WO2024251378A1 - Lentille photochromique - Google Patents

Lentille photochromique Download PDF

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Publication number
WO2024251378A1
WO2024251378A1 PCT/EP2023/065549 EP2023065549W WO2024251378A1 WO 2024251378 A1 WO2024251378 A1 WO 2024251378A1 EP 2023065549 W EP2023065549 W EP 2023065549W WO 2024251378 A1 WO2024251378 A1 WO 2024251378A1
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dye
dyes
lens
activated state
alkyl
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Brian Shaughnessy
Nicholas Joseph PARISE
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Transitions Optical Ltd
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Transitions Optical Ltd
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Priority to CN202380099003.2A priority Critical patent/CN121241281A/zh
Priority to PCT/EP2023/065549 priority patent/WO2024251378A1/fr
Priority to AU2023451662A priority patent/AU2023451662A1/en
Publication of WO2024251378A1 publication Critical patent/WO2024251378A1/fr
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/041—Lenses

Definitions

  • the present invention relates to an optical article such as a photochromic lens.
  • Exemplary embodiments of the invention relate to a photochromic lens that meets the ANSI Z80.3 regulations for driving sun glasses (when fully activated at 23°C).
  • ANSI Z80.3 regulations ensure that the tint of sunglasses do not alter too much the green and yellow colors of traffic lights and that it allows their recognition by the wearer.
  • Red and red-violet tints sunglasses are best known for increasing the user’s contrast perception and vi sual depth. However, they cause more color imbalance than other tints such as gray.
  • Sunglasses are also classified according to their visible light transmission (VET).
  • VET visible light transmission
  • Cat 3 corresponds to a dark tint with a Y value in the range 8-18%, while for compari son Cat 2 has a Y value in the range 18-43% and lets more light go through the lens.
  • Photochromic lenses are optical lenses with a variable tint, with usually a substantially uncolored non-activated state and a colored activated state that is obtained in reaction to light stimulation.
  • the lens returns to the non-activated state when light stimulation ceases, according to a fading rate.
  • a value of Y> 80 %T is highly desirable.
  • the different dyes should have comparable fading rates to ensure that the hue does not vary too much when the lens returns to the non-activated state.
  • the combination of all dyes should provide in the activated state the desired visible light transmission attenuation while at the same time not impairing too much traffic light color recognition, these conditions being more difficult to satisfy when the tint of the lens causes color imbalance, which is the case of red-violet tint.
  • the dyes should be compatible with the process of manufacture of the photochromic lens.
  • US8608988 discloses a photochromic article comprising a coating of a curable composition containing photochromic dyes applied to the surface of a plastic substrate.
  • Exemplary embodiments of the invention aim at providing a photochromic lens meeting ANSI Z80.3 regulations, having a VLT Y value in the range 12 to 18, better 12 to 17.5, and even better 13 to 17 %T, and having a substantially red-violet tint in the activated state.
  • Such lens provides the advantages linked to the red-violet tint in the activated state, i.e., increases the user’s contrast perception and visual depth, while still ensuring satisfying color recognition of traffic lights and the required visible light transmission.
  • the first dye has an absorbance spectrum having a first relative maximum of 552nm +/- 30nm in the range 500-650nm, preferably 552nm +/- 20nm, more preferably 552nm +/- lOnm in the activated state;
  • the first dye has an absorbance spectrum having a second relative maximum of 442nm +/- lOnm in the range 420-470nm, preferably 442nm +/- 5nm, the absorbance at the second relative maximum being preferably less than at the first relative maximum in the activated state;
  • the first dye has an absorbance spectrum having a relative minimum of 475nm +/- 30nm in the range 400-600nm, preferably 475nm +/- 20nm, more preferably 475nm +/- lOnm, the first dye having preferably an absorbance spectrum is similar as the one shown in Fig. 1 in the activated state;
  • the second dye has an absorbance spectrum having a first relative maximum of 482nm +/- 30nm in the range 500-650nm, preferably 482nm +/- 20nm, more preferably 482nm +/- lOnm in the activated state, the second dye having preferably an absorbance spectrum having a second relative maximum of 472nm +/- lOnm in the range 450- 490nm, preferably 472nm +/- 5nm in the activated state, the absorbance at the second relative maximum being preferably less than at the first relative maximum;
  • the second dye has an absorbance spectrum having a relative minimum of 420nm +/- lOnm in the range 400-500nm, the second dye having preferably an absorbance spectrum similar as the one shown in Fig. 2 in the activated state;
  • the third dye having an absorbance spectrum having a relative maximum of 570nm +/- 30nm in the range 500-650nm, preferably 570nm +/- 20nm, more preferably 570nm +/- lOnm, and/or the third dye has an absorbance spectrum having a relative minimum of 420nm +/- lOnm in the range 400-500nm, the third dye having preferably an absorbance spectrum similar as the one shown in Fig. 3 in the activated state;
  • the first, second and third photochromic dyes are indeno-fused naphtopyrans, in particular of formula (I) wherein
  • R’ I is selected from hydrogen and R’sO — , wherein R’5 is selected from linear or branched (C1-C20) alkyl,
  • R2 is selected from halo (CiCe) alkyl, substituted aryl and substituted heteroaryl in which the aryl ring is directly bonded to position- 11 with the aryl, substituent being selected from hydroxyl, halo, carbonyl, (Ci-Ce) alkoxycarbonyl, cyano, halo(CiCe) alkyl, (Ci-Ce) alkyl and/or (Ci-Ce) alkoxy,
  • Rs and R4 are in each case independently selected from optionally substituted linear or branched (C1-C20) alkyl, optionally substituted (C3-C12) cycloalkyl, optionally substituted (C3-C12) heterocycloalkyl and optionally substituted aryl
  • B and B’ are in each case independently, an aryl group that is mono-substituted or di- substitued with the substituent being selected from halo, -Re, ORe wherein Re is selected from linear or branched (C1C20) alkyl, (C3-C12) cycloalkyl, and (C3-C12) heterocycloalkyl.
