Photochromic article comprising a photochromic layer and a UV-absorbing layer

Abstract

The present invention relates to a photochromic article comprising: (a) a substrate; (b) a photochromic layer on the substrate, the photochromic layer comprising a photochromic compound; and (c) a UV-absorbing layer on the photochromic layer, the UV-absorbing layer comprising a UV absorber. The photochromic layer has an absorbance in an unactivated state that exceeds zero over at least a portion of the wavelength range from 250 nm to 450 nm. The UV-absorbing layer has a terminal minimum absorbance wavelength value that is at least 45 nm less than the terminal minimum absorbance wavelength value of the photochromic layer in a first, unactivated state. The present invention also relates to ophthalmic articles, such as corrective lenses.

Description

[Technical Field]

[0001] The present invention relates to a photochromic article comprising: a substrate; a photochromic layer on the substrate comprising a photochromic compound; and an ultraviolet (UV) absorbing layer on the photochromic layer comprising a UV absorber, wherein the UV absorbing layer has a terminal minimum absorbance wavelength value that is at least 45 nm less than the terminal minimum absorbance wavelength value of a first, unactivated state of the photochromic layer. [Background technology]

[0002] For example, photochromic compounds and materials can be used in compositions to form layers such as films, such as photochromic coating layers, that are photochromic. In some cases, photochromic compositions are curable, and a cured photochromic layer, such as a cured photochromic coating layer, can be formed therefrom. Upon exposure of the photochromic layer to actinic radiation, such as sunlight, including ultraviolet (UV) light / radiation, the photochromic material of the photochromic layer typically and desirably transforms from an inactive (or bleached, e.g., substantially colorless) state to an activated (or colored) state. Upon cessation of exposure to actinic radiation, such photochromic compounds and materials are reversibly transformed from the activated (or colored) state back to the inactive (or bleached) state.

[0003] After prolonged and repeated exposure to actinic radiation, undesirable destabilization or fatigue of the photochromic material of the photochromic layer can occur. Destabilization and fatigue of the photochromic material can result in, for example, a decrease in the efficiency and magnitude of the color change of the photochromic material, a color shift of the activated photochromic material, and progressive discoloration, such as yellowing of the matrix of the photochromic layer. Typically, the decrease in the efficiency of the color change of the photochromic material occurs over a period of time known as the half-life (T 1 / 2 A decrease in the magnitude of the color change of a photochromic material is typically associated with a decrease in the change in optical density (ΔOD) value.

[0004] In an attempt to improve the stability and fatigue resistance of the photochromic layer, one or more UV absorbers can be included in the photochromic layer and / or in another layer thereon. The presence of a UV absorber in and / or on the photochromic layer is often associated with undesirable effects, such as undesirable weakening of the photochromic material. The weakening of the photochromic material is typically indicated by a decrease in the level or magnitude of the coloration of the photochromic material when fully activated. Summary of the Invention [Problem to be solved by the invention]

[0005] It would be desirable to develop photochromic articles that have improved stability and fatigue resistance of the photochromic materials contained therein. It is also desirable that such newly developed photochromic articles minimize weakening of the photochromic materials. [Means for solving the problem]

[0006] According to the present invention, there is provided a photochromic article comprising: (a) a substrate; (b) a photochromic layer comprising a photochromic material, the photochromic layer being overlaid on the substrate and having an absorbance in an unactivated state greater than zero over at least a portion of the wavelength range from 250 nm to 450 nm and a first unactivated state terminal minimum absorbance wavelength value; and (c) a UV absorbing layer comprising a UV absorber, the UV absorbing layer being overlaid on the photochromic layer and having a terminal minimum absorbance wavelength value at least 45 nm less than the terminal minimum absorbance wavelength value of the photochromic layer in the first unactivated state.

[0007] The features that characterize the present invention are pointed out with particularity in the claims annexed to and forming a part of this disclosure. These and other features of the invention, its operating advantages, and particular objectives attained by its uses will be more fully understood from the following detailed description, in which non-limiting embodiments of the invention are shown and described. [Brief explanation of the drawings]

[0008] [Figure 1] 1 is a representative cross-sectional side view of a photochromic article according to the present invention. [Figure 2] 1 is a graphical representation of absorbance versus wavelength plots obtained from photochromic test samples (Examples 1 and 2) and UV absorbing layer test samples (Examples BH) described in further detail in the Examples herein. DETAILED DESCRIPTION OF THE INVENTION

[0009] In Figures 1 and 2, like characters may refer to the same components and / or elements, unless otherwise specified.

[0010] As used herein, the articles "a," "an," and "the" include plural referents unless otherwise stated and are expressly limited to one referent.

[0011] Unless otherwise indicated, all ranges or ratios disclosed herein should be understood to include any and all values ​​and subranges or subratios subsumed therein. For example, a range or ratio specified as "1 to 10" should be deemed to include any and all values ​​therebetween, including the recited endpoints (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10); and subranges between a minimum value of 1 and a maximum value of 10 (inclusive), i.e., all subranges or subratios beginning with a minimum value of 1 or greater and ending with a maximum value of 10 or less, such as, but not limited to, 1 to 6.1, 3.5 to 7.8, and 5.5 to 10.

[0012] Unless otherwise indicated, as used herein, left-to-right designations of linking groups, such as divalent linking groups, include other suitable orientations, such as, but not limited to, right-to-left orientations. [ka] or the equivalent left-to-right representation of -C(O)O-, its right-to-left representation [ka] or the equivalents -O(O)C- or -OC(O)-.

[0013] Except where otherwise noted in the examples, all numbers expressing quantities of ingredients, reaction conditions, and the like used in the specification and claims should be understood to be rounded in all instances by the term "about."

[0014] As used herein, the term "polymer" refers to homopolymers (e.g., prepared from one monomeric species), copolymers (e.g., prepared from at least two monomeric species), and graft polymers.

[0015] As used herein, the term "(meth)acrylate" and similar terms such as "(meth)acrylic acid ester" refer to methacrylate and / or acrylate. As used herein, the term "(meth)acrylic acid" refers to methacrylic acid and / or acrylic acid.

[0016] As used herein, the term "photochromic" and similar terms such as "photochromic compound" refer to having an absorption spectrum of at least visible light that changes in response to the absorption of at least actinic radiation. Additionally, as used herein, the term "photochromic material" refers to any substance that is adapted to exhibit photochromic properties (e.g., adapted to have an absorption spectrum of at least visible light that changes in response to the absorption of at least actinic radiation) and that includes at least one photochromic compound.

