceived. For example, shooting glasses appear to bring out yellow and block out blue light. Shooting glasses often make certain colors more apparent when looking at a blue sky, allowing the shooter to see the targeted object sooner and more accurately. While this works well for shooting glasses, it would be unacceptable for many ophthalmic applications. In particular, these ophthalmic systems may not be cosmetically appealing because of a yellow or amber tint that is produced in lenses by blocking blue. More specifically, a common technique for blue blocking involves tinting or tinting lenses with a blue blocking tint, for example, “BPI Filter Vision 450” or “BPI Diamond Dye 500”. Staining can be achieved, for example, by immersing the lens in a heated tinting pot containing a blue blocking dye solution for a predetermined period of time. Typically, the solution has a yellow or amber color and thus imparts a yellow or amber tint to the lens. For many people, the appearance of this yellow or amber dye can be cosmetically undesirable. Also, tinting can interfere with a lens wearer's normal color perception, making it difficult, for example, to correctly perceive the color of a light or traffic sign.
[00292] It has been found that blocking conventional blue reduces visible transmission which, in turn, stimulates pupil dilation. Pupil dilation increases the flow of light to the internal structures of the eye, including the lens and retina. As radiant flow to these structures increases pupil diameter, a lens that blocks half of the blue light but with reduced visible transmission relaxes the pupil from 2 mm to 3 mm in diameter, and will actually increase the dose of blue photons. to the retina by 12.5%. Protection of the retina from phototoxic light depends on the amount of light that reaches the retina, which depends on the transmission properties of the ocular media and also on the dynamic opening of the pupil. Previous work was silent on pupil contrition for phototoxic blue light prophylaxis.
[00293] Another problem with conventional blue blocking is that it can degrade night vision. Blue light is more important for low-light vision or scotopic vision than for bright light vision or photooptic vision, a result that is expressed quantitatively in the light sensitivity spectra for scotopic and photopic vision. Photochemical and oxidative reactions cause the absorption of light from 400 to 450 nm by lens tissue to naturally increase with age. Although the number of rod photoreceptors in the retina that are responsible for low light vision also decreases with age, increased absorption by the lens is important for the degradation of night vision. For example, scotopic visual sensitivity is reduced by 33% in a 53-year-old lens and 75% in a 75-year-old lens. The tension between retinal protection and scotopic sensitivity is further described in Mainster and Sparrow, "How Much Light Should an IOL Transmit " Br. J. Oftalmol, 2003, v. 87, pages 1523-29.
[00294] Conventional blue blocking approaches can also include cut-off or high-pass filters to reduce transmission below a specified blue or violet wavelength to zero. For example, all light below a threshold wavelength can be blocked completely or almost completely. For example, U.S. Patent Application Published No. 2005/0243272 to Mainster and Mainster, "Intraocular Lenses Should Block UV Radiation and Violet but not Blue Light", Arch. Ophthalm., v. 123, page 550 (2005) describes blocking all light below a threshold wavelength between 400 and 450 nm. Such blockage may be undesirable, as as the edge of the long-pass filter is switched to longer wavelengths, pupil dilation acts to increase the total flow. As described previously, this can degrade scotopic sensitivity and increase color distortion.
[00295] Recently there have been debates in the field of intraocular lenses (IOLs) regarding proper UV and blue light blocking while maintaining acceptable photooptic vision, scotopic vision, color vision and circadian rhythms.
[00296] In another embodiment using a contact lens, a dye or pigment is provided which causes a yellowish tint that is located over the 2-9 mm center diameter of the contact lens and to which a second tint color is added peripherally to that of the central dyeing. In this modality, the dye concentration that provides wavelength selective filtering of light is increased to a level that provides the user with very good contrast sensitivity and, again, without significantly compromising photopic vision, scotopic vision, vision colors or circadian rhythms of the user (one or more, or all).
[00297] In yet another embodiment that uses a contact lens, the dye or pigment is provided in such a way that it is located over the entire diameter of the contact lens, from approximately one edge to the other edge. In this modality, the dye concentration that provides wavelength selective filtering of light is increased to a level that provides the user with very good contrast sensitivity and, again, without significantly compromising photopic vision, scotopic vision, vision colors or circadian rhythms of the user (one or more, or all).
[00298] When various modalities are used in or on human or animal tissue, the dye is formulated so as to chemically bond to the embedded substrate material thereby ensuring that it does not migrate into the surrounding corneal tissue. Methods for providing a chemical hook that allows such a connection are well known within the chemical and polymer industries.
[00299] In yet another embodiment, an intraocular lens includes a selective light wavelength filter that has a yellowish tint, yet provides the wearer with increased contrast sensitivity without significantly compromising photooptic vision, vision scotopic, color vision or circadian rhythms of the user (one or more, or all). When the selective filter is used over or inside an intraocular lens, it is possible to increase the level of dye or pigment beyond that of an eyeglass lens, as the intraocular lens cosmetic is invisible to those looking for the user. This gives the possibility to increase the dye or pigment concentration and provides even greater levels of increased contrast sensitivity and/or retinal protection, without significantly compromising the user's photooptic vision, scotopic vision, color vision or circadian rhythms (a or more, or all).
[00300] In yet another embodiment, an eyeglass lens includes a selective light wavelength filter that comprises a dye, wherein the dye formulation provides an eyeglass lens that has a predominantly colorless appearance and, in addition, which provides the user with increased contrast sensitivity without significantly compromising the user's photooptic vision, scotopic vision, color vision or circadian rhythm (one or more, or all).
[00301] Other modalities include a wide range in how the selective filter can be added to any system at varying concentrations and/or zones and/or rings and/or layers. For example, in an eyeglass lens, the selective filter does not necessarily need to be uniform throughout the system or at any fixed concentration. An ophthalmic lens could have one or more zones and/or rings and/or layers of varying filter concentration or any combination or combinations thereof.
[00302] One way to economically incorporate selective visible light filtration into an ophthalmic or non-ophthalmic system is through a coating that includes the filtering system. As an example only, the described coating may be incorporated into one or more than one: base coats, scratch resistant coatings, anti-reflective coatings, hydrophobic coatings or other coatings known in the ophthalmic or non-ophthalmic industry, or any combination or combinations thereof.
[00303] In light of the foregoing, there is a pressing need for an ophthalmic or non-ophthalmic system that can provide one or more of the following: 1) Blue blocking with an acceptable level of blue light protection. acceptable color, that is, perceived as predominantly neutral in color by someone observing the ophthalmic system when used by a user. 3) Acceptable color perception for a user. In particular, there is a need for an ophthalmic system that does not impair the user's color vision and yet reflections from the back surface of the system into the user's eye are at a level that is not unpleasant to the user. 4) Acceptable level of light transmission for wavelengths other than the wavelengths of blue light. In particular, there is a need for an ophthalmic system that allows selective blocking of blue light wavelengths while at the same time transmitting more than 80% visible light. 5) Photooptic vision, scotopic vision, acceptable color vision and/or circadian rhythms. 6) Exceptional durability and UV stability characteristics to promote the longevity of the blue light wavelength selective filter system.
[00304] A blue light wavelength filter can “selectively” filter blue light. A filter is “selective” when the amount of light it attenuates at each wavelength within a specified range of wavelengths is greater than the amount of light it attenuates at most wavelengths in the visible spectrum (400- 700 nm) outside the specified range. Preferably, a "selective" filter attenuates light more at each wavelength within the specified wavelength range than it attenuates light at all wavelengths in the visible spectrum (400 -700 nm) outside the specified range.
[00305] A non-limiting example of a transmission spectrum displayed by a wavelength selective filter of blue light is that of a dye that has a Soret band or a Soret peak. Another non-limiting example is a rugate filter and similar filters based on dielectric batteries. In many cases, the blue light filtering band is designed to reduce lipofuscin accumulation within retinal pigment epithelial (RPE) cells. A common lipofuscin chromophore is A2E, which has a peak at approximately 430 nm. Therefore, it is prudent to filter light at 430 nm, 420 nm, or within a range that includes 430 nm, to preserve retinal integrity. In other embodiments, more than one selective filter can be added to include filtering to target other chromophores or target wavelengths associated with circadian equilibrium.
[00306] There are many dye compounds on the market that can provide some type of blocking in the high energy visible light (HEVL) portion of the electromagnetic spectrum. However, not all of these dyes are selective, meaning they have narrow absorption peaks to block the necessary part of HEVL and not affect the other part of the spectrum that is necessary for normal biological functions. Furthermore, many of these dyes do not have satisfactory thermal and/or UV stability for many applications. Therefore, there is a need for a dye or dye mixture that has these selective blocking properties on the harmful portion of HEVL and is stable under various environmental conditions, including humidity, exposure to sunlight (UV), heat etc. Porphyrin dyes are good candidates to be used in coatings and/or substrates that can provide selective blocking of harmful HEVL due to their Soret band in the spectral range of 400-500 nm. Particularly, Copper (Cu)-porphyrins exhibit greater UV stability than other porphyrin compounds. By molecular design, the absorption peak of Cuporphyrins can be adjusted in the range of 400-500 nm. Cuporphyrins can be synthesized from non-metallated porphyrins, which are readily available from commercial suppliers, eg, Frontier Scientific (Logan, Utah).
[00307] The Soret band of a dye is a relatively narrow band of the visible electromagnetic spectrum located in the region of the blue light spectrum in which the dye has intense absorption of blue light. A Soret peak is thus a local maximum in the Soret band.
[00308] In one embodiment, a first system is provided. The first system comprises an optical filter comprising a Cu-porphyrin compound. The compound of Cu-
or a salt, or a tautomeric form thereof, wherein X is carbon or nitrogen, each of R1 through R8 is independently H, Cl, Br, F, I, Me, a straight chain alkyl having 2-20 (by example, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15,16, 17, 18, 19 or 20) carbon atoms, a branched alkyl having 2- 20 (for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20) carbons, or a portion represented by -LP; each of R9 through R28 is independently H, F, Br, Cl, I, CH3, a straight chain alkyl having 2-20 (e.g., 2, 3, 4, 5, 6, 7, 8 , 9, 10, 11, 12, 13, 14, 15,16, 17, 18, 19 or 20) carbon atoms, a branched alkyl having 2-20 (eg 2, 3, 4, 5, 6, 7,8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20) carbon atoms, nitro, sulfonic acid, carboxylic acid, a carboxylic ester, -R100-OH, -O -R200, -R100-N(R110R111), -R100-N+(R110R111R112), one aryl, one heteroaryl, acrylate, acryloyl, acrylamide, methacrylate, methacrylate ide, thiol, amide, or a moiety represented by -LP, or two of adjacent R9 to R28 may also form an aromatic or non-aromatic ring structure; R100 is a bond, -(CH2)n-, or a branched alkyl that has 2-20 (for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20) carbon atoms, in that n is 1-20 (for example, 1, 2, 3, 4, 5, 6, 7,8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20) ; and R110, R111, R112 and R200 are each independently H,Me, a straight-chain alkyl having 2-20 (for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19 or 20) carbon atoms, a branched alkyl having 2-20 (eg 2, 3, 4, 5, 6, 7, 8, 9 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20) carbon atoms or a moiety represented by -LP; wherein P is a polymer moiety or a polymerizable group and L is null or a linker, provided that when X is nitrogen then R11, R16, R21 and R26 are each independently a single pair or as defined above.
[00309] In some embodiments, X is carbon. In some embodiments, X is nitrogen and R11, R16, R21, and R26 are each independently an isolated pair. In some embodiments, X is nitrogen and R11, R16, R21, and R26 are each independently a Me.
[00310] In some embodiments, each of R1 through R8 is independently H, Cl, Br, F, I, Me, a straight-chain alkyl that has 2-20 (eg, 2, 3, 4, 5, 6 , 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20) carbon atoms or a branched alkyl having 2-20 (eg 2, 3, 4 , 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20) carbons. In some embodiments, each of R1 through R8 is H. In some embodiments, each of R1 through R8 is independently H, Cl, Br, F, a straight chain alkyl that has 2-20 (e.g., 2, 3 , 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20) carbon atoms or a branched alkyl having 2-20 (for example , 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20) carbons.
[00311] In some embodiments, each of R9 through R28 is independently H, F, Br, Cl, I, CH3, a straight-chain alkyl that has 2-20 (eg, 2, 3, 4, 5, 6 , 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20) carbon atoms, a branched alkyl having 2-20 (eg 2, 3, 4 , 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20) carbon atoms, nitro, sulfonic acid, carboxylic acid, a carboxylic ester, - R100-OH, -O-R200, -R100-N(R110R111), -R100-N+(R110R111R112), an aryl, a heteroaryl, acrylate, acryloyl, acrylamide, methacrylate, methacrylamide, thiol or amide. In some embodiments, each of R9 through R28 is independently H, F, Br, CH3, ethyl, propyl, isopropyl, butyl, isobutyl, carboxylic acid, a carboxylic ester, -R100-OH, -O-R200, -R100- N(R110R111), -R100-N+(R110R111R112), an aryl, a heteroaryl, acrylate, acryloyl, acrylamide, methacrylate, methacrylamide, thiol or amide. In some embodiments, each of R11, R16, R21, and R26 is Cl. In some embodiments, each of R11, R16, R21, and R26 is independently an O-R200 (e.g., OH, OMe, OEt etc.). In some embodiments, each of R11, R16, R21, and R26 is independently a straight-chain or branched alkyl having 2-20 carbons (e.g., tert-butyl). In some embodiments, each of R11, R16, R21, and R26 is a sulfonic acid. In some embodiments, each of R11, R16, R21, and R26 is Br. In some embodiments, each of R11, R16, R21, and R26 is COOH. In some embodiments, one of R11 and R21 is NH2 and the other of R11 and R21 is COOH. In some embodiments, each of R9 through R28 is F. In some embodiments, each of R10, R12, R15, R17, R20, R22, R25, and R27 is a straight or branched chain alkyl having 2-20 carbons ( for example tert-butyl). In some embodiments, R11 is -R100-N(R110R111)(e.g., N(R110R111), e.g., NH2). In some embodiments, R11 and R21 are each independently -R100-N(R110R111)(e.g., N(R110R111), e.g., NH2) and R16 and R26 are each COOH.
[00312] In some embodiments, two adjacent R9 to R28 form a ring. For example, R9 and R10 (and/or any other two adjacent R9-R28 groups, for example, R10 and R11, R11 and R12, R12 and R13, R14 and R15, R15 and R16, R16 and R17,R17 and R18, R19 and R20, R20 and R21, R21 and R22, R22 and R23, R24 and R25, R25 and R26, R26 and R27, R27 and R28 etc.), together with the phenyl ring (or pyridine ring if X is nitrogen) to to which they are attached, may form a bicyclic aromatic ring, for example a naphthyl ring, a quinoline ring or an isoquinoline ring. In some embodiments, R11 and R12, R15 and R16, R20 and R21 and R25 and R26, together with the respective phenyl ring to which they are attached, can form a naphthyl ring; see, for example, Formula I-7. In some embodiments, R9 and R10, R14 and R15, R19 and R20 and R24 and R25, together with the respective phenyl ring to which they are attached, can form a naphthyl ring; see, for example, Formula I-15. In some embodiments, R10 and R11, R16 and R17, R20 and R21, and R25 and R26, together with the respective phenyl ring to which they are attached, can form a quinoline ring; see, for example, Formula I-9. In some embodiments, quinoline is an N-methylated quinoline salt:
which is optionally substituted.
[00313] In one embodiment, the Cu-porphyrin compound has a structure in accordance with Formulas I-1 to I-16:





