Curable compositions and articles made therefrom

Abstract

The present invention relates to a curable composition comprising: (a) a component having one or more carbonyl-containing compounds having a number average molecular weight (Mn) of at least 500 g / mole, wherein each carbonyl group is independently a keto group or an aldehyde group; (b) a polyamine compound having at least two primary amine groups per molecule; and (c) a polyisocyanate compound. Also provided are articles coated with the curable composition.

Description

Technical Field

[0001] The present invention relates to curable compositions, such as curable photochromic compositions comprising photochromic compounds, and also provides articles prepared from such compositions. Background Art

[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, wherein each form has a characteristic or distinguishable absorption spectrum associated therewith. Typically, upon exposure to actinic radiation, many photochromic compounds transform 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 transform from the activated (or colored) state back to the unactivated (or bleached) state without exposure to actinic radiation. Compositions containing photochromic compounds typically exhibit colorless (e.g., transparent) and colored states corresponding to the colorless and colored states of the photochromic compound contained therein. Articles (such as optical lenses) containing photochromic compounds or having photochromic compounds applied thereto (e.g., in the form of photochromic coating compositions) typically exhibit colorless (e.g., transparent) and colored states corresponding to the colorless and colored states of the photochromic compound 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, adhesive or sheet. For the photochromic film (such as the photochromic coating) of solidification, it is typically desired that they provide a combination of hardness and photochromic performance. Typically, the kinetics associated with the reversible transition between the closed form (unactivated / colorless) and the open form (activated / colored) of the 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). The solidified photochromic film with a soft matrix typically has a reduced hardness, while those with a hard matrix typically have an increased hardness. Although harder matrix can provide desired mechanical properties such as scratch resistance, the photochromic properties are typically affected, resulting in undesirable properties such as slow fading rate.

[0004] It would be desirable to develop curable compositions, especially curable photochromic compositions, that provide cured photochromic layers having improved hardness without compromising photochromic performance. Summary of the Invention

[0005] The present invention provides a curable composition comprising: (a) a component comprising one or more carbonyl-containing compounds having a number average molecular weight (Mn) of at least 500 g / mole, wherein each carbonyl group is independently a keto group or an aldehyde group; (b) a polyamine compound having at least two primary amine groups per molecule; and (c) a polyisocyanate compound.

[0006] The present invention also provides a coated article comprising a substrate and a cured coating on at least a portion of the substrate, wherein the cured coating is formed from a curable composition. DETAILED DESCRIPTION

[0007] As used herein, the articles "a," "an," and "the" include plural referents unless expressly and unequivocally limited to one referent.

[0008] Unless otherwise indicated, all ranges or ratios disclosed herein are to be understood to encompass any and all subranges or subratios contained therein. For example, a recited range or ratio of "1 to 10" is to be considered to include any and all subranges between (and including) a minimum of 1 and a maximum of 10; that is, all subranges or subratios starting with a minimum of 1 or greater and ending with a maximum of 10 or less, such as, but not limited to, 1 to 6.1, 3.5 to 7.8, and 5.5 to 10.

[0009] 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."

[0010] As used herein, molecular weight values ​​such as weight average molecular weight (Mw) and number average molecular weight (Mn) of a polymer are determined by gel permeation chromatography using appropriate standards (such as polystyrene standards).

[0011] 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).

[0012] As used herein, the term "polymer" is intended to refer to homopolymers (eg, prepared from a single monomer species), copolymers (eg, prepared from at least two monomer species), and grafted polymers.

[0013] As used herein, the term "(meth)acrylate" and similar terms (e.g., "(meth)acrylic acid ester") means methacrylate and / or acrylate. For example, unless otherwise specified herein, the term "(meth)acrylic acid" includes methacrylic acid and / or acrylic acid.

[0014] As used herein, the term "photochromic" and similar terms (e.g., "photochromic compound") means a compound or material having an absorption spectrum for at least visible radiation that changes in response to the absorption of at least actinic radiation. Additionally, as used herein, the term "photochromic material" means any substance suitable for exhibiting photochromic properties (e.g., suitable for having an absorption spectrum for at least visible radiation that changes in response to the absorption of at least actinic radiation) and comprising at least one photochromic compound.

[0015] As used herein, the term "actinic radiation" means electromagnetic radiation capable of inducing a response in a material, such as, but not limited to, transforming a photochromic material from one form or state to another, as discussed in further detail herein.

[0016] As used herein, the term "photochromic material" includes both thermally reversible photochromic materials and compounds and non-thermally reversible photochromic materials and compounds. As used herein, the term "thermally reversible photochromic compound / material" means a compound / material that is capable of switching from a first state (e.g., a "transparent state") to a second state (e.g., a "colored state") in response to actinic radiation, and returning to the first state in response to thermal energy. As used herein, the term "non-thermally reversible photochromic compound / material" means a compound / material that is capable of switching from a first state (e.g., a "transparent state") to a second state (e.g., a "colored state") in response to actinic radiation, and returning to the first state in response to actinic radiation of substantially the same wavelength as that of absorption of the colored state.

[0017] As used herein, the term "photochromic-dichroic" and similar terms (e.g., photochromic-dichroic compound) means a compound having and / or providing photochromic properties (i.e., having an absorption spectrum for at least visible radiation that varies in response to at least actinic radiation), and dichroic properties (i.e., being capable of absorbing one of two orthogonal plane-polarized components of at least transmitted radiation more strongly than the other), which also varies in response to at least actinic radiation.

[0018] As used herein, the terms "first" and "second," to modify the term "state," are not intended to refer to any particular order or temporal sequence, but rather to two different conditions or properties. For purposes of non-limiting illustration, the first and second states of a photochromic compound may differ in at least one optical property, such as, but not limited to, absorption of visible radiation and / or UV radiation. Thus, the photochromic compounds of the present invention may have different absorption spectra in each of the first and second states. For example, although not limiting herein, the photochromic compounds of the present invention may be transparent in the first state and tinted in the second state. Alternatively, the photochromic compounds of the present invention may have a first color in the first state and a second color in the second state.

[0019] 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, 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.

[0020] As used herein, the term "ophthalmic" means pertaining to or associated with 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).

[0021] 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.

[0022] 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.

[0023] As used herein, the term "mirror" means a surface that specularly reflects a substantial portion of incident light.

[0024] 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.

[0025] As used herein, spatial or directional terms, such as "left," "right," "inner," "outer," "above," "below," etc., relate to various orientations of the invention, such as the articles and multilayer articles of the invention, as may be further described herein. 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.

[0026] As used herein, the terms “formed over,” “deposited over,” “provided over,” “applied over,” “residing over,” or “positioned over” mean formed, deposited, provided, applied, applied, residing, or positioned over, but not necessarily in direct (or abutting) contact with an underlying element, or a surface of an underlying element. For example, a layer “disposed on a substrate” does not preclude the presence of one or more other layers, coatings, or films of the same or different composition between the deposited or formed layer and the substrate.

[0027] All documents (such as, but not limited to, published patents and patent applications) mentioned herein, and unless otherwise indicated, are deemed to be "incorporated by reference" in their entirety.

[0028] As used herein, the description of a "straight or branched chain" group (such as a straight or branched chain alkyl) is understood herein to include methylene or methyl; straight chain groups, such as a straight chain C2-C 20 Alkyl; and appropriately branched groups, such as branched C3-C 20 alkyl.

[0029] As used herein, the recitation of an "optionally substituted" group means a group including, but not limited to, alkyl, cycloalkyl, heterocycloalkyl, aryl, and / or heteroaryl groups in which at least one hydrogen has been optionally replaced or substituted with a group other than hydrogen, such as, but not limited to, a halogen group (e.g., F, Cl, I, and Br), a hydroxyl group, an ether group, a thiol group, a thioether group, a carboxylic acid group, a carboxylate group, a phosphate group, a phosphate ester group, a sulfonic acid group, a sulfonate group, a nitro group, a cyano group, a hydrocarbon group (including, but not limited to, alkyl; alkenyl; alkynyl; cycloalkyl, including poly-fused-ring cycloalkyl and poly-fused-ring alkyl; heterocycloalkyl; aryl, including hydroxy-substituted aryl, such as phenol, and including poly-fused-ring aryl; heteroaryl, including poly-fused-ring heteroaryl; and aralkyl), and an amine group, such as -N(R 11 ′)(R 12 ′), where R11 ′ and R 12 ' are each independently selected from hydrogen, straight or branched C1-C 20 Alkyl, C3-C 12 Cycloalkyl, C3-C 12 Heterocycloalkyl, aryl and heteroaryl.

[0030] As used herein, the description 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 at most and including all available hydrogen groups are replaced by a halogen group. The term "halogen-substituted" includes "perhalogen-substituted". As used herein, the term perhalogen-substituted group and related terms (such as but not limited to perhaloalkyl, perhaloalkenyl, perhaloalkynyl, perhaloaryl and perhaloheteroaryl) means a group in which all available hydrogen groups are replaced by a halogen group. For example, perhalomethyl is -CX3; perhalophenyl is -C6X5, where X represents one or more halogen groups, such as but not limited to F.

[0031] 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 substituents. Representative heterocycloalkyl groups include, but are not limited to, imidazolyl, tetrahydrofuranyl, tetrahydropyranyl, and piperidinyl. Representative aryl groups include, but are not limited to, phenyl, naphthyl, anthracenyl, and triptycyl. Representative heteroaryl groups include, but are not limited to, furanyl, pyranyl, pyridinyl, isoquinolinyl, and pyrimidinyl. Representative aralkyl groups include, but are not limited to, benzyl and phenethyl.

