Curable photochromic composition comprising isocyanate and imine functional components

Abstract

The present invention relates to a curable photochromic composition comprising: (a) a photochromic compound; (b) a polyisocyanate comprising at least two isocyanate groups; and (c) a reactive component having at least two reactive groups each reactive with an isocyanate group of the polyisocyanate. Each reactive group of the reactive component is independently selected from a primary amine and an imine, with the proviso that at least one reactive group of the reactive component is selected from an imine. The curable photochromic composition further includes (d) a non-reactive component that is free of functional groups that react with the polyisocyanate and the reactive component. The invention also relates to an article comprising: a substrate; and a photochromic layer on at least one surface of the substrate, wherein the photochromic layer is formed from the curable photochromic composition of the present invention.

Description

Technical Field

[0001] The present invention relates to a curable photochromic composition comprising a photochromic compound, a polyisocyanate, a reactive component having an imine group and optionally a primary amine group, and a non-reactive component having no functional groups reactive with the polyisocyanate and the reactive component. Background Art

[0002] In response to certain wavelengths of electromagnetic radiation (or "actinic radiation"), photochromic compounds such as indeno-fused naphthopyrans typically undergo a transition from one form or state to another, wherein each form has a characteristic or distinguishable absorption spectrum associated therewith. Typically, upon exposure to actinic radiation, many photochromic compounds transition from a closed form corresponding to an unactivated (or bleached, e.g., substantially colorless) state of the photochromic compound to an open form corresponding to an activated (or colored) state of the photochromic compound. Such photochromic compounds can reversibly transition from an activated (or colored) state back to an unactivated (or bleached) state without exposure to actinic radiation. Compositions and articles (such as optical lenses) containing photochromic compounds or having photochromic compounds applied thereto (e.g., in the form of photochromic coating compositions) typically display colorless (e.g., transparent) and colored states corresponding 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, a photochromic cured layer, such as a cured film or sheet. For cured photochromic films (such as cured photochromic coatings), it is typically desirable that they provide a combination of hardness and photochromic properties. Typically, the kinetics associated with the reversible transition between a closed form (unactivated / colorless) and an open form (activated / colored) of a photochromic compound are faster in a soft matrix (of the cured film in which the photochromic compound resides), but slower in a hard matrix (of the cured film in which the photochromic compound resides). Cured photochromic films with a soft matrix typically have a reduced hardness, while those with a hard matrix typically have an increased hardness.

[0004] It would be desirable to develop curable photochromic compositions that provide cured photochromic layers having improved hardness without degrading the photochromic properties. Summary of the invention

[0005] According to 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 reactive component comprising at least two reactive groups each reactive with an isocyanate group, wherein each reactive group of the reactive component is independently selected from primary amines and imines, provided that at least one reactive group of the reactive component is selected from imines; and (d) a non-reactive component. The non-reactive component does not contain a functional group reactive with the polyisocyanate and the reactive component.

[0006] According to the present invention, there is further provided an article comprising: (A) a substrate; and (B) a photochromic layer on at least one surface of the substrate, wherein the photochromic layer is formed from the curable photochromic composition of the present invention as described above and further described herein.

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

[0008] As used herein, the articles "a," "an," and "the" include plural referents unless expressly and unequivocally limited to the one referent.

[0009] Unless otherwise indicated, all ranges or ratios disclosed herein should be understood to include any and all values ​​and subranges or subratios contained therein. For example, the range or ratio of "1 to 10" should be deemed to include: any and all values ​​therebetween, including the end values ​​(such as 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10); and the subranges between the minimum value 1 and the maximum value 10 (and including the end values), that is, all subranges or subratios starting with a minimum value of 1 or greater and ending with a maximum value of 10 or less, such as but not limited to 1 to 6.1, 3.5 to 7.8, and 5.5 to 10.

[0010] As used herein, unless otherwise indicated, a left-to-right representation of a linking group, such as a divalent linking group, includes other suitable orientations, such as but not limited to a right-to-left orientation. For non-limiting illustration purposes, a divalent linking group or equivalently -C(O)O- from

[0011] Left-to-right representation includes its right-to-left representation or equivalently -O(O)C- or -OC(O)-.

[0012] 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".

[0013] As used herein, molecular weight values ​​of polymers, such as weight average molecular weight (Mw) and number average molecular weight (Mn), are determined by gel permeation chromatography (GPC) using appropriate standards, such as polystyrene standards.

[0014] As used herein, the polydispersity index (PDI) value represents the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of a polymer (ie, Mw / Mn).

[0015] As used herein, the term "polymer" means homopolymers (eg, prepared from a single monomer species), copolymers (eg, prepared from at least two monomer species), and grafted polymers.

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

[0017] As used herein, the term "photochromic" and similar terms (such as "photochromic compound") means having an absorption spectrum for at least visible radiation that changes in response to the absorption of at least actinic radiation. Further, as used herein, the term "photochromic material" means any substance suitable for displaying photochromic properties (such as suitable for having an absorption spectrum for at least visible radiation that changes in response to the absorption of at least actinic radiation) and containing at least one photochromic compound.

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

[0019] As used herein, the term "photochromic material" includes both thermoreversible photochromic materials and compounds and non-thermoreversible photochromic materials and compounds. As used herein, the term "thermoreversible photochromic compound / material" means a compound / material that can be converted from a first state (e.g., a "transparent state") to a second state (e.g., a "colored state") in response to actinic radiation and can return to the first state in response to thermal energy. As used herein, the term "non-thermoreversible photochromic compound / material" means a compound / material that can be converted from a first state (e.g., a "transparent state") to a second state (e.g., a "colored state") in response to actinic radiation and can return to the first state in response to actinic radiation of substantially the same wavelength as the absorption of the colored state.

[0020] As used herein, the terms "first" and "second" are not intended to refer to any particular order or timing, but rather to two different conditions or properties, for purposes of non-limiting illustration. For purposes of non-limiting illustration, the first state and the second state of the photochromic compound may differ in at least one optical property, such as, but not limited to, the absorption of visible radiation and / or UV radiation. Thus, according to various non-limiting embodiments disclosed herein, the photochromic compounds of the present invention may have different absorption spectra in each of the first and second states. For example, although not limited herein, the photochromic compounds of the present invention may be transparent in the first state and colored in the second state. Alternatively, the photochromic compounds of the composition of the present invention may have a first color in the first state and a second color in the second state.

[0021] As used herein, the term "optical" means relating 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 selected from: ophthalmic articles, elements and devices, display articles, elements and devices, windows, mirrors, and active and passive liquid crystal cell articles, elements and devices.

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

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

[0024] As used herein, the term "window" means an aperture adapted to allow radiation to be transmitted therethrough. Non-limiting examples of windows include automotive and aircraft transparencies, windshields, filters, shutters, and optical switches.

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

[0026] As used herein, the term "liquid crystal cell" refers to a structure containing liquid crystal material that is capable of being ordered. A non-limiting example of a liquid crystal cell element is a liquid crystal display.

[0027] As used herein, spatial or directional terms, such as "left", "right", "inner", "outer", "above", "below", etc., relate to various orientations of the invention as may be further described herein, such as articles and multilayer articles of the invention. However, it should be understood that the invention may assume various alternative orientations to those described herein, and therefore, such terms should not be considered limiting.

[0028] As used herein, the terms "formed over", "deposited over", "provided over", "applied over", "residing over", or "positioned over" mean formed, deposited, provided, applied, applied, present, or positioned on an underlying element, or on a surface of an underlying element, but not necessarily in direct (or adjacent) contact therewith. For example, a layer "positioned on a substrate" does not exclude 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.

[0029] All documents (such as but not limited to issued patents and patent applications) mentioned herein and unless otherwise indicated are deemed to be "incorporated by reference" in their entirety.

[0030] As used herein, the description of a "straight or branched" group (such as a straight or branched alkyl group) is understood herein to include: methylene or methyl; straight chain groups, such as a straight chain C2-C 20Alkyl; and appropriately branched groups, such as branched C3-C 20 alkyl.

[0031] As used herein, the term "alkyl" refers to a linear or branched, cyclic or non-cyclic C1-C 25 Alkyl. A straight chain or branched chain alkyl may include C1-C 25 Alkyl, such as C1-C 20 Alkyl, such as C2-C 10 Alkyl, such as C1-C 12 Alkyl groups such as C1-C6 alkyl groups. Examples of alkyl groups from which the various alkyl groups of the present invention may be selected include, but are not limited to, those further listed herein. Alkyl groups may include "cycloalkyl groups". As used herein, the term "cycloalkyl group" means a suitable cyclic group such as, but not limited to, a C3-C6 alkyl group. 12 Cycloalkyl (including but not limited to cyclic C3-C 10 alkyl, or cyclic C5-C7 alkyl). Examples of cycloalkyl include, but are not limited to, those further listed herein. As used herein, the term "cycloalkyl" also includes: bridged ring polycycloalkyl group (or bridged ring polycyclic alkyl group), such as but not limited to bicyclo[2.2.1]heptyl (or norbornyl) and bicyclo[2.2.2]octyl; and condensed ring polycycloalkyl (or condensed ring polycycloalkyl (polycyclic alkyl)), such as but not limited to octahydro-1H-indenyl, and decahydronaphthyl.