or a salt, or a tautomeric form thereof, wherein R1 to R28, R110, R111, R120, R121, R200-R203, R300-R315, R400-R411, R500-R515 are described herein.
[00314] In some embodiments, each of R1 through R8 is independently H, Cl, Br, F, methyl, ethyl, propyl, isopropyl, or a moiety represented by -L-P. In some embodiments, each of R9 to R28, R300-R315, R400-R411, R500-R515 is independently H, F, Br, CH3, ethyl, propyl, isopropyl, butyl, isobutyl, carboxylic acid, a carboxylic ester, - R100-OH, -O-R200, -R100-N(R110R111), -R100-N+(R110R111R112), an aryl, a heteroaryl, acrylate, acryloyl, acrylamide, methacrylate, methacrylamide, thiol, amide, or a moiety represented by -LP. In some embodiments, two of adjacent R9 through R28 form an aromatic or non-aromatic ring structure, for example, as described herein. In some embodiments, R100 is a bond, -(CH2)n-, or a branched alkyl that has 2-20 (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 , 13, 14, 15, 16, 17, 18, 19 or 20) carbon atoms, where n is 1-20 (eg 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20). In some embodiments, R110, R111, R120, R121, R200-R203 are each independently H, Me, a straight-chain alkyl that has 2-20 (e.g., 2, 3, 4, 5, 6, 7 , 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20) carbon atoms, a branched alkyl having 2-20 (eg 2, 3, 4, 5 , 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20) carbon atoms or a moiety represented by -LP.
[00315] In one embodiment, the Cu-porphyrin compound has the structure according to Formula I-1:
or a salt, or a tautomeric form thereof, wherein R1 through R28 are described herein.
[00316] In some embodiments, R9 through R28 are independently H, F, Br, CH3, a straight-chain alkyl that has 2-20 (eg, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20) carbon atoms, a branched alkyl having 2-20 (eg 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20) carbons, carboxylic acid, carboxylic ester, -R100-OH, -O-R200, -R100-N(R110R111 ), -R100-N+(R110R111R112), an aryl, a heteroaryl, acrylate, acryloyl, acrylamide, methacrylate, methacrylamide, thiol, amide, or a moiety represented by -LP. In some embodiments, two of adjacent R9 through R28 form an aromatic or non-aromatic ring structure, for example, as described herein.
[00317] In one embodiment, the Cu-porphyrin compound has the structure according to Formula I-2:
or a salt, or a tautomeric form thereof, wherein R1 through R28 are described herein.
[00318] In some embodiments, R9 through R28 are independently H, F, Br, CH3, a straight-chain alkyl that has 2-20 (eg, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20) carbon atoms, a branched alkyl having 2-20 (eg 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20) carbons, carboxylic acid, carboxylic ester, -R100-OH, -O-R200, -R100-N(R110R111 ), -R100-N+(R110R111R112), an aryl, a heteroaryl, acrylate, acryloyl, acrylamide, methacrylate, methacrylamide, thiol, amide, or a moiety represented by -LP. In some embodiments, two of adjacent R9 through R28 form an aromatic or non-aromatic ring structure, for example, as described herein.
[00319] In one embodiment, the Cu-porphyrin compound
or a salt, or a tautomeric form thereof, wherein R1 through R28 and R100-R103 are described herein.
[00320] In some embodiments, R9 through R28 are independently H, F, Br, CH3, a straight-chain alkyl that has 2-20 (eg, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20) carbon atoms, a branched alkyl having 2-20 (eg 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20) carbons, carboxylic acid, carboxylic ester, -R100-OH, -O-R200, -R100-N(R110R111 ), -R100-N+(R110R111R112), an aryl, a heteroaryl, acrylate, acryloyl, acrylamide, methacrylate, methacrylamide, thiol, amide, or a moiety represented by -LP. In some embodiments, two of adjacent R9 through R28 form an aromatic or non-aromatic ring structure, for example, as described herein. In some embodiments, R200-R203 are each independently H, Me, a straight-chain alkyl that has 2-20 (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19 or 20) carbon atoms or a branched alkyl having 2-20 (eg 2, 3, 4, 5, 6, 7, 8, 9 , 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20) carbon atoms.
[00321] In one embodiment, the Cu-porphyrin compound has the structure according to Formula I-4:
or a salt, or a tautomeric form thereof, wherein R1 through R28 are described herein.
[00322] In some embodiments, R9 through R28 are independently H, F, Br, CH3, a straight-chain alkyl that has 2-20 (eg, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20) carbon atoms, a branched alkyl having 2-20 (eg 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20) carbons, carboxylic acid, carboxylic ester, -R100-OH, -O-R200, -R100-N(R110R111 ), -R100-N+(R110R111R112), an aryl, a heteroaryl, acrylate, acryloyl, acrylamide, methacrylate, methacrylamide, thiol, amide, or a moiety represented by -LP. In some embodiments, two of adjacent R9 through R28 form an aromatic or non-aromatic ring structure, for example, as described herein.
[00323] In one embodiment, the Cu-porphyrin compound has the structure according to Formula I-5:
or a salt, or a tautomeric form thereof, wherein R1 through R28 are described herein.
[00324] In some embodiments, R9 through R28 are independently H, F, Br, CH3, a straight-chain alkyl that has 2-20 (eg, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20) carbon atoms, a branched alkyl having 2-20 (eg 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20) carbons, carboxylic acid, carboxylic ester, -R100-OH, -O-R200, -R100-N(R110R111 ), -R100-N+(R110R111R112), an aryl, a heteroaryl, acrylate, acryloyl, acrylamide, methacrylate, methacrylamide, thiol, amide, or a moiety represented by -LP. In some embodiments, two of adjacent R9 through R28 form an aromatic or non-aromatic ring structure, for example, as described herein.
[00325] In one embodiment, the Cu-porphyrin compound has the structure according to Formula I-6:
or a salt, or a tautomeric form thereof, wherein R1 through R28 are described herein.
[00326] In some embodiments, R9 through R28 are independently H, F, Br, CH3, a straight-chain alkyl that has 2-20 (eg, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20) carbon atoms, a branched alkyl having 2-20 (eg 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20) carbons, carboxylic acid, carboxylic ester, -R100-OH, -O-R200, -R100-N(R110R111 ), -R100-N+(R110R111R112), an aryl, a heteroaryl, acrylate, acryloyl, acrylamide, methacrylate, methacrylamide, thiol, amide, or a moiety represented by -LP. In some embodiments, two of adjacent R9 through R28 form an aromatic or non-aromatic ring structure, for example, as described herein.
[00327] In one embodiment, the Cu-porphyrin compound has the structure according to Formula I-7:
or a salt, or a tautomeric form thereof, wherein R1 through R28 and R300-R315 are described herein.
[00328] In some embodiments, R9 through R28 and R300-R315 are independently H, F, Br, CH3, a straight-chain alkyl that has 2-20 (eg, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20) carbon atoms, a branched alkyl having 2-20 (eg 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20) carbons, carboxylic acid, carboxylic ester, -R100-OH, -O-R200, -R100 -N(R110R111), -R100-N+(R110R111R112), an aryl, a heteroaryl, acrylate, acryloyl, acrylamide, methacrylate, methacrylamide, thiol, amide, or a moiety represented by -LP. In some embodiments, two of adjacent R9 through R28 form an aromatic or non-aromatic ring structure, for example, as described herein.
[00329] In one embodiment, the Cu-porphyrin compound has the structure according to Formula I-8:
or a salt, or a tautomeric form thereof, wherein R1 through R28 are described herein.
[00330] In some embodiments, R9 through R28 are independently H, F, Br, CH3, a straight-chain alkyl that has 2-20 (eg, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20) carbon atoms, a branched alkyl having 2-20 (eg 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20) carbons, carboxylic acid, carboxylic ester, -R100-OH, -O-R200, -R100-N(R110R111 ), -R100-N+(R110R111R112), an aryl, a heteroaryl, acrylate, acryloyl, acrylamide, methacrylate, methacrylamide, thiol, amide, or a moiety represented by -LP. In some embodiments, two of adjacent R9 through R28 form an aromatic or non-aromatic ring structure, for example, as described herein.
[00331] In one embodiment, the Cu-porphyrin compound has the structure according to Formula I-9:
or a salt, or a tautomeric form thereof, wherein R1 through R28 and R400-R411 are described herein.
[00332] In some embodiments, R9 through R28 and R400-R411 are independently H, F, Br, CH3, a straight-chain alkyl that has 2-20 (eg, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20) carbon atoms, a branched alkyl having 2-20 (eg 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20) carbons, carboxylic acid, carboxylic ester, -R100-OH, -O-R200, -R100 -N(R110R111), -R100-N+(R110R111R112), an aryl, a heteroaryl, acrylate, acryloyl, acrylamide, methacrylate, methacrylamide, thiol, amide, or a moiety represented by -LP. In some embodiments, two of adjacent R9 through R28 form an aromatic or non-aromatic ring structure, for example, as described herein.
[00333] In one embodiment, the Cu-porphyrin compound has the structure according to Formula I-10: either a salt, or a tautomeric form thereof, wherein R1 through R8 are described herein.

[00334] In one embodiment, the Cu-porphyrin compound has the structure according to Formula I-11:Os. J3H
Her x)or a salt, or a tautomeric form thereof, wherein R1 through R28 are described herein.
[00335] In some embodiments, R9 through R28 are independently H, F, Br, CH3, a straight-chain alkyl that has 2-20 (eg, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20) carbon atoms, a branched alkyl having 2-20 (eg 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20) carbons, carboxylic acid, carboxylic ester, -R100-OH, -O-R200, -R100-N(R110R111 ), -R100-N+(R110R111R112), an aryl, a heteroaryl, acrylate, acryloyl, acrylamide, methacrylate, methacrylamide, thiol, amide, or a moiety represented by -LP. In some embodiments, two of adjacent R9 through R28 form an aromatic or non-aromatic ring structure, for example, as described herein.
[00336] In one embodiment, the Cu-porphyrin compound
or a salt, or a tautomeric form thereof, wherein R1 through R28 are described herein.
[00337] In some embodiments, R9 through R28 are independently H, F, Br, CH3, a straight-chain alkyl that has 2-20 (eg, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20) carbon atoms, a branched alkyl having 2-20 (eg 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20) carbons, carboxylic acid, carboxylic ester, -R100-OH, -O-R200, -R100-N(R110R111 ), -R100-N+(R110R111R112), an aryl, a heteroaryl, acrylate, acryloyl, acrylamide, methacrylate, methacrylamide, thiol, amide, or a moiety represented by -LP. In some embodiments, two of adjacent R9 through R28 form an aromatic or non-aromatic ring structure, for example, as described herein.
[00338] In one embodiment, the Cu-porphyrin compound has the structure according to the Formula
or a salt, or a tautomeric form thereof, wherein R1 through R28 are described herein.
[00339] In some embodiments, R9 through R28 are independently H, F, Br, CH3, a straight-chain alkyl that has 2-20 (eg, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20) carbon atoms, a branched alkyl having 2-20 (eg 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20) carbons, carboxylic acid, carboxylic ester, -R100-OH, -O-R200, -R100-N(R110R111 ), -R100-N+(R110R111R112), an aryl, a heteroaryl, acrylate, acryloyl, acrylamide, methacrylate, methacrylamide, thiol, amide, or a moiety represented by -LP. In some embodiments, two of adjacent R9 through R28 form an aromatic or non-aromatic ring structure, for example, as described herein.
[00340] In one embodiment, the Cu-porphyrin compound has the structure according to Formula I-14:
or a salt, or a tautomeric form thereof, wherein R1 through R28 and R110 and R111 are described herein.
[00341] In some embodiments, R9 through R28 are independently H, F, Br, CH3, a straight-chain alkyl that has 2-20 (eg, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20) carbon atoms, a branched alkyl having 2-20 (eg 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20) carbons, carboxylic acid, carboxylic ester, -R100-OH, -O-R200, -R100-N(R110R111 ), -R100-N+(R110R111R112), an aryl, a heteroaryl, acrylate, acryloyl, acrylamide, methacrylate, methacrylamide, thiol, amide, or a moiety represented by -LP. In some embodiments, two of adjacent R9 through R28 form an aromatic or non-aromatic ring structure, for example, as described herein.
[00342] In one embodiment, the Cu-porphyrin compound has the structure according to Formula I-15:
or a salt, or a tautomeric form thereof, wherein R1 through R28 and R500-R515 are described herein.
[00343] In some embodiments, R9 through R28 and R500-R515 are independently H, F, Br, CH3, a straight-chain alkyl that has 2-20 (eg, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20) carbon atoms, a branched alkyl having 2-20 (eg 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20) carbons, carboxylic acid, carboxylic ester, -R100-OH, -O-R200, -R100 -N(R110R111), -R100-N+(R110R111R112), an aryl, a heteroaryl, acrylate, acryloyl, acrylamide, methacrylate, methacrylamide, thiol, amide, or a moiety represented by -LP. In some embodiments, two of adjacent R9 through R28 form an aromatic or non-aromatic ring structure, for example, as described herein.
[00344] In one embodiment, the Cu-porphyrin compound has the structure according to Formula I-16:
or a salt, or a tautomeric form thereof, wherein R1 through R28, R110, R111, R120 and R121 are described herein.
[00345] In some embodiments, R9 through R28 are independently H, F, Br, CH3, a straight-chain alkyl that has 2-20 (eg, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20) carbon atoms, a branched alkyl having 2-20 (eg 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20) carbons, carboxylic acid, carboxylic ester, -R100-OH, -O-R200, -R100-N(R110R111 ), -R100-N+(R110R111R112), an aryl, a heteroaryl, acrylate, acryloyl, acrylamide, methacrylate, methacrylamide, thiol, amide, or a moiety represented by -LP. In some embodiments, two of adjacent R9 through R28 form an aromatic or non-aromatic ring structure, for example, as described herein. In some embodiments, R110, R111, R120, and R121 are each independently H, Me, a straight-chain alkyl that has 2-20 (e.g., 2, 3, 4, 5, 6, 7, 8, 9 , 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20) carbon atoms or a branched alkyl having 2-20 (eg 2, 3, 4, 5, 6, 7 , 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20) carbon atoms.
[00346] Cu-porphyrin compounds that can be used in the optical filter of the first system include any of the Cu-porphyrin compounds discussed previously (for example, any of the compounds according to Formula I and Formulas I-1 through I -16). In one embodiment, the Cu-porphyrin compound has a structure in accordance with any one of Formula I and Formulas I-1 through I-16, wherein each of R1 through R28, R110-R111, R120, R121, R200- R203, R300-R315, R400-R411, R500-R515 discussed above is H. In some embodiments, the Cu-porphyrin compound has a structure of Formula I, where X is nitrogen, and each of R1 through R28 is H, except that R11, R16, R21 and R26 are each an isolated pair. In other words, those Cu-porphyrin compounds are not further substituted other than what is shown in Formula I and Formulas I-1 to I-16, all respective R groups in the formulas are H or an isolated pair.
[00347] Various methods can be used to prepare the Cu-porphyrin compounds disclosed herein. Just as an example, several Cu-porphyrin compounds are presented below along with their chemical structures, their UV-vis absorption peaks in solution, and exemplary synthetic procedures that can be used to produce them:

FS-201: Cu(II) meso-Tetraphenylporphine can be synthesized from meso-Tetraphenylporphine using the procedure described in Inorganic Chemistry Communications, 14(9), 1,311-1,313; 2011. UV-vis (CH2Cl2): 572, 538, 414.

[00349] FS-202: Cu(II) meso-Tetra(4-chlorophenyl)porphine can be synthesized from meso-Tetra(4-chlorophenyl)porphine using the procedure described in Journal of Porphyrins and Phthalocyanines, 11(2) , 77-84;2007. UV-vis (CH2Cl2): 538, 415.

[00350] FS-203: Cu(II) meso-Tetra(4-methoxyphenyl)porphine can be synthesized from meso-Tetra(4-methoxyphenyl)porphine using the procedure described in Bioorganic & Medicinal Chemistry Letters, 16 (3030-3033 );2006. UV-vis (CH2Cl2): 578, 541, 419.

[00351] FS-204: Cu(II) meso-Tetra(4-tert-butylphenyl)porphine can be synthesized from meso-Tetra(4-tert-butylphenyl)porphine using the procedure described in Journal of Organometallic Chemistry, 689 (6), 1078-1,084; 2004. UV-vis (CH2Cl2): 541, 504, 418.

[00352] FS-205: Cu(II) meso-Tetra(3,5-di-tert-butylphenyl)porphine can be synthesized from meso-Tetra(3,5-di-tert-butylphenyl)porphine using the procedure described in Journal of Organometallic Chemistry, 689 (6), 1078-1,084; 2004. UV-vis (CH2Cl2): 575, 540, 501, 418.

FS-206: Cu(II) meso-Tetra(2-naphthyl)porphine can be synthesized from meso-Tetra(4-chlorophenyl)porphine using the procedure described in Polyhedron, 24 (5), 679684; 2005. UV-vis (CH2Cl2): 541, 420.

[00354] FS-207: Cu(II) meso-Tetra(N-methyl-4-pyridyl)porphine tetrachloride can be synthesized from meso-Tetra(N-methyl-4-pyridyl)porphine tetrachloride using the procedure described in Journal of Porphyrins and Phthalocyanines, 11 (8), 549-555; 2007. UV-vis (IN HCl):550.430.

[00355] FS-208: Cu(II)Methyl-6-quinolinyl)porphine tetrachloride can be synthesized from meso-Tetra(N-Methyl-6-quinolinyl)porphine tetrachloride using the procedure described in Polyhedron Vol. , No. 20, 2527-2,531; 1990. UV-vis (CH2Cl2): 572, 538, 414.

[00356] FS-209: Cu(II) meso-Tetra(1-naphthyl) porphine

[00357] FS-210: Cu(II) meso-Tetra(4-bromophenyl)porphine

[00358] Cu1: Cu(II) meso-Tetra(pentafluorophenyl)porphine

[00359] Cu2: Cu(II) meso-Tetra(4-sulfonatophenyl)porphine (acid form)

[00360] Cu3: Cu(II) meso-Tetra(N-methyl-4-pyridyl)porphyrin tetraacetate

[00361] Cu4: Cu(II) meso-Tetra(4-pyridyl)porphine

[00362] Cu5: Cu(II) meso-Tetra(4-carboxyphenyl)porphine
As described in that specification, useful Cu-porphyrin compounds also include compounds of Formula I and Formulas I-1 through I-16, wherein not all of the respective R groups in the formulas are H or an isolated pair. In other words, such Cu-porphyrin compounds are further substituted with one or more various groups (eg, various R groups described herein). In some embodiments, these additional substituted Cu-porphyrin compounds have a desired filtering ability. One way to determine whether or not a compound has a desired filtering ability is to measure the transmission spectrum of the compound or a system that incorporates that specific compound. Additionally, other values, for example, delta E, delta saturation, and similar values, as discussed elsewhere in this descriptive report, can also be used.
[00364] In one embodiment, the Cu-porphyrin compounds of Formula I and Formulas I-1 through I-16 are not a polymer or are not otherwise attached to a polymer. In some embodiments, each of R1 through R8 is independently H, Cl, Br, F, I, CH3, a straight-chain alkyl that has 220 carbon atoms or a branched alkyl that has 220 carbons. In some embodiments, each of R9 through R28 is independently H, F, Br, Cl, I, CH3, a straight chain alkyl having 2-20 carbon atoms, a branched alkyl having 2-20 carbon atoms, nitro, sulfonic acid, carboxylic acid, a carboxylic ester, -R100-OH, -O-R200, -R100-N(R110R111), -R100-N+(R110R111R112), one aryl, one heteroaryl, acrylate, acryloyl, acrylamide, methacrylate, methacrylamide, thiol or amide. In some embodiments, R100 is a bond, -(CH2)n-, or a branched alkyl having 2-20 carbon atoms, where n is 1-20; and R110, R111, R112 and R200 are each independently H, Me, a straight chain alkyl having 2-20 carbon atoms or a branched alkyl having 2-20 carbon atoms. In some embodiments, two of adjacent R9 through R28 form an aromatic or non-aromatic ring structure, for example, as described herein.
In one embodiment, the Cu-porphyrin compounds of Formula I and Formulas I-1 through I-16 contain one or more polymerizable groups. The addition of such polymerizable groups (including, without limitation, a polymerizable group, eg, acrylate, methacrylate, acrylamide, methacrylamide, amines, amides, thiols, carboxylic acids, etc.) can be used to functionalize the optical filter and make it polymerizable , for example, by free radical polymerization. These polymerizable groups can be attached to existing porphyrin ring pendants, or directly to the porphyrin ring. The reactive porphyrin will allow chemical bonding to a polymer matrix, in which it is dispersed, through UV light, electron beam, heat and/or their combination.
[00366] In one embodiment, at least one of R1 to R28, R110-R112, R120, R121, R200-R203, R300-R315, R400-R411, R500-R515 in Formula I and Formulas I-1 to 1-16 is a -LP. When there is more than one -L-P, each -L-P can be the same or different. In one embodiment, 1-8 (for example, 1, 2, 3, 4, 5, 6, 7 or 8) from R1 to R28, R110-R112, R120, R121, R200-R203, R300-R315, R400- R411, R500-R515 are -LP. Each -L-P can be the same or different. In some embodiments, there is only one -L-P in a structure according to Formula I and Formulas I-1 through I-16. In some embodiments, there are two -L-P in a structure according to Formula I and Formulas I-1 through I-16. In some embodiments, one of R1 through R8 is a -L-P group. In some embodiments, one of R9 through R28 is a -L-P group. In some embodiments, one of R110-R112, R120, R121, R200-R203, R300-R315, R400-R411, R500-R515 is a -L-P group.
[00367] In one embodiment, P is a polymerizable group. Useful polymerizable groups include any of those known in the art. For example, the polymerizable group can be selected from the group consisting of acrylates, acryloyl, acrylamides, methacrylates, methacrylamides, carboxylic acids, thiols, amides, terminal or internal alkynyl groups, terminal or internal alkenyl groups, iodides, bromides, chlorides, azides , carboxylic esters, amines, alcohols, epoxides, isocyanates, aldehydes, acid chlorides, siloxanes, boronic acids, stannanes, and benzyl halides. Some of these groups are shown in FIG. 28A. In any of the modalities described in this descriptive report, the polymerizable group may have a total number of carbons less than 20 (for example, less than 16, less than 12, less than 8, less than 4, less than that 2, or do not have carbon atoms). In some embodiments, the polymerizable group is COOH. In some embodiments, the polymerizable group is one of the following:

