Curable photochromic compositions containing hydrazide and carbonyl functional components

Abstract

The present invention relates to a curable photochromic composition comprising: (a) a photochromic compound; (b) a hydrazide-functional material having at least two hydrazide groups reactive with carbonyl groups selected from ketone groups and aldehyde groups; (c) a first carbonyl-functional component comprising a (meth)acrylate polymer having at least two carbonyl groups reactive with hydrazide groups; and (d) at least one of (d1) a second carbonyl-functional component having at least one carbonyl group reactive with hydrazide groups and / or (d2) a non-reactive component. The non-reactive component does not contain functional groups reactive with the hydrazide-functional material, the first carbonyl-functional component, or the second carbonyl-functional component. The present invention also relates to an article comprising a substrate and a photochromic layer on at least one surface of the substrate, wherein the photochromic layer is formed from the curable photochromic composition of the present invention.

Description

[Technical Field]

[0001] The present invention relates to a curable photochromic composition comprising a photochromic compound, a hydrazide-functional material having at least two hydrazide groups, a first carbonyl-functional component comprising a (meth)acrylate polymer having at least two carbonyl groups, a second carbonyl-functional component having at least one carbonyl group, and / or at least one non-reactive component. [Background technology]

[0002] In response to specific wavelengths of electromagnetic radiation (or "actinic radiation"), photochromic compounds such as indeno-fused naphthopyrans typically undergo a transformation from one form or state to another, with each form having its own unique or distinguishable absorption spectrum. Typically, upon exposure to actinic radiation, many photochromic compounds are transformed from a closed form corresponding to the unactivated (or faded, e.g., substantially colorless) state of the photochromic compound to an open form corresponding to the activated (or colored) state of the photochromic compound. In the absence of exposure to actinic radiation, such photochromic compounds reversibly transform from the activated (or colored) state back to the unactivated (or faded) state. Compositions containing or coated with photochromic compounds (e.g., in the form of photochromic coating compositions) and articles such as optical lenses typically exhibit colorless (e.g., clear) and colored states corresponding to the colorless and colored states of the photochromic compound contained therein or coated thereon.

[0003] Photochromic compounds can be used in curable compositions to form cured layers, such as cured films or sheets that are photochromic. In cured photochromic films, such as cured photochromic coatings, it is typically desirable to provide a combination of hardness and photochromic performance. Generally, the reaction rate for the reversible transformation of a photochromic compound between a closed form (non-activated / colorless) and an open form (activated / colored) is faster in a soft matrix and slower in a hard matrix (of the cured film in which the photochromic compound resides). Cured photochromic films with a soft matrix typically have reduced hardness, while those with a hard matrix typically have increased hardness. Summary of the Invention [Problem to be solved by the invention]

[0004] It would be desirable to develop a curable photochromic composition that provides a cured photochromic layer with improved hardness without a loss in photochromic performance. [Means for solving the problem]

[0005] In accordance with the present invention, there is provided a curable photochromic composition comprising: (a) a photochromic compound; (b) a hydrazide-functional material comprising at least two hydrazide groups reactive with carbonyl groups selected from ketone groups and aldehyde groups; and (c) a first carbonyl-functional component comprising a (meth)acrylate polymer having at least two carbonyl groups reactive with hydrazide groups, wherein each carbonyl group of the first carbonyl-functional component is independently selected from ketone groups and aldehyde groups. The curable photochromic composition further comprises (d) (d1) a second carbonyl-functional component comprising at least one carbonyl group reactive with a hydrazide group, the second carbonyl-functional component comprising at least one of a polycarbonate carbonyl, a polyester carbonyl, a polyether carbonyl, a polyurethane carbonyl, or a combination thereof, wherein each carbonyl group of the second carbonyl-functional component is independently selected from a ketone group and an aldehyde group, and / or (d2) at least one non-reactive component, wherein the non-reactive component does not comprise a functional group reactive (forming a covalent bond) with the hydrazide-functional material, the first carbonyl-functional component, and the second carbonyl-functional component.

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

[0007] The features that characterize the invention are pointed out with particularity in the claims, which are annexed to and form a part of this disclosure. These and other features of the invention, the advantages of its operation, and specific objects attained by its uses will be more fully understood from the following detailed description, wherein non-limiting embodiments of the invention are shown and described. DETAILED DESCRIPTION OF THE INVENTION

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

[0009] Unless otherwise indicated, all ranges or ratios disclosed herein should be understood to encompass all values and subranges or subratios subsumed therein. For example, a stated range or ratio of "1 to 10" should be considered to include every value therebetween, including the stated end values (such as 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10), as well as subranges between (and including) a minimum value of 1 and a maximum value of 10, i.e., all subranges or subratios beginning with a minimum value of 1 or greater and ending with a maximum value of 10 or less, such as, but not limited to, 1 to 6.1, 3.5 to 7.8, and 5.5 to 10.

[0010] As used herein, unless otherwise indicated, left-to-right representations of a linking group, such as a divalent linking group, include other suitable orientations, such as, but not limited to, a right-to-left direction. For non-limiting illustrative purposes, left-to-right representations of a divalent linking group [ka] or equivalently -C(O)O-, its right-to-left representation [ka] or equivalently, -O(O)C- or -OC(O)-.

[0011] Except in the 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 being modified in all instances by the term "about."

[0012] As used herein, molecular weight values of polymers, such as weight average molecular weight (Mw) and number average molecular weight (Mn), are determined by gel permeation chromatography (GPC) in a suitable solvent (such as dimethylformamide DMF or tetrahydrofuran THF) using appropriate standards, such as polystyrene standards.

[0013] 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).

[0014] As used herein, the term "polymer" refers to homopolymers (e.g., prepared from a single monomer species), copolymers (e.g., prepared from at least two monomer species), and graft polymers.

[0015] As used herein, the terms "(meth)acrylate" and similar terms such as "(meth)acrylic acid ester" refer to methacrylate and / or acrylate. As used herein, the term "(meth)acrylic acid" refers to methacrylic acid and / or acrylic acid.

[0016] As used herein, the term "photochromic" and similar terms such as "photochromic compound" refer to having an absorption spectrum of at least visible light that changes in response to the absorption of at least actinic radiation. Additionally, as used herein, the term "photochromic material" refers to any substance adapted to display photochromic properties (e.g., adapted to have an absorption spectrum of at least visible light that changes in response to the absorption of at least actinic radiation) and that includes at least one photochromic compound.

[0017] As used herein, the term "actinic radiation" means electromagnetic radiation that is capable of producing a response in a material, such as, but not limited to, converting a photochromic material from one form or state to another, as described in more detail herein.

[0018] As used herein, the term "photochromic material" encompasses thermally reversible photochromic materials and compounds as well as non-thermally reversible photochromic materials and compounds. As used herein, the term "thermally reversible photochromic compound / material" refers to a compound / material that can convert from a first state, e.g., a "transparent state," to a second state, e.g., a "colored state," in response to actinic radiation and revert to the first state in response to thermal energy. As used herein, the term "non-thermally reversible photochromic compound / material" refers to a compound / material that can convert from a first state, e.g., a "transparent state," to a second state, e.g., a "colored state," in response to actinic radiation and revert to the first state in response to actinic radiation of substantially the same wavelength(s) as the absorption(s) of the colored state.

[0019] When used herein to modify the term "state," the terms "first" and "second" are not intended to refer to any particular order or chronological sequence, but rather to two different states or properties. For non-limiting illustrative purposes, the first and second states of a photochromic compound may differ with respect to at least one optical property, such as, but not limited to, the absorption of visible light and / or UV radiation. Thus, according to various non-limiting embodiments disclosed herein, the photochromic compounds of the present invention may have different absorption spectra in their first and second states. For example, but not limited to, the photochromic compounds of the present invention may be clear in their first state and colored in their second state. Alternatively, the photochromic compounds of the present compositions may have a first color in their first state and a second color in their second state.

[0020] 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, optical articles or elements or devices 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.

[0021] As used herein, the term "ophthalmic" means relating to or associated with the eye and vision. Non-limiting examples of ophthalmic articles or elements include corrective and non-corrective lenses, including multivision lenses, which may be single vision or segmented or non-segmented multivision lenses (such as, but not limited to, bifocal lenses, trifocal lenses, and progressive lenses), as well as other elements used to correct, protect, or enhance vision (cosmetic or otherwise), such as, but not limited to, contact lenses, intraocular lenses, magnifying lenses, and protective lenses or visors.

[0022] As used herein, the term "display" means a visible or machine-readable representation of information in words, numbers, symbols, designs, or drawings. Non-limiting examples of display elements include screens, monitors, and security elements such as security marks.

[0023] As used herein, the term "window" means an opening adapted to allow the transmission of radiation. Non-limiting examples of windows include automobile and aircraft transparencies, windshields, filters, shutters, and optical switches.

[0024] As used herein, the term "mirror" means a surface that specularly reflects a large portion of incident light.

[0025] As used herein, the term "liquid crystal cell" refers to a structure containing liquid crystal material that can be aligned. A non-limiting example of a liquid crystal cell element is a liquid crystal display.

[0026] As used herein, spatial or directional terms such as "left," "right," "inner," "outer," "upper," "lower," and the like, relate to various orientations of the present invention, including the articles and multi-layer articles of the present invention, which may be further described herein. However, it should be understood that the present invention may assume various alternative orientations to those described herein, and therefore such terms should not be considered limiting.

[0027] As used herein, the terms "formed on," "deposited on," "provided on," "coated on," "present on," or "disposed on" mean formed, deposited, provided, applied, present, or disposed on, but not necessarily in direct (or adjacent to) contact with, an underlying element or the surface of an underlying element. For example, a layer "disposed on" a substrate does not exclude the presence of one or more other layers, coatings, or films of the same or different composition located between the disposed or formed layer and the substrate.

[0028] All documents, including but not limited to issued patents and patent applications, mentioned herein are to be deemed "incorporated by reference" in their entirety unless otherwise indicated.

[0029] As used herein, references to "straight or branched chain" groups, such as straight or branched chain alkyl, are used herein to include methylene or methyl groups; groups that are straight chain, such as straight chain C-C alkyl groups; 20 alkyl groups, etc.; and appropriately branched groups, e.g., branched chain C3-C 20 The term "alkyl group" is intended to include alkyl groups and the like.

[0030] As used herein, the term "alkyl" refers to a straight or branched chain, cyclic or non-cyclic C1-C6 alkyl group.25 The straight or branched chain alkyl is C1 to C 25 Alkyl, e.g., C1-C 20 Alkyl, e.g., C2-C 10 Alkyl, e.g., C1-C 12 Examples of alkyl groups from which the various alkyl groups of the present invention can be selected include, but are not limited to, those further listed herein. The alkyl group may include a "cycloalkyl" group. As used herein, the term "cycloalkyl" refers to a group that is suitably cyclic, for example, but not limited to, C3 to C6 alkyl. 12 Cycloalkyl (including but not limited to, cyclic C3-C 10 "cycloalkyl" refers to a cycloalkyl group, such as a cyclic alkyl or cyclic C5-C7 alkyl group. Examples of cycloalkyl groups include, but are not limited to, those further enumerated herein. As used herein, the term "cycloalkyl" also encompasses bridged-ring polycycloalkyl groups (or bridged-ring polycyclic alkyl groups), such as, but not limited to, bicyclo[2.2.1]heptyl (or norbornyl) and bicyclo[2.2.2]octyl, as well as fused-ring polycycloalkyl groups (or fused-ring polycyclic alkyl groups), such as, but not limited to, octahydro-1H-indenyl and decahydronaphthalenyl.

