Curable photochromic compositions comprising oxazoline-functional materials

Abstract

The present invention relates to curable photochromic compositions comprising: at least a difunctional oxazoline functional material; at least a difunctional first carboxylic acid functional material; an optional second carboxylic acid functional material having at least three carboxylic acid groups, optionally comprising a carboxylic acid functional polymer; and a photochromic compound. The curable photochromic compositions have an equivalent ratio of oxazoline equivalents of the oxazoline functional material to total carboxylic acid equivalents of the first and optional second carboxylic acid functional materials of from 0.5:1 to 10:1 when the second carboxylic acid functional material is absent and from 0.5:1 to 3:1 when the second carboxylic acid functional material is present. More particularly, the present invention relates to curable photochromic adhesive compositions and curable photochromic coating compositions.

Description

TECHNICAL FIELD

[0001] The present invention relates to curable photochromic compositions comprising: at least a difunctional oxazoline functional material, at least a difunctional first carboxylic acid functional material, an optional second carboxylic acid functional material optionally comprising a carboxylic acid functional polymer, and a photochromic compound, wherein the equivalent ratio of oxazoline equivalents of the oxazoline functional material to the total carboxylic acid equivalents of the first and optional second carboxylic acid functional materials is from 0.5: 1 to 10: 1 (when the second carboxylic acid functional material is not present) and from 0.5: 1 to 3: 1 (when the second carboxylic acid functional material is present). BACKGROUND

[0002] In response to certain wavelengths of electromagnetic radiation (or "actinic radiation"), photochromic compounds, such as indeno-fused naphthopyrans, typically undergo a transition from one form or state to another, where each form has a characteristic or distinguishable absorption spectrum associated with it. Typically, upon exposure to actinic radiation, many photochromic compounds transition from a closed form corresponding to an unactivated (or bleached, e.g., substantially colorless) state of the photochromic compound to an open form corresponding to an activated (or colored) state of the photochromic compound. In the absence of exposure to actinic radiation, such photochromic compounds reversibly transition from the activated (or colored) state back to the unactivated (or bleached) state. Compositions and articles, such as optical lenses, containing photochromic compounds or having photochromic compounds applied thereto (e.g., in the form of a photochromic coating composition) typically exhibit colorless (e.g., transparent) and colored states corresponding to the colorless and colored states of the photochromic compounds contained therein or applied thereto.

[0003] Photochromic compounds can be used in curable compositions to form, for example, photochromic cured layers, such as cured films or sheets. For cured photochromic films, such as cured photochromic coatings, it is typically desirable for them to provide a combination of hardness and photochromic performance. Photochromic coatings with increased hardness can be desirable for reasons including, but not limited to, improved scratch resistance and / or improved support for one or more additional layers applied thereon. Generally, the kinetics associated with the reversible transition of photochromic compounds between the closed form (unactivated / colorless) and the open form (activated / colored) are faster in soft matrices (of the cured films in which the photochromic compounds are present) but slower in hard matrices (of the cured films in which the photochromic compounds are present). Cured photochromic films with soft matrices typically have reduced hardness, while those with hard matrices typically have increased hardness.

[0004] Photochromic compounds can also be used in curable compositions to form, for example, photochromic cured adhesive layers. In addition to the photochromic properties, for cured photochromic adhesive layers, it is typically desired that they provide good adhesion and toughness. Adhesive compositions comprising blocked or free isocyanate functional materials can provide adhesive layers with desired adhesion and toughness. When containing free isocyanate groups, the isocyanate functional component and the active hydrogen functional component (including catalyst) are typically kept separate from each other in a two-pack configuration and combined before application. If there is no proper mixing and / or no timely application after the combination, the properties of the resulting adhesive layer may be affected. In addition, exposure to free isocyanates can cause it to sensitize people. The use of blocked isocyanate materials can allow single-pack configurations, in which blocked isocyanate functional components, active hydrogen functional components, and catalysts are kept together. For single-pack configurations, curing requires unblocking the blocking groups, such as alcohol, from the blocked isocyanate groups. The unblocked groups may result in the formation of voids within the adhesive matrix and / or excessive plasticization of the adhesive matrix, and an adhesive layer having degraded properties.

[0005] It would be desirable to develop curable photochromic adhesive compositions that provide cured photochromic adhesive layers having desirable levels of photochromic properties, adhesive properties, and toughness without the difficulties associated with typical adhesive chemistries (e.g., isocyanate-based chemistries), such as processing, mixing, and curing. It would be further desirable to develop curable photochromic compositions that provide cured photochromic coatings having improved hardness without compromising photochromic performance. Summary of the Invention

[0006] According to the present invention, a curable photochromic adhesive composition is provided, comprising: (a) an oxazoline-functional material comprising at least two oxazoline groups; (b) a carboxylic acid-functional material having at least two carboxylic acid groups and having an acid equivalent weight greater than or equal to 600 g / mole; and (c) a photochromic compound. The curable photochromic adhesive composition has an equivalent ratio of oxazoline equivalents of the oxazoline-functional material to carboxylic acid equivalents of the carboxylic acid-functional material of from 0.5:1 to 10:1.

[0007] According to the present invention, a curable photochromic coating composition is provided, comprising: (a) an oxazoline-functional material comprising at least two oxazoline groups; (b) a first carboxylic acid-functional material having at least two carboxylic acid groups and an acid equivalent weight greater than or equal to 600 g / mole; (c) a second carboxylic acid-functional material having at least three carboxylic acid groups and an acid equivalent weight less than or equal to 580 g / mole; and (d) a photochromic compound. The curable photochromic coating composition has an equivalent ratio of the oxazoline equivalents of the oxazoline-functional material to the total carboxylic acid equivalents of the first carboxylic acid-functional material and the second carboxylic acid-functional material of from 0.5:1 to 3:1.

[0008] The features that characterize the invention are pointed out with particularity in the claims, which are incorporated into and constitute a part of this disclosure. These and other features of the invention, its operating advantages and specific objects attained by its use will be more fully understood from the following detailed description, in which non-limiting embodiments of the invention are shown and described. DETAILED DESCRIPTION

[0009] As used herein, the articles "a," "an," and "the" include plural referents unless expressly and unequivocally limited to one referent.

[0010] Unless otherwise indicated, all ranges or ratios disclosed herein are to be understood to encompass any and all subranges or subratios contained therein. For example, a recited range or ratio of "1 to 10" is to be considered to include any and all subranges between (and including) a minimum of 1 and a maximum of 10; that is, all subranges or subratios starting with a minimum of 1 or greater and ending with a maximum of 10 or less, such as, but not limited to, 1 to 6.1, 3.5 to 7.8, and 5.5 to 10.

[0011] Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as modified in all instances by the term "about."

[0012] As used herein, molecular weight values ​​such as weight average molecular weight (Mw) and number average molecular weight (Mn) of polymers are determined by gel permeation chromatography in the presence of a suitable eluent (such as tetrahydrofuran) and using suitable standards (such as polystyrene standards). In some cases, and where noted, NMR (such as 1 H NMR) to determine the Mn value.

[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" is intended to refer to homopolymers (eg, prepared from a single monomer species), copolymers (eg, prepared from at least two monomer species), and grafted polymers.

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

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

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

[0018] As used herein, the term "photochromic" and similar terms (e.g., "photochromic compound") means having an absorption spectrum of at least visible radiation that changes in response to the absorption of at least actinic radiation. Furthermore, as used herein, the term "photochromic material" means any substance that is suitable for exhibiting photochromic properties (e.g., suitable for having an absorption spectrum of at least visible radiation that changes in response to the absorption of at least actinic radiation) and that includes at least one photochromic compound.

