Curable photochromic compositions comprising segmented polymers

Abstract

The present invention relates to a curable photochromic composition comprising (a) a photochromic compound; (b) a segmented polymer having active hydrogen groups, at least one first segment, and at least one second segment, wherein (i) each first segment independently comprises a fluorinated polymeric segment, and (ii) each second segment independently comprises a segment selected from the group consisting of polycarbonate segments, polyester segments, polyether segments, polyurethane segments, and copolymers thereof; and (c) a curing agent having a reactive functional group reactive with the active hydrogen groups of the segmented polymer, wherein the curing agent comprises at least one of a polyisocyanate, a polyisothiocyanate, or an aminoplast. Also provided are photochromic films and articles, including multilayer articles, comprising the curable photochromic composition.

Description

Technical Field

[0001] The present invention relates to a curable photochromic composition comprising a photochromic compound, a segmented polymer comprising at least one first segment and at least one second segment, and a curing agent. Also provided are photochromic articles prepared from such a composition. Background Art

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

[0004] It would be desirable to develop curable photochromic compositions that provide a cured photochromic layer with acceptable hardness, improved kinetics, and improved dye fatigue. Summary of the Invention

[0005] The present invention relates to a curable photochromic composition comprising:

[0006] (a) Photochromic compounds;

[0007] (b) a segmented polymer comprising active hydrogen groups, at least one first segment, and at least one second segment, wherein:

[0008] (i) each first segment independently comprises a fluorinated polymer segment, and

[0009] (ii) each second segment independently comprises a segment selected from the group consisting of a polycarbonate segment, a polyester segment, a polyether segment, a polyurethane segment, and a segment of copolymers thereof; and

[0010] (c) a curing agent comprising reactive functional groups reactive with the active hydrogen groups of the segmented polymer, wherein the curing agent comprises at least one of a polyisocyanate, a polyisothiocyanate, or an aminoplast.

[0011] The present invention also provides photochromic films and articles, including multilayer articles, comprising the curable photochromic composition.

[0012] The features that characterize the invention are pointed out with particularity in the claims, which are incorporated into and constitute a part of this disclosure. These and other features of the invention, its operating advantages and specific objects attained by its use will be more fully understood from the following detailed description, in which non-limiting embodiments of the invention are shown and described. DETAILED DESCRIPTION

[0013] As used herein, the articles "a," "an," and "the" include plural referents unless expressly and unequivocally limited to one referent.

[0014] 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.

[0015] Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as modified in all instances by the term "about."

[0016] As used herein, "at least one of" is synonymous with "one or more of," regardless of whether the elements are listed conjointly or separately. For example, the phrases "at least one of A, B, and C" and "at least one of A, B, or C" each mean any one of A, B, or C, or any combination of any two or more of A, B, or C. For example, A alone; or B alone; or C alone; or A and B; or A and C; or B and C; or all of A, B, and C.

[0017] As used herein, "selected from" is synonymous with "chosen from," regardless of whether the elements are listed conjunctively or separately. Further, the phrases "selected from A, B, and C" and "selected from A, B, or C" each mean any one of A, B, or C, or any combination of any two or more of A, B, or C. For example, A alone; or B alone; or C alone; or A and B; or A and C; or B and C; or all of A, B, and C.

[0018] 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).

[0019] 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).

[0020] 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.

[0021] As used herein, the term "(meth)acrylate" and similar terms (such as "(meth)acrylic acid ester") means methacrylate and / or acrylate. As used herein, the term "(meth)acrylic acid" means methacrylic acid and / or acrylic acid.

[0022] As used herein, the term "photochromic" and similar terms (e.g., "photochromic compound") means a substance having an absorption spectrum for at least visible radiation that changes in response to the absorption of at least actinic radiation. Furthermore, 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.

[0023] 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.

[0024] 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.

[0025] As used herein, the terms "first" and "second," to modify the term "state," are not intended to refer to any particular order or sequence, but rather to two different conditions or properties. For non-limiting purposes, the first and second states of a photochromic compound can 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 can 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 can be transparent in the first state and tinted in the second state. Alternatively, the photochromic compounds of the present invention can have a first color in the first state and a second color in the second state.

[0026] 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.

[0027] 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).

[0028] 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.

[0029] 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.

[0030] As used herein, the term "mirror" means a surface that specularly reflects a substantial portion of incident light.

[0031] 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.

[0032] 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.

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

[0034] 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.

[0035] 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.

[0036] As used herein, the recitation of an "optionally substituted" group refers to a group including, but not limited to, an alkyl, cycloalkyl, heterocycloalkyl, aryl, and / or heteroaryl group 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, an alkyl group (including an aralkyl group); an alkenyl group; an alkynyl group; a haloalkyl group; a perhaloalkyl group; a heterocycloalkyl group; an aryl group (including an alkaryl group, including hydroxy-substituted aryl groups such as phenol, and including multiple fused ring aryl groups); a heteroaryl group (including multiple fused ring heteroaryl groups); or an amine group such as -N(R 11 ')(R 12 '), where R 11 ' 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 or heteroaryl.

[0037] 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 or 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.

[0038] 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, phenanthrenyl, 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.

[0039] 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 12 Cycloalkyl (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.

[0040] 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 heterocycloalkyl, such as but not limited to 7-oxabicyclo[2.2.1]heptanyl; and fused polycyclic heterocycloalkyl, such as but not limited to octahydrocyclopenta[b]pyranyl and octahydro-1H-isochromenyl.

[0041] As used herein, the term "heteroaryl" includes but is not limited to C5-C 18 Heteroaryl, such as but not limited to C5-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 refers to an aryl group substituted with an alkyl group. Examples of aralkyl groups include, but are not limited to, those previously listed herein. As previously mentioned, the curable photochromic composition of the present invention comprises a segmented polymer (b) having an active hydrogen group. The segmented polymer (b) comprises (i) at least one first segment; and (ii) at least one second segment. Either or both of (i) at least one first segment and (ii) at least one second segment may comprise an active hydrogen group, as discussed in detail below.

[0042] Each of the at least one first segment (i) independently comprises a fluorinated polymer segment. Suitable examples of fluorinated polymers from which the fluorinated polymer segments are derived can include, but are not limited to, fluoroethylene-alkyl vinyl ether alternating copolymers available from Asahi Glass Company under the name LUMIFLON (such as those described in U.S. Patent No. 4,345,057); and fluoroaliphatic polymer esters commercially available from 3M Company, St. Paul, Minnesota under the name FLUORAD.

[0043] The fluorinated polymer segment (i) may comprise an active hydrogen group such as any of the active hydrogen groups mentioned below, for example, a hydroxyl group. Typically, the first segment (i) is present in the segmented polymer (b) in an amount from 5 weight percent to 70 weight percent, such as from 5 weight percent to 60 weight percent, such as from 8 weight percent to 55 weight percent, based on the total weight of the segmented polymer.

[0044] Additionally, the first segment (i) can comprise from 2 weight percent to 40 weight percent, such as from 2 weight percent to 30 weight percent, of the curable photochromic composition based on the weight of the total solids present in the curable photochromic composition.

[0045] The segmented polymer (b) of the curable photochromic composition of the present invention further comprises at least one second segment (ii), wherein each second segment independently comprises at least one of a polycarbonate segment, a polyester segment, a polyether segment, a polyurethane segment, a combination of two or more thereof, or a copolymer of two or more thereof.

[0046] At least one second segment (ii) may be terminated with a group derived from (i.e., a residue of) an active hydrogen-containing compound. Suitable active hydrogen-containing compounds include art-recognized blocking agents (e.g., one or more of the blocking agents described below for blocked polyisocyanate curing agents).

[0047] Each polycarbonate segment of each second segment of segmented polymer can be prepared independently according to art-recognized methods.For non-limiting illustrative purpose, each polycarbonate segment can be independently by the reaction of polyvalent alcohol (such as glycol) and carbonyl dihalide (such as carbonyl dichloride), and remove the halide acid (such as HCl) of gained and prepare.For further non-limiting illustrative purpose, each polycarbonate segment can be independently by the transesterification reaction of polyvalent alcohol (such as glycol) and dialkyl carbonate (such as diphenyl carbonate), and remove the hydroxyl functional alkyl (such as phenol) of gained and prepare.

[0048] Examples of polyols having at least two hydroxyl groups from which each polycarbonate segment can be independently prepared include, but are not limited to, glycerol, trimethylolpropane, trimethylolethane, trishydroxyethyl isocyanurate, pentaerythritol, ethylene glycol, propylene glycol, trimethylene glycol, 1,3-, 1,2-, and 1,4-butanediol, pentanediol (such as, but not limited to, 1,5-pentanediol), heptanediol, hexanediol, octanediol, 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′-methylenebiphenol, and similar polyols.