[00368] In some embodiments, the Cuporphyrin compound has a structure, or is a homo- or copolymer characterized by having a monomeric structure, according to Formula I-1,
or a salt, or a tautomeric form thereof, wherein each of R1 to R8 is H, and each of R9, R10, R12R22 — R25, R27 and R28 is F, and each of R11, R16, R21 is selected from following:

[00369] See also Figure 28B. In some modes, R11, R16, R21 and R26 are the same.
[00370] In some embodiments, the Cuporphyrin compound has a structure, or is a homo- or copolymer characterized by having a monomeric structure, according to Formula I-15,
or a salt, or a tautomeric form thereof, wherein each of R1 to R8 is H, each of R11 - R13 and R500 - R503, each of R16 - R18 and R504 -R507, each of R21 - R23 and R508 -R511, and each of R26 - R28 and R512 - R515 is independently H or selected from the following:

[00371] In some embodiments, substitution for the four naphthyl rings is the same, that is, the corresponding R groups on the naphthyl rings are the same. In some embodiments, at least one of R11 -R13 and R500 -R503, at least one of R16 -R18 and R504 -R507, at least one of R21 - R23 and R508 -R511, and at least one of R26 -R28 and R512 -R515 is selected from the following:

[00372] See Figure 28C.
[00373] In some embodiments, the Cu-porphyrin compound has a structure in accordance with Formula I-7
or a salt, or a tautomeric form thereof, wherein each of R1 to R8 is H, wherein each of R9, R10, R13 and R300 - R303 each of R14, R17, R18 and R304 - R307 each one of R19, R22, R23 and R308 - R311, and each of R24, R27, R28and R312 - R315 is independently H or selected from the following:

[00374] In some embodiments, the substitution pattern for the four naphthyl rings is the same, that is, the corresponding R groups on the naphthyl rings are the same. In some embodiments, at least one of R9, R10, R13 and R300 - R303, at least one of R14, R17, R18 and R304 - R307, at least one of R19, R22, R23 and R308 - R311, and at least one deR24, R27, R28 and R312 - R315 is selected from the following:

[00375] See Figure 28D.
[00376] Polymeric forms of the Cu-porphyrin compounds described herein may be advantageous compared to non-polymer Cu-porphyrin compounds. For example, polymerizable optical filters disperse (on a molecular level) and blend better in a polymer matrix than their non-polymerizable counterparts. These compounds are especially useful in applications where the filter is applied inside the product rather than as a coating. For example, polymerizable absorptive dyes with acrylate functional groups are expected to be well dispersed in acrylate-based matrices used for the manufacture of contact lenses or intraocular lenses (IOLs), as a result of the similar chemical structures between dyes and The matrix. Polymerizable dyes added to raw materials used to manufacture polyvinyl butyral (PVB), polyurethane (PU), poly(ethylene-vinyl acetate)(EVA) interlayer materials are expected to disperse better than their non-polymerizable parts. Another possibility is the addition of the polymerizable dye to the PVB, PU or EVA material before its extrusion into sheets/layers, where thermal polymerization of the dyes is expected to occur during extrusion.
[00377] In one embodiment, P is a polymer moiety. The polymer portion can be selected from biopolymers, polyvinyl alcohol, polyacrylates, polyamides, polyamines, polyepoxides, polyolefins, polyanhydrides, polyesters and polyethylene glycols. In some modalities, P can be PVB, PU or EVA.
[00378] In any of the modalities described in this descriptive report, L can be null or a linker. In some modalities, L is null. In some embodiments, L is a linker. Useful linkers include any of those known in the art. For example, the linker can be -C(O)-, -O-, -OC(O)O-, -C(O)CH2CH2C(O)-, -SS-, -NR130-, -NR130C(O) O-, - OC(O)NR130-, -NR130C(O)-, -C(O)NR130-, - NR130C(O)NR130-, -alkylene-NR130C(O)O-, -alkylene- NR130C(O )NR130-, -alkylene-OC(O)NR130-, -alkylene-NR130-, -alkylene-O-, -alkylene-NR130C(O)-, -alkylene-C(O)NR130-, - NR130C(O) O-alkylene-, -NR130C(O)NR130-alkylene-, - OC(O)NR130-alkylene, -NR130-alkylene-, -O-alkylene-, - NR130C(O)-alkylene-, -C(O) NR130-alkylene-, -alkylene- NR130C(O)O-alkylene-, -alkylene-NR130C(O)NR130-alkylene-, - alkylene-OC(O)NR130-alkylene-, -alkylene-NR130-alkylene-, - alkylene-O-alkylene-, -alkylene-NR130C(O)-alkylene-, -C(O)NR130-alkylene-, where R130 is hydrogen, or optionally substituted alkyl.
[00379] In some embodiments, the Cuporphyrin compounds can be a homopolymer or a copolymer characterized by having a monomeric structure of Formula I (m):
or a salt, or a tautomeric form thereof, wherein X and R1 to R28 are described herein, provided there is 1-8 (e.g. 1, 2, 3, 4, 5, 6, 7 or 8) -Lm- Pm in Formula I(m) and each -Lm-Pm can be the same or different, where Pm is a polymerizable group and Lm is null or a linker. In some embodiments, one of R1 through R8 is a -Lm-Pm group. In some embodiments, one of R9 through R28 is a -Lm-Pm group. In some embodiments, one of R1 through R28 includes a -Lm-Pm group. In some embodiments, each of R1 through R8 is independently H, Cl, Br, F, I, CH3, a straight chain alkyl that has 2-20 carbon atoms, a branched alkyl that has 2-20 carbons, or a portion represented by -Lm-Pm. In some embodiments, each of R9 through R28 is independently H, F, Br, Cl, I, CH3, a straight chain alkyl having 2-20 carbon atoms, a branched alkyl having 2-20 carbon atoms, nitro, sulfonic acid, carboxylic acid, a carboxylic ester, -R100-OH, -O-R200, -R100-N(R110R111), -R100-N+(R110R111R112), one aryl, one heteroaryl, acrylate, acryloyl, acrylamide, methacrylate, methacrylamide, thiol or amide, or a moiety represented by -Lm-Pm. In some embodiments, two of adjacent R9 through R28 form an aromatic or non-aromatic ring structure, for example, as described herein. In some embodiments, R100 is a bond, -(CH2)n-, or a branched alkyl having 2-20 carbon atoms, where n is 1-20; R110, R111, R112 and R200 are each independently H, Me, a straight-chain alkyl having 2-20 carbon atoms, a branched alkyl having 2-20 carbon atoms, or a moiety represented by -Lm -Pm. In some embodiments, X is carbon or nitrogen, provided that when X is nitrogen, then R11, R16, R21, and R26 are each independently a single pair or as defined above. Suitable polymerizable groups and linkers are described herein.
[00380] In one embodiment, the Cu-porphyrin compound of the first system is a homopolymer or a copolymer characterized by having a monomeric structure of Formula I (m)
or a salt, or a tautomeric form thereof, wherein X and R1 to R28 are described herein.
In some embodiments, each of R1 through R8 is independently H, Cl, Br, F, I, CH3, a straight-chain alkyl that has 2-20 carbon atoms or a branched alkyl that has 2-20 carbons ; and each of R9 through R28 is independently H, F, Br, Cl, I, CH3, a straight chain alkyl having 2-20 carbon atoms, a branched alkyl having 2-20 carbon atoms, nitro, acid sulfonic, carboxylic acid, a carboxylic ester, -R100-OH, -O-R200, -R100-N(R110R111), -R100-N+(R110R111R112), an aryl, a heteroaryl, acrylate, acryloyl, acrylamide, methacrylate, methacrylamide , thiol or amide; or two of adjacent R9 to R28 form aromatic or non-aromatic ring structure. In some embodiments, R100 is a bond, -(CH2)n-, or a branched alkyl having 2-20 carbon atoms, where n is 1-20; R110, R111, R112 and R200 are each independently H, Me, a straight chain alkyl having 2-20 carbon atoms or a branched alkyl having 2-20 carbon atoms. In some embodiments, X is carbon or nitrogen, provided that when X is nitrogen, then R11, R16, R21, and R26 are each independently a single pair or as defined above.
[00382] In one embodiment, the Cu-porphyrin compound of the first system is a homopolymer or a copolymer characterized by having a monomeric structure of Formula I(m)
or a salt, or a tautomeric form thereof, wherein X and R1 through R28 are described herein, provided there is 1-4 (e.g., 1, 2, 3, or 4)-Lm-Pm in Formula I(m) and each -Lm-Pm can be the same or different, where Lm is nil, and each Pm is the same polymerizable group or a different polymerizable group, wherein the polymerizable group is selected from the group consisting of acrylates, acryloyl, acrylamides , methacrylates, methacrylamides, carboxylic acids, thiols, amides, terminal or internal alkynyl groups having 2 to 20 carbons, terminal or internal alkenyl groups having 2 to 20 carbons, iodides, bromides, chlorides, azides, carboxylic esters, amines, alcohols , epoxides, isocyanates, aldehydes, acid chlorides, siloxanes, boronic acids, stannanes, and benzyl halides. In some embodiments, one of R1 through R8 is a -Lm-Pm group. In some embodiments, one of R9 to R28 is a -Lm-Pm group. In some embodiments, one of R1 through R28 includes a -Lm-Pm group.
In some embodiments, each of R1 through R8 is independently H, Cl, Br, F, I, CH3, a straight-chain alkyl that has 2-20 carbon atoms, a branched alkyl that has 2-20 carbons , or a portion represented by -Lm-Pm; and each of R9 through R28 is independently H, F, Br, Cl, I, CH3, a straight chain alkyl having 2-20 carbon atoms, a branched alkyl having 2-20 carbon atoms, nitro, acid sulfonic, carboxylic acid, a carboxylic ester, -R100-OH, -O-R200, -R100-N(R110R111), -R100-N+(R110R111R112), an aryl, a heteroaryl, acrylate, acryloyl, acrylamide, methacrylate, methacrylamide , thiol, amide, or a moiety represented by -Lm-Pm. In some embodiments, two of adjacent R9 through R28 form an aromatic or non-aromatic ring structure, for example, as described herein. In some embodiments, R100 is a bond, -(CH2)n-, or a branched alkyl having 2-20 carbon atoms, where n is 1-20. In some embodiments, R110, R111, R112 and R200 are each independently H, Me, a straight-chain alkyl that has 2-20 carbon atoms, a branched alkyl that has 2-20 carbon atoms, or a moiety represented by - Lm-Pm. In some embodiments, X is carbon or nitrogen, provided that when X is nitrogen, then R11, R16, R21, and R26 are each independently a single pair or as defined above.
[00384] As used herein and those skilled in the art can readily observe, a polymer or polymer portion characterized by having a monomeric structure as shown means that the polymer can be synthesized or prepared using the indicated monomer, or using the indicated monomer in combination with one or more other monomers, in the case of a copolymer. Depending on the monomer used, the structure of the final polymer can be readily verified by those skilled in the art. As used herein, the term "polymer" broadly refers to a compound or a mixture of compounds that have two or more repetitive structural units.
[00385] Several methods are known for the preparation of polymeric Cu-porphyrin compounds. For example, a synthesis of one type of polyporphyrins is described in U.S. Patent No. 6,429,310. Other exemplary methods are known for preparing homo- or copolymers from a monomer having a Formula I(m), which contains one or more polymerizable groups, the same or different. For example, such methods may include radical polymerization, photoinduced polymerization, thermoinduced polymerization, cationic polymerization, anionic polymerization, metal-catalyzed polymerization, etc. See generally Odian, George G. 2004. "Principles of Polymerization", 4th Edition, Hoboken, N.J.: Wiley and Hiemenz, Paul C and Timothy Lodge. 2007. “Polymer Chemistry”, Second Edition, Boca Raton: CRC Press.
[00386] An example of a Cu-porphyrin compound that is polymerizable is Cu5, shown in FIG. 1D. This Cu5 compound has a carboxylic group.
[00387] Other examples are given in FIGS. 28B-28D. Note that the R numbering in these chemical structures does not match the R numbering used elsewhere in this order. FIG. 28A shows tetrafluor acrylate. FIG. 28B shows 1-naphthyl acrylate, and FIG. 28C shows 2-naphthyl acrylate.
[00388] FIGS. 1A-3B show non-limiting chemical structures of porphyrin dye compounds that can be used in the optical filters disclosed in this specification.
[00389] FIGS. 1A, 1B, 1C and 1D show examples of the FS series of dye compounds and the FS series of dye compounds. All of these belong to the category of porphyrins with copper as a central metal within the porphyrin ring, or Cu-porphyrins.
[00390] FIGS. 2A-2B show examples of the TPP compound series, in which porphyrin dyes with different core metals and pendant only phenyl are shown. Dye FS-201 is provided in FIG. 2 for comparison, due to its similar structure with the TPP series of dye compounds.
[00391] FIGS. 3A-3B show examples of the series of PF dye compounds, related to porphyrins with penta-fluor-phenyl pendants and different core metals. For comparative purposes, and due to the similar structure to the dye compound category PF, the dye compound Cu1 is also shown in FIG. 3.
[00392] The Cu-porphyrin compounds discussed above can be used as an optical filter dye in a system. In one embodiment, the optical filter comprises a coating that is disposed on a surface of the system. As a non-limiting example, the surfaces on a CR39 semi-finished lens block include both the unfinished face and the finished face. Other examples of surfaces include a lens block face, a mirror reflective face, and a screen on an electronic device.
[00393] In such an arrangement, a coating that includes the Cu-porphyrin compound is disposed on a surface of the system.
[00394] In another embodiment, the optical filter comprising the Cu-porphyrin dye is dispersed through a substrate of the first system.
[00395] The compounds disclosed herein are applicable to many applications. Some of these applications include, without limitation, ophthalmic systems, non-ophthalmic ocular systems, and non-ocular systems.
[00396] In one embodiment, the system is an ophthalmic system. Common ophthalmic systems can include an eyeglass lens, a contact lens, an intraocular lens, an intracorneal implant, and an extracorneal implant.
[00397] In order to further protect the human eye from exposure to both harmful high energy visible light wavelengths and UV light and optionally IR light, non-ophthalmic applications are also envisioned.
[00398] Thus, in one modality, the system is a non-ophthalmic ocular system. This includes a system through which light passes on its way to the eye of a user who is not an ophthalmic system. Common, non-limiting examples include a window (including aircraft windows); an automotive windshield (including cars, trucks and buses); an automotive side window; an automotive rear window; a sunroof window; a mirror on an automobile, truck, bus, train, airplane, helicopter, boat, motorcycle, recreational vehicle, farm tractor, construction vehicle or equipment, spacecraft, military vessel; commercial glass; residential glass; skylights; a bulb and camera flash lens; an artificial lighting device; a magnifying glass (including over-the-counter); a fluorescent light or diffuser; a medical instrument (including equipment used by ophthalmologists and other eye health professionals to examine patients' eyes); a telescope; a surgical instrument; a hunting scope for rifles, hunting rifles and pistols; a binoculars; a computer monitor; a television screen; an illuminated sign; any electronic devices that emit or transmit visible light; and a patio lamp. In another modality, the optical filter can be incorporated in any electronic device that emits visible light, portable or non-portable. Just as an example, an electronic device could include: a computer monitor (mentioned above), a laptop, an Ipad, any telephone or other telecommunication device, tablet, visual gaming systems, surfaces, or GPS or other navigational devices.
[00399] In one embodiment, the system is a non-ophthalmic eye system, and the optical filter may be disposed between a first surface 251A and a second surface 251B of a first system 2500, shown in FIG. 25. In one embodiment, the first and second surfaces can be glass. The optical filter can be incorporated into an interlayer 252. In some embodiments, the interlayer 252 can be polyvinyl butyral (PVB), polyvinyl alcohol (PVA), ethylene vinyl acetate (EVA) or polyurethane (PU), or copolymers in which a of the copolymers is PVB, PVA, EVA or PU. Other suitable polymers with similar characteristics to the listed polymers are also envisioned. FIG. 26 shows the chemical structures for the chemicals that can be used to form these interlayers. This mode can be particularly useful as an automotive windshield. Automotive windshields often have the structure illustrated in FIG. 25. An optical filter, eg a copper-porphyrin dye, can be incorporated into the interlayer of such a structure.
[00400] In another modality, the first system is a non-ocular system. As defined in the Glossary, a non-ocular system includes systems that do not pass light through a wearer's eye. Just as an example, non-ocular systems can include any type of skin or hair care product such as shampoo, tanning and sun care products, anti-aging skin care products, oils, lipstick, lip balm, lipstick glitter, eye shadow, eye pencil, eye foundation or acne products, or products used to treat skin cancer, skin beauty products such as foundations, foundation creams, moisturizing creams, powders, bronzers, blush, skin color enhancers, lotions (skin or dermatological), or any type of dermatological product. Thus, modalities include any type of skin or hair care product for a health or beauty benefit. The addition of the Cu-porphyrin compounds listed above or in combination with other porphyrins or other porphyrin derivatives to these types of non-ocular systems can be used for the detection or treatment of cancer in the human body. For example, adding these compounds to a skin lotion, skin cream, or sunscreen can add a selective blue light filter to inhibit harmful wavelengths known to cause cancer.
[00401] Furthermore, the systems disclosed in this descriptive report also include military and space applications, as acute and/or chronic exposure to high energy visible light, UV and also IR can potentially have a deleterious effect on soldiers and astronauts.
[00402] The systems disclosed in this specification have transmission spectra such that the systems are capable of blocking harmful and undesirable blue wavelengths while having a relatively high transmission through wavelengths outside the blocked blue wavelengths . As used herein, the terms "inhibit, "block" and "filter" (when used as verbs) have the same meaning.
[00403] Through the wavelength range of 460 nm - 700 nm, the transmission spectrum of the first system has a transmission average (TSRG) that is greater than or equal to 51%, 54%, 57%, 60%, 63 %, 66%, 69%, 72%, 75%, 78%, 80%, 85%, 90% or 95%. The average transmission of the system over this wavelength range depends on the system application. For example, in ophthalmic systems, it may be desirable to have an average transmission of at least 95% in some applications. However, in some non-ophthalmic systems, it may be desirable to have a lower average transmission across the 460 nm - 700 nm wavelength range, for example in car windshields. In a preferred embodiment, TSRG is equal to or greater than 80%.
[00404] Through the wavelength range of 400 nm - 460 nm, the first system has an average transmission defined as TSBlue. TSBlue is less than TSRG -5%. So, for example, if TSRG is 85%, then TSBlue is less than 80%. The average transmission of a spectrum over a wavelength range can be calculated as defined in the Glossary.
[00405] FIGS. 41-48 show exemplary transmission spectra of different systems comprising an optical filter. FIG. 41 shows transmission spectra of five ophthalmic systems. Each system comprises a CR39 lens block coated with an optical filter that contains the Cu-porphyrin FS-206 dye with 40% blue light blocking.
[00406] FIG. 42 shows transmission spectra of five ophthalmic systems. Each system comprises a CR39 lens block coated with an optical filter that contains the Cu-porphyrin FS-206 compound with 30% blue light blocking.
[00407] FIG. 43 shows transmission spectra for five ophthalmic systems. Each system comprises a 1.55 medium index block coated with an optical filter containing the Cu-porphyrin FS-206 compound with 40% blue light blocking.
[00408] FIG. 44 shows transmission spectra for five ophthalmic systems, each system comprising a 1.55 average index block coated with an optical filter containing the Cu-porphyrin FS-206 compound with 30% blue light blocking.
[00409] FIG. 45 shows transmission spectra of three ophthalmic systems. System 1 comprises a CR-39 lens with a craft surface coated with an optical filter comprising FS-206 with 15% blue light blocking. System 2 comprises a CR-39 lens with a craft surface coated with an optical filter comprising FS-206 with 20% blue light blocking. System 3 comprises a CR-39 lens with a craft surface coated with an optical filter comprising FS-206 with 25% blue light blocking.
[00410] FIG. 46 shows the transmission spectrum of a system comprising a polycarbonate lens coated with an optical filter comprising FS-206 with 15% blue blocking.
[00411] FIG. 47 shows the transmission spectra of five systems. Each system comprises a PVB interlayer impregnated with an optical filter comprising FS-206 with 20% blue light blocking. FIG. 48 shows the transmission spectra of five systems. Each system comprises a PVB interlayer impregnated with an optical filter comprising FS-206 with 25% blue light blocking.
[00412] In a modality, in addition to having an average through the specified wavelength range, the transmission spectrum of the system has a specific value at each wavelength within the specified wavelength range. In one modality, the first system transmits at least 51%, 54%, 57%, 60%, 63%, 66%, 69%, 72%, 75%, 78%, 80%, 85%, 90% or 95 % light at each wavelength across the 460 nm-700 nm range. In a preferred embodiment, the system transmits at least 80% light in each wavelength range from 460 nm - 700 nm.
[00413] The optical filter of the system also has its own transmission spectrum. The optical filter transmission spectrum and the system transmission spectrum may be different or similar to each other. In a preferred embodiment, the two spectra are different from each other.
[00414] Through the wavelength range of 460 nm - 700 nm, the optical filter transmission spectrum has a transmission average (TFRG) that is equal to or greater than 60%, 65%, 70%, 75%, 80%, 85%, 90% or 95%. As discussed above with respect to the system, the average filter transmission through this band may also depend on the system application. In a preferred embodiment, TFRG is equal to or greater than 80%.
[00415] Through the wavelength range of 400 nm - 460 nm, the optical filter also has a transmission average defined as TFBlue. TFBlue is less than TFRG-5%. The average transmission of a spectrum over a wavelength range is calculated as defined in the Glossary.
[00416] The optical filter transmission spectrum also has a first local minimum in transmission at a first wavelength within the wavelength range 400 - 500 nm, preferably within the wavelength range 400 - 460 nm and more preferably within the wavelength range of 405 - 440 nm.
[00417] The first wavelength can be any wavelength that falls within the ranges discussed above including, without limitation: within 2 nm of 420 nm, within 2 nm of 409 nm, within 10 nm of 425 nm , within 5 nm of 425 nm and within 30 nm of 430 nm. Preferably, the first wavelength is within 10 nm of 420 nm. The location of the first wavelength is determined based on the specific application of the system. It is affected by the Cu-porphyrin dye that is used in the filter. For example, as seen in FIG. 19, FS-206 has a local minimum in the first wavelength transmission around 420 nm, while Cu1 has a local transmission in the first wavelength transmission that is below 420 nm. Those skilled in the art would be able to determine, based on this disclosure, which Cu-porphyrin compound to use to obtain the desired transmission spectrum.
[00418] In one mode, the filter transmits at most 70%, at most 65%, at most 55%, at most 50%, at most 45%, at most 40% of light and preferably at most 60% of light in the first wavelength. The amount of light that the filter transmits (or the amount of light that the filter inhibits) in the first wavelength can be adjusted by changing the specific Cu-porphyrin compound that is used in the optical filter and the concentration of that compound. For example, FIG. 15 shows the transmission spectrum of 12 different optical filters. Each of the optical filters contains different concentrations of the coloring compound Cuporphyrin FS-206. As another example, FIG. 16 shows the transmission spectra of 5 different optical filters. Each optical filter (or coating) contains a different concentration of Cu-porphyrin FS-207 coloring compound.
[00419] It should be noted that the amount of light that is ultimately transmitted at the first wavelength in the first system depends on other variables, for example, without limitation, where the optical filter is applied, how it is applied, and for the that it is applied. Just as an example, if both sides of a lens in an ophthalmic system are coated with a coating that contains the optical filter with the Cu-porphyrin compound, then the coating formulation may contain less compound as the % of light blocking blue is additive blocking both sides of the lens. If a lens block is coated on both sides, then a more concentrated coating formulation is prepared as the back side of the lens block will subsequently be removed by a face milling step and only the front coating will remain in the final lens product. Furthermore, a more concentrated formulation is required if the final lens is coated on the side by spin coating, spraying or other method.
[00420] It should also be noted that the transmission spectrum of the system, although affected by the transmission spectrum of the optical filter, does not need to be the same as the transmission spectrum of the system. For example, the system's transmission spectrum may not have a local minimum at the same wavelength as the optical filter's transmission spectrum. In one embodiment, for at least one wavelength within 10 nm of the first wavelength on the negative side, the slope of the transmission spectrum of the first system has an absolute value that is less than the absolute value of the slope of the spectrum of transmission at a third wavelength. The third wavelength is more than 10 nm from the first wavelength on the negative side. So, for example, the first system may have a “bounce” on the first wavelength, not a local minimum.
[00421] In this way, the concentration of compound in the coating, the thickness of the coating containing the dye pack or the coating parameters can be adjusted to obtain the desired % blue light blocking. Using these parameters and others like them, the desired transmission spectrum could be obtained with the benefit of this disclosure.
[00422] Another way to characterize the optical filter transmission spectrum at the first wavelength is to compare the transmission value at the first wavelength with the transmission values at wavelengths around the first wavelength. In one embodiment, the filter has an average transmission over a wavelength range that is 5 nm below the first wavelength to 5 nm above the first wavelength. This average transmission value is labeled T5. For example, if the first wavelength is at 420 nm, the range for T5 would be 415 nm - 425 nm, inclusive. The optical filter transmission spectrum also has an average transmission over a wavelength range of 400 nm to 460 nm, excluding a range that is 5 nm below to 5 nm above the first wavelength. This average transmission value is defined by T6. In the example discussed above with the first wavelength range at 420 nm, T6 would be calculated for the wavelength range from 400 nm to 414 nm and 426 nm to 460 nm. T5 is at least 5% smaller than T6.
[00423] It is noted that the same calculation can be done for narrower and wider bands, including 2 nm above and below the first wavelength, 7 nm above and below the first wavelength, 10 nm above and below the first wavelength and 15 nm above and below the first wavelength. Thus, as another non-limiting example, the filter average transmission over a wavelength range from 10 nm below the first wavelength to 10 nm above the first wavelength is defined by T7. The average filter transmission over a wavelength range from 400 nm to 460 nm that excludes the range from 10 nm below the first wavelength to 10 nm above the first wavelength is T8. In this modality, if the first wavelength is 420 nm, T7 would be calculated for the wavelength range 410 nm-430 nm, and T8 would be calculated for the wavelength range 400 nm - 409 nm and 431 nm - 460 nm. T7 is at least 5% smaller than T8.
[00424] In one embodiment, the optical filter may have a second local minimum at a second wavelength that is different from the first wavelength. This second wavelength can be between 400 nm - 460 nm, 460 - 500 nm or 500 nm - 700 nm. Whether or not the optical filter has a second local minimum depends on which Cu-porphyrin compound or compounds are used in the optical filter. Optical filters with a first local minima and a second local minima can be obtained by using a Cu-porphyrin compound that independently has two local minima in its transmission spectrum or a mixture of 2, 3, 4 or more Cu- compounds porphyrin that together exhibit two local minima.
[00425] Systems that incorporate optical filters are generally subjected to constant exposure to UV. UV radiation from this exposure can cause the compound to degrade over time. In this way, over time, the ability of the compound, and therefore the ability of the filter, to inhibit light transmission is diminished. These systems can also be subjected to climatic conditions with rapidly fluctuating temperatures. These rapidly fluctuating temperatures will also degrade the compound and reduce the optical filter's ability to inhibit the desired amount of light.
[00426] The Cu-porphyrin compounds discussed in this descriptive report are superior to other compounds used in optical filters due, in part, to their stability over long periods of exposure to UV and climate. Thus, these Cu-porphyrin dye compounds and the optical filters comprising these dye compounds are photostable and thermostable.
[00427] To assess the stability, particularly the photostability, of optical filters containing the Cu-porphyrin compounds, several UV exposure and accelerated climate change tests were performed on optical filters containing the Cu-porphyrin dye compounds. As a comparison, UV exposure and accelerated climate change tests were also performed on optical filters that contain other porphyrin dye compounds that are not Cu-porphyrin compounds. These non-Cu-porphyrin compounds also have local minimum transmission in the wavelength range 400 nm - 460 and are available from Frontier Scientific. Some of these non-Cu-porphyrin compounds include:

[00428] TPP1: meso-Tetraphenylporphine (1-3% chlorine) [ID. Frontier: NT614]
[00429] TPP2: Ni(II) meso-Tetraphenylporphine (13% chlorine) [ID. Frontier: NiT614]

[00430] TPP3: Pt(II) meso-Tetraphenylporphine [IDFrontier: T40548]

[00431] TPP4: Zn(II) meso-Tetraphenylporphine (13% chlorine) [ID. Frontier: T40942]

[00432] TPP5: Pd(II) meso-Tetraphenylporphine [Frontier ID: T40372]

[00433] TPP6: Co(II) meso-Tetraphenylporphine (contains 1-3%) chlorine [ID. Frontier: T40823]

[00434] TPP7: Vanadyl meso-tetraphenylporphine (chlorin1-3%) [ID. Frontier: VOT614]

[00435] PF1 (or 5F): meso-Tetra(pentafluorophenyl)porphine(chlorin free) [ID. Frontier: T975]

[00436] 4F: meso-Tetra(2,3,5,6-tetrafluorophenyl)porphine[ID. Frontier: T14199]

[00437] 3F: meso-Tetra[2,3,4-trifluorotenyl)porphine [Frontier ID: T14198]

[00438] PF2: Ni(II)-meso-Tetra(pentafluorophenyl)porphine[ID. Frontier: T40274]

[00439] PF3: Mg(II)-meso-Tetra(pentafluorophenyl)porphine[ID. Frontier: T40900]

[00440] PF4: Pt(II)-meso-Tetra(pentafluorophenyl)porphine[ID. Frontier: PtT975]

[00441] PF5: Zn(II)-meso-Tetra(pentafluorophenyl)porphine[ID. Frontier: T40728]

[00442] PF6: Pd(II)-meso-Tetra(pentafluorophenyl)porphine[ID. Frontier: PdT975]

[00443] PF7: Mn(III)-meso-Tetra(pentafluorophenyl) porphine chloride [ID. Frontier: T40169]

[00444] PF8: Fe(III)-meso-Tetra(pentafluorophenyl) porphine chloride [ID. Frontier: T41158]

[00445] PF9: Ru(II)-carbonyl meso-Tetra(pentafluorophenyl) porphine [ID. Frontier: T14557]
[00446] The UV exposure and accelerated climate change tests performed on optical filters are as follows: (A) The laboratory exposure test to visible UV was performed with a BlueWave 200 (Dymax) lamp, whose light output appears to:
[00447] Total light in the spectral range of 280-450 nm: - Visible (400-450 nm) - 41.5% - UVA (320-395 nm) - 41.5% e - UVB (280-320 nm) - 17%
[00448] Samples of selective blue blocking coatings coated on pre-cleaned UV-transparent glass microscope slides (available from Corning) were subjected to visible UV exposure for 30 min, 60 min, 90 min and 120 min, which correspond to the total fluence of 7 J/cm2, 14 J/cm2, 21 J/cm2 and 28 J/cm2, respectively. The blue blocking coatings tested were composed of a base matrix (available from SDC Technologies) and Cu-porphyrin dye compound to be tested is added to the base via the appropriate solvent (eg, chlorinated solvent). The slides were coated with the colored base formulations prepared previously by a dip coating method. After drying the basecoat for 15 min at room temperature, a scratch resistant hard coating (SDC Technologies) was applied by dip coating and baked for 2 hours at 110°C in air. The samples were monitored for the duration of the test and their transmission spectra and CIE coordinates were evaluated. The results of this test are given in FIGS. 19A-19D for the FS and Cu series compounds. As discussed above, the FS and Cu series of compounds are all Cu-porphyrins. As comparative examples, this UV test was also performed on the TPP-porphyrin series, a non-Cu-porphyrin compound. FIGS. 18A-18B show the results of this test. FIG. 18B also shows the result of the FS-201 UV test as a comparison. Generally, the filtering ability of the TPP-porphyrin series significantly degraded after being exposed to the UV wavelengths used in the testing methods, while the filtering ability of the FS and Cu series dyes showed significant stability.
[00449] (B) The outdoor weathering test was done by exposure to weather conditions in Virginia (location 37°5'28”N 80°24'28”W) in the period October-December, when the weather changes Temperatures during the day and night are large, ranging from around 70 F (21.11°C) to below freezing temperatures, coupled with exposure to sunlight, rain and snow exposure. The samples were prepared in the same way as the samples for the visible UV laboratory exposure test: glass microscope slides were coated with a base containing the dye compound to be tested, and then with a scratch-resistant hard coating. The samples were monitored for the duration of the test and their transmission and CIE coordinates were evaluated. The results of this test are given in FIGS. 22A-22D for Cu series and FS series colorants. For comparative purposes, this weathering test was also performed for porphyrin dye compounds in the TPP series, PF series, and F series. The results for these series are shown in FIGS. 20A-20B and 21A-21D. As an easy comparison, test results for FS-201 are also shown in FIG. 20B. Generally, the filtering ability of the TPP, PF and F series dyes degraded significantly after the weathering tests, while the filtering ability of the FS and Cu series dyes showed significant stability.
[00450] Both tests, the laboratory exposure test to visible UV light and the outdoor weathering test, yielded the most stable blue selective blocking coatings. When coatings containing porphyrin dyes with different phenyl pendants and different core metal elements were tested (TPP dye compound series, structures are given in FIG. 2), the dye compounds showed different stability and were classified according to their photostability . Tests of the PF dye compound series (whose structures are shown in FIG. 3) yielded similar results. The listing below shows porphyrin dye compounds with different core metals and phenyl pendants, starting with the most stable metal (position #1):
[00451] Metal-porphyrin listing:1) Copper2) Nickel; vanadium3) Metal-free4) Cobalt5) Platinum; Palladium; Ruthenium6) Iron; Manganese; Magnesium7) ZincCu > Ni; V > No metal > Co > Pt; Pd; Ru > Fe; Mn; Mg > Zn
[00452] These results are also presented schematically in FIG. 23.
[00453] After the most stable porphyrin core metal has been determined to be copper (Cu), dye compounds with Cu as a core metal in the porphyrin ring and various pendants (ie the FS dye series and the dye series of Cu shown in Fig. 1) were subjected to both tests, the laboratory exposure test to visible UV light and the outdoor weathering test. Test results generated the most stable pendant for Cu-porphyrins and they are shown in the listing below, starting with the most stable pendant (position #1).
[00454] Cu-porphyrins with different pendant listing: 1) Penta-fluoro-phenyl2) Carboxy-phenyl3) Phenyl; Sulfonate-phenyl; Chloro-phenyl; Di-butyl-phenyl4) 1-naphthyl; 2-naphthyl; Methoxy-phenyl; Bromo-phenyl5) Pyridyl; N-methyl-pyridyl; N-methyl quinolinyl
[00455] These results are presented schematically in FIG. 24.
[00456] Both tests mentioned above resulted in the following observation: the central metal has a primary effect on the photostability of the dye compound, while the pendants have a secondary effect. Through a comparison of testing done with TPP dyes, it was determined that Cu-porphyrin is the most stable, while pendants were kept the same for all dyes (phenyl pendants). After the most stable metal was determined, an assessment was made for the photostability of the pendant. This evaluation yielded pentafluorophenyl as the most stable pendant when Cuporphyrins (FS dye and Cu compound series) were tested. This initiated the testing of the PF compound series, in which compounds with penta-fluor-phenyl pendants and different core metals were used. Again, this series resulted in the observation above that the metal, not the pendant, has the greatest contribution to the photostability of the composite. Compound Cu1 was the absolute “winner” (the most stable dye) in all tests performed.
[00457] As seen from FIGS. 22A-22D, the coloring compounds Cu1, Cu2, Cu5, FS-201, FS-202 and FS-205 exhibited the greatest stability in the outdoor weathering test. Thus, additional tests were performed on optical filters containing these compounds. FIGS. 22E-22G show the transmission spectra for optical filters comprising these Cuporphyrin compounds before and during the 60-day outdoor weathering test. These sets of compounds were selected for testing in this category to determine the most stable pendant attached to a porphyrin with copper (Cu) as a core metal.(C) Thermal stability test
[00458] As the incorporation of the optical filter in some systems is done at high temperatures, the compounds (dyes) that are used in these systems must also be able to withstand high temperatures. For example, incorporation of the Cu-porphyrin coloring compound into a PVB interlayer can include a processing step (extrusion) that is carried out at 180°C for ten minutes. Therefore, a thermal stability test was also performed on certain Cu-porphyrin coloring compounds, including FS-206, FS-209, Cu1 and Cu5. Optical filters were made with glass slides coated with colored base (a base with the Cu-porphyrin compound) and hard coating (fired for 3 hours at 110°C). The slides were exposed to a heating step at 180°C (which took about 40 min). The slides were then heated to 180°C for different periods of time (5 min, 10 min, 15 min and 30 min). The results are shown in FIGS. 50A-50D. As shown in the Figures, the ability of the tested optical filters did not degrade. Thus, the dye compounds tested exhibited excellent thermal stability at 180°C for the time periods tested. In fact, it should be noted that FIG. 50A shows an increase in filtering at the first wavelength for FS-205. This can be caused by the fact that the colorant is not completely dissolved in the solvent when the coating is done. In this way, when it was heated to 180°C, the clumps of undissolved material dissociated and became more monomeric in nature.
[00459] Additionally, an accelerated weathering test of industrial glass was performed. This test can be applicable to all different types of systems, but is specifically applicable to non-ophthalmic eye systems.(A) The accelerated weathering test on industrial glass was carried out in a 45°C chamber with exposure to UV light centered on 340 nm and intensity of 0.73 W/m2 for up to 2000 hours. The samples were laminated glass with PVB interlayer comprising the optical filter.
[00460] Laminated glass is commonly used in automotive and architectural applications, predominantly as safety glasses for automobile windshields, safety windows, puncture-proof buildings, and the like. It comprises a protective interlayer, typically rigid and flexible polymer bonded between two glass panels 251A and 251B, as shown in FIG. 25. The bonding process takes place under heat and pressure. When laminated under these conditions, the interlayer joins the two glass panels together. The most used polymer for laminated glass applications has been polyvinyl butyral (or PVB) because of its strong bonding capacity, optical clarity, adhesion to many surfaces, strength and flexibility. The main applications for laminated glass are automobile windshields, security windows, puncture-proof buildings, etc. Trade names for PVB films include, without limitation: Saflex (Eastman, USA), Butacite (DuPont, USA), WinLite (Chang Chung Petrochemicals Co. Ltd, Taiwan), S-Lec (Sekisui, Japan) and Trosifol (Kuraray Europe GmbH, Germany). There are other types of interlayer materials in use, including polyurethanes, eg Duraflex thermoplastic polyurethane (Bayer MaterialScience, Germany), ethylene vinyl acetate (EVA), polyvinyl alcohol (PVA) etc. The chemical structures of various interlayer materials are shown in FIG. 26.
[00461] For the purpose of the accelerated weathering test, first of all, the impregnation of PVB sheets occurred in previously prepared base formulations containing a certain amount of coloring compound FS-206, generating PVB sheets with blue light filtration with 20 %, 25% and 33% blue light blocking. Next, the PVB sheets were dried and laminated between two glass panels under high temperature (eg 135°C) and high pressure. The laminated samples were characterized prior to testing and verified after 500 hours, 1000 hours and 2000 hours of exposure to the above conditions for their transmission and CIE La*b* coordinate changes. All samples tested met the criteria for passing the test, which are: delta a* and delta b* of less than 1, delta E* < 2.0, transmittance > 70% and changes in transmittance of less than 1, 5% after 2000 hours exposure.
[00462] The luminance and other parameters for the tested construction were measured in accordance with ISO 13837: "Road Vehicles-Safety Glazing Materials - Method for the Determination of Solar Transmmitance", which specifies the test methods for determining the direct solar transmittance and total safety glazing materials for road vehicles. Two computational conventions (called the “A” convention and the “B” convention) are included, both consistent with current international needs and practices. Although another convention can be used, the results described here used Method “A”. The ISO standard applies to monolithic or laminated, transparent or colored samples of security glazing materials.
[00463] All parameters monitored and measured before, during and after the test are presented in Tables 2 and 3.
[00464] Table 2 provides the values for the transmittance of all tested laminated glass constructions, glass/PVB-A/glass (20% blue blocking), glass/PVB-B/glass (25% blue blocking), blue), glass/PVB-C/glass (33% blue blocking), and glass/PVB/glass as a control sample (sample that does not filter blue), which is in the range of about 86-89% before the test, and remained in this range after the 2000 hour test. The L*, a*, and b* coordinates, also given in Table 2, are similar for all tested samples (blue blocking samples and the control sample), and do not change significantly during the 2000 hours of exposure to test.Table 2. Light transmission and CIE La*b* color coordinates of tested blue blocking laminated glass samples before and after 500 hour, 1000 hour and 2000 hour accelerated weathering test.Construction Control - before exposure 500 hours