[0032] As used herein, the term "alkyl" means a straight chain or branched chain alkyl group, such as but not limited to a straight chain or branched C1-C 25 Alkyl, or linear or branched C1-C 10 Alkyl, or linear or branched C2-C 10 Alkyl. Examples of alkyl groups from which the various alkyl groups of the present invention may be selected include, but are not limited to, those previously listed herein. As used herein, the term "cycloalkyl" means a suitable cyclic group, such as, but not limited to, a C3-C 12Cycloalkyl (including but not limited to cyclic C5-C7 alkyl) groups. Examples of cycloalkyl groups include those previously listed herein. As used herein, the term "cycloalkyl" also includes bridged ring polycycloalkyl (or bridged ring polycycloalkyl (polycyclic alkyl)), 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.

[0033] As used herein, the term "heterocycloalkyl" refers to a suitable cyclic group, such as but not limited to C3-C 12 Heterocycloalkyl or 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, those previously listed herein. As used herein, the term "heterocycloalkyl" also includes bridged polycyclic heterocycloalkyls, such as but not limited to 7-oxabicyclo[2.2.1]heptanyl; and fused polycyclic heterocycloalkyls, such as but not limited to octahydrocyclopenta[b]pyranyl and octahydro-1H-isochromenyl.

[0034] As used herein, the term "heteroaryl" includes, but is not limited to, C2-C 18 Heteroaryl, such as but not limited to C2-C 10 Heteroaryl (including fused-ring polycyclic heteroaryl) and means an aryl group having at least one heteroatom in an aromatic ring or in at least one aromatic ring in the case of a fused-ring polycyclic heteroaryl. Examples of heteroaryl groups include, but are not limited to, those previously listed herein. As used herein, the term "aralkyl" includes, but is not limited to, C6-C 24 Aralkyl, such as but not limited to C6-C 10 Aralkyl, and means an aryl group substituted by an alkyl group. Examples of aralkyl groups include, but are not limited to, those previously listed herein.

[0035] As previously mentioned, the present invention relates to a curable composition comprising: (a) a component comprising one or more carbonyl-containing compounds having a number average molecular weight (Mn) of at least 500 g / mole, wherein each carbonyl group is independently a keto group or an aldehyde group; (b) a polyamine compound having at least two primary amine groups per molecule; and (c) a polyisocyanate compound.

[0036] Component (a) comprises one or more carbonyl-containing compounds. One or more carbonyl-containing compounds have a number average molecular weight (Mn) of at least 500 g / mole, such as at least 800 g / mole, or at least 1,000 g / mole, or at least 1,500 g / mole. One or more carbonyl-containing compounds can have an Mn of 120,000 g / mole or less, such as 80,000 g / mole or less, or 60,000 g / mole or less, or 50,000 g / mole or less. The scope of the Mn of one or more carbonyl-containing compounds can be between any of the values, including the values.

[0037] The carbonyl groups contained in the compounds of component (a) are each independently a keto group or an aldehyde group. That is, component (a) may contain one or more compounds containing one or more keto groups; one or more compounds containing one or more aldehyde groups; one or more compounds containing one or more keto groups and one or more aldehyde groups; or a mixture of any of the foregoing.

[0038] For the purposes of the present invention, references to "carbonyl" include keto and aldehyde groups and are intended to exclude other functional groups containing C=O units, such as esters, carbonates, urethanes (urethanes), amides, ureas, etc. Likewise, references to equivalent weights refer to the equivalent weight of the sum of the keto and aldehyde groups and exclude the aforementioned functional groups.

[0039] Component (a) may comprise (i) a compound having 1 to 4 carbonyl groups per molecule and an equivalent weight of 500 to 30,000 g / mole; or (ii) a compound having 2 or more carbonyl groups per molecule and an equivalent weight of 130 to 480 g / mole; or (iii) a mixture of (i) and (ii).

[0040] The compound (i) having 1 to 4 carbonyl groups per molecule and an equivalent weight of 500 to 30,000 g / mole may be selected from the group consisting of carbonyl-containing polycarbonates, carbonyl-containing polyethers, carbonyl-containing polyesters, carbonyl-containing polyurethanes, copolymers thereof, and mixtures thereof.

[0041] Suitable for use as per molecule there is 1 to 4 carbonyl groups and an equivalent weight of 500 to 30,000g / mole of compound (i) carbonyl functional polycarbonate can be prepared according to methods generally recognized in the art. For non-limiting purposes, suitable for use as per molecule there is 1 to 4 carbonyl groups and an equivalent weight of 500 to 30,000g / mole of compound (i) carbonyl functional polycarbonate can be prepared by first preparing a hydroxyl or isocyanate functional polycarbonate intermediate, and then modifying the polycarbonate intermediate to include a carbonyl group to prepare. The method for preparing carbonyl-containing materials by hydroxyl or isocyanate functional intermediates generally recognized in the art is as follows. Hydroxy functional intermediates can react with aliphatic or aromatic carboxylic acids containing keto or aldehyde groups, such as but not limited to levulinic acid, 4-acetylbenzoic acid, 4-formylbenzoic acid, which results in the formation of carbonyl functional materials. In addition, hydroxy functional intermediates can react with tert-butyl acetoacetate to form ketone functional materials. Alternatively, an isocyanate functional intermediate may be prepared first and then reacted with a hydroxy-functional aliphatic or aromatic ketone or aldehyde, such as, but not limited to, 4-hydroxy-4-methyl-2-pentanone, optionally with a catalyst, followed by art-recognized work-up procedures, which results in the formation of a carbonyl-functional material.

[0042] Commercially available hydroxyl functional polycarbonates useful as intermediates in the formation of carbonyl functional polycarbonates suitable for use as compound (i) having 1 to 4 carbonyl groups per molecule and an equivalent weight of 500 to 30,000 g / mole may include, but are not limited to, commercially available polycarbonate diols such as those sold under the trade names Other suitable polycarbonate polyols are available from Asahi Kasei under the trade name DURANOL TM Polycarbonate diol is commercially available as DURANOL T5652 polycarbonate diol and PC-1122 polycarbonate diol from Stahl, USA.

[0043] Carbonyl-functional polyethers suitable for use as compound (i) having 1 to 4 carbonyl groups per molecule and an equivalent weight of 500 to 30,000 g / mole can be prepared according to methods recognized in the art. For the purpose of non-limiting illustration, suitable carbonyl-functional polyethers can be prepared by first preparing a polyether intermediate having hydroxyl or isocyanate functional groups, and then modifying the polyether intermediate to include carbonyl groups.

[0044] Non-limiting examples of suitable polyether polyols include polyoxyalkylene polyols and polyalkoxylated polyols, such as, for example, poly(oxyalkylene) polyols. Examples of polyoxyalkylene polyols may include, but are not limited to, glycols such as polyoxyethylene glycol (i.e., polyethylene glycol) having a molecular weight greater than 1000, polyoxypropylene glycol (i.e., polypropylene glycol) having a molecular weight greater than 1000, polytetramethylene ether glycol, and combinations thereof. Non-limiting examples of commercially available polyether polyols include polyoxyalkylene glycols available from Dow Chemicals under the trade name VORANOL TM Trade name, from BASF and Trade name, and from Bayer AG (Bayer) and Those available under the trade name.

[0045] Carbonyl-functional polyesters suitable for use as compound (i) having 1 to 4 carbonyl groups per molecule and an equivalent weight of 500 to 30,000 g / mole can be prepared according to methods recognized in the art. In addition, carbonyl-functional polyesters can be prepared by first preparing a polyester intermediate having hydroxyl or isocyanate functional groups and then modifying the polyester intermediate to include carbonyl groups.

[0046] Polyester polyols can be prepared by esterification of polyfunctional carboxylic acids with polyols.

[0047] Alternatively, polyester polyols can be prepared by ring-opening polymerization of cyclic carboxylates and polyols. Examples of cyclic carboxylates from which hydroxyl-functional polyesters can be prepared include, but are not limited to, lactones having from 4 to 8 atoms in the cyclic ring, wherein the ester oxygen and carbonyl carbon are directly bonded to each other, such as β-propiolactone, γ-butyrolactone, δ valerolactone, ε caprolactone, and combinations of two or more thereof. Suitable examples of commercially available polyester polyols for use as compound (i) having 1 to 4 carbonyl groups per molecule and an equivalent weight of 500 to 30,000 g / mole can include, but are not limited to, linear aliphatic polyester polyols, such as STEPANOL PC polyester polyols commercially available from Stepan Company. Also suitable are those commercially available from DIC Corporation, such as OD-X-286, OD-X-102, OD-X-355, OD-X-2330, OD-X-240, OD-X-668, OD-X-21068, OD-X-2547, OD-X-2420, OD-X-2523, OD-X-2555, and OD-X-2560 polyester polyols; OD-X-2155 and OD-X-640 polycaprolactone diols; and OD-X-2586 triol. Also suitable are polyester polyols commercially available from TRiiSO Corporation, such as PERSTORP BOLTORN H2004 hyperbranched polyester polyol; and INGEVITY CAPA polycaprolactone polyol. Suitable polyester polyols may also include polyester diols, such as polycaprolactone diols. Non-limiting examples of commercially available polyester polyols may also include polyesters commercially available from BASF Corporation under Trade name, or from Evonik Industries Trade name, or from Bayer AG and Those available under the trade name.