[0032] As used herein, the term "heterocycloalkyl" refers to a suitable cyclic group, such as but not limited to C2-C 12 Heterocycloalkyl, such as C2-C 10 Heterocycloalkyl, such as C5-C7 heterocycloalkyl, and it has at least one heteroatom in the cyclic ring, such as but not limited to O, S, N, P, and combinations thereof. Examples of heterocycloalkyl include, but are not limited to, imidazolyl, tetrahydrofuranyl, tetrahydropyranyl, and piperidinyl. As used herein, the term "heterocycloalkyl" also includes: bridged polycyclic heterocycloalkyl, such as but not limited to 7-oxabicyclo[2.2.1]heptyl; and fused polycyclic heterocycloalkyl, such as but not limited to octahydrocyclopenta[b]pyranyl, and octahydro-1H-isochromenyl.

[0033] The descriptions, species and examples provided herein for alkyl, cycloalkyl, heterocycloalkyl, haloalkyl, etc. also apply to alkane groups, cycloalkane groups, heterocycloalkane groups, haloalkane groups, etc., such as but not limited to multivalent alkane groups, such as multivalent alkane linking groups, such as divalent alkane linking groups.

[0034] 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 a stability (due to the delocalization of π electrons) that is significantly greater than the stability of the assumed local structure. Examples of aryl groups include C6-C 14 Aryl groups such as, but not limited to, phenyl, naphthyl, phenanthrenyl, and anthracenyl.

[0035] As used herein, the term "heteroaryl" includes, but is not limited to, C3-C 18 Heteroaryl, such as but not limited to C3-C 10 Heteroaryl (including fused polycyclic heteroaryl) and means an aryl having at least one heteroatom in an aromatic ring or in at least one aromatic ring in the case of a fused polycyclic heteroaryl. Examples of heteroaryl include, but are not limited to, furanyl, pyranyl, pyridyl, quinolyl, isoquinolyl, and pyrimidinyl.

[0036] As used herein, the term "aralkyl" includes, but is not limited to, C6-C 24 Arylalkyl, such as but not limited to C6-C 10 Aralkyl refers to an alkyl group substituted by an aryl group. Examples of aralkyl groups include, but are not limited to, benzyl and phenethyl.

[0037] Representative alkyl includes but is not limited to methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl and decyl. Representative alkenyl includes but is not limited to vinyl, allyl and propenyl. Representative alkynyl includes but is not limited to ethynyl, 1-propynyl, 2-propynyl, 1-butynyl and 2-butynyl. Representative cycloalkyl includes but is not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cyclooctyl.

[0038] As used herein, the term "halo" and related terms, such as "halo group", "halo substituent", "halogen group", and "halogen substituent" refer to singly bonded halogen groups, such as -F, -Cl, -Br, and -I.

[0039] As used herein, the recitation of "halogen-substituted" and related terms (such as, but not limited to, haloalkyl, haloalkenyl, haloalkynyl, haloaryl, and haloheteroaryl) means a group in which at least one, and up to and including all available hydrogen groups, are replaced by a halogen group (such as, but not limited to, F, Cl, or Br). The term "halogen-substituted" includes "perhalogen-substituted".

[0040] As used herein, "at least one of" is synonymous with "one or more of," whether the elements are listed in conjunction or separately. 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.

[0041] As used herein, "selected from" is synonymous with "chosen from", regardless of whether the elements are listed in combination or separately. 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.

[0042] As used herein, and according to some embodiments, the term "ester" (as with respect to the compounds and components of the present invention, and substituents of various groups) and related terms such as "ester group" and "ester substituent" means a carboxylate group represented by -C(O)OR, wherein R is selected from those groups other than hydrogen as described below.

[0043] As used herein, and according to some embodiments, the term "carbonate" (as with respect to the compounds and components of the present invention, and substituents of various groups) and related terms such as "carbonate group" and "carbonate substituent" include materials represented by -OC(O)OR, wherein R is selected from those groups other than hydrogen as described below.

[0044] As used herein, and according to some embodiments, the term "carbamate" (as with respect to the compounds and components of the present invention and substituents of various groups) and related terms such as "carbamate group" and "carbamate substituent" include materials represented by -OC(O)N(R)(H) or -N(H)C(O)OR, wherein R is independently selected at each occurrence from those groups other than hydrogen as described below.

[0045] Unless otherwise indicated, each R group of each of the above-described ketone, ester (carboxylic acid ester), carbonate, and carbamate groups is independently selected at each occurrence from hydrogen, alkyl, haloalkyl, perhaloalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and combinations thereof (including those species and examples thereof as previously listed herein).

[0046] The curable photochromic composition of the present invention comprises a polyisocyanate having at least two isocyanate groups. For some embodiments, the polyisocyanate comprises 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. For some embodiments, the polyisocyanate comprises at least one of the following: a linear or branched aliphatic polyisocyanate, an alicyclic polyisocyanate, a biuret thereof, an allophanate thereof, an isocyanurate thereof, and a combination thereof.

[0047] Examples of linear or branched aliphatic polyisocyanates from which the polyisocyanate for curing the photochromic composition may be selected include, but are not limited to: 1,2-diisocyanatoethane (ethylene diisocyanate); tetramethylene-1,4-diisocyanate; hexamethylene-1,6-diisocyanate; 2,2,4-trimethylhexane-1,6-diisocyanate; 2,4,4-trimethylhexane-1,6-diisocyanate; and dodecane-1,12-diisocyanate.

[0048] Examples of alicyclic 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; methylcyclohexyl 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 norbornane diisocyanate.

[0049] For some embodiments, the polyisocyanate of the curable photochromic composition has an isocyanate equivalent weight of 95 to 500 g / mol, or 150 to 400 g / mol, or 150 to 350 g / mol.

[0050] According to some embodiments, at least some of the isocyanate groups of the polyisocyanate are reversibly blocked (or end-capped) by a blocking agent (or end-capping agent).

[0051] As used herein, the term "reversibly blocked" and related terms, such as "reversibly blocked", with respect to the isocyanate groups of polyisocyanates, means that the isocyanate groups are blocked or blocked with a blocking or blocking agent. Under controlled conditions, such as exposure to high temperatures, the blocking / blocking agent is separated (or unblocked or unblocked) from the blocked isocyanate groups, allowing its free / unblocked isocyanate groups to react with the reactive groups of the reactive components and form covalent bonds. After being unblocked or unblocked by the blocked isocyanate groups of the polyisocyanates, the blocking / blocking agent can be volatilized from the curable photochromic composition (before the composition becomes vitrified) and / or retained in the curable photochromic composition, such as a plasticizer. For some embodiments, it is desirable that the blocking / blocking agent does not form bubbles or voids in the curable photochromic composition and / or does not over-plasticize the curable photochromic composition after unblocking / unblocking.

[0052] As used herein, and according to some embodiments, "at least some of the isocyanate groups of the polyisocyanate are independently and reversibly blocked by a blocking agent" means that 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.

[0053] For some embodiments, the blocking / end-capping group of the blocked isocyanate group of the polyisocyanate can be selected from hydroxyl-functional compounds, 1H-azoles, lactams, ketoximes, and mixtures thereof. The types of hydroxyl-functional compounds include, but are not limited to, aliphatic, alicyclic, or aromatic alkyl monoalcohols or phenolics. Specific examples of hydroxyl-functional compounds that can be used as blocking / end-capping agents include, but are not limited to, lower aliphatic alcohols such as methanol, ethanol, and n-butanol; alicyclic alcohols such as cyclohexanol and tetrahydrofuran; aromatic-alkyl alcohols such as phenylcarbinol and methylphenylcarbinol; and glycol ethers such as ethylene glycol butyl ether, diethylene glycol butyl ether, ethylene glycol methyl ether, and propylene glycol methyl ether. For some embodiments, the hydroxyl-functional blocking / end-capping group includes phenols, examples of which include, but are not limited to, phenol itself and substituted phenols such as cresols, nitrophenols, and p-hydroxymethylbenzoates.

[0054] Examples of 1H-azoles that can be used as blocking / capping groups include, but are not limited to, 1H-imidazole, 1H-pyrazole, 1H-dialkylpyrazoles (such as 1H-3,5-dimethylpyrazole and 1H-2,5-dimethylpyrazole), 1H-1,2,3-triazole, 1H-1,2,3-benzotriazole, 1H-1,2,4-triazole, 1H-5-methyl-1,2,4-triazole, and 1H-3-amino-1,2,4-triazole.