[0019] As used herein, the term "actinic radiation" means electromagnetic radiation capable of inducing a response in a material, such as, but not limited to, transforming a photochromic material from one form or state to another, as discussed in further detail herein.

[0020] As used herein, the term "photochromic material" includes both thermoreversible photochromic materials and compounds and non-thermoreversible photochromic materials and compounds. As used herein, the term "thermoreversible photochromic compound / material" means a compound / material that is capable of switching from a first state (e.g., a "transparent state") to a second state (e.g., a "colored state") in response to actinic radiation, and returning to the first state in response to thermal energy. As used herein, the term "non-thermoreversible photochromic compound / material" means a compound / material that is capable of switching from a first state (e.g., a "transparent state") to a second state (e.g., a "colored state") in response to actinic radiation, and returning to the first state in response to actinic radiation of substantially the same wavelength as the absorption of the colored state.

[0021] As used herein, the terms "first" and "second," to modify the term "state," are not intended to refer to any particular order or temporal sequence, but rather to two distinct conditions or properties. For non-limiting illustrative purposes, the first and second states of a photochromic compound can differ in at least one optical property, such as, but not limited to, absorption of visible radiation and / or UV radiation. Thus, according to various non-limiting embodiments disclosed herein, a photochromic compound used in conjunction with the present invention can have a different absorption spectrum in each of the first and second states. For example, although not limiting herein, a photochromic compound used in conjunction with the present invention can be transparent in the first state and colored in the second state. Alternatively, a photochromic compound used in conjunction with the present invention can have a first color in the first state and a second color in the second state. Additionally, a photochromic-dichroic compound used in conjunction with the present invention can have a first alignment in the first state and a second alignment in the second state, wherein one of the first and second alignments is substantially unaligned.

[0022] As used herein, the term "optical" means relating to or associated with light and / or vision. For example, according to various non-limiting embodiments disclosed herein, the optical article, element, or device can be selected from: ophthalmic articles, elements, and devices, display articles, elements, and devices, windows, mirrors, and active and passive liquid crystal cell articles, elements, and devices.

[0023] As used herein, the term "ophthalmic" means pertaining to or associated with the eye and vision. Non-limiting examples of ophthalmic articles or components include corrective and non-corrective lenses (including single-vision or multi-vision lenses, which may be segmented or non-segmented multi-vision lenses (such as, but not limited to, bifocal lenses, trifocal lenses, and progressive lenses)), and other components used to correct, protect, or enhance (cosmetic or other) vision (including, but not limited to, contact lenses, intraocular lenses, magnifying lenses, and protective lenses or goggles).

[0024] As used herein, the term "display" means a visible or machine-readable representation of information in the form of words, numbers, symbols, designs, or diagrams. Non-limiting examples of display elements include screens, monitors, and security elements such as security markings.

[0025] As used herein, the term "window" means an aperture adapted to allow radiation to be transmitted therethrough. Non-limiting examples of windows include automotive and aircraft transparencies, windshields, filters, shutters, and optical switches.

[0026] As used herein, the term "mirror" means a surface that specularly reflects a substantial portion of incident light.

[0027] As used herein, the term "liquid crystal cell" refers to a structure containing liquid crystal material that is capable of being ordered. A non-limiting example of a liquid crystal cell element is a liquid crystal display.

[0028] As used herein, spatial or directional terms, such as "left," "right," "inner," "outer," "above," "below," etc., relate to the present invention as described herein. However, it should be understood that the present invention can assume various alternative orientations, and therefore, such terms should not be considered limiting.

[0029] As used herein, the terms "formed over," "deposited over," "provided over," "applied over," "residing over," or "positioned over" mean formed, deposited, provided, applied, applied, residing, or positioned over, but not necessarily in direct (or abutting) contact with an underlying element, or a surface of an underlying element. For example, a layer "positioned on a substrate" does not preclude the presence of one or more other layers, coatings, or films of the same or different composition between the positioned or formed layer and the substrate.

[0030] All references (such as, but not limited to, published patents and patent applications) mentioned herein, and unless otherwise indicated, are deemed to be "incorporated by reference in their entirety."

[0031] As used herein, the description of a "straight or branched" group (such as a straight or branched alkyl group) is understood to include: a methylene group or a methyl group; a straight chain group such as a straight C2-C 20 Alkyl; and appropriately branched groups, such as branched C3-C 20 alkyl.

[0032] As used herein, the term "halogen" and related terms (such as "halogen group" and / or "halo group") refer to a singly bonded halogen atom such as selected from fluorine (F), chlorine (Cl), bromine (Br), and / or iodine (I).

[0033] As used herein, and unless expressly stated otherwise, the term "hydrogen" and related terms (such as "hydrogen group") mean singly bonded hydrogen (-H).

[0034] As used herein, and unless otherwise expressly indicated, the term "acid equivalent weight," as with respect to the first carboxylic acid-functional material and the second carboxylic acid-functional material, means the "carboxylic acid equivalent weight" and is determined according to art-recognized methods, such as ASTM International ASTM D1639; and / or by determining the molecular weight or average molecular weight and the average number of carboxylic acid groups per molecule, such as by NMR analysis, and calculating the acid equivalent weight by dividing the molecular weight by the number of carboxylic acid groups per molecule.

[0035] As used herein, the term "aliphatic" and related terms (such as "aliphatic group") refer to a non-cyclic and non-aromatic hydrocarbon group that includes at least one carbon atom, such as 1 to 20 carbon atoms, such as C1-C 20Aliphatic group, or C1-C 10 Aliphatic groups, or C1-C6 aliphatic groups; can be straight or branched; optionally include one or more internal and / or terminal alkenyl groups (alkene group) (or alkenyl group); and optionally include one or more internal and / or terminal alkynyl groups (alkyne group) (or alkynyl group). When two or more alkenyl groups are included, the alkenyl groups of the aliphatic group can be conjugated and / or non-conjugated. When two or more alkynyl groups are included, the alkynyl groups of the aliphatic group can be conjugated and / or non-conjugated. When at least one alkenyl group and at least one alkynyl group are included, the alkenyl and alkynyl groups of the aliphatic group can be conjugated and / or non-conjugated relative to each other.

[0036] Examples of aliphatic groups include, but are not limited to, alkyl groups. As used herein, the term "alkyl" and related terms (such as "alkyl group(s)") refer to groups that include at least one carbon atom, such as 1 to 20 carbon atoms, such as C1-C 20 Alkyl, or C1-C 10 Alkyl, or C1-C6 alkyl; is straight or branched; and is saturated (and correspondingly free of alkenyl and alkynyl). Examples of alkyl include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, straight or branched pentyl, straight or branched hexyl, straight or branched heptyl, straight or branched octyl, straight or branched nonyl, straight or branched decyl, straight or branched undecyl, straight or branched dodecyl, straight or branched tridecyl, straight or branched tetradecyl, straight or branched pentadecyl, straight or branched hexadecyl, straight or branched heptadecyl, straight or branched octadecyl, straight or branched nonadecyl, and straight or branched eicosyl.