[0031] As used herein, the term "heterocycloalkyl" includes, for example, but not limited to, C-C 12 Heterocycloalkyl groups, such as C2-C 10Heterocycloalkyl groups refer to groups that are suitably cyclic, such as, for example, a C5-C7 heterocycloalkyl group, and have at least one heteroatom in the cyclic ring, such as, but not limited to, O, S, N, P, and combinations thereof. Examples of heterocycloalkyl groups include, but are not limited to, imidazolyl, tetrahydrofuranyl, tetrahydropyranyl, and piperidinyl. As used herein, the term "heterocycloalkyl" also includes bridged-ring polycyclic heterocycloalkyl groups, such as, but not limited to, 7-oxabicyclo[2.2.1]heptanyl, and fused-ring polycyclic heterocycloalkyl groups, such as, but not limited to, octahydrocyclopenta[b]pyranyl and octahydro-1H-isochromenyl.

[0032] The descriptions, species and examples given herein for alkyl groups, cycloalkyl groups, heterocycloalkyl groups, haloalkyl groups, etc. also apply to alkane groups, cycloalkane groups, heterocycloalkane groups, haloalkane groups, etc., including, but not limited to, polyvalent alkane groups, e.g., polyvalent alkane linking groups, e.g., divalent alkane linking groups.

[0033] As used herein, the term "aryl" and related terms such as "aryl group" refer to an aromatic cyclic monovalent hydrocarbon radical. As used herein, the term "aromatic" and related terms such as "aromatic group" refer to a cyclic conjugated hydrocarbon that has significantly greater stability (due to delocalization of π electrons) than a hypothetical localized structure. Examples of aryl groups include, but are not limited to, C6-C8 14 Aryl groups include, for example, phenyl, naphthyl, phenanthryl, and anthracenyl.

[0034] As used herein, the term "heteroaryl" includes, but is not limited to, C3-C 18 Heteroaryl, including but not limited to, C-C 10Heteroaryl (including fused-ring polycyclic heteroaryl groups) refers to an aryl group having at least one heteroatom in an aromatic ring or, in the case of a fused-ring polycyclic heteroaryl group, in at least one aromatic ring. Examples of heteroaryl groups include, but are not limited to, furanyl, pyranyl, pyridinyl, quinolinyl, isoquinolinyl, and pyrimidinyl.

[0035] As used herein, the term "aralkyl" includes, but is not limited to, C-C 24 Aralkyl, for example, but not limited to, C-C 10 aralkyl, which refers to an alkyl group substituted with an aryl group. Examples of aralkyl groups include, but are not limited to, benzyl and phenethyl.

[0036] 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.

[0037] As used herein, the term "halo" and related terms such as "halo group," "halo substituent," "halogen group," and "halogen substituent" refer to a single-bonded halogen radical such as -F, -Cl, -Br, and -I.

[0038] As used herein, references to "halo-substituted" and related terms (including but not limited to haloalkyl, haloalkenyl, haloalkynyl, haloaryl and halo-heteroaryl) refer to groups having at least one, and up to all, of their available hydrogen radicals replaced with a halo group, such as, but not limited to, F, Cl or Br. The term "halo-substituted" includes "perhalo-substituted."

[0039] As used herein, "at least one of" is synonymous with "one or more of," regardless of whether the elements are listed in a conjunctive or non-conjunctive manner. For example, phrases such as "at least one of A, B, and C" and "at least one of A, B, or C" mean any one of A, B, or C, respectively, or any combination of any two or more of A, B, or C. For example, A only, or B only, or C only, or A and B, or A and C, or B and C, or all of A, B, and C.

[0040] As used herein, "selected from" is synonymous with "selected from," regardless of whether the elements are listed in a conjunctive or non-conjunctive manner. For example, phrases such as "selected from A, B, and C" and "selected from A, B, or C" mean any one of A, B, or C, or any combination of any two or more of A, B, or C, respectively. For example, A only, or B only, or C only, or A and B, or A and C, or B and C, or all of A, B, and C.

[0041] As used herein, according to some embodiments, the term "ketone" and related terms such as "ketone group," "keto group," "ketone substituent," and "keto substituent," as they relate to groups and substituents of various groups of the compounds and components of the present invention, refer to a substance represented by -C(O)R, where R is selected from the groups described below, other than hydrogen.

[0042] As used herein, according to some embodiments, the term "aldehyde," and related terms such as "aldehyde group," "aldo group," "aldehyde substituent," and "aldosing substituent," in reference to groups and substituents of various groups of compounds and components of the present invention, includes entities represented by -C(O)H.

[0043] As used herein, according to some embodiments, the term "carboxylic acid" and related terms such as "carboxylic acid group" and "carboxylic acid substituent," as they relate to groups and substituents of various groups of the compounds and components of the present invention, include substances represented by -C(O)OH.

[0044] As used herein, according to some embodiments, the term "ester" and related terms such as "ester group" and "ester substituent," such as with respect to groups and substituents of various groups of the compounds and components of the present invention, refer to a carboxylic acid ester group represented by -C(O)OR, where R is selected from the groups described below, other than hydrogen.

[0045] As used herein, according to some embodiments, the term "carboxylate" and related terms such as "carboxylate group" and "carboxylate substituent," as they relate to groups and substituents of various groups of compounds and components of the present invention, include substances represented by -OC(O)R, where R is selected from the groups described below.

[0046] As used herein, according to some embodiments, the term "amide" and related terms such as "amide group" and "amide substituent," such as with respect to groups and substituents of various groups of the compounds and components of the invention, includes entities represented by -C(O)N(R)(R) or -N(R)C(O)R, where each R is independently selected from the groups described below.

[0047] As used herein, according to some embodiments, the term "carbonate" and related terms such as "carbonate group" and "carbonate substituent," as they relate to groups and substituents of various groups of the compounds and components of the present invention, include substances represented by -OC(O)OR, where R is selected from the groups described below, other than hydrogen.

[0048] As used herein, according to some embodiments, the term "urethane" and related terms such as "urethane group" and "urethane substituent," such as in reference to groups and substituents of various groups of compounds and components of the present invention, include materials represented by -OC(O)N(R)(H) or -N(H)C(O)OR, where R in each instance is independently selected from the groups described below, other than hydrogen.

[0049] As used herein, according to some embodiments, the term "urea" and related terms such as "urea group" and "urea substituent," as they relate to groups and substituents of various groups of the compounds and components of the present invention, include substances represented by -N(R)C(O)N(R)(R), where each R is independently selected from the groups described below.

[0050] As used herein, according to some embodiments, the term "siloxy" and related terms such as "siloxy group" and "siloxy substituent," as they relate to groups and substituents of various groups of the compounds and components of the present invention, include materials represented by -O-Si(R)3, where each R is independently selected from the groups described below, other than hydrogen.

[0051] Unless otherwise specified, each R group in each of the above ketones, esters (carboxylic acid esters), carboxylates, amides, carbonates, urethanes, ureas, and siloxy groups is independently selected in each instance from hydrogen, alkyl, haloalkyl, perhaloalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and combinations thereof, including those types and examples listed previously herein.

[0052] The photochromic compositions of the present invention comprise hydrazide-functional materials having at least two hydrazide groups that are reactive in each case with carbonyl groups selected from ketone and aldehyde groups. As used herein, "reactive with carbonyl groups selected from ketone and aldehyde groups" and similar expressions mean that the hydrazide groups and ketone and / or aldehyde groups react together to form a covalent bond or bond, e.g., a hydrazone bond, between them.

[0053] According to some embodiments of the present invention, each hydrazide group of the hydrazide-functional material, at each occurrence, is independently selected from an acylhydrazide group (-C(O)-NHNH), a sulfonohydrazide group (-S(O)(O)-NHNH), and a phosphinic acid hydrazide group (-P(O)(R')-NHNH), where R', at each occurrence, is independently selected from alkyl, haloalkyl, perhaloalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and combinations thereof, including the classes and examples thereof listed previously herein. In some embodiments, each hydrazide group of the hydrazide-functional material, at each occurrence, is an acylhydrazide group (-C(O)-NHNH).

[0054] In some embodiments, the hydrazide-functional material has a hydrazide equivalent weight of 250 g / mol to 10,000 g / mol, or 300 g / mol to 8000 g / mol, or 500 g / mol to 5000 g / mol. In some further embodiments, the hydrazide-functional material has a Mw of 500 g / mol to 50,000 g / mol, or 1000 g / mol to 40,000 g / mol, or 2000 g / mol to 40,000 g / mol, as measured by GPC in DMF / LiBr eluent using polystyrene standards.

[0055] In some embodiments, the hydrazide-functional material contains 2 to 60 hydrazide groups, or 2 to 55 hydrazide groups, or 2 to 50 hydrazide groups, in each case reactive with carbonyl groups selected from ketone groups and aldehyde groups.

[0056] In some embodiments, the hydrazide-functional material comprises at least one of a non-polymeric hydrazide-functional material and / or a polymeric hydrazide-functional material. In some embodiments, the non-polymeric hydrazide-functional material does not comprise the same or different repeating monomer units (or monomer residues). In some embodiments, the polymeric hydrazide-functional material comprises multiple monomer units (or monomer residues).

[0057] Examples of non-polymeric hydrazide-functional materials that can be included in the curable photochromic compositions of the present invention include, but are not limited to, fumaric acid dihydrazide, maleic acid dihydrazide, itaconic acid dihydrazide, phthalic acid dihydrazide, terephthalic acid dihydrazide, trimellitic acid trihydrazide, oxalic acid dihydrazide, succinic acid dihydrazide, 2-methylsuccinic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, cyclohexanedicarboxylic acid dihydrazide, and cyclohexanetricarboxylic acid trihydrazide.

[0058] The hydrazide-functional polymers (or polymeric hydrazides) that can be used in the curable photochromic compositions of the present invention can have any suitable polymer backbone, which can have any suitable structure, such as linear, branched, hyperbranched, star-shaped, and comb-shaped structures. Examples of polymer backbones for hydrazide-functional polymers include, but are not limited to, polyethers, polyesters, polycarbonates, polyurethanes, and combinations of two or more thereof. In some embodiments, the hydrazide-functional polymers can include, in addition to hydrazide groups, one or more substituents, such as hydroxyl (—OH), carboxylic acid (—C(O)—OH), carboxylic acid ester (—C(O)—OR), sulfonic acid, sodium sulfonate, and / or amino (—N(R)(R)) groups, where each R is independently selected from the groups described hereinabove.

[0059] In some further embodiments, the hydrazide-functional polymer comprises one or more linking groups (or linkages), each linking group, in each occurrence independently, selected from an ether linkage (-O-), a thioether linkage (-S-), a urea linkage (-N(R)-C(O)-N(R)-, where each R is independently as defined above), a carbonate linkage (-OC(O)-O-), a carboxylic acid ester linkage (-OC(O)-), a urethane linkage (-N(H)-C(O)-O-), a thiourethane linkage (-SC(O)-N(H)-), a thiourea linkage (-N(R)-C(S)-N(R)-, where each R is independently as defined above), and an amide linkage (-C(O)-N(R)-, where R is as defined above).

[0060] In some embodiments, the hydrazide-functional material comprises a polyurethane comprising at least two hydrazide groups that are reactive with carbonyl groups selected from ketone groups and aldehyde groups. Hydrazide-functional materials comprising polyurethanes comprising at least two hydrazide groups may be referred to herein as hydrazide-functional polyurethanes.