[0048] Carbonyl functional polyurethanes suitable for use as compound (i) having 1 to 4 carbonyl groups per molecule and an equivalent weight of 500 to 30,000 g / mole can be prepared according to methods generally recognized in the art. For non-limiting purposes, carbonyl functional polyurethanes can be prepared by first forming a polyurethane intermediate with a hydroxyl or isocyanate functional group, and then modifying the polyurethane intermediate to include a carbonyl group. Polyurethane intermediates can be prepared according to methods generally recognized in the art (such as, but not limited to, the reaction of polyols (such as diols) with polyisocyanates (such as diisocyanates, triisocyanates). Polyols that can be used to prepare polyurethane intermediates can be selected from those kinds and examples of polyols previously listed herein. Polyisocyanates that can be used to prepare polyurethane intermediates can be selected from those kinds and examples of polyisocyanates further listed herein.

[0049] Carbonyl-functional materials suitable for use as compound (i) can also be prepared from hydroxyl-functional thermoplastic polyurethane copolymers according to art-recognized methods. Commercially available hydroxyl-functional thermoplastic polyurethanes that can be used as intermediates in the formation of carbonyl-functional polyurethane copolymers include, but are not limited to, PEARLSTICK, PEARLBOND, ESTANE, TECOFLEX, and CARBOTHANE hydroxyl-functional polyurethanes commercially available from Lubrizol; CHRONOFLEX AL, CHRONOFLEX C, CHRONOTHANE P, and CHRONOSIL hydroxyl-functional polyurethanes commercially available from AdvanSource Biomaterials Corporation (Wilmington, Massachusetts); ELAST-EON hydroxyl-functional polyurethanes commercially available from AorTech International Plc (Dundee, England); and QUADRATHANE hydroxyl-functional polyurethanes commercially available from Biometrics.

[0050] As mentioned previously, component (a) may also comprise (ii) a compound having 2 or more carbonyl groups per molecule and an equivalent weight of 130 to 480 g / mole.

[0051] The compound (ii) that every molecule has 2 or more carbonyls and equivalent weight is 130 to 480g / mole can use art-recognized method to be prepared by polyhydroxy (polyvalent alcohol), carboxylic acid or isocyanate functional intermediate.The intermediate with two or more hydroxyls can react with the carboxylic acid or ester containing keto or aldehyde group under esterification / transesterification condition.The limiting examples of ketone or aldehyde functional carboxylic acid comprises levulinic acid, 4-acetyl benzoic acid and 4-formyl benzoic acid.The example of suitable keto functional carboxylic acid ester is tert-butyl acetoacetate.

[0052] Examples of polyols that can be reacted with carbonyl-containing acids to prepare carbonyl-functional polyesters suitable for use as compound (ii) can include, but are not limited to, glycerol, trimethylolpropane, trimethylolethane, trishydroxyethyl isocyanurate, pentaerythritol, and diols such as pentanediol, hexanediol, and the like, 4,4′-(propane-2,2-diyl)dicyclohexanol, 4,4′-methylenedicyclohexanol, neopentyl glycol, 2,2,3-trimethylpentane-1,3-diol, 1,4-dimethylolcyclohexane, 2,2,4-trimethylpentanediol, 4,4′-(propane-2,2-diyl)biphenol, 4,4′-methylenediphenol, and similar polyols.

[0053] Similarly, the polyacid functional intermediate can be reacted with a hydroxyl-functional keto- or aldehyde-containing compound under esterification conditions. Examples of polyfunctional carboxylic acids that can be used to prepare carbonyl-functional compounds (ii) include, but are not limited to, benzene-1,2,4-tricarboxylic acid, hexahydrophthalic acid, cyclohexane diacid, isophthalic acid, terephthalic acid, maleic acid, trimesic acid, adipic acid, sebacic acid, anhydrides thereof, and / or esters thereof.

[0054] Compounds with 2 or more isocyanate groups can react with hydroxyl-functional aliphatic or aromatic ketones or aldehydes, such as, but not limited to, 4-hydroxy-4-methyl-2-pentanone. Examples of polyfunctional isocyanates that can be used to prepare carbonyl-functional polyurethanes include, but are not limited to, any of those described in detail herein. Compound (ii) having 2 or more carbonyl groups per molecule and an equivalent weight of 130 to 480 g / mole can also comprise poly(meth)acrylate copolymers. Poly(meth)acrylate copolymers can be formed by polymerization of a mixture of ethylenically unsaturated compounds comprising at least one ethylenically unsaturated monomer comprising at least one ketone or aldehyde group and at least one unsaturated monomer not having a ketone or aldehyde group (i.e., not containing a carbonyl functional group).

[0055] At least one ethylenically unsaturated monomer containing at least one ketone group or aldehyde group may be present in an amount from 40 mole percent and up to 90 mole percent of the total ethylenically unsaturated monomers to achieve the desired equivalent weight range. Examples of ethylenically unsaturated monomers containing at least one ketone group or aldehyde group that can be used to prepare compound (ii) may include, but are not limited to: diacetone (meth)acrylamide; acetoacetoxyethyl (meth)acrylate; vinyl acetoacetate; 2-propenoic acid, 3-oxobutyl ester; 2-propenoic acid, 3-oxopentyl ester; 2-propenoic acid, 2-methyl-, 3-oxobutyl ester; 2-propenoic acid, 3-oxoheptyl ester; 2-propenoic acid, 5-methoxy-3-oxopentyl ester; 2-propenoic acid, 2-Methyl-, 1-methyl-3-oxobutyl ester; 2-propenoic acid, 4-methyl-3-oxopentyl ester; butyric acid, 3-oxo-, anhydride with 2-propenoic acid; benzoic acid, 4-vinyl-, 3-oxobutyl ester; 2-propenoic acid, 1-methyl-1-(4-methyl-2-oxocyclohexyl)ethyl ester; 10-undecen-2-one, 1,1,1-trifluoro-; ethyl ketone, 2,2,2-trifluoro-1-[2-(4-pentenyl)phenyl]-(9CI) and combinations thereof.

[0056] The ethylenically unsaturated monomers containing no carbonyl functional group that can be used to prepare compound (ii) include, but are not limited to: (meth)acrylates, such as C1-C 20 (Meth)acrylate; vinyl aromatic monomer; vinyl carboxylate; allyl monomer; C2 to C 24Olefins; and combinations thereof. Non-limiting examples of ethylenically unsaturated free-radically polymerizable monomers that do not contain carbonyl functionality include, but are not limited to, vinyl alcohol; vinyl chloride; acrylonitrile; trimethyl(4-methyl-4-penten-1-yl)-silane; 1-octene; 1-undecene; 1-octadecene; 4-heptenal; 6-methyl-,9-decen-3-one; 5-methyl-1-heptene; vinylcyclopentane; bicyclo[2.2.1]hept-2-ene; vinylcyclohexane; 2-propenoic acid, cyclohexyl ester; 2-propenoic acid, bicyclo[2.2.1]hept-2-yl ester; 2-propenoic acid, 4-(1,1-dimethylethyl)cyclohexyl ester; 2-propenoic acid, tricyclo[3.3.1.13,7]dec-2-yl ester; and combinations of two or more thereof.

[0057] C1-C 20 C1-C (meth)acrylate 20 The group may be selected from, for example, C1-C 20 Straight chain alkyl, C3-C 20 Branched alkyl, C3-C 20 Cycloalkyl, C3-C 20 Condensed-ring polycyclic alkyl, C5-C 20 Aryl and C 10 -C 20 Fused ring aryl.

[0058] C1-C without carbonyl functional group 20 Examples of (meth)acrylates include, but are not limited to, methyl (meth)acrylate; ethyl (meth)acrylate; propyl (meth)acrylate; isopropyl (meth)acrylate; n-butyl (meth)acrylate; isobutyl (meth)acrylate; tert-butyl (meth)acrylate; 2-ethylhexyl (meth)acrylate; lauryl (meth)acrylate; isobornyl (meth)acrylate; cyclohexyl (meth)acrylate; and 3,3,5-trimethylcyclohexyl (meth)acrylate. Examples of vinyl aromatic monomers that do not contain carbonyl functionality that can be used include, but are not limited to, styrene; p-chloromethylstyrene; divinylbenzene; vinylnaphthalene; and divinylnaphthalene. Examples of vinyl carboxylates that do not contain carbonyl functionality include, but are not limited to, vinyl acetate; vinyl butyrate; vinyl 3,4-dimethoxybenzoate; and vinyl benzoate. Examples of allyl monomers that do not contain a carbonyl functional group include, but are not limited to, allyl chloride; allyl acetate, allyl alcohol, allyl benzyl ether, allyl phenyl ether, 3-allyloxy-1,2-propanediol, and allyl methyl ether.

[0059] The hydroxyl functional acrylic polymer can be reacted with a keto or aldehyde containing carboxylic acid or ester under the esterification / transesterification conditions described above.Hydroxy functional (meth)acrylates are known in the art and can be copolymerized with any of the ethylenically unsaturated (meth)acrylates mentioned above.

[0060] Similarly, carboxylic acid functional acrylic polymers can be reacted with hydroxyl-containing ketones or aldehydes under the esterification / transesterification conditions described above.Carboxylic acid functional (meth)acrylates are known in the art and can be copolymerized with any of the ethylenically unsaturated (meth)acrylates mentioned above.

