OPTICAL ELEMENT COMPRISING MIX OF NIR DYES FOR BROADER NIR CUT AND BETTER AESTHETIC
20230056732 · 2023-02-23
Inventors
- Pierre Fromentin (Bangkok, TH)
- Harutsai WAIPUNYA (Bangkok, TH)
- Haifeng SHAN (Dallas, TX, US)
- Hao-Wen Chiu (Dallas, TX, US)
Cpc classification
G02B5/208
PHYSICS
G02B5/223
PHYSICS
International classification
Abstract
Disclosed are optical elements that contains two or more near infrared absorbers and methods of producing the same. Two near infrared absorbers with different near infrared wavelengths absorption ranges and residual colors are mixed with a precursor of an optical substrate. The resulting mixture is subsequently processed to produce optical elements that have a broad near infrared wavelength absorption range and a neutral residual color.
Claims
1. An optical element comprising an optical substrate and two or more near infrared absorbers mixed in the optical substrate, wherein the two or more near infrared absorbers have different near infrared cut ranges and different residual colors.
2. The optical element of claim 1, wherein the two or more near infrared absorbers are mixed in the optical substrate substantially homogenously.
3. The optical element of claim 1, wherein the two or more near infrared absorbers in the optical substrate are adapted to generate a synergistic infrared absorption level that is higher than individual near infrared absorption level of any of the two or more near infrared absorbers.
4. The optical element of claim 1, wherein the two or more near infrared absorbers in the optical substrate are adapted to generate a synergistic infrared absorption range that is broader than individual infrared absorption range of each of the two or more near infrared absorbers.
5. The optical element of claim 1, wherein the two or more near infrared absorbers in the optical substrate are adapted to generate a synergistic color intensity that is lower than individual color intensity of each of the two or more near infrared absorbers.
6. The optical element of claim 5, wherein the two or more near infrared absorbers in the optical substrate are synergistically neutral colored.
7. The optical element of claim 1, wherein the two or more near infrared absorbers are adapted to synergistically cause less than 10% reduction on the average optical transmittance in the 380-780 nm wavelength range for the optical substrate.
8. The optical element of claim 1, wherein the optical element comprises an ophthalmic lens.
9. The optical element of claim 1, wherein the optical substrate comprises allyl diglycol carbonate, polyurethane, acrylic, polycarbonate, polyamide, poly(methyl methacrylate), co-polyester, cellulose triacetate, polyepisulfides, trivex, polyacrylics, polyols, polyamines, polyanhydrides, polycarboxilic acids, polyepoxides, polyisocyanates, polynorbornenes, polysiloxanes, polysilazanes, polystyrenes, polyolefinics, polyesters, polyimides, polyurethanes, polythiourethanes, polyallylics, polysulfides, polyvinylesters, polyvinylethers, polyarylenes, polyoxides, polysulfones, poly cyclo olefins, polyacrylonitriles, polyethylene terephtalates, polyetherimides, polypentenes, or any combinations thereof.
10. The optical element of claim 1, wherein the two or more near infrared absorbers comprise polymethine, phthalocyanine, porphyrine, triphenylmethane, iminium, squarylium, croconium, dithiolene, quinone,polyperylene, pyrilium, thiopyrilium, cyanine, or any combination thereof.
11. The optical substrate of claim 1, wherein the optical element comprises 1 to 500 ppm of the two or more near infrared absorbers.
12. A method of preparing the optical element of claim 1, the method comprising: providing a precursor material for the optical substrate and the two or more near infrared absorbers that have different near infrared cut ranges and/or different residual colors; determining a concentration for each of the two or more infrared absorbers in the optical substrate, at which the synergistic color intensity of the two or more near infrared absorbers is lower than the individual color intensity of any of the two or more near infrared absorbers; mixing the precursor material with the two or more infrared absorbers at the determined concentrations to produce a substantially homogenous mixture; and producing the optical element using the mixture of the optical substrate and the two or more near infrared absorbers.
13. The method of claim 12, wherein the producing step comprises casting, injection molding, extrusion compression molding, compression molding, transfer molding, 3D printing, or any combination thereof.
14. The method of claim 12, further comprising mixing one or more of an ultraviolet light absorbing dye, a color balancing dye, a color enhancing dye, a blue light absorbing dye, and other visible light absorbing dyes with the precursor material before the producing step.
15. A method of preparing an optical element of claim 1, the method comprising: providing a precursor material for the optical substrate and two or more near infrared absorbers that have different near infrared cut ranges and/or different residual colors; determining a concentration for each of the two or more infrared absorbers in the substrate, at which synergistic color intensity of two or more near infrared absorbers is lower than the individual color intensity of any of the two or more near infrared absorbers; dissolving the two or more infrared absorbers in a first amount of the precursor material to produce a near infrared dye master batch; mixing a second amount of the precursor material with one or more of an ultraviolet dye, a monomer, a catalyst, and a releasing agent at a temperature of 23 to 27° C. under vacuum to produce a first mixture that is substantially homogenous; cooling the first mixture to a temperature of 0 to 4° C.; flowing an inert gas over the cooled first mixture; mixing the near infrared dye master batch into the first mixture under vacuum at a temperature of 0 to 4° C. to produce a second mixture, which is a substantially homogenous mixture with each of the two or more near infrared absorbers at its determined concentration; and producing the optical element using the second mixture via casting.
16. The optical element of claim 5, wherein the two or more near infrared absorbers in the optical substrate are achromatic.
Description
DESCRIPTION OF THE DRAWINGS
[0020] For a more complete understanding, reference is now made to the following descriptions taken in conjunction with the accompanying drawings, in which:
[0021]
[0022]
[0023]
DETAILED DESCRIPTION OF THE INVENTION
[0024] The currently available optical articles with NIR protection function suffer the deficiencies including complicated production process, high production cost, protection against insufficient NIR wavelengths range, effects on users color perception, and change on the color of optical articles. The present invention provides a solution to at least some of these problems.