  • a photochromic lens according to these embodiments may present all or part of the features listed above.
  • Exemplary embodiments of the invention also relate to a photochromic lens having a substantially red-violet tint in the activated state, comprising at least first, second and third photochromic dyes,
  • the third dye having an absorbance spectrum having a relative maximum of 570nm +/- 30nm in the range 500-650nm, preferably 570nm +/- 20nm, more preferably 570nm +/- lOnm,
  • the weight proportion of the second dye being not less than 5% relative to the total weight of first, second and third dyes
  • the weight proportion of the third dye being not less than 1% relative to the total weight of first, second and third dyes, - the first, second and third dyes providing all together a transmission spectrum in the activated state having a relative minimum at 550 nm +/- 30nm.
  • a photochromic lens according to these embodiments may present all or part of the features listed above, in particular % transmittance values in activated state.
  • Exemplary embodiments of the invention also relate to a photochromic lens having a substantially red-violet tint in the activated state, comprising at least first, second and third photochromic dyes, the first dye is of formula (III) wherein R9, Rio and Ru are in each case independently (Ci-Ce) alkyl and preferably
  • the second dye is of formula (IV) wherein R9, Rio and Ru are in each case independently (Ci-Ce) alkyl and preferably (C1-C4) alkyl.
  • the third dye is of formula (V) wherein R9 and Rio are in each case independently (Ci-Ce) alkyl and preferably (C1-C4) alkyl;
  • the weight proportion of the second dye being not less than 5% relative to the total weight of first, second and third dyes
  • the weight proportion of the third dye being not less than 1% relative to the total weight of first, second and third dyes
  • a photochromic lens according to these embodiments may present all or part of the features listed above, in particular % transmittance values in activated state.
  • Such lens provides the advantages linked to the red-violet tint in the activated state, i.e., increases the user’s contrast perception and visual depth, while still ensuring satisfying color recognition of traffic lights and the required visible light transmission.
  • “Substantially red-violet tint” means that the color of the lens in the fully activated state at 23°C falls in the following range : a* in the range 15 to 25, preferably from 16 to 20, and b* in the range -5.0 to 0, preferably from -2.0 to O.
  • the a* and b* values as used herein in the specification and the claims refer to the a* and b* values measured at 23°C in accordance with CIE 15: 2004 space colorimetry, employing a D65 illuminant and 10° observer, as measured using a Hunter UltraScan Pro unit for example.
  • Activated state refers to the colored darkened state the photochromic lens takes at 23 °C, after an activation at saturation as described in more details hereunder in part 3 of the examples section.
  • the Fade Half-Life Tl/2 is the time interval in seconds for the change in optical density AOD of the activated form of the photochromic material in the sample to reach one half the AOD at 73.4 ° F. (23 °C.), after removal of the activating light source, as detailed in part 3 of the examples section below.
  • the Fade Half-life 1 Tl/2 is the time interval in seconds for the change in optical density AOD from saturation (fully activated state at 23 °C). To reach this fully activated state, the article may be exposed during 15 minutes to actinic radiation, as detailed in the examples section.
  • ANSI Z80.3 standards refer to the standards “Nonprescription Sunglass and Fashion Eyewear Requirements” are dated March 13, 2018 by the American National Standards Institutes, Inc and published by the Vision Council under ANSI Z80.3 - 2018 and correspond to the Revision of ANSI Z80.3- 2015.
  • 3.8.2 and 4.10.2 refers to transmittance properties related to traffic signal recognition, at a temperature of 23°C. x and y chromaticity coordinates of traffic signals and average daylight (D65) as viewed through the lens shall not fall outside prescribed regions on the CIE (1931) standard chromaticity, the green, yellow and average daylight (D65) regions being defined by some points of specific color coordinates listed in corresponding tables of the standards.
  • these ANSI standards are also used to determine if a prescription lens meets these chromaticity conditions.
  • Cat 3 is defined in Table 2 (page 5) of the international standard ISO 8980-3:2013 (E) Third edition 2013-10-01 Part 3 “Transmittance specifications and test methods”, as “dark tint” having a luminous transmittance Y from over 8% up to 18%T.
  • the minimum requirement of the luminous transmittance of spectacle lenses for road use and driving during daylight is 8% at the design reference point.
  • Y values below 12 %T are considered too dark, and thus not satisfactory.
  • Desired Cat 3 range is thus considered to go from 12 to 17.5, and more preferably from 13 to 17 %T.
  • the color coordinates a* and b* are those measured in the Color Space CIE 15:2004 space colorimetry, employing a D65 illuminant and 10° observer, as detailed in the experimental set up for measurements section above.
  • each of the photochromic dye is incorporated into a polyurethane coating system as described in US Pat. No. 8,608,988 examples 1-3 at mol 4 % and applied at a thickness of 20 microns to 2” x 2” test chips made from CR-39® monomer (PPG Industries, Inc.).
  • the coated test chip is then cured at 125 °C for 1 hour.
  • An absorbance spectrum is similar to a measured reference spectrum if when comparing the candidate absorbance spectrum to the reference absorbance spectrum in the range 400-680nm, for any wavelength in this range, Acandidate(k)-Areference(k)
  • Fig. l is an example of absorbance spectrum curve for an example of first photochromic dye
  • Fig.3 is an example of absorbance spectrum for an example of third photochromic dye
  • Fig.4 is an example of absorbance curve for an example of fourth photochromic dye
  • Fig.5 shows the color coordinates for example 3 in accordance with the invention in the CIE 1931 standard chromaticity diagram together with the regions of acceptance for the yellow and green traffic signals and average daylight D65
  • Fig.6 shows the color coordinates for a first comparative example CE-1 in the CIE 1931 standard chromaticity diagram together with the regions of acceptance for the yellow and green traffic signals and average daylight D65
  • Fig.8 shows the absorbance curves for Comparative Example CE-1 and Comparative Example CE-2 and Example 3 according to the invention.