[0049] Each polycarbonate segment of each second segment can independently be free of active hydrogen functionality, or comprise one or more active hydrogen functional groups independently selected from hydroxyl, thiol, primary amine or secondary amine. According to methods generally recognized in the art, active hydrogen functionality can be independently introduced into each polycarbonate segment during or after the formation of each polycarbonate segment. For some embodiments, at least some of the polycarbonate segments have hydroxy functionality. For some embodiments, the polycarbonate segments with hydroxy functionality can be prepared by polycarbonate polyols such as polycarbonate diols. For some other embodiments, polycarbonate polyols (such as polycarbonate diols) can be selected from commercially available polycarbonate polyols, such as but not limited to ETERNACOLL polycarbonate diols from Ube Industries, Ltd. (UBE Industries).

[0050] Each polycarbonate segment of each second segment can have any suitable molecular weight. For example, each polycarbonate segment of each second segment can independently have an Mn of less than 20,000, such as less than 15,000. Each polycarbonate segment of each second segment can have an Mn greater than 3,000, such as from 3,000 to 20,000, or such as from 3,000 to 15,000.

[0051] Each polyester segment of each second segment of the segmented polymer can be independently prepared according to art-recognized methods. For non-limiting illustrative purposes, each polyester segment can be independently prepared by reacting a carboxylic acid functional material (and / or its cyclic anhydride, and / or its ester) having a carboxylic acid functionality of at least 2 (or an effective carboxylic acid functionality, such as in the case of cyclic anhydrides and carboxylic acid esters) with a polyol having a hydroxyl functionality of at least 2. The molar equivalent ratio of carboxylic acid groups to hydroxyl groups of the reactants is selected so that the resulting polyester segment has a hydroxyl functionality and / or a carboxylic acid functionality, and a desired molecular weight.

[0052] Examples of polyfunctional carboxylic acids that can be used to prepare each polyester segment include, but are not limited to, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endobicyclo-2,2,1,5-heptyne-2,3-dicarboxylic acid, tetrachlorophthalic acid, cyclohexane dicarboxylic acid, succinic acid, isophthalic acid, terephthalic acid, azelaic acid, maleic acid, trimellitic acid, 3,6-dichlorophthalic acid, adipic acid, sebacic acid, and similar polyfunctional carboxylic acids (optionally including appropriate cyclic anhydrides and / or esters thereof).

[0053] Examples of polyols that can be used to prepare each polyester segment of the second segment include, but are not limited to, those polyol examples previously listed herein.

[0054] Each polyester segment of each second segment may independently be free of active hydrogen functionality or contain one or more active hydrogen functional groups each independently selected from hydroxyl, thiol, primary amine, or secondary amine. Active hydrogen functionality may be independently introduced into each polycarbonate segment during or after the formation of each polyester segment according to methods recognized in the art.

[0055] Each polyester segment of each second segment can have any suitable molecular weight. For example, each polyester segment of each second segment can independently have an Mn of less than 20,000, such as less than 15,000. Each polyester segment of each second segment can have an Mn greater than 3,000, such as from 3,000 to 20,000, or such as from 3,000 to 15,000.

[0056] Each polyether segment of each second segment of the segmented polymer can be independently prepared according to methods recognized in the art. For non-limiting purposes, each polyether segment can be independently prepared by the reaction of a polyol having two or more hydroxyl groups with a polyepoxide having two or more epoxy (or ethylene oxide) groups, which react in such a ratio that the resulting polyether has hydroxyl functionality and / or ethylene oxide functionality. The polyols and polyepoxides used to prepare the polyether segments can be selected from, for example, aliphatic, alicyclic or aromatic polyols or polyepoxides, or mixtures thereof. Specific examples of polyols include those previously listed herein. Polyepoxides that can be used to prepare polyether segments may include those obtained by the reaction of polyols and epichlorohydrin. One or more of the polyols previously listed herein can react with epichlorohydrin to form polyepoxides. For non-limiting purposes, each polyether segment can independently be prepared from: 4,4'-(propane-2,2-diyl)biphenol and the diglycidyl ether of 4,4'-(propane-2,2-diyl)biphenol; or 4,4'-(propane-2,2-diyl)dicyclohexanol and the diglycidyl ether of 4,4'-(propane-2,2-diyl)dicyclohexanol.

[0057] Each polyether segment of each second segment may independently be free of active hydrogen functionality or contain one or more active hydrogen functional groups each independently selected from hydroxyl, thiol, primary amine, or secondary amine. Active hydrogen functionality may be independently introduced into each polycarbonate segment during or after the formation of each polyether segment according to methods recognized in the art.

[0058] Each polyether segment of each second segment can have any suitable molecular weight. For example, each polyether segment of each second segment can independently have an Mn of less than 20,000, such as less than 15,000. Each polyether segment of each second segment can have an Mn greater than 3,000, such as from 3,000 to 20,000, or such as from 3,000 to 15,000.

[0059] Each polyurethane segment of each second segment of the segmented polymer can be independently prepared according to art-recognized methods. For non-limiting purposes, each polyurethane segment can be independently prepared by reacting a polyisocyanate having at least two isocyanate groups with a polyol having at least two hydroxyl groups, with an appropriate molar excess of hydroxyl groups to form a hydroxy-functional polyurethane having at least two hydroxyl groups; or an appropriate molar excess of isocyanate groups to form a polyurethane having at least two isocyanate groups. Examples of polyisocyanates that can be used to prepare the polyurethane segments include, but are not limited to, aliphatic, aromatic, alicyclic, and heterocyclic polyisocyanates, as well as mixtures of such polyisocyanates.

[0060] Additional examples of polyisocyanates that can be used to prepare polyurethane segments 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; 2,4,4-trimethylhexane-1,6-diisocyanate; lysine methyl diisocyanate; diisocyanate (Isocyanatoethyl) fumarate; isophorone 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.

[0061] Examples of polyols having at least two hydroxyl groups from which the second segment of the polyurethane segment can be prepared include, but are not limited to, those polyols previously listed herein.

[0062] Each polyurethane segment of each second segment may independently be free of active hydrogen functionality or contain one or more active hydrogen functional groups each independently selected from hydroxyl, thiol, primary amine, or secondary amine. Active hydrogen functionality may be independently introduced into each polycarbonate segment during or after the formation of each polyurethane segment according to methods recognized in the art.

[0063] Each polyurethane segment of each second segment can have any suitable molecular weight. For example, each polyurethane segment of each second segment can independently have an Mn of less than 20,000, such as less than 15,000. Each polyurethane segment of each second segment can have an Mn greater than 3,000, such as from 3,000 to 20,000, or such as from 3,000 to 15,000.

[0064] Each second segment of the segmented polymer of the curable composition of the present invention can independently comprise at least one of a polycarbonate segment, a polycarbonate-polyester segment, a polycarbonate-polyurethane segment, a polyether-polyurethane segment, or a polycarbonate-polyester-polyurethane segment. Each second segment can comprise a combination of polyols chain-extended with a bifunctional linker, such as, but not limited to, a dicarboxylic acid to produce an ester linkage, a bischloroformat to produce a carbonate linkage, a diisocyanate to produce a urethane linkage, or a diol to produce an ether linkage or a combination of ester and urethane linkages, such that the second segment has a final Mn of less than 20,000 and greater than 3,000, such as from 3,000 to 15,000.

[0065] Each polycarbonate-polyester segment of each second segment of the segmented polymer can be independently prepared according to methods recognized in the art. For non-limiting illustrative purposes, each polycarbonate-polyester segment can be independently prepared according to the description provided previously herein for the preparation of polyester segments, wherein at least some of the polyols are polycarbonate polyols. Polycarbonate polyols can be prepared according to the description provided previously herein for the preparation of polycarbonate segments, wherein the molar ratios of the reactants are adjusted so that the resulting polycarbonate has hydroxyl functionality and is, accordingly, a polycarbonate polyol.

[0066] Each polycarbonate-urethane segment of each second segment of segmented polymer can be prepared independently according to methods generally recognized in the art. For non-limiting illustrative purposes, each polycarbonate-urethane segment can be prepared independently according to the description previously provided for the preparation of polyurethane segments herein, wherein at least some of the polyols are polycarbonate polyols. Polycarbonate polyols can be prepared according to the description previously provided for the preparation of polycarbonate segments herein, wherein the mol ratio of the reactants is adjusted so that the polycarbonate of the gained has hydroxy functionality, and are correspondingly polycarbonate polyols.

[0067] Each polyether-polyurethane segment of each second segment of the segmented polymer can independently be prepared according to art-recognized methods. For non-limiting illustrative purposes, each polyether-polyurethane segment can independently be prepared according to the description provided previously herein for the preparation of polyurethane segments, wherein at least some of the polyols are polyether polyols. Polyether polyols can be prepared according to the description provided previously herein for the preparation of polyether segments, wherein the molar ratios of the reactants are adjusted such that the resulting polyether has hydroxyl functionality and is, accordingly, a polyether polyol.

[0068] Each polycarbonate-polyester-polyurethane segment of each second segment of segmented polymer can be prepared independently according to methods generally recognized in the art. For non-limiting illustrative purposes, each polycarbonate-polyester-polyurethane segment can be prepared independently according to the description previously provided for the preparation of polyurethane segments herein, wherein at least some of the polyols are polycarbonate-polyester polyols. Polycarbonate-polyester polyols can be prepared according to the description previously provided herein, wherein the mol ratio of the reactants is adjusted so that the polymer of the gained has hydroxy functionality, and is correspondingly polycarbonate-polyester polyols.