[0025] The solution is premised on an optical element that includes two or more NIR absorbers mixed in a polymeric substrate. The two or more near infrared absorbers may have different NIR absorption ranges such that the optical element has a broader NIR absorption range than each of the near infrared absorbers. Additionally, the two or more near infrared absorbers can have different residual colors such that the near infrared absorbers synergistically have a neutral residual color.
[0026] These and other non-limiting aspects of the present invention are discussed in further detail in the following sections.
A. Optical Element with Near Infrared Protection
[0027] Near infrared radiation has been proved to cause damage in the eyes. Optical elements, such as ophthalmic lenses, can incorporate near infrared protection function to protect users' eyes. However, conventionally, a near infrared absorber is generally incorporated in an optical filter, which requires further processes to be applied on the optical element, or in an optical coating, which can be negatively affected in terms of mechanical strength by the near infrared absorber. Furthermore, the near infrared absorber can also affect the user's color perception and change the cosmetic look of the optical element.
[0028] The optical element disclosed herein is capable of expanding the near infrared wavelengths cut range of an optical element and minimizing the residual color of the optical element by incorporating, in the substrate of the optical element, two or more near infrared absorbers with different absorption ranges and/or different residual colors. Some embodiments include an optical element. In some instances, the optical element can be an ophthalmic lens. The optical element may comprise a front surface and a back surface. The front surface of the optical element may comprise a convex surface of the ophthalmic lens. The back surface of the optical element may comprise a concave surface of the ophthalmic lens.
[0029] In embodiments of the invention, the optical element can comprise an optical substrate and two or more near infrared absorbers mixed in the optical substrate. In some aspects, the two or more near infrared absorbers may have different near infrared cut ranges and/or different residual colors. Non limiting examples of the optical substrate include allyl diglycol carbonate, polyurethane, acrylic, polycarbonate, polyamide, poly(methyl methacrylate), co-polyester, cellulose triacetate, polyepisulfides, trivex, polyacrylics, polyols, polyamines, polyanhydrides, polycarboxilic acids, polyepoxides, polyisocyanates, polynorbornenes, polysiloxanes, polysilazanes, polystyrenes, polyolefinics, polyesters, polyimides, polyurethanes, polythiourethanes, polyallylics, polysulfides, polyvinylesters, polyvinylethers, polyarylenes, polyoxides, polysulfones, poly cyclo olefins, polyacrylonitriles, polyethylene terephtalates, polyetherimides, polypentenes, or any combination thereof. Non-limiting examples of the near infrared absorbers can include polymethine, phthalocyanine, porphyrine, triphenylmethane, iminium, squarylium, croconium, dithiolene, quinone, polyperylene, pyrilium, thiopyrilium, cyanine, or any combination thereof.
[0030] In some aspects, the total concentration of the two or more near infrared absorbers may be in a range of 1 to 500 ppm and all ranges and values there between including ranges of 1 to 25 ppm, 25 to 50 ppm, 50 to 75 ppm, 75 to 100 ppm, 100 to 125 ppm, 125 to 150 ppm, 150 to 175 ppm, 175 to 200 ppm, 200 to 225 ppm, 225 to 250 ppm, 250 to 275 ppm, 275 to 300 ppm, 300 to 325 ppm, 325 to 350 ppm, 350 to 375 ppm, 375 to 400 ppm, 400 to 425 ppm, 425 to 450 ppm, 450 to 475 ppm, and 475 to 500 ppm. In some aspects, the two or more near infrared absorbers can be mixed in the optical substrate substantially homogenously. Alternatively, the two or more near infrared absorbers may be mixed in the optical substrate non-homogeneously. In some aspects, the two or more near infrared absorbers may have a concentration gradient (increase or decrease) along any direction in the optical substrate, including directions of horizontal, vertical, and depth of the optical substrate. In some instances, the two or more near infrared absorbers may be mixed with a higher concentration in the front portion and/or the back portion of the optical substrate than the middle portion of the optical substrate. The front portion may include about a third of the thickness of the optical substrate that is proximal to a front surface of the optical substrate. The back portion may include about a third of the thickness of the optical substrate that is proximal to a back surface of the optical substrate.
[0031] In some aspects, the two or more near infrared absorbers in the optical substrate can be adapted to generate a synergistic infrared absorption level that is higher than individual near infrared absorption level of any of the two or more near infrared absorbers. The optical element may be capable of absorbing near infrared radiation of the wavelengths range of 780 to 2000 nm and all ranges and values there between including ranges of 780-820 nm, 820 to 860 nm, 860 to 900 nm, 900 to 940 nm, 940 to 980 nm, 980 to 1020 nm, 1020 to 1060 nm, 1060 to 1100 nm, 1100 to 1140 nm, 1140 to 1180 nm, 1180 to 1200 nm, 1200 to 1240 nm, 1240 to 1280 nm, 1280 to 1320 nm, 1320 to 1360 nm, 1360 to 1400 nm, 1400 to 1440 nm, 1440 to 1480 nm, 1480 to 1520 nm, 1520 to 1560 nm, 1560 to 1600 nm, 1600 to 1640 nm, 1640 to 1680 nm, 1680 to 1720 nm, 1720 to 1760 nm, 1760 to 1800 nm, 1800 to 1840 nm, 1840 to 1880 nm, 1880 to 1920 nm, 1920 to 1960 nm, 1960 to 2000 nm. In some aspects, the two or more near infrared absorbers in the optical substrate are adapted to generate a synergistic infrared absorption level that is higher than individual near infrared absorption level of any of the two or more near infrared absorbers. In some instances, the two or more near infrared absorbers can be adapted to synergistically reduce the intensity of near infrared radiation by 15 to 95% (determined as TsIR.sub.780-2000(%)) and all ranges and values there between including ranges of 15 to 20%, 20 to 25%, 25 to 30%, 30 to 35%, 35 to 40%, 40 to 45%, 45 to 50%, 50 to 55%, 55 to 60%, 60 to 65%, 65 to 70%, 70 to 75%, 75 to 80%, 80 to 85%, 85 to 90%, and 90 to 95%. In some aspects, the two or more near infrared absorbers are adapted to synergistically cause less than 10% (determined as Tv% (D65)) reduction on the average optical transmittance in the 380-780 nm wavelength range for the optical substrate.