  • photochromic lenses according to the invention contain photochromic dyes or have photochromic dyes applied thereto (e.g., in form of a photochromic coating composition) and by this way, typically display colorless (e.g., clear) and colored states that correspond to the colorless and colored states of the photochromic dyes contained therein or applied thereto.
  • the photochromic dyes of the present invention transition quickly from their optically colorless state to their colored state and/or from their colored state to their optically colorless state, that is, a photochromic material having “fast” activation and/or fade rates.
  • the photochromic lens according to the invention contains at least first, second and third photochromic dyes that are indeno[2',3':3,4]naphtho [l,2-b]pyran also named indenofused naphthopyrans.
  • indeno[2',3':3,4] naphthofl, 2-b]pyran refers to a photochromic group that may be represented by the general structure (i) (below), and which comprises one or more group(s) bonded to the pyran ring at an available position adjacent to the oxygen atom (i.e., indicated at the 3 -position in structure (i) below), which may aid in stabilizing the open-form of the indenofused naphthopyran.
  • Indeno[2',3':3,4]naphtho[l,2-b]pyran derivatives are well-known photochromic dyes and are in particular disclosed in US 8 748 634 and US 9 028 728.
  • first, second and third photochromic dyes are an indeno[2',3':3,4]naphtho[l,2-b]pyran having an electronwithdrawing, directly or not, bonded at the 11-position of the indeno[2',3':3,4]naphtho[l,2- b]pyran; and two groups bonded at the 13-position of the indeno[2',3':3,4]naphtho[l,2-b]pyran both groups being not combined.
  • first, second and third photochromic dyes are represented by the following Formula (I) wherein
  • R’ and R being each independently selected from hydrogen, substituted or unsubstituted (C1-C20) alkyl, substituted or unsubstituted (C3-C20) cycloalkyl and substituted or unsubstituted (C5-C20) aryl, provided that at least one of R’ and R” is other than hydrogen or with R’and R”forming together a (C3-C20) cycloalkyl ring or a (C3- C20) cycloheteroalkyl, in particular morpholinyl or piperazinyl, or
  • R2 is selected from halo (Ci-Ce) alkyl, substituted aryl and substituted heteroaryl in which the aryl ring is directly bonded to position- 11 and with the aryl substituent being selected from hydroxyl, halo, carbonyl, (Ci-Ce) alkoxycarbonyl, cyano, halo(Ci-Ce) alkyl, (Ci-Ce) alkyl and/or (Ci-Ce) alkoxy,
  • R3 and R4 are in each case independently selected from optionally substituted linear or branched (C1-C20) alkyl, optionally substituted (C3-C12) cycloalkyl, optionally substituted (C3-C12) heterocycloalkyl and optionally substituted aryl,
  • B and B’ are in each case independently, an aryl group that is mono-substituted or di- substitued with the substituent being selected from halo in particular being fluorine, - Re, O-Re wherein Re is selected from linear or branched (C1-C20) alkyl, (C3-C12) cycloalkyl, and (C3-C12) heterocycloalkyl.
  • linear or branched groups such as linear or branched alkyl
  • linear or branched alkyl are herein understood to include: a methylene group or a methyl group; groups that are linear, such as linear (C2-C20) alkyl groups; and groups that are appropriately branched, such as branched (C3-C20) alkyl groups.
  • optionally substituted group means a group, including but not limited to, alkyl group, cycloalkyl group, heterocycloalkyl group, aryl group, and/or heteroaryl group, in which at least one hydrogen thereof has been optionally replaced or substituted with a group that is other than hydrogen, such as, but not limited to, halo groups (e.g., F, Cl, I, and Br), hydroxyl groups, ether groups.
  • halo groups e.g., F, Cl, I, and Br
  • halo substituted and related terms (such as, but not limited to, haloalkyl groups, means a group in which at least one, and up to and including all of the available hydrogen groups thereof is substituted with a halo group.
  • halo-substituted is inclusive of “perhalo-substituted.”
  • perhalo-substituted group and related terms means a group wherein each hydrogen atom is replaced by a halogen atom.
  • alkyl means linear or branched (C1-C20) alkyl, such as, but not limited to linear or branched (C1-C10) alkyl or linear or branched (C2-C10) alkyl.
  • alkyl groups from which the various alkyl groups of the present invention can be selected from include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tertbutyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl and decyl.
  • heterocycloalkyl means groups that are appropriately cyclic, such as (C3-C12) heterocycloalkyl groups or (C5-C7) heterocycloalkyl groups, and which have at least one hetero atom in the cyclic ring, such as, but not limited to, O, S, N, P, and combinations thereof.
  • heterocycloalkyl groups include, but are not limited to, imidazolyl, tetrahydrofuranyl, tetrahydropyranyl, piperidinyl, pyrrolidinyl and morpholinyl.
  • a heterocycloalkyl substituent comprising at least one nitrogen atom may be linked with said nitrogen atom and may be commonly named N-heterocycloalkyl, such as but not limited to N- morpholinyl and N-piperidinyl.
  • aryl includes, but is not limited to, (Cs-Cis) aryl, such as but not limited to, (C5-C10) aryl (including fused ring polycyclic aryl groups).
  • aryl groups include, but are not limited to, phenyl, naphthyl, indenyl and anthracenyl.
