Curable photochromic compositions including isocyanate and amine functional components

Abstract

The present invention relates to, a curable photochromic composition that includes: (a) a photochromic compound; (b) a polyisocyanate including at least two isocyanate groups; (c) a polyamine including at least two amine groups that are each reactive with the isocyanate groups of the polyisocyanate; and (d) a non-reactive, non-volatile component that is free of functional groups that are reactive with the polyamine and the polyisocyanate. The molar ratio of moles of isocyanate groups of the polyisocyanate (b) to total moles of amine groups of the polyamine (c) is from 1:1 to 10:1. The present invention also relates to an optical article that includes: (A) a first substrate; (B) a second substrate, where the first and second substrates are opposed to each other; and (C) a photochromic layer interposed between the first and second substrates, where the photochromic layer is formed from the curable photochromic composition of the present invention.

Description

CURABLE PHOTOCHROMIC COMPOSITIONS INCLUDING ISOCYANATE AND AMINE FUNCTIONAL COMPONENTSFIELD

[0001] The present invention relates to curable photochromic compositions, which include: a photochromic compound; a polyisocyanate having at least two isocyanate groups; a polyamine having at least two amine groups that are each reactive with the isocyanate groups of the polyisocyanate; and a non-reactive, non-volatile component that is free of functional groups that are reactive with the polyisocyanate and the polyamine.BACKGROUND

[0002] In response to certain wavelengths of electromagnetic radiation (or “actinic radiation”), photochromic compounds, such as indeno-fused naphthopyrans, typically undergo a transformation from one form or state to another form, with each form having a characteristic or distinguishable absorption spectrum associated therewith. Typically, upon exposure to actinic radiation, many photochromic compounds are transformed from a closed-form, which corresponds to an unactivated (or bleached, e.g., substantially colorless) state of the photochromic compound, to an open-form, which corresponds to an activated (or colored) state of the photochromic compound. In the absence of exposure to actinic radiation, such photochromic compounds are reversibly transformed from the activated (or colored) state, back to the unactivated (or bleached) state. Compositions and articles, such as optical lenses, that contain photochromic compounds or have photochromic compounds applied thereto (e.g., in form of a photochromic coating composition) typically display colorless (e.g., clear) and colored states that correspond to the colorless and colored states of the photochromic compounds contained therein or applied thereto.

[0003] Photochromic compounds can be used in curable compositions to form, for example, cured layers, such as cured films or sheets that are photochromic. With cured photochromic films, such as cured photochromic coatings, it is typically desirable that they provide a combination of hardness and photochromic performance. Generally, the kinetics associated with the reversible transformation of a photochromic compound between a closed-form (unactivated / colorless) and an open-form (activated / colored) is faster in a soft matrix, but slower in a hardmatrix (of the cured film in which the photochromic compound resides). Cured photochromic films having a soft matrix typically have reduced hardness, while those having a hard matrix typically have increased hardness.

[0004] It would be desirable to develop curable photochromic compositions that provide cured photochromic layers having improved hardness without a reduction in photochromic performance.SUMMARY

[0005] In accordance with the present invention, there is provided a curable photochromic composition comprising: (a) a photochromic compound; (b) a polyisocyanate comprising at least two isocyanate groups; (c) a polyamine comprising at least two amine groups that are each reactive with isocyanate groups of said polyisocyanate; and (d) a non-reactive, non-volatile component that is free of functional groups that are reactive with the polyamine and the polyisocyanate. A molar ratio of moles of isocyanate groups of the polyisocyanate (b) to total moles of amine groups of the polyamine (c) is from 1: 1 to 10:1.

[0006] In accordance with the present invention, there is further provided an article comprising: (A) a first substrate; (B) a second substrate, wherein the first substrate and the second substrate are in spaced opposition relative to each other; and (C) a photochromic layer interposed between the first substrate and the second substrate, wherein the photochromic layer is formed from a curable photochromic composition according to the present invention.

[0007] In accordance with the present invention, there is additionally provided an optical article comprising: (A) a substrate; and (B) a photochromic coating layer over at least a portion of a surface of the substrate, wherein the photochromic coating layer is formed from a curable photochromic composition according to the present invention.

[0008] 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

[0009] FIG. 1 is a representative side elevational sectional view of an optical article according to the present invention that includes first and second substrates, and a photochromic layer interposed therebetween; and

[0010] FIG. 2 a representative side elevational sectional view of an optical article according to the present invention that includes a substrate and a photochromic coating layer over a surface thereof.

[0011] 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

[0012] As used herein, the articles "a," "an," and "the" include plural referents unless otherwise expressly and unequivocally limited to one referent.

[0013] 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 there-between, 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.

[0014] 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-0right representation of the divalent linking group C O or equivalently -C(O)O-, isoinclusive of the right-to-left representation thereof,, or equivalently -O(O)C- or -OC(O)-.

[0015] 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.”

[0016] As used herein, molecular weight values of polymers, such as weight average molecular weights (Mw) and number average molecular weights (Mn), are determined by gel permeation chromatography (GPC) using appropriate standards, such as polystyrene standards.

[0017] As used herein, polydispersity index (PDI) values represent a ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the polymer (i.e., Mw / Mn).

[0018] 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.

[0019] 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.

[0020] 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.

[0021] 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.

[0022] 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 in response to actinic radiation of substantially the same wavelength(s) as the absorption(s) of the colored state.

[0023] 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 nonlimiting 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.

[0024] 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.

[0025] 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 eithersegmented 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, or enhance (cosmetically or otherwise) vision, including without limitation, contact lenses, intraocular lenses, magnifying lenses, and protective lenses or visors.

[0026] 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.

[0027] 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.

[0028] As used herein the term “mirror” means a surface that specularly reflects a large fraction of incident light.

[0029] 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.

[0030] 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.

[0031] 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.

[0032] 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.

[0033] As used herein, the term “aliphatic” means a group, compound, or component that is not aromatic, and which may include no carbon-carbon unsaturated groups or linkages, or may include at least one carbon-carbon unsaturated group or linkage, and which may be linear or branched, or cyclic.

[0034] 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-C20 alkyl groups; and groups that are appropriately branched, such as branched C3-C20 alkyl groups.

[0035] The term “alkyl” as used herein means linear or branched, acyclic C1-C25 alkyl or cyclic C3-C25 alkyl. Linear or branched alkyl can include C1-C25 alkyl, such as C1-C20 alkyl, such as C2-C10 alkyl, such as C1-C12 alkyl, such as Ci-Ce 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-C12 cycloalkyl (including, but not limited to, cyclic C3-C10 alkyl, or cyclic C5-C7 alkyl) groups. Examples of cycloalkyl groups include, but are not limited to, those recited further herein. The term “cycloalkyl” as used herein also includes: bridged ring polycycloalkyl groups (or bridged ring polycyclic alkyl groups), such as, but not limited to, bicyclo[2.2.1]heptyl (or norbomyl) and bicyclo[2.2.2]octyl; and fused ring polycycloalkyl groups (or fused ring polycyclic alkyl groups), such as, but not limited to, octahydro- IH-indenyl, and decahydronaphthalenyl.

[0036] The term “heterocycloalkyl” as used herein means groups that are appropriately cyclic, such as, but not limited to, C2-C12 heterocycloalkyl groups, such as C2-C10 heterocycloalkyl groups, such as C5-C7 heterocyclo alkyl groups, and which have at least one hetero atom in the cyclic ring, such as, but not limited to, O, S, N, P, and combinations thereof. Examples of heterocycloalkyl groups include, but are not limited to, imidazolyl, tetrahydrofuranyl, tetrahydropyranyl and piperidinyl. The term “heterocycloalkyl” as used herein also includes:bridged ring polycyclic heterocycloalkyl groups, such as, but not limited to, 7-oxabicyclo[2.2.1]heptanyl; and fused ring polycyclic heterocycloalkyl groups, such as, but not limited to, octahydrocyclopenta[b]pyranyl, and octahydro- IH-isochromenyl.

[0037] The descriptions, classes, and examples provided herein with regard to alkyl groups, cycloalkyl groups, heterocycloalkyl groups, haloalkyl groups, and the like, are also applicable to alkane groups, cycloalkane groups, heterocycloalkane groups, haloalkane groups, etc., such as, but not limited to, polyvalent alkane groups, such as polyvalent alkane linking groups, such as divalent alkane linking groups.

[0038] As used herein, the term “aryl” and related terms, such as “aryl group”, means an aromatic cyclic monovalent hydrocarbon radical. As used herein, the term “aromatic” and related terms, such as “aromatic group,” means a cyclic conjugated hydrocarbon having stability (due to delocalization of pi-electrons) that is significantly greater than that of a hypothetical localized structure. Examples of aryl groups include Ce-Cu aryl groups, such as, but not limited to, phenyl, naphthyl, phenanthryl, and anthracenyl.

[0039] The term “heteroaryl”, as used herein, includes, but is not limited to, C3-C18 heteroaryl, such as, but not limited to, C3-C10 heteroaryl (including fused ring polycyclic heteroaryl groups) and means an aryl group having at least one hetero atom in the aromatic ring, or in at least one aromatic ring in the case of a fused ring polycyclic heteroaryl group. Examples of heteroaryl groups include, but are not limited to, furanyl, pyranyl, pyridinyl, quinolinyl, isoquinolinyl, and pyrimidinyl.

[0040] The term “aralkyl”, as used herein, includes, but is not limited to, C6-C24 aralkyl, such as, but not limited to, Ce-Cio aralkyl, and means an alkyl group substituted with an aryl group. Examples of aralkyl groups include, but are not limited to, benzyl and phenethyl.

[0041] 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 alkenyl groups include, but are not limited to, vinyl, allyl, and propenyl. Representative alkynyl groups include, but are not limited to, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, and 2-butynyL Representative cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl.

[0042] As used herein, the term “halo” and related terms, such as “halo group,” “halo substituent,” “halogen group,” and “halogen substituent,” means a single bonded halogen group, such as -F, -Cl, -Br, and -I.

[0043] As used herein, recitations of “halo substituted” and related terms (such as, but not limited to, haloalkyl groups, haloalkenyl groups, haloalkynyl groups, haloaryl groups, and halo- heteroaryl groups) means a group in which at least one, and up to and including all of the available hydrogen groups thereof is substituted with a halo group, such as, but not limited to F, Cl or Br. The term “halo-substituted” is inclusive of “perhalo-substituted.”

[0044] 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.

[0045] 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.