[0055] Ketoximes useful as blocking / capping groups include those prepared from aliphatic or cycloaliphatic ketones. Examples of ketone oxime capping groups include, but are not limited to, 2-propanone oxime (acetone oxime), 2-butanone oxime (also known as methyl ethyl ketone oxime), 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.

[0056] Examples of lactam end-capping groups include, but are not limited to, e-caprolactam and 2-pyrrolidone. Other suitable end-capping groups include morpholine, 3-aminopropylmorpholine, and N-hydroxyphthalimide.

[0057] For some embodiments of the present invention, the blocked isocyanate groups of the polyisocyanate are each independently blocked with a blocking / capping agent selected from the group consisting of methyl ethyl ketone oxime, pyrazole (more particularly, 1H-pyrazole), and dialkylpyrazole (more particularly, 1H-dialkylpyrazole, such as 1H-3,5-dimethylpyrazole and 1H-2,5-dimethylpyrazole).

[0058] For some embodiments, the polyisocyanate is present in the curable photochromic composition of the present invention in an amount of 40 weight percent to 90 weight percent, or 45 weight percent to 90 weight percent, or 50 weight percent to 85 weight percent, the weight percents being in each case based on the total resin solids weight.

[0059] As used herein, and with respect to curable photochromic compositions, the term "total weight of resin solids" and similar terms (such as "total resin solids weight" and "total resin solids") means the total weight of the polyisocyanate, reactive components, and non-reactive components, and does not include the weight of the photochromic compound and other optional additives unless otherwise specified.

[0060] For some embodiments of the curable photochromic composition of the present invention, the molar ratio of the moles of isocyanate groups of the polyisocyanate to the total moles of reactive groups of the reactive component is 1:1 to 20:1, or 1:1 to 18:1, or 1:1 to 17:1, or 1:1 to 16.5:1.

[0061] The curable photochromic composition of the present invention comprises a reactive component having at least two reactive groups each reacting with the isocyanate group of a polyisocyanate compound. The reactive groups of the reactive component are independently selected from primary amines (-NH2) and imines in each case. At least one reactive group of the reactive component is selected from imines. For some embodiments, the reactive component has 2 to 25 reactive groups, or 3 to 20 reactive groups, or 4 to 15 reactive groups.

[0062] According to some embodiments, the imine group of the reactive component is represented by the following formula (B):

[0063]

[0064] With reference to formula (B), and according to some embodiments, R 1 and R 2 Each independently selected from hydrogen (H), a straight chain or branched C1-C 20 Alkyl, and cyclic C3-C 10 Alkyl, or R 1 and R 2 Together they form a cyclic alkyl group having 3 to 10 carbon atoms in the ring. For some embodiments, R 1 and R 2 At least one of is not hydrogen (H). For some other embodiments, R 1 and R 2 In each case independently other than hydrogen (H). While not intending to be bound by any theory, it is believed that the reaction between the imine groups of the reactive component (as represented by formula (B)) and the isocyanate groups of the polyisocyanate results in the formation of a cyclic linkage between the polyisocyanate and the reactive component.

[0065] For some embodiments, the reactive component includes at least one of: an aliphatic polyether, an aliphatic polyester, an aliphatic polycarbonate, an aliphatic polyethyleneimine, and / or an aliphatic polyurethane, each independently having at least two reactive groups, the reactive groups being independently selected in each case from primary amines and imines, with the proviso that at least one reactive group is selected from imines.

[0066] The aliphatic polyether having at least two reactive groups comprises a plurality of ether linkages (—O—) and is free of aromatic groups. For some embodiments, the aliphatic polyether comprises a linear or branched C2-C4-C6-C8 ... 20 Alkyl linker and / or C3-C 10Cycloalkyl linker. Aliphatic polyethers having at least two reactive groups can be prepared according to methods recognized in the art. For some embodiments, a hydroxy-functional polyether having at least two hydroxy groups is reacted with an aziridine, which results in the formation of an amine-functional polyether intermediate having at least two primary amine groups. Next, at least some of the primary amines of the amine-functional polyether intermediate can be reacted with one or more ketones, which results in the formation of a polyether having an imine group and an optional primary amine group. For some embodiments, the aliphatic polyether having at least two reactive groups has an Mn of 175 g / mol to 20,000 g / mol, or 200 g / mol to 15,000 g / mol, or 200 g / mol to 10,000 g / mol.

[0067] The aliphatic polyester having at least two reactive groups comprises a plurality of carboxylate linkages (-C(O)-O-) and is free of aromatic groups. For some embodiments, the aliphatic polyester comprises linear or branched C2-C2-C2-O- independently extending between and / or from each carboxylate linkage. 20 Alkyl linker and / or C3-C 10 Cycloalkyl linker. Aliphatic polyesters having at least two reactive groups can be prepared according to methods recognized in the art. For 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 intermediate having at least two primary amine groups. Next, at least some of the primary amines of the amine-functional polyester intermediate can be reacted with one or more ketones, which results in the formation of a polyester having an imine group and an optional primary amine group. According to some other embodiments, the hydroxyl-terminated aliphatic polyester undergoes a condensation reaction with an N-benzyloxycarbonyl amino acid in a first step and then undergoes catalytic hydrogenation in a second step, which results in the formation of a primary amine-functional aliphatic polyester intermediate, as described in Bioconjugate Chemistry, 2002, 13 (5), pages 1159-1162. In a third step, at least some of the primary amines of the primary amine-functional aliphatic polyester intermediate are reacted with one or more ketones, which results in the formation of an aliphatic polyester having an imine group and an optional primary amine group. For some embodiments, the aliphatic polyester having at least two reactive groups has an Mn of 210 g / mol to 20,000 g / mol, or 250 g / mol to 15,000 g / mol, or 250 g / mol to 10,000 g / mol.

[0068] The aliphatic polycarbonate having at least two reactive groups comprises a plurality of carbonate linkages (-OC(O)-O-) and is free of aromatic groups. For some embodiments, the aliphatic polycarbonate comprises linear or branched C2-C4-C6-C8-C12-C16-C18-C19-C20-C21-C22-C23-C24-C25-C26-C28-C29-C29-C28 ...8-C29-C28-C28-C28-C28-C28-C28-C28-C28-20 Alkyl linker and / or C3-C 10 Cycloalkyl connecting key. Aliphatic polycarbonates with at least two reactive groups can be prepared according to methods generally recognized in the art. For some embodiments, a hydroxy-functional polycarbonate with at least two hydroxyl groups is reacted with aziridine, which results in the formation of an amine-functional polycarbonate intermediate with at least two primary amine groups. Next, at least some of the primary amines of the amine-functional polycarbonate intermediate can be reacted with one or more ketones, which results in the formation of a polycarbonate with an imine group and an optional primary amine group. For some other embodiments, aliphatic polycarbonates with at least two reactive groups are prepared in a first step by the ring-opening of trimethylene carbonate in the presence of a nitrophenyl functional initiator, and then in a second step by a reduction reaction that results in the formation of a primary amine, as described in Macromolecules [macromolecules], 1997, 30, 6074. In a third step, at least some of the primary amine groups of the primary amine-functional aliphatic polycarbonate intermediate are reacted with one or more ketones, which results in the formation of an aliphatic polycarbonate with an imine group and an optional primary amine group. For some embodiments, the aliphatic polycarbonate having at least two reactive groups has an Mn of 275 g / mol to 20,000 g / mol, or 300 g / mol to 15,000 g / mol, or 300 g / mol to 10,000 g / mol.

[0069] The aliphatic polyurethane polycarbonate having at least two reactive groups comprises a plurality of urethane linkages (-OC(O)-N(H)-) and is free of aromatic groups. For some embodiments, the aliphatic polyurethane comprises linear or branched C1-C2 independently extending between and / or from each urethane linkage. 20 Alkyl linker and / or C3-C 10 Cycloalkyl connecting key.The aliphatic polyurethane with at least two reactive groups can be prepared according to methods generally recognized in the art.For some embodiments, the hydroxyl-functional polyurethane with at least two hydroxyls is reacted with aziridine, which results in the formation of an amine-functional polyurethane intermediate with at least two primary amine groups.Next, at least some of the primary amines of the amine-functional polyurethane intermediate can be reacted with one or more ketones, which results in the formation of a polyurethane with imine groups and optional primary amine groups.For some embodiments, the aliphatic polyurethane with at least two reactive groups has an Mn of 350g / mol to 20,000g / mol, or 400g / mol to 15,000g / mol, or 400g / mol to 10,000g / mol.