[0032] In some aspects, the two or more near infrared absorbers in the optical substrate can be adapted to generate a synergistic color intensity that is lower than individual color intensity of each of the two or more near infrared absorbers. In some instances, the synergistic color intensity of the two or more infrared absorbers in the optical substrate can be in a range of 0 to 5 and all ranges and values there between including ranges of 0 to 0.5, 0.5 to 1, 1 to 1.5, 1.5 to 2, 2 to 2.5, 2.5 to 3, 3 to 3.5, 3.5 to 4, 4 to 4.5, and 4.5 to 5. In some aspects, the two or more near infrared absorbers in the optical substrate are synergistically neutral colored, or preferably achromatic. In some instances, the optical substrate of the optical element can be colorless (or achromatic) and the optical element, which includes the optical substrate and the two or more near infrared absorbers, can be neutral colored or preferably achromatic.
[0033] Alternatively, in some instances, the optical element can include an ophthalmic sunglasses, and the two or more near infrared absorbers have a high synergistic chroma. The two or more near infrared absorbers can be adapted to cause 10 to 95% (determined as Tv% (D65)) reduction on the average optical transmittance in the 380-780 nm wavelength range for the optical element and all ranges and values there between including ranges of 10 to 15%, 15 to 20%, 20 to 25%, 25 to 30%, 30 to 35%, 35 to 40%, 40 to 45%, 45 to 50%, 50 to 55%, 55 to 60%, 60 to 65%, 65 to 70%, 70 to 75%, 75 to 80%, 80 to 85%, 85 to 90%, and 90 to 95%.
[0034] In some aspects, the optical element may further comprise one or more additional coatings in a covering relationship with the front surface and/or the back surface of the optical element. Non-limiting examples of the one or more additional coatings may include a polarizing coating, a mirror coating, an anti-reflective coating, an abrasion-resistant coating, a photochromic coating, an anti-smudge coating, an anti-fog coating, a tintable coating, a self-healing coating, an anti-rain coating, an anti-static coating, an anti-ultraviolet coating, an anti-blue light coating, or any combination thereof.
B. Method of Producing Optical Element with NIR Absorbers
[0035] Conventionally, near infrared light absorbing optical elements (e.g., ophthalmic lenses) can be produced by incorporating an multifunctional optical filter that integrates near infrared absorbing and antireflective functions to a surface of the optical element, or by depositing an optical coating that incorporates a near infrared absorbers in an conventional optical coating (e.g., antireflective coating). However, for an optical filter, a high NIR absorption level can be detrimental to the antireflective performance of optical filter. For the optical coating that includes a near infrared absorbers, the production cost can be high and, at the same time, the mechanical properties of the optical coating can be degraded.
[0036] The method disclosed herein avoids the use of optical filters and optical coatings for near infrared absorbing purposes by directly mixing the near infrared absorbers in an optical substrate. Furthermore, the method disclosed herein selects two or more near infrared absorbers with different absorption ranges (NIR cut ranges) and/or different residual colors that result in broader near infrared absorption range and neutral color for the produced optical element. As shown in
[0037] In some embodiments, as shown in block 101, method 100 may comprise providing a precursor material for the optical substrate and the two or more near infrared absorbers that have different near infrared cut ranges and/or different residual colors. Non limiting examples of the precursor material for the optical substrate can include allyl monomers including allyl diglycol carbonate and thiourethane polymer precursors (e.g., blends of isocyanates and thiols), polyurethane, acrylic, polycarbonate, polyamide, poly(methyl methacrylate), co-polyester, cellulose triacetate, polyepisulfides, trivex, polyacrylics, polyols, polyamines, polyanhydrides, polycarboxilic acids, polyepoxides, polyisocyanates, polynorbornenes, polysiloxanes, polysilazanes, polystyrenes, polyolefinics, polyesters, polyimides, polyurethanes, polythiourethanes, polyallylics, polysulfides, polyvinylesters, polyvinylethers, polyarylenes, polyoxides, polysulfones, poly cyclo olefins, polyacrylonitriles, polyethylene terephtalates, polyetherimides, polypentenes, or any combination thereof. Non-limiting examples of the near infrared absorbers can include polymethine, phthalocyanine, porphyrine, triphenylmethane, iminium, squarylium, croconium, dithiolene, quinone,polyperylene, pyrilium, thiopyrilium, cyanine, or any combination thereof. In some aspects, non-limiting examples of isocyanates can include 1,3-Bis(isocyanatomethyl)cyclohexane, 1,4-Bis(isocyanatomethyl)cyclohexane, m-Xylylene diisocyanate, 5-Isocyanato-1-(isocyanatomethyl)-1,3,3-trimethylcyclohexane, 4,4′-Methylene dicyclohexyl diisocyanate, 4,4′-Methylenebis(phenyl isocyanate), Hexane-1,6-diisocyanate, Trans-1,4-Diisocyanatocyclohexane, Toluene diisocyanate, 1,5-pentamethylene diisocyanate, 2,5-bicyclo [2,2,1] heptane bis (methyl isocyanate), bis(isocyanate methyl ethyl) benzene and for thiols: 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 2,3-Bis(2-mercaptoethylthio)propane-1-thiol OR 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol, bis-(2,2-sulphydryl) ethyl tetrasulfide, Pentaerythritol tetrakis(3-mercaptopropionate), Pentaerythritol tetrakis(3-mercaptoacetate), thiodiglycol mercaptan, OR 3-Thiapentane-1,5-diol, 2,5-dimercaptomethyl-1,4-dithiane, 1,5-dimercapto-3-thiapentane, propane-trithiol, bis(b-epithiopropyl) sulfide, bis(b-epithiopropyl) disulfide, 4,6-(mercaptomethylthio)-1,3-dithiane, 4,5-(mercaptomethylthio)-1,3-dithiolane, 1, 1,3,3-tetrakis(mercaptomethylthio)ethane, 1,1,3,3-tetrakis(mercaptomethylthio)propane. Non-limiting examples of the near infrared absorbers can include polymethine, phthalocyanine, porphyrine, triphenylmethane, iminium, squarylium, croconium, dithiolene, quinone,polyperylene, pyrilium, thiopyrilium, cyanine, or any combination thereof. In some aspects, the providing at block 101 may include selecting two or more of the near infrared absorbers in view of a target near infrared wavelengths absorption range and/or a target residual color.