[0046] As used herein, and in accordance with some embodiments, the term “ester” such as with regard to groups, and substituents of various groups, of the compounds and components of the present invention, and related terms, such as “ester group” and “ester substituent” means a carboxylic acid ester group represented by -C(O)OR, where R is selected from those groups as described below, other than hydrogen.

[0047] As used herein, and in accordance with some embodiments, the term “carbonate” such as with regard to groups, and substituents of various groups, of the compounds and components of the present invention, and related terms, such as “carbonate group” and “carbonate substituent” includes a material represented by -OC(O)OR, where R is selected from those groups as described below, other than hydrogen.

[0048] As used herein, and in accordance with some embodiments, the term “urethane,” such as with regard to groups, and substituents of various groups, of the compounds and components of the present invention, and related terms, such as “urethane group,” and “urethane substituent,” includes a material represented by -OC(O)N(R)(H) or -N(H)C(O)OR, where R in each case is independently selected from those groups as described below, other than hydrogen.

[0049] Unless otherwise stated, each R group of each of the above described ketone, ester (carboxylic acid ester), carbonate, and urethane groups, is in each case independently selected from hydrogen, alkyl, haloalkyl, perhaloalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and combinations thereof (including those classes and examples thereof as recited previously herein).

[0050] As used herein, recitations of “substituted” group, with regard to the components and compounds of the present invention, means a group including, but not limited to, alkyl group, heterocycloalkyl group, aryl group, and / or heteroaryl group, in which at least one hydrogen thereof has been replaced or substituted with a group that is other than hydrogen. The substituents of the “substituted” groups of the components and compounds according to the present invention, with some embodiments, are in each case independently selected from: alkoxy groups; halo groups (e.g., F, Cl, I, and Br); hydroxyl groups; thiol groups; alkylthio groups; arylthio groups; ketone groups; aldehyde groups; ester groups; carboxylic acid groups; cyano groups; alkyl groups; alkenyl groups; alkynyl groups; haloalkyl groups; perhaloalkyl groups; cycloalkyl groups; heterocycloalkyl groups; aryl groups (including alkaryl groups, including hydroxyl substituted aryl, such as phenol, and including poly-fused-ring aryl); 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, heterocycloalkyl, aryl, or heteroaryl; carboxylate groups; amide groups; urethane groups; carbonate groups; urea groups; vinylphenyl groups; acrylate groups; methacrylate groups; acrylamide groups; methacrylamide groups; nitrogen-containing heterocycles; or combinations thereof, including those classes and examples as described further herein. With some further embodiments, the substituents of the “substituted” groups of the components and compounds according to the present invention, are in each case independently selected from: alkoxy groups; halo groups (e.g., F, Cl, I, and Br); hydroxyl groups; thiol groups; ketone groups; aldehyde groups; ester groups; carboxylic acid groups; cyano groups; alkyl groups; haloalkyl groups; perhaloalkyl groups; cycloalkyl groups; heterocycloalkyl groups; aryl groups; and heteroaryl groups. Inaccordance with some embodiments of the present invention, the substituents of a substituted group are more particularly recited.

[0051] The curable photochromic compositions of the present invention include a polyisocyanate that has at least two isocyanate groups. With some embodiments, the polyisocyanate includes 2 to 10 isocyanate groups, or 2 to 8 isocyanate groups, or 2 to 6 isocyanate groups, or 2 to 5 isocyanate groups, or 2 to 4 isocyanate groups.

[0052] With some embodiments, the polyisocyanate includes at least one of, linear or branched aliphatic polyisocyanates, cycloaliphatic polyisocyanates, biurets thereof, allophanates thereof, isocyanurates thereof, and combinations thereof.

[0053] Examples of linear or branched aliphatic polyisocyanates from which the polyisocyanate of the curable photochromic composition can be selected include, but are not limited to: 1,2-diisocyanatoethane (ethylene diisocyanate); tetramethylene- 1,4-diisocyanate; hexamethylene- 1,6-diisocyanate; 2,2,4-trimethyl hexane- 1,6-diisocyanate; 2,4,4-trimethyl hexane- 1,6-diisocyanate; and dodecane- 1,12-diisocyanate.

[0054] Examples of cycloaliphatic polyisocyanates from which the polyisocyanate of the curable photochromic composition can be selected include, but are not limited to: cyclobutane- 1,3-diisocyanate; cyclohexane- 1,3-diisocyanate; cyclohexane- 1,4-diisocyanate; methyl cyclohexyl diisocyanate; hexahydrotoluene-2,4-diisocyanate; hexahydrotoluene-2,6- diisocyanate; hexahydrophenylene- 1 ,3-diisocyanate; hexahydrophenylene- 1 ,4-diisocyanate; perhydrodiphenylmethane-2,4'-diisocyanate; perhydrodiphenylmethane-4,4'-diisocyanate; and norbomane diisocyanate.

[0055] The polyisocyanate of the curable photochromic composition, with some embodiments, has an isocyanate equivalent weight of from 95 to 500 g / mole, or from 150 to 400 g / mole, or from 150 to 350 g / mole.

[0056] In accordance with some embodiments, at least some isocyanate groups of the polyisocyanate are reversibly blocked (or capped) with a blocking agent (or capping agent).

[0057] As used herein, the term “reversibly blocked” and related terms, such as “reversibly capped” with regard to the isocyanate groups of the polyisocyanate, means isocyanate groups thereof that are blocked or capped with a blocking or capping agent. Under controlledconditions, such as exposure to elevated temperature, the blocking / capping agent separates (or deblocks or decaps) from the blocked isocyanate groups, allowing the free / unblocked isocyanate groups thereof to: react and form covalent bonds with the amine groups of the polyamine. After unblocking or decapping from the blocked isocyanate groups of the polyisocyanate, the blocking / capping agent can volatize out of the curable photochromic composition (prior to the composition becoming vitrified) and / or remain in the curable photochromic composition, such as a plasticizer. With some embodiments, it is desirable that the blocking / capping agent not form bubbles or voids in the curable photochromic composition and / or not overly plasticize the curable photochromic composition after deblocking / decapping.

[0058] As used herein, and in accordance with some embodiments, “at least some isocyanate groups of the polyisocyanate being independently and reversibly blocked with a blocking agent,” means at least 10%, or at least 20%, or at least 25%, or at least 50%, or at least 75%, or at least 90%, or at least 95%, or 100% of the isocyanate groups are reversibly blocked.

[0059] The blocking / capping groups of the blocked isocyanate groups of the polyisocyanate can be selected from, with some embodiments hydroxy functional compounds, IH-azoles, lactams, ketoximes, and mixtures thereof. Classes of hydroxy functional compounds include, but are not limited to, aliphatic, cycloaliphatic, or aromatic alkyl monoalcohols or phenolics. Specific examples of hydroxy functional compounds useful as blocking / capping agents, include, but are not limited to: lower aliphatic alcohols such as methanol, ethanol, and n-butanol; cycloaliphatic alcohols such as cyclohexanol and tetrahydrofuran; aromatic-alkyl alcohols, such as phenyl carbinol and methylphenyl carbinol; and glycol ethers, such as ethylene glycol butyl ether, diethylene glycol butyl ether, ethylene glycol methyl ether and propylene glycol methyl ether. With some embodiments, the hydroxy functional blocking / capping groups include phenolics, examples of which include, but are not limited to, phenol itself and substituted phenols, such as cresol, nitrophenol and p-hydroxy methylbenzoate.

[0060] Examples of IH-azoles that are useful as blocking / capping groups include, but are not limited to IH-imidazole, IH-pyrazole, IH-dialkyl pyrazoles (such as, 1H- 3, 5 -dimethyl pyrazole and lH-2,5-dimethyl pyrazole), lH-l,2,3-triazole, lH-l,2,3-benzotriazole, lH-l,2,4-triazole, lH-5-methyl-l,2,4-triazole, and lH-3-amino-l,2,4-triazole.

[0061] Ketoximes useful as blocking / capping groups include those prepared from aliphatic or cycloaliphatic ketones. Examples of ketoxime capping groups include, but are limited to, 2- propanone oxime (acetone oxime), 2-butanone oxime (also referred to as, methylethyl ketoxime),2-pentanone oxime, 3-pentanone oxime, 3-methyl-2-butanone oxime, 4-methyl-2-pentanone oxime, 3,3-dimethyl-2-butanone oxime, 2-heptanone oxime, 3-heptanone oxime, 4-heptanone oxime, 5-methyl-3-heptanone oxime, 2,6-dimethyl-4-heptanone oxime, cyclopentanone oxime, cyclohexanone oxime, 3-methylcyclohexanone oxime, 3,3,5-trimethylcyclohexanone oxime, and 3 ,5 ,5-trimethyl-2-cyclohexene-5 -one oxime.

[0062] Examples of lactam capping groups include, but are not limited to, epsilon-caprolactam and 2-pyrolidinone. Other suitable capping groups include, morpholine,3-aminopropyl morpholine, and N-hydroxy phthalimide.

[0063] With some embodiments of the present invention, the blocked isocyanate groups of the polyisocyanate are each independently blocked with a blocking / capping agent selected from methylethyl ketoxime, pyrazole (more particularly, IH-pyrazole), and dialkyl pyrazole (more particularly, IH-dialkyl pyrazole, such as lH-3,5-dimethyl pyrazole and lH-2,5-dimethyl pyrazole).

[0064] The polyisocyanate, with some embodiments, in present in the curable photochromic composition of the present invention, in an amount of from 35 percent by weight to 90 percent by weight, or from 40 percent by weight to 85 percent by weight, or from 44 percent by weight to 80 percent by weight, the percent weights in each case being based on the total solids weight of the polyisocyanate (b), the polyamine (c), and the non-reactive, non-volatile component (d).

[0065] As used herein, and with regard to the curable photochromic composition, the term “total weight of resin solids” and similar terms, such as “total resin solids weight” and “total resin solids” means the total solids weight the polyisocyanate (b), the polyamine (c), and the non-reactive, non-volatile component (d), and unless otherwise stated, does not include the weight of the photochromic compound(s) and other optional additives.

[0066] With some embodiments of the curable photochromic compositions of the present invention, a molar ratio of moles of isocyanate groups of the polyisocyanate to total moles of amine groups of the polyamine is from 1:1 to 10:1, or from 1:1 to 8:1, or from 1: 1 to 5:1.

[0067] The curable photochromic compositions of the present invention include a polyamine having at least two amine groups that are each reactive with isocyanate groups of the polyisocyanate compound. Each amine group of the polyamine is independently selected from primary amine group (-NH2) and secondary amine group. With some embodiments, each amine group of the polyamine is independently selected from primary amine group and secondary amine group, provided that the polyamine includes at least one primary amine group. With some further embodiments, each amine group of the polyamine is independently selected from primary amine group and secondary amine group, provided that the poly amine includes at least two primary amine groups. With some additional embodiments, each amine group of the polyamine is a primary amine group.