Table 3. Changes in light transmission and changes in CIE La*b* color coordinates of blue blocking laminated glass tested samples after 500 hour, 1000 hour, and 2000 hour accelerated weathering test. The delta E* parameter was also calculated from the changes in the CIE La*b* coordinates.

[00465] Note: The construction tested was PVB sheet laminated between two glass panels. PVB-A is PVB sheet impregnated with FS-206 dye compound with 20% blue light blocking. PVB-B is PVB sheet impregnated with FS-206 with 25% blue light blocking. PVB-C is FS=206 impregnated PVB sheet with 33% blue light blocking.
[00466] In Table 3, it can also be seen that all constructions tested, glass/PVB-A/glass (20% blue blocking), glass/PVB-B/glass (25% blue blocking), glass /PVB-C/glass (33% blue blocking) and glass/PVB/glass as a control sample (sample that does not filter blue) exhibited similar values for the total color difference parameter, delta E* calculated for the samples after 500 hours, 1000 hours and 2000 hours with respect to the initial state of the sample (used as a “standard” in the calculation). Similar values for delta E* for blue-blocking and non-blue-blocking samples imply that PVB layers containing porphyrin dye compound do not change (degrade) during prolonged and intense exposure to UV light at temperature high.
[00467] In another modality, the interlayers of PVB, PVA, PU or EVA used for the manufacture of laminated glass, whose structures are shown in FIG. 26, can be coated with selective blue light filtration coating.
[00468] In another embodiment, blue light blocking dye package can be added during the interlayer synthesis step (PVB, PVA, EVA, PU).
[00469] Light or heat induced degradation (mainly oxidation) of organic dyestuffs is a complex process of radicals, when free radicals (R) are generated. Therefore, UV absorbers and/or radical scavengers (antioxidants, light stabilizers) can be added to the coating to increase its stability. These additives can be purchased from BASF under the trade names Tinuvin® and the Chimassorb® series of UV absorbers, hindered amine light stabilizer HALS and others.
[00470] In one embodiment, UV stabilizer/UV blocker can be added to the selective blue light coating to further enhance its UV and heat stability. Schematically, the addition of UV stabilizer and/or UV blocker is depicted in FIG. 27. The simplest way is to add the UV blocking layer on top of the blue blocking filtration coating (FIG. 27a). Thus, in this mode, the UV blocking element is arranged on the filter. Another way is for the blue blocking coating to be immersed in a UV blocking dyebath where the UV blocker diffuses into the selective blue light filtration coating (FIG. 27b). Another way is for the UV blocker and/or stabilizer to be added to the base or hard coat formulation along with the blue blocking dyes (FIG. 27c). Yet another option is for them to be chemically bonded to the dye, as shown schematically in FIG. 27d.
[00471] All Cu-porphyrins disclosed in this descriptive report are thermally stable for many hours at elevated temperatures. Tests carried out in air at 110 degrees C showed no signs of thermal degradation of Cu-porphyrin (oxidation, dye bleaching and so on).
[00472] Intense UV exposure tests carried out in the air with an intense UV and visible light (provided by light source “Dymax BlueWave200”) have demonstrated satisfactory photostability of all Cu-porphyrins.
[00473] The coatings comprising porphyrin dyes in the present disclosure can be characterized with the yellowing index (YI parameter, which is actually a number computed by the colorimetric or spectrophotometric data that indicate the degree of color offset of a sample from colorless (or a preferred white) to yellow). Negative YI values are also possible, and represent the color shift of the sample toward blue. The yellowing index by the ASTM E313 Method was calculated as follows:
where the C coefficients depend on the illuminant (type of light source) and the observer, and X, Y and Z are tristimulus values, whose calculation is shown schematically in FIG. 4. The X, Y, and Z tristimulus values for a certain object, which is illuminated by a certain light source, can be calculated for the CIE standard observer by the sum of the products of all these distributions (light source spectrum, spectrum of the object and CIE color matching functions for the standard observer) over the wavelength range typically 380 nm to 780 nm.
[00474] The first systems discussed in this descriptive report have a low yellowing index, indicating a low color change. In one modality, the first system has a YI of at most 30, at most 27.5, at most 25, at most 22.5, at most 20, at most 17.5, at most 15, at most 12.5 , maximum 10, maximum 9, maximum 8, maximum 7, maximum 6, maximum 5, maximum 4, maximum 3, maximum 2 and maximum 1. Preferably, in ophthalmic systems, in which applications may be more sensitive to system appearance, the system has a YI of maximum 15. Preferably, in non-ophthalmic systems where system appearance may not be a factor, the system has a YI of maximum 35 .
[00475] The optical filters discussed in this descriptive report also have a low yellowing index. In one modality, the filter has a YI of at most 30, at most 27.5, at most 25, at most 22.5, at most 20, at most 17.5, at most 15, at most 12.5, maximum 10, maximum 9, maximum 8, maximum 7, maximum 6, maximum 5, maximum 4, maximum 3, maximum 2, and maximum 1. Preferably, in ophthalmic systems, in which applications may be more sensitive to system appearance, the filter has a YI of maximum 15. Preferably, in non-ophthalmic systems where system appearance may not be a factor, the filter has a YI of maximum 35 The yellowing index of the optical filter can be the same or different from the yellowing index of the system.
[00476] In addition to YI values, other color parameters and color space systems can be used to characterize optical systems and filters (for example, blue selective blocking coatings or other types of blue selective blocking filters) revealed in this descriptive report. They are presented below:
[00477] (B) CIE LAB color space (FIGS. 5A and 5B): Three parameters, L, a* and b*, represent samples (eg coatings) in the CIE LAB color space of the following:- L* - Represents the position of a sample on the light axis in the CIE LAB color space;- a* - Represents the position of a sample on the green/red axis in the CIE LAB color space, green being in the negative direction and red being in the positive direction ; e- b* - Represents the position of a sample on the blue/yellow axis in the CIE LAB color space, blue being in the negative direction and yellow being in the positive direction.
[00478] Additional information regarding the CIE LAB color space can be found in the Glossary. The CIE LAB coordinates of a sample can be calculated by the method discussed in the Glossary using the transmission spectrum of the sample. The light source that is used for measuring the transmission spectrum of the sample generally does not matter as long as the light source is a broad-spectrum light source.
[00479] After this transmission spectrum has been determined, it is used to calculate the CIE LAB coordinates of the sample. Although discussed in the Glossary in more detail, as a general topic, CIE LAB coordinates are calculated using the transmission spectrum of the sample and the spectrum of a reference light source. This second reference light source can be the same or different from the light source used to determine the transmission spectrum of the sample. In a preferred embodiment, the reference light source is D65.
[00480] (C) CIE LCH color space (FIG. 6): Three parameters, L, C* and h*, represent samples (coatings) in the CIE LCH color space as follows:- The L* axis represents Clarity. - The C* axis represents Chroma or “saturation”. This ranges from 0 at the center of the circle, which is completely unsaturated (ie a neutral grey, black or white) to 100 or more at the edge of the circle for very high Chroma (saturation) or “color purity”.- h* describes the hue angle. It ranges from 0 to 360.
[00481] You can easily transform CIE LAB color coordinates into CIE LCH coordinates and vice versa. For example, the coordinates C* and h* can be calculated from a* and b* using the following equations: Chroma C/E 1976 a,b (CIELAB): C*ab = (ax2 + bx2)1/2Hue Angle CIE 1976 a,b (CIELAB): hab = inverse tangent (b*/a*)
[00482] (C) 1931 CIE chromaticity diagram (or CIE xy color space, FIG. 7): The CIE chromaticity diagram or CIE color space has undergone several modifications over the years, with 1931 and 1976 being the most used . The CIE chromaticity coordinates (x, y, z) can be derived from the tristimulus values (X, Y, Z):

[00483] (D) CIE 1976 color space (or L'u'v' color space or CIE LUV color space, FIG. 8): The CIE 1976 chromaticity diagram is a more uniform color space than the diagram CIE 1931. It is produced by tabulating u' as abscissa and v' as ordinate, where u' and v' are calculated according to:
where X, Y, and Z are the tristimulus values. The third chromaticity coordinate w' is equal to (1 - u' - v'), because:(E) Color parameter differences and total color difference (delta E*):(i) Color parameter differences in CIE LAB space: The position of a certain sample (coating) in CIE LAB can also be expressed through the difference of LAB coordinates with respect to a standard.- If delta L* is positive; the sample is lighter than the standard. If negative; it would be darker than standard.- If delta a* is positive; the sample is redder (or less green) than the standard. If negative, it would be greener (or less red).- If delta b* is positive; the sample is more yellow (or less blue) than the standard. If negative, it would be bluer (or less yellow).(ii) Total color difference, ΔE* or DE or delta E* between two-color stimuli is calculated as the Euclidean distance between the points representing them in the CIE LAB space or CIE LCH.
[00484] The total color difference delta E* CIE LAB is a function of delta L*, delta a* and delta b* and is given in FIG. a), as total color difference delta E* CIE LCH is a function of delta L*, delta C* and delta h* and is given in FIG. 9.
[00485] The formulas for calculating delta E in the CIE LAB and CIE LCH spaces are presented below:

[00486] The meaning of all these color differences (color coordinate differences and total color difference delta E*) is presented below:ΔL* = difference in lightness/darkness value+ = lighter - = darkerΔa* = difference in red/green+ axis = redder - = greenerΔb* = difference on yellow/blue axis+ = more yellow - = bluerΔC* = difference in chroma+ = brighter - = more blurryΔH* = difference in hue

[00487] Delta E can be one of the parameters that serve as a basis to determine the color change of a sample. A detailed description of the meaning of the delta E* values is presented below:
[00488] Color difference equations are configured in such a way that their units correspond to the only perceptible difference JND and thus it is commonly stated that it is predicted that any color difference below 1 unit is not noticeable for samples viewed side by side.
[00489] A study found that a JND is equal to ΔE* = 2.3 (M. Mahy, L. Van Eycken and A. Oosterlinck, “Evaluation of Uniform Color Space Developed After the Adoption of CIELAB and CIELUV”, Color Research and Application, vol. 19, 2, pages 105-121, 1994).
[00490] Schlapfer suggests for two-color samples viewed side by side the following classification:ΔE* < 0.2 as “Not visible”,ΔE* between 0.2 and 1.0 as “Very small”,ΔE* between 1 ,0 and 3.0 as "Small", ΔE* between 3.0 and 6.0 as "Medium" and ΔE* > 6.0 as "Large"
[00491] (K. Schlapfer, Farbmetrik in “der Reproduktionstechnik und im Mehrfarbendruck”, 2nd Edition: UGRA, 1993).
[00492] Hardeberg proposes a good rule of thumb for practical interpretation of an ΔE*, in which: ΔE * < 3 are classified as "Hardly noticeable", ΔE* < 6 is defined as "perceivable but acceptable" and ΔE* > 6 as "Not acceptable"
[00493] (J.Y. Hardeberg, "Acquisition and Reproduction of Color Images, Colorimetric and Multispectral Approaches", Dissertation.com, 2001).
[00494] Another study states that Δ E * between 4 and 8 is generally considered acceptable in, for example, print and color imaging (A. Sharma, “Understanding Color Management. Thompson Delmar Learning: New York,” 2004). In the study by Stokes et al., values of ΔE* approximately = 6 were considered acceptable for their experimental images and observers (M. Stokes, M. Fairchild, and R. Berns, “Colorimetrically Quantified Visual Tolerances for Pictorial Images,” in “Proc TAG A - Technical Association of the Graphic Arts, Proceedings of the 44th Annual Meeting”, Williamsburg, VA, USA, 1992, pages 757-777).
[00495] Discrepancies in the meaning of delta E* across these different studies are predominantly because the assessment of color acceptability is highly subjective and depends largely on the experiences and expectations of the observers, as well as the application for which the samples are intended. However, they must be considered when talking about JND or delta E*, as the human eye is more sensitive to certain colors than others. A good metric should take this into account in order for a color parameter, for example delta E* or JND, to have meaning. For example, a certain value of ΔE* may be insignificant between two colors to which the eye is insensitive, but it may be very significant in another part of the spectrum, to which the eye is more sensitive.
[00496] FIGS. 10-14 present various measured and calculated color parameters for blue selective blocking coatings consistent with modalities revealed in this descriptive report. FIG. 10 shows the a* and b* coordinates (in the CIE LAB color system) for blue selective blocking coatings comprising FS-206 dye with blue light blocking ranging from 10% to 40%. FIG. 11 shows the Delta a* and Delta b* coordinates (CIE LAB color system) for blue selective blocking coatings comprising FS-206 dye with blue light blocking ranging from 10% to 40%. FIG. 12 shows YI vs. Delta E for blue selective blocking coatings comprising FS-206 dye. Each symbol represents the measured coating; all coatings shown provide blue light blocking in the 10-40% range and exhibited YI between 2 and 8. In FIG. 12, the color difference (Delta E) was calculated as: La*b* (SAMPLE) - La*b* (STANDARD) with polycarbonate lens with a worked surface used as a STANDARD. This is an example of how the filter effect can be isolated.
[00497] FIG. 13 shows the yellowing index vs. Chroma for blue interlocking finishes. The symbols shown in the Figure designate coatings with about 20% blue light blocking, while the broken ellipsoid gives the range for coatings with 10-40% blue light blocking. FIG. 14 shows Hue vs. Chroma for optical filter coatings. The symbols represent coatings with about 20% blue light blocking, while the broken ellipsoid gives the range for coatings with 10-40% blue light blocking.
[00498] FIGS. 15 and 16 show the adjustability of % blue light blocking as a function of dye concentration for FS-206 and FS-207 dyes coated on glass substrates, respectively. Increased dye concentration at a certain coating thickness generates increased light blocking and higher YI values. The ability to fine-adjust the % blue light blocking and YI can be obtained by adjusting the dye concentration in the coating. It is noted that although the filters described here were coated on a glass substrate, the glass substrate does not contribute to the transmission spectrum or the YI. FIG. 15 shows the transmission spectra of selective filtration coatings on glass substrates comprising the Cu(II) dye meso-Tetra(2-naphthyl)porphine (FS-206) at different concentrations. Generally speaking, FIG. 15 shows that as the dye concentration is increased, the amount of transmitted light is decreased. For example, the transmission spectrum for a dye concentration of 0.1 is represented by the line in FIG. 15 which has the lowest transmittance at a wavelength of 420 nm and the transmission spectrum for the dye concentration of 0.091 is represented by the line which has the second lowest transmittance at a wavelength of 420 nm. Table 7 below further discusses dye concentration, YI and % blue light blocking dependencies for coatings containing the FS-206 dye. FIG. 16 shows the transmission spectra of selective filtration coating on glass substrates comprising dye FS-207 at different concentrations. The lines of the graph in FIG. 16 represent, in order from top to bottom of the chart, YI as follows: YI = 10.61, YI = 14.03, YI = 15.51, YI = 17.58, and YI = 19.57. Generally, FIG. 16 shows that as YI is increased, transmittance is decreased. Table 8 below further discusses the relationships between dye concentration, YI and % blue blocking for coatings containing FS-207 dye.
[00499] FIGS. 17A-17F are related to % blue light blockage as a function of YI, but also slight variations in % blockage are observed depending on the spectral range where the calculation is made. FIGS. 17A-17F show the yellowing index (YI) vs. % blue light blocking, calculated for different spectral ranges for coatings on glass substrates comprising FS-206 dye at different concentrations. Note: The glass substrate does not contribute to the final/recorded YI (Glass YI is 0). FIG. 17A is for the 420 nm - 425 nm wavelength ranges. FIG. 17B is for the 420 nm - 425 nm wavelength ranges. FIG. 17B is for the 420 nm-430 nm wavelength ranges. FIG. 17C is for the 415 nm - 435 nm wavelength ranges. FIG. 17D is for the 420 nm - 440 nm wavelength ranges. FIG. 17E is for the 410 nm - 430 nm wavelength ranges. FIG. 17F is for the 410 nm - 450 nm wavelength ranges.
[00500] Thus, the systems revealed in this descriptive report have a very low color change both in transmittance and reflectance. Using some of the parameters discussed above, this low color shift can be characterized by how the system transmits or reflects a certain reference light source. “CIE Standard Illuminant D65” light source has CIE LAB coordinates represented by (a*1, b*1, L*1). In one embodiment, when this D65 CIE light source is transmitted through or reflected by the first system, and the resulting light has CIE LAB coordinates represented by (a*2, b*2, L*2). A total color difference ΔE between (a*1, b*1, L*1) and (a*2, b*2, L*2) is less than 6.0, preferably less than 5.0 e , even more preferably less than 4.0 or 3.0. A total saturation difference between (a*1, b*1, L*1) and (a*2, b*2, L*2) is less than 6.0, preferably less than 5.0, and even more preferably less than 4.0 or 3.0.
[00501] The low color change in both transmittance and reflectance of the systems disclosed in this descriptive report can also be characterized in how the optical filter transmits and reflects a certain reference light source.
[00502] One way to characterize the effect of an optical filter on a system is to measure how a first system comprising the optical filter transmits and reflects a reference light source. Next, the same reference light source must be transmitted through and/or reflected by a second system. The second system is identical to the first system in all except that it doesn't include the optical filter. Using the numbers obtained for the first system and the second system, the color change of the optical filter can be determined. For example, in one modality, “CIE Standard Illuminant D65” light source had CIE LAB coordinates represented by (a*1, b*1, L*1). When this D65 CIE light source is transmitted through or reflected by the first system, the resulting light has CIE LAB coordinates represented by (a*2, b*2, L*2). This D65 CIE light source is then transmitted through or reflected by a second system. The second system is identical to the first system at all, except that it doesn't contain an optical filter. When the D65 CIE light source is transmitted through or reflected by the second system, the resulting light has CIE LAB coordinates represented by (a*3, b*3, L*3) . A total color difference ΔE between (a*2, b*2, L*2) and (a*3, b*3, L*3) is less than 6.0, preferably less than 5.0 e , even more preferably less than 4.0 or 3.0. A total saturation difference between (a*2, b*2, L*2) and (a*3, b*3, L*3) is less than 6.0, preferably less than 5.0 and, even more preferably less than 4.0 or 3.0.
[00503] Thus, the optical filters revealed in this descriptive report are superior to others, at least in part, due to the low color change. Examples of measured and calculated color parameters and color coordinates are given in Tables 4-6 for an optical filter coating comprising the colorant compound FS-206 and providing 20% blue light blocking. What are noticeable are the low “color” values of the coating compared to broadband filtering coatings. For example, among other color parameters, its saturation C was measured to be 1.98, YI was calculated to be 3.5, the total color difference delta E* to be only 3.91, which corresponds to JND around 1.7, while mean and luminous transmittances were above 90%. Furthermore, all other coatings comprising other porphyrin dyes were characterized with "low color" values. This can be seen from FIG. 10-14, for blue light filtering coatings, which can provide up to 40% blue light blocking: Table 4. Color parameters C, YI, hue, a*, b*, delta E and JND, for color coating selective blue blocking that contains the FS-206 dye with 20% blue light blocking.
Table 5. Mean Tavg transmittance, Tv light transmittance, and CIE LAB L* brightness for blue selective blocking coating containing FS-206 dye with 20% blue light blocking.
Table 6 . CIE 1931 color coordinates x and y and CIE 1976 uv color coordinates for blue selective blocking coating containing FS-206 dye with 20% blue light blocking.