[0061] According to some embodiments, the hydrazide-functional material has the following formula (I): [ka] is expressed by

[0062] With respect to formula (I), R 1 is a residue of a polymer, such as a polyether, polyester, polycarbonate, and / or polyurethane. In some embodiments, R in formula (I) 1 may optionally contain one or more substituents such as hydroxyl (-OH), carboxylic acid (-C(O)-OH), carboxylic acid ester (-C(O)-OR), sulfonic acid, sodium sulfonate, and / or amino (-N(R)(R)) groups, where R is in each case independently selected from the groups previously described herein. Further with respect to formula (I), R 2 is, independently for each n, a straight or branched chain divalent alkane, e.g., a divalent straight or branched chain C1-C 10 an alkane, a divalent cycloalkane group, such as a divalent C5-C8 cycloalkane group, or a divalent aromatic group, such as a divalent C6-C 10 Further with respect to formula (I), n is 2 to 60, for example 2 to 55, or 2 to 50, 2 to 40, or 2 or 30.

[0063] In some embodiments, R of formula (I) 1 is a residue of a polyurethane. In some further embodiments, R 1 is the residue of an isocyanate-terminated polyurethane.

[0064] In some embodiments, at least some of the hydrazide groups of the hydrazide-functional material are independently and reversibly blocked with an aldehyde or a ketone. In some further embodiments, at least some of the hydrazide groups of the hydrazide-functional material are independently and reversibly blocked with an aldehyde having a formula weight of less than 250 g / mol (e.g., from 44 g / mol to less than 250 g / mol) or a ketone having a formula weight of less than 250 g / mol (e.g., from 58 g / mol to less than 250 g / mol). Examples of aldehyde blocking groups include, but are not limited to, methyl aldehyde, ethyl aldehyde, propyl aldehyde, butyraldehyde, pentyl aldehyde, hexyl aldehyde, cyclohexyl formaldehyde, and benzaldehyde. Examples of ketone blocking groups include, but are not limited to, dimethyl ketone, methyl ethyl ketone, diethyl ketone, cyclopentanone, ethyl acetoacetate, and acetophenone.

[0065] As used herein, according to some embodiments, "at least some of the hydrazide groups of the hydrazide-functional material are independently reversibly blocked with an aldehyde or ketone" means that at least 10%, or at least 20%, or at least 25%, or at least 50%, or at least 75%, or at least 90%, or at least 95%, or 100% of the hydrazide groups are reversibly blocked. As used herein, according to some embodiments, "reversibly blocked with an aldehyde or ketone" means that under controlled conditions, such as elevated temperature, the blocked hydrazide groups become unblocked or free hydrazide groups, in which case the aldehyde and / or ketone blocking groups can volatilize from the curable photochromic composition or plasticize the curable photochromic composition, for example, when the curable photochromic composition is in the form of a layer.

[0066] In some embodiments, the curable photochromic composition has a ratio of (i) the total carbonyl equivalents of the first carbonyl-functional component and the second carbonyl-functional component to (ii) the total equivalents of hydrazide equivalents of the hydrazide-functional material of from 1:0.8 to 1:4, or from 1:0.8 to 1:3, or from 1:1 to 1:2.

[0067] The first carbonyl-functional component of the curable photochromic composition of the present invention comprises a (meth)acrylate polymer having at least two carbonyl groups reactive with hydrazide groups, each carbonyl group independently selected from a ketone group and an aldehyde group.

[0068] The monomers from which the (meth)acrylate polymer of the first carbonyl-functional component is prepared include, but are not limited to, C1-C acrylates that do not contain a carbonyl group that is reactive with the hydrazide group of the hydrazide-functional material. 20 (Meth)acrylates; ethylenically unsaturated radical polymerizable monomers having one or more carbonyl groups reactive with the hydrazide groups of the hydrazide-functional material; and optionally, ethylenically unsaturated radical polymerizable monomers other than (meth)acrylates that do not contain carbonyl groups reactive with the hydrazide groups of the hydrazide-functional material. 20 The group may be, for example, C1-C 20 Straight chain alkyl, C3-C 20 Branched alkyl, C3-C 20 Cycloalkyl, C3-C 20 Fused-ring polycycloalkyl, C5-C 20 Aryl and C 10 ~C 20 It may be selected from fused ring aryls.

[0069] C1-C, where a (meth)acrylate polymer of the first carbonyl-functional component is prepared. 20Examples of (meth)acrylates (which do not contain a carbonyl group that is reactive with the hydrazide group of the hydrazide-functional material) include, but are not limited to, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, and 3,3,5-trimethylcyclohexyl (meth)acrylate.

[0070] The (meth)acrylate polymer having at least two carbonyl groups is prepared from an ethylenically unsaturated radically polymerizable monomer having one or more carbonyl groups reactive with the hydrazide groups of the hydrazide-functional material. The type of ethylenically unsaturated radically polymerizable monomer having one or more carbonyl groups reactive with the hydrazide groups of the hydrazide-functional material includes, but is not limited to, carbonyl-functional (meth)acrylamide monomers, such as ketone-functional (meth)acrylamide monomers and aldehyde-functional (meth)acrylamide monomers. A non-limiting example of a carbonyl-functional (meth)acrylamide monomer is N-(2-methyl-4-oxopentan-2-yl)acrylamide, also known as diacetone acrylamide. Further examples of ethylenically unsaturated radically polymerizable monomers having one or more carbonyl groups reactive with the hydrazide groups of the hydrazide-functional material include acetoacetoxyethyl (meth)acrylate; vinyl acetoacetate; 2-propenoic acid, 3-oxobutyl ester; 2-propenoic acid, 3-oxopentyl ester; 2-propenoic acid, 2-methyl-, 3-oxobutyl ester; 2-propenoic acid, 3-oxoheptyl ester; 2-propenoic acid, 5-methoxy-3-oxopentyl ester; 2-propenoic acid, 2-methyl-, 1-methyl ester; butanoic acid, 3-oxo-, anhydride with 2-propenoic acid; benzoic acid, 4-ethenyl-, 3-oxobutyl ester; 2-propenoic acid, 1-methyl-1-(4-methyl-2-oxocyclohexyl)ethyl ester; 10-undecen-2-one, 1,1,1-trifluoro-; ethanone, 2,2,2-trifluoro-1-[2-(4-pentenyl)phenyl]-(9CI), and combinations of two or more thereof.

[0071] The types of ethylenically unsaturated radical polymerizable monomers other than (meth)acrylates that do not contain a carbonyl group and are reactive with the hydrazide group of the hydrazide-functional material include, but are not limited to, vinyl aromatic monomers, vinyl esters of carboxylic acids, allylic monomers, C2 to C6 24Examples of ethylenically unsaturated radically polymerizable monomers other than (meth)acrylates that do not contain a carbonyl group and are reactive with the hydrazide group of the hydrazide-functional material include, but are not limited to, vinyl alcohol; vinyl chloride; acrylonitrile; trimethyl(4-methyl-4-penten-1-yl)silane; 1-octene; 1-undecene; 1-octadecene; 4-heptenal; 5-methyl-1-heptene; ethenylcyclopentane; bicyclo[2.2.1]hept-2-ene; ethenylcyclohexane; 2-propenoic acid, cyclohexyl ester; 2-propenoic acid, bicyclo[2.2.1]hept-2-ene; but-2-yl ester; 2-propenoic acid, 4-(1,1-dimethylethyl)cyclohexyl ester; 2-propenoic acid, tricyclo[3.3.1.13,7]dec-2-yl ester; styrene; p-chloromethylstyrene; divinylbenzene; vinylnaphthalene; divinylnaphthalene; vinyl acetate; vinyl butyrate; vinyl 3,4-dimethoxybenzoate; vinyl benzoate; allyl chloride; allyl acetate, allyl alcohol, allyl benzyl ether, allyl phenyl ether, 3-allyloxy-1,2-propanediol, allyl methyl ether, and combinations of two or more thereof.

[0072] In some embodiments, (meth)acrylate polymers having at least two carbonyl groups reactive with hydrazide groups can be prepared by first forming a hydroxyl-functional (meth)acrylate polymer intermediate using monomers including hydroxyl-functional (meth)acrylate monomers and / or hydroxyl-functional ethylenically unsaturated radically polymerizable monomers. The hydroxyl-functional (meth)acrylate polymer intermediate is then reacted with a carbonyl-functional carboxylic acid ester under transesterification conditions widely accepted in the art, thereby forming a (meth)acrylate polymer having at least two carbonyl groups reactive with hydrazide groups.

[0073] In some embodiments, the first carbonyl-functional component comprises at least two ketone groups. According to some embodiments, the (meth)acrylate polymer of the first carbonyl-functional component comprises ketone-functional (meth)acrylamide monomer residues (or monomer units). According to some further embodiments, the (meth)acrylate polymer of the first carbonyl-functional component comprises N-(2-methyl-4-oxopentan-2-yl)acrylamide monomer residues (or monomer units).

[0074] The (meth)acrylate polymer of the first carbonyl-functional component, in some embodiments, has a carbonyl equivalent weight of 165 g / mol to 550 g / mol, or 200 g / mol to 450 g / mol, or 250 g / mol to 400 g / mol. In some further embodiments, the (meth)acrylate polymer of the first carbonyl-functional component has a Mw of 1000 g / mol to 10,000 g / mol, or 3000 g / mol to 9000 g / mol, or 5000 g / mol to 9000 g / mol, as measured in THF solvent.

[0075] The (meth)acrylate polymer of the first carbonyl-functional component has at least two carbonyl groups, which in each case are independently selected from ketone and aldehyde groups. In some embodiments, the (meth)acrylate polymer of the first carbonyl-functional component has 2 to 30 carbonyl groups, or 5 to 30 carbonyl groups, or 10 to 25 carbonyl groups, which in each case are independently selected from ketone and aldehyde groups.

[0076] The curable photochromic composition may optionally include a second carbonyl-functional component containing at least one carbonyl group reactive with a hydrazide group. The second carbonyl-functional component includes at least one of a polycarbonate carbonyl, a polyester carbonyl, a polyether carbonyl, a polyurethane carbonyl, or a combination of two or more thereof. Each carbonyl group of the second carbonyl-functional component is independently selected from a ketone group and an aldehyde group. In some embodiments, the second carbonyl-functional component is not or does not include a (meth)acrylate polymer having at least one carbonyl group.

[0077] The polycarbonate carbonyl of the second carbonyl-functional component can be prepared according to methods generally accepted in the art. In some embodiments, for non-limiting illustrative purposes, the polycarbonate carbonyl can be prepared by reacting an aliphatic polyol, such as a diol, with a carbonyl dihalide, such as carbonyl dichloride, followed by removal of the resulting halide acid, such as HCl. For further non-limiting illustrative purposes, the polycarbonate carbonyl can be prepared by transesterification of a polyol, such as a diol, with a dihydrocarbyl carbonate, such as diphenyl carbonate, followed by removal of the resulting hydroxyl-functional hydrocarbyl, such as phenol.

[0078] In some embodiments, the preparation of polycarbonate carbonyls involves first forming a hydroxyl-terminated polycarbonate intermediate, which is then reacted with a carbonyl-functional carboxylic acid, such as an oxoalkenoic acid, e.g., 4-oxopentanoic acid (levulinic acid), or 4-acetylbenzoic acid, or a carbonyl-functional carboxylic acid ester, such as an oxoalkenoic acid ester, e.g., ethyl 4-oxopentanoate (ethyl levulinate), or ethyl acetoacetate, to form a polycarbonate carbonyl having at least one carbonyl group (such as a ketone group) that is reactive with a hydrazide group.

[0079] Examples of polyols having at least two hydroxyl groups from which polycarbonate carbonyls can be prepared include, but are not limited to, glycerin, trimethylolpropane, trimethylolethane, trishydroxyethyl isocyanurate, pentaerythritol, ethylene glycol, propylene glycol, trimethylene glycol, 1,3-, 1,2-, and 1,4-butanediol, pentanediols (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, and similar polyols.

