Photochromic article including a photochromic layer and a UV absorbing layer

Abstract

The present invention relates to a photochromic article that includes: (a) a substrate; (b) a photochromic layer that includes a photochromic compound over the substrate; and (c) a UV absorbing layer that includes a UV absorber over the photochromic layer. The photochromic layer has an unactivated state absorbance of greater than 0 over at least a portion of wavelengths of 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 a first unactivated state terminal minimum absorbance wavelength value of the photochromic layer. The present invention also relates to ophthalmic articles such as corrective lenses.

Description

PHOTOCHROMIC ARTICLE INCLUDING A PHOTOCHROMIC LAYER AND A UV ABSORBING LAYERFIELD

[0001] The present invention relates to photochromic articles, which include: a substrate; a photochromic layer that includes a photochromic compound over the substrate; and an ultraviolet (UV) absorbing layer that includes a UV absorber over the photochromic layer, in which the UV absorbing layer has a terminal minimum absorbance wavelength value that is at least 45 nm less than a first unactivated state terminal minimum absorbance wavelength value of the photochromic layer.BACKGROUND

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

[0003] After prolonged and repeated exposure to actinic radiation, the photochromic material of the photochromic layer can become undesirably destabilized or fatigued. Destabilization and fatigue of the photochromic material can result in, for example, reduced efficiency and magnitude of color change of the photochromic material, color shifts of the activated photochromic material, and the development of discoloration, such as yellowing, of the matrix of the photochromic layer. Typically, reduced efficiency of color change of a photochromic material is associated with increased half-life (T1 / 2) values. Reduced magnitude of color change of the photochromic material is typically associated with reduced change in optical density (AOD) values.

[0004] In an attempt to improve the stability and fatigue resistance of a photochromic layer, one or more UV absorbers can be included in the photochromic layer and / or in a separate layer thereover. The presence of UV absorbers within and / or over a photochromic layer, often have associated therewith undesirable effects, such as undesirable attenuation of the photochromic material thereof. Attenuation of a photochromic material is typically evidenced by a reduced level or magnitude of color development of the photochromic material when fully activated.

[0005] It would be desirable to develop photochromic articles that have improved stability and fatigue resistance of the photochromic materials thereof. It would also be desirable that such newly developed photochromic articles have minimal attenuation of the photochromic materials thereof.SUMMARY

[0006] In accordance with the present invention, there is provided a photochromic article comprising: (a) a substrate; (b) a photochromic layer comprising a photochromic material, where the photochromic layer is superposed over the substrate, the photochromic layer having an unactivated state absorbance of greater than 0 over at least a portion of wavelengths of 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, said UV absorbing layer being superposed over said photochromic layer, said UV absorbing layer having a terminal minimum absorbance wavelength value. The terminal minimum absorbance wavelength value of said UV absorbing layer is at least 45 nm less than said first unactivated state terminal minimum absorbance wavelength value of said photochromic layer.

[0007] The features that characterize the present invention are pointed out with particularity in the claims, which are annexed to and form a part of this disclosure. These and other features of the invention, its operating advantages and the specific objects obtained by its use will be more fully understood from the following detailed description in which non-limiting embodiments of the invention are illustrated and described.BRIEF DESCRIPTION OF THE DRAWINGS

[0008] FIG. 1 is representative side elevation sectional view of a photochromic article according to the present invention; and

[0009] FIG. 2 is a graphical representation of plots of absorbance vs. wavelength obtained from photochromic layer test samples (Examples 1 and 2) and UV absorbing layer test samples (Examples B-H) as described in further detail in the Examples herein.

[0010] In FIG’s 1 and 2 like characters refer to the same components and / or elements, as the case may be, unless otherwise stated.DETAILED DESCRIPTION[OH] As used herein, the articles "a," "an," and "the" include plural referents unless otherwise expressly and unequivocally limited to one referent.

[0012] Unless otherwise indicated, all ranges or ratios disclosed herein are to be understood to encompass any and all values, and subranges or subratios subsumed therein. For example, a stated range or ratio of "1 to 10" should be considered to include: any and all values therebetween, including the stated terminal values (such as 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10); and subranges between (and inclusive of) the minimum value of 1 and the maximum value of 10, that is, all subranges or subratios beginning with a minimum value of 1 or more 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.

[0013] As used herein, unless otherwise indicated, left-to-right representations of linking groups, such as divalent linking groups, are inclusive of other appropriate orientations, such as, but not limited to, right-to-left orientations. For purposes of non-limiting illustration, the left-to-Oright representation of the divalent linking grouporequivalently -C(O)O-, is Oinclusive of the right-to-left representation thereof,, or equivalently -O(O)C- or -OC(O)-.

[0014] Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as modified in all instances by the term “about.”

[0015] As used herein, the term “polymer” means homopolymers (e.g., prepared from a single monomer species), copolymers (e.g., prepared from at least two monomer species), and graft polymers.

[0016] As used herein, the term “(meth)acrylate” and similar terms, such as “(meth)acrylic acid ester” means methacrylates and / or acrylates. As used herein, the term “(meth)acrylic acid” means methacrylic acid and / or acrylic acid.

[0017] As used herein, the term “photochromic” and similar terms, such as “photochromic compound” means having an absorption spectrum for at least visible radiation that varies in response to absorption of at least actinic radiation. Further, as used herein the term “photochromic material” means any substance that is adapted to display photochromic properties (such as, adapted to have an absorption spectrum for at least visible radiation that varies in response to absorption of at least actinic radiation) and which includes at least one photochromic compound.

[0018] As used herein, the term “actinic radiation” means electromagnetic radiation that is capable of causing a response in a material, such as, but not limited to, transforming a photochromic material from one form or state to another as will be discussed in further detail herein.