[0037] Examples of aliphatic groups include, but are not limited to, alkenyl. As used herein, the term "alkenyl" and related terms (such as "alkenyl group") refer to a group that includes at least two carbon atoms, such as 2 to 20 carbon atoms, such as C2-C 20 Alkenyl, or C2-C 10Alkenyl, or C2-C6 alkenyl; is straight or branched; and includes one or more internal and / or terminal alkenyl groups (alkene group) (or alkenyl group). Examples of alkenyl include, but are not limited to, those examples of straight or branched alkyl groups previously listed herein, which have at least two carbon atoms and at least one alkenyl group (alkene group) (or alkenyl group), such as, but not limited to, vinyl, straight or branched propenyl, straight or branched butenyl, straight or branched pentenyl, straight or branched hexenyl, etc.

[0038] Examples of aliphatic groups include, but are not limited to, alkynyl groups. As used herein, the term "alkynyl" and related terms (such as "alkynyl group(s)") refer to groups that include at least two carbon atoms, such as 2 to 20 carbon atoms, such as C2-C 20 Alkynyl, or C2-C 10 Alkynyl, or C2-C6 alkynyl; is straight or branched; and includes one or more internal and / or terminal alkyne groups (alkyne group) (or alkynyl group). Examples of alkynyl include, but are not limited to, those examples of straight or branched alkyl groups previously listed herein, which have at least two carbon atoms and at least one alkyne group (or alkynyl group), such as, but not limited to, ethynyl, straight or branched propynyl, straight or branched butynyl, straight or branched pentynyl, straight or branched hexynyl, etc.

[0039] As used herein, the term "cycloaliphatic" and related terms (such as "cycloaliphatic group") refer to a cyclic and non-aromatic hydrocarbon group that includes at least three carbon atoms, such as 3 to 20 carbon atoms, such as C3-C 20 Cycloaliphatic group, or C3-C 10 A cycloaliphatic group, or a C3-C8 cycloaliphatic group; optionally comprising at least one unsaturated group selected from olefins and / or alkynes; and optionally comprising two or more fused cycloaliphatic rings.

[0040] Examples of cycloaliphatic groups include, but are not limited to, cycloalkyl groups. As used herein, the term "cycloalkyl" and related terms (such as "cycloalkyl group(s)") refer to groups that include at least three carbon atoms, such as 3 to 20 carbon atoms, such as C3-C 20 Cycloalkyl, or C3-C 10Cycloalkyl, or C3-C8 cycloalkyl; optionally including at least one unsaturated group selected from olefins and / or alkynes; and optionally including two or more fused cycloalkyl rings. Examples of cycloalkyl include, but are not limited to, cyclopropyl; cyclobutyl; cyclopentyl; cyclohexyl; cycloheptyl; cyclooctyl; cyclononyl; cyclodecyl; cycloundecyl; cyclododecyl; bicyclo[2.2.1]heptanyl; decahydronaphthyl; tetradecahydroanthracenyl; tetradecahydrophenanthrenyl; and dodecahydro-1H-phenalenyl.

[0041] As used herein, the term "heterocycloaliphatic" and related terms (such as "heterocycloaliphatic group") refer to a cyclic and non-aromatic group that includes at least two carbon atoms, such as 2 to 20 carbon atoms, such as C2-C 20 Heterocyclic aliphatic group, or C2-C 10 a heterocycloaliphatic group, or a C2-C8 heterocycloaliphatic group; and having at least one heteroatom in the cyclic ring, such as, but not limited to, O, S, N, P, and combinations thereof; optionally including at least one unsaturated group selected from olefins and / or alkynes; and optionally including two or more fused non-aromatic cyclic rings, at least one of which is a fused heterocycloaliphatic ring.

[0042] Examples of heterocycloaliphatic groups include, but are not limited to, heterocycloalkyl groups. As used herein, the term "heterocycloalkyl" and related terms (such as "heterocycloalkyl group") refer to groups that include at least two carbon atoms, such as 2 to 20 carbon atoms, such as C2-C 20 Heterocycloalkyl group, or C2-C 10 Heterocycloalkyl groups, or C2-C8 heterocycloalkyl groups; and it has at least one heteroatom in the cyclic ring, such as but not limited to O, S, N, P, and combinations thereof; optionally including at least one unsaturated group selected from olefins and / or alkynes; and optionally including two or more fused non-aromatic cyclic rings, at least one of which is a fused heterocycloalkyl ring. Examples of heterocycloalkyl groups include, but are not limited to, imidazolyl, tetrahydrofuranyl, tetrahydropyranyl, piperidinyl, piperazinyl, morpholinyl, 7-oxabicyclo[2.2.1]heptyl, octahydrocyclopenta[b]pyranyl, and octahydro-1H-isochromenyl.

[0043] As used herein, the term "aryl" and related terms (such as "aryl group(s)") refer to cyclic aromatic groups that include at least 6 carbon atoms, such as C6-C 20 Aryl, or C6-C 14and optionally comprising at least two fused rings, at least one of which is a fused aromatic ring. Examples of aryl groups include, but are not limited to, phenyl, naphthyl, anthracenyl, phenanthrenyl, triphenylalkenyl, 9,10-dihydroanthracenyl, 9,10-dihydrophenanthrenyl, and triptycenyl.

[0044] As used herein, the term "arylaliphatic" and related terms, such as "arylaliphatic group," means an aryl group substituted with at least one aliphatic group. In some embodiments, an arylaliphatic group is covalently bonded to another group through at least one of its aliphatic groups. The aryl and aliphatic groups of the arylaliphatic group are each as previously described herein. One class of arylaliphatic groups includes, but is not limited to, aralkyl groups. Examples of aralkyl groups include, but are not limited to, benzyl and phenethyl.

[0045] As used herein, the term "heteroaryl" and related terms (such as "heteroaryl group(s)") refer to cyclic aromatic groups that include at least 3 carbon atoms, such as C3-C 20 Heteroaryl, or C5-C 14 Heteroaryl; at least one heteroatom in an aromatic ring, such as -O-, -N-, and / or -S-; and optionally including at least two fused rings, at least one of which is a fused heteroaromatic ring. Examples of heteroaryl include, but are not limited to, pyrazolyl, imidazolyl, triazinyl, furanyl, thienyl, pyranyl, pyridinyl, isoquinolinyl, and pyrimidinyl.

[0046] As used herein, the recitation of a "substituted" group is intended to include, but is not limited to, aliphatic, cycloaliphatic, heterocycloaliphatic, aryl, arylaliphatic, and heteroaryl groups in which at least one hydrogen has been replaced or substituted by a group other than hydrogen, such as, but not limited to, alkoxy; halo (e.g., F, Cl, I, and Br); hydroxy; thiol; alkylthio; arylthio; ketone; aldehyde; carboxylic acid; carboxylate; phosphate; phosphate; sulfonic acid; sulfonate; nitro; cyano; alkyl (including aralkyl); alkenyl; alkynyl; haloalkyl; perhaloalkyl; heterocycloalkyl; aryl (including alkaryl, including hydroxy-substituted aryl, such as phenol); heteroaryl; amino, such as -N(R 11’ )(R 12’ ), where R 11’ and R 12’Each is independently selected from, for example, hydrogen, an aliphatic group, a cycloaliphatic group, a heterocycloaliphatic group, an aryl group, an arylaliphatic group, and a heteroaryl group; a carboxylate group (-OC(O)-R, wherein R is, for example, selected from an aliphatic group, a cycloaliphatic group, a heterocycloaliphatic group, an aryl group, an arylaliphatic group, and a heteroaryl group); a siloxane group; an alkoxysilane group; a polysiloxane group; an amide group; a urethane group; a carbonate group; a urea group; a polyester group; a polyether group; a polycarbonate group; a polyurethane group; an acrylate group; a methacrylate group; a nitrogen-containing heterocyclic compound; or a combination thereof, including those species and examples described herein.