[0017] As used herein, the term "actinic radiation" means electromagnetic radiation that can produce a response in a material, such as, but not limited to, the transformation of a photochromic material from one form or state to another, as discussed in more detail herein.

[0018] As used herein, the term "photochromic material" includes both thermally reversible and non-thermally reversible photochromic materials and compounds. As used herein, the term "thermally reversible photochromic compound / material" refers to a compound / material that can be transformed from a first state, e.g., a "transparent state," to a second state, e.g., a "colored state," in response to actinic radiation and can return to the first state in response to thermal energy. As used herein, the term "non-thermally reversible photochromic compound / material" refers to a compound / material that can be transformed from a first state, e.g., a "transparent state," to a second state, e.g., a "colored state," in response to actinic radiation and can return to the first state in response to actinic radiation of substantially the same wavelength(s) as the absorption(s) of the colored state.

[0019] As used herein, the terms "first" and "second" to modify the term "state" are not intended to imply any particular order or temporal sequence, but instead refer to two different conditions or properties. For non-limiting illustrative purposes, the first and second states of a photochromic compound can differ with respect to at least one optical property, such as, but not limited to, the absorption of visible light and / or UV radiation. Thus, according to various non-limiting embodiments disclosed herein, the photochromic compounds of the present invention can have different absorption spectra in each of the first and second states. For example, but not limited to, the photochromic compounds of the present invention can be clear in the first state and colored in the second state. Alternatively, the photochromic compounds of the present compositions can have a first color in the first state and a second color in the second state.

[0020] The first state (e.g., clear state or first color) of a photochromic compound / material (either thermoreversible or not) may also be referred to herein as the "unactivated state" of the photochromic compound / material. The second state (e.g., colored state or second color) of a photochromic compound / material (either thermoreversible or not) may also be referred to herein as the "activated state" of the photochromic compound / material.

[0021] As used herein, the term "optical" means pertaining to or relating to light and / or vision. For example, according to various non-limiting embodiments disclosed herein, optical articles or elements or devices can be selected from ophthalmic articles, elements, and devices, display articles, elements, and devices, windows, mirrors, and active and passive liquid crystal cell articles, elements, and devices.

[0022] As used herein, the term "ophthalmic" means pertaining to or relating to the eye and vision. Non-limiting examples of ophthalmic articles or elements include corrective and non-corrective lenses, such as single vision lenses or multivision lenses, which may be either segmented or non-segmented multivision lenses (such as, but not limited to, bifocal, trifocal, and progressive lenses), as well as other elements used to correct, protect, or enhance vision (cosmetic or otherwise), such as, but not limited to, contact lenses, intraocular lenses, magnifying glasses, and protective lenses or visors.

[0023] As used herein, the term "display" means a visible or machine-readable representation of information in words, numbers, symbols, designs, or graphics. Non-limiting examples of display elements include screens, monitors, and security elements such as security marks.

[0024] As used herein, the term "window" means an opening adapted to allow radiation to pass therethrough. Non-limiting examples of windows include automobile and aircraft transparencies, windshields, filters, shutters, and light switches.

[0025] As used herein, the term "mirror" means a surface that specularly reflects a large portion of incident light.

[0026] As used herein, the term "liquid crystal cell" means a structure containing a liquid crystal material that can be oriented. A non-limiting example of a liquid crystal cell element is a liquid crystal display.

[0027] As used herein, the term "unactivated state" with respect to a photochromic layer of a photochromic article means that the photochromic layer is in the "first state" described herein above (e.g., is transparent or has a first color).

[0028] As used herein, the term "terminal minimum absorbance wavelength value in the first unactivated state" refers to the wavelength at which a photochromic layer (including a photochromic material) in the unactivated state has a terminal (or upper) minimum absorbance. In some embodiments, the terminal minimum absorbance wavelength value in the first unactivated state of a photochromic layer corresponds to a wavelength above which the absorbance does not exceed 0.05 AU. This can be determined by determining the absorbance as a function of wavelength over a specified wavelength range using a Varian Cary 300 UV / VIS spectrophotometer (averaging time 0.100 s, data interval 1.100, and scan speed 600 nm / min) in the range of 550-250 nm, and evaluating the raw data to determine the minimum wavelength at which the absorbance is 0.05 or less.

[0029] As used herein, the term "terminal minimum absorbance wavelength value" with respect to a UV-absorbing layer refers to the wavelength value at which the UV-absorbing layer (including the UV absorber) has a terminal (or upper) minimum absorbance. In some embodiments, the terminal minimum absorbance wavelength value of a UV-absorbing layer corresponds to a wavelength above which the absorbance does not exceed 0.05 AU. This can be measured using the same method as for the terminal minimum absorbance wavelength value of the first, unactivated state described above.

[0030] As used herein, unless otherwise indicated, "percent transmittance" was determined by a spectrophotometer such as a Varian Cary 300 UV / VIS spectrophotometer or a ZEISS® Model MCS 601 spectrophotometer, as further described herein.

[0031] As used herein, spatial or directional terms such as "left," "right," "inside," "outside," "above," "below," etc., relate to various orientations of the present invention, which may be further described herein, such as articles of the present invention and multi-layer articles, etc. However, it should be understood that the present invention may contemplate various alternative orientations relative to those described herein, and therefore such terms should not be considered limiting.

[0032] As used herein, the terms "formed on," "deposited on," "provided on," "coated on," "on," or "disposed on" mean formed on, deposited on, provided on, applied to, being, or disposed on, but not necessarily in direct (or adjacent to) contact with, or the surface of, an underlying element. For example, a layer "disposed on" a substrate does not exclude the presence of one or more additional layers, coatings, or films of the same or different composition located between the disposed or formed layer and the substrate.

[0033] As used herein, "at least one" is synonymous with "one or more," regardless of whether the elements are listed conjunctively or disjunctively. For example, the phrases "at least one of A, B, or C" and "at least one of A, B, or C" mean any one of A, B, or C, or any combination of any two or more of A, B, or C, respectively. For example, A only; or B only; or C only; or A and B; or A and C; or B and C; or all of A, B, and C.

[0034] As used herein, "selected from" is synonymous with "chosen from," regardless of whether the elements are listed conjunctively or disjunctively. Furthermore, the phrases "selected from A, B, and C" and "selected from A, B, or C" mean any one of A, B, or C, or any combination of any two or more of A, B, or C, respectively. For example, A only; or B only; or C only; or A and B; or A and C; or B and C; or all of A, B, and C.