[0019] As used herein, the term “photochromic material” includes thermally reversible photochromic materials and compounds and non-thermally reversible photochromic materials and compounds. The term “thermally reversible photochromic compounds / materials” as used herein means compounds / materials capable of converting from a first state, for example a “clear state,” to a second state, for example a “colored state,” in response to actinic radiation, and reverting back to the first state in response to thermal energy. The term “non-thermally reversible photochromic compounds / materials” as used herein means compounds / materials capable of converting from a first state, for example a “clear state,” to a second state, for example a “colored state,” in response to actinic radiation, and reverting back to the first state inresponse to actinic radiation of substantially the same wavelength(s) as the absorption(s) of the colored state.

[0020] As used herein to modify the term “state,” the terms “first” and “second” are not intended to refer to any particular order or chronology, but instead refer to two different conditions or properties. For purposes of non -limiting illustration, the first state and the second state of a photochromic compound can differ with respect to at least one optical property, such as but not limited to the absorption of visible and / or UV radiation. Thus, according to various non-limiting embodiments disclosed herein, the photochromic compounds of the present invention can have a different absorption spectrum in each of the first and second states. For example, while not limiting herein, a photochromic compound of the present invention can be clear in the first state and colored in the second state. Alternatively, a photochromic compound of compositions of the present invention can have a first color in the first state and a second color in the second state.

[0021] The first state (e.g., the clear state or first color) of a photochromic compound / material (whether thermally or non-thermally reversible) is also referred herein to as the “unactivated state” of the photochromic compound / material. The second state (e.g., the colored state or second color) of a photochromic compound / material (whether thermally or non-thermally reversible) is also referred to herein as the “activated state” of the photochromic compound / material.

[0022] As used herein the term “optical” means pertaining to or associated with light and / or vision. For example, according to various non-limiting embodiments disclosed herein, the optical article or element or device can be chosen from ophthalmic articles, elements and devices, display articles, elements and devices, windows, mirrors, and active and passive liquid crystal cell articles, elements and devices.

[0023] As used herein the term “ophthalmic” means pertaining to or associated with the eye and vision. Non-limiting examples of ophthalmic articles or elements include corrective and non-corrective lenses, including single vision or multi-vision lenses, which can be either segmented or non-segmented multi-vision lenses (such as, but not limited to, bifocal lenses, trifocal lenses and progressive lenses), as well as other elements used to correct, protect, orenhance (cosmetically or otherwise) vision, including without limitation, contact lenses, intraocular lenses, magnifying lenses, and protective lenses or visors.

[0024] As used herein the term “display” means the visible or machine-readable representation of information in words, numbers, symbols, designs or drawings. Non-limiting examples of display elements include screens, monitors, and security elements, such as security marks.

[0025] As used herein the term “window” means an aperture adapted to permit the transmission of radiation there-through. Non-limiting examples of windows include automotive and aircraft transparencies, windshields, filters, shutters, and optical switches.

[0026] As used herein the term “mirror” means a surface that specularly reflects a large fraction of incident light.

[0027] As used herein the term “liquid crystal cell” refers to a structure containing a liquid crystal material that is capable of being ordered. A non-limiting example of a liquid crystal cell element is a liquid crystal display.

[0028] As used herein, the term “unactivated state” with regard to photochromic layer of the photochromic article, means the photochromic layer is in a “first state” as described previously herein (such as in a clear state or having a first color).

[0029] As used herein, the term “a first unactivated state terminal minimum absorbance wavelength value” means the wavelength at which the photochromic layer (which includes a photochromic material), in an unactivated state, has a terminal (or upper) minimum absorbance. With some embodiments the first unactivated state terminal minimum absorbance wavelength value of the photochromic layer corresponds to the wavelength above which no absorbance is greater than 0.05 AU. This can be determined using a Varian Cary 300 UV / VIS spectrophotometer with a range of 550-250 nm (avg. time 0.100s, data interval 1.100, and scan rate of 600 nm / min) to determine absorbance as a function of wavelength over the specified wavelength range, and evaluating the raw data to identify the lowest wavelength at which absorbance reaches 0.05 or below.

[0030] As used herein, and with regard to the UV absorbing layer, the term “a terminal minimum absorbance wavelength value” means the wavelength value at which the UVabsorbing layer (which includes a UV absorber) has a terminal (or upper) minimum absorbance. With some embodiments, the terminal minimum absorbance wavelength value of the UV absorbing layer corresponds to the wavelength above which no absorbance is greater than 0.05 AU. This can be determined using the same method as for the first unactivated state terminal minimum absorbance wavelength value discussed above.

[0031] As used herein, and unless otherwise indicated, “percent transmittance” was determined from a spectrophotometer, such as a Varian Cary 300 UV / VIS spectrophotometer or a ZEISS® Model MCS 601 spectrophotometer as described further herein.

[0032] As used herein, spatial or directional terms, such as "left", "right", "inner", "outer", "above", "below", and the like, relate to various orientations of the invention as may be described further herein, such as articles and multilayer articles of the present invention. It is to be understood, however, that the invention can assume various alternative orientations to those described herein and, accordingly, such terms are not to be considered as limiting.

[0033] As used herein, the terms "formed over,” "deposited over," "provided over," “applied over,” residing over,” or “positioned over,” mean formed, deposited, provided, applied, residing, or positioned on but not necessarily in direct (or abutting) contact with the underlying element, or surface of the underlying element. For example, a layer "positioned over" a substrate does not preclude the presence of one or more other layers, coatings, or films of the same or different composition located between the positioned or formed layer and the substrate.