[0069] Typically, the second segment (ii) is present in the segmented polymer (b) in an amount from 30 weight percent to 95 weight percent, such as from 40 weight percent to 95 weight percent, such as from 45 weight percent to 92 weight percent, based on the total weight of the segmented polymer. In addition, the second segment (ii) comprises from 15 weight percent to 70 weight percent, such as 20 to 60 weight percent, or such as 22 to 55 weight percent of the curable photochromic composition based on the total solid weight present in the curable photochromic composition. The total solid weight of the curable photochromic composition does not include the weight of any volatile components, such as solvents, and includes the weight of non-volatile components, including photochromic compounds; segmented polymers; curing agents; and any optional non-volatile additives, such as, but not limited to, UV stabilizers, thermal stabilizers, etc., as further described herein.

[0070] As previously mentioned, the segmented polymers (b) of the curable photochromic composition of the present invention contain active hydrogen groups. For example, at least one first segment and / or at least one second segment of each segmented polymer independently may contain one or more active hydrogen groups.

[0071] The active hydrogen equivalent weight of the segmented polymer (b) is generally selected so that a cured article, such as a cured coating or a cured polymer film (or sheet), prepared from the curable photochromic composition of the present invention has desired properties, including but not limited to a desired hardness level or a desired photochromic performance (such as a reduced fade half-life (T 1 / 2 )value).

[0072] The segmented polymer (b) may have an active hydrogen equivalent weight of less than or equal to 20,000 grams per equivalent (g / eq), such as less than 18,000 g / eq, or less than 15,000 g / eq. The segmented polymer (b) may have an active hydrogen equivalent weight of from 1,000 to 15,000 g / eq, or from 1,000 to 13,000 g / eq, or from 1,000 to 10,000 g / eq. Each active hydrogen group of the segmented polymer (b) is independently selected from a hydroxyl group (—OH), a thiol group (—SH), a primary amine (—NH2), or a secondary amine (—NHR′ or cyclic amine).

[0073] The R' group of each secondary amine group (-NHR') can be selected from any suitable organic group, such as a linear or branched C1-C 20 Alkyl, cycloalkyl or aryl, including those species and examples thereof previously listed herein. Cyclic amines from which the secondary amine group may be selected include, but are not limited to, those represented by the following formula (A):

[0074]

[0075] With reference to formula (A): subscript p is at least 3, such as 3, 4, 5, 6, or 7; and for each p, Y is independently selected from -CH2-, -CH(R"), or -C(R")2-, provided that one Y includes a single bond to the segmented polymer. Each R" can be selected from any suitable organic group, such as a linear or branched C1-C 20 Alkyl, cycloalkyl or aryl, including those species and examples thereof previously listed herein. Examples of cyclic amine groups from which each secondary amine group of the segmented polymer can be independently selected include, but are not limited to, azetidinyl, pyrrolidinyl, piperidinyl, azepanyl and azoconyl.

[0076] Each active hydrogen group of the segmented polymer can be a hydroxyl group. The segmented polymer (b) can have a hydroxyl equivalent weight of less than or equal to 18,000 grams per equivalent (g / eq). For example, the segmented polymer can have a hydroxyl equivalent weight of from 1,000 to 15,000 g / eq, or from 1,200 to 13,000 g / eq, or from 1,500 to 11,000 g / eq. The hydroxyl equivalent weight of the segmented polymer can be calculated by dividing the mass of the resin solids by the difference between the sum of the moles of alcohol of the alcohol-containing component and the sum of the moles of isocyanate of the isocyanate-containing component.

[0077] Each first segment (i) and each second segment (ii) of the segmented polymer (b) can be formed separately. Subsequently, the previously formed first segment and the previously formed second segment are combined together (e.g., reacted together to form a covalent bond therebetween) to form the segmented polymer of the curable photochromic composition of the present invention. Alternatively, each first segment can be formed first, and then each second segment can be formed by polymerization from (or off of) the backbone of the previously formed first segment.

[0078] For the segmented polymer of the curable photochromic composition of the present invention, at least one first segment and at least one second segment are covalently bonded to each other via a linking group selected from the group consisting of a carboxylate linking group (—C(O)O—), a thioester linking group (—C(O)—S—), an amide linking group (—C(O)—N(R 1 )-), carbamate linking group (-N(H)-C(O)-O-), thiocarbamate linking group (-N(H)-C(O)-S-), urea linking group (-N(R 1 )-C(O)-N(R 1 )-), thiourea linker (-N(R 1 )-C(S)-N(R 1 )-), carbonate linking group (-OC(O)-O-), ether linking group (-O-) and thioether linking group (-S-). Each R in the above-listed linking groups 1 The groups may be independently selected from hydrogen or any suitable organic group, such as a linear or branched C1-C 20 Alkyl, cycloalkyl, or aryl groups include those species and examples thereof previously listed herein.

[0079] Typically, each second segment is covalently bonded to at least one first segment. The segmented polymer of the curable photochromic composition of the present invention is not gelled (not gelled). In addition, at least one first segment and at least one second segment of the segmented polymer (b) are covalently bonded (or connected) to each other through a multifunctional linking group such as a difunctional linking group. Each functional group of the multifunctional linking group can be selected from the precursors of the above-mentioned linking groups. For non-limiting purposes, isocyanate functional group (-NCO) is a precursor of a linking group, such as but not limited to a carbamate linking group (-N(H)-C(O)-O-), a thiocarbamate linking group (-N(H)-C(O)-S-) or a urea linking group (-N(H)-C(O)-N(R 1 )-), where R 1 is selected from hydrogen and any suitable organic group, as previously described herein.

[0080] For non-limiting purposes, a difunctional linking group (such as, but not limited to, a diisocyanate, or a dicarboxylic acid, or a dicarboxylate, or a dihaloformate functional linking group) and an active hydrogen functional second segment (such as a hydroxyl functional second segment) can be reacted together so that the second segment comprises at least one functional group of the difunctional linking group. For further non-limiting purposes, a diisocyanate functional linking group and a dihydroxyl functional second segment (or second segment precursor) can be reacted together at a functional ratio of isocyanate groups to hydroxyl groups of 1.1:1 to 3:1 or 1.5:1 to 2:1. The resulting isocyanate functional second segment can then be reacted with an active hydrogen functional first segment to form a segmented polymer according to the present invention. For purposes including, but not limited to, controlling molecular weight and / or crosslinking, at least a portion (e.g., 1% to 60%, or 30% to 50%) of the isocyanate groups of the isocyanate-functional second segment can be capped (or blocked) with a capping agent (e.g., one or more of the capping agents further listed herein for blocked polyisocyanate curing agents) prior to reacting with the active hydrogen-functional first segment. Alternatively, at least a portion (e.g., 1% to 50%, or 30% to 60%) of the isocyanate groups of the diisocyanate-functional linking group can be capped with a capping agent prior to (and / or during) reacting with the dihydroxy-functional second segment.

[0081] Without intending to be bound by any theory, it is believed that the cured coating or cured film prepared from the curable photochromic composition of the present invention includes a domain consisting essentially of the second segment, which may be referred to herein as the "second segment domain". It is further believed, without intending to be bound by theory, that at least some (e.g., at least a substantial amount) of the photochromic compound of the curable photochromic composition of the present invention is present within the second segment domain of the cured coating or film. It is also believed, without intending to be bound by any theory, that the photochromic compound present within the second segment domain has an enhanced molecular freedom / range of motion, which allows the photochromic compound to more easily and quickly transition between an open form and a closed form, such as in response to exposure to and removal of an actinic radiation source, thereby resulting in enhanced photochromic performance characteristics associated with the cured article.

[0082] For some embodiments, the segmented polymer (b) can be present in the curable photochromic composition of the present invention in an amount from 20 to 98 weight percent, or from 30 to 98 weight percent, or from 40 to 98 weight percent, or from 35 to 80 weight percent, in each case based on the total weight of resin solids of the curable photochromic composition.

[0083] As used herein, the term "total weight of resin solids" means the total weight of the staged polymer and curing agent and does not include the weight of the photochromic compound.

[0084] The curable photochromic composition of the present invention comprises a curing agent (c) comprising reactive functional groups reactive with active hydrogen groups of the segmented polymer (b), wherein the curing agent comprises at least one of a polyisocyanate, a polyisothiocyanate or an aminoplast.

[0085] The polyisocyanate curing (or cross-linking) agent contains at least two isocyanate groups (-NCO). Examples of isocyanate functional materials from which the polyisocyanate curing agent can be selected 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 diisocyanate; bis(isocyanatoethyl) Fumarates; isophorone 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.

[0086] The polyisocyanate curing agent can be selected from polyisocyanates prepared from dimers and trimers of diisocyanate monomers. Dimers and trimers of diisocyanate monomers can be prepared by methods 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 linker selected from the group consisting of isocyanurates, uretdiones, biuret, allophanates, and combinations thereof.