  • R? and Rs located at the para position being selected from a radical — [O — (CH2 )t- CH3] with t being 0, 1, 3 or 4, and a N-morpholinyl,
  • R’7 is hydrogen or halogen, in particular fluorine.
  • Ri can, with some embodiments, be selected from radicals diethylamino, morpholino, piperidinyl and R5-O — , wherein R5 is selected from linear or branched (Ci-Ce) alkyl.
  • first photochromic dye represented by Formula (III) is 3,3-bis-(4-butoxyphenyl)-7-methoxy-l l(4-trifluoromethylphenyl)-13, 13-dipropyl-3H, 13H- indeno[2',3':3,4]naphtho[l,2-b]pyran, which is represented by the following Formula (Illa),
  • Ri is methoxy
  • R’i is hydrogen
  • R2 is 4- trifluorom ethylphenyl
  • R3 and R4 are each n-propyl
  • B and B' are each 4-butoxyphenyl.
  • the absorbance curve of this dye of Formula (Illa) is represented in Fig.1.
  • Fig.l shows the absorbance curve for the first dye, in non-activated state (B) and activated state (A).
  • the dye shows two absorption peaks, one at 442 nm and the other at 552 nm.
  • the absorbance in the non-activated state is very low, under 0,15, in the range 430- 700 nm.
  • second photochromic dye represented by Formula (I) is of Formula (IV)
  • R9, Rio and Rn are in each case independently (Ci-Ce) alkyl and preferably (C1-C4) alkyl.
  • second photochromic dye is 3,3-bis-(4-butoxyphenyl)-7- piperidinyl-8-methoxy- 11 (trifluoromethyl)- 13,13 -dipropyl-3H, 13H- indeno[2',3':3,4]naphtho[l,2-b]pyran, which is represented by the following Formula (IVa)
  • Ri is N-piperidinyl
  • R’i is methoxy
  • R2 is trifluoromethyl
  • R3 and R4 are each n-propyl
  • B and B' are each 4-butoxy phenyl.
  • the absorbance curve of this dye of Formula (IVa) is represented in Fig.2.
  • Fig.2 shows the absorbance curve for the second dye, in non-activated state (B) and activated state (A).
  • the dye shows one absorption peak at 482 nm.
  • the absorbance in the non-activated state is very low, under 0,15, in the range 430-700 nm.
  • third photochromic dye represented by Formula (I) is of Formula (V) wherein R9 and Rio are in each case independently (Ci-Ce) alkyl and preferably (C1-C4) alkyl.
  • third photochromic dye is 3 -(4-methoxy-3 -fluorophenyl) 3 -(4-morpholinophenyl)-7-methoxy- 11 -(4-trifluoromethyl-2-fluorophenyl)- 13,13 -dipropyl- 3H,13H-indeno[2',3':3,4]naphtho[l,2-b]pyran, which is represented by the following Formula (Va)
  • Ri is methoxy
  • R’i is hydrogen
  • R2 is 4- trifluoromethyl-2-fluoro-phenyl
  • R3 and R4 are each n-propyl
  • B is 4-morpholinophenyl
  • B' is 4-methoxy-3 -fluorophenyl.
  • Fig.3 shows the absorbance curve for the third dye, in non-activated state (B) and activated state (A).
  • the dye shows a main absorption peak at 570 nm, and a second one of less amplitude at 472 nm.
  • the absorbance in the non-activated state is very low, under 0,15, in the range 430-700 nm.
  • the photochromic dyes of formula (I), (II), (III), (IV), (V), (Illa), (IVa) and/or (Va) can be prepared by art-recognized methods.
  • the indeno-fused naphthopyran compounds of the present invention can be synthesized in accordance with the description provided in U.S. Pat. No. 6,296,785, at column 10, line 52 through column 29, line 18, which disclosure is incorporated herein by reference.
  • the indenofused naphthopyran compounds of the present invention can be synthesized in accordance with the description provided in U.S. Pat. No.
  • the weight proportion of the first dye, in particular of Formula (III) or (Illa) ranges from 45% to 90 % and in particular from 60 to 80% relative to the total weight of first, second and third dyes in particular having respectively Formula (III) or (Illa), Formula (IV) or (IVa) and Formula (V) or (Va).
  • the weight proportion of the second dye, in particular of Formula (IV) or (IVa) is not less than 5 % and in particular from 10 to 30% relative to the total weight of first, second and third dyes in particular having respectively Formula (III) or (Illa), Formula (IV) or (IVa) and Formula (V) or (Va).
  • the weight proportion of the third dye, in particular of Formula (V) or (Va) is not less than 1 % and in particular from 5 to 15% relative to the total weight of first, second and third dyes in particular having respectively Formula (III) or (Illa), Formula (IV) or (IVa) and Formula (V) or (Va).
  • photochromic lenses according to the invention contain first, second and third dyes, in particular, first, second and third dyes respectively of formula (III), (IV) and (V) and in particular respectively of formula (Illa), (IVa) and (Va) in weight ratio 70/20/10 +/-5 for each dye.
  • photochromic lenses according to the invention comprises a substrate and first, second and third dyes incorporated in contact with at least a portion of the substrate.
  • the term “in contact with” means associated with, either directly or indirectly through another material or structure.
  • the term “on” means that the subject coating is connected to the surface or object such that the subject coating is supported or carried by the surface or object.
  • a coating that is “on” a surface may be applied directly over the surface or it may be applied over one or more other coatings, at least one of which is applied directly over the surface.
  • Non-limiting embodiments of the shape the surface of the substrate include round, flat, cylindrical, spherical, planar, substantially planar, plano-concave and/or plano-convex, curved, including but not limited to, convex and/or concave, as exemplified by the various base curves used for ophthalmic lenses.