[0035] All documents mentioned herein, including but not limited to issued patents and patent applications, should be deemed to be "incorporated by reference" in their entirety unless otherwise indicated.

[0036] As used herein, the term "aliphatic group" and similar terms such as "aliphatic substituent" refer to a linear or branched aliphatic and / or cycloaliphatic group that is not aromatic and optionally contains at least one carbon-carbon unsaturated bond, e.g., at least one alkene bond (-C=C-) and / or at least one alkyne bond (-C≡C-). In some embodiments, linear or branched aliphatic groups herein contain 1 to 10 carbon atoms, and cycloaliphatic groups contain 3 to 10 carbon atoms.

[0037] As used herein, the recitation of a "straight chain or branched" group, such as straight chain or branched alkyl, includes a methylene group or a methyl group; a straight chain C-C 10 Straight-chain groups such as alkyl groups; and branched C3-C 10 It is understood herein to include suitably branched groups such as alkyl groups.

[0038] As used herein, the term "alkyl" refers to a C1-C2 alkyl group that is linear or branched, cyclic or acyclic. 10 A straight chain or branched alkyl is a C1-C 15 Alkyl, e.g., C1-C 10The alkyl group may include, but is not limited to, alkyl, such as C1-C5 alkyl, such as C2-C5 alkyl, such as C2-C4 alkyl. Examples of alkyl groups from which the various alkyl groups of the present invention can be selected include, but are not limited to, those further listed herein. The alkyl group may include a "cycloalkyl" group. As used herein, the term "cycloalkyl" refers to, but is not limited to, C3-C4 alkyl. 10 It refers to a group that is suitably cyclic, such as a cycloalkyl (for example, but not limited to, a cyclic C3-C8 alkyl, or a cyclic C5-C7 alkyl) group.

[0039] Representative alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, and decyl. Representative cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl.

[0040] As used herein, the term "aromatic group" and similar terms such as "aromatic substituent" or "aryl group" or "aryl substituent" refer to a group that is aromatic and can contain one ring or two or more fused rings. Each aromatic group can be unsubstituted or substituted with one or more substituents. Examples of substituents on substituted aromatic groups include, but are not limited to, aliphatic groups, aliphatic ether groups, and aliphatic carboxylic acid ester groups. Examples of aromatic groups include, but are not limited to, phenyl, naphthyl, anthracenyl, and phenanthrenyl.

[0041] As used herein, the recitation of "substituted" groups refers to groups including, but not limited to, alkyl, cycloalkyl, and / or aryl groups having at least one hydrogen replaced with a group or "substituent" other than hydrogen, i.e., substituted, such as, but not limited to: alkoxy groups; halo groups (e.g., F, Cl, I, and Br); hydroxyl groups; thiol groups; alkylthio groups; arylthio groups; ketone groups; aldehyde groups; carboxylic acid ester groups; carboxylic acid groups; phosphoric acid groups; phosphate ester groups; sulfonic acid groups; sulfonate ester groups; nitro groups; cyano groups; alkyl groups; alkenyl groups; alkynyl groups; haloalkyl groups; perhaloalkyl groups; heterocycloalkyl groups; aryl groups (e.g., alkaryl groups, e.g., hydroxyl-substituted aryl, e.g., phenol, e.g., multi-fused ring aryl); aralkyl groups; heteroaryl groups (e.g., multi-fused ring heteroaryl groups); amino groups, e.g., -N(R 11’ )(R 12’ ) (where R 11’ and R 12’ are each independently selected from, for example, hydrogen, alkyl, or aryl); a carboxylate group; a siloxane group; an alkoxysilane group; a polysiloxane group; an amide group; a urethane group; a carbonate group; a urea group; a trialkylsilyl group; a nitrogen-containing heterocycle; or a combination thereof.

[0042] For non-limiting illustrative purposes, and with reference to FIG. 1 , a photochromic article 2 according to the present invention is depicted. Photochromic article 2 includes a substrate 11 having a first surface 14 and a second surface 17, where first surface 14 and second surface 17 are opposite one another. First surface 14 of substrate 11 faces incident actinic radiation, indicated by arrow 20. Photochromic article 2 further includes a photochromic layer 23 on (e.g., adjacent to) substrate 11, particularly on (e.g., adjacent to) first surface 14 of substrate 11. Photochromic article 2 further includes a UV-absorbing layer 26 on (e.g., adjacent to) photochromic layer 23. Photochromic article 2, in some embodiments, optionally includes one or more additional layers, as further described herein.

[0043] According to the present invention, the terminal minimum absorbance wavelength value of the UV absorbing layer is at least 45 nm less than the terminal minimum absorbance wavelength value of the photochromic layer in the first, unactivated state.

[0044] In some embodiments of the present invention, the terminal minimum absorbance wavelength value of the UV absorbing layer is at least 50 nm less than the terminal minimum absorbance wavelength value of the photochromic layer in the first, unactivated state.

[0045] In some further embodiments of the present invention, the terminal minimum absorbance wavelength value of the UV absorbing layer is at least 55 nm less than the terminal minimum absorbance wavelength value of the first, unactivated state of the photochromic layer.

[0046] According to some further embodiments, the terminal minimum absorbance wavelength value of the UV absorbing layer is 45 nm to 80 nm less, or 50 nm to 80 nm less, or 55 nm to 80 nm less than the terminal minimum absorbance wavelength value of the photochromic layer in the first, unactivated state.

[0047] 2, for non-limiting illustration, the photochromic layer of Example 1 has a terminal minimum absorbance wavelength value 29 in the first, unactivated state of 422 nm. Still referring to FIG. 2, the UV-absorbing layer of Example B has a terminal minimum absorbance wavelength value 32 of 350 nm. Correspondingly, the terminal minimum absorbance wavelength value 32 of the UV-absorbing layer of Example B is 72 nm less than the terminal minimum absorbance wavelength value 29 in the first, unactivated state of the photochromic layer of Example 1.

[0048] The photochromic layer has an absorbance in the unactivated state that exceeds 0 over at least a portion of the wavelength range from 250 nm to 450 nm. The absorbance spectrum can be measured using a UV / VIS spectrophotometer such as those described previously herein.