[0080] In some embodiments, the polycarbonate carbonyl is prepared from commercially available polycarbonate polyols such as, but not limited to, ETERNACOLL® polycarbonate diol from Ube Industries, Ltd., and DURANOL polycarbonate diol from Asahi Kasei.

[0081] The polyester carbonyl of the second carbonyl-functional component can be prepared according to methods generally accepted in the art. In some embodiments, for non-limiting illustrative purposes, the polyester carbonyl can be prepared by reacting an aliphatic carboxylic acid-functional material (and / or its cyclic anhydride and / or ester) having at least two carboxylic acid functional groups (or available carboxylic acid functional groups, e.g., as in the case of cyclic anhydrides and carboxylic acid esters) with a polyol having at least two hydroxyl functional groups. The molar equivalent ratio of carboxylic acid groups to hydroxyl groups in the reactants is selected to provide a polyester intermediate having hydroxyl and / or carboxylic acid functional groups and the desired molecular weight.

[0082] Examples of polyfunctional carboxylic acids useful in preparing polyester carbonyls include, but are not limited to, tetrahydrophthalic acid, hexahydrophthalic acid, endobicyclo-2,2,1,5-heptyne-2,3-dicarboxylic acid, cyclohexanedioic acid, succinic acid, azelaic acid, maleic acid, adipic acid, sebacic acid, and similar polyfunctional carboxylic acids (optionally including appropriate cyclic anhydrides and / or esters thereof).

[0083] Examples of polyols that can be used to prepare each polyester carbonyl of the second carbonyl-functional component include, but are not limited to, the examples of polyols previously described herein.

[0084] In some embodiments, the preparation of a polyester carbonyl involves first forming a hydroxyl-terminated polyester intermediate, which is then reacted with a carbonyl-functional carboxylic acid, such as an oxoalkenoic acid, e.g., 4-oxopentanoic acid (levulinic acid) or 4-acetylbenzoic acid, or a carbonyl-functional carboxylic acid ester, such as an oxoalkenoic acid ester, e.g., ethyl 4-oxopentanoate (ethyl levulinate) or ethyl acetoacetate, to form a polyester carbonyl having at least one carbonyl group (such as a ketone group) that is reactive with a hydrazide group.

[0085] Polyester carbonyls can, in some embodiments, be prepared using one or more commercially available hydroxyl-functional polyesters as intermediates, which are reacted with a carbonyl-functional carboxylic acid, such as those exemplified above. Examples of commercially available hydroxyl-functional polyesters that can be used as such intermediates include, but are not limited to, those commercially available from Stepan Company, such as STEPANOL PC polyester polyol; those commercially available from DIC Corporation, such as OD-X-286, OD-X-102, OD-X-355, OD-X-2330, OD-X-240, OD-X-668, OD-X-21068, OD-X-2547, OD-X-2420, OD-X-2523, OD-X-2555, and OD-X-2560 polyester polyols, OD-X-2155 and OD-X-640 polycaprolactone diols, and OD-X-2586 triol; and those commercially available from TRiiSO, such as PERSTORP BOLTORN Examples include H2004 hyperbranched polyester polyol, commercially available from GINGEVITY, such as CAPA polycaprolactone polyol, commercially available from BASF, such as LUPRAPHEN polyester polyol, commercially available from Evonik Industries, such as DYNACOLL polyester polyol, and commercially available from Bayer, such as DESMOPHEN polyester polyol, and BAYCOLL polyester polyol.

[0086] The polyethercarbonyl of the second carbonyl-functional component can be prepared according to methods generally recognized in the art. In some embodiments, the polyethercarbonyl is prepared from a hydroxyl-functional polyether (or polyether polyol), such as a polyalkylene glycol, including but not limited to, polyethylene glycol, polypropylene glycol, poly(1,2-butylene glycol), polyethylene glycol-polypropylene glycol copolymer, and polytetrahydrofuran. Examples of commercially available hydroxyl-functional polyethers that can be used to prepare the polyethercarbonyl include, but are not limited to, those available from Dow Chemicals, such as VORANOL polyether polyols, those available from BASF, such as LUPRANOL, PLURACOL, PLURONIC®, and PolyTHF polyether polyols, and those available from Bayer, such as DESMOPHEN and ACCLAIM polyether polyols. In some embodiments, a hydroxyl-functional polyether (or a hydroxyl-functional polyether intermediate) is reacted with a carbonyl-functional carboxylic acid, such as an oxoalkenoic acid, e.g., 4-oxopentanoic acid (levulinic acid), or 4-acetylbenzoic acid, or a carbonyl-functional carboxylic acid ester, such as an oxoalkenoic acid ester, e.g., ethyl 4-oxopentanoate (ethyl levulinate) or ethyl acetoacetate, to form a polyether carbonyl having at least one carbonyl group (such as a ketone group) that is reactive with a hydrazide group.

[0087] The polyurethane carbonyl of the second carbonyl-functional component can be prepared according to methods generally accepted in the art. In some embodiments, for non-limiting illustrative purposes, the polyurethane carbonyl can be prepared from the reaction of a polyisocyanate having at least two isocyanate groups with a polyol having at least two hydroxyl groups, with a molar excess of hydroxyl groups to form a hydroxyl-functional polyurethane intermediate having at least two hydroxyl groups, or with a molar excess of isocyanate groups to form a polyurethane intermediate having at least two isocyanate groups. Examples of polyisocyanates useful for preparing the polyurethane carbonyl include, in some embodiments, aliphatic, cycloaliphatic, and heterocyclic polyisocyanates, as well as mixtures of such polyisocyanates.

[0088] Further examples of polyisocyanates useful in the preparation of polyurethane carbonyls include tetramethylene-1,4-diisocyanate, hexamethylene-1,6-diisocyanate, 2,2,4-trimethylhexane-1,6-diisocyanate, 2,4,4-trimethylhexane-1,6-diisocyanate, lysine methyl ester diisocyanate, bis(isocyanatoethyl) fumarate, isophorone diisocyanate, ethylene diisocyanate, dodecane-1,12-diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane- These include, but are not limited to, 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.

[0089] Examples of polyols having at least two hydroxyl groups from which the polyurethane carbonyl of the second carbonyl-functional component can be prepared include, but are not limited to, the polyols previously described herein.

[0090] In some embodiments, the polyurethane carbonyl of the second carbonyl-functional component is prepared from the reaction of a hydroxy-functional polyurethane intermediate with a carbonyl-functional carboxylic acid, such as an oxoalkenoic acid, e.g., 4-oxopentanoic acid (levulinic acid), or 4-acetylbenzoic acid, or a carbonyl-functional carboxylic acid ester, such as an oxoalkenoic acid ester, e.g., ethyl 4-oxopentanoate (ethyl levulinate) or ethyl acetoacetate, to form a polyurethane carbonyl having at least one carbonyl group (such as a ketone group) that is reactive with a hydrazide group.

[0091] In some embodiments, the polyurethane carbonyl of the second carbonyl-functional component is prepared from a commercially available hydroxy-functional polyurethane intermediate, such as a commercially available hydroxy-functional thermoplastic polyurethane intermediate. Examples of commercially available hydroxy-functional polyurethanes include, but are not limited to, those available from Lubrizol, such as PEARLSTICK, PEARLBOND, ESTANE, TECOFLEX, and CARBOTHANE hydroxyl-functional polyurethanes, those available from AdvanSource Biomaterials Corporation, such as CHRONOFLEX AL, CHRONOFLEX C, CHRONOTHANE P, and CHRONOSIL hydroxyl-functional polyurethanes, those available from AorTech International Plc, such as ELAST-EON hydroxyl-functional polyurethanes, and those available from Biometrics, such as QUADRATHANE hydroxyl-functional polyurethanes.

[0092] In some further embodiments, the polyurethane carbonyl of the second carbonyl-functional component is prepared from the reaction of an isocyanate-functional polyurethane intermediate with a hydroxyl-functional carbonyl compound, such as a hydroxyalkan-2-one, e.g., 5-hydroxypentan-2-one, resulting in the formation of a polyurethane carbonyl having at least one carbonyl group (such as a ketone group) that is reactive with a hydrazide group.

[0093] In some embodiments, the second carbonyl-functional component of the curable photochromic composition has an equivalent weight of 580 g / mol to 10,000 g / mol, or 800 g / mol to 8000 g / mol, or 1000 g / mol to 5000 g / mol. In some further embodiments, the second carbonyl-functional component has a Mw of 580 g / mol to 40,000 g / mol, or 1000 g / mol to 30,000 g / mol, or 2000 g / mol to 15,000 g / mol.

[0094] The second carbonyl-functional component comprises at least one carbonyl group, in each instance independently selected from a ketone group and an aldehyde group, hi some embodiments, the second carbonyl-functional component comprises 1 to 20 carbonyl groups, or 1 to 10 carbonyl groups, or 1 to 8 carbonyl groups, in each instance independently selected from a ketone group and an aldehyde group.

[0095] According to some embodiments of the present invention, the first carbonyl-functional component comprises at least two ketone groups and the second carbonyl-functional component comprises at least one ketone group.

[0096] The curable photochromic composition of the present invention may optionally include a hydrazide-functional material, a first carbonyl-functional component, and a non-reactive component that does not include a functional group reactive with the second carbonyl-functional component. At least one of (d1) the second carbonyl-functional component and / or (d2) the non-reactive component is present in the curable photochromic composition of the present invention. According to some embodiments of the curable photochromic composition of the present invention, the second carbonyl-functional component is present, and the non-reactive component may optionally be present.

[0097] The non-reactive component, in some embodiments, comprises at least one of a polyether, a polyester, a polycarbonate, a polyurethane, and / or an organic phosphate. Further according to the present invention, the non-reactive component comprises at least one of an aliphatic polyether, an aliphatic polyester, an aliphatic polycarbonate, an aliphatic polyurethane, and / or an organic phosphate. According to some embodiments, the polyether, polyester, polycarbonate, and polyurethane from which the non-reactive component can be selected each independently have an Mn of 300 g / mol to 10,000 g / mol, or 300 g / mol to 8000 g / mol, or 400 g / mol to 6000 g / mol.

[0098] The polyether of the non-reactive component contains multiple ether linkages (-O-) and, in the case of an aliphatic polyether, does not contain aromatic groups. In some embodiments, the polyether is an aliphatic polyether and independently contains linear or branched C1-C6 chains between and / or extending from each ether linkage. 20 Alkyl bond and / or C3-C 10 In some embodiments, the non-reactive component polyether contains a terminal -OR a group, and R a are independently in each case hydrogen (H), straight or branched C1-C 20 Alkyl group or C3-C 10 In some further embodiments, the non-reactive component polyether is a terminal -OC(O)Ra and having a terminal carboxylic acid ester group such as a group, wherein R a are in each case independently linear or branched C1-C 20 Alkyl group or C3-C 10 In some further embodiments, the non-reactive component polyether is a terminal -OC(O)NHR a It has a terminal urethane group such as an R a are in each case independently linear or branched C1-C 20 Alkyl group or C3-C 10 It is a cycloalkyl group.

[0099] The polyester of the non-reactive component contains a plurality of carboxylic acid ester linkages (—C(O)—O—) and, in the case of an aliphatic polyester, does not contain aromatic groups. In some embodiments, the polyester of the non-reactive component is an aliphatic polyester and independently contains linear or branched C1-C6 chains between and / or extending from each carboxylic acid ester linkage. 20 Alkyl bond and / or C3-C 10 In some further embodiments, the non-reactive component polyester contains a terminal -OC(O)R a Group and / or terminal -C(O)OR a and having a terminal carboxylic acid ester group such as a group, wherein R a are in each case independently linear or branched C1-C 20 Alkyl group or C3-C 10 In some additional embodiments, the non-reactive component polyester is a terminal —OC(O)NHR a It has a terminal urethane group such as an R a are in each case independently linear or branched C1-C 20 Alkyl group or C3-C 10 It is a cycloalkyl group.