  • the substrate of the photochromic lens according to the invention comprises organic material and first, second and third dyes may be in contact with at least a portion of the substrate by incorporating the dyes into at least a portion of the organic material of the substrate, or by incorporating the dyes into at least a portion of the organic material from which the substrate is formed.
  • the organic material can be a transparent polymeric material.
  • the polymeric material can be an optically clear polymeric material prepared from a thermoplastic polycarbonate resin, such as the resin derived from bisphenol A and phosgene, which is sold under the trademark, LEXAN®; a polyester, such as the material sold under the trademark, MYLAR®; a poly(methyl methacrylate), such as the material sold under the trademark, PLEXIGLAS®; and polymerizates of a polyol(allyl carbonate) monomer, especially diethylene glycol bis(allyl carbonate), which monomer is sold under the trademark CR-39®; and polyureapolyurethane (polyurea urethane) polymers, which are prepared, for example, by the reaction of a polyurethane oligomer and a diamine curing agent, a composition for one such polymer being sold
  • suitable polymeric materials include polymerizates of copolymers of a polyol (allyl carbonate), e.g., diethylene glycol bis(allyl carbonate), with other copolymerizable monomeric materials, such as, but not limited to: copolymers with vinyl acetate, copolymers with a polyurethane having terminal diacrylate functionality, and copolymers with aliphatic urethanes, the terminal portion of which contain allyl or acrylyl functional groups.
  • a polyol allyl carbonate
  • other copolymerizable monomeric materials such as, but not limited to: copolymers with vinyl acetate, copolymers with a polyurethane having terminal diacrylate functionality, and copolymers with aliphatic urethanes, the terminal portion of which contain allyl or acrylyl functional groups.
  • Still other suitable polymeric materials include, without limitation, poly(vinyl acetate), polyvinylbutyral, polyurethane, polythiourethanes, polymers chosen from diethylene glycol dimethacrylate monomers, diisopropenyl benzene monomers, ethoxylated bisphenol A dimethacrylate monomers, ethylene glycol bismethacrylate monomers, polyethylene glycol)bismethacrylate monomers, ethoxylated phenol bismethacrylate monomers and ethoxylated trimethylol propane triacrylate monomers, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, polystyrene and copolymers of styrene with methyl methacrylate, vinyl acetate and acrylonitrile.
  • poly(vinyl acetate), polyvinylbutyral, polyurethane, polythiourethanes polymers chosen from diethylene glycol dimethacrylate
  • the polymeric material can be an optical resins sold by PPG Industries, Inc. under the CR-designation, e.g., CR-307, CR-407, and CR-607.
  • polycarbonate substrates e.g., allyl diglycol carbonate (CR-39), and polyurethane (Tri vex).
  • first, second and third dyes may also be in contact with at least a portion of the substrate of the photochromic lens as part of a coating that is applied to at least a portion of a substrate.
  • the substrate has at least one surface that is capable of accommodating one photochromic coating containing first, second and third dyes.
  • the photochromic dyes are present in a same coating.
  • This coating is preferably made by coating a curable composition containing the dyes on a rigid substrate, and then curing the composition.
  • coating means a structure comprising one or more complete or partial layers (which may or may not have a uniform composition and/or cross-sectional thickness) derived from flowable compositions.
  • the flowable compositions from which coatings may be formed include, for example, liquid or powder compositions, which may be applied to the substrate using conventional methods.
  • the substrate may be a polymeric substrate or an inorganic substrate (such as, but not limited to, a glass substrate).
  • the first, second and third dyes may be incorporated into at least a portion of a coating composition prior to application of the coating composition to the substrate, or alternatively, a coating composition may be applied to the substrate, at least partially set, and thereafter the first, second and third dyes may be imbibed into at least a portion of the coating.
  • a coating composition may be applied to the substrate, at least partially set, and thereafter the first, second and third dyes may be imbibed into at least a portion of the coating.
  • set and “setting” are intended to include processes, such as, but not limited to, curing, polymerizing, cross-linking, cooling, and drying.
  • Specific non-limiting examples of coating compositions into which the first, second and third dyes may be incorporated include, but are not limited to, those coating compositions known in the art for use in connection with photochromic materials.
  • Non-limiting examples of coating compositions into which the photochromic materials may be incorporated include the monoisocyanate containing coating compositions disclosed in U.S. Pat. No. 6,916,537
  • Other nonlimiting examples of coating compositions into which the photochromic materials may be incorporated include the compositions disclosed in WO 2021/129941 or in US 10,954,397.
  • Other non-limiting examples of coating compositions into which the photochromic materials may be incorporated include the poly(urea-urethane) compositions disclosed in U.S. Pat. No. 6,531,076.
  • Still other non-limiting examples of coating compositions into which the photochromic materials may be incorporated include the polyurethane compositions disclosed in U.S. Pat. No. 6,187,444, at col. 2, line 52 to col.
  • coating compositions into which the photochromic materials may be incorporated include the poly(meth)acrylic coating compositions described in U.S. Pat. No. 6,602,603, at col. 2, line 60 to col. 7, line 50; the aminoplast resin coating compositions described in U.S. Pat. No. 6,506,488, at col. 2, line 43 to col. 12, line 23 and U.S. Pat. No. 6,432,544, at col. 2, line 32 to col. 14, line 5; the polyanhydride coating compositions described in U.S. Pat. No. 6,436,525, at col. 2, line 15 to col. 11, line 60; the epoxy resin coating compositions described in U.S. Pat. No.
  • the photochromic coating compositions may further comprise other additives that aid in the processing and/or performance of the composition or coating derived therefrom.
  • additives include photoinitiators, thermal initiators, polymerization inhibitors, solvents, light stabilizers (such as, but not limited to, ultraviolet light absorbers and light stabilizers, such as, hindered amine light stabilizers (HALS)), heat stabilizers, mold release agents, rheology control agents, leveling agents (such as, but not limited to, surfactants), free radical scavengers, adhesion promoters (such as, hexanediol diacrylate and coupling agents), and combinations and mixtures thereof.