[0049] In some embodiments, the terminal minimum absorbance wavelength value of the photochromic layer in the first, unactivated state is greater than 390 nm. In some further embodiments, the terminal minimum absorbance wavelength value of the photochromic layer in the first, unactivated state is greater than 410 nm. According to some embodiments, the terminal minimum absorbance wavelength value of the photochromic layer in the first, unactivated state is less than 450 nm. In some further embodiments, the terminal minimum absorbance wavelength value of the photochromic layer in the first, unactivated state is greater than 410 nm and less than 450 nm.

[0050] The photochromic material or compound of the photochromic layer can be selected from one or more art-recognized classes of photochromic materials or compounds. In some embodiments, the photochromic material of the photochromic layer is selected from at least one of naphthopyrans, benzopyrans, phenanthropyrans, indenonaphthopyrans, spiro(indoline)naphthoxazines, spiro(indoline)pyridobenzoxazines, spiro(benzindoline)pyridobenzoxazines, spiro(benzindoline)naphthoxazines, spiro(indoline)benzoxazines, fulgides, diarylethenes, and / or fulgimides. In some further embodiments, the photochromic material of the photochromic layer includes one or more indeno-naphthopyrans, such as one or more indeno[2',3':3,4]naphtho[1,2-b]pyrans having hydrogen and / or various substituents at the 3- and 5-13-positions.

[0051] Further examples of alternative photochromic materials and compounds that can be used in the photochromic layer of the present invention include, but are not limited to, those disclosed in U.S. Pat. No. 9,028,728 B2 at column 34, line 20 to column 35, line 13, the disclosure of which is specifically incorporated herein by reference.

[0052] The photochromic material can be present in the photochromic layer in any suitable amount, e.g., a photochromically effective amount, so long as the photochromic article has the desired level of photochromic properties. In some embodiments, the photochromic material is present in the photochromic layer in an amount of 0.001 to 40 weight percent, or 0.001 to 10 weight percent, or 0.01 to 5 weight percent, or 0.1 to 2.5 weight percent, where the weight percent in each case is based on the total solids weight of the photochromic layer. The photochromic material can be incorporated into the photochromic layer by art-recognized methods, including, but not limited to, imbibition and / or mixing with the components from which the photochromic layer is formed.

[0053] The UV absorbing layer has a terminal minimum absorbance wavelength value, in some embodiments, greater than 330 nm and less than 380 nm, or greater than 340 nm and less than 370 nm.

[0054] The UV absorbing layer can include any suitable UV absorber or combination of UV absorbers, provided that the terminal minimum absorbance wavelength value of the UV absorbing layer is at least 45 nm less than the terminal minimum absorbance wavelength value of the photochromic layer in the first, unactivated state. The UV absorber, in some embodiments, is present in the UV absorbing layer in an amount of 0.25 to 7 weight percent, or 0.50 to 6 weight percent, or 1 to 5 weight percent, where the weight percentage in each case is based on the total solids weight of the UV absorbing layer.

[0055] In some embodiments, the UV absorbing layer includes at least one of an unsubstituted oxanilide, a substituted oxanilide, a cinnamate, a salicylate, and / or a cyanoacrylate.

[0056] As used herein, the term "unsubstituted oxanilide" refers to N,N'-diphenyloxamide. As used herein, the term "substituted oxanilide" refers to N,N'-diphenyloxamide, one or both of whose phenyl rings have one or more substituents covalently attached thereto, including one or more of the substituents described herein above. In some embodiments, each substituent of a substituted oxanilide is independently: an aliphatic group, e.g., a linear or branched C-C alkyl group; 12 alkyl groups; cycloalkyl groups, such as C3-C7 cycloalkyl groups; and / or aliphatic ether groups, such as linear or branched C1-C 12 The alkyl group is selected from the group consisting of:

[0057] As used herein, the term "cinnamate" refers to an ester of cinnamic acid. Each cinnamate, in some embodiments, can be independently: an aliphatic ester of cinnamic acid, such as a linear or branched C-C ester of cinnamic acid. 12 alkyl esters; and aromatic esters of cinnamic acid, such as unsubstituted phenyl esters of cinnamic acid and substituted phenyl esters of cinnamic acid. Each substituent of the substituted phenyl esters of cinnamic acid is, in some embodiments, independently selected from the substituents described herein.

[0058] As used herein, the term "salicylate" refers to an ester of salicylic acid (or 2-hydroxybenzoic acid). Each salicylate, in some embodiments, can be independently: an aliphatic ester of salicylic acid, such as a linear or branched C1-C6 ester of salicylic acid. 12 and aromatic esters of salicylic acid, such as unsubstituted phenyl esters of salicylic acid and substituted phenyl esters of salicylic acid. Each substituent of the substituted phenyl esters of salicylic acid is, in some embodiments, independently selected from the substituents described herein.

[0059] As used herein, the term "cyanoacrylate" refers to an ester of cyanoacrylic acid. Each cyanoacrylate, in some embodiments, can be independently: an aliphatic ester of cyanoacrylic acid, such as a linear or branched C-C ester of cyanoacrylic acid. 12 alkyl esters; and aromatic esters of cyanoacrylic acid, such as unsubstituted phenyl esters of cyanoacrylic acid and substituted phenyl esters of cyanoacrylic acid. Each substituent of the substituted phenyl esters of cyanoacrylic acid, in some embodiments, is independently selected from the substituents described above. The 3,3-substituents of the cyanoacrylate, in some embodiments, are each independently selected from: hydrogen (—H); aliphatic groups, such as linear or branched alkyl groups and optionally substituted cycloalkyl groups; and optionally substituted aryl groups, such as optionally substituted phenyl (wherein each substituent of the substituted cycloalkyl and substituted aryl groups is independently selected from the substituents described above). According to some embodiments, a non-limiting example of a cyanoacrylate is 2-ethylhexyl 2-cyano-3,3-diphenylacrylate (also known as octocrylene).

[0060] According to some embodiments, the UV absorbing layer comprises one or more substituted oxanilides. According to some further embodiments, the UV absorbing layer comprises at least one of N-(2-ethoxyphenyl)-N'-(4-(10-methylundecyl)phenyl)oxalamide and / or N-(2-ethoxyphenyl)-N'-(4-ethylphenyl)oxalamide.

[0061] In some embodiments, the photochromic article of the present invention can optionally include one or more additional layers, such as, but not limited to, a primer layer, a topcoat layer, an antireflective layer, a hardcoat layer, a polarizing layer, and an alignment layer. Types and examples of such additional optional layers are described in U.S. Pat. No. 8,828,284 B2, column 20, line 30 to column 21, line 38, the disclosure of which is incorporated herein by reference.