[0087] The polyisocyanate curing agent may also be selected from oligomeric polyisocyanate functional adducts. The oligomeric polyisocyanate functional adduct may contain a compound selected from carbamate (-NH-C(O)-O-), thiocarbamate (-NH-C(O)-S-), urea (-N(R 1 )-C(O)-N(R 1 )-, where each R 1 structural linkers, independently as previously described herein), and combinations of such structural linkers.

[0088] 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.

[0089] 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 can be a diisocyanate monomer, for example, any of those previously described herein.

[0090] The isocyanate groups of polyisocyanate curing agents can be blocked or sealed with end-blocking agent / sealing agent. After being exposed to high temperature, end-blocking agent / sealing agent is separated from isocyanate functional material, makes its free / unblocked isocyanate group reaction and forms covalent bond with the active hydrogen group of segmented polymer. After being unblocked or unblocked by polyisocyanate, end-blocking agent can be volatilized from composition (before composition becomes vitrified) and / or retained in composition, as plasticizer. Expect end-blocking agent not to form bubble in composition and / or not to make composition excessive plasticizing after unblocking.

[0091] The end-capping group of the blocked polyisocyanate curing agent can be selected from hydroxyl functional compounds, 1H-azoles, lactams, ketoximes, or mixtures thereof. The types of hydroxyl functional compounds can include but are not limited to aliphatic, alicyclic, or aromatic alkyl monoalcohols or phenolics. Specific examples of hydroxyl functional compounds that can be used as end-capping agents include but are not limited to lower aliphatic alcohols such as methanol, ethanol, and n-butanol; alicyclic alcohols such as cyclohexanol and tetrahydrofuran; aromatic-alkyl alcohols such as phenylcarbinol and methylphenylcarbinol; and glycol ethers such as ethylene glycol butyl ether, diethylene glycol butyl ether, ethylene glycol methyl ether, and propylene glycol methyl ether. The hydroxyl functional end-capping group can include phenols, examples of which include but are not limited to phenol itself and substituted phenols such as cresol, nitrophenol, and p-hydroxymethyl benzoate.

[0092] Examples of 1H-azoles that can be used as capping 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.

[0093] Ketoximes useful as blocking groups may include those prepared from aliphatic or alicyclic ketones. Examples of ketoxime capping groups include, but are not limited to, 2-propanone oxime (acetone oxime), 2-butanone oxime (also known as methyl ethyl ketone oxime), 2-pentanone oxime, 3-pentanone oxime, 3-methyl-2-butanone oxime, 4-methyl-2-pentanone oxime, 3,3-dimethyl-2-butanone oxime, 2-heptanone oxime, 3-heptanone oxime, 4-heptanone oxime, 5-methyl-3-heptanone oxime, 2,6-dimethyl-4-heptanone oxime, cyclopentanone oxime, cyclohexanone oxime, 3-methylcyclohexanone oxime, 3,3,5-trimethylcyclohexanone oxime, and 3,5,5-trimethyl-2-cyclohexen-5-one oxime.

[0094] Examples of lactam end-capping groups may include, but are not limited to, e-caprolactam and 2-pyrrolidone. Other suitable end-capping groups include morpholine, 3-aminopropylmorpholine, and N-hydroxyphthalimide.

[0095] In the curable photochromic composition of the present invention, at least some of the reactive functional groups of the curing agent may be blocked with a blocking group, and each blocking group may be independently selected from the group consisting of methyl ethyl ketoxime, pyrazole (more specifically, 1H-pyrazole) and dialkylpyrazole (more specifically, 1H-dialkylpyrazole).

[0096] The polyisothiocyanate curing (or cross-linking) agent of the curable photochromic composition of the present invention comprises at least two isothiocyanate groups (-NCS). The polyisothiocyanate curing agent can be selected from those types and examples of polyisocyanate curing agents previously described herein (including those in which the isocyanate groups are blocked or blocked), wherein the isocyanate groups (-NCO) thereof are replaced by isothiocyanate groups (-NCS).

[0097] The curable photochromic composition of the present invention generally also includes one or more curing catalysts for catalyzing the reaction between the isocyanate groups and / or isothiocyanate groups of the polyisocyanate curing agent and / or the polyisothiocyanate curing agent and the active hydrogen groups of the segmented polymer. The types of useful catalysts include, but are not limited to, metal compounds, such as, but not limited to, organotin compounds, organobismuth compounds, organozinc compounds, organozirconium compounds, organoaluminum compounds, organonickel compounds, organomercury compounds, and alkali metal compounds; and amine compounds, such as tertiary amine compounds and quaternary ammonium compounds. Examples of organotin compounds include, but are not limited to, tin (II) salts of carboxylic acids, such as tin (II) acetate, tin (II) octoate, tin (II) ethylhexanoate, and tin (II) laurate; tin (IV) compounds, such as dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, and dioctyltin diacetate. Examples of suitable tertiary amine catalysts include, but are not limited to, diazabicyclo[2.2.2]octane and 1,5-diazabicyclo[4,3,0]non-5-ene. Examples of organobismuth compounds include, but are not limited to, bismuth carboxylates. Examples of alkali metal compounds include, but are not limited to, alkali metal carboxylates, such as, but not limited to, potassium acetate and potassium 2-ethylhexanoate. Examples of quaternary ammonium compounds include, but are not limited to, N-hydroxyalkyl quaternary ammonium carboxylates. The catalyst may be selected from tin(II) octoate, dibutyltin(IV) dilaurate, and / or bismuth 2-ethylhexanoate.

[0098] The curing (or crosslinking) agent of the curable photochromic composition of the present invention can be an aminoplast curing agent. The aminoplast curing agent can be selected from aminoplast curing agents (or crosslinking agents) recognized in the art. Examples of suitable aminoplast curing agents include, but are not limited to, aminoplasts containing hydroxymethyl and / or hydroxymethyl ether groups.

[0099] Aminoplasts are typically obtained by the reaction of formaldehyde with amines or amides. Examples of amines or amides include, but are not limited to, melamine, urea, and / or benzoguanamine. Condensates with other amines or amides, such as aldehyde condensates of glycolurils, can also be used to produce high-melting-point crystalline products that can be used in powder coatings. Although formaldehyde is typically used to prepare aminoplast crosslinking agents, other aldehydes, such as acetaldehyde, crotonaldehyde, and / or benzaldehyde, can be used.

[0100] Aminoplast curing agents typically contain methylol. At least a portion of these methylols are typically etherified with alcohol to change the curing response. Any monohydric alcohol can be used for this purpose, examples of which include but are not limited to methanol, ethanol, butanol, isobutanol, and / or hexanol. Aminoplast curing agents can be selected from melamine-, urea-, and / or benzoguanamine-formaldehyde condensates containing alcohol etherification from one to four carbon atoms.

[0101] When there is an aminoplast curing agent, the curable photochromic composition of the present invention typically includes one or more catalysts to promote the curing of the aminoplast curing agent with the active hydrogen groups of the segmented polymer. Suitable catalysts for aminoplast curing include but are not limited to acid such as acid phosphate and sulfonic acid or substituted sulfonic acid. Examples include dodecylbenzenesulfonic acid, p-toluenesulfonic acid, phenyl acid phosphate, ethylhexyl acid phosphate etc. Catalyst typically exists in an amount of about 0.05 to about 5.0 weight percents or about 0.25 to about 2.0 weight percents based on the gross weight of the resin solids in the curable photochromic composition.

[0102] The curing (or cross-linking) agent (c) may be present in the curable photochromic composition of the present invention in an amount of from 2 to 80 weight percent, or from 2 to 70 weight percent, or from 2 to 60 weight percent, or from 20 to 65 weight percent, the weight percents being in each case based on the total weight of resin solids of the curable photochromic composition and inclusive of the recited values.

[0103] The segmented polymer (b) can be present in the curable photochromic composition in an amount from 30 to 98 weight percent, based on the total resin solids weight of the curable photochromic composition; and, for some embodiments, the curing agent can be present in the curable photochromic composition in an amount from 2 to 70 weight percent, based on the total resin solids weight of the curable photochromic composition.

[0104] The curable photochromic composition of the present invention may include a curing agent comprising at least one of a polyisocyanate and a polyisothiocyanate, wherein each reactive functional group of the curing agent is independently selected from an isocyanate or an isothiocyanate. The molar ratio of the reactive functional groups of the curing agent (c) to the active hydrogen groups of the segmented polymer (b) may be at least 4:1.

[0105] In addition, the curing agent may include at least one of a polyisocyanate and / or a polyisothiocyanate, wherein each reactive functional group of the curing agent is independently selected from an isocyanate or an isothiocyanate. The molar ratio of the reactive functional groups of the curing agent (c) to the active hydrogen groups of the segmented polymer (b) is at least 5:1 and less than or equal to 60:1, such as from 6:1 to 50:1, or from 7:1 to 40:1.