[0061] In any of the above curable compositions of the present invention, component (a) may comprise a mixture of a compound (i) having 1 to 4 carbonyl groups per molecule and an equivalent weight of 500 to 30,000 g / mole and a compound (ii) having 2 or more carbonyl groups per molecule and an equivalent weight of 130 to 480 g / mole.

[0062] The curable composition of the present invention also includes (b) a polyamine compound having at least two primary amine groups per molecule. The polyamine compound (b) can have a number average molecular weight (Mn) of at least 60 g / mole, such as at least 100 g / mole, or at least 150 g / mole, or at least 200 g / mole, or at least 250 g / mole. In addition, the polyamine compound (b) can have an Mn of 100,000 g / mole or less, such as 70,000 g / mole or less, or 50,000 g / mole or less, or 20,000 g / mole or less. The Mn of the polyamine compound (b) can range between any of the values, including the values.

[0063] The polyamine compound (b) may have an equivalent weight based on the sum of the primary and secondary amine groups present of at least 30 g / mole, such as 50 g / mole, or 100 g / mole, or 500 g / mole, or 1000 g / mole, based on the sum of the primary and secondary amine groups present. Additionally, the polyamine compound (b) may have an equivalent weight based on the sum of the primary and secondary amine groups present of 50,000 g / mole or less, such as 35,000 g / mole or less, or 20,000 g / mole or less. The polyamine compound (b) may have an Mn of at least 60 g / mole and an equivalent weight based on the sum of the primary and secondary amine groups present of at least 30 g / mole.

[0064] The polyamine compound (b) having at least two primary amine groups per molecule may have at least a portion of the primary amine groups protected to prevent premature reaction with either or both of the carbonyl-containing compound and the polyisocyanate compound (c) of component (a) (as described below). Protection of the primary amine groups can be achieved by methods well known in the art. For example, the primary amine groups can be protected by protonation, alkylation, acylation, addition, or coupling.

[0065] Examples of polyamines suitable for use in the curable composition of the present invention may include, but are not limited to, Epomin series SP-003, SP-006, SP-012, SP-018, SP-200, P-1050 polyamines commercially available from Nippon Shokubai Co., Ltd. (URL http: / / www.shokubai.co.jp / ); Polyment series, NK-350 and NK-380 are solvent-based polyamines, also commercially available from Nippon Shokubai Co., Ltd. Other polyamines, such as tris(2-aminoethyl)amine, tetraethylenepentamine, and pentaethylenehexamine, are also commercially available from Sigma-Aldrich.

[0066] Some other examples of polyamines may include, but are not limited to, polycarbonate amines, polyester amines, polyether amines, and combinations thereof. Suitable polycarbonate amines and polyester amines that may be used may be synthesized using various methods known in the art. For example, suitable polycarbonate diamines may be prepared by ring opening of trimethylene carbonate using a nitrophenyl functionalized initiator followed by reduction to the amine, as described in Macromolecules, 1997, 30, 6074, which is incorporated herein by reference. Additionally, suitable polyester diamines may be prepared by condensation of a hydroxyl terminated polyester with an N-benzyloxycarbonyl amino acid followed by catalytic hydrogenation to produce the amine, as described in Bioconjugate Chemistry, 2002, 13(5), 1159-1162, which is incorporated herein by reference. Non-limiting examples of polyether amines include those sold under the trade name Diamines and triamines are those commercially available from Huntsman.

[0067] The molar ratio of the total combined primary and secondary amine group equivalents of the polyamine compound (b) to the total carbonyl equivalents of the carbonyl-containing compounds of component (a) is at least 1:2, such as at least 1:1, or at least 2:1, or at least 3:1, or at least 6:1.

[0068] The curable composition of the present invention further comprises (c) a polyisocyanate compound having at least two isocyanate groups per molecule and an isocyanate equivalent weight of less than or equal to 500 g / mole (e.g., less than or equal to 450 g / mole, or less than or equal to 400 g / mole, or less than or equal to 380 g / mole). In addition, the polyisocyanate compound (c) having at least two isocyanate groups per molecule may have an isocyanate equivalent weight greater than or equal to 80 g / mole, such as greater than or equal to 110 g / mole, or greater than or equal to 150 g / mole, or greater than or equal to 160 g / mole. The equivalent weight of the polyisocyanate compound may range between any of the recited values, including the recited values.

[0069] The polyisocyanate compound (c) contains at least two isocyanate groups (-NCO). Examples of suitable polyisocyanates may include, but are not limited to, toluene-2,4-diisocyanate; toluene-2,6-diisocyanate; diphenylmethane-4,4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; p-phenylene diisocyanate; biphenyl diisocyanate; 3,3'-dimethyl-4,4'-diphenylene diisocyanate; tetramethylene-1,4-diisocyanate; hexamethylene-1,6-diisocyanate; 2,2,4-trimethylhexane-1,6-diisocyanate; lysine methyl ester diisocyanate; bis(isocyanatoethyl)fumarate; isophorate Ketone diisocyanate; ethylene diisocyanate; dodecane-1,12-diisocyanate; 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; norbornane diisocyanate; and mixtures thereof.

[0070] In addition, the polyisocyanate compound (c) can be selected from polyisocyanates prepared from dimers and trimers of diisocyanate monomers. Dimers and trimers of diisocyanate monomers can be prepared by methods generally recognized in the art, such as described in U.S. Patent No. 5,777,061, column 3, line 44 to column 4, line 40. The dimers and trimers of the diisocyanate monomers listed above can contain a link selected from the group consisting of isocyanurates, uretdiones, biuret, allophanates, and combinations thereof.

[0071] The polyisocyanate compound (c) may also be selected from oligomeric polyisocyanate functional adducts. The oligomeric polyisocyanate functional adducts may contain structural linkages selected from urethane (-NH-C(O)-O-), thiourethane (-NH-C(O)-S-), urea (-N(R 1 )-C(O)-N(R 1 )-, where each R 1 are independently selected from hydrogen and any suitable organic group, such as a straight or branched C1-C 20 Alkyl, cycloalkyl, aryl, and combinations thereof.

[0072] As used herein, "oligomeric polyisocyanate functional adduct" means a material that is substantially free of polymer chain extension. Oligomeric polyisocyanate functional adducts can be prepared by art-recognized methods, for example, from a compound containing three or more active hydrogen groups, such as trimethylolpropane (TMP), and an isocyanate monomer, such as 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), in a molar ratio of 1:3. In the case of TMP and IPDI, an oligomeric adduct having an average isocyanate functionality of 3 ("TMP-3IPDI") can be prepared by employing art-recognized starved feed and / or dilute solution synthesis techniques.

[0073] The active hydrogen group-containing compound used to prepare the oligomeric polyisocyanate functional adduct can be aliphatic, such as TMP, trihydroxy isocyanurate, pentaerythritol and trimethylolpropane tris(thioglycolate). The isocyanate monomer used to prepare the oligomeric polyisocyanate functional adduct can be a diisocyanate monomer, such as any of those previously described herein.

[0074] The isocyanate groups of polyisocyanate compounds (c) can be blocked with blocking agents. After being exposed to high temperatures, blocking agents are separated from isocyanate functional materials to react their free / unblocked isocyanate groups with the active hydrogen groups of polyamine compounds (b) and / or with the isocyanate groups of themselves and form covalent bonds (to form biuret or isocyanurate). After deblocking from polyisocyanates, blocking agents can be volatilized from the composition (before the composition becomes solidified) and / or retained in the composition, such as plasticizers. It is expected that blocking agents do not form bubbles in the composition and / or do not overplasticize the composition after deblocking.

[0075] The blocking group of the blocked polyisocyanate compound can be selected from hydroxyl-functional compounds, 1H-azoles, lactams, ketoximes, and mixtures thereof. The type of hydroxyl-functional compound can include but is not limited to aliphatic, alicyclic, or aromatic alkyl monoalcohols or phenolics. Specific examples of hydroxyl-functional compounds that can be used as blocking 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, for example, ethylene glycol butyl ether, diethylene glycol butyl ether, ethylene glycol methyl ether, and propylene glycol methyl ether. The hydroxyl-functional blocking group can include phenols, examples of which include but are not limited to phenol itself and substituted phenols, such as cresols, nitrophenols, and p-hydroxymethyl benzoates.

[0076] Examples of 1H-azoles that can be used as blocking groups can 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.

[0077] Ketoximes useful as blocking groups may include those prepared from aliphatic or alicyclic ketones. Examples of ketoxime blocking 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-cyclohexen-5-one oxime.

[0078] Examples of lactam blocking groups may include, but are not limited to, e-caprolactam and 2-pyrrolidone. Other suitable blocking groups include morpholine, 3-aminopropylmorpholine, and N-hydroxyphthalimide.

[0079] In the curable composition of the present invention, at least some of the reactive functional groups of the polyisocyanate compound (c) may be blocked with a blocking agent, and each blocking agent is independently selected from the group consisting of methyl ethyl ketoxime, pyrazole (more specifically, 1H-pyrazole; 3,5-dimethylpyrazole) and dialkylpyrazole (more specifically, 1H-dialkylpyrazole).

[0080] Blocked polyisocyanates may also include those sold under the trade names Those commercially available from Baxenden, such as BI 7950, BI 7951, BI 7960, BI 7961, BI 7963, and BI 7982. Other commercially available blocked polyisocyanates include those sold under the trade names Those commercially available from Bayer AG, such as BL 3175A, BL 3272, BL 3370, BL 3475, and BL 4265SN.