[0070] Aliphatic polyethyleneimine with at least two reactive groups does not contain aromatic groups.Aliphatic polyethyleneimine can be referred to as the polyethyleneimine with at least two reactive groups in this article.For some embodiments, in the first step, aliphatic polyethyleneimine is prepared by the ring-opening polymerization of aziridine.For some embodiments, the gained polyethyleneimine intermediate is branched and comprises the combination of primary amine group, secondary amine group and tertiary amine group.At least some of the primary amine of polyethyleneimine intermediate are reacted with one or more ketones, which results in the formation of aliphatic polyethyleneimine with imine group and optional primary amine group.For some embodiments, commercially available polyethyleneimine (such as EPOMIN polyethyleneimine) with primary amine group is reacted with one or more ketones, which results in the formation of aliphatic polyethyleneimine with imine group and optional primary amine group. For some embodiments, the aliphatic polyethyleneimine having at least two reactive groups has an Mn of 140 g / mol to 5000 g / mol, or 150 g / mol to 2500 g / mol, or 200 g / mol to 2500 g / mol.

[0071] For some embodiments, the reactive component has a reactive group equivalent weight of 70 g / mol to 2600 g / mol, or 75 g / mol to 2000 g / mol, or 80 g / mol to 1500 g / mol. The listed reactive group equivalent weight values ​​and related ranges represent in each case the combination (or sum) of the primary amine group equivalent weight and the imine group equivalent weight.

[0072] For some embodiments, the reactive component is formed by the reaction of a polyamine comprising at least two primary amine groups (-NH2) and at least one ketone (ketone type). The reaction between the primary amine and the ketone results in the formation of an imine group, as represented by the above formula (B). For some embodiments, each ketone reacted with the primary amine of the polyamine has a formula weight of less than 300g / mol (such as 58g / mol to less than 300g / mol). Examples of such ketones include, but are not limited to, dimethyl ketone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-propyl ketone, methyl isopropyl ketone, cyclopentanone, and acetophenone. For some additional embodiments, at least 80 percent of the primary amine groups, or at least 85 percent of the primary amine groups, or at least 90 percent of the primary amine groups, or at least 95 percent of the primary amine groups, or 100 percent of the primary amine groups (including ranges thereof, such as 80% to 100%, or 85% to 100%, or 90% to 100%, or 95% to 100% of the primary amine groups) of the polyamine are reacted with ketones and thereby converted into imine groups.

[0073] For some embodiments, the reactive component comprises: 0% to 20% primary amine groups, and 80% to 100% imine groups; or 0% to 15% primary amine groups, and 85% to 100% imine groups; or 0% to 10% primary amine groups, and 90% to 100% imine groups; or 0% to 5% primary amine groups, and 95% to 100% imine groups, the percentages being in each case based on the total number of primary amine groups and imine groups.

[0074] For some embodiments, the reactive component is present in the curable photochromic composition in an amount of 1 weight percent to 20 weight percent, or 1 weight percent to 15 weight percent, or 2 weight percent to 14 weight percent, the weight percents being in each case based on total resin solids weight.

[0075] The curable photochromic composition of the present invention comprises a non-reactive component that does not contain a functional group that reacts with: a polyisocyanate; and a reactive component. More particularly, the non-reactive component does not contain a functional group that reacts with: an isocyanate group of a polyisocyanate; and a reactive group (primary amine group and imine group) of the reactive component.

[0076] For some embodiments, the non-reactive component includes at least one of: a polyether, a polyester, a polycarbonate, a polyurethane, and / or an organophosphate. Further in accordance with the present invention, the non-reactive component includes at least one of: an aliphatic polyether, an aliphatic polyester, an aliphatic polycarbonate, an aliphatic polyurethane, and / or an organophosphate. According to some embodiments, the polyether, polyester, polycarbonate, and polyurethane from which the non-reactive component can be selected each independently have an Mn of 300 to 10,000 g / mol, or 300 to 8000 g / mol, or 300 to 7000 g / mol.

[0077] The polyether of the non-reactive component comprises a plurality of ether linkages (-O-) and, in the case of aliphatic polyethers, contains no aromatic groups. For some embodiments, the polyether is an aliphatic polyether and comprises a linear or branched C2-C4-C6-C8 ... 20 Alkyl linker and / or C3-C 10 Cycloalkyl linkage. The polyether of the non-reactive component can be prepared according to methods recognized in the art. For some embodiments, the polyether of the non-reactive component has a terminal ether group, such as a terminal -OR a Group, where R a is independently in each case a linear or branched C1-C 20 Alkyl or C3-C 10 For some additional embodiments, the polyether of the non-reactive component has a terminal carboxylate group, such as a terminal -OC(O)Ra Group, where R a is independently in each case a linear or branched C1-C 20 Alkyl or C3-C 10 Cycloalkyl.

[0078] The polyester of the non-reactive component comprises a plurality of carboxylate linkages (-C(O)-O-) and, in the case of an aliphatic polyester, is free of aromatic groups. For some embodiments, the polyester of the non-reactive component is an aliphatic polyester and comprises linear or branched C2-C ... 20 Alkyl linker and / or C3-C 10 The polyester of the non-reactive component can be prepared according to methods recognized in the art. For some additional embodiments, the polyester of the non-reactive component has a terminal carboxylate group, such as a terminal -OC(O)R a Group and / or terminal -C(O)OR a Group, where R a is independently in each case a linear or branched C1-C 20 Alkyl or C3-C 10 Cycloalkyl.

[0079] The polycarbonate of the non-reactive component comprises a plurality of carbonate linkages (-OC(O)-O-) and, in the case of aliphatic polycarbonates, is free of aromatic groups. For some embodiments, the polycarbonate of the non-reactive component is an aliphatic polycarbonate and comprises linear or branched C2-C4-C6-C8-C10-C12-C16-C18-C19-C20-C19-C21-C19-C18 ...8-C19-C18-C18-C19-C18-C18-C19-C18-C18-C18-C19-C18-C18-C18-C 20 Alkyl linker and / or C3-C 10 Cycloalkyl linkage. The polycarbonate of the non-reactive component can be prepared according to methods recognized in the art. For some additional embodiments, the polycarbonate of the non-reactive component has a terminal carbonate group, such as a terminal -OC(O)-OR a Group, where R a is independently in each case a linear or branched C1-C 20 Alkyl or C3-C 10 Cycloalkyl.

[0080] The polyurethane of the non-reactive component comprises a plurality of urethane linkages (-OC(O)-N(H)-) and, in the case of aliphatic polyurethanes, is free of aromatic groups. For some embodiments, the polyurethane of the non-reactive component is an aliphatic polyurethane and comprises linear or branched C2-C4 groups independently extending between and / or from each urethane linkage. 20 Alkyl linker and / or C3-C10 Cycloalkyl linkage. The polyurethane of the non-reactive component can be prepared according to methods recognized in the art. For some additional embodiments, the polyurethane of the non-reactive component has a terminal carbamate group, such as a terminal -N(H)-C(O)-OR a Group, where R a is independently in each case a linear or branched C5-C 20 Alkyl or C6-C 10 Cycloalkyl.

[0081] For some embodiments, the organic phosphate from which the non-reactive component may be selected is represented by the following formula (C),

[0082] Formula (C)

[0083] P(O)(OR')3

[0084] With reference to formula (C), each R' is independently selected at each occurrence from alkyl, haloalkyl, perhaloalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and combinations thereof (including those species and examples thereof as previously listed herein). For some further embodiments, each R' of formula (C) is independently selected at each occurrence from alkyl, cycloalkyl, aryl, and combinations thereof. With further reference to formula (C), and according to some further embodiments, each R' is independently selected at each occurrence from C1-C 20 Straight chain alkyl, C3-C 20 Branched alkyl, C3-C 20 Cycloalkyl, C5-C 20 aryl, and combinations thereof. With additional reference to formula (C), and according to some additional embodiments, each R' is independently selected at each occurrence from: phenyl; 20 Straight chain alkyl, C3-C 20 Branched alkyl, or C3-C 20 At least one phenyl substituted in the cycloalkyl group; C1-C 20 Straight chain alkyl; C3-C substituted with at least one phenyl group 20 Branched alkyl; and C3-C 20 Non-limiting examples of organic phosphates from which the non-reactive component may be selected include tricresyl phosphate, tris(2-phenylethyl) phosphate, tris(2-chloroethyl) phosphate, tris(1,3-dichloro-2-propyl) phosphate, cresyl diphenyl phosphate, tris(2,3-dibromopropyl) phosphate, tris(2-ethylhexyl) phosphate, and tris(2-methylphenyl) phosphate.

[0085] For some embodiments, the non-reactive components of the curable photochromic composition of the present invention have a viscosity (at 25° C.) of 1 cP to 60,000 cP, or 1 cP to 10,000 cP, or 1 cP to 7500 cP (where cP means centipoise in each case). The viscosity can be measured according to methods recognized in the art. For some embodiments, the viscosity is measured using a rotational viscometer (such as a Brookfield CAP 2000+ viscometer available from AMETEK, Inc.) according to the manufacturer's instructions. Additional methods for measuring viscosity include, but are not limited to, those described in ASTM D789 or ASTM D4878.