[00504] Thus, in one modality, the first system has:- Chroma C below 5.0,- |a*| and |b*| are below 2 and 4, respectively, - YI is below 8.0, - delta E* is below 5.0 and - JND is below 2 units, while the values of clarity L and transmission (Tavg, Tv ) are above 90%.
[00505] In Table 7 are presented values for the % blue light blocking, calculated in different spectral ranges (all within the “retinal hazardous blue wavelength region” mentioned previously) for coatings comprising Cu(II) ) meso-Tetra(2-naphthyl)porphine (FS-206) dye on glass substrates. The concentration of dye in the coating is given as % by weight of dye/base. The % blue light blocking values and YFs are given for glass substrates, where both surfaces have been coated with the coating comprising the dye. The glass substrate does not contribute to the final YI value recorded (ie YI for the glass substrate used is 0).
[00506] It is clear that the % blue light blocking and the YI of the coating comprising dye FS-206 can be adjusted precisely by the concentration of dye in the coating and the thickness of the coating. In Table 7, the thickness of the coatings was kept constant, that is, all coatings were made by the dip coating method under the same conditions (immersion rate, withdrawal rate, room temperature, formulation viscosity) and thus the registered % blue block and YI were controlled solely by the dye concentration in the coating. Table 7. Dye concentration, yellowing index (YI) and % blue light block for light selective coating coated glass substrates blue that comprises the dye Cu(II) meso-Tetra(2-naphthyl)porphine (FS-206).
• Recorded YI values are measured for coatings on dip-coated glass substrates, where the substrate does not contribute to the final (recorded) YI value [Glass YI = 0].
[00507] Table 8 shows similar data for coatings comprising FS-207 dye coated on glass substrates. The glass substrate does not contribute to the final recorded YI value (ie YI for the glass substrate used is 0). Note that due to the red shift of the FS-207 absorption peak compared to that of FS-206, the YIs of coatings comprising FS-207 are higher than those for coatings with FS-206 dye at the same % level Block. In Table 8, the thickness of the coatings was kept constant, that is, all coatings were made by the dip coating method under the same conditions (immersion rate, withdrawal rate, room temperature, formulation viscosity) and thus the registered % blue block and YI were controlled solely by the dye concentration in the coating. Table 8. Dye concentration, yellowing index (YI) and % blue light block for light selective coating coated glass substrates blue which comprises dye FS-207.*Recorded YI values are measured for coatings on dip-coated glass substrates where the substrate does not contribute to the final (recorded) YI value [Glass YI = 0].

[00508] Dye FS-208 has a broader peak and red shift compared to that of dye FS-206 and therefore exhibited much higher YI values for coatings that provide the same % blocking as FS -206.
[00509] In Table 9, the measured YI for flat surface-worked lens blocks is presented. These values are given as an example only; values for lens blocks with a machined surface may vary to a large extent depending on the actual lens material manufacturer, final lens block thickness, lens optical power, etc. Table 9. YI measured for lens blocks Flat lens crafted on the surface.

[00510] Just as an example, Table 10 presents the approximate values of the YI for flat lens blocks worked on the surface coated with selective blue light coating comprising dye FS-206. The final recorded values for the YI of lens blocks with a coated worked surface are the sum of YI (coating) and YI (substrate). comprises FS-206 dye.


[00511] From Table 7 and FIG. 15 and 17A-17F, it can be seen that the YI and selective blue light filtration performance of the coating can be fine-tuned by adjusting the concentration of FS-206 dye in the coating. Additionally, this dye has good solubility, especially in chlorinated solvents.
[00512] Finally, it is observed that the solvent may play a particular role in the methods disclosed here. This is discussed below. Particular examples of the role of solvent are described below in the context of additional embodiments.
[00513] a) The FS-206 dye is dissolved in methylene chloride and added to the base at a concentration of 1% by weight of dye/base. Then, the solution is further diluted with a fresh base, reducing it to the necessary concentration for a certain application. After filtration, the solution is applied to form an optical filter. For example, it can be used for dip coating of lenses. Next, a hard clear coating can be coated on the lens. The final lenses exhibit about 30-35% blue light blocking in the spectral range around 420 nm and YI = 5.0-6.0, depending on the lens material.
[00514] b) Dye FS-206 is dissolved in chloroform and added to the base at a concentration of 1% by weight of dye/base. The solution is sonicated for 1 hour at 50°C. Then, the solution is further diluted with a fresh base reducing it to the final concentration needed for a certain application. After filtration, the solution is used for dip coating of the lenses, followed by clear hard coating. The final lenses exhibit about 30-35% blue light blocking in the spectral range around 420 nm and YI = 5.0-6.0, depending on the lens material. Chloroform appears to be a better solvent for dye FS-206 compared to example (a) above. The same level of light blocking in the spectral range around 420 nm is obtained with a lower concentration of dye in chloroform.
[00515] In another embodiment, the blue selective blocking filter contains a color neutralizing component, for example, Pigment Blue 15 (Sigma Aldrich), shown below:

[00516] Copper(II) phthalocyanine [546682 Aldrich]; Synonym: CuPc, Phthalocyanine Blue, Pigment Blue 15. The coating may contain other optical bleaches (eg BASFrighteners Tinopal®) to lighten or improve the appearance of coatings by masking the yellowing.
[00517] In an ophthalmic system, selective blue blocking filtration can be incorporated into the lens system in several ways. Just as an example, the filter could be located: in one or more base coats, one or more hard coatings, one or more hydrophobic coatings, one or more anti-reflective coatings, within a photochromic lens, within the lens substrate, within contact lens visibility tinting, rugate, interference, bandpass, band blocking, notched, dichroic, at varying concentrations and at one or more filtering peaks, or any combination thereof.
[00518] In one modality, the selective filter is incorporated in a sunglasses (prescription or over-the-counter) that passes traffic light recognition patterns or, in other modalities, does not pass traffic light recognition patterns. traffic signs. Additionally, UV blocking and/or IR blocking is incorporated into sunglasses.
[00519] In one embodiment, the selective blue blocking filter contains carotenoids, eg, lutein, zeaxanthin and others, melanin, or a combination thereof. In another embodiment, the selective blue blocking filter may contain: lutein, zeaxanthin or melanin in a natural, synthetic or derivative form, or in any combination thereof. Furthermore, in other embodiments, lutein, zeaxanthin and melanin or any combination of these can be engineered to migrate out of a system so as to be absorbed by human tissue. For example, a contact lens could be designed in such a way that lutein is intentionally released into the eye to provide a health benefit.
[00520] In another modality the selective blue blocking filter can be incorporated in: PVA, PVB, sol-gel, or any type of film or laminate or any combination thereof.
[00521] In other modalities UV and/or IR light is blocked or inhibited.
[00522] In another modality the filter can be incorporated throughout the product or incorporated in less than the entire product or in rings, layers or zones, or in any combination of these. For example, on a contact lens that is 14.2 mm in diameter. The blue selective blocking filter may be situated within 14.2 mm total, or less than 14.2 mm, or in rings, layers or zones, or any combination thereof. This is also true for any product that incorporates such a filter.
[00523] Modalities could include only as an example: any type of windows, or glass sheet, or any transparent material, automotive windshields, aircraft windows, camera flash bulbs and lenses, any type of artificial lighting device ( the lamp or the filament or both), fluorescent lighting, LED lighting or any type of diffuser, medical instruments, surgical instruments, rifle sights, binoculars, computer monitors, television screens, illuminated signs or any other item or system by which light is emitted or transmitted or passes through filtered or unfiltered.
[00524] Modalities may allow non-ophthalmic systems. Any non-ophthalmic system in which light is transmitted through or by the non-ophthalmic system is also envisioned. Just as an example, a non-ophthalmic system could include: automobile windows and windshields, aircraft windows and windshields, any type of window, computer monitors, televisions, medical instruments, diagnostic instruments, lighting products, fluorescent lighting , or any type of lighting product or light diffuser.
[00525] Any amount of light reaching the retina can be filtered and can be included in any type of system: ophthalmic, non-ophthalmic, dermatological or industrial.
[00526] In another embodiment, the dye pack can be added to the lens material during lens block production or during contact lens or intraocular lens manufacture. In addition, the dyes presented above, polymerizable dyes and other types of reactive dyes can be used to allow chemical connection of the dye system to the surrounding lens material.
[00527] In one embodiment, a manufacturing process is provided that combines the synergistic balance of yellowing index, system light transmission, selective light filtering to protect the retina and/or enhance contrast, dye formation, dye stability , coating thickness, compatibility with substrates to which it is applied, solubility in resin, dye refractive index, UV light protection, and normal wearer and tear protection.
[00528] The selective filter is located within the base that is applied to the posterior surface of the lens (ocular surface closest to the eye) with a scratch-resistant coating applied to the front surface of the lens (the ocular surface furthest from the eye) with a UV stopper applied to the front surface or optionally both the front surface and the back surface of the lens. The UV inhibitor works to protect the dye from UV degradation along with reducing the dose of UV to the eye.
[00529] The manufacture of the selective high energy visible light coating using FS-206 or FS-209 or Cu1 or Cu2 or Cu5 dye is described as follows:
[00530] In coating fabrication, the UV coating may be on the front surface of the lens, within the polymer and/or selective filter, or on the back surface of the lens, or any possible combination of these. However, in one modality, the UV block is in front of the lens, at the location furthest away from the eye. This allows for protection of the foundation and/or colorant as well as the eye. In another modality, applying UV blocking to the back of the lens, closest to the eye, allows for further reduction of UV light entering the eye by reflecting light from the back surface of the lens.
[00531] In other embodiments, the dye is dried on the lens surface during the manufacturing process by air drying and/or oven drying. UV light must be avoided during this step.
[00532] In other embodiments, the dye can be filtered before being applied to the lens.
[00533] In other embodiments, during a dip coating process, the front and back surfaces of a lens are coated with the base and dye. In that case, the dye on the front surface will fade over time as a function of exposure to UV light relative to the front basecoat, which is not protected from UV light. This fading will allow approximately 20% of the colorant to fade over a two-year period. Therefore, the back surface can be coated so that it has +20% more blocking than the front base. This modality initially artificially elevates the yellowing index, which increases eye protection, but as fading occurs over time, the yellowing index will decrease.
[00534] The modalities revealed in this descriptive report allow the YI to be variable depending on the intended application. Just as an example, an ophthalmic application such as an eyeglass lens can provide optimal retinal protection and cosmetics with a YI of 5.0, while a non-ophthalmic application such as a window in a house or building commercial, it can be a much higher YI of 15.0 in order to reduce overall light transmission with an even higher level of retinal protection, while cosmetic is less important than an ophthalmic spectacle lens.
[00535] Modalities include one or more dyes designed to filter out wavelengths of high energy blue light. Such dyes can include porphyrins or derivatives, with or without Soret bands. Dyes can include one or more peaks based on the targeted target wavelengths. Colorants can also vary in slope. Additional filtering rings, layers, or zones can be incorporated into the systems disclosed in this descriptive report. Just as an example, in non-ophthalmic use of an automotive windshield, it may be prudent to incorporate a layer of filtration on the upper horizontal aspect of the front windshield, both to reduce sun glare and to provide greater retinal protection than other parts of the windshield.
[00536] In one embodiment, the first system includes UV and/or IR (infrared) blocking. Thus, the first system may further include an IR blocking element or a UV blocking element, as discussed above. The modalities disclosed in this specification can be applied to a static focus lens comprising a non-changing color, a static focus lens comprising a changeable color such as, just for example, a photochromic lens such as, for example, Transitions, a lens dynamic focusing lens comprising a non-changing color, a dynamic focusing lens comprising a changing color such as, for example, a photochromic lens such as Transitions.
[00537] FIGS. 29-37 present examples of various versions of steps in blue-selective ophthalmic lens fabrications starting with non-UV-blocking and UV-blocking ophthalmic lens material substrates. The application flexibility of the blue selective filtration coating is presented: it can be applied at different stages of lens fabrication with a crafted surface (with or without prescription), depending on the UV blocking character of the lens material used as a substrate of the lens. Generally, a Cu-porphyrin compound is first dissolved in a solvent to produce a solution. The solution is then diluted with a base and filtered to remove dust, contaminants and undissolved aggregates from the dye. The solution is then applied to form an optical filter.
[00538] In FIG. 29A, manufacturing steps for CR-39 lenses are shown. In step 1, the UV blocking element is added to the semi-finished CR-39 lens. In step 2, the optical filter comprising the Cuporphyrin compound is applied by dip coating, spin coating or spray coating. In step 3, the semi-finished CR-39 lens is surface-worked, ground and/or polished. In step 4, a hard coating is added.
[00539] In FIG. 29B, another way to manufacture CR-39 lenses is shown. In step 1, the optical filter comprising the Cu-porphyrin compound is coated onto the CR-39 lens by dip coating, spin coating or spray coating. In step 2, the semi-finished CR-39 lens is surface-worked, ground and/or polished. In step 3, a hard coating is added. In step 4, the UV blocking element is added to the semi-finished CR-39 lens.
[00540] In FIG. 29C, another way to manufacture CR-39 lenses is shown. In step 1, the optical filter comprising the Cu-porphyrin compound is coated onto the CR-39 lens by dip coating, spin coating or spray coating. In step 2, the semi-finished CR-39 lens is surface-worked, ground and/or polished. In step 3, a hard coating is added. In step 4, an AR UV blocking coating is added to the semi-finished CR-39 lens.
[00541] In FIG. 30, a way to manufacture PC lenses is shown. In step 1, the optical filter comprising the Cu-porphyrin compound is coated onto the PC lens by dip coating, spin coating or spray coating. In step 2, the PC lens is surface-worked, ground and/or polished. In step 3, a hard coating is added.
[00542] In FIG. 31, a way to manufacture the MR-8 lenses is shown. In step 1, the optical filter comprising the Cu-porphyrin compound is coated onto the MR-8 lens by dip coating, spin coating or spray coating. In step 2, the MR-8 lens is surface-worked, ground and/or polished. In step 3, a hard coating is added.
[00543] In FIG. 32A, a way to manufacture MR-8 lenses with an additional UV blocker is shown. This manufacturing method is similar to that shown in FIG. 31, except that it has an additional step 4 of adding the UV blocking element. FIG. 32B shows another way to manufacture MR-8 lenses with an additional UV blocker. It is similar to the method shown in FIG. 31, except that the pre-step is added before step 1, where the pre-step includes the addition of the UV blocking element. FIG. 32C shows one way to manufacture MR-8 lenses with additional UV blocking AR coating. It is similar to the method shown in FIG. 31, except that step 3 comprises the use of an AR UV coating.
[00544] In FIG. 33, an embodiment of manufacturing steps for MR-7 lenses is shown. These steps are similar to the steps shown in FIG. 31. In FIG. 34, an embodiment of manufacturing steps for MR-10 lenses is shown. These steps are similar to the steps shown in FIG. 31.
[00545] FIG. 35 shows a manufacturing embodiment in which a removable protective layer is used. In step 1, the lens block is surface worked, ground and/or polished. In step 2, a surface of the lens block is protected using a removable layer. In step 3, the optical filter comprising the Cu-porphyrin compound is coated by dip coating, spin coating, spray coating or similar processes. In step 4, the protective layer is removed by peeling, washing and other similar processes. In step 5, the hard coating is added.
[00546] FIG. 36 shows an example of both optical filter coated surfaces on inherently non-UV blocking lens substrates. In step 1, the lens block is surface worked, ground and/or polished. In step 2, the optical filter comprising the Cuporphyrin compound is coated onto the lens by dip coating, spin coating or spray coating. In step 3, a hard coating is added. In step 4, a UV blocking element is added.
[00547] FIG. 37 shows an example of both surfaces coated with the optical filter on inherently UV-blocking lens substrates. In step 1, the lens block is surface worked, ground and/or polished. In step 2, the optical filter comprising the Cuporphyrin compound is coated onto the lens by dip coating, spin coating or spray coating. In step 3, a hard coating is added.
[00548] FIG. 38 presents lens transmission spectra, both sides of which are coated with a selective blue blocking coating (HPO coating), and lens transmission spectra upon removal of the coated posterior surface, for example, by the so-called face milling step. Note that the % blue light blocking after face milling (removing the back surface of the lens) is approximately half of the initial blocking %.
[00549] FIG. 39 presents a schematic representation of cross-sections of various blocks (semi-finished, thick, thin) and lenses used in the ophthalmic industry.
[00550] FIG. 40 shows the yellowing index (YI) vs. % blue light blocking, calculated for different spectral ranges for coatings on glass substrates comprising FS-206 dye at different concentrations. Note: The glass substrate does not contribute to the final/recorded YI (Glass YI is 0) and the blue light blocking % may vary slightly depending on the spectral range in which it is calculated.
[00551] FIG. 51 shows an exemplary transmission spectrum of a glass slide.
[00552] FIG. 52 shows an exemplary transmission spectrum of the glass slide in FIG. 51 coated with base and a hard coating.
[00553] FIG. 53 shows the transmission spectra of a glass slide used in FIG. 51 coated (1) with HPO selective filter with about 20% blue light blocking and (2) with the hard coating used in FIG. 52. The HPO selective filter used in FIG. 53 comprises the coloring compound FS-206 and the base used in FIG. 52.
[00554] FIG. 54 shows the transmission spectra of a glass slide used in FIG. 51 coated with HPO selective filter with about 30% blue light blocking and with the hard coating used in FIG. 52. The HPO selective optical filter used in FIG. 54 comprises the coloring compound FS-206 and the base used in FIG. 52.
[00555] FIG. 55 shows the transmission spectra of a glass slide used in FIG. 51 coated with HPO selective filter with about 40% blue light blocking and with the hard coating used in FIG. 52. The HPO selective filter used in FIG. 55 comprises the coloring compound FS-206 and the base used in FIG. 52. The systems used in FIGS. 53, 54 and FIG. 55 are identical to the system used in FIG. 52, except for the addition of coloring compound FS-206. Thus, in the system of FIGS. 53, 54 and 55, the transmission spectrum of the dye alone could be determined by comparing those spectra with the spectrum in FIG. 52.
[00556] In one embodiment, the system may contain one or more anti-reflective (AR) coatings. In addition to its primary purpose, the AR coating can significantly block (reflect) blue light in the 400-460 nm spectral range.
[00557] In one embodiment, the system may contain the blue selective blocking coating and one or more AR coatings. The % total blue light blocking by the system may result solely from the selective blue light absorptive coating, or it may be a sum of the blocking provided by the selective blue blocking coating (by absorption) and the blocking (reflection) provided by the AR coating .
[00558] Although this disclosure describes many modalities, some of which show specific layers and layer arrangements, these specific layers and layer arrangements are non-limiting. Those skilled in the art will readily understand that the provision of blue selective blocking layers and/or components in light transmitting devices can be achieved using the teachings disclosed in this specification, without specifically using the aforementioned disclosed specific layers and layer arrangements previously.
[00559] In addition, references made in this descriptive report to "a modality", "an example modality" or similar phrases indicate that the described modality may include a particular feature, structure or characteristic, but each modality need not necessarily include the particular feature, structure or feature. Furthermore, these phrases do not necessarily refer to the same modality. In addition, when a particular feature, structure or feature is described in connection with a modality, it would be within the knowledge of those skilled in the relevant technique (or techniques) to incorporate that feature, structure or feature into other modalities, whether explicitly or not mentioned or described in this descriptive report. The breadth and scope of the invention is not to be limited by any of the exemplary embodiments described above, but is to be defined only in accordance with the following claims and their equivalents.