  • photoinitiators such as, but not limited to, ultraviolet light absorbers and light stabilizers, such as, hindered amine light stabilizers (HALS)
  • HALS hindered amine light stabilizers
  • leveling agents such as, but not limited to, surfactants
  • free radical scavengers such as,
  • An at least partial coating comprising the dyes may be in contact with at least a portion of a substrate of a photochromic article, for example, by applying a coating composition comprising the photochromic material to at least a portion of a surface of the substrate and at least partially setting the coating composition. Additionally, or alternatively, the at least partial coating comprising the dyes may be connected to the substrate, for example, through one or more additional at least partial coatings. For example, while not limiting herein, an additional coating composition may be applied to a portion of the surface of the substrate, at least partially set, and thereafter a coating composition comprising first, second and third dyes may be applied over the additional coating and at least partially set. Non-limiting methods of applying coatings compositions to substrates are discussed herein below.
  • Non-limiting examples of additional coatings and films that may be used in conjunction with the photochromic articles disclosed herein include primer or compatibilizing coatings; protective coatings, including transitional coatings, abrasion-resistant coatings and other coatings that protect against the effects of polymerization reaction chemicals and/or protect against deterioration due to environmental conditions, such as, moisture, heat, ultraviolet light, and/or oxygen (e.g., UV-shielding coatings and oxygen barrier coatings); anti-reflective coatings; conventional photochromic coating; polarizing coatings and polarizing stretched- films; and combinations thereof.
  • protective coatings including transitional coatings, abrasion-resistant coatings and other coatings that protect against the effects of polymerization reaction chemicals and/or protect against deterioration due to environmental conditions, such as, moisture, heat, ultraviolet light, and/or oxygen (e.g., UV-shielding coatings and oxygen barrier coatings); anti-reflective coatings; conventional photochromic coating; polarizing coatings and polarizing stretched- films;
  • Non-limiting examples of primer or compatibilizing coatings that may be used in conjunction with various non-limiting embodiments disclosed herein include coatings comprising coupling agents, at least partial hydrolysates of coupling agents, and mixtures thereof.
  • the term “coupling agent” means a material having a group capable of reacting, binding and/or associating with a group on a surface.
  • Coupling agents according to various non-limiting embodiments disclosed herein may include organometallics, such as, silanes, titanates, zirconates, aluminates, zirconium aluminates, hydrolysates thereof, and mixtures thereof.
  • the phrase “at least partial hydrolysates of coupling agents” means that some to all of the hydrolyzable groups on the coupling agent are hydrolyzed.
  • primer coatings that are suitable for use in conjunction with the various non-limiting embodiments disclosed herein include those primer coatings described U.S. Pat. No. 6,025,026 at col. 3, line 3 to col. 11, line 40 and U.S. Pat. No. 6,150,430 at col. 2, line 39 to col. 7, line 58, which disclosures are hereby specifically incorporated herein by reference.
  • transitional coating means a coating that aids in creating a gradient in properties between two coatings.
  • a transitional coating may aid in creating a gradient in hardness between a relatively hard coating (such as, an abrasion-resistant coating) and a relatively soft coating (such as, a photochromic coating).
  • a relatively hard coating such as, an abrasion-resistant coating
  • a relatively soft coating such as, a photochromic coating.
  • Non-limiting examples of transitional coatings include radiation-cured, acrylate-based thin films as described in U.S. Patent Application Publication No. 2003/0165686 at paragraphs [0079]-[0173], which disclosure is hereby specifically incorporated by reference herein.
  • Non-limiting examples of abrasionresistant coatings include abrasion-resistant coatings comprising organosilanes, organosiloxanes, abrasion-resistant coatings based on inorganic materials, such as, silica, titania and/or zirconia, and organic abrasion-resistant coatings that are ultraviolet light curable.
  • Non-limiting examples of antireflective coatings include a monolayer coating or multilayer coatings of metal oxides, metal fluorides, or other such materials, which may be deposited onto the articles disclosed herein (or onto self supporting films that are applied to the articles), for example, through vacuum deposition, sputtering, etc.
  • an additional at least partial coating or film may be formed on the substrate prior to forming the coating comprising the photochromic material on the substrate.
  • a primer or compatibilizing coating may be formed on the substrate prior to applying the coating composition comprising the photochromic material.
  • one or more additional at least partial coating(s) may be formed on the substrate after forming the coating comprising the photochromic material on the substrate, for example, as an overcoating on the photochromic coating.
  • a transitional coating may be formed over the coating comprising the photochromic material, and an abrasion-resistant coating may then be formed over the transitional coating.
  • Curable photochromic compositions were prepared from the components listed in Table 1 below. All components are listed in % weight. Table 1
  • a hindered amine light stabilizer commercially available from BASF.
  • a PDQ® coated Gentex® polycarbonate piano lens having a diameter of 76 millimeters was Corona treated prior to being coated with the compositionsCE-1, CE-2 and example 3, using a spin coating process. Approx 2 mL of each composition was dispensed onto the substrate and then rotated for eight seconds at a spin speed sufficient to deposit 0.25-0.37g of wet coating onto the lens.
  • the coated substrates were then cured in a forced air oven at 125°C for one hour and subsequently cooled to room temperature.
  • the substrates having a cured photochromic layer thereover were further Corona treated and further coated (over the cured photochromic layer) with a protective coating according to the formulation reported in Table 1 of Example 1 in U.S. Patent No. 7,410,691, which is incorporated herein by reference, using an additional 0.5% polybutyl acrylate.