[0068] The secondary amine groups of the polyamine, with some embodiments, are each independently represented by at least one of the following Formula (I) and (II):-NH(R’) (I)

[0069] With reference to Formula (I), R’ is other than hydrogen, and is selected from substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, or substituted or unsubstituted aryl, such as substituted or unsubstituted phenyl. In accordance with some embodiments, each secondary amine of the polyamine is represented by Formula (I).

[0070] With reference to Formula (II), Ring-A is a carbocyclic ring including at least two carbon atoms, such as from 2 to 10 carbon atoms (such as at least two -CH2- groups) that optionally includes at least one (such as one or two) heteroatoms, such as S, O, and / or N (provided that an additional ring nitrogen is a secondary or tertiary amine). Examples of secondary amines represented by Formula (II) include, but are not limited to: azetidine;pyrrolidine; piperidine; morpholine; thiomorpholine; 1- alkylpiperazine (such as 1- methylpiperazine); l,4-diazabicyclo[2,2,l]octane; and 2,4,6-tris(piperazine-l-yl)-l,3,5-triazine.

[0071] In accordance with some embodiments, the polyamine includes at least one of polyether, polyester, polycarbonate, polyethylenimine, and / or polyurethane, each independently having at least two amine groups (that are each reactive with the isocyanate groups of the polyisocyanate), and which in each case may independently and optionally include one or more aromatic groups.

[0072] In accordance with some further embodiments, the poly amine includes at least one of aliphatic polyether, aliphatic polyester, aliphatic polycarbonate, aliphatic polyethylenimine, and / or aliphatic polyurethane, each independently having at least two amine groups (that are each reactive with the isocyanate groups of the polyisocyanate).

[0073] The aliphatic polyether having at least two amine groups includes a plurality of ether linkages (-O-), and is free of aromatic groups. With some embodiments, the aliphatic polyether includes a linear or branched C2-C20 alkyl linkage and / or a C3-C10 cycloalkyl linkage, independently between and / or extending from each ether linkage. The aliphatic poly ether having at least two amine groups can be prepared in accordance with art recognized methods. With some embodiments, a hydroxyl functional polyether having at least two hydroxyl groups is reacted with an aziridine, which results in the formation of an amine functional polyether having at least two primary amine groups. The aliphatic polyether having at least two amine groups, with some embodiments, has an Mn of from 76 g / mole to 20,000 g / mole, or from 100 g / mole to 15,000 g / mole, or from 100 g / mole to 5000 g / mole.

[0074] The aliphatic polyester having at least two amine groups includes a plurality of carboxylic acid ester linkages (-C(O)-O-), and is free of aromatic groups. With some embodiments, the aliphatic polyester includes a linear or branched C2-C20 alkyl linkage and / or a C3-C10 cycloalkyl linkage, independently between and / or extending from each carboxylic acid ester linkage. The aliphatic polyester having at least two amine groups can be prepared in accordance with art recognized methods. With some embodiments, a hydroxyl functional polyester having at least two hydroxyl groups is reacted with an aziridine, which results in the formation of an amine functional polyester having at least two primary amine groups. In accordance with some further embodiments, a hydroxyl terminated aliphatic polyester, in a firststep undergoes a condensation reaction with N-benzyloxycarbonyl amino acid, followed by catalytic hydrogenation, in a second step, which results in the formation of a primary amine functional aliphatic polyester, such as described in Bioconjugate Chemistry, 2002, 13(5), pp 1159-1162. The aliphatic polyester having at least two amine groups, with some embodiments, has an Mn of from 104 g / mole to 20,000 g / mole, or from 200 g / mole to 15,000 g / mole, or from 200 g / mole to 5000 g / mole.

[0075] The aliphatic polycarbonate having at least two amine groups includes a plurality of carbonate linkages (-O-C(O)-O-), and is free of aromatic groups. With some embodiments, the aliphatic polycarbonate includes a linear or branched C2-C20 alkyl linkage and / or a C3-C10 cycloalkyl linkage, independently between and / or extending from each carbonate linkage. The aliphatic polycarbonate having at least two amine groups can be prepared in accordance with art recognized methods. With some embodiments, a hydroxyl functional polycarbonate having at least two hydroxyl groups is reacted with an aziridine, which results in the formation of an amine functional polycarbonate having at least two primary amine groups. With some further embodiments, the aliphatic polycarbonate having at least two amine groups is prepared in a first step by ring-opening of trimethylene carbonate in the presence of a nitrophenyl functionalized initiator, followed by, in a second step, a reduction reaction resulting in the formation of primary amines, such as described in Macromolecules, 1997, 30, 6074. The aliphatic polycarbonate having at least two amine groups, with some embodiments, has an Mn of from 120 g / mole to 20,000 g / mole, or from 150 g / mole to 15,000 g / mole, or from 150 g / mole to 5000 g / mole.

[0076] The aliphatic polyurethane having at least two amine groups includes a plurality of urethane linkages (-O-C(O)-N(H)-), and is free of aromatic groups. With some embodiments, the aliphatic polyurethane includes a linear or branched C1-C20 alkyl linkage and / or a C3-C10 cycloalkyl linkage, independently between and / or extending from each urethane linkage. The aliphatic polyurethane having at least two amine groups can be prepared in accordance with art recognized methods. With some embodiments, a hydroxyl functional polyurethane having at least two hydroxyl groups is reacted with an aziridine, which results in the formation of an amine functional polyurethane having at least two primary amine groups. The aliphatic polyurethane having at least two amine groups, with some embodiments, has an Mn of from 119 g / mole to 20,000 g / mole, or from 150 g / mole to 15,000 g / mole, or from 150 g / mole to 5000 g / mole.

[0077] The aliphatic polyethylenimine having at least two amine groups is free of aromatic groups. The aliphatic polyethylenimine, can be referred to herein as a polyethylenimine having at least two amine groups. With some embodiments, the aliphatic polyethylenimine, in a first step, is prepared by ring-opening polymerization of aziridine. The resulting polyethylenimine intermediate, with some embodiments, is branched and includes a combination of primary amine groups, secondary amine groups, and tertiary amine groups. With some embodiments, polyethylenimine having at least two amine groups is selected from a commercially available polyethylenimine having primary amine groups (such as an EPOMIN polyethylenimine). The aliphatic polyethylenimine having at least two amine groups, with some embodiments, has an Mn of from 103 g / mole to 5000 g / mole, or from 150 g / mole to 2500 g / mole, or from 200 g / mole to 2500 g / mole.

[0078] The poly amine having at least two amine groups (that are each reactive with the isocyanate groups of the polyisocyanate), with some embodiments, has an amine group equivalent weight of from 30 g / mole to 1520 g / mole, or from 30 g / mole to 500 g / mole, or from 30 g / mole to 200 g / mole. The recited amine group equivalent weight values, and related ranges, in each case represent a combination (or sum) of primary amine group equivalent weight and secondary amine group equivalent weight.

[0079] With some embodiments, the polyamine component includes: from 0% to 50% secondary amine groups, and from 50% to 100% primary amine groups; or from 0% to 40% secondary amine groups, and from 60% to 100% primary amine groups; or from 0% to 30% secondary amine groups, and from 70% to 100% primary amine groups; or from 0% to 20% secondary amine groups, and from 80% to 100% primary amine groups, the percentages in each case based on the total number of primary amine groups and secondary amine groups.

[0080] The poly amine component, with some embodiments, is present in the curable photochromic composition in an amount of from 1 percent by weight to 20 percent by weight, or from 2 percent by weight to 15 percent by weight, or from 3 to 10 percent by weight, the percent weights in each case being based on total resin solids weight of the polyisocyanate (b), the poly amine (c), and the non-reactive, non-volatile component (d).

[0081] The curable photochromic composition of the present invention includes a non-reactive, non-volatile component that is free of functional groups that are reactive with: thepolyisocyanate; and the poly amine. More particularly, the non-reactive component is free of functional groups that are reactive with: the isocyanate groups of the polyisocyanate; and the amine groups (primary amine groups and secondary amine groups) of the poly amine.

[0082] The non-reactive, non-volatile component, with some embodiments, includes at least one of polyethers, polyesters, polycarbonates, polyurethanes, poly((meth)acrylates), organo phosphates, and / or ionic liquids, which in each case may independently and optionally include one or more aromatic groups. In further accordance with the present invention, the non-reactive component includes at least one of aliphatic polyethers, aliphatic polyesters, aliphatic polycarbonates, aliphatic polyurethanes, aliphatic poly((meth)acrylates), organo phosphates, and / or aliphatic ionic liquids. In accordance with some embodiments, the polyethers, polyesters, polycarbonates, polyurethanes, and poly((meth)acrylates (including aliphatic versions thereof) from which the non-reactive component can be selected, each independently have an Mn of 300 to 10,000 g / mole, or from 300 to 8000 g / mole, or from 300 to 7000 g / mole.

[0083] The poly ethers of the non-reactive component, with some embodiments, include a plurality of ether linkages (-O-), and are free of aromatic groups in the case of aliphatic poly ethers. With some embodiments, the poly ether is an aliphatic poly ether and includes a linear or branched C2-C20 alkyl linkage and / or a C3-C10 cycloalkyl linkage, independently between and / or extending from each ether linkage. The polyethers of the non-reactive component can be prepared in accordance with art recognized methods. The poly ether of the non-reactive component, with some embodiments has terminal ether groups, such as terminal -ORagroups, where Rain each case is independently a linear or branched C1-C20 alkyl group or a C3-C10 cycloalkyl group. With some additional embodiments, the polyether of the non-reactive component has terminal carboxylic acid ester groups, such as terminal -OC(O)Ragroups, where Rain each case is independently a linear or branched C1-C20 alkyl group or a C3-C10 cycloalkyl group.

[0084] The polyesters of the non-reactive component include a plurality of carboxylic acid ester linkages (-C(O)-O-), and are free of aromatic groups in the case of aliphatic polyesters. With some embodiments, the polyester of the non-reactive component is an aliphatic polyester and includes a linear or branched C2-C20 alkyl linkage and / or a C3-C10 cycloalkyl linkage, independently between and / or extending from each carboxylic acid ester linkage. The polyestersof the non-reactive component can be prepared in accordance with art recognized methods. With some additional embodiments, the polyester of the non-reactive component has terminal carboxylic acid ester groups, such as terminal -OC(O)Ragroups and / or terminal -C(O)ORagroups, where Rain each case is independently a linear or branched C1-C20 alkyl group or a C3-C10 cycloalkyl group.