[0062] In some embodiments of the present invention, the photochromic layer, UV absorber layer, and one or more additional optional layers of the photochromic article can each optionally independently comprise at least one additive, provided that the terminal minimum absorbance wavelength value of the UV absorbing layer is at least 45 nm less than the terminal minimum absorbance wavelength value of the photochromic layer in its first, unactivated state. In some embodiments, each additive is independently selected from static dyes, alignment promoters, speed enhancing additives, photoinitiators, thermal initiators, polymerization inhibitors, solvents, light stabilizers, heat stabilizers, mold release agents, rheology control agents, leveling agents, free radical scavengers, adhesion promoters, blue light blocking agents, or combinations of two or more thereof. Examples and types of blue light blocking (or filtering) agents include, but are not limited to, those described in U.S. Pat. No. 9,683,102 B2 and U.S. Patent Application Publication No. 2015 / 0234208 A1, the relevant portions of which are incorporated herein by reference.

[0063] In some embodiments, the photochromic layer, the UV-absorbing layer, and any additional optional layers disposed on the substrate of the photochromic article of the present invention each independently comprise an organic matrix, which may be a cured (or crosslinked) organic matrix, such as an organic polymer matrix, a thermoplastic organic matrix, or a combination thereof. Correspondingly, each layer (including the photochromic layer and the UV-absorbing layer) of the photochromic article of the present invention can each independently be selected from a cured (or crosslinked) layer and a thermoplastic layer. The organic matrix of each layer of the photochromic article of the present invention can each independently comprise bonds such as, but not limited to, ether bonds; carboxylic acid ester bonds; urethane bonds; amide bonds; urea bonds; carbonate bonds; bonds formed by radical polymerization of radically polymerizable ethylenically unsaturated groups, such as, but not limited to, vinyl groups, allyl groups, and / or (meth)acrylate groups; and combinations of two or more thereof.

[0064] Each layer of the photochromic article of the present invention (including the photochromic layer and the UV-absorbing layer) can be formed by art-recognized methods, such as, but not limited to, lamination and coating methods. Coating methods include, but are not limited to, spray coating, spin coating, curtain coating, dip coating, micro-jet coating (such as inkjet coating), in-mold coating, and combinations thereof. Lamination methods include, but are not limited to, extrusion lamination (e.g., directly onto a substrate), in-mold lamination (a laminate placed in a mold and a substrate formed therein), thermal lamination (a laminate heat-sealed onto a substrate), adhesive lamination (a laminate bonded to a substrate via an intervening adhesive layer), and combinations thereof.

[0065] In some embodiments, the substrate of the photochromic article may be composed of one or more suitable materials, such as, but not limited to, organic materials, such as organic polymeric materials (e.g., crosslinked organic polymeric materials and / or thermoplastic organic polymeric materials), including, but not limited to, thermoplastic polycarbonates, crosslinked polycarbonates, poly(meth)acrylates, and combinations thereof; glass, such as silica-based glass; metals; ceramic materials; and combinations of two or more thereof. Examples of substrates that can be included in the photochromic articles of the present invention include, but are not limited to, those described in U.S. Pat. No. 8,628,685 B2, column 35, line 5 to column 36, line 57, the disclosure of which is incorporated herein by reference.

[0066] In some embodiments, the photochromic article is selected from an ophthalmic article, a display article, a window, a mirror, an active liquid crystal cell article, and a passive liquid crystal cell article.

[0067] In some further embodiments, the photochromic article is selected from an ophthalmic article, and the ophthalmic article is selected from a corrective lens, a non-corrective lens, a contact lens, an intraocular lens, a magnifying glass, a protective lens, and a visor.

[0068] In some further embodiments, the photochromic article is selected from a display article, and the display article is selected from a screen, a monitor, and a security element.

[0069] The present invention may be further customized by one or more of the following non-limiting provisions.

[0070] Clause 1: A photochromic article comprising: (a) a substrate; (b) a photochromic layer comprising a photochromic material overlying the substrate, the photochromic layer having an unactivated state absorbance greater than 0 (or in some embodiments greater than 0.05) over at least a portion of the wavelength range from 250 nm to 450 nm, and a first unactivated state terminal minimum absorbance wavelength value; (c) a UV absorbing layer comprising a UV absorber, the UV absorbing layer overlying the photochromic layer and having a terminal minimum absorbance wavelength value; Including, A photochromic article, wherein the UV absorbing layer has a terminal minimum absorbance wavelength value that is at least 45 nm less than the terminal minimum absorbance wavelength value of the photochromic layer in the first, unactivated state.

[0071] Clause 2: The photochromic article of clause 1, wherein the UV absorbing layer has a terminal minimum absorbance wavelength value that is at least 50 nm less than the terminal minimum absorbance wavelength value of the photochromic layer in the first, unactivated state.

[0072] Clause 3: The photochromic article of clause 1 or clause 2, wherein the terminal minimum absorbance wavelength value of the UV absorbing layer is at least 55 nm less than the terminal minimum absorbance wavelength value of the photochromic layer in the first, unactivated state.

[0073] Clause 4: The photochromic article of any one of clauses 1 to 3, wherein the terminal minimum absorbance wavelength value of the UV absorbing layer is at least 60 nm less than the terminal minimum absorbance wavelength value of the photochromic layer in the first, unactivated state.

[0074] Clause 5: The photochromic article of any one of clauses 1 to 4, wherein the terminal minimum absorbance wavelength value of the UV absorbing layer is 45 nm to 80 nm less, or 45 nm to 75 nm less, or 45 nm to 70 nm less, or 45 nm to 65 nm less, or 45 nm to 60 nm less, or 45 nm to 55 nm less, or 45 nm to 50 nm less than the terminal minimum absorbance wavelength value of the photochromic layer in the first, unactivated state.

[0075] Clause 6: The photochromic article of any one of clauses 1 to 5, wherein the terminal minimum absorbance wavelength value of the photochromic layer in the first, unactivated state is greater than 410 nm and less than or equal to 450 nm.

[0076] Clause 7: The photochromic article of any one of clauses 1 to 6, wherein the UV absorbing layer has a terminal minimum absorbance wavelength value greater than 330 nm and less than 380 nm.