[0038] In some embodiments, as shown in block 102, method 100 may comprise determining a concentration for each of the two or more infrared absorbers in the optical substrate, at which the synergistic color intensity of the two or more near infrared absorbers is lower than the individual color intensity of any of the two or more near infrared absorbers. In some aspects, the two or more near infrared absorbers can be adapted to generate a synergistic infrared absorption range that is broader than the individual infrared absorption range of each of the two or more near infrared absorbers. In some aspects, the determining may include a trial-and-error method to obtain concentration for each near infrared absorbers that can achieve a target synergistic near infrared absorption range, a target synergistic near infrared absorption level, and/or a target synergistic residual color.
[0039] In some embodiments, as shown in block 103, method 100 may comprise mixing the precursor material with the two or more infrared absorbers at the concentrations determined at block 102 to produce a mixture. In some aspects, the mixture can be substantially homogenous. In some aspects, mixing at block 103 may comprise dissolving the two or more infrared absorbers in a first amount of the precursor material to produce a near infrared dye master batch. The infrared dye master batch may comprise about 10 to 45 ppm of the two or more near infrared absorbers and all ranges and values there between including ranges of 10 to 15 ppm, 15 to 20 ppm, 20 to 25 ppm, 25 to 30 ppm, 30 to 35 ppm, 35 to 40 ppm, and 40 to 45 ppm. In some aspects, mixing at block 103 may comprise optionally mixing a second amount of the precursor material with one or more of an ultraviolet dye, a monomer, a catalyst, and a releasing agent, or any combination thereof to produce a first mixture. The first mixture may be produced at a temperature of 23 to 27° C. and all ranges and values there between. The first mixture may be produced under vacuum. In some instances, the first mixture can be substantially homogenous. In some aspects, the mixing at block 103 may include cooling the first mixture to a temperature of 0 to 4° C. and all ranges and values there between including range of 0 to 0.5° C., 0.5 to 1.0° C., 1.0 to 1.5° C., 1.5 to 2.0° C., 2.0 to 2.5° C., 2.5 to 3.0° C., 3.0 to 3.5° C., 3.5 to 4.0° C. The first mixture may be cooled by a water bath from room temperature to about ° C.
[0040] In some aspects, mixing at block 103 may comprise flowing an inert gas over the cooled first mixture. In some instances, the inert gas may include nitrogen, argon, or any combination thereof. The inert gas may be adapted to prevent moisture in the air from contaminating the cooled first mixture. In some aspects, mixing at block 103 may comprise mixing the near infrared dye master batch into the cooled first mixture to produce a second mixture with each of the two or more near infrared absorbers at its concentration determined at block 202. The second mixture may be produced at a temperature in a range of 0 to 4° C. and all ranges and values there between including range of 0 to 0.5° C., 0.5 to 1.0° C., 1.0 to 1.5° C., 1.5 to 2.0° C., 2.0 to 2.5° C., 2.5 to 3.0° C., 3.0 to 3.5° C., 3.5 to 4.0° C. The second mixture may be produced under vacuum. In some instances, the second mixture is substantially homogenous.
[0041] In some embodiments, as shown in block 104, method 100 may comprise producing the optical element using the second mixture. In some aspects, the optical element may be produced via casting, injection molding, film extrusion, extrusion compression molding, compression molding, transfer molding, 3D printing, or any combination thereof. In some instances, the casting process at block 104 may be performed at a casting temperature of 20 to 25° C. and all ranges and values there between including 21° C., 22° C., 23° C., and 24° C. In some instances, the injection molding processing at block 104 may be performed at a molding temperature in a range of 200 to 400° C. and all ranges and values there between including ranges of 200 to 210° C., 210 to 220° C., 220 to 230° C., 230 to 240° C., 240 to 250° C., 250 to 260° C., 260to 270° C., 270 to 280° C., 280 to 290° C., 290 to 300° C., 300 to 310° C., 310 to 320° C., 320 to 330° C., 330 to 340° C., 340 to 350° C., 350 to 360° C., 360 to 370° C., 370 to 380° C., 380 to 390° C., and 390 to 400° C. In some embodiments, method 100 may comprise mixing one or more of an ultraviolet light absorbing dye, a color balancing dye, a color enhancing dye, a blue light absorbing dye, and other visible light absorbing dyes with the precursor material before the producing step at block 104.