[0034] As used herein, “at least one of’ is synonymous with “one or more of,” whether the elements are listed conjunctively or disjunctively. For example, the phrases “at least one of A, B, and C” and “at least one of A, B, or C” each mean any one of A, B, or C, or any combination of any two or more of A, B, or C. For example, A alone; or B alone; or C alone; or A and B; or A and C; or B and C; or all of A, B, and C.

[0035] As used herein, “selected from” is synonymous with “chosen from” whether the elements are listed conjunctively or disjunctively. Further, the phrases “selected from A, B, and C” and “selected from A, B, or C” each mean any one of A, B, or C, or any combination of any two or more of A, B, or C. For example, A alone; or B alone; or C alone; or A and B; or A and C; or B and C; or all of A, B, and C.

[0036] All documents, such as but not limited to issued patents and patent applications, referred to herein, and unless otherwise indicated, are to be considered to be "incorporated by reference" in their entirety.

[0037] As used herein, the term “aliphatic group” and similar terms, such as “aliphatic substituent” means linear or branched aliphatic groups and / or cycloaliphatic groups, which are not aromatic, and which optionally include at least one carbon-carbon unsaturated linkage, such as at least one alkene linkage (-C=C-) and / or at least one alkyne linkage (-C=C-). With some embodiments, linear or branched aliphatic groups herein include 1 to 10 carbon atoms, and cycloaliphatic groups include 3 to 10 carbon atoms.

[0038] As used herein, recitations of “linear or branched” groups, such as linear or branched alkyl, are herein understood to include: a methylene group or a methyl group; groups that are linear, such as linear C2-C10 alkyl groups; and groups that are appropriately branched, such as branched C3-C10 alkyl groups.

[0039] The term “alkyl” as used herein means linear or branched, cyclic or acyclic C1-C10 alkyl. Linear or branched alkyl can include C1-C15 alkyl, such as C1-C10 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 from, include, but are not limited to, those recited further herein. Alkyl groups can include “cycloalkyl” groups. The term “cycloalkyl” as used herein means groups that are appropriately cyclic, such as, but not limited to, C3-C10 cycloalkyl (including, but not limited to, cyclic C3-C8 alkyl, or cyclic C5-C7 alkyl) groups.

[0040] 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.

[0041] As used herein, the term “aromatic group” and similar terms, such as “aromatic substituent” or “aryl group,” or “aryl substituent” means a group that is aromatic and which may include one ring, or two or more fused rings. Each aromatic group may be unsubstituted or substituted with one or more substituents. Examples of substituents of a substituted aromatic group include, but are not limited to, aliphatic groups, aliphatic ether groups, and aliphaticcarboxylic ester groups. Examples of aromatic groups include, but are not limited to, phenyl, naphthyl, anthracenyl, and phenanthrenyl.

[0042] As used herein, recitations of “substituted” group, means a group including, but not limited to, alkyl group, cycloalkyl group, and / or aryl group, in which at least one hydrogen thereof has been replaced or substituted with a group or “substituent” that is other than hydrogen, 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 ester groups; carboxylic acid groups; phosphoric acid groups; phosphoric acid ester groups; sulfonic acid groups; sulfonic acid ester groups; nitro groups; cyano groups; alkyl groups; alkenyl groups; alkynyl groups; haloalkyl groups; perhaloalkyl groups; heterocycloalkyl groups; aryl groups (including alkaryl groups, including hydroxyl substituted aryl, such as phenol, and including poly-fused-ring aryl); aralkyl groups; heteroaryl groups (including poly-fused-ring heteroaryl groups); amino groups, such as -N(Rn)(R12) where R11and R12are each independently selected from, for example, hydrogen, alkyl, or aryl; carboxylate groups; siloxane groups; alkoxysilane groups; polysiloxane groups; amide groups; urethane groups; carbonate groups; urea groups; trialkylsilyl groups; nitrogen-containing heterocycles; or combinations thereof.

[0043] With reference to FIG. 1, and for purposes of non-limiting illustration, a photochromic article 2 according to the present invention is depicted. Photochromic article 2 includes a substrate 11 having a first surface 14 and second surface 17, in which first 14 and second 17 surfaces are opposed to each other. First surface 14 of substrate 11 faces incident actinic radiation depicted by arrow 20. Photochromic article 2 further includes a photochromic layer 23 over (e.g., abutting) substrate 11 and in particular over (e.g., abutting) first surface 14 of substrate 11. Photochromic article 2 further includes a UV absorbing layer 26 over (e.g., abutting) photochromic layer 23. Photochromic article 2, with some embodiments, optionally includes one or more additional layers, as will be described further herein.

[0044] In accordance with the present invention, the terminal minimum absorbance wavelength value of the UV absorbing layer is at least 45 nm less than the first unactivated state terminal minimum absorbance wavelength value of the photochromic layer.

[0045] With 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 first unactivated state terminal minimum absorbance wavelength value of the photochromic layer.

[0046] With some additional embodiments of the present invention, the terminal minimum absorbance wavelength value of the UV absorbing layer is at least 55 nm less than the first unactivated state terminal minimum absorbance wavelength value of the photochromic layer.

[0047] In accordance with some further embodiments, the terminal minimum absorbance wavelength value of the UV absorbing layer is from 45 nm to 80 nm less than, or from 50 nm to 80 nm less than, or from 55 nm to 80 nm less than, the first unactivated state terminal minimum absorbance wavelength value of the photochromic layer.

[0048] With reference to FIG. 2, and for purposes of non-limiting illustration, the photochromic layer of Example 1 has a first unactivated state terminal minimum absorbance wavelength value 29 of 422 nm. With further reference 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 first unactivated state terminal minimum absorbance wavelength value 29 of the photochromic layer of Example 1.