[0106] Suitable polyisocyanates for use in the curable composition of the present invention may include at least one of a linear or branched aliphatic polyisocyanate, an alicyclic polyisocyanate, a dimer thereof, and a trimer thereof, in each case including, but not limited to, those species and examples thereof as previously described herein. Examples of linear or branched aliphatic polyisocyanates include, but are not limited to, ethylene diisocyanate; tetramethylene-1,4-diisocyanate; hexamethylene-1,6-diisocyanate; 2,2,4-trimethylhexane-1,6-diisocyanate; and dodecane-1,12-diisocyanate. Examples of alicyclic polyisocyanates include, but are not limited to, cyclobutane-1,3-diisocyanate; cyclohexane-1,3-diisocyanate; cyclohexane-1,4-diisocyanate; methylcyclohexyl diisocyanate; hexahydrotoluene-2,4-diisocyanate; hexahydrotoluene-2,6-diisocyanate; hexahydrophenylene-1,3-diisocyanate; hexahydrophenylene-1,4-diisocyanate; perhydrodiphenylmethane-2,4′-diisocyanate; and perhydrodiphenylmethane-4,4′-diisocyanate.

[0107] The curable photochromic composition of the present invention further comprises (a) at least one photochromic compound. The photochromic compound (a) may be selected from known types and examples of photochromic compounds, and may include combinations or mixtures thereof.

[0108] 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.

[0109] The photochromic compound suitable for use in the curable photochromic 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.

[0110] Additional examples of photochromic compounds that can be used in the curable photochromic composition of the present invention include, but are not limited to, those disclosed in US Pat. No. 9,028,728 B2, column 34, line 20 to column 35, line 13, the disclosure of which is specifically incorporated herein by reference.

[0111] The photochromic compound (a) is present in the curable photochromic composition 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 photochromic compound present in the curable photochromic composition can range from 0.001 weight percent to 40 weight percent, or from 0.001 to 10 weight percent, or from 0.01 to 5 weight percent, or from 0.1 to 2.5 weight percent, based on the total solids weight of the curable photochromic composition (including the weight of the photochromic compound, and inclusive of the recited values).

[0112] The curable photochromic composition of the present invention may optionally contain additives such as, but not limited to, waxes for flow and wetting; flow control agents such as poly(2-ethylhexyl)acrylate; antioxidants; and ultraviolet (UV) light absorbers. Examples of useful antioxidants and UV light absorbers include, but are not limited to, those commercially available from BASF under the trademarks IRGANOX and TINUVIN. When used, these optional additives may be present in an amount of up to 20 weight percent based on the total solid weight (excluding solvent) of the curable photochromic composition.

[0113] The curable photochromic compositions of the present invention may further comprise 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" refer to dyes that are non-photosensitive materials that are not physically or chemically responsive to electromagnetic radiation associated with their visually observed color. As used herein, the term "fixed-tint dye" and related terms exclude and are distinguishable from photochromic compounds. As used herein, the term "non-photosensitive material" refers to a material that is not physically or chemically responsive to electromagnetic radiation associated with its visually observed color, including but not limited to fixed-tint dyes.

[0114] One or more fixed hue dyes may be present in the curable photochromic compositions of the present invention for purposes including, but not limited to, providing to a cured article prepared from the curable photochromic composition: at least a primary (or first) color characteristic of the fixed hue dye when the photochromic compound is not activated; and optionally, a second color characteristic of the combination of the fixed hue dye and the photochromic compound when activated (e.g., by exposure to actinic radiation).

[0115] The optional fixed hue dye of the curable photochromic composition includes at least one of azo dyes, anthraquinone dyes, xanthene dyes, azime dyes, iodine, iodide salts, polyazo dyes, stilbene dyes, pyrazolone dyes, triphenylmethane dyes, quinoline dyes, oxazine dyes, thiazine dyes, or polyene dyes.

[0116] The fixed hue dye can be present in the curable photochromic composition in varying amounts to provide a desired effect in a cured article prepared therefrom. For example, the fixed hue dye can be present in the curable photochromic composition in an amount from 0.001 to 15 weight percent, or from 0.01 to 10 weight percent, or from 0.1 to 2.5 weight percent, the weight percents being in each case based on the total solids weight of the curable photochromic composition (including the weight of the fixed hue dye; and inclusive of the recited values).

[0117] The curable photochromic composition of the present invention may comprise a solvent, such as those selected from water, organic solvents, and combinations thereof.

[0118] Examples of organic solvents that may be present in the curable photochromic composition of the present invention include, but are not limited to, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, isobutanol, furfuryl alcohol, and tetrahydrofurfuryl alcohol; ketones or ketone alcohols such as acetone, methyl ethyl ketone, and diacetone alcohol; ethers such as dimethyl ether and methyl ethyl ether; cyclic ethers such as tetrahydrofuran and dioxane; esters such as ethyl acetate, ethyl lactate, ethylene carbonate, and propylene carbonate; hydroxy-functional ethers of alkylene glycols such as butyl 2-hydroxyethyl ether, methyl 2-hydroxypropyl ether, and phenyl 2-hydroxypropyl ether; nitrogen-containing cyclic compounds such as pyrrolidone, N-methyl-2-pyrrolidone, and 1,3-dimethyl-2-imidazolidinone; sulfur-containing compounds such as dimethyl sulfoxide and tetramethylene sulfone; aromatic compounds such as toluene, xylene, anisole, and butyl benzoate; and mixtures of aromatic compounds such as, but not limited to, aromatic benzoates. 100 Fluid, which is commercially available C9-C 10 Mixtures of dialkyl- and trialkyl-benzenes.

[0119] The solvent may be present in the curable photochromic composition of the present invention in an amount from 5 to 95 weight percent, or from 15 to 80 weight percent, or from 30 to 60 weight percent, in each case based on the total weight of the curable photochromic composition (including the weight of the solvent).

[0120] The present invention also relates to articles and in particular photochromic articles prepared using the curable photochromic compositions of the present invention as previously described herein. Examples of photochromic articles that can be prepared using the curable photochromic compositions of the present invention can include, but are not limited to, ophthalmic articles, display articles, windows, and mirrors.

[0121] The curable photochromic composition of the present invention can be used to prepare photochromic layers such as photochromic coatings and photochromic films (or sheets). As used herein, the term "coating" means a non-self-supporting cured layer, which is generally formed from a liquid composition applied to and attached to a substrate and which may or may not have a uniform thickness. As used herein, the term "film" (or "sheet") means a self-supporting (i.e., free-standing) cured polymer layer having a substantially uniform thickness.

[0122] The curable photochromic composition of the present invention can be cured by any suitable method. The curable photochromic composition can be cured under ambient conditions, such as at 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 (such as between the active hydrogen groups of the segmented polymer and the reactive functional groups of the curing agent). When cured at high temperatures, the curable photochromic composition can be referred to as a thermosetting curable photochromic composition in this article. The temperature at which the thermosetting curable photochromic composition of the present invention is cured is variable and depends in part on the amount of time during which the curing is performed. The curable photochromic composition of the present invention can be cured at high temperatures of from 90°C to 204°C, or from 100°C to 177°C, or from 110°C to 140°C for a period of 20 to 240 minutes.

[0123] The present invention also relates to an article, such as a photochromic article, comprising: (A) a substrate; and (B) a photochromic layer on at least one surface of the substrate, wherein the photochromic layer is formed from any one of the above-mentioned curable photochromic compositions of the present invention.

[0124] An article comprising a substrate and a photochromic layer (formed from a curable photochromic composition of the present invention) on at least one surface of the substrate can be selected from an ophthalmic article, a display article, a window, or a mirror. Accordingly, the substrate of the article can be selected from an ophthalmic substrate, a display, a window, or a mirror. 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.

[0125] 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 / or 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 monomers are available from PPG Industries (PPG). Industries, Inc.) sold 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 one such polymer being sold under the trademark TRIVEX by PPG Industries; 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 carbonate-linked resins 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 (e.g., to form block copolymers or interpenetrating network products) are also contemplated.

[0126] 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 photochromic material / compound present in the substrate may be the same as or different from the photochromic compound of the photochromic layer. The optional fixed hue dye may be the same as or different from the optional fixed hue dye of the photochromic layer.

[0127] The photochromic layer of the article can be a photochromic coating and / or a photochromic film (or sheet). The photochromic film or sheet can be formed according to methods generally recognized in the art, such as, but not limited to, extrusion and casting methods. The photochromic layer of the article can be a photochromic coating formed by a curable photochromic composition of the present invention. The curable photochromic coating composition can be applied to a substrate according to methods generally 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.

[0128] After applying a curable photochromic composition to at least one surface of the substrate, the applied curable photochromic coating composition is cured as previously described herein to form a photochromic coating. The photochromic coating can be in the form of a single layer or multiple layers. When in the form of multiple layers, each layer of the photochromic layer can be prepared from a curable photochromic composition according to the present invention (having the same or different compositions, such as the same or different photochromic compounds).