[0081] The molar ratio of isocyanate equivalents of the polyisocyanate compound (c) to the total combined primary and secondary amine group equivalents of the polyamine compound (b) is at least 1:1, such as at least 3:1 or at least 6:1.

[0082] Each of the component (a) comprising one or more carbonyl-containing compounds as described above, the polyamine compound (b) having at least two primary groups as described above, and the polyisocyanate compound (c) as described above can be added as a separate component to form the curable composition of the present invention. Alternatively, the component (a) comprising one or more carbonyl-containing compounds and the polyamine compound (b) having at least two primary groups can be pre-reacted to form a poly(imine) prepolymer before adding the polyisocyanate compound (c) to form the curable composition of the present invention. The resulting poly(imine) prepolymer will depend on the relative amounts of the component (a) comprising one or more carbonyl-containing compounds and the polyamine compound (b) used, as well as the reaction conditions, time and temperature as described below.

[0083] Any of the above curable compositions may further comprise a photochromic compound.The photochromic compound may be selected from known types and examples of photochromic compounds, and may include combinations or mixtures thereof.

[0084] For example, although not limiting herein, mixtures of photochromic compounds can be used to obtain certain activated colors, such as a near-neutral gray or a near-neutral brown. See, for example, U.S. Patent No. 5,645,767 at column 12, line 66 to column 13, line 19, which describes parameters defining neutral gray and brown colors and the disclosure of which is specifically incorporated herein by reference.

[0085] The photochromic compound suitable for use in the curable composition of the present invention can be selected from the group consisting of naphthopyrans, benzopyrans, phenanthropyrans, indenonaphthopyrans, spiro(dihydroindole)naphthoxazines, spiro(dihydroindole)pyridobenzoxazines, spiro(benzodihydroindole)pyridobenzoxazines, spiro(benzodihydroindole)naphthoxazines, spiro(dihydroindole)-benzoxazines, fulgides, fulgimides, diarylethenes, and mixtures of such photochromic compounds. Additional examples of other photochromic compounds that can be used in the curable composition of the present invention can include, but are not limited to, those disclosed in U.S. Pat. No. 9,028,728 B2 (the disclosure of which is specifically incorporated herein by reference) at column 34, line 20 to column 35, line 13.

[0086] The photochromic compound is typically present in the curable photochromic composition of the present invention in at least a sufficient amount to provide the desired level of photochromic properties to the article prepared from the composition, which is referred to as the photochromic amount. The amount of the one or more photochromic compounds present in the curable composition can range from 0.001 weight percent to 40 weight percent, or from 0.001 to 10 weight percent, or from 0.1 to 10 weight percent, or from 1 to 6 weight percent, based on the total solids weight of the curable composition (including the weight of the one or more photochromic compounds, and inclusive of the recited values).

[0087] The curable composition of the present invention may optionally contain additives such as, but not limited to, waxes for flow and wetting; plasticizers, thermoplastics, flow control agents such as poly(2-ethylhexyl)acrylate; antioxidants; hindered amine light stabilizers, ultraviolet (UV) light absorbers, UV stabilizers, surfactants, adhesion promoters, fixed hue dyes, and solvents. Examples of useful antioxidants include, but are not limited to, those commercially available from BASF under the trademarks IRGANOX and TINUVIN. When used, these optional additives may be present in an amount of up to 30 weight percent based on the total solids weight of the curable composition (excluding solvent).

[0088] Commercially available plasticizer additives include, but are not limited to, benzoflex 9-88, benzoflex 9-88SG, enhancer 400, admex 6995, admex 6187, admex 760, and admex 770, all commercially available from Eastman Chemical Company; polybutadiene-based plasticizers are polyvest 130, polyvest MA 75, polyvest HT, polyvest EP ST M, and polyvest EP ST E-100, all available from Evonik; and polymeric plasticizers D-1116, G-1701MU, G-1643, G-1652MU, G-1657MS, G-1657VS, G-1701MU, and MD-1648, all available from Kraton Corporation.

[0089] Commercially available thermoplastic polyurethane (TPU) additives are similar to those hydroxy-functional thermoplastic polyurethane copolymers as previously described herein.

[0090] As mentioned above, the curable 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" mean a dye that is a non-photosensitive material that does not physically or chemically respond to electromagnetic radiation associated with its visually observed color. As used herein, the term "fixed-tint dye" and related terms do not include and can be distinguished from photochromic compounds. As used herein, the term "non-photosensitive material" means a material that does not physically or chemically respond to electromagnetic radiation associated with its visually observed color, including but not limited to fixed-tint dyes.

[0091] One or more fixed hue dyes may be present in the curable compositions of the present invention for purposes including, but not limited to, providing to a cured article prepared from the curable composition: at least a primary (or first) color characteristic of the fixed hue dye when the photochromic compound (if used) 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). The optional fixed hue dye of the curable photochromic composition may include 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.

[0092] The curable composition of the present invention may comprise a solvent, such as those selected from water, organic solvents, and combinations thereof.

[0093] The types of organic solvents that may be present in the curable photochromic composition 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, 2-butoxyethyl acetate, ethyl lactate, ethylene carbonate, and propylene carbonate, particularly 1,2-propylene glycol cyclic carbonate; alkylene glycol ethers such as dialkyl ethers of ethylene glycol and dialkyl ethers of propylene glycol; nitrogen-containing cyclic compounds such as pyrrolidone, 1-methyl-2-pyrrolidone, 1-butylpyrrolidin-2-one, 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 a C9-C 10mixture of dialkylbenzenes and trialkylbenzenes), or Aromatic 150 (which is a commercially available C9-C 11 mixture of alkylbenzenes).

[0094] One or more solvents may be present in the curable compositions of the present invention in an amount from 5 to 95 weight percent, or from 15 to 80 weight percent, or from 20 to 60 weight percent, in each case based on the total weight of the curable composition (including the weight of the solvent).

[0095] The curable composition of the present invention can be cured by any suitable method. The curable composition can be cured under ambient conditions, such as at a room temperature of about 25°C. Alternatively, the curable photochromic composition can be cured by exposure to high temperatures (exceeding ambient room temperature). As used herein, "curing" means forming a three-dimensional crosslinked network by covalent bond formation. When cured at high temperatures, the curable composition can be referred to as a thermosetting curable composition in this article. The time and temperature for curing the thermosetting curable composition of the present invention can vary. For example, the curable composition of the present invention can be cured at a high temperature of from 50°C to 204°C, or from 80°C to 177°C, or from 90°C to 140°C for a period of 20 to 240 minutes.

[0096] Any curable composition described herein may comprise a curable coating composition or a curable adhesive composition. Additionally, either or both of the curable coating composition and the curable adhesive composition may comprise one or more photochromic compounds, such as any of those described above.

[0097] It has been noted that photochromic coatings formed from curable compositions comprising only carbonyl-containing compounds and polyamine compounds (without polyisocyanates) result in poly(imine) coating matrices that are soft and exhibit a yellow color and a slow photochromic fade rate. In contrast, the curable compositions of the present invention comprising (a) a component comprising one or more carbonyl-containing compounds, (b) a polyamine compound, and (c) a polyisocyanate compound are believed to result in a phase-separated poly(urea)-poly(imine) matrix having multiple softer (i.e., poly(imine)) domains within the cured composition with a Tg range of from -100°C to 0°C, and multiple harder (i.e., poly(urea)) domains within the cured composition with a Tg range of from 5°C to 120°C. Without being bound by any theory, it is believed that at least a portion of the one or more photochromic compounds resides within the softer poly(imine) domains of the cured coating. Thus, when applied to a substrate and cured, the compositions of the present invention provide an improved photochromic fade rate, acceptable hardness, and improved color.

[0098] The present invention also relates to a coated article, such as a coated optical article, comprising a substrate; and a cured coating on at least a portion of the substrate, wherein the cured coating is formed from any of the aforementioned curable compositions of the present invention.

[0099] An article comprising a substrate and a cured coating on at least a portion of the substrate (formed from any of the previously described curable compositions of the present invention) can be selected from ophthalmic articles (e.g., lenses), 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; glass, such as silica-based glass; metal; ceramic materials; and combinations thereof.

[0100] Non-limiting examples of organic materials that can be used to form the substrate of the article of the present invention include polymeric materials, such as homopolymers and copolymers, prepared from the monomers and monomer mixtures disclosed in U.S. Patent No. 5,962,617 and U.S. Patent No. 5,658,501 from column 15, line 28 to column 16, line 17, the disclosures of which are specifically incorporated herein by reference. For example, such polymeric materials can be thermoplastic or thermosetting polymeric materials, can be transparent or optically clear, and can have any refractive index desired. Non-limiting examples of such disclosed monomers and polymers include polyol (allyl carbonate) monomers, for example, allyl diglycol carbonate, such as diethylene glycol bis (allyl carbonate), which is available from PPG Industries (PPG). Industries, Inc.) under the trademark CR-39; polyurea-polyurethane (polyurea-urethane) polymers, prepared, for example, by the reaction of a polyurethane prepolymer with a diamine curing agent, a composition for which is sold by PPG Industries under the trademark TRIVEX; polyol (meth)acryloyl-terminated carbonate monomers; diethylene glycol dimethacrylate monomers; ethoxylated phenol methacrylate monomers; diisopropenylbenzene monomers; ethoxylated trimethylolpropane triacrylate monomers; ethylene glycol dimethacrylate monomers; poly(ethylene glycol) dimethacrylate monomers; urethane acrylate monomers; poly(ethoxylated bisphenol A dimethacrylate); poly(vinyl acetate) ; poly(vinyl alcohol); poly(vinyl chloride); poly(vinylidene chloride); polyethylene; polypropylene; polyurethane; polythiourethane; thermoplastic polycarbonates, such as the carbonate-linked resin derived from bisphenol A and phosgene, one such material sold under the trademark LEXAN; polyesters, such as the material sold under the trademark MYLAR; poly(ethylene terephthalate); polyvinyl butyral; poly(methyl methacrylate) (such as the material sold under the trademark PLEXIGLAS), and polymers prepared by reacting a polyfunctional isocyanate with a polythiol or polycyclosulfide monomer, homopolymerized or copolymerized and / or terpolymerized with polythiols, polyisocyanates, polyisothiocyanates, and optionally ethylenically unsaturated monomers or halogenated aromatic-containing vinyl monomers. Copolymers of such monomers and blends of the described polymers and copolymers with other polymers, for example, to form block copolymers or interpenetrating network products, are also contemplated.