  • the protective coating was applied by spin coating, and UV cured in an EyeUV oven equipped with D bulbs. Following this, each coated substrate (further including the protective coating layer) was further cured at 105°C for three hours.
  • the lenses (test specimens) were then evaluated for photochromic properties.
  • the photochromic performance of each of the aforementioned test specimens was performed as follows.
  • the coated lenses (test specimens) prepared as described above were tested in the Photochromic Performance Test on the Advanced Bench for Measuring Photochromies (“A- BMP”) optical bench.
  • the A-BMP optical bench was maintained at a constant temperature of 73.4°F (23 °C) during testing.
  • Prior to testing on the A-BMP optical bench each of the coated lenses were exposed to 365-nanometer ultraviolet light for 5 minutes at a distance of 10 centimeters to activate the photochromic materials.
  • the UVA (315 to 380 nm) irradiance at the lens was measured with a Goosch & Housego OL 756 spectroradiometer with OL 86-T cosine receptor and found to be 7.7 watts per square meter.
  • the lenses were then heated up to 70°C, at which time the lenses were maintained at this temperature and exposed F17T8 yellow fluorescent light for 25 minutes at a distance of 10 centimeters to further inactivate the photochromic materials.
  • the irradiance at the lens was measured with the OL 756 and found to be 9Klux.
  • the lenses were then kept in a dark environment at room temperature (from 70 to 75°F, or 21 to 24°C.) for at least 1 hour prior to testing on the A-BMP optical bench.
  • the power output of the optical bench i.e., the dosage of light that the lens was exposed to
  • the power output of the optical bench was adjusted to 6.7 Watts per square meter (W/m 2 ) UVA, integrated from 315-380 nm and 50 Klux illuminance, integrated from 380-780 nm. Measurement of this power set point was made using an irradiance probe and the calibrated Zeiss spectrophotometer.
  • the lens sample cell was fitted with a quartz window and self-centering sample holder. The temperature in the sample cell was controlled through the software with an AirJet XE custom-coupled to a bubbling water bath to deliver 50% RH air maintained at 23°C +/- 0.1C.
  • Measurement of the sample’s dynamic photochromic response and color measurements was made using the same Zeiss spectrophotometer, with fiber optic cables for light delivery from a tungsten halogen lamp and through the sample.
  • the collimated monitoring light beam from the fiber optic cable was maintained perpendicular to the test sample while passing through the sample and directed into a receiving fiber optic cable assembly attached to the spectrophotometer.
  • the exact point of placement of the sample in the sample cell was where the activating xenon arc beam and the monitoring light beam intersected to form two concentric circles of light.
  • the angle of incidence of the xenon arc beam at the sample placement point was 30° from perpendicular.
  • AOD logio(% Tb/% Ta) where % Tb is the percent transmittance in the bleached state, and % Ta is the percent transmittance in the activated state.
  • Delta Optical density measurements were based on photopic optical density.
  • Fig.5 shows the results in the ANSI Z80.3 chromaticity diagram for a composition corresponding to Example 3.
  • the green activated, yellow activated and D65 activated are within the specifications for traffic light recognition.
  • Fig.6 shows the results in the ANSI Z80.3 chromaticity diagram for a composition corresponding to Comparative Example 1.
  • Fig.7 shows the results in the ANSI Z80.3 chromaticity diagram for a composition corresponding to Comparative Example 2.
  • Fig.8 shows the respective absorbance spectra for CE-1, CE-2 and Example 3.
  • the first, second and third dyes provide all together an absorption spectrum having a relative maximum around 550nm, thus a transmission spectrum in the activated state having a relative minimum close to 550 nm.
  • the absorption around 550nm remains however less for Example 3 than for CE-1, and higher than CE-2.

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Abstract

L'invention concerne des lentilles photochromiques répondant aux normes de conduite ANSI Z80.3, ayant une transmittance en pourcentage Y basée sur des coordonnées CIE Y à un observateur de 10° utilisant un illuminant D65 de 12 à 18, mieux de 12 à 17,5, de préférence de 13 à 17%T et comprenant des colorants photochromiques en particulier des colorants naphtopyranes indéno-fusionnés spécifiques.