[0042] Although embodiments of the present invention have been described with reference to blocks of
[0043] As part of the disclosure of the present invention, specific examples are included below. The examples are for illustrative purposes only and are not intended to limit the invention. Those of ordinary skill in the art will readily recognize parameters that can be changed or modified to yield essentially the same results.
EXAMPLE 1
(Preparation of Near Infrared Absorbing Lenses with MR8™ Precursors)
[0044] Various near infrared absorbers and precursor materials for optical substrate were used to produce ophthalmic lenses with infrared absorbing ability. The effect of ophthalmic lenses with two near infrared absorbers on infrared absorption wavelengths range and lens residual colors were tested. The specific near infrared absorbers, precursor materials, UV absorbers, and a catalyst used for producing the ophthalmic lenses are listed in Table 1 (λ.sub.max means the highest peak of NIR dye spectrum).
TABLE-US-00001 TABLE 1 Materials Used for Producing Ophthalmic Lenses Chemical Trade Function Name λmax Supplier Monomer MR8-A — Mitsui Chemicals Monomer MR8-B1 — Mitsui Chemicals Monomer MR8-B2 — Mitsui Chemicals Catalyst Dimethyltin — Honjo Chemical dichloride (DMC) UV Absorber Seesorb 703 — Shipro Kasei Kaisha, UV Absorber Seesorb 709 — Shipro Kasei Kaisha, NIR Absorber Lumogen IR765 794 BASF NIR Absorber NIR 920A 951 QCR NIR Absorber NIR S2007 1030 Few Chemical NIR Absorber Epolight 4831 1025 Epolin
[0045] Table 2 shows the composition for each sample that uses near infrared absorber(s) of S2007 and/or 920A. The control sample did not include any near infrared absorber. Table 3 shows the composition for each sample that uses near infrared absorber(s) of 920A and/or IR765 with a control sample that did not include any near infrared absorber. Table 4 shows the composition for each sample that uses near infrared absorber(s) of Epolight 4831 and/or IR785 with a control sample that did not include any near infrared absorber.
TABLE-US-00002 TABLE 2 Compositions of Lenses Using S2007 and/or 920A NIR Absorbers Sample # Control Formulation No. 1 2 3 4 5 6 7 8 9 8 MR 8 A 50.60 50.60 50.60 50.60 50.60 50.60 50.60 50.60 50.60 50.600 MR 8 B1 23.90 23.90 23.90 23.90 23.90 23.90 23.90 23.90 23.90 23.900 MR 8 B2 24.50 23.50 22.50 20.50 15.50 10.50 19.50 14.50 9.50 25.500 Stan DMC 0.040 0.040 0.040 0.040 0.040 0.040 0.040 0.040 0.040 0.040 (ppm) UV709 (ppm) 1.200 1.200 1.200 1.200 1.200 1.200 1.200 1.200 1.200 1.200 UV703 (ppm) 0.0125 0.0125 0.0125 0.0125 0.0125 0.0125 0.0125 0.0125 0.0125 0.0125 Zelec UN (ppm) 0.070 0.070 0.070 0.070 0.070 0.070 0.070 0.070 0.0700 0.0700 NIR S2007 1.000 2.000 3.000 — — — 1.000 1.000 1.000 — (0.05% MB in MR8-B2) NIR 920A — — — 5.000 10.00 15.00 5.000 10.00 15.000 — (0.01% MB in MR8-B2) Total 101.32 101.32 101.32 101.32 101.32 101.32 101.32 101.32 101.32 101.32
TABLE-US-00003 TABLE 3 Compositions of Lenses Using 920A and/or IR765 NIR Absorbers Sample # Control Formulation No. 1 2 3 4 5 6 7 8 9 8 MR 8 A 49.600 48.600 46.600 50.600 50.600 50.600 48.600 48.600 48.600 50.600 MR 8 B1 23.900 23.900 23.900 23.900 23.900 23.900 23.900 23.900 23.900 23.900 MR 8 B2 25.500 25.500 25.500 24.500 23.500 22.500 25.100 24.700 24.300 25.500 Stan DMC 0.040 0.040 0.040 0.040 0.040 0.040 0.040 0.040 0.040 0.040 (ppm) UV709 (ppm) 1.200 1.200 1.200 1.200 1.200 1.200 1.200 1.200 1.200 1.200 UV703 (ppm) 0.0125 0.0125 0.0125 0.0125 0.0125 0.0125 0.0125 0.0125 0.0125 0.0125 Zelec UN 0.0700 0.0700 0.0700 0.0700 0.0700 0.0700 0.0700 0.0700 0.0700 0.0700 (ppm) NIR 920A 1.000 2.000 4.000 — — — 2.000 2.000 2.000 — (0.05% MB in MR8-A) IR765 (0.05% — — — 1.000 2.000 3.000 0.400 0.800 1.200 — MB in MR8- B2) Total 101.32 101.32 101.32 101.32 101.32 101.32 101.32 101.32 101.32 101.32
TABLE-US-00004 TABLE 4 Compositions of Lenses Using Epolight 4831 and/or IR765 NIR Absorbers Sample # Control Formulation No. 1 2 3 4 5 6 7 8 9 8 MR 8 A 50.600 50.600 50.600 50.600 50.600 50.600 50.600 50.600 50.600 50.600 MR 8 B1 23.900 23.900 23.900 23.900 23.900 23.900 23.900 23.900 23.900 23.900 MR 8 B2 20.500 21.000 10.500 20.500 15.500 10.500 20.200 19.800 19.400 25.500 Stan DMC 0.040 0.040 0.040 0.040 0.040 0.040 0.040 0.040 0.040 0.040 (ppm) UV709 (ppm) 1.200 1.200 1.200 1.200 1.200 1.200 1.200 1.200 1.200 1.200 UV703 (ppm) 0.0125 0.0125 0.0125 0.0125 0.0125 0.0125 0.0125 0.0125 0.0125 0.0125 Zelec UN 0.0700 0.0700 0.0700 0.0700 0.0700 0.0700 0.0700 0.0700 0.0700 0.0700 (ppm) Epolight 4831 2.500 4.500 7.500 — — — 4.500 4.500 4.500 — (0.01% MB in MR8-B2) IR765 (0.05% — — — 1.000 2.000 3.000 0.800 1.200 1.600 — MB in MR8- B2) Total 101.32 101.32 101.32 101.32 101.32 101.32 101.32 101.32 101.32 101.32