[0101] The substrate may optionally contain a photochromic material and / or a fixed hue dye, each of which may be selected from the classes and examples of photochromic materials and fixed hue dyes as previously described herein. The optional one or more photochromic materials / compounds present in the substrate may be the same as or different from the one or more photochromic compounds that may be used to cure the coating. The optional one or more fixed hue dyes may be the same as or different from the optional one or more fixed hue dyes of the cured coating.

[0102] The cured coating of the article may be a coating formed from any of the previously described curable compositions of the present invention. The curable composition may be applied to the substrate according to methods recognized in the art, including but not limited to spray 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 a curable photochromic composition according to the present invention) and combinations thereof.

[0103] After applying the curable composition on at least one surface of the substrate, the applied curable composition is cured to form a cured coating as previously described herein. The coating can be in the form of a single layer or multiple layers. When in the form of multiple layers, each layer can be prepared by a curable composition according to the present invention (having the same or different compositions, such as the same or different one or more photochromic compounds).

[0104] The cured layer can have any suitable thickness, such as from 2 microns to 250 microns, or from 10 microns to 100 microns.

[0105] In addition to the cured coating, the article optionally can comprise one or more additional art-recognized layers, such as, but not limited to, one or more primer layers; one or more adhesive layers; one or more protective layers (e.g., a hard coat); one or more polarizing layers; one or more birefringent layers; one or more antireflective layers; and / or one or more photochromic layers prepared from a composition other than the curable composition of the present invention.

[0106] The present disclosure may also be characterized by one or more of the following aspects:

[0107] In a first aspect, the curable composition of the present invention may comprise: (a) a component comprising one or more carbonyl-containing compounds having a number average molecular weight (Mn) of at least 500 g / mole, wherein each carbonyl group is independently a keto group or an aldehyde group; (b) a polyamine compound having at least two primary amine groups per molecule; and (c) a polyisocyanate compound.

[0108] In a second aspect, component (a) of the first aspect may comprise: (i) a compound having 1 to 4 carbonyl groups per molecule and an equivalent weight of 500 to 30,000 g / mole; or (ii) a compound having 2 or more carbonyl groups per molecule and an equivalent weight of 130 to 480 g / mole; or (iii) a mixture of (i) and (ii).

[0109] In a third aspect, the compound (i) of the second aspect may be selected from the group consisting of carbonyl-containing polycarbonates, carbonyl-containing polyethers, carbonyl-containing polyesters, carbonyl-containing polyurethanes, copolymers thereof, and mixtures thereof.

[0110] In a fourth aspect, the polyamine compound (b) according to any one of the first to third aspects may have a number average molecular weight of at least 60 g / mole and an equivalent weight based on the sum of primary and secondary amine groups present of at least 30 g / mole.

[0111] In a fifth aspect, at least two primary amine groups per molecule of the polyamine compound (b) according to any one of the first to fourth aspects may have at least partially protected amino groups.

[0112] In a sixth aspect, the polyisocyanate compound (c) according to any one of the first to fifth aspects may have at least two isocyanate groups per molecule and an equivalent weight of less than or equal to 500 g / mole.

[0113] In a seventh aspect, the curable composition according to any one of the first to sixth aspects may further include a photochromic compound.

[0114] In an eighth aspect, the photochromic compound of the seventh aspect may be selected from the group consisting of naphthopyrans, benzopyrans, phenanthropyrans, indenonaphthopyrans, spiro(dihydroindole)naphthoxazines, spiro(dihydroindole)pyridobenzoxazines, spiro(benzodihydroindole)pyridobenzoxazines, spiro(benzodihydroindole)naphthoxazines, spiro(dihydroindole)-benzoxazines, fulgides, fulgimides, diarylethenes, and mixtures thereof.

[0115] In a ninth aspect, the curable composition according to any one of the first to eighth aspects may have a molar ratio of the total combined primary and secondary amine group equivalents of the polyamine compound (b) to the total carbonyl equivalents of component (a) of at least 1:1.

[0116] In a tenth aspect, the curable composition according to any one of the first to ninth aspects may have a molar ratio of isocyanate equivalents of the polyisocyanate compound (c) to the total combined primary and secondary amine group equivalents of the polyamine compound (b) of at least 1:1.

[0117] In an eleventh aspect, the curable composition according to any one of the first to tenth aspects may be a curable coating composition or a curable adhesive composition.

[0118] In a twelfth aspect, the curable composition according to any one of the first to eleventh aspects may further comprise a material selected from the group consisting of antioxidants, hindered amine light stabilizers, ultraviolet light stabilizers, plasticizers, thermoplastics, flow control agents, surfactants, adhesion promoters, solvents, fixed hue dyes, and mixtures thereof.

[0119] In a thirteenth aspect, the curable composition according to any one of the first to twelfth aspects, when applied to a substrate and cured, can form a phase-separated layer having multiple soft domains with a Tg range of from -100°C to 0°C and multiple hard domains with a Tg range of from 5°C to 120°C.

[0120] In a fourteenth aspect, the curable composition of the thirteenth aspect can comprise a photochromic compound residing within the soft domains of the phase-separated layer.

[0121] In a fifteenth aspect, the curable composition of any one of aspects one to fourteen may comprise a component (a) comprising one or more carbonyl-containing compounds and a polyamine compound (b) having at least two primary groups that are pre-reacted to form a poly(imine) prepolymer prior to the addition of a polyisocyanate compound (c) to form the curable composition.

[0122] In a sixteenth aspect, a coated article is provided, comprising a substrate and a cured coating on at least a portion of the substrate, wherein the cured coating is formed from the curable coating composition of any one of the first to fifteenth aspects (eg, the eleventh aspect).

[0123] In a seventeenth aspect, the coated article according to the sixteenth aspect comprises a curable coating composition comprising a photochromic compound.

[0124] In an eighteenth aspect, the coated article according to the sixteenth or seventeenth aspect may have a cured coating having a strength of at least 25 N / mm 2 Fisher microhardness.

[0125] In a nineteenth aspect, the coated article according to any one of the sixteenth to eighteenth aspects may be an optical article, a display element, a mirror, or a window.

[0126] In a twentieth aspect, the optical article of the nineteenth aspect can be a lens, such as an ophthalmic lens.

[0127] The following examples serve to illustrate the invention, but these examples should not, however, be considered as limiting the invention to its details.

[0128] Examples

[0129] Part 1. Preparation of formulation components

[0130] Example 1

[0131] Example 1 describes the preparation of polycarbonate diketone as follows.

[0132] UBE Industries, Ltd. PH100D polycarbonate diol ("PH-100D", 100 g), available with a reported molecular weight of 1000 g / mole and an average hydroxyl equivalent weight of 500 g / mole, levulinic acid (29 g), N,N-dicyclohexylcarbodiimide ("DCC", 51 g), N,N-dimethylaminopyridine ("DMAP", 6.1 g) and dichloromethane ("DCM", 250 ml) were combined and stirred under nitrogen overnight. The precipitated N,N-dicyclohexylurea ("DCU") was removed by filtration, and the remaining solution was washed with HCl (1 N, 250 ml x 2), saturated aqueous NaHCO3 (250 ml x 2) and brine (250 ml x 2). The organic phase was then dried over MgSO4 and filtered through celite. The solvent was removed to give 95 g of a pale yellow liquid, to which 100 ml of methanol was added. After allowing the layers to separate, the methanol layer was decanted and the product was dried under vacuum to yield 70 g of a colorless liquid.The ketone equivalent weight was calculated by NMR to be 1094 g / mole.

[0133] Example 2

[0134] Example 2 describes the preparation of polycarbonate diketone as follows.

[0135] To a 250 ml 4-necked round bottom flask equipped with a Dean-Stark trap under nitrogen was added 50 ml of xylene (50 ml) obtained from Ube Industries, Ltd. PH200D is available as a polycarbonate diol ("PH200D", 100 g) having a reported molecular weight of 2000 g / mole and an average hydroxyl equivalent weight of 1000 g / mole, levulinic acid (11.6 g), p-toluenesulfonic acid ("p-TSA", 0.22 g) and triphenyl phosphite ("TPP", 0.56 g). The reaction mixture is heated to 140°C for 3 hours to remove collected water. The temperature is then raised to 160°C for 1.5 hours, then held at 165°C for 1 hour, followed by 0.5 hours at 170°C to remove accumulated water and xylene throughout the process. The residue is then dried under vacuum to produce 110 g of product. The ketone equivalent weight is calculated by NMR to be 1076 g / mole.