[0086] According to some embodiments of the curable photochromic composition of the present invention, the non-reactive component is present in an amount of 10 weight percent to 40 weight percent, or 15 weight percent to 35 weight percent, or 20 weight percent to 35 weight percent, wherein the weight percentages are in each case based on the total resin solids of the curable photochromic composition.

[0087] The curable photochromic composition of the present invention comprises a photochromic compound. The photochromic compound may be selected from known types and examples of photochromic compounds, and may include combinations or mixtures thereof.

[0088] For example, although not limiting herein, mixtures of photochromic compounds can be used to obtain certain activated colors, such as near-neutral gray or near-neutral brown. See, for example, U.S. Pat. No. 5,645,767 at column 12, line 66 to column 13, line 19, which describes parameters defining neutral gray and brown, the disclosure of which is specifically incorporated herein by reference.

[0089] For some embodiments, the photochromic compound of the curable photochromic composition of the present invention is selected from the group consisting of naphthopyrans, benzopyrans, phenanthropyrans, indenonaphthopyrans, spiro(indoline)naphthooxazines, spiro(indoline)pyridobenzoxazines, spiro(benzidinolline)pyridobenzoxazines, spiro(benzidinolline)naphthooxazines, spiro(indoline)-benzoxazines, fulgides, fulgimides, diarylethenes, and mixtures of such photochromic compounds.

[0090] Additional examples of other photochromic compounds that may be used in the curable photochromic composition of the present invention include, but are not limited to, those disclosed in US Pat. No. 9,028,728 B2, column 34, line 20 to column 35, line 13, the disclosure of which is specifically incorporated herein by reference.

[0091] The photochromic compound is present in the curable photochromic composition of the present invention in at least a sufficient amount to provide a desired level of photochromic properties to an article prepared from the composition, which in some embodiments is referred to as a photochromic amount. For some embodiments, the amount of the photochromic compound present in the curable photochromic composition is 0.001 weight percent to 40 weight percent, or 0.001 to 10 weight percent, or 0.01 to 8 weight percent, or 0.1 to 2.5 weight percent, wherein the weight percents are in each case based on the total resin solids weight.

[0092] For some embodiments, the curable photochromic composition of the present invention may optionally include additives, such as, but not limited to: waxes, such as waxes for flow and wetting; flow control agents, such as poly (2-ethylhexyl) acrylate; antioxidants; adhesion promoters, such as (3-glycidyloxypropyl) trimethoxysilane; surfactants; and ultraviolet (UV) light absorbers. Examples of useful antioxidants and UV light absorbers include, but are not limited to, those commercially available from BASF under the trademarks IRGANOX and TINUVIN. A non-limiting class of antioxidants is hindered amine light stabilizers (HALS), which may include one or more 2,2,6,6-tetraalkylpiperidin-4-yls, such as one or more 2,2,6,6-tetramethylpiperidin-4-yls. When used, these optional additives may be present in an amount up to 20 weight percent based on the total resin solids weight.

[0093] For some embodiments, the curable photochromic composition of the present invention may 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 a dye that is a non-photosensitive material that has no physical or chemical response to electromagnetic radiation in terms of its visually observed color. As used herein, the term "fixed-tint dye" and related terms do not include photochromic compounds and can be distinguished from photochromic compounds. As used herein, the term "non-photosensitive material" means a material that has no physical or chemical response to electromagnetic radiation in terms of its visually observed color, including but not limited to fixed-tint dyes.

[0094] One or more fixed hue dyes may be present in the curable photochromic composition of the present invention for purposes including, but not limited to, providing a cured article prepared from the curable photochromic composition with: at least one primary (or first) color characteristic of the fixed hue dye when the photochromic compound is not activated; and optionally, a second color characteristic of the combination of the fixed hue dye and the photochromic compound when activated (e.g., by exposure to actinic radiation).

[0095] For some embodiments, the optional fixed hue dye of the curable photochromic composition includes at least one of an azo dye, an anthraquinone dye, a xanthene dye, an azime dye, iodine, an iodide salt, a polyazo dye, a stilbene dye, a pyrazolone dye, a triphenylmethane dye, a quinoline dye, an oxazine dye, a thiazine dye, and a polyene dye.

[0096] The fixed hue dye can be present in the curable photochromic composition in various amounts to provide the desired effect in the cured article prepared therefrom. For some embodiments, the fixed hue dye is present in the curable photochromic composition in an amount of 0.001 to 15 weight percent, or 0.01 to 10 weight percent, or 0.1 to 2.5 weight percent, the weight percent being in each case based on the total resin solids weight of the curable photochromic composition.

[0097] For some embodiments, the curable photochromic compositions of the present invention may include one or more solvents, such as one or more organic solvents.

[0098] The types of organic solvents that may be present in the curable photochromic composition of the present invention include, but are not limited to, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; 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-pyrrolidone, 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 commercially available as C9-C 10 A mixture of dialkyl-benzenes and trialkyl-benzenes), and Aromatic 150 Fluid (which is a commercially available C 10 -C 12 mixture of alkylbenzenes and alkylnaphthalenes).

[0099] The solvent may be present in the curable photochromic composition of the present invention in an amount of 5 to 95 weight percent, or 15 to 80 weight percent, 30 to 70 weight percent, or 30 to 60 weight percent, the weight percents being in each case based on the total weight of the curable photochromic composition (including the weight of the solvent).

[0100] For some embodiments, the curable photochromic composition of the present invention may include one or more curing catalysts for catalyzing the reaction between the unblocked and / or blocked isocyanate groups of the polyisocyanate component and the reactive groups of the reactive component. Useful catalyst types include, but are not limited to, metal compounds, such as, but not limited to, organotin compounds, organobismuth compounds, organozinc compounds, organozirconium compounds, organoaluminum compounds, organonickel compounds, organomercury compounds, and alkali metal compounds; and amine compounds, such as tertiary amine compounds, and quaternary ammonium compounds. Examples of organotin compounds include, but are not limited to, tin (II) salts of carboxylic acids, such as tin (II) acetate, tin (II) octoate, 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-hydroxyalkyl quaternary ammonium carboxylates. For some embodiments, the catalyst is selected from tin (II) octoate, dibutyltin (IV) dilaurate, and / or bismuth 2-ethylhexanoate.

[0101] For some embodiments of the present invention, the curable photochromic composition comprises a curing catalyst comprising an organotin compound selected from a tin(II) salt of a carboxylic acid, a tin(IV) compound, or a combination thereof.

[0102] For some additional embodiments of the present invention, the curable photochromic composition comprises an organic tin compound selected from the group consisting of tin(II) acetate, tin(II) octoate, tin(II) ethylhexanoate, tin(II) laurate, dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, dioctyltin diacetate, or combinations thereof.

[0103] The curing catalyst is typically present in an amount of about 0.05 to about 5.0 weight percent, or about 0.25 to about 2.0 weight percent, based on the total weight of resin solids of the curable photochromic composition.

[0104] The curable photochromic composition of the present invention can be cured by any suitable method, which results in the formation of covalent bonds between the isocyanate groups of the polyisocyanate and the reactive groups (primary amine groups and imine groups) of the reactive component. For some embodiments, the curable photochromic composition is cured by exposure to high temperatures (exceeding ambient room temperature, such as above 25°C). For some embodiments, exposure to high temperatures results in the deblocking of the blocked isocyanate groups of the polyisocyanate (when it contains blocked isocyanate groups). As used herein, "cured" means that the three-dimensional cross-linked network is formed by covalent bond formation, which is generated by the reaction between the isocyanate groups of the polyisocyanate and the reactive groups (primary amine groups and imine groups) of the reactive component. When cured at high temperatures, the curable photochromic composition can be referred to as a thermosetting curable photochromic composition herein. 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 the curing is performed. For some embodiments, the curable photochromic composition is cured at an elevated temperature of 80°C to 175°C, or 85°C to 150°C, or 90°C to 130°C for a period of 15 to 240 minutes.

[0105] The present invention also relates to articles and in particular photochromic articles prepared from the curable photochromic compositions of the present invention as previously described herein.For some embodiments, the photochromic article is selected from a layer (including a film and / or sheet) and a 3-dimensional article.

[0106] Types 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.

[0107] More typically, the curable photochromic composition of the present invention is used to prepare a photochromic layer, such as a photochromic film and a photochromic sheet. As used herein, the term "film" means a non-self-supporting layer, such as, but not limited to, a coating. As used herein, the term "sheet" means a self-supporting layer, such as, but not limited to, an extruded sheet.

[0108] The present invention also relates to an article, such as a photochromic article, comprising: (A) a substrate; and (B) a photochromic layer on at least one surface of the substrate, wherein the photochromic layer is formed from the curable photochromic composition of the present invention.