[0077] Clause 8: The photochromic article of any one of clauses 1-7, wherein the UV absorbing layer comprises at least one of an unsubstituted oxanilide, a substituted oxanilide, a cinnamate, a salicylate, or a cyanoacrylate.

[0078] Clause 9: The photochromic article of any one of clauses 1 to 8, wherein the UV absorbing layer comprises at least one substituted oxanilide, each substituted oxanilide independently selected from N-(2-ethoxyphenyl)-N'-(4-(10-methylundecyl)phenyl)oxalamide and N-(2-ethoxyphenyl)-N'-(4-ethylphenyl)oxalamide.

[0079] Clause 10: The photochromic article of any one of clauses 1 to 9, wherein the photochromic material of the photochromic layer comprises at least one of naphthopyrans, benzopyrans, phenanthropyrans, indenonaphthopyrans, spiro(indoline)naphthoxazines, spiro(indoline)pyridobenzoxazines, spiro(benzindoline)pyridobenzoxazines, spiro(benzindoline)naphthoxazines, spiro(indoline)-benzoxazines, fulgides, diarylethenes, and / or fulgimides.

[0080] Clause 11: The photochromic article of any one of clauses 1 to 10, wherein the photochromic article is selected from the group consisting of an ophthalmic article, a display article, a window, a mirror, an active liquid crystal cell article, and a passive liquid crystal cell article.

[0081] Clause 12: The photochromic article of any one of clauses 1 to 11, wherein the photochromic article is selected from an ophthalmic article, the ophthalmic article being selected from the group consisting of corrective lenses, non-corrective lenses, contact lenses, intraocular lenses, magnifying glasses, protective lenses, and visors.

[0082] Clause 13: The photochromic article of any one of clauses 1 to 12, wherein the photochromic article is selected from a display article, the display article being selected from the group consisting of a screen, a monitor, and a security element.

[0083] The present invention is more particularly described in the following examples, which are intended to be illustrative only, since numerous modifications and variations of the examples will be apparent to those skilled in the art. Unless otherwise specified, all parts and percentages are by weight. [Example]

[0084] Part 1 of the following examples describes the preparation of a curable photochromic composition. Part 2 describes the preparation of a composition from which a UV absorber layer is formed. Part 3 describes a method for determining the terminal minimum absorbance wavelength value. Part 4 describes the preparation of a photochromic article test specimen. Part 5 describes the procedure used to test the photochromic article test specimen. Part 6 describes a procedure for determining photochromic fatigue.

[0085] Part 1 - Preparation of the curable photochromic composition A curable photochromic composition was prepared according to the procedure described in Example 8 of US Pat. No. 10,954,397 B2.

[0086] Example 1 contains a mixture of five indeno-fused naphthopyran dyes formulated to produce a gray color upon activation.

[0087] Example 2 contains a mixture of two indeno-fused naphthopyran dyes formulated to give a gray color upon activation.

[0088] Part 2 - Formation of UV absorbing layer The UV absorbing layer was formed according to the following instructions.

[0089] In the first step, a stock solution (Control Solution A) was prepared by mixing the ingredients listed in Table 1 in an appropriate amber glass bottle equipped with a magnetic stir bar. This solution was stirred at 25°C for 2 hours.

[0090] [Table 1]

[0091] In each case, 5.0 g of Control Solution A was introduced into seven separate 20 mL amber glass vials equipped with stir bars. UV absorber was then added to each vial in the amount (in grams) listed in Table 2 and stirred thoroughly.

[0092] [Table 2]

[0093] Part 3 - Determination of terminal minimum absorbance wavelength value. Substrate preparation: Pre-conditioned substrates were prepared using the following procedure. CR-39 poly(allyl diglycol carbonate) substrates (treated without UV absorbers) measuring 2 x 2 inches (5.1 x 5.1 cm) were obtained from Piedmont Plastics. Each substrate was cleaned by wiping with an isopropanol-soaked tissue, dried using an airflow, and then corona-treated by passing it on a conveyor belt through a Tantec EST Systems Serial No. 020270 Power Generator HV 2000 Series corona treatment unit with a high-voltage transformer. While moving on the conveyor at a belt speed of 3 feet / minute (0.91 meters / minute), the substrates were exposed to a corona generated at 70.00 KV and 1000 watts.

[0094] The photochromic coating compositions of Examples 1 and 2 were applied separately to the pre-conditioned substrates by dispensing approximately 1.5 mL of the photochromic coating composition onto the surface of each pre-conditioned substrate and then spinning the substrate at 1050 revolutions per minute (rpm) for 8 seconds. The photochromic-coated substrates were placed in a forced air oven maintained at 125°C for 60 minutes to form photochromic layer test samples.

[0095] Control solution A and the UV absorbing compositions of Examples A-H were each separately spin-coated onto the pre-conditioned substrate at 700 revolutions per minute (rpm) for 2 seconds, followed by 1900 rpm for 2 seconds. The UV absorber-coated substrate was moved on a conveyor belt at a speed of 6 feet per minute while being heated under four ultraviolet lamps at 1.50 W / cm in a UV Curing Oven Machine designed and manufactured by Belcan Engineering. 2 UVA peak intensity of 4.5-5.0J / cm 2 The UV absorber coated test samples were then placed in a forced air oven at 105°C for 3 hours to form the Control Solution A test sample and the UV absorbing layer test sample.

[0096] The photochromic layer test samples, Control Solution A test samples, and UV-absorbing layer test samples were each analyzed using a Varian Cary 300 UV / VIS spectrophotometer in the 550-250 nm range (averaging time 0.100 s, data interval 1.100, and scan speed 600 nm / min). The photochromic layer test samples were scanned and analyzed directly. Scans of each UV-absorbing layer test sample were performed after forming a baseline scan of a test specimen prepared using Control Solution A alone (no UV absorber added), followed by zeroing each sample. The raw data used to generate the absorbance vs. wavelength graph shown in Figure 1 were also used to determine the terminal minimum absorbance wavelength value (TMAW value) for each layer. The shortest (minimum) wavelength with an absorbance (AU) of less than 0.0500 was identified as the terminal minimum absorbance wavelength value for the corresponding layer, and each is reported in Table 3.

[0097] [Table 3]

[0098] Part 4 - Procedure used to prepare the photochromic article. Preparation of substrate. Polycarbonate plano lenses (6 base; 76 mm diameter) were obtained from Gentex Optical. Each substrate was cleaned by wiping with an isopropanol-soaked tissue, dried using an airflow, and then corona-treated under the conditions described above in Part 3 to form a pre-conditioned lens.