[0085] The polycarbonates of the non-reactive component include a plurality of carbonate linkages (-O-C(O)-O-), and are free of aromatic groups in the case of aliphatic polycarbonates. With some embodiments, the polycarbonate of the non-reactive component is an aliphatic polycarbonate and includes a linear or branched C2-C20 alkyl linkage and / or a C3-C10 cycloalkyl linkage, independently between and / or extending from each carbonate linkage. The polycarbonates of the non-reactive component can be prepared in accordance with art recognized methods. With some additional embodiments, the polycarbonate of the non-reactive component has terminal carbonate groups, such as terminal -O-C(O)-O-Ragroups, where Rain each case is independently a linear or branched C1-C20 alkyl group or a C3-C10 cycloalkyl group.

[0086] The polyurethanes of the non-reactive component include a plurality of urethane linkages (-O-C(O)-N(H)-), and are free of aromatic groups in the case of aliphatic polyurethanes. With some embodiments, the polyurethane of the non-reactive component is an aliphatic polyurethane and includes a linear or branched C2-C20 alkyl linkage and / or a C3-C10 cycloalkyl linkage, independently between and / or extending from each urethane linkage. The polyurethanes of the non-reactive component can be prepared in accordance with art recognized methods. With some additional embodiments, the polyurethane of the non-reactive component has terminal urethane groups, such as terminal -N(H)-C(O)-ORagroups, where Rain each case is independently a linear or branched C1-C20 alkyl group or a C3-C10 cycloalkyl group.

[0087] The poly((meth)acrylates) of the non-reactive component are, with some embodiments, prepared from one or more (meth) acrylate monomers. With some embodiments, the poly((meth)acrylate) of the non-reactive component is an aliphatic poly((meth)acrylate), which is prepared, in accordance with art-recognized methods, from one or more aliphatic (meth) acrylate monomers, such as, but not limited to: alkyl (meth)acrylate monomers, such as linear or branched C1-C20, or C1-C10, or C1-C7 alkyl (meth)acrylate monomers; cycloalkyl (meth) acrylate monomers, such as C3-C10 or C3-C7 cycloalkyl (meth) acrylate monomers; or bridged cycloalkyl(meth) acrylate monomers. Examples of (meth) acrylate monomers from which the poly((meth)acrylates) of the non-reactive component can be prepared include, but are not limited to: methyl (meth) acrylate; ethyl (meth) acrylate); n-propyl (meth)arylate; iso-propyl(meth) acrylate; linear or branched butyl (meth)acrylate; linear or branched pentyl (meth) acrylate; linear or branched hexyl (meth) acrylate; 2-ethylhexyl (meth) acrylate; cyclohexyl (meth) acrylate; and bicyclo[2.2.1]heptyl (meth) acrylate.

[0088] The organo phosphates from which the non-reactive component can be selected, with some embodiments, are represented by the following Formula (A),Formula (A) P(O)(ORb)3

[0089] With reference to Formula (A), each Rbis in each case independently selected from alkyl, haloalkyl, perhaloalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and combinations thereof (including those classes and examples thereof as recited previously herein). With some further embodiments, each Rbof Formula (A) is in each case independently selected from alkyl, cycloalkyl, aryl, and combinations thereof. With further reference to Formula (A), and in accordance with some further embodiments, each Rbis in each case independently selected from C1-C20 linear alkyl, C3-C20 branched alkyl, C3-C20 cycloalkyl, C5-C20 aryl, and combinations thereof. With additional reference to Formula (A), and in accordance with some additional embodiments, each Rbis in each case independently selected from: phenyl; phenyl substituted with at least one of C1-C20 linear alkyl, C3-C20 branched alkyl, or C3-C20 cycloalkyl; C1-C20 linear alkyl substituted with at least one phenyl; C3-C20 branched alkyl substituted with at least one phenyl; and C3-C20 cycloalkyl substituted with at least one phenyl. Non-limiting examples of organo phosphates, from which the non-reactive component can be selected include, tricresyl phosphate, tris(2-phenylethyl) phosphate, tris(2-chloroethyl) phosphate, tris(l,3-dichloro-2- propyl)phosphate, cresyl diphenyl phosphate, tris(2,3-dibromopropyl)phosphate, tris-(2- ethylhexyl)phosphate, and tris(2-methylphenyl)phosphate.

[0090] The ionic liquids from which the non-reactive component can be selected, with some embodiments, are organic salts having a melting point below 0°C. In accordance with some embodiments, the ionic liquids include organic cations and appropriate anions. Classes of organic cations that can be used as ionic liquids in the present invention include, but are notlimited to, N-heterocyclic cations and quaternary ammonium cations, where the cationic nitrogen groups are bonded to aliphatic groups, such as linear or branched C1-C25 alkyl groups (including cycloalkyl groups). Classes of suitable N-heterocyclic cations include, but are not limited to, imidazolium cations, pyridinium cations, isoquinolinium cations, piperidinium cations, and pyrrolinium cations. Anions that can be used with the organic cations of the ionic liquids of the non-reactive components of the present invention include, but are not limited to: halides, such as bromide and chloride; carboxylic acid anions, such as aliphatic carboxylic acid anions; tetrafluoroborate ; hexafluorophosphate ; bistrifluoroalkanesulfonimides ; trifluoroalkanesulfonates; dicyanamide; hydrogensulfate; and alkyl sulfates. In accordance with some embodiments, the ionic liquids, from which the non-reactive component can be selected, include: 1,3-dialkylimidazolium cations, where each alkyl group is independently selected from linear or branched C1-C25 alkyl groups (including cycloalkyl groups); and an anion selected from those anions recited above, such as bromide, chloride, carboxylic acid anions, dicyanamide, and hexafluoropho sphate .

[0091] The non-reactive, non-volatile component of the curable photochromic compositions of the present invention, with some embodiments, has a viscosity (at 25 °C) of from 1 cP to 60,000 cP, or from 1 cP to 10,000 cP, or from 1 cP to 7500 cP (where cP in each case means centipoise). Viscosity can be measured in accordance with art-recognized methods. With some embodiments, viscosity is measured using a rotation viscometer such as a Brookfield CAP 2000+ viscometer, available from AMETEK, Inc., according to the manufacturer’s instructions. Additional methods of measuring viscosity include, but are not limited to, those as described in ASTM D789, or ASTM D4878.

[0092] The non-reactive, non-volatile component, with some embodiments, is non-volatile under the conditions that the curable photochromic composition of the present invention is cured. With some embodiments, the non-reactive, non-volatile component, has a boiling point of greater than 250°C, or greater than 280°C. With some embodiments, the non-reactive, non-volatile component has a percent non-volatile solids of at least 95 percent by weight (such as from 95 to 100, or 96 to 100, or 98 to 100 percent by weight) based on the total weight of the non-volatile component (the solids weight being measured in accordance with art-recognized methods, such as described in ASTM-D2369).

[0093] In accordance with some embodiments of the curable photochromic compositions of the present invention, the non-reactive, non-volatile component is present in an amount of from 5 percent by weight to 60 percent by weight, or from 10 percent by weight to 55 percent by weight, or from 20 percent by weight to 50 percent by weight, where the percent weights are in each case based on total resin solids weight of the polyisocyanate (b), the poly amine (c), and the non- reactive, non-volatile component (d).

[0094] The curable photochromic compositions of the present invention include a photochromic compound(s). The photochromic compound can be selected from known classes and examples of photochromic compounds, and can include combinations or mixtures thereof.

[0095] For example, although not limiting herein, mixtures of photochromic compounds can be used to attain certain activated colors, such as a near neutral gray or near neutral brown. See, for example, U.S. Patent No. 5,645,767, col. 12, line 66 to col. 13, line 19, which describes the parameters that define neutral gray and brown colors, which disclosure is specifically incorporated by reference herein.

[0096] With some embodiments, the photochromic compound, of the curable photochromic compositions of the present invention, is selected from the group consisting of naphthopyrans, benzopyrans, phenanthropyrans, indenonaphthopyrans, spiro(indoline)naphthoxazines, spiro(indoline)pyridobenzoxazines, spiro(benzindoline)pyridobenzoxazines, spiro(benzindoline)naphthoxazines, spiro(indoline)-benzoxazines, fulgides, fulgimides, diarylethenes, and mixtures of such photochromic compounds.

[0097] Further examples of other photochromic compounds that can be used in curable photochromic compositions 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.

[0098] The photochromic compound is present in the curable photochromic compositions of the present invention in an amount at least sufficient so as to provide an article prepared from the composition with a desirable level of photochromic properties, which in some embodiments is referred to as a photochromic amount. With some embodiments, the amount of photochromic compound(s) present in the curable photochromic composition is 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 8 percent byweight, or from 0.1 to 2.5 percent by weight, where the percent by weights are in each case based on the total resin solids weight.

[0099] The curable photochromic compositions of the present invention, with some embodiments, optionally include additives such as, but not limited to: waxes, such as for flow and wetting; flow control agents, such as poly(2-ethylhexyl)acrylate; antioxidants; adhesion promoters, such as (3-glycidoxypropyl) trimethoxysilane; surfactants; and ultraviolet (UV) light absorbers. Examples of useful antioxidants and UV light absorbers include, but are not limited to, those available commercially from BASF under the trademarks IRGANOX and TINUVIN. A non-limiting class of antioxidants are hindered amine light stabilizers (HALS), which can include one or more 2,2,6,6-tetralkylpiperindin-4-yl groups, such as one or more 2, 2,6,6- tetramethylpiperidin-4-yl groups. These optional additives, when used, can be present in amounts up to 20 percent by weight, based on total resin solids weight.

[0100] The curable photochromic compositions of the present invention can, with some embodiments, further include one or more fixed-tint dyes. As used herein, the term “fixed-tint dye” and related terms, such as “fixed-colorant,” “static colorant,” “fixed dye,” and “static dye” means dyes that are: non-photosensitive materials, which do not physically or chemically respond to electromagnetic radiation with regard to the visually observed color thereof. The term “fixed-tint dye” and related terms as used herein does not include and is distinguishable from photochromic compound. As used herein, the term “non-photosensitive materials” means materials that do not physically or chemically respond to electromagnetic radiation with regard to the visually observed color thereof, including, but not limited to, fixed-tint dyes.