[0109] For some embodiments, the article comprising a substrate and a photochromic layer (formed by the curable photochromic composition of the present invention) on at least one surface of the substrate can be selected from ophthalmic articles, display articles, windows, and mirrors. Accordingly, the substrate of the article can be selected from ophthalmic substrates, displays, windows, and mirrors. The substrate can be composed of one or more suitable materials, including but not limited to: organic materials, such as organic polymer materials, such as but not limited to thermoplastic polycarbonates, cross-linked polycarbonates, poly (meth) acrylates, and combinations thereof; glass, such as silica-based glass; metals; ceramic materials; and combinations thereof. Examples of substrates that can be included in the articles (including optical elements) of the present invention include but are not limited to those described in US8,628,685 B2 (the disclosure of which is incorporated herein by reference) at column 35, line 5 to column 36, line 57.

[0110] For some embodiments, the substrate may optionally include a photochromic material and / or a fixed hue dye, each of which may be selected from those classes and examples of photochromic materials and fixed hue dyes as previously described herein. The optional photochromic material / compound present in the substrate may be the same or different from the photochromic compound of the photochromic layer. The optional fixed hue dye may be the same or different from the optional fixed hue dye of the photochromic layer.

[0111] The photochromic layer of the article can be a photochromic film or a photochromic sheet. For some embodiments, the photochromic film of the article is a photochromic coating, and the curable photochromic composition of the present invention is a curable photochromic coating composition.

[0112] The curable photochromic coating composition can be applied to the substrate according to methods recognized in the art, including but not limited to spraying application methods, curtain coating application methods, doctor blade (or rod) application methods, dip coating application methods, spin coating application methods, jet printing methods (such as inkjet printing methods, wherein "ink" is replaced by the curable photochromic composition according to the present invention), and combinations thereof.

[0113] After applying the curable photochromic composition on at least one surface of the substrate, the applied curable photochromic composition is cured as previously described herein. The photochromic coating can be in the form of a single layer or multiple layers. When in the form of multiple layers, each layer of the photochromic layer can be prepared by a curable photochromic composition according to the present invention (having the same or different compositions, such as the same or different photochromic compounds). The photochromic layer can have any suitable thickness, such as 10 microns to 250 microns, or 15 microns to 75 microns.

[0114] In addition to the photochromic layer, the article may optionally include one or more additional art-recognized layers, such as, but not limited to: a primer layer; an adhesive layer; a protective layer (such as a hard coat); a polarizing layer; a birefringent layer; an antireflective layer; and / or an additional photochromic layer prepared from a composition other than the curable photochromic composition of the present invention.

[0115] The present invention further relates to a photochromic multilayer article comprising at least one photochromic layer formed by a curable photochromic composition of the present invention. Each layer of the photochromic multilayer article can be independently in the form of a film or sheet. For some embodiments, the photochromic multilayer article can include two or more layers formed by the same or different curable photochromic compositions of the present invention.

[0116] The multilayer articles of the present invention may optionally include one or more additional art-recognized layers, such as, but not limited to: an adhesive layer; a protective layer (e.g., a hard coat); a polarizing layer; a birefringent layer; an antireflective layer; and / or an additional photochromic layer prepared from a composition other than the curable photochromic composition of the present invention.

[0117] The multilayer articles of the present invention may have any suitable thickness, such as from 10 micrometers to 1000 micrometers, or from 15 micrometers to 750 micrometers, or from 25 to 100 micrometers.

[0118] The multilayer articles of the present invention may be used alone or in combination with another article, such as a substrate. The substrate may be selected from those types and examples of substrates as previously described herein for articles of the present invention, such as ophthalmic substrates, displays, windows, and / or mirrors. The substrate may be composed of one or more suitable materials, including, but not limited to: organic materials, such as organic polymer materials; glass, such as silica-based glass; metals; ceramic materials; and combinations thereof.

[0119] The multilayer articles of the present invention may be attached to the surface of the substrate by methods recognized in the art, such as, but not limited to: electrostatic adsorption, such as with static electricity; one or more interposed adhesive layers; melt bonding, such as hot melt bonding; and in-mold forming, such as where the multilayer article is placed in a mold and the substrate is formed against at least one surface of the multilayer article in the mold. For some embodiments, the multilayer articles of the present invention may be supported by one or more supports that are retainedly engaged with one or more peripheral regions of the multilayer article.

[0120] The present invention may be further characterized by one or more of the following non-limiting clauses.

[0121] Item 1: A curable photochromic composition comprising:

[0122] (a) photochromic compounds;

[0123] (b) a polyisocyanate comprising at least two isocyanate groups;

[0124] (c) a reactive component comprising at least two reactive groups each reactive with an isocyanate group of a polyisocyanate, wherein each reactive group of the reactive component is independently selected from primary amines and imines, with the proviso that at least one reactive group of the reactive component is selected from imines; and

[0125] (d) A non-reactive component that does not contain functional groups that react with the polyisocyanate and the reactive component.

[0126] Item 2: A curable photochromic composition as described in Item 1, wherein the molar ratio of the number of moles of isocyanate groups of the polyisocyanate to the total number of moles of reactive groups of the reactive component is 1:1 to 20:1, or 1:1 to 18:1, or 1:1 to 17:1, or 1:1 to 16.5:1.

[0127] Item 3: The curable photochromic composition of Item 1 or Item 2, wherein the polyisocyanate comprises at least one of the following: a linear or branched aliphatic polyisocyanate, an alicyclic polyisocyanate, a biuret thereof, an allophanate thereof, an isocyanurate thereof, and a combination thereof.

[0128] Clause 4: The curable photochromic composition of any of Clauses 1-3, wherein the polyisocyanate has an isocyanate equivalent weight of 95 to 500 g / mol, or 150 to 400 g / mol, or 150 to 350 g / mol.

[0129] Item 5: The curable photochromic composition of any of Items 1-4, wherein at least some of the isocyanate groups of the polyisocyanate are reversibly blocked by a blocking agent.

[0130] Clause 6: A curable photochromic composition as described in any of clauses 1-5, wherein the polyisocyanate is present in an amount of 40 weight percent to 90 weight percent, or 45 weight percent to 90 weight percent, or 50 weight percent to 85 weight percent, the weight percentages being in each case based on the total resin solids weight.

[0131] Item 7: The curable photochromic composition of any of Items 1-6, wherein the reactive component comprises at least one of an aliphatic polyether, an aliphatic polyester, an aliphatic polycarbonate, an aliphatic polyethyleneimine, or an aliphatic polyurethane, each independently having at least two reactive groups.

[0132] Item 8: The curable photochromic composition of any of Items 1-7, wherein the reactive component has a reactive group equivalent weight of 70 g / mol to 2600 g / mol, or 75 g / mol to 2000 g / mol, or 80 g / mol to 1500 g / mol.

[0133] Item 9: The curable photochromic composition of any of Items 1-8, wherein the reactive component is formed from the reaction of a polyamine comprising primary amine groups and at least one ketone.

[0134] Item 10: The curable photochromic composition of Item 9, wherein each ketone independently has a formula weight of less than 300 g / mol.

[0135] Item 11: The curable photochromic composition of Item 9 or Item 10, wherein each ketone independently has a formula weight of 58 g / mol to less than 300 g / mol.

[0136] Item 12: A curable photochromic composition as described in any of Items 9-11, wherein at least 80 percent of the primary amine groups of the polyamine, or at least 85 percent of the primary amine groups of the polyamine, or at least 90 percent of the primary amine groups of the polyamine, or at least 95 percent of the primary amine groups of the polyamine, or 100 percent of the primary amine groups of the polyamine are converted to imine groups by reaction with a ketone.

[0137] Item 13: A curable photochromic composition as described in any of Items 1-12, wherein the reactive component is present in an amount of 1 weight percent to 20 weight percent, or 1 weight percent to 15 weight percent, or 2 weight percent to 14 weight percent, the weight percentages being in each case based on the total resin solids weight of the curable photochromic composition.

[0138] Item 14: The curable photochromic composition of any of Items 1-13, wherein the non-reactive component has a viscosity of 1 cP to 60,000 cP, or 1 cP to 10,000 cP, or 1 cP to 7500 cP, in each case at 25°C.

[0139] Clause 15: The curable photochromic composition of any of Clauses 1-14, wherein the non-reactive component comprises at least one of: a polyether, a polyester, a polycarbonate, a polyurethane, and / or an organic phosphate.

[0140] Clause 16: The curable photochromic composition of any of Clauses 1-15, wherein the non-reactive component comprises at least one of a polyether, a polyester, a polycarbonate, and / or a polyurethane, each independently having an Mn of 300 to 10,000 g / mol, or 300 to 8000 g / mol, or 300 to 7000 g / mol.