[0099] The curable photochromic coating compositions of each of Examples 1 and 2 were applied to the pre-conditioned lenses by dispensing approximately 1.5 mL of the curable photochromic coating composition onto the surface of each pre-conditioned lens, followed by spinning at 1050 revolutions per minute (rpm) for 8 seconds (repeated twice for the examples shown in Table 4). The photochromically-coated pre-conditioned lenses were placed in a forced air oven maintained at 125°C for 60 minutes. After the photochromically-coated lenses were cooled to room temperature, Control Solution A and solutions of the UV absorber coating compositions of Examples B-H were spin-coated onto the cured photochromic coating layers formed from Examples 1 and 2 at 700 revolutions per minute (rpm) for 2 seconds, followed by 1900 rpm for 2 seconds. The coated substrates were then rotated on a conveyor belt at a speed of 6 feet per minute while being heated under four ultraviolet lamps at 1.50 W / cm in a UV Curing Oven Machine designed and manufactured by Belcan Engineering. 2 UVA peak intensity of 4.5-5.0J / cm 2 The coated samples were then placed in a forced air oven at 105°C for 3 hours to form photochromic article test samples.

[0100] [Table 4]

[0101] Part 5 - Test procedures for the performance of photochromic article test specimens. Photochromic performance of the photochromic article test samples, each replicated twice and summarized in Table 4, was evaluated using the Photochromic Performance Test on the Advanced Bench for Measuring Photochromics ("A-BMP") optical bench, which was maintained at a constant temperature of 23°C for each sample.

[0102] Prior to testing on the optical bench, each photochromic article test sample was exposed to 365 nanometer ultraviolet light for approximately 10 minutes at a distance of approximately 14 centimeters to activate the photochromic material. The UVA (315-380 nm) irradiance at the photochromic article test sample was measured using a Goosch & Hausgo OL 756 spectroradiometer with an OL 86-T cosine receptor and found to be 22.2 watts per square meter. The photochromic article test sample was then placed under a 500-watt high-intensity halogen lamp at a distance of approximately 36 centimeters for approximately 10 minutes to bleach (inactivate) the photochromic material. The illuminance at the photochromic article test sample was measured using the OL 756 spectroradiometer and found to be 21.9 Klux. The photochromic article test sample was then maintained in a dark environment at room temperature (21°C-24°C) for at least one hour before testing on the optical bench. Prior to the optical bench measurement, the ultraviolet absorbance at 390 nanometers of the photochromic article test samples was measured.

[0103] Two 150-watt ORIEL® Model #66057 xenon arc lamps were mounted at right angles to each other on an A-BMP optical bench. The light path from Lamp 1 was directed through a 3 mm SCHOTT KG-2 bandpass filter and appropriate neutral density filters to contribute the required UV and partial visible irradiance levels. The light path from Lamp 2 was directed through a 3 mm SCHOTT KG-2 bandpass filter, a SCHOTT GG400 shortwave cutoff filter, and appropriate neutral density filters to provide supplemental visible irradiance. A 2-inch x 2-inch (5.1 cm x 5.1 cm) 50% polka dot beamsplitter was used at 45° to each lamp to mix the two beams. Irradiance was adjusted using a combination of neutral density filters and the voltage control of the xenon arc lamps. Proprietary software, i.e., PTSoft version 6.7, was used for the A-BMP to control timing, irradiance, air cell and sample temperature, shutter operation, filter selection, and response measurements. A ZEISS® Model MCS 601 spectrophotometer with a fiber optic cable for light delivery through the lens was used for response and color measurements. Photopic response measurements were collected for each photochromic article test sample.

[0104] The output of the optical bench, i.e., the light dose to which the photochromic article test specimens were exposed, was adjusted to 6.7 watts per square meter (W / m²) of UVA light integrated from 315 to 380 nm and 50 Klux irradiance integrated from 380 to 780 nm. Measurement of this output setpoint was performed using an irradiance probe and a calibrated Zeiss spectrophotometer. The lens sample cell was fitted with a quartz window and a self-centering sample holder. The temperature within the sample cell was controlled via software using an AirJet XE spectrophotometer specifically connected to a bubbling water bath to deliver 50% RH air maintained at the desired temperature. Measurements of the dynamic photochromic response and color of the photochromic article test specimens were performed using the same Zeiss spectrophotometer with a fiber optic cable to deliver light from a tungsten halogen lamp to the test specimens. The collimated monitoring light beam from the fiber optic cable was passed through the photochromic article test sample while being maintained perpendicular to the test sample and directed to a receiving fiber optic cable assembly attached to the spectrophotometer. The photochromic article test sample was placed in the sample cell at the exact location 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 location was 30° from normal.

[0105] Response measurements of the change in optical density (ΔOD) from the unactivated or bleached state to the activated or colored state were made by establishing an initial unactivated transmittance, opening the shutter from the xenon lamp, and measuring the transmittance through activation at selected time intervals. The change in optical density was determined by the formula: ΔOD = log(10)(%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 made based on photopic optical density.

[0106] The ΔOD at saturation was recorded after 15 min of activation at 23°C. 1 / 2The "T" value is the time interval, in seconds, for the ΔOD of the activated form of the photochromic material in the coating layer, after removal of the activating light source, to reach half of the ΔOD recorded after 15 minutes of activation at 23°C as described above. The T fade time intervals, in seconds, were then calculated using the same method as described above, using ΔODs of 3 / 4 ΔOD (second T), 7 / 8 ΔOD (third T), and 15 / 16 ΔOD (fourth T), etc., to determine the time intervals, in seconds, for the photochromic article test sample to fade to its respective ΔOD after 15 minutes of activation at 23°C as described above, after removal of the activating light source. The time to T70%T was determined by recording the fade of the photochromic article test sample to 70% photopic %T in minutes after removal of the activating light source at the end of 15 minutes of activation at 23°C.

[0107] Performance data for photochromic article test samples including a photochromic layer formed from the curable photochromic composition of Example 1 are shown in Table 5. Performance data for photochromic article test samples including a photochromic layer formed from the curable photochromic composition of Example 2 are shown in Table 6.

[0108] [Table 5]

[0109] [Table 6]

[0110] Part 6 - Test procedure for determining photochromic fatigue The photochromic article test samples used in the performance testing in Part 5 above, and their respective replicates, were evaluated for fatigue according to the following procedure (data for each sample set were averaged).