[0100] The polycarbonate of the non-reactive component contains multiple carbonate linkages (-OC(O)-O-) and, in the case of an aliphatic polycarbonate, does not contain aromatic groups. In some embodiments, the polycarbonate of the non-reactive component is an aliphatic polycarbonate and independently contains linear or branched C1-C6 alkyl groups between and / or extending from each carbonate linkage. 20 Alkyl bond and / or C3-C 10 In some further embodiments, the non-reactive component polycarbonate contains a terminal -OC(O)-OR a and having a terminal carbonate group such as a group, wherein R a are in each case independently linear or branched C1-C 20 Alkyl group or C3-C 10 In some additional embodiments, the non-reactive component polycarbonate has a terminal —OC(O)NHR a It has a terminal urethane group such as an R a are in each case independently linear or branched C1-C 20 Alkyl group or C3-C 10 It is a cycloalkyl group.

[0101] The non-reactive component polyurethane contains a plurality of urethane linkages (-OC(O)-N(H)-) and, in the case of an aliphatic polyurethane, does not contain aromatic groups. In some embodiments, the non-reactive component polyurethane is an aliphatic polyurethane and independently contains linear or branched C1-C6 chains between and / or extending from each urethane linkage. 20 Alkyl bond and / or C3-C 10 In some additional embodiments, the non-reactive component polyurethane contains a terminal —N(H)—C(O)—OR a Group and / or terminal -OC(O)NHR a It has a terminal urethane group such as an R a are in each case independently linear or branched C1-C 20 Alkyl group or C3-C 10 It is a cycloalkyl group.

[0102] The organophosphate from which the non-reactive component can be selected is, in some embodiments, represented by the following formula (II): Formula (II) P(O)(OR')3

[0103] With respect to Formula (II), each R', in each occurrence, is independently selected from alkyl, haloalkyl, perhaloalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and combinations thereof (including those classes and examples thereof listed hereinabove). In some further embodiments, each R', in each occurrence, of Formula (II) is independently selected from alkyl, cycloalkyl, aryl, and combinations thereof. Further with respect to Formula (II), according to some further embodiments, each R', in each occurrence, is independently selected from C1-C 20 Straight chain alkyl, C3-C 20 Branched alkyl, C3-C 20 Cycloalkyl, C5-C 20 Further with respect to Formula (II), according to some further embodiments, each R' is independently selected from phenyl; C1-C 20 Straight chain alkyl, C3-C 20 Branched alkyl or C3-C 20 Phenyl substituted by at least one cycloalkyl; C1-C substituted by at least one phenyl 20 Straight chain alkyl; C3-C substituted with at least one phenyl 20 Branched alkyl; and C3-C substituted with at least one phenyl 20Non-limiting examples of organic phosphates from which the non-reactive component can be selected include tricresyl phosphate, tris(2-phenylethyl)phosphate, tris(2-chloroethyl)phosphate, tris(1,3-dichloro-2-propyl)phosphate, cresyldiphenyl phosphate, tris(2,3-dibromopropyl)phosphate, tris-(2-ethylhexyl)phosphate, and tris(2-methylphenyl)phosphate.

[0104] The non-reactive components of the curable photochromic compositions of the present invention, in some embodiments, have a viscosity (at 25° C.) of from 1 cP to 60,000 cP, or from 1 cP to 10,000 cP, or from 1 cP to 7500 cP. The viscosity of the non-reactive components can be measured according to methods generally accepted in the art. In some embodiments, the viscosity is measured using a rotational viscometer, such as a Brookfield CAP 2000+ viscometer available from AMETEK, Inc., according to the manufacturer's instructions. Additional methods for measuring viscosity include, but are not limited to, those described in ASTM D789 or ASTM D4878.

[0105] In some embodiments, the non-reactive component is selected from a polymeric non-reactive component, such as an amorphous polymeric non-reactive component, and / or a crystalline non-reactive component.

[0106] According to some further embodiments, the non-reactive component of the curable photochromic composition of the present invention has a Tg of less than 50° C., or less than 30° C., or less than 10° C. when the non-reactive component is an amorphous polymeric non-reactive component. In some further embodiments, the non-reactive component of the curable photochromic composition of the present invention has a melting point of less than 50° C., or less than 30° C., or less than 10° C. when the non-reactive component is a crystalline non-reactive component.

[0107] In some embodiments, the Tg of the non-reactive component is measured according to art-accepted methods, for example, using differential scanning calorimetry (DSC) at a heating rate of 2° C. / min. In some embodiments, the melting point of the non-reactive component is determined according to art-accepted methods, such as DSC, or according to the capillary tube method or optical microscopy with a heating step.

[0108] In some embodiments of the curable photochromic composition of the present invention, the second carbonyl-functional component and the non-reactive component are present in a combined amount of from 10 to 50 weight percent, or from 15 to 45 weight percent, or from 20 to 40 weight percent, where the weight percent is, in each case, based on the total resin solids of the curable photochromic composition.

[0109] As used herein, with respect to the curable photochromic composition, the term "total weight of resin solids" and similar terms, such as "total weight of resin solids" and "total resin solids," refer to the total weight of the hydrazide-functional material, the first carbonyl-functional component, the second carbonyl-functional component, and the non-reactive components, and in some further embodiments does not include the weight of the photochromic compound or other optional additives.

[0110] The curable photochromic compositions of the present invention comprise a photochromic compound, which may be selected from known types and examples of photochromic compounds and may include combinations or mixtures thereof.

[0111] For example, but not limited to, a mixture of photochromic compounds can be used to achieve certain activated colors, such as near-neutral gray or near-neutral brown. See, for example, U.S. Pat. No. 5,645,767, column 12, line 66 to column 13, line 19, which describes the parameters defining neutral gray and brown colors. The disclosure of which is specifically incorporated herein by reference.

[0112] In some embodiments, the photochromic compound of the curable photochromic composition of the present invention is selected from the group consisting of naphthopyrans, benzopyrans, phenanthropyrans, indenonaphthopyrans, spiro(indoline)naphthoxazines, spiro(indoline)pyridobenzoxazines, spiro(benzindoline)pyridobenzoxazines, spiro(benzindoline)naphthoxazines, spiro(indoline)-benzoxazines, fulgides, fulgimides, diarylethenes, and mixtures of such photochromic compounds.

[0113] Further examples of other photochromic compounds that may be used in the curable photochromic compositions of the present invention include, but are not limited to, those disclosed in U.S. Pat. No. 9,028,728 at column 34, line 20 to column 35, line 13, the disclosure of which is specifically incorporated herein by reference.

[0114] The photochromic compound is present in the curable photochromic composition of the present invention in an amount at least sufficient to provide an article prepared from the composition with a desired level of photochromic properties, which in some embodiments is referred to as a photochromic amount. In some embodiments, the amount of photochromic compound(s) present in the curable photochromic composition is 0.001 to 40 weight percent, or 0.001 to 10 weight percent, or 0.01 to 5 weight percent, or 0.1 to 2.5 weight percent, in each case based on the weight of the total resin solids.

[0115] In some embodiments, the curable photochromic compositions of the present invention may optionally contain additives, such as, but not limited to, waxes, e.g., for flow and wetting, flow modifiers such as poly(2-ethylhexyl)acrylate, antioxidants, and ultraviolet (UV) light absorbers. Examples of useful antioxidants and UV absorbers include, but are not limited to, those commercially available from BASF under the trademarks IRGANOX and TINUVIN. A non-limiting class of antioxidants is hindered amine light stabilizers (HALS), which may contain one or more 2,2,6,6-tetraalkylpiperidin-4-yl groups, such as one or more 2,2,6,6-tetramethylpiperidin-4-yl groups. When used, these optional additives may be present in an amount of up to 20 weight percent based on the total resin solids content.

[0116] The curable photochromic compositions of the present invention, in some embodiments, 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 a dye that is a non-photosensitive material that does not physically or chemically react to electromagnetic radiation with respect to its visually observed color. As used herein, the term "fixed-tint dye" and related terms do not include and are distinguished from photochromic compounds. As used herein, the term "non-photosensitive material" refers to a material, such as, but not limited to, a fixed-tint dye, that does not physically or chemically react to electromagnetic radiation with respect to its visually observed color.

[0117] One or more fixed shade dyes may be present in the curable photochromic compositions of the present invention for purposes including, but not limited to, imparting to a cured article prepared from the curable photochromic composition at least a base (or first) color characteristic of the fixed shade dye when the photochromic compound is not activated, and optionally a second color characteristic of the combination of the fixed shade dye and the photochromic compound when activated, for example, by exposure to actinic radiation.

[0118] The optional fixed shade dye of the curable photochromic composition, in some embodiments, comprises at least one of an azo dye, an anthraquinone dye, a xanthene dye, an azime dye, iodine, an iodide salt, a polyazo dye, a stilbene dye, a pyrazolone dye, a triphenylmethane dye, a quinoline dye, an oxazine dye, a thiazine dye, and a polyene dye.

[0119] The fixed shade dye can be present in the curable photochromic composition in various amounts to provide a desired effect in the cured article produced therefrom. In some embodiments, the fixed shade dye is present in the curable photochromic composition in an amount of 0.001 to 15 weight percent, or 0.01 to 10 weight percent, or 0.1 to 2.5 weight percent, in each case based on the total resin solids weight of the curable photochromic composition.

[0120] The curable photochromic compositions of the present invention, in some embodiments, comprise one or more solvents selected from water, organic solvents, and combinations thereof.

[0121] Types of organic solvents that may be present in the curable photochromic compositions of the present invention include alcohols such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butyl alcohol, tert-butyl alcohol, iso-butyl alcohol, furfuryl alcohol, and tetrahydrofurfuryl 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, methylene-1,2-hydroxypropyl ether, and phenyl-2-hydroxypropyl ether; nitrogen-containing cyclic compounds such as pyrrolidone, N-methyl-2-pyrrolidone, 1-butyl-pyrrolidinone, and 1,3-dimethyl-2-imidazolidinone; sulfur-containing compounds such as dimethyl sulfoxide and tetramethylene sulfone; aromatic compounds such as toluene, xylene, anisole, and butyl benzoate; and mixtures of aromatic compounds, including, but not limited to, C9-C 10 Aromatic 100 Fluid and C, commercial mixtures of di- and tri-alkylbenzenes. 10 ~C 12 Examples include, but are not limited to, Aromatic 150 Fluid, a commercially available mixture of alkylbenzenes and alkylnaphthalenes.

[0122] The solvent may be present in the curable photochromic composition of the present invention in an amount of 5 to 95 weight percent, or 15 to 80 weight percent, 30 to 70 weight percent, or 30 to 60 weight percent, in each case based on the total weight of the curable photochromic composition (including the weight of the solvent).

[0123] The present invention also relates to articles, particularly photochromic articles, prepared from the curable photochromic compositions of the present invention described hereinabove. In some embodiments, the photochromic articles are selected from layers (including films and / or sheets) and three-dimensional articles.

[0124] Classes of three-dimensional articles that can be prepared from the curable photochromic compositions of the present invention include, but are not limited to, ophthalmic articles, display articles, windows and mirrors.

[0125] More typically, the curable photochromic compositions of the present invention are used to prepare photochromic layers, such as photochromic films and photochromic sheets. As used herein, the term "film" refers to a non-freestanding layer, such as, but not limited to, a coating. As used herein, the term "sheet" refers to a freestanding layer, such as, but not limited to, an extruded sheet.