权利要求:
Claims (23)
[0001]
1. First system characterized by comprising: (a) an object; and (b) an optical filter applied to the object wherein the optical filter comprises a Cuporphyrin compound having the following structure:
[0002]
2. First system, according to claim 1, characterized in that the Cu-porphyrin compound is selected from the group consisting of:
[0003]
3. First system, according to claim 1, characterized in that the Cu-porphyrin compound has the structure:
[0004]
4. First system, according to claim 1, characterized in that the Cu-porphyrin compound has the structure:
[0005]
5. First system, according to claim 1, characterized in that the Cu-porphyrin compound has the structure:
[0006]
6. First system, according to claim 1, characterized in that the Cu-porphyrin compound has the structure:
[0007]
7. First system, according to claim 1, characterized in that, in the compound of Cu-porphyrin, each one of R9 to R28 is, independently, H, carboxylic acid or a carboxylic ester.
[0008]
8. First system, according to claim 7, characterized in that, in the compound of Cu-porphyrin, each one of R9 to R28 is, independently, H or a carboxylic acid.
[0009]
9. First system, according to claim 7, characterized in that, in the compound of Cu-porphyrin, each one of R9 to R28 is, independently, H or a carboxylic ester.
[0010]
10. First system, according to claim 1, characterized in that the Cu-porphyrin compound is Cu(II) meso-Tetra(1-naphthyl)porphine.
[0011]
11. First system, according to claim 1, characterized in that the Cu-porphyrin compound is Cu(II) meso-Tetra(4-carboxyphenyl)porphine.
[0012]
The first system according to any one of claims 1 to 11, further comprising: a surface; wherein the optical filter is a coating disposed on the surface, and the coating includes the Cu-porphyrin compound, or further comprising: a substrate; wherein the optical filter is the Cu-porphyrin compound, and wherein the Cu-porphyrin compound is dispersed throughout the substrate.
[0013]
13. First system according to any one of claims 1 to 12, characterized in that the first system is an ophthalmic system, optionally wherein the first system is selected from a group consisting of: an eyeglass lens, a contact lens, an intraocular lens, an intracorneal implant, and an extracorneal implant.
[0014]
14. First system according to any one of claims 1 to 12, characterized in that the first system is a non-ophthalmic eye system, optionally wherein the first system is selected from the group consisting of: one window, one stop -automotive windshield, an automotive side window, an automotive rear window, a sunroof window, commercial glass, residential glass, skylights, a bulb and camera flash lens, an artificial lighting device, a fluorescent light or diffuser, a medical instrument, a surgical instrument, a rifle sight, a binoculars, a computer monitor, a television screen, an illuminated sign, an electronic device screen, and a patio lamp.
[0015]
15. First system, according to claim 14, characterized in that the optical filter is incorporated in a layer of polyvinyl butyral (PVB), polyvinyl alcohol (PVA), ethylene vinyl acetate (EVA), or polyurethane (PU ).
[0016]
16. First system, according to any one of claims 1 to 15, characterized in that: TSRG is the average transmission of the first system over the wavelength range 460 nm - 700 nm; TSBlue is the average transmission of the first system over the wavelength range 400 nm - 460 nm; TSRG > 80%; TSBlue < TSRG - 5%; or where: TFRG is the average transmission of the filter through the wavelength range 460 nm - 700 nm;TFBlue is the average transmission of the filter over the wavelength range 400 nm - 460 nm; TFRG > 80%; TFBlue < TFRG - 5%; and the filter has a first local minimum in transmission at a first wavelength within the wavelength range 400 nm - 460 nm.
[0017]
17. First system, according to any one of claims 1 to 16, characterized by the fact that: light "CIE Standard Illuminant D65" which has the CIE LAB coordinates (a*1, b*1, L*1), when transmitted through the first system, results in transmitted light that has the CIE LAB coordinates (a*2, b*2, L*2), and a total color difference ΔE between (a*1, b*1, L*1) and (a*2, b*2, L*2) is less than 5.0; or where: “CIE Standard Illuminant D65” light that has CIE LAB coordinates (a*1, b*1, L*1), when transmitted through the first system, results in transmitted light that has CIE LAB coordinates (a* 2, b*2, L*2), and a total saturation difference between (a*1, b*1, L*1) and (a*2, b*2, L*2) is less than 5, 0.
[0018]
18. First system, according to any one of claims 1 to 17, characterized in that the first system has a YI of a maximum of 35, a maximum of 30, a maximum of 25, or a maximum of 20, or in which the filter has a YI of maximum 35, maximum 30, maximum 25, or maximum 20.
[0019]
19. First system, according to any one of claims 1 to 18, characterized in that: for at least one wavelength within 10 nm of the first wavelength on the negative side, the slope of the transmission spectrum of the first system has an absolute value that is less than the absolute value of the slope of the transmission spectrum at a third wavelength, where the third wavelength is more than 10 nm from the first wavelength on the negative side.
[0020]
20. A method comprising: dissolving a Cu-porphyrin compound in a solvent to produce a solution; diluting the solution with a base; filtering the solution; and applying the solution to form an optical filter, in which the Cu-porphyrin compound has a structure of:
[0021]
21. First system, according to any one of claims 1 to 11, characterized in that the first system is a non-ocular system, optionally in which the first system is a dermatological product.
[0022]
22. First system, according to claim 21, characterized in that the dermatological product is a skin product or a hair product, optionally in which the dermatological product is a lipstick, a lip balm, a gloss lipstick, is it a tanning product or sunscreen, or is it a shampoo.
[0023]
23. Use of the first system as defined in any one of claims 1 to 11, characterized in that it is in the preparation of a dermatological product to treat cancer.

类似技术:

---

公开号 | 公开日 | 专利标题

---

BR112016025859B1|2021-08-24|PHOTOSTABLE AND THERMALLY STABLE COLORING COMPOUNDS FOR SELECTIVE FILTERED OPTICS FOR BLUE LIGHT

---

US10610472B2|2020-04-07|High energy visible light filter systems with yellowness index values

---

US20140093661A1|2014-04-03|Selective Blue Light Filtered Optic

---

JP5917622B2|2016-05-18|High-performance selective optical wavelength filtering provides improved contrast sensitivity

---

CN104360495B|2016-09-14|The photochromic ophthalmic system of the specific blue light wavelength of selective filter

---

TW201418821A|2014-05-16|Selective blue light filtered optic

---

US8360574B2|2013-01-29|High performance selective light wavelength filtering providing improved contrast sensitivity

---

US9377569B2|2016-06-28|Photochromic ophthalmic systems that selectively filter specific blue light wavelengths

---

US20120075577A1|2012-03-29|High performance selective light wavelength filtering providing improved contrast sensitivity

---

KR20090045922A|2009-05-08|System and method for selective light inhibition

---

US20210026054A1|2021-01-28|Photo-stable and thermally-stable dye compounds for selective blue light filtered optic

---

TW201224577A|2012-06-16|High energy visible light filter systems with yellowness index values

同族专利:

---

公开号 | 公开日

---

AU2015256283A1|2016-11-24|

---

JP6753783B2|2020-09-09|

---

JP2017515822A|2017-06-15|

---

CA2947865A1|2015-11-12|

---

US20150316688A1|2015-11-05|

---

SG11201609140SA|2016-11-29|

---

WO2015171507A1|2015-11-12|

---

BR112016025859A2|2018-09-25|

---

AU2015256283B2|2019-12-05|

---

EP3140306B1|2021-11-17|

---

EP3140306A1|2017-03-15|

---

CN106715442A|2017-05-24|

---

CN106715442B|2020-01-31|

---

US9683102B2|2017-06-20|

---

EP3140306A4|2017-12-13|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

NL300132A|1962-11-19|

---

US3687863A|1970-05-25|1972-08-29|Gen Telephone & Elect|Optical filters containing tetraphenyl-porphins and method of making same|

---

US4043637A|1973-06-15|1977-08-23|American Optical Corporation|Photochromic light valve|

---

US4390676A|1976-11-15|1983-06-28|Schering Corporation|Ultraviolet absorbing lenses|

---

US4017292A|1975-11-28|1977-04-12|Corning Glass Works|Process for making multifocal photochromic ophthalmic lens|

---

US5054902B1|1975-12-29|1998-06-23|William J King|Light control with color enhancement|

---

US4247177A|1979-01-15|1981-01-27|Marks Alvin M|3D Multichrome filters for spectacle frames|

---

US4952046A|1982-02-26|1990-08-28|Stephens James B|Optical lenses with selective transmissivity functions|

---

US4581288A|1983-10-20|1986-04-08|Corning Glass Works|Composite photochromic lenses|

---

US4698374A|1984-06-08|1987-10-06|Gallas James M|Optical lens system incorporating melanin as an absorbing pigment for protection against electromagnetic radiation|

---

US4679918A|1984-10-23|1987-07-14|Ace Ronald S|Ophthalmic glass/plastic laminated lens having photochromic characteristics and assembly thereof|

---

US4656186A|1985-04-30|1987-04-07|Nippon Petrochemicals Co., Ltd.|Tetrapyrrole therapeutic agents|

---

DE3544627C2|1985-12-17|1988-12-15|Optische Werke G. Rodenstock, 8000 Muenchen, De|

---

WO1988002871A1|1986-10-16|1988-04-21|Suntiger, Incorporated|Ultraviolet radiation and blue light blocking polarizing lens|

---

US4878748A|1987-02-26|1989-11-07|Suntiger, Inc.|Ultraviolet radiation and blue light blocking polarizing lens|

---

US5177509A|1987-02-26|1993-01-05|Suntiger, Inc.|Ultraviolet radiation and blue light blocking polarizing lens|

---

WO1989000779A1|1987-07-17|1989-01-26|Kabushiki Kaisha Komatsu Seisakusho|Apparatus for controlling laser wavelength|

---

US4793669A|1987-09-11|1988-12-27|Coherent, Inc.|Multilayer optical filter for producing colored reflected light and neutral transmission|

---

US5172256A|1988-01-19|1992-12-15|Sethofer Nicholas L|Liquid crystal variable color density lens and eye protective devices incorporating the same|

---

JPH0824694B2|1988-02-09|1996-03-13|ホーヤ株式会社|Contact lenses for correcting blue eyes|

---

US5374663A|1988-03-03|1994-12-20|Hoya Corporation|Process for producing cyanopsia-correctable intraocular lens|

---

US4826286A|1988-05-06|1989-05-02|Thornton Jr William A|Filter with three-band transmission for good seeing|

---

DE3828382A1|1988-08-20|1990-02-22|Zeiss Carl Fa|SUN PROTECTION FILTER|

---

DE3837884A1|1988-11-08|1990-05-10|Mutzhas Maximilian F|LIGHT FILTER FOR IMPROVING VISION|

---

JPH02238061A|1989-03-13|1990-09-20|Mitsubishi Kasei Corp|Hydroxyflorin-based compound and optical absorbing material using the same|

---

US5200443A|1991-03-29|1993-04-06|Kimberly-Clark Corporation|Radiation stabilized fabric having improved odor characteristics containing an hindered amine compound|

---

JP3188050B2|1993-05-17|2001-07-16|ダイセル網干産業株式会社|Eyeglass lens|

---

US5470932A|1993-10-18|1995-11-28|Alcon Laboratories, Inc.|Polymerizable yellow dyes and their use in opthalmic lenses|

---

JPH07113710A|1993-10-19|1995-05-02|Asatsuku Giken Kk|Pressure sensor|

---

US5512371A|1994-03-18|1996-04-30|Innotech, Inc.|Composite lenses|

---

FR2717385B1|1994-03-21|1996-04-19|Oreal|Cosmetic composition containing in combination a superoxide dismutase and a porphyrin.|

---

JPH07306387A|1994-05-12|1995-11-21|Tokai Kogaku Kk|Lens for light shielding|

---

US5694240A|1994-06-24|1997-12-02|Bausch & Lomb Incorporated|Multilayer anti-reflective and ultraviolet blocking coating for sunglasses|

---

US5521765A|1994-07-07|1996-05-28|The Boc Group, Inc.|Electrically-conductive, contrast-selectable, contrast-improving filter|

---

WO1998026326A1|1994-08-10|1998-06-18|Moore J Paul|Apparatus for enhancing visual perception of selected objects in recreational and sporting activities|

---

US5729379A|1994-10-26|1998-03-17|Donnelly Corporation|Electrochromic devices|

---

US5846457A|1994-10-28|1998-12-08|Hoffman; William C.|Light filtering contact lens method|

---

US5617154A|1994-10-28|1997-04-01|Flexlens|Light filtering contact lens|

---

US5534041A|1994-11-07|1996-07-09|Corning Incorporated|Method of making laser eyewear protection|

---

JPH08254603A|1995-03-15|1996-10-01|Mizunokaku Megane Kk|Half dimming plastic lens and manufacture thereof|

---

JP4006039B2|1995-09-13|2007-11-14|生化学工業株式会社|Photocrosslinked hyaluronic acid contact lens|

---

EP0763754B1|1995-09-13|2003-01-08|Seikagaku Kogyo Kabushiki Kaisha |Photocured crosslinked-hyaluronic acid contact lens|

---

US5891229A|1996-03-29|1999-04-06|Kimberly-Clark Worldwide, Inc.|Colorant stabilizers|

---

AU5589698A|1996-11-27|1998-06-22|Kimberly-Clark Worldwide, Inc.|Improved substrates and colorant stabilizers|

---

JPH10186291A|1996-12-26|1998-07-14|Toray Ind Inc|Plastic lens|

---

JPH1152101A|1997-08-01|1999-02-26|Seiko Epson Corp|Production of plastic lens|

---

US6524379B2|1997-08-15|2003-02-25|Kimberly-Clark Worldwide, Inc.|Colorants, colorant stabilizers, ink compositions, and improved methods of making the same|

---

US6326448B1|1997-08-20|2001-12-04|Menicon Co., Ltd.|Soft intraocular lens material|

---

US6277940B1|1997-08-20|2001-08-21|Menicon Co. Ltd|Material for a soft intraocular lens|

---

JPH11101901A|1997-09-26|1999-04-13|Matsushita Electric Ind Co Ltd|Lens|

---

US6793339B1|1997-10-21|2004-09-21|Sola-International Holdings, Ltd.|Coated sunglass lens|

---

US6158862A|1997-12-04|2000-12-12|Alcon Laboratories, Inc.|Method of reducing glare associated with multifocal ophthalmic lenses|

---

US6145984A|1997-12-23|2000-11-14|Maui Jim, Inc.|Color-enhancing polarized lens|

---

US6334680B1|1998-02-23|2002-01-01|Optimieyes Limited Partnership|Polarized lens with oxide additive|

---

US6604824B2|1998-02-23|2003-08-12|Charles P. Larson|Polarized lens with oxide additive|

---

US5926248A|1998-06-26|1999-07-20|Bausch & Lomb, Incorporated|Sunglass lens laminate|

---

EP1018038B1|1998-07-23|2002-09-18|Optische Werke G. Rodenstock|Photochromic plastic object|

---

US6021001A|1998-07-30|2000-02-01|Raytheon Company|Rugate induced transmission filter|

---

JP3503053B2|1998-11-06|2004-03-02|伊藤光学工業株式会社|Plastic lens|

---

JP2002530686A|1998-11-16|2002-09-17|オプティッシュ．ウエルケ．ゲー．ローデンストック|Neutral color photochromic plastic articles|

---

EP1173790A2|1999-03-01|2002-01-23|Boston Innovative Optics, Inc.|System and method for increasing the depth of focus of the human eye|

---

JP2000277262A|1999-03-29|2000-10-06|Matsushita Electric Ind Co Ltd|Implantation type electorluminescent device|

---

JP3449406B2|1999-04-07|2003-09-22|Ｈｏｙａヘルスケア株式会社|Novel pyrazolone compound and ophthalmic plastic lens using the same|