[0129] The photochromic layer can have any suitable thickness, such as from 10 microns to 250 microns, or from 15 microns to 75 microns.

[0130] In addition to the photochromic layer, the article optionally can comprise one or more additional art-recognized layers, such as, but not limited to, a primer layer; an adhesive layer; a protective layer (e.g., a hard coat); a polarizing layer; a birefringent layer; an antireflective layer; and / or an additional photochromic layer prepared from a composition other than the curable photochromic composition of the present invention.

[0131] The present invention further relates to a photochromic multilayer article comprising at least one photochromic layer formed from a curable photochromic composition of the present invention. Each layer of the photochromic multilayer article can independently be in the form of a coating or a film / sheet. The photochromic multilayer article can comprise two or more layers formed from the same or different curable photochromic compositions of the present invention.

[0132] The multilayer articles of the present invention optionally may comprise one or more additional art-recognized layers, such as, but not limited to, an adhesive layer; a protective layer (e.g., a hard coat or one or more polymer film layers); a polarizing layer; a birefringent layer; an antireflective layer; and / or an additional photochromic layer prepared from a composition other than the curable photochromic composition of the present invention.

[0133] The multilayer articles of the present invention can have any suitable thickness, such as from 10 micrometers to 1,000 micrometers, or from 15 micrometers to 750 micrometers, or from 25 to 100 micrometers.

[0134] The multilayer articles of the present invention can be used alone or in combination with another article, such as a substrate. The substrate can be selected from the types and examples of substrates previously described herein with respect to the articles of the present invention, such as ophthalmic substrates, displays, windows, and / or mirrors. The substrate can be composed of one or more suitable materials, including but not limited to organic materials, such as organic polymeric materials; glass, such as silica-based glass; metal; ceramic materials; and combinations thereof.

[0135] The multilayer articles of the present invention can be attached to the surface of the substrate by methods recognized in the art, such as, but not limited to, electrostatic adsorption, such as electrostatic adsorption; one or more intervening adhesive layers; melt bonding, such as hot melt bonding; and in-mold forming, such as where the multilayer article is placed in a mold and the substrate is formed against at least one surface of the multilayer article within the mold. The multilayer articles of the present invention can be supported by one or more supports that are retainingly engaged with one or more peripheral regions of the multilayer article.

[0136] The present invention may be further characterized by one or more of the following non-limiting clauses.

[0137] Item 1. A curable photochromic composition comprising:

[0138] (a) Photochromic compounds;

[0139] (b) a segmented polymer comprising active hydrogen groups, at least one first segment, and at least one second segment, wherein:

[0140] (i) each first segment independently comprises a fluorinated polymer segment, and

[0141] (ii) each second segment independently comprises a segment selected from the group consisting of a polycarbonate segment, a polyester segment, a polyether segment, a polyurethane segment, and a segment of copolymers thereof; and

[0142] (c) a curing agent comprising reactive functional groups reactive with the active hydrogen groups of the segmented polymer, wherein the curing agent comprises at least one of a polyisocyanate, a polyisothiocyanate, or an aminoplast.

[0143] Item 2. The curable photochromic composition of Item 1, wherein at least a portion of each second segment (ii) is terminated with a group derived from a compound containing an active hydrogen selected from the group consisting of 1H-azoles, alkyl alcohols, and mixtures thereof.

[0144] Clause 3. The curable photochromic composition of Clause 1 or 2, wherein:

[0145] The segmented polymer (b) has an active hydrogen equivalent weight of from 1,000 to 15,000 g / eq, and

[0146] Each active hydrogen group of the segmented polymer (b) is independently selected from the group consisting of a hydroxyl group, a thiol group, a primary amine group, and a secondary amine group.

[0147] Item 4. The curable photochromic composition of any one of Items 1 to 3, wherein each active hydrogen group of the segmented polymer (b) is a hydroxyl group.

[0148] Clause 5. The curable photochromic composition of any one of clauses 1 to 4, wherein at least one first segment (i) and at least one second segment (ii) are covalently bonded to each other via a linking group selected from the group consisting of a carboxylate linking group, a thioester linking group, an amide linking group, a carbamate linking group, a thiourethane linking group, a urea linking group, a thiourea linking group, a carbonate linking group, an ether linking group, and a thioether linking group.

[0149] Clause 6. The curable photochromic composition of any one of Clauses 1 to 5, wherein the second segment (ii) is present in the segmented polymer (b) in an amount from 40 weight percent to 95 weight percent based on the total weight of the segmented polymer.

[0150] Item 7. The curable photochromic composition of any one of Items 1 to 6, wherein the curable photochromic composition comprises a total amount of the second segment (ii) of from 15 weight percent to 50 weight percent based on the total solid weight of the curable photochromic composition.

[0151] Item 8. The curable photochromic composition of any one of Items 1 to 7, wherein each second segment (ii) independently comprises at least one of a polycarbonate segment, a polycarbonate-polyester segment, a polycarbonate-polyurethane segment, a polyether segment, and / or a polycarbonate-polyester-polyurethane segment.

[0152] Clause 9. The photochromic composition of any one of Clauses 1 to 8, wherein:

[0153] The curing agent (c) comprises at least one of the following: a polyisocyanate containing a reactive isocyanate group, and / or a polyisothiocyanate containing a reactive isothiocyanate group, and

[0154] The molar ratio of the reactive functional groups of the curing agent (c) to the active hydrogen groups of the segmented polymer (b) is at least 4:1.

[0155] Item 10. The curable photochromic composition of any one of Items 1 to 9, wherein the molar ratio of reactive functional groups of the curing agent (c) to active hydrogen groups of the segmented polymer (b) is at least 5:1 and less than or equal to 60:1.

[0156] Item 11. The curable photochromic composition of any one of Items 1 to 10, wherein the curing agent (c) comprises a polyisocyanate containing reactive isocyanate groups.

[0157] Item 12. The curable photochromic composition of Item 11, wherein the polyisocyanate is an aliphatic polyisocyanate.

[0158] Clause 13. The curable photochromic composition of any one of Clauses 1 to 12, wherein the curing agent (c) comprises a polyisocyanate, and at least some of the reactive isocyanate groups comprising the polyisocyanate curing agent are blocked with a blocking agent, and each blocking agent is independently selected from the group consisting of methyl ethyl ketoxime, pyrazole, and dialkylpyrazole.

[0159] Item 14. The curable photochromic composition of any one of Items 1 to 13, wherein the photochromic compound (a) 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, and mixtures of such photochromic compounds.

[0160] Item 15. The curable photochromic composition of any one of Items 1 to 14, wherein the fluorinated polymer segments comprise active hydrogen groups.

[0161] Item 16. A photochromic polymer film comprising the curable photochromic composition of any one of Items 1 to 15.

[0162] Clause 17. An article of manufacture comprising:

[0163] (A) a substrate; and

[0164] (B) a photochromic layer on at least one surface of the substrate, wherein the photochromic layer is formed from the curable photochromic composition according to any one of clauses 1 to 15.

[0165] Item 18. A photochromic multilayer article comprising at least one photochromic layer formed from the curable photochromic composition of any one of Items 1 to 15.

[0166] Item 19. The photochromic multilayer article of Item 18, wherein the at least one photochromic layer is a photochromic coating and / or a photochromic polymer film layer.

[0167] The present invention is more particularly described in the following examples, which are intended to be illustrative only, as many modifications and variations therein will be apparent to those skilled in the art. Unless otherwise indicated, all parts and all percentages are by weight.

[0168] Examples

[0169] Part A: Preparation of the Second Segment of the Segmented Polymer

[0170] The materials used in the preparation of the polycarbonate-polyester diol segments are summarized in Table 1. Each polycarbonate-polyester diol segment was synthesized in a round-bottom flask equipped with a mechanical stirrer and a Dean Stark trap. After the introduction of Charge 1, each reaction mixture was heated to 170° C. under a nitrogen blanket to produce a strong reflux. Xylene and water were removed from the Dean Stark trap as needed to maintain the temperature below 180° C. for up to 7 hours, at which time the acid value was measured to be <1 mg KOH / g. At this point, the reaction mixture was cooled to 130° C. and then reduced to the solids level shown in Table 1 by the addition of Charge 2.

[0171] Table 1: Preparation of segmented polymer second segments S-1 to S-6.

[0172]

[0173] 1. Polycarbonate diol from Asahi Kasei Corporation

[0174] 2. Polycarbonate diol from Ube Industries Co., Ltd. (Ube)

[0175] 3. % solids measured after one hour in a 120°C oven.

[0176] 4. OH number as determined by the method of ASTM D4274.

[0177] 5. Residual acidic matter as determined by the method of ASTM D1639.

[0178] Part B: Preparation of segmented polymers

[0179] The preparation of segmented polymers (CE.1) to (Ex.8) is described below with reference to Table 2.

[0180] Table 2: Preparation of segmented polymers

[0181]

[0182] 6. Methyl-branched diisocyanate from Evonik Industries with an NCO equivalent weight of 105 (approximately a 1:1 mixture of 2,2,4- and 2,4,4-trimethyl-hexamethylene diisocyanate).