[0141] Clause 17: A curable photochromic composition as described in any of clauses 1-16, wherein the non-reactive component includes at least one of the following: an aliphatic polyether, an aliphatic polyester, an aliphatic polycarbonate, and / or an aliphatic polyurethane, each independently having an Mn of 300 to 10,000 g / mol, or 300 to 8000 g / mol, or 300 to 7000 g / mol.

[0142] Clause 18: The curable photochromic composition of any one of Clauses 1 to 17, wherein the non-reactive component comprises an organic phosphate represented by the following formula (C),

[0143] Formula (C)

[0144] P(O)(OR')3

[0145] wherein R' at each occurrence is independently selected from alkyl, haloalkyl, perhaloalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and combinations thereof.

[0146] Item 19: A curable photochromic composition as described in Item 18, wherein R' is independently selected from: phenyl; 20 Straight chain alkyl and / or C3-C 20 At least one phenyl substituted in the branched alkyl group; C1-C 20 Straight chain alkyl; and C3-C 20 Branched chain alkyl.

[0147] Item 20: A curable photochromic composition as described in any of Items 1-19, wherein the non-reactive component is present in an amount of 10 weight percent to 40 weight percent, or 15 weight percent to 35 weight percent, or 20 weight percent to 35 weight percent, the weight percentages being in each case based on the total resin solids of the curable photochromic composition.

[0148] Item 21: A curable photochromic composition as described in any of Items 1 to 20, wherein the photochromic compound (a) comprises at least one of the following: naphthopyran, benzopyran, phenanthropyran, indenonaphthopyran, spiro(dihydroindole)naphthooxazines, spiro(dihydroindole)pyridobenzoxazines, spiro(benzodihydroindole)pyridobenzoxazines, spiro(benzodihydroindole)naphthooxazines, spiro(dihydroindole)-benzoxazines, fulgated anhydrides, fulgated imides, and / or diarylethenes.

[0149] Item 22: The curable photochromic composition of any of Items 1-21, wherein the curable photochromic composition further comprises an additive selected from the group consisting of waxes, flow control agents, antioxidants, surfactants, adhesion promoters, ultraviolet light absorbers, and combinations thereof.

[0150] Item 23: The curable photochromic composition of any of Items 1-22, wherein the curable photochromic composition further comprises a curing catalyst selected from the group consisting of metal compounds, amine compounds, and combinations thereof.

[0151] Clause 24: An article of manufacture comprising:

[0152] (A) a substrate; and

[0153] (B) a photochromic layer on at least one surface of the substrate, wherein the photochromic layer is formed from the curable photochromic composition according to any one of clauses 1-23.

[0154] 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 indicated, all parts and all percentages are by weight.

[0155] Examples

[0156] In Section 1 of the following Examples, the preparation of polyethylene imine having primary amine groups and imine groups is described (Example 1). In Section 2, the preparation of comparative curable photochromic compositions is described (CE-2, CE-3, and CE-4). In Section 3, the preparation of curable photochromic compositions according to the present invention is described (Examples 5-12). In Section 3, the preparation of photochromic test samples is described. In Section 4, physical testing and evaluation of test samples prepared using comparative curable photochromic compositions and curable photochromic compositions of the present invention are described and summarized.

[0157] Part 1. Preparation of polyethyleneimine having primary amine groups and imine groups.

[0158] Example 1

[0159] EPOMIN TM SP006 polyethyleneimine (10 g; branched polyethyleneimine with a reported number average molecular weight of 600 g / mol and a calculated primary amine equivalent weight of 142.8 g / mol, available from Nippon Shokubai Co., Ltd.) and methyl ethyl ketone (21.63 g) were combined in a closed 100 ml amber vial and stirred at 60° C. for 1 hour using a magnetic stir bar. From NMR analysis, the estimated conversion of primary amine to imine was determined to be approximately 82%, with a calculated equivalent weight of reactive groups (the sum of primary and imine groups) of 178.5 g / mol. The resulting solution, which had a theoretical solids of 69 wt.%, was used in the following compositions without any further purification or modification.

[0160] Part 2. Preparation of comparative curable photochromic compositions.

[0161] Comparative Examples CE-2 to CE-4

[0162] Comparative Examples (CE) CE-2, CE-3 and CE-4 were prepared using the components listed in Table 1 (shown in parts by weight). The components of Charge 1 were combined and heated to 70°C and stirred for a minimum of 1 hour until the solids were observed to have completely dissolved. Once cooled to room temperature, the components of Charge 2 were added and the solution was stirred for 1 hour. The components of Charge 3 were added and the solution was stirred for at least 1 hour before use.

[0163] Table 1 Comparative Examples

[0164]

[0165] (1) The formulated blend of photochromic indeno-fused naphthopyran dyes provides a grey color upon activation.

[0166] (2) Hindered amine light stabilizers are commercially available from BASF.

[0167] (3) Antioxidant, commercially available from BASF.

[0168] (4) Polyether-modified dimethylpolysiloxane copolymers, available from BYK-Chemie.

[0169] (5)Blocked hexamethylene diisocyanate biuret available from Baxenden Chemical Co. has an isocyanate equivalent weight (on a solids basis) of 287 g / mol and is provided at 70% solids in propylene glycol monomethyl ether.

[0170] (6) Polycarbonate diol, having an average equivalent weight of 500 g / mol, commercially available from Ube Americas Inc.,

[0171] (7) The material had a reported viscosity of 15.8 cP at 20°C.

[0172] Example 5-7

[0173] Examples 5-7 are curable photochromic compositions according to the present invention, prepared using the components listed in Table 2 below (shown in parts by weight) and according to the description provided above for Comparative Examples 2-4. For the following Examples 5-7, the ratio of isocyanate to reactive groups (the sum of primary amine groups and imine groups) is increased, where the level of non-reactive components is the same for Examples 5 and 6, and is reduced for Example 7.

[0174] Table 2

[0175]

[0176]

[0177] Example 8-12

[0178] Examples 8-12 are curable photochromic compositions according to the present invention, prepared using the components listed in Table 3 below (shown in parts by weight) and according to the description provided above for Comparative Examples 2-4. For the following Examples 8-12, the ratio of isocyanate to reactive groups (the sum of primary amine groups and imine groups) was maintained at 5:1 in each case, while the amount and / or type of non-reactive components was varied.

[0179] Table 3

[0180]

[0181] ___________________

[0182] (8)Polymer adipates commercially available from Eastman Chemical Company have reported viscosities of 4800 to 6400 cP at 25°C and a molecular weight (Mw) of 5860 g / mol as determined by GPC with polystyrene standards using THF as solvent.

[0183] Part 3. Preparation of Photochromic Test Samples.

[0184] The curable photochromic compositions of Comparative Examples 2-4 and Examples 5-12 were in each case applied by spin coating to Coated The polycarbonate flat lenses were applied individually, each lens having a diameter of 76 mm. Prior to the spin coating application, each lens was corona treated using a Tantec device with a 70 KV and 1000 W setting. Approximately 2 mL of each composition was dispensed onto the substrate, which was then spun for six seconds at a rotation speed sufficient to deposit the following on the lens: 0.28-0.35 g wet coating (wet weight depending on non-volatile solids %) for each curable photochromic composition. Test samples of CE-2, CE-3, CE-4, and Examples 5 to 12 were prepared in duplicate and then cured in a forced air electric oven at 125° C. for 1 hour.

[0185] Section 4. Evaluation of test samples.

[0186] Part 4a. Microhardness evaluation.

[0187] A set of replicated test samples were subjected to additional heat curing at 105°C for three hours and set aside for microhardness measurement. These samples were then subjected to microhardness testing using a Fischerscope HCV, model H100SMC, available from Fischer Technology, Inc. Hardness was measured at a penetration depth of 2 microns after 15 seconds under a 100 millinewtons load. Each test sample was measured at least twice and the resulting data was averaged. Microhardness results are further listed in Tables 4-6 herein.

[0188] Section 4b. Photochromic Properties.

[0189] The second set of replicate test samples were further corona treated 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 B2. The test samples were cured in a UV oven equipped with a D bulb. Thereafter, each test sample was thermally cured at 105° C. for three hours.

[0190] The photochromic properties of the test samples were tested on a photochromic measurement platform ("BMP") manufactured by Essilor, Ltd. France. During the test, the BMP was maintained at a constant temperature of 73.4°F (23°C). Prior to testing, each of the coated test samples was exposed to 365 nanometer ultraviolet light at a distance of about 14 centimeters for about 10 minutes to activate the photochromic material. The UVA (315 to 380 nm) irradiance at the lens was measured using a model Li-1800 spectroradiometer and found to be 22.2 watts per square meter. Each test sample was then placed under a 500 watt high intensity halogen lamp at a distance of about 36 cm for about 10 minutes to bleach (deactivate) the photochromic material. The spectroradiometer measured the illuminance at the sample and found to be 21.9 Klux. Each test sample was then kept in a dark environment at room temperature (70°F to 75°F, or 21°C to 24°C) for at least one hour before testing on the BMP. Prior to measurement, the UV absorbance of each lens at 390 nanometers (Abs 390nm) was measured.