[0101] One or more fixed-tint dyes can be present in the curable photochromic compositions of the present invention for purposes including, but not limited to, providing a cured article prepared from the curable photochromic compositions with: at least a base (or first) color characteristic of the fixed-tint dye, when the photochromic compound is not activated; and optionally a second color characteristic of the combination of the fixed-tint dye and the photochromic compound when activated, such as by exposure to actinic radiation.

[0102] The optional fixed-tint dye of the curable photochromic composition, with some embodiments, includes at least one of azo dyes, anthraquinone dyes, xanthene dyes, azime dyes,iodine, iodide salts, polyazo dyes, stilbene dyes, pyrazolone dyes, triphenylmethane dyes, quinoline dyes, oxazine dyes, thiazine dyes, and polyene dyes.

[0103] The fixed-tint dye can be present in the curable photochromic composition in varying amounts to provide the intended effect in the cured article prepared therefrom. With some embodiments, the fixed-tint dye is present in the curable photochromic composition in an amount of from 0.001 to 15 percent by weight, or from 0.01 to 10 percent by weight, or from 0.1 to 2.5 percent by weight, the percent weights in each case being based on the total resin solids weight of the curable photochromic composition.

[0104] The curable photochromic compositions of the present can, with some embodiments, include one or more solvents, such as one or more organic solvents.

[0105] Classes of organic solvents that can be present in the curable photochromic compositions of the present invention include, but are not limited to: ethers, such as, dimethyl ether and methyl ethyl ether; cyclic ethers, such as, tetrahydrofuran and dioxane; esters, such as, ethyl acetate, ethyl lactate, ethylene carbonate and propylene carbonate; nitrogen containing cyclic compounds, such as, pyrrolidone, N-methyl-2-pyrrolidone, 1-butyl-pyrrolidinone, and 1,3- dimethyl-2-imidazolidinone; sulfur containing compounds, such as, dimethyl sulfoxide and tetramethylene sulfone; aromatic compounds, such as, toluene, xylene, anisole, and butyl benzoate; and mixtures of aromatic compounds, such as, but not limited to, Aromatic 100 Fluid, which is a commercially available mixture of C9-C10 dialkyl- and trialkyl-benzenes, and Aromatic 150 Fluid, which is a commercially available mixture of C10-C12 alkylbenzenes and alkylnaphthalenes .

[0106] Solvent(s) can be present in the curable photochromic compositions of the present invention, in an amount of from 0 to 95 percent by weight, or from 5 to 95 percent by weight, or from 15 to 80 percent by weight, from 30 to 70 percent by weight, or from 30 to 60 percent by weight, in each case based on the total weight of the curable photochromic composition (including the weight of the solvent). When the curable photochromic compositions of the present invention are used to form laminates (such as to form a photochromic layer that is interposed between first and second substrates) they typically include less than 5 percent by weight of solvent, such as from 0 to 2 percent by weight solvent, or from 0 to 1 percent byweight solvent, and with some embodiments are substantially free (or essentially free, or free) of solvent.

[0107] The curable photochromic compositions of the present can, with some embodiments, include one or more cure catalysts for catalyzing the reaction between the unblocked and / or blocked isocyanate groups of the polyisocyanate component and the amine groups of the poly amine component. Classes of useful catalysts include, but are not limited to: metal compounds, such as, but not limited to, organic tin compounds, organic bismuth compounds, organic zinc compounds, organic zirconium compounds, organic aluminum compounds, organic nickel compounds, organic mercury compounds, and alkali metal compounds; and amine compounds, such as tertiary amine compounds, and quaternary ammonium compounds. Examples of organic tin compounds include, but are not limited to: tin(II) salts of carboxylic acids, such as, tin(II) acetate, tin(II) octanoate, tin(II) ethylhexanoate and tin(II) laurate; tin(IV) compounds, such as, dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate and dioctyltin diacetate. Examples of suitable tertiary amine catalysts include, but are not limited to, diazabicyclo[2.2.2]octane and 1,5- diazabicyclo[4,3,0]non-5-ene. Examples of organic bismuth compounds include, but are not limited to, bismuth carboxylates. Examples of alkali metal compounds include, but are not limited to, alkali metal carboxylates, such as, but not limited to, potassium acetate, and potassium 2-ethylhexanoate. Examples of quaternary ammonium compounds include, but are not limited to, N-hydroxy alkyl quaternary ammonium carboxylates. With some embodiments, the catalyst is selected from tin(II) octanoate, dibutyltin(IV) dilaurate, and / or bismuth 2- ethylhexanoate.

[0108] With some embodiments of the present invention, the curable photochromic composition includes a cure catalyst that includes an organic tin compound selected from tin(II) salts of carboxylic acids, tin(IV) compounds, or combinations thereof.

[0109] With some further embodiments of the present invention, the curable photochromic composition includes an organic tin compound that is selected from tin(II) acetate, tin(II) octanoate, tin(II) ethylhexanoate, tin(II) laurate, dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, dioctyltin diacetate, or combinations thereof.

[0110] The cure catalyst is typically present in an amount of about 0.05 to about 5.0 percent by weight, or about 0.25 to about 2.0 percent by weight, based on the total solids weight of the polyisocyanate (b), the polyamine (c), and the non-reactive, non-volatile component (d).

[0111] The curable photochromic composition of the present invention can be cured by any suitable methods that result in the formation of covalent bonds between isocyanate groups of the polyisocyanate and the amine groups (primary amine groups and secondary amine groups) of the polyamine component. With some embodiments, the curable photochromic composition is cured by exposure to elevated temperature (in excess of ambient room temperature, such as above 25°C). Exposure to elevated temperatures, with some embodiments, results in deblocking of blocked isocyanate groups of the polyisocyanate (when it includes blocked isocyanate groups). As used herein, by "cured" is meant a three dimensional crosslink network is formed by covalent bond formation, resulting from reaction between isocyanate groups of the polyisocyanate and amine groups (primary amine groups and secondary amine groups) of the polyamine. When cured at elevated temperature, the curable photochromic composition can be referred to herein as a thermosetting curable photochromic composition. The temperature at which the thermosetting curable photochromic composition of the present invention is cured is variable and depends in part on the amount of time during which curing is conducted. With some embodiments, the curable photochromic composition is cured at an elevated temperature of from 50°C to 175°C, or from 75°C to 150°C, or from 90°C to 130°C, for a period of 15 to 240 minutes.

[0112] The present invention also relates to articles, and in particular, photochromic articles that are prepared from the curable photochromic composition of the present invention as described previously herein. With some embodiments, the photochromic article is selected from layers (including films and / or sheets), and 3-dimensional articles.

[0113] Classes of 3-dimensional articles, that can be prepared from the curable photochromic compositions of the present invention, include, but are not limited to, ophthalmic articles, display articles, windows, and mirrors.

[0114] More typically, the curable photochromic compositions of the present invention are used to prepare photochromic layers, such as photochromic films and photochromic sheets. As used herein, the term “film” means a layer that is not self-supporting, such as, but not limited to, a coating. As used herein, the term “sheet” means a layer that is self-supporting, such as, but notlimited to, an extruded sheet. In accordance with some embodiments, the photochromic layer is a photochromic coating layer, which is formed in accordance with art-recognized coating processes, such as, but not limited to, spray coating and spin coating, as described further herein.

[0115] The present invention also relates to an optical article, such as a photochromic optical article, that includes: (A) a first substrate; (B) a second substrate, where the first substrate and the second substrate are in spaced opposition relative to each other; and (C) a photochromic layer interposed between the first substrate and the second substrate, where the photochromic layer is formed from a curable photochromic composition according to the present invention.

[0116] The optical article, that includes opposed first and second substrates, and a photochromic layer interposed between the first and second substrates (formed from the curable photochromic composition of the present invention) can, with some embodiments, be selected from ophthalmic articles, display articles, windows, and mirrors. Correspondingly, the substrates of the optical article can be selected from ophthalmic substrates, displays, windows, and mirrors. The first and second substrates can each be independently composed of one or more suitable materials, including, but not limited to: organic materials, such as 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 thereof. Examples of substrates that can be included in the optical article (including optical elements) 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.

[0117] The first substrate and the second substrate may have the same or different thicknesses. In accordance with some embodiments, the first substrate and second substrate each independently have a thickness of from 1 mm to 10 mm, or from 1 mm to 5 mm, or from 1 mm to 3 mm. In accordance with some further embodiments, the first substrate faces a source of actinic radiation (such as sunlight) and is described as a forward substrate, and the second substrate is described as an underlying substrate. The forward substrate, with some embodiments, has a thickness that is less than that of the underlying substrate. In accordance with some embodiments, the forward substrate has a thickness that is less than or equal to 80%, or less than or equal to 70%, or less than or equal to 50%, or less than or equal to 30%, or lessthan or equal to 20%, or less than or equal to 10%, and greater than 0% (such as greater than or equal to 2% or greater than or equal to 5%) of the thickness of the underlying substrate.

[0118] In accordance with some embodiments, the photochromic layer is interposed between and abuts the first substrate and the second substrate. In accordance with some further embodiments, the photochromic layer is interposed between, abuts the first substrate and the second substrate, and serves to bind (or adhere) the first substrate and the second substrate together.

[0119] The first and second substrates, with some embodiments, can each optionally and independently include a photochromic material and / or a fixed-tint dye, which can each be selected from those classes and examples of photochromic materials and fixed-tint dyes as described previously herein. The optional photochromic material(s) / compound(s) present in the first substrate and / or second substrate can be the same or different than the photochromic compound(s) of the photochromic layer. The optional fixed-tint dye(s) can be the same or different than the optional fixed-tint dye(s) of the photochromic layer.

[0120] The curable photochromic coating composition can be applied to the first substrate and / or the second substrate in accordance with art-recognized methods, which include, but are not limited to, spray application methods, curtain coating application methods, draw-down blade (or bar) application methods, dip-coating application methods, spin-coating application methods, jet printing methods (such as inkjet printing methods, where the “ink” is replaced with a curable photochromic composition according to the present invention), and combinations thereof.

[0121] The photochromic layer interposed between the first substrate and the second substrate can have any suitable thickness, such as from 10 micrometers to 250 micrometers, or from 15 micrometers to 75 micrometers.

[0122] In addition to the photochromic layer, the optical article, including first and second substrates, can optionally include one or more further art-recognized layers, such as, but not limited to: a primer layer(s); an adhesive layer(s); a protective layer(s) (such as a hard-coat layer); a polarizing layer(s); a birefringent layer(s); an antireflective layer(s); and / or another photochromic layer(s) that is prepared from a composition other than the curable photochromic composition of the present invention. In accordance with some embodiments, at least one further layer, such as a primer layer and / or an adhesive layer, can be interposed between: (i) the firstsubstrate and the photochromic layer; and / or (ii) between the second substrate and the photochromic layer.