[0049] The photochromic layer has an unactivated state absorbance of greater than 0 over at least a portion of wavelengths from 250 nm to 450 nm. The absorbance spectrum can be measured using a UV / VIS spectrophotometer such as described previously herein.

[0050] The first unactivated state terminal minimum absorbance wavelength value of the photochromic layer, with some embodiments is greater than 390 nm. The first unactivated state terminal minimum absorbance wavelength value of the photochromic layer, with some further embodiments is greater than 410 nm. In accordance with some embodiments, the first unactivated state terminal minimum absorbance wavelength value of the photochromic layer is less than 450 nm. The first unactivated state terminal minimum absorbance wavelength value of the photochromic layer, with some further embodiments, is greater than 410 nm, and less than 450 nm.

[0051] The photochromic material or compound of the photochromic layer can be selected from one or more art-recognized classes of photochromic materials or compounds. With some embodiments, the photochromic material of the photochromic layer is selected from at last 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. With 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[l,2-b]pyrans, with hydrogen and / or various substituents at positions 3 and 5-13 thereof.

[0052] Further examples of other photochromic materials and compounds that can be used in photochromic layer of the present invention include, but are not limited to, those disclosed at column 34, line 20 through column 35, line 13 of US 9,028,728 B2, which disclosure is specifically incorporated by reference herein.

[0053] The photochromic material can be present in the photochromic layer in any suitable amount, provided the photochromic article has a desirable level of photochromic properties, such as a photochromically effective amount. With some embodiments, the photochromic material is present in the photochromic layer in an amount of from 0.001 percent by weight to 40 percent by weight, or from 0.001 to 10 percent by weight, or from 0.01 to 5 percent by weight, or from 0.1 to 2.5 percent by weight, where the percent by weights are in each case based on the total solids weight of the photochromic layer. The photochromic material can be introduced into the photochromic layer in accordance with art-recognized methods including, but not limited to, imbibition and / or mixing with the components from which the photochromic layer is prepared.

[0054] The terminal minimum absorbance wavelength value of the UV absorbing layer is, with some embodiments, greater than 330 nm and less than 380 nm, or greater than 340 nm and less than 370 nm.

[0055] The UV absorbing layer can include any suitable UV absorber or combination of UV absorbers, provided: the terminal minimum absorbance wavelength value of the UV absorbing layer is at least 45 nm less than the first unactivated state terminal minimum absorbancewavelength value of the photochromic layer. The UV absorber, with some embodiments, is present in the UV absorbing layer in an amount of from 0.25 percent by weight to 7 percent by weight, or from 0.50 percent by weight to 6 percent by weight, or from 1 percent by weight to 5 percent by weight, the percent weights in each case being based on the total solids weight of the UV absorbing layer.

[0056] With 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.

[0057] As used herein, the term “unsubstituted oxanilide” means N,N’ -diphenyloxamide. As used herein, the term “substituted oxanilide” means an N,N’ -diphenyloxamide in which one or both of the phenyl rings thereof has covalently bonded thereto one or more substituents including one or more of those substituents recited previously herein. With some embodiments, each substituent of the substituted oxanilide is independently selected from: aliphatic groups, such as linear or branched C1-C12 alkyl groups; cycloalkyl groups, such as C3-C7 cycloalkyl groups; and / or aliphatic ether groups, such as linear or branched C1-C12 alkyl groups.

[0058] As used herein, the term “cinnamate” means an ester of cinnamic acid. Each cinnimate, with some embodiments, is independently selected from: aliphatic esters of cinnamic acid, such as linear or branched C1-C12 alkyl esters of cinnamic acid; 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, with some embodiments, is independently selected from those substituents recited previously herein.

[0059] As used herein, the term “salicylate” means an ester of salicylic acid (or 2-hydroxybenzoic acid). Each salicylate, with some embodiments, is independently selected from: aliphatic esters of salicylic acid, such as linear or branched C1-C12 alkyl esters of salicylic acid; 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, with some embodiments, is independently selected from those substituents recited previously herein.

[0060] As used herein, the term “cyanoacrylate” means an ester of cyanoacrylic acid. Each cyanoacrylate, with some embodiments, is independently selected from: aliphatic esters ofcyanoacrylic acid, such as linear or branched C1-C12 alkyl esters of cyanoacrylic acid; 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, with some embodiments, is independently selected from those substituents recited previously herein. The 3, 3 -substituents of the cyanoacrylate are, with some embodiments, 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 (where each substituent of the substituted cycloalkyl and substituted aryl groups are independently selected from those substituents recited previously herein). In accordance with some embodiments, a non-limiting example of a cyanoacrylate is 2-ethylhexyl 2-cyano-3, 3 -diphenylacrylate (also referred to as octocrylene).

[0061] In accordance with some embodiments, the UV absorbing layer includes one or more substituted oxanilides. In accordance with some further embodiments, the UV absorbing layer includes at least one of N-(2-ethoxyphenyl)-N’-(4-(10-methylundecyl)phenyl)oxalamide, and / or N-(2-ethoxyphenyl)-N’-(4-ethylphenyl)oxal amide.

[0062] The photochromic article of the present invention can, with some embodiments, optionally include one or more additional layers, such as, but not limited to: primer layer(s); topcoat layer(s); anti reflective layer(s); hardcoat layer(s); polarizing layer(s); and alignment layer(s). Classes and examples of such additional optional layers are described at column 20, line 30 through column 21, line 38 of US 8,828,284 B2, which disclosure is incorporated herein by reference.