[0126] The curable photochromic compositions of the present invention can be cured by any suitable method that results in the formation of covalent bonds between the hydrazide groups of the hydrazide-functional material and the carbonyl groups of the first and optional second carbonyl-functional components. In some embodiments, the curable photochromic compositions are cured by exposure to elevated temperatures (above ambient room temperature, e.g., greater than 25°C). As used herein, "curing" refers to the formation of a three-dimensional crosslinked network through the formation of covalent bonds, such as hydrazone bonds or units, resulting from the reaction between the hydrazide groups of the hydrazide-functional material and the carbonyl groups of the first and optional second carbonyl-functional components. When curing is performed at elevated temperatures, the curable photochromic composition may be referred to herein as a thermosetting photochromic composition. The temperature at which the thermosetting photochromic compositions of the present invention cure can vary and depends in part on the time over which curing is performed. In some embodiments, the curable photochromic composition is cured at elevated temperatures of 60° C. to 175° C., or 65° C. to 150° C., or 70° C. to 130° C. for a period of 15 to 240 minutes.

[0127] 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 a curable photochromic composition of the present invention.

[0128] In some embodiments, an article comprising a substrate and a photochromic layer (formed from the curable photochromic composition of the present invention) on at least one surface of the substrate may be selected from ophthalmic articles, display articles, windows, and mirrors. Correspondingly, the substrate of the article may be selected from ophthalmic substrates, displays, windows, and mirrors. The substrate may be composed of one or more suitable materials, including, but not limited to, organic materials such as organic polymeric materials, including, but not limited to, thermoplastic polycarbonates, crosslinked polycarbonates, poly(meth)acrylates, and combinations thereof, glasses such as silica-based glasses, metals, ceramic materials, and combinations thereof. Examples of substrates that may be included in the articles (including optical elements) of the present invention include, but are not limited to, those described in U.S. Pat. No. 8,628,685, column 35, line 5 to column 36, line 57, the disclosure of which is incorporated herein by reference.

[0129] The substrate, in some embodiments, may optionally include a photochromic material and / or a fixed-hue coloring dye, which may be selected from the classes and examples of photochromic materials and fixed-hue dyes described previously herein, respectively. 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.

[0130] The photochromic layer of the article can be a photochromic film or a photochromic sheet. In some embodiments, the photochromic film of the article is a photochromic coating, and the curable photochromic composition of the present invention is a curable photochromic coating composition.

[0131] The curable photochromic coating composition may be applied to a substrate according to methods generally accepted in the art, including, but not limited to, spray coating, curtain coating, drawdown blade (or bar) coating, dip coating, spin coating, jet printing (such as inkjet printing where the "ink" is replaced with the curable photochromic composition according to the present invention), and combinations thereof.

[0132] After application of the curable photochromic composition onto at least one surface of the substrate, the applied curable photochromic composition is cured as described hereinabove. The photochromic layer may be in the form of a single layer or multiple layers. When in the form of multiple layers, each layer of the photochromic layer may be prepared from the curable photochromic composition according to the present invention having the same or different composition, e.g., having the same or different photochromic compound(s). The photochromic layer may have any suitable thickness, for example, from 10 micrometers to 250 micrometers or from 15 micrometers to 75 micrometers.

[0133] In addition to the photochromic layer, the article may optionally include one or more additional art-recognized layers such as, but not limited to, primer layer(s), adhesive layer(s), protective layer(s) (such as a hardcoat layer), polarizing layer(s), birefringent layer(s), antireflective layer(s), and / or another photochromic layer(s) prepared from a composition other than the curable photochromic composition of the present invention.

[0134] The present invention also relates to a photochromic multilayer article comprising at least one photochromic layer formed from the curable photochromic composition of the present invention. Each layer of the photochromic multilayer article can independently be in the form of a film or sheet. In some embodiments, the photochromic multilayer article can comprise two or more layers formed from the same or different curable photochromic compositions of the present invention.

[0135] The multilayer articles of the present invention may optionally include one or more additional art-recognized layers, such as, but not limited to, adhesive layer(s), protective layer(s) (such as a hardcoat layer), polarizing layer(s), birefringent layer(s), antireflective layer(s), and / or another photochromic layer(s) prepared from a composition other than the curable photochromic composition of the present invention.

[0136] The multilayer articles of the present invention can have any suitable thickness, such as from 10 micrometers to 1000 micrometers, or from 15 micrometers to 750 micrometers, or from 25 to 100 micrometers.

[0137] The multilayer articles of the present invention can be used alone or with another article, such as a substrate. The substrate can be selected from the types and examples of substrates described herein above 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, glasses, such as silica-based glasses, metals, ceramic materials, and combinations thereof.

[0138] The multilayer articles of the present invention may be adhered to the surface of a substrate by methods well recognized in the art, including, but not limited to, electrostatic adhesion, such as by static electricity, one or more intervening adhesive layers, fusion bonding, such as heat fusion, and in-mold forming, such as when 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, in some embodiments, may be supported by one or more brackets that retainingly engage one or more peripheral regions of the multilayer article.

[0139] The present invention may be further characterized by one or more of the following non-limiting clauses.

[0140] Section 1: (a) a photochromic compound; (b) a hydrazide-functional material comprising at least two hydrazide groups reactive with carbonyl groups selected from ketone groups and aldehyde groups; (c) a first carbonyl-functional component comprising a (meth)acrylate polymer having at least two carbonyl groups reactive with hydrazide groups, wherein each carbonyl group of the first carbonyl-functional component is independently selected from a ketone group and an aldehyde group; (d) (d1) a second carbonyl-functional component comprising at least one carbonyl group reactive with a hydrazide group, the second carbonyl-functional component comprising at least one of a polycarbonate carbonyl, a polyester carbonyl, a polyether carbonyl, a polyurethane carbonyl, or a combination thereof, wherein each carbonyl group of the second carbonyl-functional component is independently selected from a ketone group and an aldehyde group; or (d2) a non-reactive component that does not contain a functional group reactive with the hydrazide-functional material, the first carbonyl-functional component, and the second carbonyl-functional component; and at least one of 1. A curable photochromic composition comprising:

[0141] Item 2: The curable photochromic composition of item 1, wherein the hydrazide-functional material has a hydrazide equivalent weight of 250 g / mole to 10,000 g / mole, or 300 g / mole to 8000 g / mole, or 500 g / mole to 5000 g / mole.

[0142] Item 3: The curable photochromic composition of item 1 or 2, wherein the hydrazide-functional material has a Mw of 500 g / mol to 50,000 g / mol, or 1000 g / mol to 40,000 g / mol, or 2000 g / mol to 40,000 g / mol.

[0143] Item 4: A curable photochromic composition according to any one of items 1 to 3, wherein the hydrazide-functional material comprises a polyurethane containing at least two hydrazide groups reactive with carbonyl groups selected from ketone groups and aldehyde groups.

[0144] Item 5: The curable photochromic composition of any one of items 1 to 4, wherein the hydrazide-functional material contains 2 to 60 hydrazide groups, or 2 to 55 hydrazide groups, or 2 to 50 hydrazide groups that are reactive with carbonyl groups selected from ketone groups and aldehyde groups.

[0145] Item 6: The curable photochromic composition of any one of items 1 to 5, wherein at least some of the hydrazide groups of the hydrazide-functional material are independently and reversibly blocked with an aldehyde having a formula weight of less than 250 g / mole, or from 44 g / mole to less than 250 g / mole.

[0146] Item 7: The curable photochromic composition of any one of items 1 to 6, wherein at least some of the hydrazide groups of the hydrazide-functional material are independently and reversibly blocked with a ketone having a formula weight of less than 250 g / mole, or from 58 g / mole to less than 250 g / mole.

[0147] Item 8: The curable photochromic composition according to any one of items 1 to 7, wherein the ratio of the total carbonyl equivalents of the first carbonyl-functional component and the second carbonyl-functional component to the total equivalents of the hydrazide equivalents of the hydrazide-functional material is 1:0.8 to 1:4, or 1:0.8 to 1:3, or 1:1 to 1:2.

[0148] Item 9: The curable photochromic composition of any one of items 1 to 8, wherein the hydrazide-functional component comprises at least one of a non-polymeric hydrazide-functional material and / or a polymeric hydrazide-functional material.

[0149] Item 10: The curable photochromic composition according to any one of items 1 to 9, wherein the hydrazide-functional component comprises a non-polymeric hydrazide comprising at least one of fumaric acid dihydrazide, maleic acid dihydrazide, itaconic acid dihydrazide, phthalic acid dihydrazide, terephthalic acid dihydrazide, trimellitic acid trihydrazide, oxalic acid dihydrazide, succinic acid dihydrazide, 2-methylsuccinic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, cyclohexanedicarboxylic acid dihydrazide, and cyclohexanetricarboxylic acid trihydrazide.

[0150] Item 11: The curable photochromic composition of any one of items 1 to 10, wherein the hydrazide-functional component comprises a hydrazide-functional polymer, and the hydrazide-functional polymer comprises a polymer backbone selected from polyethers, polyesters, polycarbonates, polyurethanes, and combinations of two or more thereof.

[0151] Item 12: The curable photochromic composition of any one of items 1 through 11, wherein the hydrazide-functional component comprises a hydrazide-functional polymer comprising one or more linking groups, each linking group, in each instance, independently selected from an ether linkage (—O—), a thioether linkage (—S—), a urea linkage (—N(R)—C(O)—N(R)—), a carbonate linkage (—O—C(O)—O—), a carboxylic acid ester linkage (—O—C(O)—), a urethane linkage (—N(H)—C(O)—O—), a thiourethane linkage (—S—C(O)—N(H)—), a thiourea linkage (—N(R)—C(S)—N(R)—), and an amide linkage (—C(O)—N(R)—), wherein each R, in each instance, is independently selected from hydrogen, alkyl, haloalkyl, perhaloalkyl, cycloalkyl, heterocycloalkyl, and combinations thereof.

[0152] Item 13: The hydrazide-functional component has the following formula (I): [ka] wherein R1 is the residue of a polymer, e.g., a polyether, polyester, polycarbonate, and / or polyurethane; R 2 is, independently for each n, a straight or branched chain divalent alkane, e.g., a divalent straight or branched chain C1-C 10 an alkane, a divalent cycloalkane group, for example, a divalent C5-C8 cycloalkane group, or a divalent aromatic group, for example, a divalent C6-C 10 13. The curable photochromic composition according to any one of items 1 to 12, wherein n is an aromatic group and n is 2 to 60, for example, 2 to 55, or 2 to 40, or 2 to 30.

[0153] Item 14: The curable photochromic composition of any one of items 1 to 13, wherein the first carbonyl-functional component comprises at least two ketone groups and the second carbonyl-functional component comprises at least one ketone group.

[0154] Item 15: The curable photochromic composition of any one of items 1 to 14, wherein the second carbonyl-functional component comprises at least one ketone group.

[0155] Item 16: The curable photochromic composition of any one of items 1 to 15, wherein the (meth)acrylate polymer of the first carbonyl-functional component comprises a ketone-functional (meth)acrylamide monomer residue.

[0156] Item 17: The curable photochromic composition of any one of items 1 to 16, wherein the (meth)acrylate polymer of the first carbonyl-functional component has a carbonyl equivalent weight of 165 g / mol to 550 g / mol, or 200 g / mol to 450 g / mol, or 250 g / mol to 400 g / mol.

[0157] Item 18: The curable photochromic composition of any one of items 1 to 17, wherein the (meth)acrylate polymer of the first carbonyl-functional component has a Mw of 1000 g / mol to 10,000 g / mol, or 3000 g / mol to 9000 g / mol, or 5000 g / mol to 9000 g / mol.