[0123] With reference to FIG. 1 of the drawings there is depicted an optical article (3) according to some embodiments of the present invention that includes a first substate (11) and a second substrate (20), where first substrate (11) and second substrate (20) are in spaced opposition to each other. First substrate (11) includes a first surface (14) and a second surface (17), and second substrate (20) includes a first surface (23) and a second surface (26). Second surface (17) of first substrate (11) and first surface (23) of second substrate (20) are in spaced opposition to each other. Optical article (3) further includes a photochromic layer (29) that is interposed between first substrate (11) and second substrate (20). Photochromic layer (29), more particularly, is interposed between second surface (17) of first substrate (11) and first surface (23) of second substrate (20). With some embodiments, and as depicted in FIG. 1, photochromic layer (29) is interposed between and in abutting relationship with second surface (17) of first substrate (11) and first surface (23) of second substrate (20). With some further embodiments, one or more additional layers (not shown) (such as, but not limited to, a primer layer and / or an adhesive layer) is optionally interposed between: (i) photochromic layer (29) and second surface (17) of first substrate (11); and / or (ii) first surface (23) of second substrate (20). With some additional embodiments, one or more additional layers (not shown) are optionally positioned over: (i) first surface (14) of first substrate (11); and / or (ii) second surface (26) of second substrate (20), of optical article (3). In accordance with some embodiments, and as discussed previously herein, first substrate (11) is described as a forward substrate (11), and second substrate (20) is described as an underlying substrate (20). The additional layers can be selected from one or more of those art-recognized layers described previously herein.

[0124] The present invention further relates to an optical article, such as a photochromic optical article, that includes: (A) substrate; and (B) a photochromic coating layer over at least a portion of a surface of the substrate, where the photochromic coating layer is formed from a curable photochromic composition according to the present invention.

[0125] The substrate, with some embodiments, can be selected from those classes and examples of substrates as described previously herein with reference to the first substrate and the second substrate. The photochromic layer can be formed over the substrate in accordance withthose methods and related conditions as described previously herein with regard to the first substrate and the second substrate. The photochromic optical article including substrate (A) and photochromic layer (B), with some embodiments may include one or more further art-recognized layers, as described previously herein.

[0126] With reference to the FIG. 2 of the drawing figures there is depicted an optical article (5) according to the present invention, which includes a substrate (32) and a photochromic coating layer (41) over at least a portion of a surface of substrate (32). With some embodiments, substrate (32) has a first surface (35) and a second surface (38), and photochromic coating layer (41) is positioned over first surface (35) of substrate (32). With some further embodiments (not shown), photochromic coating layer (41) is also positioned over second surface (38) of substrate (32), in addition to being positioned over first surface (35) of substrate (32). In accordance with some embodiments, one or more additional layers (not shown) (such as, but not limited to, a primer layer and / or an adhesive layer) are optionally interposed between first surface (35) of substrate (32) and second surface (47) of photochromic layer (41). With some additional embodiments, one or more additional layers (not shown) are optionally positioned over: (i) first surface (44) of photochromic coating layer (41); and / or (ii) second surface (38) of substrate (32). The additional layers can be selected from one or more of those additional layers described previously herein.

[0127] The present invention can be further characterized by one or more of the following non-limiting clauses.

[0128] Clause 1: A curable photochromic composition comprising:(a) a photochromic compound;(b) a polyisocyanate comprising at least two isocyanate groups;(c) a polyamine comprising at least two amine groups that are each reactive with isocyanate groups of the polyisocyanate; and(d) a non-reactive, non-volatile component that is free of functional groups that are reactive with the poly amine and the polyisocyanate, wherein a molar ratio of moles of isocyanate groups of the polyisocyanate (b) to total moles of amine groups of the polyamine (c) is from 1 : 1 to 10: 1.

[0129] Clause 2: The curable photochromic composition of clause 1, wherein a molar ratio of moles of isocyanate groups of the polyisocyanate (b) to total moles of amine groups of the polyamine (c) is from 1:1 to 8:1, or from 1:1 to 5:1.

[0130] Clause 3: The curable photochromic composition of clause 1 or clause 2, wherein the polyisocyanate comprises at least one of, linear or branched aliphatic polyisocyanates, cycloaliphatic polyisocyanates, biurets thereof, allophanates thereof, isocyanurates thereof, and combinations thereof.

[0131] Clause 4: The curable photochromic composition of any one of clauses 1 to 3, wherein the polyisocyanate has an isocyanate equivalent weight of from 95 to 500 g / mole, or from 150 to 400 g / mole, or from 150 to 350 g / mole.

[0132] Clause 5: The curable photochromic composition of any one of clauses 1 to 4, wherein at least some isocyanate groups of the polyisocyanate are reversibly blocked with a blocking agent.

[0133] Clause 6: The curable photochromic composition of any one of clauses 1 to 5, wherein the polyisocyanate is present in an amount of from 35 percent by weight to 90 percent by weight, or from 40 percent by weight to 85 percent by weight, or from 44 percent by weight to 80 percent by weight, the percent weights in each case being based on the total solids weight of the polyisocyanate (b), the polyamine (c), and the non-reactive, non-volatile component (d).

[0134] Clause 7: The curable photochromic composition of any one of clauses 1 to 6, wherein said polyamine comprises at least one of aliphatic polyether, aliphatic polyester, aliphatic polycarbonate, aliphatic polyethylenimine, or aliphatic polyurethane, each independently having at least two amine groups.

[0135] Clause 8: The curable photochromic composition of any one of clauses 1 to 7, wherein said polyamine has an amine group equivalent weight of from 30 g / mole to 1520 g / mole, or from 30 g / mole to 500 g / mole, or from 30 g / mole to 200 g / mole.

[0136] Clause 9: The curable photochromic composition of any one of clauses 1 to 8, wherein each amine group of the polyamine is independently selected from primary amine group and secondary amine group, provided that the polyamine comprises at least one primary amine group.

[0137] Clause 10: The curable photochromic composition of any one of clauses 1 to 9, wherein each amine group of the polyamine is independently selected from primary amine group and secondary amine group, provided that the polyamine comprises at least two primary amine groups.

[0138] Clause 11: The curable photochromic composition of any one of clauses 1 to 10, wherein the polyamine is present in an amount of from 1 percent by weight to 20 percent by weight, or from 2 percent by weight to 15 percent by weight, or from 3 to 10 percent by weight, the percent weights in each case being based on total resin solids weight of the polyisocyanate (b), the polyamine (c), and the non-reactive, non-volatile component (d).

[0139] Clause 12: The curable photochromic composition of any one of clauses 1 to 11, wherein the non-reactive, non-volatile component comprises at least one of polyethers, polyesters, polycarbonates, polyurethanes, poly((meth)acrylates), organo phosphates, or ionic liquids.

[0140] Clause 13: The curable photochromic composition of any one of clauses 1 to 12, wherein the non-reactive component comprises at least one of poly ethers, polyesters, polycarbonates, polyurethanes and / or poly((meth)acrylates), which in each case independently have an Mn of 300 to 10,000 g / mole, or from 300 to 8000 g / mole, or from 300 to 7000 g / mole.

[0141] Clause 14: The curable photochromic composition of any one of clauses 1-13, wherein the non-reactive component comprises at least one of aliphatic polyethers, aliphatic polyesters, aliphatic polycarbonates, aliphatic poly((meth)acrylates), and / or aliphatic polyurethanes, which in each case independently have an Mn of 300 to 10,000 g / mole, or from 300 to 8000 g / mole, or from 300 to 7000 g / mole.

[0142] Clause 15: The curable photochromic composition of any one of clauses 1 to 14, wherein the non-reactive component comprises an organo phosphate represented by the following Formula (A),Formula (A)P(O)(ORb)3wherein Rbin each case is independently selected from alkyl, haloalkyl, perhaloalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and combinations thereof.

[0143] Clause 16: The curable photochromic composition of clause 15, wherein Rbin each case is independently selected from: phenyl; phenyl substituted with at least one of C1-C20 linear alkyl, and / or C3-C20 branched alkyl; C1-C20 linear alkyl substituted with at least one phenyl; and C3-C20 branched alkyl substituted with at least one phenyl.

[0144] Clause 17: The curable photochromic composition of any one of clauses 1 to 16, wherein said non-reactive, non-volatile component is present in an amount of from 5 percent by weight to 60 percent by weight, or from 10 percent by weight to 55 percent by weight, or from 20 percent by weight to 50 percent by weight, the percent weights in each case being based on total resin solids weight of said polyisocyanate (b), said polyamine (c), and said non-reactive, non-volatile component (d).

[0145] Clause 18: The curable photochromic composition of any one of clauses 1 to 17, wherein the photochromic compound (a) comprises at least one of of naphthopyrans, benzopyrans, phenanthropyrans, indenonaphthopyrans, spiro(indoline)naphthoxazines, spiro(indoline)pyridobenzoxazines, spiro(benzindoline)pyridobenzoxazines, spiro(benzindoline)naphthoxazines, spiro(indoline)-benzoxazines, fulgides, fulgimides, or diarylethenes.

[0146] Clause 19: The curable photochromic composition of any one of clauses 1 to 18, wherein the curable photochromic composition further comprises an additive, said additive being selected from waxes, flow control agents, antioxidants, ultraviolet light absorbers, surfactants, adhesion promoters, and combinations thereof.

[0147] Clause 20: The curable photochromic composition of any one of clauses 1 to 19, wherein said curable photochromic composition further comprises a catalyst, said catalyst comprising at least one of organic tin compounds, organic bismuth compounds, organic zinc compounds, organic zirconium compounds, organic mercury compounds, alkali metal compounds, tertiary amine compounds, or quaternary ammonium compounds.

[0148] Clause 21: An optical article comprising:(A) a first substrate;(B) a second substrate, wherein the first substrate and the second substrate are in spaced opposition relative to each other; and(C) a photochromic layer interposed between the first substrate and the second substrate, wherein the photochromic layer is formed from the curable photochromic composition according to any one of clauses 1 to 20.

[0149] Clause 22: An optical article comprising:(A) a substrate; and(B) a photochromic coating layer over at least a portion of a surface of the substrate, wherein the photochromic coating layer is formed from the curable photochromic composition of any one of clauses 1 to 20.