[0046] All the samples were prepared using bi-plano molds, which were assembled using taping process. The center thickness of the mold was adjusted to 2 mm. The near infrared master batch was prepared by dissolving the selected near infrared absorber(s) in MR8™-A or MR8™-B2 monomer precursor. Ultraviolet absorbers (Stan DMC™ and Zelec UN™) were then mixed with MR8-A precursor in duran bottle at room temperature under vacuum until a homogenous mixture is formed. The homogenous mixture was then cooled to 2° C. before vacuum was released and nitrogen gas was flowed over the mixture. The near infrared dye master batch, additional MR8™-B1 and MR8™-B2, and the cooled homogenous mixture were mixed under vacuum at 2° C. until the final mixture was homogenous. The final mixture was subsequently filled into the bi-plano mold via a clean syringe. The lens samples were then formed by following the polymerization temperature profile as shown in Table 5. For each composition, uncoated (UNC) lenses and hard multi-coated (HMC) lenses were both produced. The produced the lenses were cleaned. The transmittance in the range of 300 to 2000 nm wavelengths was measured for each lens sample using Lamda™ 950, UV spectroscopy (PerkinElmer, USA). Additionally, TsIR, TvD65, YI, C*, h*, and UV cut for each lens sample were tested, where TsIR is the % Transmittance in 780-2000 nm., TvD65 is %Transmittance in 380-780 nm. YI is Yellow Index, C* is Chroma, and h* is Hue.
TABLE-US-00005 TABLE 5 Polymerization Temperature Profile for MR8 based Lenses Temp Temp Start Finish Period (° C.) (° C.) (Hr.) 15.0 15.1 1.0 15.1 15.2 1.0 15.2 15.4 1.0 15.4 15.7 1.0 15.7 16.2 1.0 16.2 17.0 1.0 17.0 18.4 1.0 18.4 20.6 1.0 20.6 22.0 1.0 22.0 27.0 1.0 27.0 34.0 1.0 34.0 45.0 1.0 45.0 60.0 1.0 60.0 80.0 1.0 80.0 105.0 1.0 105.0 130.0 1.0 130.0 130.0 1.0 130.0 130.0 1.0 130.0 130.0 1.0 130.0 125.0 1.0 125.0 125.0 125.0
[0047] The appearance of the lens samples were shown in
[0048] Table 6 shows the test results of TsIR, TvD65, YI, C*, h*, and UV cut for uncoated (UNC) lenses sample containing NIR S2007 and 920A near infrared absorbers. Table 7 shows shows the test results of TsIR, TvD65, YI, C*, h*, and UV cut for hard multi-coated lenses sample containing NIR S2007 and 920A near infrared absorbers. These results show that the hard multi coated and uncoated lenses containing 5 ppm S2007 and 5 ppm 920A showed the best infrared absorption properties and least residual colors. These two samples have the best neutral colors, which are closest to clear lens.
TABLE-US-00006 TABLE 6 Results of MR8 UNC Lenses with NIR S2007 and 920A Sample # Control Formulation No. 1 2 3 4 5 6 7 8 9 10 NIR S2007 5 10 15 — — — 5 5 5 — (ppm) NIR 920A — — — 5 10 15 5 10 15 — (ppm) TsIR 75.05 67.50 61.65 79.73 75.37 71.57 71.33 69.45 67.53 84.70 (@780- 2000 nm) NIR cut 24.95 32.50 38.35 20.27 24.63 28.43 28.67 30.55 32.47 15.30 (@780- 2000 nm) TvD65 88.3 86.6 85.7 87.0 84.3 81.4 84.5 80.7 77.2 89.8 YI 3.0 3.8 4.6 2.5 2.9 3.4 2.1 1.8 1.1 2.1 C* 2.2 2.7 3.2 1.7 1.6 1.7 1.6 1.3 0.7 1.7 h* 110.8 109.6 107.4 103.9 91.9 80.4 115.5 110.7 112.0 114.1 UV cut 395.0 395.0 395.0 395.0 395.0 395.0 395.0 395.0 395.0 394.8
TABLE-US-00007 TABLE 7 Results of MR8 HMC Lenses with NIR S2007 and 920A near infrared absorbers Sample # Control Formulation No. 1 2 3 4 5 6 7 8 9 10 NIR S2007 5 10 15 — — — 5 5 5 — (ppm) NIR 920A — — — 5 10 15 5 10 15 — (ppm) TsIR 67.80 60.60 56.70 72.10 68.10 63.90 63.90 62.10 59.90 76.20 (@780- 2000 nm) NIR cut 32.20 39.40 43.30 27.90 31.90 36.10 36.10 37.90 40.10 23.80 (@780- 2000 nm) TvD65 96.4 95.1 93.4 96.5 94.3 91.7 92.7 88.9 84.7 97.9 YI 2.3 3.6 4.3 2.9 4.8 6.7 1.6 2.0 1.7 1.2 C* 1.47 2.10 2.49 1.74 2.55 3.36 1.27 1.16 0.89 1.07 h* 97.30 91.70 91.70 92.10 80.20 74.60 110.10 94.80 82.70 112.50 UV cut 396.0 396.0 396.0 396.0 396.0 396.0 395.0 395.0 395.0 395.0
[0049] Table 8 shows the test results of TsIR, TvD65, YI, C*, h*, and UV cut for uncoated (UNC) lenses sample containing 930A and IR765 near infrared absorbers. Table 9 shows the test results of TsIR, TvD65, YI, C*, h*, and UV cut for uncoated (UNC) lenses sample containing 930A and IR765 near infrared absorbers. These results show that the hard multi coated lenses containing 10 ppm 920A and 4 ppm IR765 showed the best infrared absorption properties and least residual colors. These two samples have the best neutral colors, which are closest to clear lens.