[0047] The curable photochromic adhesive composition of the present invention comprises at least one oxazoline-functional material comprising at least two oxazoline groups, such as at least three oxazoline groups, or at least four oxazoline groups. In some embodiments, the oxazoline-functional material comprises from 2 to 60 oxazoline groups, or from 2 to 55 oxazoline groups, or from 2 to 10 oxazoline groups, in each case inclusive of the recited values.

[0048] According to some embodiments, the oxazoline-functional material comprises an average of at least three oxazoline groups.

[0049] As used herein, the term "oxazoline" and related terms, such as "oxazoline group," mean 2-oxazoline or a 2-oxazoline group.

[0050] In some embodiments of the present invention, each oxazoline group of the oxazoline-functional material is an unsubstituted 2-oxazoline group (unsubstituted 2-oxazoline group), which is represented by the following formula (A), wherein the 2-oxazoline group is (covalently) bonded to a multivalent group (not shown) via the 2-position:

[0051]

[0052] According to some embodiments, the oxazoline functional material of curable photochromic adhesive composition of the present invention has at least 70 grams / mol (g / mole), such as at least 90 grams / mol, or at least 100 grams / mol, or at least 110 grams / mol, or at least 200 grams / mol, or at least 300 grams / mol, or at least 350 grams / mol of oxazoline equivalent weight.In certain embodiments, the oxazoline functional material of curable photochromic adhesive composition of the present invention has from 70 grams / mol to 1000 grams / mol, or from 100 grams / mol to 500 grams / mol, or from 110 grams / mol to 500 grams / mol of oxazoline equivalent weight.In certain embodiments, the oxazoline equivalent weight of oxazoline functional material is determined by NMR or gel permeation chromatography.

[0053] According to some embodiments of the present invention, the oxazoline-functional material of the curable photochromic adhesive composition and the curable photochromic coating composition is represented by the following formula (B):

[0054]

[0055] With respect to formula (B), n is at least 2, and R 1 is a single bond or a multivalent group. In some embodiments, R 1 is a polyvalent group selected from the group consisting of a polyvalent aliphatic group, a polyvalent cycloaliphatic group, a polyvalent heterocycloaliphatic group, a polyvalent aromatic group, a polyvalent heteroaromatic group, and a combination of two or more thereof. In some embodiments, n is 2 and R 1 It is a single bond.

[0056] Further with respect to Formula (B), and according to some embodiments, R 1 Selected from polyvalent benzene, polyvalent biphenyl, polyvalent naphthalene, polyvalent dinaphthalene, polyvalent pyridine, polyvalent straight or branched C1-C 20 Alkyl, polyvalent straight chain or branched C1-C 20 perfluoroalkyl groups and combinations of two or more thereof.

[0057] Further with respect to Formula (B), and according to some additional embodiments, R 1 is a multivalent polymer selected from, for example, multivalent polyesters, multivalent polycarbonates, multivalent polyethers, multivalent polyurethanes, multivalent polymers comprising residues of free-radically polymerizable ethylenically unsaturated monomers, and combinations thereof.

[0058] In some embodiments, the oxazoline-functional material of the curable photochromic adhesive composition and curable photochromic coating composition of the present invention comprises the residue of a free-radically polymerizable monomer having an oxazoline functional group.

[0059] In some further embodiments, the oxazoline-functional material of the curable photochromic adhesive composition and the curable photochromic coating composition of the present invention comprises a free radical polymerizable ethylenically unsaturated monomer having an oxazoline functional group. In some embodiments, the free radical polymerizable ethylenically unsaturated portion of the free radical polymerizable monomer having an oxazoline functional group is selected from a vinyl group, an isopropenyl group, an allyl group, an acrylate group, a methacrylate group, an acrylamide group, and a methacrylamide group.

[0060] Examples of free radical polymerizable monomers having oxazoline functional groups that can be used to prepare the oxazoline functional materials of the curable photochromic adhesive composition and the curable photochromic coating composition of the present invention include, but are not limited to, 2-vinyl-2-oxazoline; 2-(4-vinylphenyl)oxazoline; 2-isopropenyl-2-oxazoline; 2-(pent-4-ynyl)-2-oxazoline; 2-(4-(2-oxazolin-2-yl)phenoxy)ethyl acrylate; 2-(4-(2-oxazolin-2-yl)phenoxy)ethyl methacrylate; N-(4-(2-oxazolin-2-yl)phenyl)acrylamide; N-(4-(2-oxazolin-2-yl)phenyl)methacrylamide; 2-(4,5-dihydrooxazol-2-yl)propyl methacrylate ; 2-(1-(vinyloxy)prop-2-yl)-4,5-dihydrooxazole; 4-(4,5-dihydrooxazol-2-yl)phenyl acrylate; 2-(4-(vinyloxy)phenyl)-4,5-dihydrooxazole; 2-((vinyloxy)methyl)-4,5-dihydrooxazole; (4,5-dihydrooxazol-2-yl)methyl acrylate; 2-(9-decenyl)-1,3-oxazoline; 2-(3-butynyl)-2-oxazoline; 2-(3-cyclohexen-1-yl)-4,5-dihydrooxazole; 2-((allyloxy)methyl)4,5-dihydrooxazole; 2-(1-(allyloxy)prop-2-yl)-4,5-dihydrooxazole; 2-(4-(allyloxy)phenyl)-4,5-dihydrooxazole, and combinations thereof.

[0061] In some embodiments, the oxazoline-functional material of the curable photochromic adhesive composition and the curable photochromic coating composition of the present invention includes (i) the residue of a free radical polymerizable ethylenically unsaturated monomer having an oxazoline functional group; and (ii) the residue of a free radical polymerizable ethylenically unsaturated monomer that does not have an oxazoline functional group (i.e., does not contain an oxazoline functional group).

[0062] The types of free radical polymerizable ethylenically unsaturated monomers without oxazoline functional groups that can be used to prepare oxazoline functional materials include, but are not limited to, (meth)acrylates, such as C1-C 20 (Meth)acrylates; vinyl aromatic monomers; vinyl carboxylates; allyl monomers; olefins, such as C2 to C 24 Olefins; and combinations thereof.

[0063] C1-C 20 C1-C (meth)acrylate 20 The group may be selected from, for example, C1-C 20 Straight chain alkyl, C3-C 20 Branched alkyl, C3-C 20 Cycloalkyl, C3-C 20 Condensed-ring polycyclic alkyl, C5-C 20 Aryl and C10 -C 20 Fused ring aryl.

[0064] The C1-C ... 20 Examples of (meth)acrylates include, but are not limited to, methyl (meth)acrylate; ethyl (meth)acrylate; propyl (meth)acrylate; isopropyl (meth)acrylate; n-butyl (meth)acrylate; isobutyl (meth)acrylate; tert-butyl (meth)acrylate; 2-ethylhexyl (meth)acrylate; lauryl (meth)acrylate; isobornyl (meth)acrylate; cyclohexyl (meth)acrylate; 3,3,5-trimethylcyclohexyl (meth)acrylate; and combinations of two or more thereof.

[0065] Examples of vinyl aromatic monomers without oxazoline functionality that can be used to form the oxazoline functional materials of the present invention include, but are not limited to, styrene; p-chloromethylstyrene; divinylbenzene; vinylnaphthalene; divinylnaphthalene; and combinations of two or more thereof.

[0066] Examples of vinyl carboxylates without oxazoline functionality that can be used to form the oxazoline-functional material of the present invention include, but are not limited to, vinyl acetate; vinyl butyrate; vinyl 3,4-dimethoxybenzoate; vinyl benzoate; and combinations of two or more thereof.