[0111] An Atlas Ci5000 Weather-Ometer was used to conduct simulated solar radiation accelerated exposure (i.e., fatigue). Photochromic article test specimens were exposed to a 1-hour dark cycle followed by a 65-hour light cycle using a boro / borosilicate-filtered xenon arc lamp with an output of 0.25 watts per square meter at 340 nm. The temperature inside the Atlas Ci4000 Weather-Ometer during the light cycle was maintained at 45°C, and the relative humidity was controlled at 70% humidity. A thermometer was connected, and the temperature of the black panel representing the test specimen was maintained at 55°C. The photochromic article test specimens were then subjected to this accelerated exposure procedure a second time.

[0112] After the photochromic article test samples were subjected to this second UV exposure fatigue cycle, they were preconditioned and measured on an optical bench under the same conditions as described in the initial test to determine the final photopic response (ΔOD final The difference between the ΔOD of the photochromic article test sample before and after the accelerated exposure was measured, and % Fatigue = (ΔOD initial -ΔOD final ) / ΔOD initial The percent fatigue was calculated using the formula: Δb × 100. * The value was also calculated. * Values ​​are measurements on a Hunter UltraScan Pro unit before exposure in an Atlas Ci4000 Weather-Ometer. * initial Measurement of the bleaching state of the lenses after 65 hours of this UV exposure fatigue cycle. * final The bleached state b is calculated by subtracting the value * The measured difference in the values ​​was Δb * The values ​​represent the amount of yellowing of the lens that occurred during fatigue.

[0113] Fatigue data for photochromic article test specimens including a photochromic layer formed from the curable composition of Example 1 is summarized in Table 7. Fatigue data for photochromic article test specimens including a photochromic layer formed from the curable composition of Example 2 is summarized in Table 8.

[0114] [Table 7]

[0115] [Table 8]

[0116] Referring to the data summarized in Tables 5 and 6, Examples B through D, in which the difference in terminal minimum absorbance wavelength between the photochromic layer and the overlying UV-absorbing layer was 45 nm or greater, had activated optical density ΔOD values ​​equal to or greater than those of Control Examples 1-A or 2-A (without a UV-absorber layer). Comparative examples with a terminal minimum absorbance wavelength difference (relative to the photochromic layer) of less than 45 nm were confirmed to exhibit weakened (decreased) optical density in the activated state. Furthermore, the presence of a UV-absorber layer with a terminal minimum absorbance wavelength difference (relative to the photochromic layer) of 45 nm or greater was found to maintain or improve late-stage fading (as best evidenced by the fourth T1 / 2 measurement); whereas, UV-absorber layers with a terminal minimum absorbance wavelength difference (relative to the photochromic layer) of 45 nm exhibited slower fading rates. Furthermore, Tables 7 and 8 show that when compared to the control (no UV absorber layer), each UV absorbing layer provides equivalent or improved fatigue as evidenced by less yellowing after exposure and an equivalent or lesser loss in optical density after exposure. Thus, the presence of a UV absorbing layer with a terminal minimum absorbance wavelength value difference (relative to the photochromic layer) of at least 45 nm provides stability without sacrificing darkness or fade rate.

[0117] The present invention has been described with reference to specific details of particular embodiments thereof. It is not intended that such details be deemed to limit the scope of the invention except to the extent and to the extent that they are included in the appended claims.

Claims

1. 1. A photochromic article comprising: (a) a substrate; (b) a photochromic layer comprising a photochromic material overlying the substrate, the photochromic layer having an unactivated state absorbance greater than 0 over at least a portion of the wavelength range from 250 nm to 450 nm and a first unactivated state terminal minimum absorbance wavelength value; (c) a UV absorbing layer comprising a UV absorber, the UV absorbing layer overlying the photochromic layer and having a terminal minimum absorbance wavelength value; Including, a terminal minimum absorbance wavelength value of said UV absorbing layer that is at least 45 nm less than a terminal minimum absorbance wavelength value of said photochromic layer in said first, unactivated state;

2. 10. The photochromic article of claim 1, wherein the terminal minimum absorbance wavelength value of the UV absorbing layer is at least 50 nm less than the terminal minimum absorbance wavelength value of the first, unactivated state of the photochromic layer.

3. 10. The photochromic article of claim 1, wherein the terminal minimum absorbance wavelength value of the UV absorbing layer is at least 55 nm less than the terminal minimum absorbance wavelength value of the first, unactivated state of the photochromic layer.

4. 10. The photochromic article of claim 1, wherein the first, unactivated state of the photochromic layer has a terminal minimum absorbance wavelength value greater than 410 nm.

5. 5. The photochromic article of claim 4, wherein the terminal minimum absorbance wavelength value of the UV absorbing layer is greater than 330 nm and less than 380 nm.

6. 10. The photochromic article of claim 1, wherein the UV absorbing layer comprises at least one of an unsubstituted oxanilide, a substituted oxanilide, a cinnamate, a salicylate, or a cyanoacrylate.

7. 7. The photochromic article of claim 6, wherein the substituted oxanilide comprises at least one of N-(2-ethoxyphenyl)-N'-(4-(10-methylundecyl)phenyl)oxalamide, or N-(2-ethoxyphenyl)-N'-(4-ethylphenyl)oxalamide.

8. 10. The photochromic article of claim 1, wherein the photochromic material of the photochromic layer comprises at least one of naphthopyrans, benzopyrans, phenanthropyrans, indenonaphthopyrans, spiro(indoline)naphthoxazines, spiro(indoline)pyridobenzoxazines, spiro(benzindoline)pyridobenzoxazines, spiro(benzindoline)naphthoxazines, spiro(indoline)-benzoxazines, fulgides, diarylethenes, or fulgimides.

9. 10. The photochromic article of claim 1, wherein the photochromic article is selected from the group consisting of an ophthalmic article, a display article, a window, a mirror, an active liquid crystal cell article, and a passive liquid crystal cell article.

10. 10. The photochromic article of claim 9, wherein the photochromic article is selected from an ophthalmic article, the ophthalmic article being selected from the group consisting of corrective lenses, non-corrective lenses, contact lenses, intraocular lenses, magnifying glasses, protective lenses, and visors.

11. 10. The photochromic article of claim 9, wherein the photochromic article is selected from a display article, the display article being selected from the group consisting of a screen, a monitor, and a security element.

Images