[0136] Example 3

[0137] Example 3 describes the preparation of polycarbonate diacetophenone as follows.

[0138] Polycarbonate diacetophenone was prepared according to the procedure of Example 1 using the following reagents: polycarbonate diol ("PH-200D", 50 g), 4-acetylbenzoic acid (8.6 g), DCC (10.8 g), DMAP (0.3 g), and DCM (300 ml). Yield: 58 g. The molecular weight was calculated by NMR to be 2500 g / mole and the ketone equivalent weight was 1250 g / mole. Prior to use, the material was diluted to 80% solids with 1-methyl-2-pyrrolidone.

[0139] Example 4

[0140] Example 4 describes the preparation of a polycarbonate dialdehyde as follows.

[0141] Example 4 was prepared according to the procedure of Example 1, substituting an equal molar amount of 4-formylbenzoic acid for levulinic acid to produce 66 g of dialdehyde. The molecular weight calculated by NMR was 1536 g / mole, and the aldehyde equivalent weight was 768 g / mole.

[0142] Example 5

[0143] Example 5 describes the preparation of a thermoplastic polyurethane dione ("TPU dione") as follows.

[0144] According to the procedure of Example 1, the diketone was synthesized using the following reagents: CARBOTHANE TM PC-3575A, 50 g (a thermoplastic polyurethane diol available from Lubrizol Corporation, with a molecular weight (Mn) of 39,460 g / mole as measured by GPC using THF as the eluent), levulinic acid (1.0 g), DCC (1.6 g), DMAP (1.0 g), and DCM (500 ml). Yield: 50 g. Ketone equivalent weight is 19,828 g / mole, based on molecular weight.

[0145] Example 6

[0146] Example 6 describes the preparation of polycaprolactone monoacetoacetate as follows.

[0147] Step-1:

[0148] To a solution of 1-octanol (10 g) and caprolactone (131.4 g) in DCM (100 ml) was added diphenyl phosphate (3.85 g) under nitrogen. The solution was stirred at room temperature for 8 hours. The resulting organic solution was washed with saturated NaHCO3 aqueous solution (250 ml x 2) and brine (250 ml x 2), followed by a short silica gel plug. The solvent was removed and the crude product was dried under vacuum. Yield: 140 g. The product was used in the next step without further purification.

[0149] Step-2:

[0150] The product of step-1 (140 g) and tert-butyl acetoacetate (12.3 g) were dissolved in toluene (500 ml) and heated under reflux overnight. Volatiles were removed by distillation and the residue was dried under vacuum to obtain 150 g of a white solid which was used without further purification. The ketone equivalent weight calculated by NMR was 1926 g / mole.

[0151] Example 7

[0152] Example 7 describes the preparation of polycarbonate diacetoacetate as follows.

[0153] PH-200D (100 g) and t-butyl acetoacetate (16.2 g) were dissolved in toluene (300 ml) and heated under reflux overnight. Volatiles were removed by distillation. The residue was then dried under vacuum (50° C. for 6 hours) to give 115 g of a colorless oil. The ketone equivalent weight was calculated to be 1008 g / mole by NMR.

[0154] Example 8

[0155] Example 8 describes the preparation of a polyurethane polycarbonate polyketone ("PU-PC polyketone") as follows.

[0156] Step-1:

[0157] Using dibutyltin dilaurate (20 mg) as catalyst, the mixture was heated at 75 °C. N 3200 (2 g) (aliphatic polyisocyanate available from Covestro) was added dropwise over 1 hour to a mixture of 1% PEGylated polyisocyanate obtained from Ube Industries, Ltd. A solution of PH-300D polycarbonate diol having a reported average molecular weight of 3000 g / mole ("PH-300D", 33 g) was prepared in anhydrous toluene (200 ml). The resulting reaction mixture was stirred under nitrogen for about 6 hours until the isocyanate was consumed. The solvent was removed to obtain 35 g of crude product, which was used directly in Step-2.

[0158] Step-2:

[0159] The product from Step-1 (25 g), levulinic acid (2.75 g), DCC (4.88 g), DMAP (0.5 g) and DCM (250 ml) were combined and subjected to the same reaction and separation conditions as in Example 1. Yield: 24 g. The molecular weight was calculated by NMR to be 10,500 g / mole and the ketone equivalent weight was 3500 g / mole.

[0160] Example 9

[0161] Example 9 describes the preparation of pentaerythritol tetraketone as follows.

[0162] Pentaerythritol (10 g), levulinic acid (35 g), DCC (63.5 g), DMAP (1.8 g) and DCM (200 ml) were subjected to the same reaction and separation conditions as in Example 1. Yield: 35 g. Ketone equivalent weight was calculated by NMR to be 132 g / mole.

[0163] Example 10

[0164] Example 10 describes the preparation of an acrylic polyketone as follows.

[0165] Dipropylene glycol methyl ether acetate (DMPA, 60 ml) was purged with N2 for 15 minutes and then heated to 130°C. A solution of diacetone acrylamide (89.2 g dissolved in 150 ml of DMPA), n-butyl methacrylate (75 g), 2,2'-azobis(2-methylbutyronitrile) (9.75 g), TPP (0.82 g), and tert-dodecyl mercaptan (1.65 g) was added dropwise over 60 minutes. After stirring at 130°C for 30 minutes, 2,2'-azobis(2-methylbutyronitrile) (0.5 g) in DPMA (5 ml) was added. The solution was stirred for an additional hour, cooled to 100°C, and then slowly added to cold hexane (5°C, 1.25 L) with stirring. The solution was then cooled to room temperature after which the top layer was decanted and the remaining viscous liquid was dried at 50° C. under vacuum for approximately two hours to yield 175 g of product having a weight average molecular weight (Mw) of 6060 g / mole and a number average molecular weight (Mn) of 3980 g / mole as determined by GPC using THF as the eluent relative to polystyrene standards. The ketone equivalent weight was calculated to be 288 g / mole based on NMR.

[0166] Part 2. Preparation of Curable Compositions

[0167] Examples 11-16

[0168] Coating composition examples 11-13 and comparative examples (CE) 14-16 were prepared using the components listed in Table 1 below, shown in parts by weight. The components of Charge 1 were mixed for approximately 30 minutes. Charge 2 components were added at room temperature and then stirred for 1 hour. Charge 3 components were added and the mixture was stirred for an additional 15 minutes before use.

[0169] Table 1

[0170]

[0171] iPolyether-modified dimethylpolysiloxane copolymer, available from BYK-Chemie.

[0172] ii Blocked hexamethylene diisocyanate biuret available from Baxenden Chemical Co. has an isocyanate equivalent weight (on a solids basis) of 287 g / mole and is provided at 70% solids in propylene glycol monomethyl ether.

[0173] iii Available from Nippon Shokubai Co., Ltd., it has a reported molecular weight of 600 g / mole and an amine (primary and secondary) equivalent weight of 50 g / mole.

[0174] Examples 17-33

[0175] Photochromic compositions were prepared using the components listed in each of the following tables, shown in parts by weight. For each photochromic composition, the components of Charge 1 were combined and heated to 50°C for a minimum of 30 minutes, until the solids were completely dissolved. Each solution was cooled to room temperature, and the components of Charge 2 were added to each solution, followed by stirring for 1 hour. The components of Charge 3 were added, and the mixture was stirred for an additional 15 minutes before use.

[0176] Table 2 below describes compositions with high equivalent weight dicarbonyls, with and without low equivalent weight polycarbonyls.

[0177] Table 2

[0178]

[0179]

[0180] iv The formulated blend of photochromic indeno-fused naphthopyran dyes produces a grey color upon activation.

[0181] v Hindered amine light stabilizers, commercially available from BASF.

[0182] vi Antioxidant, commercially available from BASF.

[0183] Table 3 below describes compositions having different ratios of high equivalent weight ("soft") and low equivalent weight ("hard") carbonyl components.

[0184] Table 3

[0185]

[0186]

[0187] Table 4 below describes photochromic compositions using different ratios of amine to carbonyl components.

[0188] Table 4

[0189]

[0190]

[0191] Table 5 below describes the preparation of photochromic compositions using different ratios of isocyanate to amine components.

[0192] Table 5

[0193]

[0194] Table 6 below describes the preparation of photochromic compositions using amines of varying molecular weights.

[0195] Table 6

[0196]

[0197] vii A polyamine available from Nippon Shokubai Co., Ltd. having a reported molecular weight of 300 g / mole and an amine (primary and secondary) equivalent weight of 48 g / mole.

[0198] viii A polyamine available from Nippon Shokubai Co., Ltd. having a reported molecular weight of 1200 g / mole and an amine (primary and secondary) equivalent weight of 53 g / mole.

[0199] Table 7 below describes the preparation of compositions having different carbonyl functional components.

[0200] Table 7

[0201]

[0202]

[0203] Part 3. Preparation of Photochromic Test Samples

[0204] The compositions of Examples 11 to 33 were applied to Coated Polycarbonate flat lenses, each having a diameter of 76 mm. Prior to coating, each lens was corona treated using a Tantec device with 70 kV and 1000 W settings. Approximately 1-2 mL of each composition was dispensed onto the substrate and then spun for eight seconds (for all Examples 11 to 33) at a speed sufficient to deposit 0.28-0.4 g of wet coating onto the lens.