[0067] Examples of allyl or allylic monomers that do not contain an oxazoline functional group and that can be used to form the oxazoline functional materials of the present invention include, but are not limited to, 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.

[0068] C2 to C3 containing no oxazoline functional group that can be used to form the oxazoline functional material of the present invention 24 Examples of olefins include, but are not limited to, propylene; isobutylene; 1-octadecene; and combinations of two or more thereof.

[0069] Additional examples of ethylenically unsaturated, free-radically polymerizable monomers that do not contain oxazoline functionality and that can be used to form the oxazoline-functional materials of the present invention include, but are not limited to, vinyl alcohol; vinyl chloride; acrylonitrile; trimethyl(4-methyl-4-penten-1-yl)-silane; 1-octene; 1-undecene; 1-octadecene; 4-heptenal; 6-methyl-, 9-decen-3-one; 5-methyl-1-heptene; vinylcyclopentane; bicyclo[2.2.1]hept-2-ene; vinylcyclohexane; 2-cyclohexyl acrylate; 2-acrylate, bicyclo[2.2.1]hept-2-yl ester; 2-acrylate, 4-(1,1-dimethylethyl)cyclohexyl ester; 2-acrylate; tricyclo[3.3.1.13,7]dec-2-yl ester; and combinations of two or more thereof.

[0070] According to some embodiments, when the oxazoline-functional material comprises the residue of a free-radically polymerizable monomer having an oxazoline-functional group, it has an Mn of at least 2000 g / mole, such as from 2000 g / mole to 100,000 g / mole, or from 2000 g / mole to 50,000 g / mole; and / or an Mw of at least 2000 g / mole, such as from 2000 g / mole to 200,000 g / mole, or from 2000 g / mole to 100,000 g / mole.

[0071] The carboxylic acid functional material of the curable photochromic adhesive composition of the present invention has at least two carboxylic acid groups, such as at least three carboxylic acid groups, or at least four carboxylic acid groups. In some embodiments, the first carboxylic acid functional material has from 2 to 6 carboxylic acid groups, or from 2 to 5 carboxylic acid groups, or from 2 to 4 carboxylic acid groups.

[0072] The carboxylic acid functional material of the curable photochromic adhesive composition of the present invention has an acid equivalent weight (carboxylic acid equivalent weight) greater than or equal to 600 g / mole, such as greater than or equal to 650 g / mole, or greater than or equal to 700 g / mole. In some embodiments, the carboxylic acid functional material of the curable photochromic adhesive composition of the present invention has an acid equivalent weight from 600 g / mole to 40,000 g / mole, or from 650 g / mole to 40,000 g / mole, or from 700 g / mole to 40,000 g / mole, or from 600 g / mole to 20,000 g / mole, or from 600 g / mole to 10,000 g / mole, in each case inclusive of the recited values.

[0073] In some embodiments, the carboxylic acid-functional material of the curable photochromic adhesive composition of the present invention has an Mn of less than or equal to 80,000 g / mole, such as less than or equal to 40,000 g / mole, or less than or equal to 20,000 g / mole. In some embodiments, the carboxylic acid-functional material of the curable photochromic adhesive composition of the present invention has an Mn of from 1200 g / mole to 80,000 g / mole, or from 1200 g / mole to 40,000 g / mole, or from 1200 g / mole to 20,000 g / mole, in each case inclusive of the recited values.

[0074] In some embodiments, the carboxylic acid functional material of the curable photochromic adhesive composition of the present invention is selected from carboxylic acid functional polyesters, carboxylic acid functional polycarbonates, carboxylic acid functional polyethers, carboxylic acid functional polyurethanes, carboxylic acid functional polyureas, carboxylic acid functionalized polyamides, carboxylic acid functional poly(siloxanes), their respective carboxylates, their copolymers, or combinations thereof.

[0075] The carboxylic acid functional polyesters from which the carboxylic acid functional materials of the curable photochromic adhesive composition of the present invention may be selected may be prepared according to methods generally recognized in the art. In some embodiments, and for non-limiting purposes, the carboxylic acid functional polyesters from which the carboxylic acid functional materials may be selected may be prepared by reacting a carboxylic acid functional material (and / or its cyclic anhydride, and / or its ester) having at least two carboxylic acid functional groups (or effective carboxylic acid functional groups, such 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 the carboxylic acid groups to the hydroxyl groups of the reactants is selected so that the resulting polyester has carboxylic acid functional groups and a desired molecular weight.

[0076] Examples of polyfunctional carboxylic acids from which the carboxylic acid-functional polyesters can be selected for use in preparing the carboxylic acid-functional materials of the curable photochromic adhesive composition of the present invention include, but are not limited to, benzene-1,2,4-tricarboxylic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endobicyclo-2,2,1,5-heptyne-2,3-dicarboxylic acid, tetrachlorophthalic acid, cyclohexanedioic acid, succinic acid, isophthalic acid, terephthalic acid, azelaic acid, maleic acid, trimesic acid, 3,6-dichlorophthalic acid, adipic acid, sebacic acid, and similar polyfunctional carboxylic acids (optionally including suitable cyclic anhydrides and / or esters thereof).

[0077] Carboxylic acid functional materials useful in the preparation of the curable photochromic adhesive compositions of the present application can be selected from carboxylic acid functional polyesters. Examples of polyols from which carboxylic acid functional polyesters can be selected include, but are not limited to, glycerol, trimethylolpropane, trimethylolethane, trihydroxyethyl isocyanurate, pentaerythritol, ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,2-butanediol, and 1,4-butanediol, pentanediol (such as, but not limited to, 1,5-pentanediol), heptanediol, hexanediol (such as, but not limited to, 1,6-hexanediol), octanediol, 4,4'-(propane-2,2-diyl)dicyclohexanol, 4,4'- methylene dicyclohexanol, neopentyl glycol, 2,2,3-trimethylpentane-1,3-diol, 1,4- bis(hydroxymethyl)cyclohexane, 2,2,4-trimethylpentanediol, 4,4'-(propane-2,2-diyl)diphenol, 4,4'-methylene diphenol, and similar polyols.

[0078] In some embodiments, the carboxylic acid functional materials of the curable photochromic adhesive compositions of the present application are selected from carboxylic acid functional polyesters that include or are carboxylic acid functional oligomeric or branched or hyperbranched polyesters that include at least three terminal carboxylic acid groups. The carboxylic acid functional oligomeric or branched or hyperbranched polyesters can be prepared according to art-recognized methods, such as from the reaction of a polyol having at least three hydroxyl groups with a cyclic carboxylic acid ester, in some embodiments, the reaction involves forming a hydroxyl functional polyester intermediate that is then modified to include carboxylic acid groups. Examples of polyols from which the carboxylic acid functional oligomeric or branched or hyperbranched polyesters can be prepared include, but are not limited to, glycerol, trimethylolethane, trimethylolpropane, pentaerythritol, diglycerol (such as a,a'-diglycerol), di(trimethylolethane), di(trimethylolpropane), di(pentaerythritol), and combinations of two or more thereof. Examples of cyclic carboxylic acid esters from which the carboxylic acid functional oligomeric or branched or hyperbranched polyesters can be prepared include, but are not limited to, lactones having from 4 to 8 atoms in the ring in which the ester oxygen and carbonyl carbon are directly bonded to one another, such as b-propiolactone, g-butyrolactone, d-valerolactone, e-caprolactone, and combinations of two or more thereof.