PCT/EP2023/065549 2023-06-09 2023-06-09 Lentille photochromique Pending WO2024251378A1 (fr)

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CN202380099003.2A CN121241281A (zh) 2023-06-09 2023-06-09 光致变色镜片
PCT/EP2023/065549 WO2024251378A1 (fr) 2023-06-09 2023-06-09 Lentille photochromique
AU2023451662A AU2023451662A1 (en) 2023-06-09 2023-06-09 Photochromic lens

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Citations (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5645767A (en) 1994-11-03 1997-07-08 Transitions Optical, Inc. Photochromic indeno-fused naphthopyrans
US6025026A (en) 1997-06-30 2000-02-15 Transitions Optical, Inc. Process for producing an adherent polymeric layer on polymeric substrates and articles produced thereby
US6060001A (en) 1998-12-14 2000-05-09 Ppg Industries Ohio, Inc. Alkoxyacrylamide photochromic coatings compositions and photochromic articles
US6150430A (en) 1999-07-06 2000-11-21 Transitions Optical, Inc. Process for adhering a photochromic coating to a polymeric substrate
US6187444B1 (en) 1997-02-21 2001-02-13 Ppg Industries Ohio, Inc. Photochromic polyurethane coating and articles having such a coating
US6268055B1 (en) 1997-12-08 2001-07-31 Ppg Industries Ohio, Inc. Photochromic epoxy resin coating composition and articles having such a coating
US6296785B1 (en) 1999-09-17 2001-10-02 Ppg Industries Ohio, Inc. Indeno-fused photochromic naphthopyrans
US6432544B1 (en) 1998-12-18 2002-08-13 Ppg Industries Ohio, Inc. Aminoplast resin photochromic coating composition and photochromic articles
US6436525B1 (en) 1998-12-11 2002-08-20 Ppg Industries Ohio, Inc. Polyanhydride photochromic coating composition and photochromic articles
US6506488B1 (en) 1998-12-18 2003-01-14 Ppg Industries Ohio, Inc. Aminoplast resin photochromic coating composition and photochromic articles
US6531076B2 (en) 2000-02-04 2003-03-11 Ppg Industries Ohio, Inc. Photochromic organic resin composition
US6602603B2 (en) 1999-07-02 2003-08-05 Ppg Industries Ohio, Inc. Poly(meth)acrylic photochromic coating
US20030165686A1 (en) 2001-12-27 2003-09-04 Blackburn William P. Photochromic optical article
US6916537B2 (en) 2001-11-01 2005-07-12 Transitions Optical Inc. Articles having a photochromic polymeric coating
US7410691B2 (en) 2001-12-27 2008-08-12 Ppg Industries Ohio, Inc. Photochromic optical article
US7527754B2 (en) 2005-12-21 2009-05-05 Transitions Optical, Inc. Photochromic indeno-fused naphthopyrans
US8608988B2 (en) 2010-11-23 2013-12-17 Transitions Optical, Inc. Curable photochromic compositions and optical articles prepared therefrom
US8748634B2 (en) 2006-10-30 2014-06-10 Transitions Optical, Inc. Photochromic materials demonstrating improved fade rates
US9028728B2 (en) 2005-04-08 2015-05-12 Transitions Optical, Inc. Photochromic materials that include indeno-fused naphthopyrans
US10954397B2 (en) 2015-08-17 2021-03-23 Transitions Optical, Inc. Curable photochromic compositions
US20210179931A1 (en) * 2017-03-01 2021-06-17 Younger Mfg. Co. Dba Younger Optics Optical articles comprising photochromic poly(urea-urethane)
WO2021129941A1 (fr) 2019-12-27 2021-07-01 Transitions Optical, Ltd. Composition photochromique durcissable comprenant un polymère segmenté

Patent Citations (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5645767A (en) 1994-11-03 1997-07-08 Transitions Optical, Inc. Photochromic indeno-fused naphthopyrans
US6187444B1 (en) 1997-02-21 2001-02-13 Ppg Industries Ohio, Inc. Photochromic polyurethane coating and articles having such a coating
US6025026A (en) 1997-06-30 2000-02-15 Transitions Optical, Inc. Process for producing an adherent polymeric layer on polymeric substrates and articles produced thereby
US6268055B1 (en) 1997-12-08 2001-07-31 Ppg Industries Ohio, Inc. Photochromic epoxy resin coating composition and articles having such a coating
US6436525B1 (en) 1998-12-11 2002-08-20 Ppg Industries Ohio, Inc. Polyanhydride photochromic coating composition and photochromic articles
US6060001A (en) 1998-12-14 2000-05-09 Ppg Industries Ohio, Inc. Alkoxyacrylamide photochromic coatings compositions and photochromic articles
US6432544B1 (en) 1998-12-18 2002-08-13 Ppg Industries Ohio, Inc. Aminoplast resin photochromic coating composition and photochromic articles
US6506488B1 (en) 1998-12-18 2003-01-14 Ppg Industries Ohio, Inc. Aminoplast resin photochromic coating composition and photochromic articles
US6602603B2 (en) 1999-07-02 2003-08-05 Ppg Industries Ohio, Inc. Poly(meth)acrylic photochromic coating
US6150430A (en) 1999-07-06 2000-11-21 Transitions Optical, Inc. Process for adhering a photochromic coating to a polymeric substrate
US6296785B1 (en) 1999-09-17 2001-10-02 Ppg Industries Ohio, Inc. Indeno-fused photochromic naphthopyrans
US6531076B2 (en) 2000-02-04 2003-03-11 Ppg Industries Ohio, Inc. Photochromic organic resin composition
US6916537B2 (en) 2001-11-01 2005-07-12 Transitions Optical Inc. Articles having a photochromic polymeric coating
US20030165686A1 (en) 2001-12-27 2003-09-04 Blackburn William P. Photochromic optical article
US7410691B2 (en) 2001-12-27 2008-08-12 Ppg Industries Ohio, Inc. Photochromic optical article
US9028728B2 (en) 2005-04-08 2015-05-12 Transitions Optical, Inc. Photochromic materials that include indeno-fused naphthopyrans
US7527754B2 (en) 2005-12-21 2009-05-05 Transitions Optical, Inc. Photochromic indeno-fused naphthopyrans
US8748634B2 (en) 2006-10-30 2014-06-10 Transitions Optical, Inc. Photochromic materials demonstrating improved fade rates
US8608988B2 (en) 2010-11-23 2013-12-17 Transitions Optical, Inc. Curable photochromic compositions and optical articles prepared therefrom
US10954397B2 (en) 2015-08-17 2021-03-23 Transitions Optical, Inc. Curable photochromic compositions
US20210179931A1 (en) * 2017-03-01 2021-06-17 Younger Mfg. Co. Dba Younger Optics Optical articles comprising photochromic poly(urea-urethane)
WO2021129941A1 (fr) 2019-12-27 2021-07-01 Transitions Optical, Ltd. Composition photochromique durcissable comprenant un polymère segmenté

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
TOWNS ANDREW: "Naphthopyran Dyes", PHYSICAL SCIENCES REVIEWS, vol. 0, no. 0, 11 April 2020 (2020-04-11), DE, XP093063216, ISSN: 2365-6581, Retrieved from the Internet <URL:http://dx.doi.org/10.1515/psr-2019-0085> DOI: 10.1515/psr-2019-0085 *

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