TABLE-US-00008 TABLE 8 Results of MR8 UNC Lenses with 920A and IR765 near infrared absorbers Sample # Control Formulation No. 1 2 3 4 5 6 7 8 9 8 NIR 920A 5 10 20 — — — 10 10 10 — (ppm) IR765 (ppm) — — — 5 10 15 2 4 6 — TsIR 78.33 72.97 64.53 80.70 76.10 73.80 71.15 69.25 68.30 84.70 (@780- 2000 nm) NIR cut 21.67 27.03 35.47 19.30 23.90 26.20 28.85 30.75 31.70 15.30 (@780- 2000 nm) TvD65 87.8 86.0 82.6 88.5 87.1 86.2 85.8 85.4 84.7 89.8 YI 2.8 3.4 4.8 0.2 −0.6 −1.7 2.6 2.0 1.5 2.1 C* 1.7 1.8 2.3 2.2 2.9 3.6 1.8 1.8 1.9 1.7 h* 101.1 90.7 75.0 148.6 157.5 165.1 106.6 119.5 129.9 114.1 UV cut 395.0 395.0 395.0 395.0 395.0 394.5 395.0 395.0 395.0 394.8
TABLE-US-00009 TABLE 9 Results of MR8 HMC Lenses with 920A and IR765 near infrared absorbers Sample # Control Formulation No. 1 2 3 4 5 6 7 8 9 8 NIR 920A 5 10 20 — — — 10 10 10 — (ppm) IR765 (ppm) — — — 5 10 15 2 4 6 — TsIR 70.70 64.90 57.60 71.30 67.90 65.90 63.50 61.70 60.60 76.20 (@780- 2000 nm) NIR cut 29.30 35.10 42.40 28.70 32.10 34.10 36.50 38.30 39.40 23.80 (@780- 2000 nm) TvD65 96.3 94.5 90.6 96.2 95.8 95.4 93.9 93.6 92.8 97.9 YI 2.1 3.3 4.9 −0.4 −1.4 −2.5 2.1 1.6 1.1 1.2 C* 1.26 1.79 2.40 1.8 2.66 3.35 1.40 1.48 1.56 1.07 h* 93.10 81.20 66.90 155.4 165.70 172.60 100.60 116.80 130.30 112.50 UV cut 395.0 395.0 395.0 395.0 396.0 396.0 395.0 395.0 395.0 395.0
[0050] Table 10 shows the test results of TsIR, TvD65, YI, C*, h*, and UV cut for uncoated (UNC) lenses sample containing Epolight 4831 and/or IR785 near infrared absorbers. Table 11 shows the test results of TsIR, TvD65, YI, C*, h*, and UV cut for hard multi coated (HMC) lenses sample containing Fpolight 4831 and/or IR785 near infrared absorbers. The results showed that the hard multi coated lenses containing 45 ppm Epolight 4831 and 6 ppm IR765 showed the best results for lenses containing Epolight 4831 and/or IR785 near infrared absorbers as these two samples have the best neutral colors, which are the closest to clear lens. Overall, the results in Tables 6-11 indicate that MR8 monomer based lenses with 2 near infrared absorbers improve the absorption level and absorption wavelengths range, and reduce the residual colors of the lenses compared to lenses containing only 1 near infrared absorber.
TABLE-US-00010 TABLE 10 Results of MR8 UNC Lenses with Epolight 4831 and IR765 NIR Absorbers Sample # Control Formulation No. 1 2 3 4 5 6 7 8 9 8 Epolight 25 45 75 — — — 45 45 45 — 4831 (ppm) IR765 (ppm) — — — 5 10 15 4 6 8 — TsIR 76.00 66.10 65.35 80.70 76.10 73.80 62.90 62.10 60.93 84.70 (@780- 2000 nm) NIR cut 24.00 33.90 34.65 19.30 23.90 26.20 37.10 37.90 39.07 15.30 (@780- 2000 nm) TvD65 88.2 85.4 85.2 88.5 87.1 86.2 84.7 84.6 84.1 89.8 YI 2.4 3.9 3.7 0.2 −0.6 −1.7 2.5 1.6 1.0 2.1 C* 1.6 2.0 1.9 2.2 2.9 3.6 1.7 1.7 1.8 1.7 h* 104.7 75.2 78.7 148.6 157.5 165.1 104.9 121.5 134.6 114.1 UV cut 395.0 395.0 395.0 395.0 395.0 394.5 395.7 395.3 395.0 394.8
TABLE-US-00011 TABLE 11 Results of MR8 HMC Lenses with Epolight 4831 and IR765 NIR Absorbers Sample # Control Formulation No. 1 2 3 4 5 6 7 8 9 8 Epolight 4831 25 45 75 — — — 45 45 45 — (ppm) IR765 (ppm) — — — 5 10 15 4 6 8 — TsIR 68.60 60.20 58.80 71.30 67.90 65.90 56.90 55.90 54.60 84.70 (@780- 2000 nm) NIR cut 31.40 39.80 41.20 28.70 32.10 34.10 43.10 44.10 45.40 15.30 (@780- 2000 nm) TvD65 96.1 93.6 92.9 96.2 95.8 95.4 92.8 92.2 91.5 89.8 YI 1.6 2.8 3.0 −0.4 −1.4 −2.5 1.4 0.6 0.1 2.1 C* 1.14 1.51 1.59 1.8 2.66 3.35 1.13 1.16 1.45 1.7 h* 100.50 66.40 66.10 155.4 165.7 172.6 105.6 132.00 144.40 114.1 UV cut 395.0 395.0 395.0 395.0 396.0 396.0 395.0 396.0 395.0 394.8
EXAMPLE 2
(Preparation of Near Infrared Absorbing Lenses with Polycarbonate Precursors)
[0051] Polycarbonate based lenses with different infrared absorbers were produced to test the synergistic effect of two infrared absorbers on the infrared absorbing properties and residual colors of the lenses. The near infrared absorbers used were shown in Table 12.