[0079] According to some embodiments, when the preparation of the carboxylic acid functional oligomeric or branched or hyperbranched polyesters involves forming a hydroxyl functional polyester intermediate, the hydroxyl functional polyester intermediate can be modified to include carboxylic acid functional groups by reaction with a cyclic anhydride, such as, but not limited to, succinic anhydride.

[0080] Commercially available examples of polyols that can be used to prepare the carboxylic acid functional polyesters of the compositions of the present invention include, but are not limited to, the following. Linear aliphatic polyester polyols include, but are not limited to, STEPANOL PC polyester polyols, which are commercially available from Stepan. The following polyols are commercially available from DIC Corporation: 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. The following polyols are commercially available from MilliporeSigma: polycaprolactone polyol with CAS number 36890-68-3; triol with CAS number 37625-56-2. The following polyols are commercially available from TriiSO: PERSTORP BOLTORN H2004 hyperbranched polyester polyol; and INGEVITY CAPA polycaprolactone polyol.

[0081] The carboxylic acid functional polycarbonate from which the carboxylic acid functional material of the curable photochromic adhesive composition of the present invention can be selected can be prepared according to methods recognized in the art. In some embodiments, and for the purpose of non-limiting illustration, the carboxylic acid functional polycarbonate is prepared by first preparing a hydroxyl functional polycarbonate intermediate and then modifying the hydroxyl functional polycarbonate intermediate to include a carboxylic acid group.

[0082] In certain embodiments, and for the purpose of non-limiting illustration, hydroxyl-functional polycarbonate intermediate can be prepared by the reaction of polyol (such as glycol) and carbonyl dihalide (such as carbonyl dichloride), wherein removing gained halide acid such as HCl.For the purpose of other non-limiting illustration, hydroxyl-functional polycarbonate intermediate can be prepared by the ring-opening polymerization of cyclic carbonate.For the purpose of further non-limiting illustration, hydroxyl-functional polycarbonate intermediate can be prepared by the transesterification reaction of polyol (such as glycol) and biscarbonate, and this biscarbonate is represented by following formula ROC (O)-OR, and wherein each R is independently selected from such as aliphatic group, cycloaliphatic group and aryl group.For the purpose of further non-limiting illustration, in the case of diphenyl carbonate, cause forming hydroxyl-functional polycarbonate intermediate with the transesterification reaction of polyol, and be accompanied by removing gained phenol. For purposes of further additional non-limiting illustration, in the case of dialkyl carbonates such as dimethyl carbonate and diethyl carbonate, transesterification reactions with polyols result in the formation of hydroxyl-functional polycarbonate intermediates with the concomitant removal of the resulting alkyl alcohol.

[0083] Commercially available hydroxyl functional polycarbonates that can be used as intermediates in forming carboxylic acid functional polycarbonates include, but are not limited to, the following. The following polycarbonate diols are commercially available from Ube Chemical: ETERNACOLL UH-100D, ETERNACOLL PH-300D, ETERNACOLL PH-200D, ETERNACOLL PH-200, and ETERNACOLL UH-200 polycarbonate diols. The following polycarbonate diols are commercially available from Stahl USA: PC-1122 polycarbonate diol. The following polycarbonate diols are commercially available from Asahi: DURANOL T5652 polycarbonate diol.

[0084] The hydroxyl functional polycarbonate intermediate can be modified to include carboxylic acid groups according to art recognized methods. In some embodiments, the hydroxyl functional polycarbonate intermediate is reacted with a cyclic anhydride such as, but not limited to, succinic anhydride, which results in the formation of a carboxylic acid functional polycarbonate.

[0085] The carboxylic acid functional polyethers from which the carboxylic acid functional materials of the curable photochromic adhesive composition of the present invention can be selected can be prepared according to methods recognized in the art. In some embodiments, and for non-limiting illustrative purposes, the carboxylic acid functional polyethers are prepared by first preparing a polyether intermediate having hydroxyl functional groups and then modifying the polyether intermediate to include carboxylic acid groups.

[0086] In certain embodiments, and for the purpose of non-limiting illustration, polyether intermediates can be prepared by the ring-opening polymerization of the cyclic ether or the mixture of cyclic ethers (including but not limited to alkylene oxide and / or tetrahydrofuran) using an acid or base catalyst and a polyhydroxy initiator or a polyhydroxy initiator mixture. The limiting examples of polyhydroxy initiators include the polyols previously listed herein. Illustrative alkylene oxides include ethylene oxide, propylene oxide, butylene oxide, pentane oxide, styrene oxide and halogenated alkylene oxides such as trichlorobutylene oxide. The example of polyether polyols includes but is not limited to poly-(tetrahydrofuran) glycol, which is also referred to as poly-(tetramethylene ether) glycol.

[0087] Examples of commercially available hydroxyl functional polyether intermediates include, but are not limited to, those sold under the trade name VORANOL TM Those available from Dow Chemicals; those available from BASF under the trade names LUPRANOL, PLURACOL, PLURONIC, and PolyTHF; and those available from Bayer under the trade names DESMOPHEN and ACCLAIM.

[0088] The carboxylic acid functional polyurethane that the carboxylic acid functional material of curable photochromic adhesive composition of the present invention can be selected from can be prepared according to art-recognized method.In certain embodiments, and for the purpose of non-limiting explanation, carboxylic acid functional polyurethane is by first forming the polyurethane intermediate with hydroxyl functional group or isocyanate functional group and then polyurethane intermediate is modified to comprise carboxylic acid group and prepare.Polyurethane intermediate can be prepared according to art-recognized method (such as but not limited to the reaction of polyol (such as glycol) and polyisocyanate (such as diisocyanate)).In certain embodiments, the polyol that can be used for preparing polyurethane intermediate can be selected from those kinds and the example of the polyol previously enumerated herein.In certain embodiments, the polyisocyanate that can be used for preparing polyurethane intermediate can be selected from those kinds and the example of the polyisocyanate further enumerated herein.

[0089] According to art-recognized methods, the hydroxyl-functional polyurethane intermediate can be modified to include carboxylic acid functional groups. In certain embodiments, the hydroxyl-functional polyurethane intermediate and cyclic acid anhydride such as but not limited to succinic anhydride react, and this causes the formation of carboxylic acid functional polyurethane. In some other embodiments, the hydroxyl-functional polyurethane intermediate and isocyanate-functional carboxylate (such as but not limited to 3-isocyanato alkyl propionate) react, carry out art-recognized post-processing procedure subsequently, this causes the formation of carboxylic acid functional polyurethane. According to art-recognized methods, the isocyanate-functional polyurethane intermediate can be modified to include carboxylic acid functional groups. In certain embodiments, the isocyanate-functional polyurethane intermediate and hydroxyl-functional carboxylate (such as but not limited to the carboxylate of suitable 3-hydroxypropionic acid) react, this causes the formation of carboxylate functional polyurethane. In certain embodiments, the carboxylate functional polyurethane is subjected to art-recognized post-processing procedure to be converted into carboxylic acid functional polyurethane.

[0090] In some embodiments, the polyisocyanates useful in preparing the polyurethane intermediate (and correspondingly the carboxylic acid functional polyurethane) can be selected from aliphatic polyfunctional isocyanates, cycloaliphatic polyfunctional isocyanates, heterocycloaliphatic polyfunctional isocyanates, aryl polyfunctional isocyanates, arylaliphatic polyfunctional isocyanates, and combinations of two or more thereof.