[0063] The photochromic layer, the UV absorber layer, and one or more additional optional layers, of the photochromic article, with some embodiments of the present invention, can each optionally and independently include at least one additive, provided the terminal minimum absorbance wavelength value of the UV absorbing layer is at least 45 nm less than the first unactivated state terminal minimum absorbance wavelength value of the photochromic layer. With some embodiments each additive is independently selected from static dyes, alignment promoters, kinetic enhancing additives, photoinitiators, thermal initiators, polymerization inhibitors, solvents, light stabilizers, heat stabilizers, mold release agents, rheology controlagents, leveling agents, free radical scavengers, adhesion promoters, blue light blockers, or combinations of two or more thereof. Classes and examples of blue light blocking (or filtering) agents include, but are not limited to, those described in US 9,683,102 B2 and US 2015 / 0234208 Al, the pertinent portions of which are incorporated herein by reference.

[0064] The photochromic layer, the UV absorbing layer, and any additional optional layers provided over the substrate of the photochromic articles of the present invention each independently include, with some embodiments, an organic matrix, such as an organic polymer matrix, which can be a cured (or crosslinked) organic matrix, a thermoplastic organic matrix, or a combination of thereof. Correspondingly, each layer (including the photochromic and UV absorbing layers) of the photochromic articles of the present invention can each be independently selected from cured (or crosslinked) layers and thermoplastic layers. The organic matrix of each layer of the photochromic articles of the present invention can each independently include linkages such as, but not limited to: ether linkages; carboxylic acid ester linkages; urethane linkages; amide linkages; urea linkages; carbonate linkages; linkages formed from the 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.

[0065] Each layer (including the photochromic and UV absorbing layers) of the photochromic articles of the present invention can be formed by art-recognized methods, such as, but not limited to, lamination methods and coating methods. Coating methods include, but are not limited to: spray coating methods; spin coating methods; curtain coating methods; dip coating methods; micro-jet coating methods (such as ink-jet coating methods); in-mold coating methods; and combinations thereof. Lamination methods include, but are not limited to: extrusion lamination methods (such as directly over the substrate); in-mold lamination methods (in which a laminate is placed in a mold, and the substrate is formed there-against within the mold); thermal lamination methods (in which a laminate is thermally fused over the substrate); adhesive lamination methods (in which the laminate is adhered over the substrate by an interposed adhesive layer); and combinations thereof.

[0066] The substrate of the photochromic article, with some embodiments, can be composed of one or more suitable materials, including, but not limited to: organic materials, such asorganic polymeric materials (such as, crosslinked organic polymeric materials and / or thermoplastic organic polymeric materials), such as, but not limited to, thermoplastic polycarbonates, crosslinked polycarbonates, poly(meth)acrylates, and combinations thereof; glasses, such as silica-based glasses; metals; ceramic materials; and combinations of two or more thereof. Examples of substrates that can be included in the photochromic article of the present invention include, but are not limited to, those described at column 35, line 5 through column 36, line 57 of US 8,628,685 B2, which disclosure is incorporated herein by reference.

[0067] With some embodiments, the photochromic article is selected from ophthalmic articles, display articles, windows, mirrors, active liquid crystal cell articles, and passive liquid crystal cell articles.

[0068] With some further embodiments, the photochromic article is selected from ophthalmic articles, and the ophthalmic articles are selected from corrective lenses, non-corrective lenses, contact lenses, intra-ocular lenses, magnifying lenses, protective lenses, and visors.

[0069] With some additional embodiments, the photochromic article is selected from display articles, and the display articles are selected from screens, monitors, and security elements.

[0070] The present invention can be further characterized by one or more of the following non-limiting clauses.

[0071] Clause 1 : A photochromic article comprising:(a) a substrate;(b) a photochromic layer comprising a photochromic material, the photochromic layer being superposed over the substrate, the photochromic layer having, an unactivated state absorbance of greater than 0 (or greater than 0.05 with some embodiments) over at least a portion of wavelengths of 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 superposed over the photochromic layer, the UV absorbing layer having a terminal minimum absorbance wavelength value, wherein the terminal minimum absorbance wavelength value of the UV absorbing layer is at least 45 nm less than the first unactivated state terminal minimum absorbance wavelength value of the photochromic layer.

[0072] Clause 2: The photochromic article of clause 1, wherein the terminal minimum absorbance wavelength value of the UV absorbing layer is at least 50 nm less than the first unactivated state terminal minimum absorbance wavelength value of the photochromic layer.

[0073] 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 first unactivated state terminal minimum absorbance wavelength value of the photochromic layer.

[0074] 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 first unactivated state terminal minimum absorbance wavelength value of the photochromic layer.

[0075] 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 from 45 nm to 80 nm less than, or from 45 nm to 75 nm less than, or from 45 nm to 70 nm less than, or from 45 nm to 65 nm less than, or from 45 nm to 60 nm less than, or from 45 nm to 55 nm less than, or from 45 nm to 50 nm less than, the first unactivated state terminal minimum absorbance wavelength value of the photochromic layer.

[0076] Clause 6: The photochromic article of any one of clauses 1 to 5, wherein the first unactivated state terminal minimum absorbance wavelength value of the photochromic layer is greater than 410 nm, and less than or equal to 450 nm.

[0077] Clause 7: The photochromic article of any one of clauses 1 to 6, wherein the terminal minimum absorbance wavelength value of the UV absorbing layer is greater than 330 nm and less than 380 nm.

[0078] Clause 8: The photochromic article of any one of clauses 1 to 7, wherein the UV absorbing layer comprises at least one of an unsubstituted oxanilide, a substituted oxanilide, a cinnamate, a salicylate, or a cyanoacrylate.

[0079] Clause 9: The photochromic article of any one of clauses 1 to 8, wherein the UV absorbing layer comprises at least one substituted oxanilide, and each substituted oxanilide isindependently selected from N-(2-ethoxyphenyl)-N’-(4-(10-methylundecyl)phenyl)oxalamide, and N-(2-ethoxyphenyl)-N’-(4-ethylphenyl)oxalamide.