[0205] Test samples of Examples 11 to 16 were prepared as one set and Examples 17 to 33 were prepared in duplicate and then cured in a forced air oven for 1 hour at 125° C. All coated and cured samples exhibited clear coatings with no visible haze.

[0206] Part 4. Characteristics of test samples

[0207] Part 4a. Microhardness Evaluation

[0208] A set of test samples were subjected to an additional heat cure at 105°C for three hours and set aside for hardness measurement. These samples were then subjected to microhardness 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 load of 100 millinewtons for 15 seconds. Each test sample was measured at least twice and the data averaged. The results for the non-photochromic coatings are shown in Table 8 below. The photochromic coating results are shown in Tables 9-14 in Section 4b.

[0209] Table 8

[0210]

[0211]

[0212] As shown in Table 8, Examples 11-13 demonstrate that formulations containing various combinations of polyamines, polyisocyanates, and high and / or low equivalent weight carbonyl compounds provide acceptable hardness (>25 N / mm 2 ). Compared to Example 13, omitting the polyisocyanate component or the polyamine component resulted in a coating that was not sufficiently crosslinked and was very soft and tacky (see CE 14 and 16, respectively). Omitting the polycarbonyl component resulted in a very hard coating (see CE-15).

[0213] Section 4b. Photochromic Properties

[0214] A second set of test samples (Examples 17-33) 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. 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.

[0215] 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 nm ultraviolet light at a distance of about 14 cm 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 centimeters for about 10 minutes to bleach (deactivate) the photochromic material. The spectroradiometer measured the illuminance at the sample and found it 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.

[0216] The BMP optical bench is equipped with two 150-watt Newport Model #6255 xenon arc lamps positioned at right angles to each other. The light path from lamp 1 is directed through a 3 mm KG-2 bandpass filter and appropriate neutral density filters, which help to achieve 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 cut-off filter and appropriate neutral density filters were used to provide supplemental visible light illumination. A 2 inch x 2 inch (5.08 cm x 5.08 cm) 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. The software, BMPSoft version 2.1e, was used on the BMP to control timing, irradiance, chamber and sample temperature, shutters, filter selection, and response measurement. A fiber optic cable with a lens was used to transmit light through the lens. Response and color measurements were performed using a spectrophotometer (Model MCS 601). Photopic response measurements were collected on each lens.

[0217] Adjust the power output of the optical platform (i.e. the dose of light to which the lens is exposed) to 6.7 W / m². 2) UVA, from 315-380nm integration, and 50Klux illumination, from 380-780nm integration. Use irradiance probe and calibrated Zeiss (Zeiss) spectrophotometer to measure this power setting point. The lens sample cell is equipped with a quartz window and an automatic centering sample holder. The temperature in the sample cell 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 carried out using the same Zeiss spectrophotometer, which has a fiber optic cable for transmitting light from a halogen tungsten lamp through the sample. The collimated monitoring beam from the fiber optic cable is maintained perpendicular to the test sample while passing through the sample and being guided into the receiving fiber optic cable assembly attached to the spectrophotometer. The exact placement point of the sample in the sample cell 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.

[0218] 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 %T b is the percent transmittance in the whitish state and %T a is the percent transmittance in the activated state. Optical density measurements are based on photopic optical density.

[0219] The results of the microhardness and photochromic performance of Examples 17 to 33 are shown below in Tables 9 to 14. 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 after the activating light source is removed at 73.4°F (23°C).

[0220] Table 9

[0221] Effects of carbonyl materials (i) and combinations of (i) and (ii)

[0222]

[0223] Comparable photochromic performance and hardness were demonstrated using only the high equivalent weight dicarbonyl (Example 17) and combining high and low equivalent weight carbonyl materials (Example 18).

[0224] Table 10

[0225] Different ratios of high equivalent weight carbonyl groups (i) to low equivalent weight carbonyl groups (ii).

[0226]

[0227] As shown in Table 10, reducing the amount of acrylic polyketone (ii) relative to the high equivalent weight carbonyl (i) in the coating improves the photochromic performance in terms of T1 / 2 with lower but acceptable hardness.

[0228] Table 11

[0229] Different ratios of amine to carbonyl groups

[0230]

[0231] As shown in Table 11, higher amine to carbonyl ratios result in harder coatings without affecting the photochromic performance.

[0232] Table 12

[0233] Different ratios of isocyanate to amine components

[0234]

[0235] As shown in Table 12, higher isocyanate to amine ratios resulted in harder coatings with only a minor effect on photochromic performance.

[0236] Table 13

[0237] Different amine molecular weights

[0238]

[0239] As shown in Table 13, Examples 25-27 demonstrate that amines with similar equivalent weights produce similar hardness regardless of molecular weight.

[0240] Table 14

[0241] Further examples using different carbonyl components (i) and (ii) and different carbonyl functionalities

[0242]

[0243]

[0244] Table 14 shows that hardness and photochromic properties can be fine-tuned by varying the introduced carbonyl components (i) and (ii), including functionality, reactivity of the carbonyl groups, molecular weight, branching, and backbone chemistry, such as polyester, polyurethane, and polycarbonate.

[0245] Section 4C: Thermal Analysis - Differential Scanning Calorimetry Data

[0246] Using the coating of Example 19, films were prepared on polypropylene sheets for thermal analysis using differential scanning calorimetry (DSC). The samples were sealed in aluminum sealing pans and scanned in a TAI Discovery DSC. The temperature cycle selected was from -75°C to 125°C with a heating rate of 20°C / minute. As shown in the DSC results in Table 15 below, the photochromic film prepared by Example 19 showed a peak (peak 1: negative) at a low glass transition temperature (Tg) and another peak (peak 2: positive) at a high Tg, indicating separation between the hard polymer domain and the soft polymer domain. These results indicate a phase separation system in which most of the photochromic dye can reside in a soft polymer domain that provides good photochromic performance (T1 / 2), while the hard polymer domain provides hardness for the coating.

[0247] Table 15

[0248]

[0249] Although specific embodiments of the present invention have been described in detail, it will be appreciated by those skilled in the art that various modifications and alternatives to these details may be developed based on the overall teachings of this disclosure. Therefore, the specific embodiments disclosed herein are intended to be illustrative only and not limiting of the scope of the invention, which is to be given the full breadth of the appended claims and any and all equivalents thereof.

Claims

1. A curable composition comprising: (a) a component comprising one or more carbonyl-containing compounds having a number average molecular weight (Mn) of at least 500 g / mole, wherein each carbonyl group is independently a keto group or an aldehyde group, wherein component (a) comprises (i) a compound having 1 to 4 carbonyl groups per molecule and an equivalent weight of 500 to 30,000 g / mole, wherein compound (i) is selected from the group consisting of carbonyl-containing polyethers, carbonyl-containing polyesters, carbonyl-containing polyurethanes, copolymers thereof, and mixtures thereof; (b) a polyamine compound having at least two primary amine groups per molecule; and (c) a polyisocyanate compound, wherein the molar ratio of the total combined primary and secondary amine group equivalents of the polyamine compound (b) to the total carbonyl equivalents of component (a) is at least 1:1, and wherein the molar ratio of the isocyanate equivalents of the polyisocyanate compound (c) to the total combined primary and secondary amine group equivalents of the polyamine compound (b) is at least 1:

1.

2. The curable composition according to claim 1, wherein The component (a) further comprises: (ii) Compounds having 2 or more carbonyl groups per molecule and an equivalent weight of 130 to 480 g / mole.

3. The curable composition according to claim 2, wherein The first component (i) is selected from carbonyl-containing polycarbonates.

4. The curable composition according to any one of claims 1 to 3, wherein The polyamine compound (b) has a number average molecular weight of at least 60 g / mole and an equivalent weight based on the sum of the primary and secondary amine groups present of at least 30 g / mole.

5. The curable composition according to any one of claims 1 to 3, wherein The polyisocyanate compound (c) has at least two isocyanate groups per molecule and an equivalent weight of less than or equal to 500 g / mole.

6. The curable composition of any one of claims 1 to 3, further comprising a photochromic compound.

7. The curable composition according to claim 6, wherein The photochromic compound is selected from the group consisting of naphthopyrans, benzopyrans, phenanthropyrans, indenonaphthopyrans, spiro(dihydroindole)naphthoxazines, spiro(dihydroindole)pyridobenzoxazines, spiro(benzodihydroindole)pyridobenzoxazines, spiro(benzodihydroindole)naphthoxazines, spiro(dihydroindole)-benzoxazines, fulgides, fulgimides, diarylethenes, and mixtures thereof.

8. The curable composition according to any one of claims 1 to 3, wherein The composition further comprises a material selected from the group consisting of antioxidants, hindered amine light stabilizers, ultraviolet light stabilizers, plasticizers, thermoplastics, flow control agents, surfactants, adhesion promoters, solvents, fixed hue dyes, and mixtures thereof.

9. A coated article comprising: substrate; as well as A cured coating on at least a portion of the substrate, wherein the cured coating is formed from the curable composition of any one of claims 1 to 8.

10. The coated article of claim 9, wherein The curable composition includes a photochromic compound.

11. The coated article according to claim 9 or 10, wherein The coated article is selected from an optical article, a display element, a mirror, or a window.

12. The coated article of claim 11, wherein The optical article is a lens.

13. The coated article of claim 11, wherein The optical article is an ophthalmic lens.

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