[0183] 7. Bismuth carboxylate catalyst from King Industries.

[0184] 8. Hindered amine light stabilizer from BASF with an OH equivalent weight of 756.

[0185] 9. The (meth)acrylic polyol segment corresponds to the acrylic polyol of Table 6 of WO 2017 / 030545 A1 and is prepared by free radical polymerization of hydroxypropyl methacrylate (40.4%), butyl methacrylate (57.6%), and acrylic acid (2.0%), and has: 61.5 wt% total solids; Mn of 3920; polydispersity index of 1.58; and a theoretical hydroxyl equivalent weight (based on solids) of 360.

[0186] 10. Available from Asahi Glass Co., Ltd. Fluoroethylene vinyl ether polyol, the sample used had an OH number of 96 and a % solids of 99%.

[0187] 11. With an OH value of 104 and a % solids of 99% LF916 batch.

[0188] 12. Available from Asahi Glass Co., Ltd. Fluoroethylene vinyl ether polyol, the sample used had an OH number of 30.9 (solution) and a % solids of 60%.

[0189] 13. Available from Asahi Glass Co., Ltd. Fluoroethylene vinyl ether polyol, the sample used had an OH number of 116 (solution) and a % solids of 70%.

[0190] 14. Available from Asahi Glass Co., Ltd. Fluoroethylene vinyl ether polyol, the sample used had an OH number of 68 (solution) and a % solids of 66.2%.

[0191] 15. OH equivalent weight is calculated by dividing the mass of resin solids by the difference between the sum of the moles of alcohol from the alcohol-containing charges (A, D, E, and F) and the sum of the moles of isocyanate from the isocyanate-containing charge (B).

[0192] Segmented Polymer CE.1

[0193] According to Table 2, Charges A, B, and C were combined with anisole (121 g) and heated at 80°C for 2.5 hours. The sample was cooled to 75°C and Charge E in anisole (16 g) was added. After 10 minutes, Charge F was added along with anisole (5 g). After 30 minutes at 75°C, the temperature was raised to 80°C for 3.5 hours. TM A test on a Surface SWYPE pad (available from CLI Laboratories, Inc., which causes a color change to orange or red when a drop of the reaction solution is dropped onto the pad when free isocyanate is present) indicated that the isocyanate was still present. 1-Propanol (2 mL) was added to quench the reaction and after 1.5 hours, the reaction was quenched using a Surface SWYPE TM A pad test indicated the absence of isocyanate and the solution was cooled to provide a viscous liquid.

[0194] Segmented polymer Ex.2

[0195] According to Table 2, Charges A, B, and C were combined with anisole (116 g) and heated at 80°C for 2.5 hours. The sample was cooled to 70°C and Charge E in anisole (13 g) was added. After 10 minutes, Charge F dissolved in anisole (28 g) was added along with additional anisole (8 g). After 30 minutes at 70°C, the temperature was raised to 80°C for 2.5 hours. TM A pad test indicated the absence of isocyanate and the solution was cooled to provide a viscous liquid.

[0196] Segmented polymer Ex.3

[0197] According to Table 2, Charges A, B, and C were combined with Aromatic 150 (87 g) and heated at 80°C for 2.5 hours. The sample was cooled to 75°C and Charge D dissolved in Aromatic 150 (27 g) was added. After 10 minutes, Charge F dissolved in Aromatic 150 (34 g) was added along with additional Aromatic 150 (8 g). After 30 minutes, the temperature was raised to 80°C for 2 hours. TM A pad test indicated the absence of isocyanate and the solution was cooled to provide a viscous liquid.

[0198] Segmented polymer Ex.4

[0199] According to Table 2, Charges A, B, and C were combined with m-xylene (129 g) and heated at 80°C for 2.5 hours. The sample was cooled to 70°C and Charge E in m-xylene (14 g) was added. After 10 minutes, Charge F was added. After 60 minutes at 70°C, the temperature was raised to 85°C for 1 hour. TM A pad test indicated the absence of isocyanate and the solution was cooled to provide a viscous liquid.

[0200] Segmented Polymer Ex.5

[0201] According to Table 2, Charges A, B, and C were combined with Aromatic 150 (90 g) and heated at 80°C for 2.5 hours. The sample was cooled to 75°C and Charge D dissolved in Aromatic 150 (11 g) was added with additional Aromatic 150 (4 g). After 30 minutes, Charge E in Aromatic 150 (7 g) was added. After 10 minutes, Charge F was added with additional Aromatic 150 (11 g). After 30 minutes, the temperature was raised to 80°C for 2 hours. TM A pad test indicated the absence of isocyanate and the solution was cooled to provide a viscous liquid.

[0202] Segmented Polymer Ex.6

[0203] According to Table 2, Charges A, B, and C were combined with Aromatic 150 (110 g) and heated at 80°C for 2.5 hours. The sample was cooled to 75°C and Charge D dissolved in Aromatic 150 (10 g) was added along with additional Aromatic 150 (4 g). After 30 minutes, Charge F dissolved in Aromatic 150 (24 g) was added along with additional Aromatic 150 (10 g). After 2.5 hours, the sample was washed with Surface Swear®. TM The pad test showed that the isocyanate was still present. 1-Propanol (2 mL) was added to quench the reaction and after 30 minutes, the reaction was quenched with Surface SWYPE TM A pad test indicated the absence of isocyanate and the solution was cooled to provide a viscous liquid.

[0204] Segmented Polymer Ex.7

[0205] According to Table 2, Charges A, B, and C were combined with Aromatic 150 (41 g) and heated at 80°C for 2.5 hours. The sample was cooled to 75°C and Charge D dissolved in Aromatic 150 (16 g) was added. After 30 minutes, Charge F dissolved in Aromatic 150 (9 g) was added. After 30 minutes, the temperature was raised to 80°C for 2 hours. TM A pad test indicated the absence of isocyanate and the solution was cooled to provide a viscous liquid.

[0206] Segmented Polymer Ex.8

[0207] According to Table 2, Charges A, B, and C were combined with Aromatic 150 (251 g) and heated at 80°C for 3 hours. The sample was cooled to 70°C and Charge E mixed with Aromatic 150 (6 g) was added. After 30 minutes, Charge F was added. After 2 hours, the sample was heated with Surface SWYPE TM A pad test indicated the absence of isocyanate and the solution was cooled to provide a viscous liquid.

[0208] Part C: Preparation of Photochromic Solution

[0209] Photochromic solutions (A) and (B) were prepared by mixing the materials listed in Table 3 at ambient temperature until all solids were observed to dissolve.

[0210] Table 3

[0211]

[0212] 16. A blend of photochromic indeno-fused naphthopyran dyes was selected to provide a green-grey color.

[0213] 17. Hindered amine light stabilizer from BASF: bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butyl malonate.

[0214] 18. Antioxidant from BASF: triethylene glycol bis(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate.

[0215] 19. Solvents available from Eastman

[0216] Preparation of comparative and inventive curable photochromic compositions.

[0217] Comparative curable photochromic composition:

[0218] Comparative curable photochromic compositions (CE-9, CE-10) were prepared from the components listed in Table 4. CE-9 is a representative curable photochromic composition that utilizes fluorinated polyol and polycarbonate diol segments added as separate components. CE-10 is a representative curable photochromic composition that utilizes a segmented polymer composed of (meth)acrylic polyol and polycarbonate-polyester diol segments.

[0219] Table 4: Comparative Examples

[0220]

[0221] 20. Polycarbonate diol having a hydroxyl equivalent weight of 1,516, available from Ube Industries, Ltd.

[0222] 21. Hexamethylene diisocyanate biuret, blocked with 3,5-dimethylpyrazole, available from Baxenden Chemical Co., having an equivalent weight of 410.

[0223] 22. Polyether-modified polydimethylsiloxane from BYK-Chemie, USA

[0224] Examples of curable photochromic compositions according to the present invention:

[0225] Curable photochromic composition Examples 11 to 17 of the present invention were prepared from the ingredients listed in Table 5. The Examples were prepared according to the procedures described above for the Comparative Examples.

[0226]

[0227] After their preparation, each of the curable photochromic compositions Examples 9 to 17 was heated to 400°C before use. 348923-A is placed on a benchtop roller for a minimum of six hours.

[0228] Part D: Preparation of test samples.

[0229] Each of the curable photochromic composition examples prepared above in Part C was applied to a Coated Polycarbonate plano lenses (available from Gentex Optics, Inc.) were deposited on the lens substrates. All lens substrates were treated with oxygen plasma at a power of 100 W and a flow rate of 100 milliliters (mL) / minute of oxygen for three minutes, and then coated with each of the curable photochromic composition examples described in Section C by spin coating. Approximately 1-2 mL of each curable photochromic composition was dispensed onto the lens substrates, which were then spun for 8-13 seconds at a speed sufficient to deposit a sufficient wet coating onto the lens to produce a similar activated optical density, as described below in Section E. The spin coating parameters are reported in Table 6.

[0230] Table 6. Spin coating parameters and coating weights measured for the preparation of test samples.