[0158] Item 19: The curable photochromic composition of any one of items 1 to 18, wherein the second carbonyl-functional component has an equivalent weight of 580 g / mole to 10,000 g / mole, or 800 g / mole to 8000 g / mole, or 1000 g / mole to 5000 g / mole.

[0159] Item 20: The curable photochromic composition of any one of items 1 to 19, wherein the second carbonyl-functional component has a Mw of 580 g / mol to 40,000 g / mol, or 1000 g / mol to 30,000 g / mol, or 2000 g / mol to 15,000 g / mol.

[0160] Item 21: The curable photochromic composition according to any one of items 1 to 20, wherein the non-reactive component has a viscosity of 1 cP to 60,000 cP, or 1 cP to 10,000 cP, or 1 cP to 7500 cP at 25°C.

[0161] Item 22: Non-reactive ingredients are If the non-reactive component is an amorphous polymeric non-reactive component, it has a Tg of less than 50°C, or less than 30°C, or less than 10°C; or 22. The curable photochromic composition according to any one of items 1 to 21, wherein when the non-reactive component is a crystalline non-reactive component, it has a melting point of less than 50°C, or less than 30°C, or less than 10°C.

[0162] Item 23: The curable photochromic composition of any one of items 1 to 22, wherein the non-reactive component comprises at least one of a polyether, a polyester, a polycarbonate, a polyurethane, and / or an organic phosphate.

[0163] Item 24: A curable photochromic composition according to any one of items 1 to 23, wherein the non-reactive component comprises, independently in each case, at least one of a polyether, a polyester, a polycarbonate, and / or a polyurethane having an Mn of 300 to 10,000, or 300 to 8000, or 400 to 6000.

[0164] Item 25: The non-reactive component is a compound represented by the following formula (II): Formula (II) P(O)(OR')3 wherein R', in each occurrence, is independently selected from alkyl, haloalkyl, perhaloalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and combinations thereof.

[0165] Item 26: R' is, in each case, phenyl; C1-C 20 Straight chain alkyl and / or C3-C 20 Phenyl substituted with at least one branched alkyl; C1-C substituted with at least one phenyl 20 Straight chain alkyl; and C3-C substituted with at least one phenyl 20 26. The curable photochromic composition of paragraph 25, wherein the alkyl groups are independently selected from branched alkyls.

[0166] Item 27. The curable photochromic composition of any one of items 1 through 26, wherein the second carbonyl-functional component and the non-reactive component are present in a combined amount of 10 weight percent to 50 weight percent, or 15 weight percent to 45 weight percent, or 20 weight percent to 40 weight percent, in each case the weight percent being based on the total resin solids of the curable photochromic composition.

[0167] Item 28: The curable photochromic composition of any one of items 1 to 27, wherein a second carbonyl-functional component is present and a non-reactive component may optionally be present.

[0168] Item 29: The curable photochromic composition of any one of items 1 to 28, wherein the photochromic compound (a) comprises at least one of naphthopyrans, benzopyrans, phenanthropyrans, indenonaphthopyrans, spiro(indoline)naphthoxazines, spiro(indoline)pyridobenzoxazines, spiro(benzindoline)pyridobenzoxazines, spiro(benzindoline)naphthoxazines, spiro(indoline)-benzoxazines, fulgides, fulgimides, diarylethenes, or fulgimides.

[0169] Section 30: (A) a substrate; (B) a photochromic layer on at least one surface of the substrate, wherein the photochromic layer is formed from the curable photochromic composition described in any one of items 1 to 29.

[0170] The present invention is more particularly described in the following examples, which are intended to be illustrative only, since numerous modifications and variations thereto will be apparent to those skilled in the art. Unless otherwise specified, all parts and percentages are by weight. [Example]

[0171] Part 1 of the Examples below describes the preparation of the components used in the curable photochromic compositions of Part 2. Part 2 of the Examples below describes the preparation of comparative and inventive curable photochromic compositions. Part 3 of the Examples below describes the preparation of test specimens using the curable photochromic compositions of Part 2. Part 4 of the Examples below describes the testing of the test specimens of Part 4 and the test results.

[0172] Part 1 Preparative composition ingredients Example 1 Preparation of polyhydrazides. Dipropylene glycol dimethyl ether (184.6 g), dimethylolpropionic acid (45.9 g), OXYMER™ HD-112 (88.9 g, 1000 g / mole molecular weight aliphatic polycarbonate diol, available from Perstorp), and isophorone diisocyanate (220 g) were added to a first reaction vessel equipped with a reflux condenser and a nitrogen blanket and heated to 70°C. After a peak exotherm was observed, dibutyltin dilaurate (0.7 g) was added and the reaction was held at 90°C for 1 hour. Deionized water (925.3 g), dimethylethanolamine (27.3 g), and adipic acid dihydrazide (131.9 g) were added to a second reaction vessel equipped with a reflux condenser and a nitrogen blanket and heated to 35°C. Ninety percent by weight of the first mixture was slowly added to the second vessel, maintaining the temperature below 45° C. The reaction mixture was held for 1 hour, and then the volatiles were removed to yield 450 g of a white crystalline material. The white crystalline material had a Mw of 38,692 g / mol and a theoretical hydrazide equivalent weight of 950 g / mol, as determined by GPC using an Asahipak 510HQ column and DMF / LiBr solvent with polystyrene standards.

[0173] Example 2 Preparation of acrylic polyketones. Di(propylene glycol) methyl ether acetate (60 ml) was flushed with N for 15 minutes and then heated to 130°C. To this was added a solution of diacetone acrylamide (89.2 g), n-butyl methacrylate (75 g), 2,2'-azobis(2-methylbutyronitrile) (9.75 g), triphenyl phosphite (0.82 g), and tert-dodecanethiol (1.65 g) dropwise over 60 minutes. After stirring at 130°C for 30 minutes, 2,2'-azobis(2-methylbutyronitrile) (0.5 g) in DPMA (5 ml) was added, and the solution was stirred for an additional hour, cooled to 100°C, and then slowly added to cold hexane (5°C, 1.25 L) with stirring. The solution was then cooled to room temperature, after which the top layer was decanted and the remaining viscous liquid was dried under vacuum at 50° C. for about 2 hours to give 175 g of product having a weight average molecular weight (Mw) of 6060 g / mol and a number average molecular weight (Mn) of 3980 g / mol as determined by GPC using a THF eluent against polystyrene standards. A ketone equivalent weight of 288 g / mol was calculated based on NMR.

[0174] Example 3 Preparation of polycarbonate diketones. ETERNACOLL® PH-100D (100 g, a polycarbonate diol with a reported molecular weight of 1000 g / mol, available from Ube Industries, Ltd.), levulinic acid (29 g), N,N-dicyclohexylcarbodiimide ("DCC", 51 g), N,N-dimethylaminopyridine ("DMAP", 6.1 g), and dichloromethane ("DCM", 250 ml) were combined in a suitable container and stirred overnight under nitrogen. The precipitated N,N-dicyclohexylurea ("DCU") was removed by filtration, and the remaining solution was washed with HCl (1 N, 250 ml × 2), saturated aqueous NaHCO3 (250 ml × 2), and brine (250 ml × 2). The organic phase was then dried over anhydrous MgSO4 and filtered through celite. The solvent was removed to give 95 g of a pale yellow liquid, to which 100 ml of methanol was added. After gentle mixing and allowing the layers to separate, the methanol layer was decanted and the product was dried under vacuum to give 70 g of a colorless liquid with a calculated ketone equivalent weight of 1094 g / mol by NMR.

[0175] Example 4 Preparation of polycarbonate diketones. Polycarbonate diketone was prepared according to the procedure of Example 3 using the following reagents: ETERNACOLL® PH-200D (100 g, a polycarbonate diol with a reported molecular weight of 2000 g / mol, available from Ube Industries, Ltd.), levulinic acid (14 g), DCC (25.7 g), DMAP (3.0 g), and DCM (250 ml). Yield: 81 g. A molecular weight of 2938 g / mol and a ketone equivalent weight of 1469 g / mol were calculated by NMR.

[0176] Example 5 Preparation of polycaprolactone monoketone. Process-1: To a solution of 1-octanol (10 g) and caprolactone (131.4 g) in DCM (100 ml) under nitrogen, diphenyl phosphate (3.85 g) was added. The solution was stirred at room temperature for 8 hours. The resulting organic solution was washed with saturated aqueous NaHCO3 (250 ml x 2) and brine (250 ml x 2), followed by a short silica gel plug eluted with 50 / 50 DCM and ethyl acetate. The solvent was removed and the crude product was dried under vacuum, yielding 140 g. The product was used in the next step without further purification.

[0177] Process-2: The product of step 1 (140 g) and t-butyl acetoacetate (12.3 g) were dissolved together in toluene (500 ml) and heated to reflux overnight. The volatiles were removed by distillation, and the resulting residue was then dried under vacuum to give 150 g of a white solid, which was used directly without further purification. The ketone equivalent weight of the white solid was determined to be 1926 g / mol, calculated from NMR.

[0178] Example 6 Preparation of polyurethane polycarbonate triketone. Process-1: DESMODUR® N 3200 (2 g) (an aliphatic polyisocyanate available from Covestro) was added dropwise over 1 hour to a solution of ETERNACOLL® PH-300D diol (33 g, a polycarbonate diol with a reported molecular weight of 3000 g / mol available from Ube Industries, Ltd.) in anhydrous toluene (200 ml) at 75° C. 20 mg of dibutyltin dilaurate was added, and the resulting reaction mixture was stirred under nitrogen for approximately 6 hours until the isocyanate was completely consumed. The solvent was removed to give 35 g of crude product, which was used directly in step 2.

[0179] Process-2: The product from step-1 (25 g), levulinic acid (2.75 g), DCC (4.88 g), DMAP (0.5 g) and DCM (250 ml) were combined and subjected to the same reaction and isolation conditions as described in Example 3. The obtained product had a yield of 24 g, a molecular weight of 10,500 g / mol, and a ketone equivalent weight of 3,500 g / mol. The molecular weight and ketone equivalent weight of the obtained product were calculated by NMR in each case.

[0180] Part 2 Preparation of Curable Photochromic Compositions Comparative Examples CE7 and CE-8 and Inventive Example 9. Comparative Examples CE7 and CE8, and Inventive Example 9 were prepared using the ingredients listed in Table 1, shown in parts by weight. The ingredients in Charge 1 were combined, heated to 80°C, and stirred for a minimum of 2 hours until the solids were observed to be completely dissolved. Once cooled to room temperature, the ingredients in Charge 2 were added, and the solution was heated to 60°C and stirred for 2 hours until the solids were observed to be completely dissolved. Once cooled to room temperature, the ingredients in Charge 3 were added, and the solution was stirred for at least 1 hour before use.

[0181] [Table 1]

[0182] Examples 10 to 13. Curable photochromic compositions according to the present invention, Examples 10-13, were prepared according to the description set forth above for Comparative Examples CE-7 and CE-8, and Inventive Example 9, using the components (shown in parts by weight) listed in Table 2 below.

[0183] [Table 2]

[0184] Examples 14 to 17. Curable photochromic compositions according to the present invention, Examples 14-17, were prepared according to the description set forth above for Comparative Examples CE-7 and CE-8, and Inventive Example 9, using the components (shown in parts by weight) listed in Table 3 below.

[0185] [Table 3]

[0186] Examples 18 to 20. Curable photochromic compositions according to the present invention, Examples 18-20, were prepared according to the description set forth above for Comparative Examples CE-7 and CE-8, and Inventive Example 9, using the components (shown in parts by weight) listed in Table 4 below.