[0080] 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.

[0081] Clause 11 : The photochromic article of any one of clauses 1 to 10, wherein the photochromic article is selected from the group consisting of ophthalmic articles, display articles, windows, mirrors, active liquid crystal cell articles, and passive liquid crystal cell articles.

[0082] Clause 12: The photochromic article of any one of clauses 1 to 11, wherein the photochromic article is selected from ophthalmic articles, and the ophthalmic articles are selected from the group consisting of corrective lenses, non-corrective lenses, contact lenses, intra-ocular lenses, magnifying lenses, protective lenses, and visors.

[0083] Clause 13: The photochromic article of any one of clauses 1 to 12, wherein the photochromic article is selected from display articles, and the display articles are selected from the group consisting of screens, monitors, and security elements.

[0084] The present invention is more particularly described in the following examples, which are intended to be illustrative only, since numerous modifications and variations therein will be apparent to those skilled in the art. Unless otherwise specified, all parts and all percentages are by weight.EXAMPLES

[0085] In Part 1 of the following examples, the preparation of curable photochromic compositions is described. In Part 2, the preparation of compositions from which UV absorber layers were prepared, is described. In Part 3, the method by which terminal minimum absorbance wavelength values was determined, is described. In Part 4, the preparation ofphotochromic article test samples, is described. In Part 5 procedures used to test the photochromic articles test samples, are described. In Part 6, the procedure by which photochromic fatigue was determined, is described. Part 1 - Preparation of Curable Photochromic Compositions

[0086] Curable photochromic compositions were prepared according to the procedure described in Example 8 of US 10,954,397 B2.

[0087] Example 1 includes a mixture of five indenofused naphthopyran dyes formulated to provide a gray color on activation.

[0088] Example 2 includes a mixture of two indenofused naphthopyran dyes formulated to provide a gray color on activation.Part 2 - Preparation of the UV Absorbing Layer

[0089] The UV absorbing layer was prepared in accordance with the following description.

[0090] In a first step, a stock solution (Control Solution A) was prepared by combining the ingredients recited in Table 1 in a suitable amber glass bottle equipped with a magnetic stir-bar. The solution was stirred at 25°C for 2 hours.Table 1Control Solution A(1)A blocked aliphatic polyisocyanate available from Covestro AG(2)A photoinitiator available from IGM Resins(3)A Type I photoinitiator available from IGM Resins

[0091] A 5.0 g portion of Control Solution A was in each case introduced into seven separate20 mL amber glass vials equipped with a stir bar. A UV absorber was then added to each vial according to the amounts (in grams) recited in Table 2, and allowed to stir thoroughly.Table 2Solutions with Various UV Absorbers(4)An oxanilide-based UV Absorber from Clariant.(5)A benzotriazole-based UV Absorber from BASF.(6)A benzophenone-based UV Absorber from Solvay.Part 3 - Determining Terminal Minimum Absorbance Wavelength Values.Substrate Preparation:

[0092] The following procedure was used to prepare preconditioned substrates. CR-39 poly(allyl diglycol carbonate) substrates having dimensions of 2 x 2 inches (5.1 x 5.1 cm) (processed without UV absorber) were obtained from Piedmont Plastics. Each substrate was cleaned by wiping with a tissue soaked with isopropanol and dried with a stream of air, and then corona treated by passing on a conveyor belt in a Tantec EST Systems Serial No. 020270 Power Generator HV 2000 series corona treatment unit having a high voltage transformer. The substrates were exposed to corona generated at 70.00 KV and 1000 Watts while traveling on the conveyor at a belt speed 3 ft / min (0.91 meters / min).

[0093] The photochromic coating compositions of Example 1 and Example 2 were separately applied to preconditioned substrates by dispensing approximately 1.5 mL of the photochromic coating compositions onto the surface of each preconditioned substrate, followed by spinning the substrates at 1050 revolutions per minute (rpm) for 8 seconds. The photochromic coatedsubstrates were placed in a forced-air oven maintained at 125°C for 60 minutes, which resulted in the formation of photochromic layer test samples.

[0094] The Control Solution A and the UV absorbing compositions of Examples A-H were in each case separately spin coated onto preconditioned substrates at a rate of 700 revolutions per minute (rpm) for 2 seconds, followed by 1900 revolutions for 2 seconds. The UV absorber coated substrates were cured under 4 ultraviolet lamps in a UV Curing Oven Machine designed and built by Belcan Engineering in nitrogen atmosphere while running on a conveyor belt at 6 ft / min speed at peak intensity of 1.50 W / cm2of UVA and UV dosage of 4.5-5.0 J / cm2of UVA. The UV absorber coated test samples were then placed in a forced-air oven at 105 °C for 3 hours, which resulted in the formation of Control Solution A test samples, and UV absorbing layer test samples.

[0095] The photochromic layer test samples, the Control Solution A test samples, and the UV absorbing layer test samples were in each case analyzed using a Varian Cary 300 UV / VIS spectrophotometer with a range of 550-250 nm (avg. time 0.100s, data interval 1.100, and scan rate of 600 nm / min). The photochromic layer test samples were scanned and analyzed directly. The scans of each of the UV absorbing layer test samples were run after creating a baseline scan of a test sample prepared with Control Solution A alone (without any UV absorber added thereto), and then zeroing each sample. The raw data used to generate the Absorbance vs. Wavelength graph shown in FIG. 1 of the drawing, was also used to determine the terminal minimum absorbance wavelength value (TMAW value) of each layer. The shortest (lowest) wavelength with an absorbance (AU) less than 0.0500 was identified as the terminal minimum absorbance wavelength value for the corresponding layer, each of which are reported in Table 3.Table 3Individual Layer Terminal Minimum Absorbance Wavelength Values* Unactivated.Part 4 - Procedures Used for Preparing Photochromic Articles. Substrate Preparation.