TABLE-US-00012 TABLE 12 List of Near Infrared Absorbers NIRAbsorber Name NIR Absorber code λmax (nm) Supplier Epolight 4831 NIR6 1040 Epolin Epolight 3169 NIR12 946 Epolin Epolight 3157 NIR13 886 Epolin
[0052] In each polycarbonate lens sample, two of these near infrared absorbers were mixed with polycarbonate pellets. The mixture was then injection-molded into ophthalmic lenses. The light transmittance and color properties of each lens sample were measured using Lamda™ 900 (Perkin Elmer, USA).
[0053] The compositions of polycarbonate lens samples that contain two near infrared absorbers and the compositions of corresponding comparative examples are list in Table 13. The first set of polycarbonate lens contained Epolight 4831 and Epolight 3169 near infrared absorbers. The second set of polycarbonate lens contained Epolight 4831 and Epolight 3157 near infrared absorbers.
TABLE-US-00013 TABLE 13 Compositions of Polycarbonate Lenses with Near Infrared Absorbers Set # Comparative Example Formulation 1 2 3 4 5 6 7 8 9 PC (wt %) 99.8 99.8 100 99.9 99.8 99.9 99.8 99.9 99.8 Epolight 0.01 0.01 NA 0.01 0.02 NA NA NA NA 4831 (wt %) Epolight 0.01 NA NA NA NA 0.01 0.02 NA NA 3169 (wt %) Epolight NA 0.01 NA NA NA NA NA 0.01 0.02 3157 (wt %)
[0054] The test results of the first set polycarbonate lenses containing Epolight 4831 and Epolight 3169 near infrared absorbers are listed in Table 14. The results of light transmittance for each sample is plotted in
TABLE-US-00014 TABLE 14 Test Results for PC Lenses with Epolight 4831 and Epolight 3169 NIR Absorbers Set# Comparative Examples Formulation 1 C3 C4 C5 C6 C7 PC (wt %) 98.8 100 99.9 99.8 99.9 99.8 Epolight 0.01 NA 0.01 0.02 NA NA 4831 (wt %) Epolight 0.01 NA NA NA 0.01 0.02 3169 (wt %) TsIR.sub.780-2000 (%) 56.6 88.1 77.8 66.3 75.6 66.0 NIR cut (100- 43.4 11.9 22.2 33.7 24.4 34.0 TsIR.sub.780-2000) (%) TvD65 (%) 77.3 89.3 84.0 76.3 83.3 76.4 YI D65 (2°) 11.2 0.9 −1.5 −4.1 7.9 15.7 C* (10°) 6.4 0.5 1.1 2.4 4.9 9.4 h* (10°) 97.4 94.5 194.6 202.2 100.6 98.1 Visual color Grey Blue Brown
[0055] The test results of the second set polycarbonate lenses containing Epolight 4831 and Epolight 3157 near infrared absorbers are listed in Table 15. The results of light transmittance for each sample is plotted in
TABLE-US-00015 TABLE 15 Test Results for PC Lenses with Epolight 4831 and Epolight 3157 NIR Absorbers Set# Comparative Examples Formulation 2 C3 C4 C5 C8 C9 PC (wt %) 99.8 100 99.9 99.8 99.9 99.8 Epolight 0.01 NA 0.01 0.02 NA NA 4831 (wt %) Epolight 0.01 NA NA NA 0.01 0.02 3157 (wt %) TsIR.sub.780-2000 (%) 57.9 88.1 77.8 66.3 76.2 63.9 NIR cut (100- 42.1 11.9 22.2 33.7 23.8 36.1 TsIR.sub.780-2000) (%) TvD65 (%) 80.8 89.3 84.0 76.3 86.2 81.1 YI D65 (2°) 5.7 0.9 −1.5 −4.1 4.5 10.3 C* (10°) 4.0 0.5 1.1 2.4 3.7 8.7 h* (10°) 111.0 94.5 194.6 202.2 117.6 118.4 Visual color Grey Blue Yellow- Green
[0056] Although embodiments of the present application and their advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the embodiments as defined by the appended claims. Moreover, the scope of the present application is not intended to be limited to the particular embodiments of the process, treatment, machine, manufacture, composition of matter, means, methods, and/or steps described in the specification. As one of ordinary skill in the art will readily appreciate from the above disclosure, processes, machines, manufacture, compositions of matter, means, methods, or steps, presently existing or later to be developed that perform substantially the same function or achieve substantially the same result as the corresponding embodiments described herein may be utilized. Accordingly, the appended claims are intended to include within their scope such processes, machines, manufacture, compositions of matter, means, methods, or steps.