[0187] [Table 4]

[0188] Part 3 Preparation of photochromic test specimens The compositions of Comparative Examples CE-7 and CE-8 and Inventive Examples 9 through 20 were each applied to PDQ®-coated Gentex® polycarbonate plano lenses having a diameter of 76 millimeters. Prior to coating, each lens was corona treated using a Tantec device set at 70 KV and 1000 W. Approximately 2 ml of each composition was dispensed onto the substrate and then spun for 6 seconds at a spin speed sufficient to deposit 0.28 to 0.4 g of wet coating (wet weight depending on percentage of nonvolatile solids) for all coatings.

[0189] Test specimens of Comparative Examples CE-7 and CE-8 and Inventive Examples 9 to 20 were prepared in duplicate and then cured in a forced air electric oven at 125° C. for 1 hour.

[0190] Part 4 Test specimen and test results Part 4a. Microhardness evaluation One set of replicate specimens was subjected to an additional heat cure at 105°C for 3 hours and reserved for hardness measurement. These specimens were then subjected to microhardness testing using a Fischerscope HCV, Model H100SMC, available from Fischer Technology, Inc. Hardness was measured at a penetration depth of 2 microns after applying a load of 100 Newtons for 15 seconds. Each specimen was measured at least twice. The resulting data were averaged.

[0191] Part 4b. Photochromic Performance A second set of duplicate specimens was further corona treated as described above and spin-coated with a protective coating according to the formulation set forth in Table 1 of Example 1 of U.S. Patent No. 7,410,691. The specimens were cured in a UV oven equipped with a D bulb. Each specimen was then heat-cured at 105°C for 3 hours.

[0192] The photochromic performance of the specimens was tested on a Photochromic Measurement Bench ("BMP") manufactured by Essilor, Ltd., France. The BMP was maintained at a constant temperature of 73.4°F (23°C) during testing. Prior to testing, each coated specimen was exposed to 365-nanometer ultraviolet light for approximately 10 minutes at a distance of approximately 14 centimeters to activate the photochromic material. The UVA (315-380 nm) irradiance at the lens was measured with a LICOR® Model Li-1800 spectroradiometer and found to be 22.2 watts per square meter. Each specimen was then placed under a 500-watt high-intensity halogen lamp at a distance of approximately 36 centimeters for approximately 10 minutes to bleach (deactivate) the photochromic material. The irradiance of the specimens was measured with the LICOR® spectroradiometer and found to be 21.9 Klux. Each specimen was then kept in a dark environment at room temperature (70°F to 75°F, i.e., 21°C to 24°C) for at least one hour before being tested with the BMP. Prior to testing, each lens was measured for ultraviolet absorbance at 390 nanometers (Abs390nm).

[0193] The BMP optical bench was equipped with two 150-watt Newport Model #6255 xenon arc lamps, set at right angles to each other. The light path from Lamp 1 was directed through a 3 mm SCHOTT® KG-2 bandpass filter and appropriate neutral density filters to contribute the required UV and partial visible irradiance levels. The light path from Lamp 2 was directed through a 3 mm SCHOTT® KG-2 bandpass filter, a SCHOTT® shortwave 400 nm cutoff filter, and appropriate neutral density filters to provide supplemental visible irradiance. A 2-inch x 2-inch (5.1 cm x 5.1 cm) 50% polka dot beamsplitter set at 45° to each lamp was used to mix the two beams. The irradiance intensity was adjusted using a combination of neutral density filters and the voltage control of the xenon arc lamps. Software (i.e., BMPSoft version 2.1e) was used in the BMP to control timing, irradiance, air cell and sample temperature, shutter, filter selection, and response measurements. Response and color measurements were performed using a ZEISS® spectrophotometer, model MCS601, equipped with a fiber optic cable to transmit light through the lens. Photopic response measurements were collected for each lens.

[0194] The output of the optical bench, i.e., the amount of light the lens is exposed to, is 6.7 watts per square meter (W / m), integrated from 315 to 380 nm. 2The sample was adjusted to 50 klux of UVA and 50 klux of irradiance integrated from 380 to 780 nm. Measurements of this output setpoint were performed using an irradiance probe and a calibrated Zeiss spectrophotometer. The lens sample cell was fitted with a quartz window and a self-centering sample holder. The temperature within the sample cell was controlled at 23 °C by a modified Facis Model FX-10 spectrophotometer and software equipped with an environmental simulator. Measurements of the sample's dynamic photochromic response and color were performed using the same Zeiss spectrophotometer equipped with a fiber optic cable to transmit light from a tungsten halogen lamp through the sample. A collimated monitor light beam from the fiber optic cable was maintained perpendicular to the test sample during its passage through the sample and directed toward a receiving fiber optic cable assembly attached to the spectrophotometer. The exact location of the sample placement within the sample cell was where the activating xenon arc beam and the monitor light beam intersected to form two concentric circles of light. The angle of incidence of the xenon arc beam at the sample placement point was approximately 30° from normal.

[0195] The response measurement of the change in optical density (ΔOD) from the unactivated or bleached state to the activated or colored state was determined by determining the initial unactivated transmittance, opening the shutter from the xenon lamp, and measuring the activated transmittance at selected time intervals. The change in optical density was determined according to the following formula: ΔOD = log 10 (%Tb / %Ta), where %T b is the percent transmittance in the bleached state, and %T a is the percent transmittance in the activated state. Optical density measurements were based on photopic optical density.

[0196] Microhardness and photochromic performance results for Comparative Examples CE-7 and CE-8 and Inventive Examples 9-20 are shown in Tables 5-8. The ΔOD at saturation is after 15 minutes of activation, and the fade half-life ("T") value is the time in seconds for the ΔOD of the activated form of the photochromic material in the coating to reach half of the ΔOD at 15 minutes at 73.4°F (23°C) after the activating light source is removed.

[0197] [Table 5]

[0198] The results summarized in Table 5 demonstrate that a comparative photochromic composition containing a polyhydrazide containing only the second carbonyl-functional material (CE-7) results in a relatively soft cured comparative photochromic coating. A similar comparative curable photochromic composition containing only the first polyfunctional carbonyl material (CE-8) results in a cured comparative photochromic coating with very high hardness but effectively no photochromic activity. Using a curable photochromic composition according to the present invention containing a combination of a first carbonyl-functional material and a second carbonyl-functional material, as in Example 9, with a 1:1 ratio of carbonyl equivalents to hydrazide equivalents, results in a cured photochromic coating according to the present invention with a combination of good photochromic performance coupled with increased hardness compared to CE-7.

[0199] [Table 6]

[0200] The results summarized in Table 6 demonstrate that curable photochromic compositions according to the present invention that include different amounts of first carbonyl and second carbonyl-functional materials relative to each other, while maintaining the same ratio of carbonyl group equivalents to hydrazide equivalents, result in cured photochromic coatings according to the present invention that have different hardness properties, but whose photochromic performance properties are not significantly affected or otherwise changed.

[0201] [Table 7]

[0202] The results summarized in Table 7 demonstrate that curable photochromic compositions according to the present invention, including a variety of monofunctional carbonyl materials, difunctional carbonyl materials, as well as blends of a second carbonyl-functional material with a non-reactive material, result in cured photochromic coatings according to the present invention in which the photochromic performance characteristics are decoupled from the measured hardness.

[0203] [Table 8]

[0204] The results summarized in Table 8 demonstrate that curable photochromic compositions according to the present invention, including non-reactive materials in the absence of a second carbonyl-functional material, result in cured photochromic coatings according to the present invention having a combination of desirable hardness and desirable photochromic performance properties.

[0205] The present invention has been described with reference to specific details of particular embodiments thereof. It is not intended that such details be considered limitations on the scope of the invention except insofar as they are included in the appended claims.

Claims

1. (a) a photochromic compound; (b) a hydrazide-functional material comprising at least two hydrazide groups reactive with carbonyl groups selected from ketone groups and aldehyde groups; (c) a first carbonyl-functional component comprising a (meth)acrylate polymer having at least two carbonyl groups reactive with hydrazide groups, wherein each carbonyl group of the first carbonyl-functional component is independently selected from a ketone group and an aldehyde group; (d) (d1) a second carbonyl-functional component comprising at least one carbonyl group reactive with a hydrazide group, the second carbonyl-functional component comprising at least one of a polycarbonate carbonyl, a polyester carbonyl, a polyether carbonyl, a polyurethane carbonyl, or a combination thereof, wherein each carbonyl group of the second carbonyl-functional component is independently selected from a ketone group and an aldehyde group; or (d2) a non-reactive component that does not contain a functional group that is reactive with the hydrazide-functional material, the first carbonyl-functional component, and the second carbonyl-functional component. with at least one of 1. A curable photochromic composition comprising:

2. 10. The curable photochromic composition of claim 1, wherein the hydrazide-functional material has a hydrazide equivalent weight of 250 g / mol to 10,000 g / mol and a Mw of 500 g / mol to 50,000 g / mol.

3. 10. The curable photochromic composition of claim 1, wherein the hydrazide-functional material comprises a polyurethane containing at least two hydrazide groups reactive with carbonyl groups selected from ketone groups and aldehyde groups.

4. 10. The curable photochromic composition of claim 1, wherein the hydrazide-functional material comprises 2 to 60 hydrazide groups reactive with carbonyl groups selected from ketone and aldehyde groups.

5. 10. The curable photochromic composition of claim 1, wherein at least some of the hydrazide groups of the hydrazide-functional material are independently reversibly blocked with an aldehyde having a formula weight of less than 250 g / mole or a ketone having a formula weight of less than 250 g / mole.

6. 2. The curable photochromic composition of claim 1, wherein the ratio of the total carbonyl equivalents of the first carbonyl-functional component and the second carbonyl-functional component to the total equivalents of hydrazide equivalents of the hydrazide-functional material is from 1:0.8 to 1:

4.

7. 10. The curable photochromic composition of claim 1, wherein the first carbonyl-functional component comprises at least two ketone groups and the second carbonyl-functional component comprises at least one ketone group.

8. 10. The curable photochromic composition of claim 1, wherein the (meth)acrylate polymer of the first carbonyl-functional component comprises residues of ketone-functional (meth)acrylamide monomers.

9. 10. The curable photochromic composition of claim 1, wherein the (meth)acrylate polymer of the first carbonyl-functional component has a carbonyl equivalent weight of 165 g / mol to 550 g / mol and a Mw of 1000 g / mol to 10,000 g / mol.

10. 10. The curable photochromic composition of claim 1, wherein the second carbonyl-functional component has an equivalent weight of 580 g / mole to 10,000 g / mole and a Mw of 580 g / mole to 40,000 g / mole.

11. The non-reactive component is If the non-reactive component is an amorphous polymeric non-reactive component, it has a Tg of less than 50°C; or 10. The curable photochromic composition of claim 1, wherein the non-reactive component, when a crystalline non-reactive component, has a melting point of less than 50°C.

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

13. 10. The curable photochromic composition of claim 1, wherein the second carbonyl-functional component and the non-reactive component are present in a combined amount of 10% to 50% by weight, based on total resin solids of the curable photochromic composition.

14. 10. The curable photochromic composition of claim 1, wherein the second carbonyl-functional component is present and the non-reactive component is optionally present.

15. 2. The curable photochromic composition of claim 1, wherein the photochromic compound (a) comprises at least one of naphthopyrans, benzopyrans, phenanthropyrans, indenonaphthopyrans, spiro(indoline)naphthoxazines, spiro(indoline)pyridobenzoxazines, spiro(benzindoline)pyridobenzoxazines, spiro(benzindoline)naphthoxazines, spiro(indoline)-benzoxazines, fulgides, fulgimides, or diarylethenes.

16. (A) a substrate; (B) a photochromic layer on at least one surface of the substrate; and 10. An article comprising:

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