[0150] 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

[0151] In Part la of the following examples there is described the preparation of comparative curable photochromic compositions and curable photochromic compositions according to the present invention. In Part lb of the following examples there is described the preparation of coated test specimens using the comparative and inventive curable photochromic compositions from Part la. The coated test specimens of Part lb were tested and evaluated as described in Part 1c of the following examples. In Part 2a of the following examples there is described the preparation of comparative curable photochromic compositions and curable photochromic compositions according to the present invention. In Part 2b of the following examples there is described the preparation of laminated test specimens using the comparative and inventive curable photochromic compositions from Part 2a. The laminated test specimens of Part 2b were tested and evaluated as described in Part 2c of the following examples.Part 1 - Coating ExamplesPart la: Preparation of Curable Photochromic Compositions.Preparation of Comparative Curable Photochromic Compositions.CE-1 - CE-3

[0152] Comparative Examples (CE) 1-3 were prepared using the components listed in Table1, shown in parts by weight. The components of Charge 1 were combined and heated to 70°C, stirred for a minimum of 1 hour or until the solids were visually observed to have dissolved completely. Once cooled to room temperature, the components of charge 2 were added and the mixture was stirred for 1 hour, followed by addition of the components of Charge 3, and the resulting mixture stirred for at least 1 hour prior to use.

[0153] Table 1Comparative Curable Photochromic Compositions(I)A blend of photochromic indenofused naphthopyran dyes formulated to give a grey color on activation.(II)A blend of antioxidant and hindered amine light stabilizers.(III)A polyether modified dimethylpolysiloxane copolymer, available from BYK-Chemie.(lv)A DMP blocked hexamethylene diisocyanate biuret available from Baxenden Chemical Co. with an isocyanate equivalent weight (on solids) of 287 g / mole, provided at 70% solids in propylene glycol monomethyl ether.(v)A polycarbonate diol with an average equivalent weight of 500g / mole, commercially available from Ube Americas Inc.(VI)A polyethyleneimine commercially available from Nippon Shokubai Co Ltd, having a molecular weight of 600g / mole and an amine (primary + secondary) equivalent weight of 71.4g / mole.(VII)Commercially available from Eastman chemical, that has 99.2% NV (non-volatile) solids as determined in accordance with ASTM D2369.Preparation of Inventive Curable Photochromic Compositions. Examples 4-13

[0154] Curable photochromic compositions according to the present invention (Examples 4 to 7) were prepared in accordance with the procedures described above with regard to the comparative curable photochromic compositions, using the ingredients listed in the following Table 2. With reference to Table 2, each composition had the same molar ratio of isocyanate to amine (the sum of primary and secondary amine groups) while the type of non-reactive, non-volatile component was varied.Table 2Medium-to-high molecular weight polymeric adipate, available from Eastman chemical, that has 99.7% NV (non-volatile) solids as determined in accordance with ASTM D2369.(lx)Adipate plasticizer commercially available from COIM, had 99.5%NV solids as determined in accordance with ASTM D2369.(x)Adipate plasticizer commercially available from COIM, has 99.6%NV solids as determined in accordance with ASTM D2369.,XI )Having an average Mwof about 12,000 by GPC, 99.7%NV solids as determined in accordance with ASTM D2369.Examples 8 and 9

[0155] Curable photochromic compositions according to the present invention (Examples 8 and 9) were prepared in accordance with the procedures described above with regard to the comparative curable photochromic compositions, using the ingredients listed in the following Table 3. With reference to Table 3, each composition had the same molar ratio of isocyanate to amine (the sum of primary and secondary amine groups) while the amount of non-reactive, non-volatile component was varied.Table 3Examples 10-13

[0156] Curable photochromic compositions according to the present invention (Examples 10 to 13) were prepared in accordance with the procedures described above with regard to the comparative curable photochromic compositions, using the ingredients listed in the following Table 4. With reference to Table 4, each composition was prepared using a different polyamine.Table 4(X11)Commercially available from Nippon Shokubai Co Ltd, having a molecular weight of300g / mole and an amine (primary + secondary) equivalent weight of 59.5g / mole.(xm) Commercially available from Nippon Shokubai Co Ltd, having a molecular weight of1200g / mole and an amine (primary + secondary) equivalent weight of 75.2g / mole. Part lb: Preparation of Photochromic Test Specimens.

[0157] The compositions of CE-1 through CE-3 and Examples 4 through 13, were used to prepare coated photochromic test specimens CE-1 a through CE-3a and Examples 4a through13a, by in each case being applied to PDQ® coated Gentex® polycarbonate piano lenses, each having a diameter of 76 millimeters. Prior to coating, each lens was corona treated using Tantec equipment with 70 KV and 1000 W settings. About 2 mL of each curable photochromic composition (coating composition) was dispensed onto the substrate and then rotated for sixseconds at a spin speed sufficient to deposit 0.25-0.4g of wet coating composition (wet weight depends on percent non-volatile solids). The test specimens were prepared in duplicate, then cured at 125°C for 1 hour in a forced air oven.Part 1c: Evaluation of Photochromic Test Specimens.Micro-hardness:

[0158] One set of test specimens, from Part lb, were subjected to an additional thermal cure for three hours at 105 °C and set aside for hardness measurements. These specimens were then subjected to micro-hardness testing using a Fischerscope HCV, Model H100SMC available from Fischer Technology, Inc. The hardness was measured at a penetration depth of 2 microns after a 100 mNewton load for 15 seconds. Each test specimen was measured at least twice, and the resulting data was averaged.Photochromic Performance:

[0159] The second set of test specimens, from Part lb, were further treated with corona as previously described and spin coated with a protective coating according to the formulation reported in Table 1 of Example 1 in U.S. Patent No. 7,410,691. The test specimens were cured in a UV oven equipped with D bulbs. Following this, each test specimen was thermally cured at 105°C for three hours.

[0160] The photochromic performance of the test specimens was tested on the Bench for Measuring Photochromies (“BMP”) made by Essilor, Ltd. France. The BMP was maintained at a constant temperature of 73.4 °F (23°C) during testing. Prior to testing, each of the coated test specimens were 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 380nm) irradiance at the lens was measured with a LICOR® Model Li- 1800 spectroradiometer and found to be 22.2 watts per square meter. Each test specimen 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 specimen was measured with the LICOR® spectroradiometer and found to be 21.9 Klux. Each test specimen was then kept in adark environment at room temperature (from 70 to 75 °F / 21 to 24 °C) for at least one hour prior to testing on the BMP. Prior to measurement, each lens was measured for ultraviolet absorbance at 390 nanometers (Abs 390 nm).

[0161] The BMP optical bench was fitted with two 150-watt Newport Model #6255 Xenon arc lamps set at right angles to each other. The light path from Lamp 1 was directed through a 3mm 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 3mm SCHOTT® KG-2 band-pass filter, a SCHOTT® short band 400 nm 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 set 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. Software i.e., BMPSoft version 2.1e was used on the BMP to control timing, irradiance, air cell and sample temperature, shuttering, filter selection, and response measurement. A ZEISS® spectrophotometer, Model MCS 601, with fiber optic cables for light delivery through the lens was used for response and color measurement. Photopic response measurements were collected on each lens.

[0162] The power output of the optical bench, i.e., the dosage of light that the lens 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 self-centering sample holder. The temperature in the sample cell was controlled at 23 °C through the software with a modified Facis, Model FX-10, environment simulator. Measurement of the sample’s dynamic photochromic response and color measurements were made using the same Zeiss spectrophotometer with fiber optic cables for light delivery from a tungsten halogen lamp through the sample. The collimated monitoring light beam from the fiber optic cable was maintained perpendicular to the test sample while passing through the sample and directed into a receiving fiber optic cable assembly attached to the spectrophotometer. The exact point of placement of the sample in the sample cell was where the activating xenon arc beam and the monitoring light beam intersected to form twoconcentric circles of light. The angle of incidence of the xenon arc beam at the sample placement point was about 30° from perpendicular.

[0163] 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 lamp(s) and measuring the transmittance through activation at selected intervals of time. Change in optical density was determined according to the formula: AOD = logio(%Tb / %Ta), where %Tb is the percent transmittance in the bleached state and %Tais the percent transmittance in the activated state. Optical density measurements were based on photopic optical density.

[0164] Test results of Comparative Examples la-3a are summarized in the following Table 5Table 5

[0165] With reference to Table 5, the self-reaction of isocyanate alone (CE-la) results in a hazy coating that was not suitable for an optical device. With CE-2a, the introduction of material including reactive groups (primary and secondary amine) provides a hard film with very slow and unacceptable photochromic performance (T1 / 2). With CE-3a, the further introduction of a “soft” material (i.e., ETERNACOLL® PH-100D polycarbonate diol) which is capable of reacting with the isocyanate, provided a suitable hardness but unacceptable photochromic performance.

[0166] Test results of Examples 4a-7a are summarized in the following Table 6.Table 6

[0167] Examples 4a-7a were prepared for purposes of demonstrating the effect of different non-reactive, non-volatile components, each being present in the same amount (or at the same level), with the same molar ratio of isocyanate to amine (NC0:amine ratio). With reference to Table 6, Examples 4a-7a each provided acceptable hardness values in combination with acceptable photochromic performance.

[0168] Test results of Examples 8a and 9a are summarized in the following Table 7.Table 7

[0169] Examples 8 a and 9a were prepared with different amounts of non-reactive, non-volatile component (the amount with Ex-9a being greater than the amount with Ex-8a), and in each case the same molar ratio of isocyanate to amine (NCO: amine ratio). With reference to Table 7, Example 9a (having a greater amount of non-reactive, non-volatile component than Example 8a)provided decreased (but acceptable) hardness in combination with slightly improved photochromic performance (T1 / 2) as compared to Example 8a.