[0091] As used herein, the term "polyfunctional isocyanate" means a material having at least two isocyanate groups. In some embodiments, the polyfunctional isocyanate used to form the carboxylic acid functional polyurethane of the curable photochromic composition of the present invention has from 2 to 6 isocyanate groups, or from 2 to 5 isocyanate groups, or from 2 to 4 isocyanate groups, or 2 to 3 isocyanate groups, in each case inclusive of the recited values.

[0092] Examples of polyfunctional isocyanates that can be used to prepare the carboxylic acid functional polyurethanes of the curable photochromic compositions of the present invention include, but are not limited to, toluene-2,4-diisocyanate; toluene-2,6-diisocyanate; diphenylmethane-4,4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; p-phenylene diisocyanate; biphenyl diisocyanate; 3,3'-dimethyl-4,4'-diphenylene diisocyanate; tetramethylene-1,4-diisocyanate; hexamethylene-1,6-diisocyanate; 2,2,4-trimethylhexane-1,6-diisocyanate; lysine methyl ester diisocyanate; bis(isocyanatoethyl)fumarate; isophorone diisocyanate; ethylene diisocyanate; dodecane-1,12-diisocyanate. -diisocyanate; cyclobutane-1,3-diisocyanate; cyclohexane-1,3-diisocyanate; cyclohexane-1,4-diisocyanate; methylcyclohexyl diisocyanate; hexahydrotoluene-2,4-diisocyanate; hexahydrotoluene-2,6-diisocyanate; hexahydrophenylene-1,3-diisocyanate; hexahydrophenylene-1,4-diisocyanate; perhydrodiphenylmethane-2,4'-diisocyanate; perhydrodiphenylmethane-4,4'-diisocyanate; norbornane diisocyanate; mixtures of two or more thereof; and respective dimers or trimers thereof or combinations thereof, comprising a linkage selected from the group consisting of isocyanurate, uretdione, biuret, allophanate, and combinations thereof.

[0093] The carboxylic acid functional materials of the curable photochromic adhesive composition of the present invention can be selected from carboxylic acid functional polyurea polymers, polyurethane polymers and polyurea-polyurethane copolymers according to methods generally recognized in the art. The preparation of carboxylic acid functional polyureas is described in, for example, US 6,610,812 B1. Typically, the carboxylic acid group can be attached to the polyol component of the polyurethane or the amine component of the polyurea. Alternatively, the carboxylic acid group can also be attached to the isocyanate component of the polyurethane or polyurea, for example, using a hydroxyl functional carboxylate material, and then the carboxylate moiety is converted into a carboxylic acid functional group. For the purpose of non-limiting illustration, carboxylic acid functional polyurethanes and carboxylic acid functional polyureas can be prepared according to the following two methods generally recognized in the art. In the first method, the carboxylic acid functional polyurethane / polyurea is prepared from a prepolymer with a carboxylic acid functional portion. In the second method, the carboxylic acid functional group is incorporated during the post-polymerization reaction, thereby introducing or attaching the carboxylic acid functional group to the polyurethane or polyurea.

[0094] Hydroxy functional polyurea intermediates and hydroxy functional polyurea-polyurethane copolymer intermediates can be prepared according to methods recognized in the art, such as by reacting polyamines (having primary and / or secondary amine groups), polyisocyanates and polyols in an appropriate order and / or a set of appropriate sequential reactions. For non-limiting purposes, polyamines can be reacted with an appropriate excess of polyisocyanates to form isocyanate functional polyureas, which are then reacted with polyols to form hydroxy functional polyurea / polyurethane intermediates. The types and examples of suitable polyols and polyisocyanates include, but are not limited to, those previously discussed herein. The types of polyamines having primary and / or secondary amine functional groups include, but are not limited to, aliphatic polyamines, cycloaliphatic polyamines, aromatic polyamines and combinations thereof.

[0095] The carboxylic acid functional polyamide from which the carboxylic acid functional material of the curable photochromic adhesive composition of the present invention can be selected can be prepared according to methods generally recognized in the art. In some embodiments, the carboxylic acid functional polyamide is prepared by the reaction of a suitable excess of difunctional carboxylic acid and a diamine (e.g., having two primary amine groups). For non-limiting purposes, the carboxylic acid functional polyamide can be prepared by the reaction of a suitable excess of adipic acid and hexamethylenediamine. In some other embodiments, the carboxylic acid functional polyamide is prepared by the reaction of a hydroxyl functional polyamide intermediate with a cyclic carboxylic acid anhydride. The hydroxyl functional polyamide intermediate can be prepared according to methods generally recognized in the art, such as, but not limited to, the reaction of a difunctional carboxylic acid with an amino alcohol; and by aminolysis, such as by the reaction of a carboxylic ester, a carboxylic acid, or a lactone with an amino alcohol. Examples of suitable diamines and amino alcohols that can be used to prepare the carboxylic acid functional polyamide include, but are not limited to, hexamethylenediamine; ethylenediamine; phenylenediamine; monoethanolamine; diethanolamine; and isophoronediamine.

[0096] The carboxylic acid functional material of the curable photochromic adhesive composition of the present invention can be selected from the carboxylic acid functional polysiloxanes according to methods recognized in the art. As described in, for example, US 2016 / 0347775 A1, the carboxylic acid functional organopolysiloxane can be prepared by the reaction of a difunctional cyclic carboxylic acid anhydride with an organopolysiloxane having two hydroxy groups. In certain embodiments, the difunctional cyclic carboxylic acid anhydride is an organopolysiloxane. The organopolysiloxane intermediate recognized in the art with a large number of diorganosiloxy repeating units, which is silanol-terminated, can be used to prepare the carboxylic acid functional polysiloxane of the present composition. The carbinol-functional organopolysiloxane intermediate recognized in the art can also be used to prepare the carboxylic acid functional polysiloxane of the present composition. For non-limiting purposes, the carbinol-functional organopolysiloxane intermediate can be prepared by hydrosilylation of an enol (such as allyl alcohol or hexadecene-1-ol) and a bis(hydrogendiorganosilyl)-terminated organopolysiloxane. Examples of commercially available carboxylic acid functional polysiloxanes that can be used in the compositions of the present invention include, but are not limited to, those available from Gelst Corporation, such as DMS-B25 carboxylic acid functional polysiloxane, which is described as a carboxydecyl end-blocked polydimethylsiloxane having a molecular weight of 10,000 g / mole; and DMS-B3 carboxylic acid functional polysiloxane, which is described as a carboxypropyl end-blocked polydimethylsiloxane having a molecular weight of 28,000 g / mole.

[0097] In some embodiments of the present invention, the carboxylic acid functional material of the curable photochromic adhesive composition is prepared from a hydroxyl-functional thermoplastic polyurethane copolymer according to methods recognized in the art. Commercially available hydroxyl-functional thermoplastic polyurethanes that can be used as intermediates in the formation of carboxylic acid functional polyurethane copolymers include, but are not limited to, PEARLSTICK, PEARLBOND, ESTANE, TECOFLEX, and CARBOTHANE hydroxyl-functional polyurethanes commercially available from Lubrizol; CHRONOFLEX AL, CHRONOFLEX C, CHHRONOTHANE P, and CHRONOSIL hydroxyl-functional polyurethanes commercially available from AdvanSource Biomaterials Corporation (Wilmington, Massachusetts); ELAST-EON hydroxyl-functional polyurethanes commercially available from AorTech International Plc (Dundee, England); and QUADRATHANE hydroxyl-functional polyurethanes commercially available from Biomerics.