[0096] Polycarbonate Plano lenses (6 base; 76mm diameter) were obtained from Gentex Optical. Each substrate was cleaned by wiping with a tissue soaked with isopropanol, dried with a stream of air and then corona treated under the conditions described above in Part 3, which resulted in the formation of preconditioned lenses.

[0097] Each curable photochromic coating composition of Example 1 and Example 2 was applied to preconditioned lenses (in duplicate for the examples shown in Table 4) by dispensing approximately 1.5 mL of the curable photochromic coating composition onto the surface of each preconditioned lens followed by spinning at 1050 revolutions per minute (rpm) for 8 seconds. The photochromic coated preconditioned lenses were placed in a forced-air oven maintained at 125 °C for 60 minutes. Once the photochromic coated lenses cooled to room temperature, the solutions of Control Solution A and the UV absorber coating compositions of Examples B-H were spin coated over the cured photochromic coating layers formed from Examples 1 and 2 at a rate of 700 revolutions per minute (rpm) for 2 seconds followed by 1900 revolutions for 2 seconds. The coated substrates were cured under 4 ultraviolet lamps in a UVCuring Oven Machine designed and built by Belcan Engineering in nitrogen atmosphere while running on a conveyor belt at 6 ft / min speed at peak intensity of 1.50 W / cm2of UVA and UV dosage of 4.5-5.0 J / cm2of UVA. The coated samples were then placed in a forced-air oven at 105 °C for 3 hours, which resulted in the formation of photochromic article test samples.Table 4 Photochromic Article Test SamplesPart 5 - Test Procedure for Performance of Photochromic Article Test Samples.

[0098] The photochromic article test samples as summarized in Table 4, and their respective duplicates, were evaluated for photochromic performance using the Photochromic Performance Test on the Advanced Bench for Measuring Photochromies (“A-BMP”) optical bench. The optical bench was maintained at a constant temperature of 23 °C for each sample.

[0099] Prior to testing on the optical bench, each of the photochromic article test samples was exposed to 365 nanometer ultraviolet light for about 10 minutes at a distance of about 14 centimeters to activate the photochromic materials. The UVA (315 to 380 nm) irradiance at the photochromic article test sample was measured with a Goosch & Housego OL 756spectroradiometer with 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 for about 10 minutes at a distance of about 36 centimeters to bleach (inactivate) the photochromic materials. The illuminance at the photochromic article test sample was measured with the OL 756 spectroradiometer and found to be 21.9 Klux. The photochromic article test samples were then kept in a dark environment at room temperature (from 21 °C to 24°C) for at least 1 hour prior to testing on the optical bench. Prior to optical bench measurement, the photochromic article test samples were measured for ultraviolet absorbance at 390 nanometers.

[0100] The A-BMP optical bench was fitted with two 150-watt ORIEL® Model #66057 Xenon arc lamps at right angles to each other. The light path from Lamp 1 was directed through a 3 mm SCHOTT KG-2 band-pass filter and appropriate neutral density filters that contributed to the required UV and partial visible light irradiance level. The light path from Lamp 2 was directed through a 3 mm SCHOTT KG-2 band-pass filter, a SCHOTT GG400 short band cutoff filter and appropriate neutral density filters in order to provide supplemental visible light illuminance. A 2 inch x 2 inch (5.1 cm x 5.1 cm) 50% polka dot beam splitter, at 45° to each lamp is used to mix the two beams. The combination of neutral density filters and voltage control of the Xenon arc lamp were used to adjust the intensity of the irradiance. Proprietary software i.e., PTSoft version 6.7 was used on the A-BMP to control timing, irradiance, air cell and sample temperature, shuttering, filter selection and response measurement. A ZEISS® Model MCS 601 spectrophotometer, with fiber optic cables for light delivery through the lens was used for response and color measurement. Photopic response measurements were collected on each photochromic article test sample.

[0101] The power output of the optical bench, i.e., the dosage of light that the photochromic article test sample was exposed to, was adjusted to 6.7 Watts per square meter (W / m2) 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 selfcentering 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 the desired temperature. Measurement of the photochromic article test sample’s dynamic photochromic response and color measurements was made using the same Zeissspectrophotometer, with fiber optic cables for light delivery from a tungsten halogen lamp and through the test sample. The collimated monitoring light beam from the fiber optic cable was maintained perpendicular to the test sample while passing through the photochromic article test sample and directed into a receiving fiber optic cable assembly attached to the spectrophotometer. The exact point of placement of the photochromic article test 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.

[0102] Response measurements, in terms of a change in optical density (AOD) from the unactivated or bleached state to the activated or colored state were determined by establishing the initial unactivated transmittance, opening the shutter from the Xenon lamps and measuring the transmittance through activation at selected intervals of time. Change in optical density was determined according to the formula: AOD=log(10)(% Tb / % Ta), where % Tb is the percent transmittance in the bleached state, % Ta is the percent transmittance in the activated state. Delta Optical density measurements were based on photopic optical density.