[0170] Test results of Examples 10a-13a are summarized in the following Table 8.Table 8

[0171] Examples 10a-13a were prepared using different polyamine components at the same weight. With reference to Table 8, Example 13a (prepared using hexamethylenediamine) provided the lowest (but acceptable) hardness, and at the same time photochromic performance that was similar to that provided by Examples 10a- 12a.Part 2 - Laminate ExamplesPart 2a: Preparation of Curable Photochromic Compositions, Examples 14-23.Examples 14-18

[0172] Curable photochromic compositions according to the present invention (Examples 14-18) were prepared using the components listed in the following Table 9, shown in parts by weight. The compositions of Examples 14-18 were prepared using the same amount of non-reactive, non-volatile component, and different amounts of polyisocyanate and poly amine. The components of Charge 1 were combined and heated to 80°C, stirred for a minimum of 1 hour or until the solids were visually observed to have dissolved completely. Once cooled toroom temperature, the components of charge 2 were added and the mixture was stirred for 1 hour prior to use.Table 9>(XIV)blend of photochromic indenofused naphthopyran dyes formulated to give a grey color on activation.(xv)Having an isocyanate equivalent weight of 287g / mole, %NV solids found to be about 94% as determined in accordance with ASTM-D2369 (HOC-lh) and 97%NV solids at 90C-lh using open aluminum cup.Examples 19-21

[0173] Curable photochromic compositions according to the present invention (Examples19-21) were prepared using the components listed in the following Table 10, shown in parts by weight. The compositions of Examples 19-21 were prepared in accordance with the procedure as described previously herein with regard to Examples 14-18. The compositions of Examples19-21 were prepared using the same amount of polyamine, and different amounts of both the non-reactive, non-volatile component and polyisocyanate.Table 10Examples 22 and 23

[0174] Curable photochromic compositions according to the present invention (Examples 22 and 23) were prepared using the components listed in the following Table 11, shown in parts by weight. The compositions of Examples 22 and 23 were prepared in accordance with the procedure as described previously herein with regard to Examples 14-18. The compositions of Examples 22 and 23 were prepared using the same amount of polyisocyanate and polyamine, and different type of ionic liquids.Table 11(XV1)A Zn-amine complex-based catalyst, commercially available from King Industries Specialty Chemicals.Part 2b: Preparation of Laminated Photochromic Test Specimens.

[0175] The curable photochromic compositions of Examples 14 through 23, were used to prepare laminated photochromic test specimens Examples 14a through 23a using CR-39 poly piano substrates having a diameter of 70mm, unless otherwise specified. Prior to lamination, each substrate was treated with corona using Tantec equipment with 70 KV and 1000 W settings. The process of assembling the laminates was as follows. A sufficient amount of curable photochromic composition (typically 0.2-0.6 g) was applied to the center of the back side of a first substrate, and then a second substrate (that is free of curable photochromic composition) was abutted against the side (backside) of the first substrate to which the curable photochromic composition had been applied. The previously applied curable photochromic composition was allowed to spread out within the gap formed between the abutted first and second substrates, optionally followed by exposure thereof to 50°C for 5 minutes if necessary to provide a uniformthickness, and then the laminated test specimens were cured in a forced air oven at a temperature of 90°C for 1 hour.

[0176] The curable photochromic compositions of Examples 22 and 23, were also used to prepare laminates of two piano mineral glass substrates (Examples 22b and 23b) each having a diameter of 70 mm, in accordance with the description with regard to the CR-39 poly piano substrates.Part 2c: Photochromic Performance of Laminated Photochromic Test Specimens.

[0177] The photochromic performance of the laminated test specimens Examples 14a-23a and Examples 22b and 23b was measured using Bench for Measuring Photochromies (“BMP”) made by Essilor, Ltd. France, as described previously herein with regard to the comparative coating Examples CEla through CE3a and the inventive coating Examples 4a through 13a.

[0178] Photochromic performance results of Examples 14a- 18a are summarized in the following Table 12.Table 12

[0179] Examples 14a- 18a were prepared using different types of non-reactive, non-volatile components and different molar ratios of NC0:amine. With reference to Table 12, the test laminate specimens of Examples 14a- 18a each provided similar and acceptable photochromic performance.

[0180] Photochromic performance results of Examples 19a-21a are summarized in the following Table 13.Table 13

[0181] Examples 19a-21a were prepared using different amounts of the same non-reactive, non-volatile component, and different molar ratios of NCO:amine. With reference to Table 13, the test laminate specimens of Examples 19a-21a each provided similar and acceptable photochromic performance.

[0182] Photochromic performance results of Examples 22a, 22b, 23a, and 23b are summarized in the following Table 14.Table 14

[0183] The test laminate specimens of Examples 22a, 22b, 23a, and 23b were prepared using the same amount of polyisocyanate and polyamine, and different types of ionic liquids. With reference to Table 14, Examples 22a, 22b, 23a, and 23b each provided similar and acceptable photochromic performance.

[0184] 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 to the extent that they are included in the accompanying claims.

Claims

AMENDED CLAIMS received by the International Bureau on 23 February 2026 (23.02.2026)1 . A curable photochromic composition comprising:(a) a photochromic compound;(b) a polyisocyanate comprising at least two isocyanate groups;(c) a polyamine comprising at least two amine groups that are each reactive with isocyanate groups of said polyisocyanate; and(d) a non-reactive, non-volatile component that is free of functional groups that are reactive with said polyamine and said polyisocyanate, wherein said non-reactive, non-volatile component has a boiling point of greater than 250°C, wherein said non-reactive, non-volatile component is present in an amount of from 10 percent of weight to 55 percent by weight, based on total resin solids weight of said polyisocyanate (b), said polyamine (c), and said non- reactive, non-volatile component (d), wherein a molar ratio of moles of isocyanate groups of said polyisocyanate (b) to total moles of amine groups of said polyamine (c) is from 1 :1 to 8:1.

2. The curable photochromic composition of claim 1 , wherein said polyisocyanate comprises at least one of, linear or branched aliphatic polyisocyanates, cycloaliphatic polyisocyanates, biurets thereof, allophanates thereof, isocyanurates thereof, and combinations thereof.

3. The curable photochromic composition of claim 1 , wherein said polyisocyanate has an isocyanate equivalent weight of from 95 to 500 g / mole.

4. The curable photochromic composition of claim 1 , wherein at least some isocyanate groups of said polyisocyanate are reversibly blocked with a blocking agent.

5. The curable photochromic composition of claim 1 , wherein said polyamine comprises at least one of aliphatic polyether, aliphatic polyester, aliphaticpolycarbonate, aliphatic polyethylenimine, or aliphatic polyurethane, each independently having at least two amine groups.

6. The curable photochromic composition of claim 1 , wherein said polyamine has an amine group equivalent weight of from 30 g / mole to 1520 g / mole.

7. The curable photochromic composition of claim 1 , wherein each amine group of said polyamine is selected from primary amine group and secondary amine group, provided that said polyamine comprises at least one primary amine group.

8. The curable photochromic composition of claim 1 , wherein said non-reactive, non-volatile component comprises at least one of polyethers, polyesters, polycarbonates, polyurethanes, poly((meth)acrylates), organo phosphates, or ionic liquids.

9. The curable photochromic composition of claim 1 , wherein said non-reactive, non-volatile component is present in an amount of from 5 percent by weight to 60 percent by weight, based on total solids weight of said polyisocyanate (b), said polyamine (c), and said non-reactive, non-volatile component (d).

10. The curable photochromic composition of claim 1 , wherein said photochromic compound (a) comprises at least one of of naphthopyrans, benzopyrans, phenanthropyrans, indenonaphthopyrans, spiro(indoline)naphthoxazines, spiro(indoline)pyridobenzoxazines, spiro(benzindoline)pyridobenzoxazines, spiro(benzindoline)naphthoxazines, spiro(indoline)-benzoxazines, fulgides, fulgimides, or diarylethenes.11 . The curable photochromic composition of claim 1 , wherein said curable photochromic composition further comprises an additive, said additive being selected from waxes, flow control agents, antioxidants, ultravioletlight absorbers, surfactants, adhesion promoters, and combinations thereof.

12. The curable photochromic composition of claim 1 , wherein said curable photochromic composition further comprises a catalyst, said catalyst comprising at least one of organic tin compounds, organic bismuth compounds, organic zinc compounds, organic zirconium compounds, organic mercury compounds, alkali metal compounds, tertiary amine compounds, or quaternary ammonium compounds.

13. An optical article comprising:(A) a first substrate;(B) a second substrate, wherein said first substrate and said second substrate are in spaced opposition relative to each other; and(C) a photochromic layer interposed between said first substrate and said second substrate, wherein said photochromic layer is formed from a curable photochromic composition comprising:(a) a photochromic compound;(b) a polyisocyanate comprising at least two isocyanate groups;(c) a polyamine comprising at least two amine groups that are each reactive with isocyanate groups of said polyisocyanate; and(d) a non-reactive, non-volatile component that is free of functional groups that are reactive with said polyamine and said polyisocyanate, wherein said non-reactive, non-volatile component has a boiling point of greater than 250°C, wherein said non-reactive, non-volatile component is present in an amount of from 10 percent of weight to 55 percent by weight, based on total resin solids weight of said polyisocyanate (b), said polyamine (c), and said non- reactive, non-volatile component (d), wherein a molar ratio of moles of isocyanate groups of said polyisocyanate (b) to total moles of amine groups of said polyamine (c) is from 1 :1 to 8:1 .

14. An optical article comprising:(A) a substrate; and(B) a photochromic coating layer over at least a portion of a surface of said substrate, wherein said photochromic coating layer is formed from a curable photochromic composition comprising:(a) a photochromic compound;(b) a polyisocyanate comprising at least two isocyanate groups;(c) a polyamine comprising at least two amine groups that are each reactive with isocyanate groups of said polyisocyanate; and(d) a non-reactive, non-volatile component that is free of functional groups that are reactive with said polyamine and said polyisocyanate, wherein said non-reactive, non-volatile component has a boiling point of greater than 250°C, wherein said non-reactive, non-volatile component is present in an amount of from 10 percent of weight to 55 percent by weight, based on total resin solids weight of said polyisocyanate (b), said polyamine (c), and said non- reactive, non-volatile component (d), wherein a molar ratio of moles of isocyanate groups of said polyisocyanate (b) to total moles of amine groups of said polyamine (c) is from 1 :1 to 8:1 .Statement Under Article 19(1)The amendments to claims 1, 13, and 14 with regard to the non-reactive, non-volatile component having a boiling point of greater than 250°C, have been made with regard to D3- D5 and D7, as cited in the Written Opinion of the International Search Authority dated 26-June-2025.The amendments to claims 1, 13, and 14 with regard to the non-volatile component being present in an amount of from 10 percent by weight to 55 percent by weight, based on total resin solids weight of said polyisocyanate (b), said polyamine (c), and said non-reactive, non-volatile component (d), have been made with regard to D2, as cited in the Written Opinion of the International Search Authority dated 26-June-2025.The amendments to claims 1, 13, and 14 with regard to the molar ratio of moles of isocyanate groups of said polyisocyanate (b) to total moles of amine groups of said polyamine (c) being from 1:1 to 8:1 (rather than from 1:1 to 10:1), have been made with regard to D1 , as cited in the Written Opinion of the International Search Authority dated 26-June-2025.

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