---

US6986579B2|1999-07-02|2006-01-17|E-Vision, Llc|Method of manufacturing an electro-active lens|

---

US6231183B1|1999-07-06|2001-05-15|Stephen M. Dillon|Optical lens structure and method of fabrication thereof|

---

US7255435B2|2001-12-11|2007-08-14|Pratt Steven G|Blue blocking tens|

---

US6955430B2|2001-12-11|2005-10-18|Pratt Steven G|Blue blocking lens|

---

US20020042653A1|1999-11-23|2002-04-11|Copeland Victor L.|Blue blocking intraocular lens implant|

---

US6305801B1|1999-12-02|2001-10-23|Peakvision, Llc|Contact lens with filtering for outdoor sporting and recreational activities|

---

US6220703B1|1999-12-29|2001-04-24|Younger Manufacturing Co., Inc.|Ophthalmic lenses utilizing polyethylene terephthalate polarizing films|

---

ES2247056T3|2000-01-12|2006-03-01|North Carolina State University|NEW COLORS AND COLOR STABILIZERS, INK COMPOSITIONS AND IMPROVED PRODUCTION METHODS OF THE SAME.|

---

JP2001200058A|2000-01-19|2001-07-24|Mitsubishi Gas Chem Co Inc|Manufacturing method for optical material|

---

JP3303053B2|2000-01-28|2002-07-15|奈良先端科学技術大学院大学長|Poly containing imidazolyl porphyrin metal complex as a structural unit|

---

AU7482701A|2000-05-09|2001-11-20|Univ California|Porphyrin-based neutron capture agents for cancer therapy|

---

DE10026717A1|2000-05-30|2001-12-13|Rodenstock Optik G|Photochromic plastic object with permanently increased contrast|

---

JP4524877B2|2000-07-17|2010-08-18|コニカミノルタホールディングス株式会社|Eyeglass lenses|

---

US7066596B2|2001-11-02|2006-06-27|Andrew Ishak|Rugate lens for glasses|

---

US8500274B2|2000-11-03|2013-08-06|High Performance Optics, Inc.|Dual-filter ophthalmic lens to reduce risk of macular degeneration|

---

US8403478B2|2001-11-02|2013-03-26|High Performance Optics, Inc.|Ophthalmic lens to preserve macular integrity|

---

US20040070726A1|2000-11-03|2004-04-15|Andrew Ishak|Waterman's sunglass lens|

---

EP1356343A2|2001-01-23|2003-10-29|Nike, Inc.|Activity-specific optical filters and eyewear using such filters|

---

US20030105130A1|2001-03-30|2003-06-05|Hurley Laurence H.|Thiaporphyrin, selenaporphyrin, and carotenoid porphyrin compounds as c-myc and telomerase inhibitors|

---

US6851074B2|2001-04-30|2005-02-01|Hewlett-Packard Development Company|System and method for recovering from memory failures in computer systems|

---

US20020159026A1|2001-04-30|2002-10-31|Bernheim Edward A.|Optical medium with tailored electromagnetic spectrum transmission|

---

US6411450B1|2001-09-07|2002-06-25|The United States Of America As Represented By The Secretary Of The Navy|Method of assessing the effectiveness of a laser eye protection device|

---

US7029758B2|2001-10-04|2006-04-18|James Gallas|Melanin polyvinyl alcohol plastic laminates for optical applications|

---

US6641261B2|2001-10-06|2003-11-04|Stryker Corporation|Lens for vision enhancement|

---

WO2003057176A2|2002-01-08|2003-07-17|Emory University|Porphyrins with virucidal activity|

---

JP2003215302A|2002-01-21|2003-07-30|Nikon-Essilor Co Ltd|Colored plastic lens and method for producing the same|

---

US20030148391A1|2002-01-24|2003-08-07|Salafsky Joshua S.|Method using a nonlinear optical technique for detection of interactions involving a conformational change|

---

AU2003212458A1|2002-02-26|2003-09-09|Board Of Regents, The University Of Texas System|Cyclopyrroles and methods thereto|

---

US7423110B2|2002-04-15|2008-09-09|Solvay Advanced Polymers, L.L.C.|Polysulfone compositions exhibiting very low color and high light transmittance properties and articles made therefrom|

---

EP1546792B1|2002-08-28|2010-05-26|Robert Casper|Use of an optical filter for the prevention of melatonin suppression by light at night|

---

US6863848B2|2002-08-30|2005-03-08|Signet Armorlite, Inc.|Methods for preparing composite photochromic ophthalmic lenses|

---

JP4023329B2|2003-02-13|2007-12-19|松下電工株式会社|Optical filter and lighting apparatus using the same|

---

US7166357B2|2003-03-20|2007-01-23|Transitions Optical, Inc.|Photochromic articles that activate behind ultraviolet radiation blocking transparencies and methods for preparation|

---

US6926405B2|2003-06-06|2005-08-09|Younger Mfg. Co.|Eyewear lens having selective spectral response|

---

US6960231B2|2003-07-14|2005-11-01|Alcon, Inc.|Intraocular lens system|

---

US7276544B2|2003-09-08|2007-10-02|Bausch & Lomb Incorporated|Process for manufacturing intraocular lenses with blue light absorption characteristics|

---

US7033391B2|2003-09-08|2006-04-25|Bausch & Lomb Incorporated|High refractive index silicone-containing prepolymers with blue light absorption capability|

---

US7098283B2|2003-09-08|2006-08-29|Bausch & Lomb Incorporated|Reactive yellow dyes useful for ocular devices|

---

US6918931B2|2003-09-08|2005-07-19|Bausch & Lomb Incorporated|Prepolymers with yellow dye moiety|

---

US20050055091A1|2003-09-08|2005-03-10|Yu-Chin Lai|Process for making silicone intraocular lens with blue light absorption properties|

---

WO2005066694A2|2003-12-29|2005-07-21|Advanced Medical Optics, Inc.|Intraocular lenses having a visible light-selective-transmissive-region|

---

US8097283B2|2004-01-15|2012-01-17|Mount Sinai School Of Medicine|Methods and compositions for imaging|

---

US7645397B2|2004-01-15|2010-01-12|Nanosys, Inc.|Nanocrystal doped matrixes|

---

US7275822B2|2004-03-18|2007-10-02|Essilor International |Progressive addition lenses with adjusted image magnification|

---

JP2005261606A|2004-03-18|2005-09-29|Ricoh Microelectronics Co Ltd|Guard against ultraviolet laser, and guard set against ultraviolet laser|

---

US20050248752A1|2004-04-30|2005-11-10|Hall Gary W|Solar rating system for intraocular lens implants|

---

WO2005111702A1|2004-04-30|2005-11-24|Advanced Medical Optics, Inc.|Ophthalmic devices having a highly selective violet light transmissive filter and related methods|

---

US20070159594A9|2004-05-13|2007-07-12|Jani Dharmendra M|Photochromic blue light filtering materials and ophthalmic devices|

---

WO2005116138A1|2004-05-27|2005-12-08|Teijin Chemicals Ltd.|Spectacle lens|

---

TWI242092B|2004-06-10|2005-10-21|Hannstar Display Corp|Repairing method of a liquid crystal display panel|

---

US8133274B2|2004-06-18|2012-03-13|Medennium, Inc.|Photochromic intraocular lenses and methods of making the same|

---

JP2006091532A|2004-09-24|2006-04-06|Toshiba Lighting & Technology Corp|Uv protection member, lamp and lighting fixture|

---

CN101048411A|2004-10-25|2007-10-03|三井化学株式会社|Optical filter and its applications, and porphyrin compound used in optical filter|

---

US20070293666A1|2004-10-25|2007-12-20|Mitsui Chemicals, Inc.|Optical Filter and Its Applications, and Porphyrin Compound Used in Optical Filter|

---

US20060126019A1|2004-12-10|2006-06-15|Junzhong Liang|Methods and systems for wavefront analysis|

---

US7429275B2|2004-12-23|2008-09-30|L'oreal S.A.|Use of at least one compound chosen from porphyrin compounds and phthalocyanin compounds for dyeing human keratin materials, compositions comprising them, a dyeing process, and compounds therefor|

---

JP4811701B2|2004-12-28|2011-11-09|山本光学株式会社|Protective eyeglass lenses|

---

CA2592585A1|2004-12-30|2006-07-06|Essilor International |Compounds that absorb ultraviolet light, methods of their preparation and optical lenses containing them|

---

JP2006265532A|2005-02-28|2006-10-05|Toray Ind Inc|Thermoplastic resin composition and method for producing the same|

---

US20060197067A1|2005-03-04|2006-09-07|Erning Xia|Radiation-absorbing materials, ophthalmic compositions containing same, and method of treating ophthalmic devices|

---

JP4716249B2|2005-03-24|2011-07-06|三菱瓦斯化学株式会社|Polymerizable composition|

---

JP4606918B2|2005-03-25|2011-01-05|三井化学株式会社|Compositions containing stabilized aliphatic and / or alicyclic isocyanates|

---

US7279538B2|2005-04-01|2007-10-09|Bausch & Lomb Incorporated|Aromatic-based polysiloxane prepolymers and ophthalmic devices produced therefrom|

---

US20060235428A1|2005-04-14|2006-10-19|Silvestrini Thomas A|Ocular inlay with locator|

---

ES2247946B2|2005-04-19|2006-10-01|Universidad Complutense De Madrid|THERAPEUTIC CONTACT LENS FOR PSEUDO-AFAQUIC EYES AND / OR IN NEURODEGENERATION PROCESS.|

---

US7842367B2|2005-05-05|2010-11-30|Key Medical Technologies, Inc.|Ultra violet, violet, and blue light filtering polymers for ophthalmic applications|

---

CN1332947C|2005-08-03|2007-08-22|浙江医药股份有限公司新昌制药厂|Method for extracting and purifying high content lutein crystal from plant oil resin|

---

TWI279165B|2005-08-09|2007-04-11|Au Optronics Corp|White organic light emitting diode|

---

US20070092831A1|2005-10-24|2007-04-26|Bausch & Lomb Incorporated|Radiation-absorbing polymeric materials and ophthalmic devices comprising same|

---

US7703917B2|2006-01-10|2010-04-27|Universidad Complutense De Madrid|Therapeutic prophylactic ophthalmologic lens for pseudoaphakic eyes and/or eyes suffering neurodegeneration|

---

US20070195262A1|2006-02-23|2007-08-23|Herbert Mosse|Method for providing a polarizing layer on an optical element|

---

US20120075577A1|2006-03-20|2012-03-29|Ishak Andrew W|High performance selective light wavelength filtering providing improved contrast sensitivity|

---

CA2670789C|2006-11-28|2016-06-07|Andrew W. Ishak|High performance selective light wavelength filtering providing improved contrast sensitivity|

---

US9377569B2|2006-03-20|2016-06-28|High Performance Optics, Inc.|Photochromic ophthalmic systems that selectively filter specific blue light wavelengths|

---

US7701641B2|2006-03-20|2010-04-20|Ophthonix, Inc.|Materials and methods for producing lenses|

---

US8360574B2|2006-03-20|2013-01-29|High Performance Optics, Inc.|High performance selective light wavelength filtering providing improved contrast sensitivity|

---

US8882267B2|2006-03-20|2014-11-11|High Performance Optics, Inc.|High energy visible light filter systems with yellowness index values|

---

US7520608B2|2006-03-20|2009-04-21|High Performance Optics, Inc.|Color balanced ophthalmic system with selective light inhibition|

---

US20070216861A1|2006-03-20|2007-09-20|Andrew Ishak|Ophthalmic system combining ophthalmic components with blue light wavelength blocking and color-balancing functionalities|

---

US8113651B2|2006-03-20|2012-02-14|High Performance Optics, Inc.|High performance corneal inlay|

---

AU2007257752B2|2006-06-12|2014-05-15|High Performance Optics, Inc.|Color balanced ophthalmic system with selective light inhibition|

---

US7364291B2|2006-06-29|2008-04-29|Johnson & Johnson Vision Care, Inc.|Contact lenses with light blocking rings|

---

US20080241951A1|2006-07-20|2008-10-02|Visigen Biotechnologies, Inc.|Method and apparatus for moving stage detection of single molecular events|

---

EP2064585A4|2006-08-23|2010-04-14|High Performance Optics Inc|System and method for selective light inhibition|

---

CA2665490C|2006-10-03|2014-06-17|The Trustees Of The University Of Pennsylvania|Method for treatment of macular degeneration|

---

FR2907922B1|2006-10-30|2009-02-13|Essilor Int|PROCESS FOR MANUFACTURING A SERIES OF OPHTHALMIC GLASSES AND FILM SHEET USED IN SUCH A METHOD.|

---

US7832903B2|2006-11-07|2010-11-16|Universidad Complutense De Madrid|Illumination system fitted with a therapeutic/prophylactic filter for healthy eyes, pseudoaphakic eyes or eyes suffering neurodegeneration|

---

US7914177B2|2006-11-07|2011-03-29|Universidad Complutense De Madrid|Prophylaxic/therapeutic vehicle filter component for healthy eyes, pseudoaphakic eyes or eyes suffering neurodegeneration|

---

FR2908898B1|2006-11-17|2009-02-06|Essilor Int|COLORED OPHTHALMIC LENSES FOR DYSLEXICS.|

---

FR2908896B1|2006-11-17|2009-02-06|Essilor Int|COLORFUL COLOR OPHTHALMIC LENSES FOR MYOPES.|

---

FR2908899B1|2006-11-17|2009-02-06|Essilor Int|MULTI-SHAPED OPHTHALMIC LENSES FOR NIGHT VISION|

---

FR2908897B1|2006-11-17|2009-03-06|Essilor Int|COLORFUL COLOR OPHTHALMIC LENSES.|

---

WO2008106449A1|2007-02-26|2008-09-04|High Performance Optics, Inc.|High performance corneal inlay|

---

ES2296552B1|2007-06-01|2009-08-25|Universidad Complutense De Madrid|ELEMENT OF PREVENTION ON TRANSPARENT SURFACES OF BUILDINGS FOR THE PROTECTION AND THERAPY OF EYES.|

---

ES2312284B1|2007-10-26|2010-01-08|Universidad Complutense De Madrid|SAFETY AND PREVENTION GLASSES WITH SURFACE TREATED FOR THE PROTECTION AND THERAPY OF EYES IN OFFICES AND SPORTS.|

---

US7688524B2|2008-04-24|2010-03-30|Sperian Eye & Face Protection, Inc.|Laser protective eyewear having improved glare protection|

---

WO2009152381A1|2008-06-13|2009-12-17|Gunnar Optiks, Llc|Low-power eyewear for reducing symptoms of computer vision syndrome|

---

US20100004330A1|2008-07-02|2010-01-07|Li Lin Huang|Anti-oxidative content material used in drink and food manufacturing method|

---

TWI379834B|2008-11-17|2012-12-21|Univ Nat Chiao Tung|Porphyrin-based photosensitizer dyes for dye-sensitized solar cells|

---

MX337922B|2008-12-16|2016-03-28|Valeant Pharmaceuticals Int|Combination of photodynamic therapy and anti-vegf agents in the treatment of unwanted choroidal neovasculature.|

---

CN102439512B|2009-03-25|2014-12-10|高效光学技术有限公司|Photochromic ophthalmic systems that selectively filter specific blue light wavelengths|

---

CN101840124B|2010-05-06|2011-12-14|宁波大学|Preparation method of porphyrin coupled silicon dioxide organic-inorganic nonlinear optical material|

---

EP2602655A1|2011-12-08|2013-06-12|Essilor International |Ophthalmic filter|

---

US20140093661A1|2012-10-02|2014-04-03|High Performance Optics, Inc.|Selective Blue Light Filtered Optic|

---

EP3087419B1|2013-12-23|2020-04-15|Essilor International|Transparent optical article having a reduced yellowness appearance|

---

EP2887129B1|2013-12-23|2020-04-22|Essilor International|Transparent optical article having a colorless appearance|

---

TWI644980B|2014-08-28|2018-12-21|九揚貿易有限公司|Composition for preparing anti-blue-violet contact lens and anti-blue-violet contact lens|ES2883183T3|2014-12-16|2021-12-07|Signify Holding Bv|Lighting device, lighting system and use thereof|

---

EP3371645A1|2015-11-06|2018-09-12|Essilor International|Optical article protecting from blue light|

---

WO2017077359A1|2015-11-06|2017-05-11|Essilor International |Optical article cutting blue light|

---

JP2018536894A|2015-11-06|2018-12-13|エシロール アンテルナショナルＥｓｓｉｌｏｒ Ｉｎｔｅｒｎａｔｉｏｎａｌ|Optical article protecting from blue light and UV light|

---

KR20180103858A|2015-11-25|2018-09-19|가부시키가이샤 진즈|Optical member|

---

TWI559043B|2016-03-16|2016-11-21|Extinction lenses and their production methods|

---

CN105762262A|2016-04-21|2016-07-13|常州市友晟电子有限公司|Glare reduction blue light prevention LED optical structure capable of increasing light extraction efficiency|

---

JP6273064B1|2017-10-03|2018-01-31|日本板硝子株式会社|Optical filter and imaging device|

---

JPWO2019102697A1|2017-11-22|2020-11-19|日本電気株式会社|Tinted contact lens, manufacturing method of tinted contact lens and iris collation system|

---

JP6439893B1|2018-05-25|2018-12-19|千住金属工業株式会社|Solder ball, solder joint and joining method|

---

BR112021008672A2|2018-11-08|2021-08-10|Transitions Optical, Ltd.|photochromic article|

---

WO2020119877A1|2018-12-10|2020-06-18|Transitions Optical, Ltd.|Mesogen compounds|

---

KR102317173B1|2018-12-13|2021-10-22|삼성에스디아이 주식회사|Compound, composition comprising the same, layer using the same, color filter and polarizing plate|

---

WO2020237363A1|2019-05-24|2020-12-03|Coloursmith Labs Inc.|Composite particles comprising a hydrophobic dye and an amphiphilic block copolymer and use thereof in optical applications|

---

WO2020239235A1|2019-05-31|2020-12-03|Transitions Optical, Ltd.|Multi-stage optical article|

---

WO2021018383A1|2019-07-30|2021-02-04|Transitions Optical, Ltd.|Mesogen compounds|

---

WO2021024962A1|2019-08-06|2021-02-11|三井化学株式会社|Optical material|

---

WO2021190765A1|2020-03-27|2021-09-30|Transitions Optical, Ltd.|Mesogen compounds|

法律状态:
2018-10-09| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

---

2019-10-15| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

---

2021-07-13| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

---

2021-08-24| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 04/05/2015, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

---

申请号 | 申请日 | 专利标题

---

US201461988360P| true| 2014-05-05|2014-05-05|

---

US61/988,360|2014-05-05|

---

US14/702,551|2015-05-01|

---

US14/702,551|US9683102B2|2014-05-05|2015-05-01|Photo-stable and thermally-stable dye compounds for selective blue light filtered optic|

---

PCT/US2015/029073|WO2015171507A1|2014-05-05|2015-05-04|Photo-stable and thermally-stable dye compounds for selective blue light filtered optic|

---