[0103] The AOD at saturation was recorded after 15 minutes of activation at 23 °C. The Fade Half-life (“T1 / 2”) value is the time interval in seconds for the AOD of the activated form of the photochromic material in the coating layer to reach one half the AOD recorded after 15 minutes of activation at 23°C described above, after removal of the activating light source. Subsequent Tl / 2 fade time intervals in seconds were calculated using the same methodology described above using the AOD such as 3 / 4 AOD (2ndTl / 2), 7 / 8 AOD (3rdTl / 2), and 15 / 16 AOD (4thTl / 2) to determine the time intervals in seconds for fading a photochromic article test sample to the respective AOD after 15 minutes of activation at 23°C described above, after removal of the activating light source. Time to 70%T was determined by recording the fade of the photochromic article test sample to 70% photopic %T in minutes after removal of the activation light source at the end of 15 minutes of activation at 23°C.

[0104] The data for the performance of photochromic article test samples containing the photochromic layer formed from the curable photochromic composition of Example 1 are shown in Table 5. The data for the performance of photochromic article test samples containingthe photochromic layer formed from the curable photochromic composition of Example 2 are shown in Table 6.Table 5Photochromic Performance of Photochromic Article Test Samples with a Photochromic Layer Formed From Example 1.Table 6 Photochromic Performance of Photochromic Article Test Samples with a Photochromic Layer Formed From Example 2.Part 6 - Testing Procedure for Determining Photochromic Fatigue

[0105] The photochromic article test samples used for performance testing in Part 5 above and their respective duplicates were evaluated for fatigue (with the data of each sample set averaged) in accordance with the following procedures.

[0106] An Atlas Ci5000 Weather-Ometer was used for conducting the simulated solar radiation accelerated weathering (i.e., fatigue). The photochromic article test samples were exposed for a one hour dark cycle and then 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 in the Atlas Ci4000 Weather-Ometer during the light cycle was maintained at 45°C and the relative humidity was controlled at 70% humidity. The temperature of the black panel which has a thermometer connected to it and is representative of the test samples wasmaintained at 55°C. This accelerated weathering procedure was then performed a second time on the photochromic article test samples.

[0107] After the photochromic article test samples underwent this 2ndUV exposure fatigue cycle, they were preconditioned and measured on the optical bench to obtain the final photopic response (AODfmai), under the same conditions as described for the initial testing. The percent fatigue was determined by measuring the difference between the AOD of the photochromic article test samples before and after accelerated weathering according to the formula % Fatigue = (AODinitiai - AODfmai) / AODinitiai x 100. The Ab* value was also determined. The Ab* value was the measured difference in the bleach state b* value as determined by the measured b initial on the Hunter UltraScan Pro unit prior to exposure in the Atlas Ci4000 Weather-Ometer minus the measured b*fmai value on the bleached state of the lens after this UV exposure fatigue cycle of 65 hours. The Ab* value represents the amount of yellowing of the lens that occurred during fatigue.

[0108] The data for the fatigue of photochromic article test samples containing the photochromic layer formed from the curable composition of Example 1 are summarized in Table 7. The data for the fatigue of the photochromic article test samples containing the photochromic layer formed from the curable composition of Example 2 are summarized in Table 8.Table 7Fatigue Data of Examples and Comparative Examples 1A-HTable 8Fatigue Data of Examples and Comparative Examples 2A-H

[0109] With reference to the data summarized in Tables 5 and 6, Examples B-D in which the difference in terminal minimum absorbance wavelength values of the photochromic layer and the overlying UV absorbing layer was 45 nm or greater, had activated optical density AOD values that were 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 value differential (relative the photochromic layer) of less than 45 nm were observed to demonstrate attenuation (lowering) of the optical density in the activated state. Additionally, the presence of UV absorber layers with terminal minimum absorbance wavelength value differentials (relative to the photochromic layer) of 45 nm or greater proved for maintained or improved late stage fade (most evident in the 4thTl / 2 measurement); while UV absorber layers with a terminal minimum absorbance wavelength value differential (relative to the photochromic layer) of less than 45 nm demonstrated slower fade rates. Further, Tables 7 and 8 show that, when compared to a control (without a UV absorber layer), each of the UV absorbing layers provided equal or improved fatigue as compared to the control, as evidenced by less yellowing and equal or lower loss of optical density after exposure. Thus, the presence of a UV absorbing layer having a terminal minimum absorbance wavelength value differential (relative to the photochromic layer) of at least 45 nm, provides stability without sacrificing darkness or fade speed.

[0110] The present invention has been described with reference to specific details of particular embodiments thereof. It is not intended that such details be regarded as limitations upon the scope of the invention except insofar as and to the extent that they are included in the accompanying claims.

Claims

CLAIMS1. A photochromic article comprising:(a) a substrate;(b) a photochromic layer comprising a photochromic material, said photochromic layer being superposed over said substrate, said photochromic layer having, an unactivated state absorbance of greater than 0 over at least a portion of wavelengths of 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, said UV absorbing layer being superposed over said photochromic layer, said UV absorbing layer having a terminal minimum absorbance wavelength value, wherein said terminal minimum absorbance wavelength value of said UV absorbing layer is at least 45 nm less than said first unactivated state terminal minimum absorbance wavelength value of said photochromic layer.

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

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

4. The photochromic article of claim 1, wherein said first unactivated state terminal minimum absorbance wavelength value of said photochromic layer is greater than 410 nm.

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

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

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

8. The photochromic article of claim 1, wherein said photochromic material of said 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. The photochromic article of claim 1, wherein the photochromic article is selected from the group consisting of ophthalmic articles, display articles, windows, mirrors, active liquid crystal cell articles, and passive liquid crystal cell articles.

10. The photochromic article of claim 9, wherein the photochromic article is selected from ophthalmic articles, and the ophthalmic articles are selected from the group consisting of corrective lenses, non-corrective lenses, contact lenses, intra-ocular lenses, magnifying lenses, protective lenses, and visors.

11. The photochromic article of claim 9, wherein the photochromic article is selected from display articles, and the display articles are selected from the group consisting of screens, monitors, and security elements.

Images