[0231]

[0232] Coated lens substrates were prepared in duplicate and designated "Lens Set A" and "Lens Set B". The coated lens substrates were then placed in a 40°C oven until all the coated lens substrates were accumulated. The coated lens substrates treated at 40°C were then cured in a forced air oven at 125°C for one hour and then cooled to room temperature. Test samples of Lens Set A were then subjected to an additional heat cure at 105°C for three hours and set aside for hardness evaluation. Test samples of Lens Set B were further treated with oxygen plasma as previously described and treated with HI- 1080S hardcoat (which is a protective coating available from PPG Industries, Inc.) was applied. The 1080S hard coat was applied by spin coating, and each lens (of Lens Set B) was then further cured for three hours at 105° C. The final lenses (test samples) of Lens Set B were then evaluated for their photochromic properties.

[0233] Part E: Test methods and test results for the test samples prepared in Part D.

[0234] Microhardness testing was performed on the test samples of lens set A at a penetration depth of 2 micrometers using a Fischerscope HCV, Model H100SMC apparatus (available from Fischer Technology, Inc.) after a load of 100 Newtons for 15 seconds. Each test sample was measured from 2 to 5 times and the microhardness results were averaged and listed in Table 15.

[0235] The photochromic properties of the test samples of lens set B 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 23°C. Prior to testing on the BMP, each of the test samples was exposed to 365 nanometer (nm) ultraviolet light at a distance of about 14 cm for about 10 minutes to activate the photochromic material. The UVA (315 nm to 380 nm) irradiance of the test sample was measured using a model Li-1800 spectroradiometer and found to be 22.2 W / m 2 Each test sample was then placed under a 500 watt (W) high intensity halogen lamp at a distance of about 36 cm for about 10 minutes to bleach (deactivate) the photochromic material. The spectroradiometer measured the illuminance of the test sample and found it to be 21.9 Klux. Each test sample was then kept in a dark environment at room temperature (21°C to 24°C) for at least one hour before testing on BMP. Prior to measurement, the UV absorbance of each test sample at 390 nm was measured.

[0236] The BMP is equipped with two 150W Newport Model #6255 xenon arc lamps set at right angles to each other. The light path from lamp 1 is directed through a 3mm KG-2 bandpass 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 (5.1 cm x 5.1 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. 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 test sample.

[0237] The power output of the BMP (i.e., the dose of light to which the test sample is exposed) was adjusted to 6.7 W / m 2UVA, from 315-380nm integration and 50Klux illumination, from 380-780nm integration. Use irradiance probe and calibrated Zeiss (Zeiss) spectrophotometer to measure the power setting point. Lens (test sample) sample cell is equipped with quartz window and automatic centering sample holder. The temperature in the sample cell is controlled at 23 ℃ by software using improved Facis, model FX-10 environmental simulator. The dynamic photochromic response and color measurement of the test sample are carried out using the same Zeiss spectrophotometer, which has a fiber optic cable for transmitting light from a tungsten halogen lamp through the sample. The collimated monitoring beam from the fiber optic cable is maintained perpendicular to the test sample, while passing through the test sample and being guided into the receiving fiber optic cable assembly attached to the spectrophotometer. The accurate placement point of the test 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 point where the test sample was placed was about 30° relative to the vertical.

[0238] The response measurement, in terms of the change in optical density (ΔOD) from the unactivated (blanched) state to the activated (tinted) state, is determined by establishing an initial unactivated transmittance, then opening the xenon lamp shutter and measuring the transmittance upon activation at selected time intervals. ΔOD at saturation is the absorbance measured after 15 minutes of exposure. The change in optical density is determined according to the following formula: ΔOD = log10 (%Tb / %Ta), where %Tb is the percent transmittance in the blanched state and %Ta is the percent transmittance in the activated state. Optical density measurements are based on photopic optical density.

[0239] Use Atlas Ci4000 weathering tester to simulate solar radiation accelerated aging. The sample is exposed to a 1 hour dark cycle in the case of a black plate and a chamber temperature of 40 ℃ and a relative humidity of 45%. This is followed by a 65 hour light cycle using a xenon arc lamp (output 0.25 watt per square meter at 340nm) filtered by boron / borosilicate. The temperature in the weathering tester is maintained at 40 ℃, and the relative humidity is controlled at 70% humidity. The temperature of the black plate is maintained at 55 ℃.

[0240] After the lenses had undergone this UV exposure fatigue cycle, the lenses were preconditioned and measured on an optical bench to obtain a final ΔOD under the same conditions as described for the initial testing. 最终 .

[0241] Percent fatigue is determined by measuring the difference between the change in optical density (ΔOD) of the test sample before and after accelerated aging according to the following formula: % fatigue = (ΔOD 初始 -△OD 最终 ) / △OD 初始 ×100.

[0242] Microhardness, fading half-life (T 1 / 2 ), ΔOD at saturation and the results of the photochromic dye fatigue test are shown in Table 7. ΔOD at saturation is after 15 minutes of activation. Fading half-life (T 1 / 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 fifteen minutes at 23° C. after removal of the activating light source. Fatigue test is the % remaining optical density after 130 hours of accelerated fatigue testing.

[0243] Table 7: Results of coating hardness, photochromic performance test and fatigue

[0244]

[0245] As shown in the test results listed in Table 7, the curable photochromic composition according to the present invention comprising a fluorinated segmented polymer provides a cured photochromic layer having photochromic performance characteristics (such as reduced T 1 / 2 value, improved surface hardness, or improved photochromic dye fatigue).

Claims

1. A curable photochromic composition comprising: (a) Photochromic compounds; (b) a segmented polymer comprising active hydrogen groups, at least one first segment, and at least one second segment, wherein: (i) each first segment independently comprises a fluorinated polymer segment, and (ii) each second segment independently comprises a segment selected from the group consisting of a polycarbonate segment, a polyester segment, and a segment of a copolymer thereof; wherein each active hydrogen group of the segmented polymer (b) is a hydroxyl group; and wherein at least one first segment (i) and at least one second segment (ii) are covalently bonded to each other via a carbamate linking group; and (c) a curing agent comprising reactive functional groups reactive with the active hydrogen groups of the segmented polymer, wherein the curing agent comprises a polyisocyanate.

2. The curable photochromic composition according to claim 1, wherein At least a portion of each second segment (ii) is terminated with a group derived from an active hydrogen-containing compound.

3. The curable photochromic composition according to claim 1, wherein: The segmented polymer (b) has an active hydrogen equivalent weight of from 1,000 to 15,000 g / eq.

4. The curable photochromic composition according to claim 1, wherein The second segment (ii) is present in the segmented polymer (b) in an amount from 40 weight percent to 95 weight percent based on the total weight of the segmented polymer.

5. The curable photochromic composition according to claim 1, wherein The curable photochromic composition comprises a total amount of the second segment (ii) of from 15 weight percent to 50 weight percent based on the total solid weight of the curable photochromic composition.

6. The curable photochromic composition according to claim 1, wherein Each second segment (ii) independently comprises a polycarbonate-polyester segment.

7. The curable photochromic composition according to claim 1, wherein: The molar ratio of the reactive functional groups of the curing agent (c) to the active hydrogen groups of the segmented polymer (b) is at least 4:

1.

8. The curable photochromic composition according to claim 7, wherein The molar ratio of the reactive functional groups of the curing agent (c) to the active hydrogen groups of the segmented polymer (b) is at least 5:1 and less than or equal to 60:

1.

9. The curable photochromic composition according to claim 1, wherein The curing agent (c) includes a polyisocyanate containing reactive isocyanate groups.

10. The curable photochromic composition according to claim 9, wherein The polyisocyanate is an aliphatic polyisocyanate.

11. The curable photochromic composition according to claim 1, wherein At least some of the reactive isocyanate groups comprising the polyisocyanate curing agent (c) are blocked with a blocking agent, and each blocking agent is independently selected from the group consisting of methyl ethyl ketoxime, pyrazole, and dialkylpyrazole.

12. The curable photochromic composition according to claim 1, wherein The photochromic compound (a) is selected from the group consisting of naphthopyran, benzopyran, phenanthropyran, indenonaphthopyran, spiro(dihydroindole)naphthoxazine, spiro(dihydroindole)pyridobenzoxazine, spiro(benzodihydroindole)pyridobenzoxazine, spiro(benzodihydroindole)naphthoxazine, spiro(dihydroindole)-benzoxazine, fulgide, fulgimide, and mixtures of such photochromic compounds.

13. The curable photochromic composition according to claim 1, wherein The fluorinated polymer segments contain active hydrogen groups.

14. A polymer film comprising the curable photochromic composition according to any one of claims 1 to 13.

15. An article comprising: (A) a substrate; and (B) a photochromic layer on at least one surface of the substrate, wherein the photochromic layer is formed from the curable photochromic composition according to any one of claims 1 to 13.

16. A photochromic multilayer article comprising at least one photochromic layer formed from the curable photochromic composition according to any one of claims 1 to 13.

Images