[0191] The BMP optical bench is equipped with two 150 watt Newport model #6255 xenon arc lamps set at right angles to each other. The light path from lamp 1 is directed through a 3mm KG-2 bandpass filters and appropriate neutral density filters, which contribute to the required UV and partial visible light irradiance levels. The light path from lamp 2 is directed through a 3mm KG-2 bandpass filter, A short band 400 nm cutoff filter and appropriate neutral density filters were used to provide supplemental visible light illumination. A 2 inch x 2 inch 50% polka dot beam splitter set at 45° to each lamp was used to mix the two beams. The intensity of the irradiance was adjusted using a combination of neutral density filters and xenon arc lamp voltage control. Software (i.e., BMPSoft version 2.1e) was used on the BMP to control timing, irradiance, gas chamber and sample temperature, shutters, filter selection, and response measurement. A 100 mm x 200 mm optical microscope was used with a fiber optic cable for light transmission through the lens. Response and color measurements were performed using a spectrophotometer (Model MCS601). Photopic response measurements were collected on each lens.

[0192] The power output of the optical bench (i.e., the dose of light to which the lens is exposed) was adjusted to 6.7 W / m 2) UVA, integrated from 315-380nm, and 50Klux illumination, integrated from 380-780nm. The measurement of this power set point is performed using an irradiance probe and a calibrated Zeiss (Zeiss) spectrophotometer. The lens sample pool is equipped with a quartz window and an automatic centering sample holder. The temperature in the sample pool is controlled at 23°C by software using an improved Facis, model FX-10 environmental simulator. The measurement of the dynamic photochromic response of the sample and the color measurement are performed using the same Zeiss spectrophotometer, which has an optical fiber cable for transmitting light from a halogen tungsten lamp through the sample. The collimated monitoring beam from the optical fiber cable is maintained perpendicular to the test sample while passing through the sample and being guided to the receiving optical fiber cable assembly attached to the spectrophotometer. The exact placement point of the sample in the sample pool is where the activation xenon arc beam and the monitoring beam intersect to form two concentric circles of light. The incident angle of the xenon arc beam at the sample placement point is about 30° relative to the vertical line.

[0193] The response measurement, expressed as the change in optical density (ΔOD) from the unactivated or whitish state to the activated or colored state, is determined by establishing an initial unactivated transmittance, opening the shutter of the xenon lamp and measuring the transmittance through activation at selected time intervals. The change in optical density is determined according to the following formula: ΔOD = log 10 (%Tb / %Ta), where %Tb is the percent transmittance in the blanch state and %Ta is the percent transmittance in the activated state. Optical density measurements are based on photopic optical density.

[0194] The results of microhardness and photochromic performance for CE-2, CE-3, CE-4 and Examples 5-12 are summarized below in Tables 4 to 6. The ΔOD at saturation was measured 15 minutes after activation and the fade half-life ("T1 / 2") value is the time interval (in seconds) for the ΔOD of the activated form of the photochromic material in the coating to reach half of the ΔOD at fifteen minutes at 73.4°F (23°C) after the activating light source is removed.

[0195] Comparative Example 2-4

[0196] The microhardness values ​​and photochromic properties of CE-2, CE-3, and CE-4 are summarized in Table 4 below.

[0197] Table 4

[0198]

[0199] The coating prepared from CE-2 cures due to the self-reaction of the isocyanate groups of the polyisocyanate alone and is hazy and accordingly unsuitable for use as part of an optical element. The coating prepared from CE-3 cures due to the reaction between the reactive groups of the polyimine / amine of Example 1 and the isocyanate groups of the polyisocyanate and has a desirable hardness but a very slow and undesirable fading half-life (T 1 / 2 The coating prepared from CE-4 cured due to the reaction between the hydroxyl groups of the polycarbonate diol (which can be characterized as a reactive soft material), the reactive groups of the polyimine / amine of Example 1, and the isocyanate groups of the polyisocyanate, and had adequate hardness but unacceptable photochromic performance characteristics.

[0200] Example 5-7

[0201] Changing the (NCO):(reactive group) ratio

[0202] The test results of Examples 5-7 are summarized in Table 5 below.

[0203] Table 5

[0204]

[0205] The results summarized in Table 5 show that increasing the (NCO):(reactive group) ratio while maintaining the same amount of non-reactive components (Examples 5 and 6) results in increased hardness and a desirable level of photochromic performance. Example 7, which has a higher (NCO):(reactive group) ratio and a lower amount of non-reactive components (compared to Examples 5 and 6), has further improved hardness and a desirable level of photochromic performance.

[0206] Example 8-12

[0207] Varying the amount and type of non-reactive components

[0208] The test results of Examples 8-12 are summarized in Table 6 below.

[0209] Table 6

[0210]

[0211] The test results summarized in Table 6 show that increasing the amount of non-reactive component while maintaining the same (NCO):(reactive group) ratio (Examples 8-10) resulted in an acceptable reduction in hardness while maintaining an acceptable level of photochromic performance. The test results of Examples 10-12, as summarized in Table 6, show that maintaining the same (NCO):(reactive group) ratio while changing the type of non-reactive component resulted in an increase in hardness while maintaining an acceptable level of photochromic performance.

[0212] The invention has been described with reference to specific details of particular embodiments of the invention. It is not intended that such details be considered limitations on the scope of the invention except to the extent they are included in the appended claims.

Claims

1. A curable photochromic composition comprising: (a) photochromic compounds; (b) a polyisocyanate comprising at least two isocyanate groups; (c) a reactive component comprising at least two reactive groups each reactive with an isocyanate group, wherein each reactive group of the reactive component is independently selected from primary amines and imines, with the proviso that at least one reactive group of the reactive component is selected from imines; and (d) a non-reactive component that does not contain a functional group that reacts with the polyisocyanate and the reactive component.

2. The curable photochromic composition according to claim 1, wherein the molar ratio of the number of moles of isocyanate groups of the polyisocyanate to the total number of moles of reactive groups of the reactive component is 1:1 to 20:

1.

3. The curable photochromic composition of claim 1, wherein the polyisocyanate comprises at least one of a linear or branched aliphatic polyisocyanate, an alicyclic polyisocyanate, a biuret thereof, an allophanate thereof, an isocyanurate thereof, and a combination thereof.

4. The curable photochromic composition of claim 1, wherein the polyisocyanate has an isocyanate equivalent weight of 95 to 500 g / mol.

5. The curable photochromic composition of claim 1, wherein at least some of the isocyanate groups of the polyisocyanate are reversibly blocked by a blocking agent.

6. The curable photochromic composition of claim 1, wherein the polyisocyanate is present in an amount of 40 weight percent to 90 weight percent based on the total resin solids weight.

7. The curable photochromic composition of claim 1, wherein the reactive component comprises at least one of an aliphatic polyether, an aliphatic polyester, an aliphatic polycarbonate, an aliphatic polyethyleneimine, or an aliphatic polyurethane, each independently having at least two reactive groups.

8. The curable photochromic composition of claim 1, wherein the reactive component has a reactive group equivalent weight of 70 g / mol to 2600 g / mol.

9. The curable photochromic composition of claim 1, wherein the reactive component is formed by the reaction of a polyamine comprising primary amine groups and at least one ketone, wherein each ketone independently has a formula weight of less than 300 g / mol, and wherein at least 80 percent of the primary amine groups of the polyamine are converted to imine groups by reaction with the ketone.

10. The curable photochromic composition of claim 1, wherein the reactive component is present in an amount of 1 weight percent to 20 weight percent based on the total resin solids weight.

11. The curable photochromic composition of claim 1, wherein the non-reactive component has a viscosity of 1 cP to 60,000 cP at 25°C.

12. The curable photochromic composition of claim 11, wherein the non-reactive component comprises at least one of a polyether, a polyester, a polycarbonate, a polyurethane, or an organic phosphate.

13. The curable photochromic composition of claim 1, wherein the non-reactive component is present in an amount of 10 weight percent to 40 weight percent based on the total resin solids of the curable photochromic composition.

14. The curable photochromic composition of claim 1, wherein the photochromic compound (a) comprises at least one of naphthopyran, benzopyran, phenanthropyran, indenonaphthopyran, spiro(dihydroindole)naphthooxazine, spiro(dihydroindole)pyridobenzoxazine, spiro(benzodihydroindole)pyridobenzoxazine, spiro(benzodihydroindole)naphthooxazine, spiro(dihydroindole)-benzoxazine, fulgide, fulgimide, or diarylethene.

15. An article comprising: (A) substrate; and (B) a photochromic layer on at least one surface of the substrate, wherein the photochromic layer is formed from the curable photochromic composition according to claim 1.

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