[0098] The carboxylate salt of the carboxylic acid functional material of the curable photochromic composition of the present invention can be prepared according to methods recognized in the art. According to some embodiments, as described in WO 2017 / 180220 Al, the carboxylic acid functional groups can be at least partially or completely neutralized with an inorganic base such as a volatile amine to form carboxylate groups. Examples of suitable amines include, but are not limited to, ammonia, dimethylamine, trimethylamine, triethylamine, monoethanolamine, and dimethylethanolamine. According to some embodiments, the volatile amine migrates out of the adhesive layer or coating layer (such as by volatilization) during formation of the layer, which results in the formation (or exposure) of carboxylic acid groups that can participate in reactions (such as crosslinking reactions) with the polycarbodiimide component of the composition.

[0099] In the curable photochromic adhesive composition of the present invention, the equivalent ratio of oxazoline equivalents of the oxazoline functional material to carboxylic acid equivalents of the carboxylic acid functional material is from 0.5: 1 to 10: 1. In some further embodiments, the curable photochromic adhesive composition has an equivalent ratio of (i) oxazoline equivalents of the oxazoline functional material to (ii) carboxylic acid equivalents of the carboxylic acid functional material of from 0.5: 1 to 10: 1, or from 0.5: 1 to 5: 1, or from 0.9: 1 to 3: 1, in each case inclusive of the recited ratios.

[0100] In some further embodiments, the curable photochromic adhesive composition has an equivalent ratio of (i) oxazoline equivalents of the oxazoline functional material to (ii) carboxylic acid equivalents of the carboxylic acid functional material of greater than 3: 1, such as from 3.5: 1 to 10: 1, or from 4: 1 to 10: 1, or from 5: 1 to 10: 1, in each case inclusive of the recited ratios.

[0101] In the curable photochromic composition of the present invention, and for purposes of non-limiting illustration, the reaction between the oxazoline groups of the oxazoline functional material and the carboxylic acid groups of the carboxylic acid functional material, such as, results in the formation of a divalent amide-ester linking group (or divalent amide-ester linkage), which can be represented by the following formula (C):

[0102]

[0103] The cured material (such as a polymeric product, a cured adhesive layer, and a cured coating) prepared from the curable photochromic composition of the present invention includes a plurality of divalent amide-ester linkages, such as represented by formula (C), which can also be referred to as divalent amide-ester crosslinks (or divalent crosslinking groups).

[0104] The curable photochromic adhesive composition of the present invention includes a photochromic compound, such as one or more photochromic compounds. Each photochromic compound of the curable photochromic adhesive composition can be selected from the known classes and examples of photochromic compounds, and can include combinations or mixtures thereof.

[0105] For example, while not limited herein, mixtures of photochromic compounds can be used to obtain certain activated colors, such as near neutral gray or near neutral brown. See, for example, U.S. Patent No. 5,645,767, column 12, line 66 to column 13, line 19, which describes parameters defining neutral gray and brown and the disclosure of which is specifically incorporated herein by reference.

[0106] In some embodiments, the photochromic compound of the curable photochromic composition of the present application is selected from the group consisting of naphthopyran, benzopyran, phenanthropyrane, indenonaphthopyran, spiro(indolinine)phenoxazine, spiro(indolinine)pyridobenzoxazine, spiro(benzindolinine)pyridobenzoxazine, spiro(benzindolinine)phenoxazine, spiro(indolinine)-benzoxazine, fulgimide, fulgimide, diarylethylene, and mixtures of such photochromic compounds.

[0107] Further examples of other photochromic compounds that can be used in the curable photochromic adhesive composition of the present application include, but are not limited to, those disclosed in US 9,028,728 B2 (the disclosure of which is specifically incorporated herein by reference) at column 34, line 20 through column 35, line 13.

[0108] The photochromic compound is present in the curable photochromic adhesive composition in an amount at least sufficient for an article made from the composition to have a desired level of photochromic properties, which amount is referred to in some embodiments as a photochromic amount. In some embodiments, the amount of photochromic compound present in the curable photochromic adhesive composition is from 0.001 wt% to 40 wt%, or from 0.001 to 30 wt%, or from 0.01 to 10 wt%, or from 0.1 to 5 wt%, based on the total solids weight of the curable photochromic adhesive composition (including the weight of the photochromic compound, and including the recited values).

[0109] In some embodiments of the present invention, the curable photochromic adhesive composition optionally comprises a solvent, such as an organic solvent. Examples of organic solvents that may be optionally included in the curable photochromic composition of the present invention include, but are not limited to, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, isobutanol, furfuryl alcohol, and tetrahydrofurfuryl alcohol; ketones or ketone alcohols such as acetone, methyl ethyl ketone, and diacetone alcohol; ethers such as dimethyl ether and methyl ethyl ether; cyclic ethers such as tetrahydrofuran and dioxane; esters such as ethyl acetate, ethyl lactate, ethylene carbonate, and propylene carbonate; hydroxyl-functional ethers of alkylene glycols such as butyl 2-hydroxyethyl ether, methyl 2-hydroxypropyl ether, and phenyl 2-hydroxypropyl ether; nitrogen-containing cyclic compounds such as pyrrolidone, N-methyl-2-pyrrolidone, and 1,3-dimethyl-2-imidazolidinone; sulfur-containing compounds such as dimethyl sulfoxide and tetramethylene sulfone; aromatic compounds such as toluene, xylene, anisole, and butyl benzoate; and mixtures of aromatic compounds such as, but not limited to, aromatic compounds. 100 Fluid (which is commercially available C9-C 10 mixture of dialkyl-benzenes and trialkyl-benzenes), and AROMATIC 150 Fluid (which is a commercially available C9-C 11 mixture of alkylbenzenes).

[0110] In some embodiments, the organic solvent optionally included in the curable photochromic composition of the present invention is selected from aprotic organic solvents. In some embodiments, the aprotic organic solvent is a polar aprotic organic solvent, such as one having a dielectric constant greater than 5. Examples of aprotic organic solvents that may be included in the curable photochromic composition of the present invention include, but are not limited to, halogenated methanes such as dichloromethane; cyclic ethers such as tetrahydrofuran and dioxane; alkyl acetates such as ethyl acetate; alkyl lactates such as ethyl lactate; alkyl nitriles (or alkyl cyanides) such as acetonitrile (or methyl cyanide); dialkyl formamides such as dimethyl formamide; dialkyl sulfoxides such as dimethyl sulfoxide; ketones such as acetone and methyl ethyl ketone; N-substituted cyclic amides (lactams) such as N-methyl-2-pyrrolidone and N-butyl-2-pyrrolidone; aromatic compounds such as toluene, xylene, anisole, butyl benzoate, dialkylbenzenes, trialkylbenzenes, AROMATIC 100 Fluid (which is commercially available as C9-C 10 mixture of dialkyl-benzenes and trialkyl-benzenes), and AROMATIC 150 Fluid (which is a commercially available C9-C 11 mixtures of alkylbenzenes); and combinations of two or more thereof.

[0111] The organic solvent can be present in a wide range of amounts in the curable photochromic adhesive composition of the present invention. In some embodiments, the organic solvent is present in the curable photochromic adhesive composition of the present invention in an amount from 5 to 95 weight percent, or from 15 to 85 weight percent, or from 20 to 80 weight percent, in each case inclusive of the recited values, and the weight percentages in each case are based on the total weight of the curable photochromic adhesive composition including the organic solvent.

[0112] In some embodiments, the curable photochromic adhesive composition of the present invention optionally includes one or more additives, such as, but not limited to, waxes for flow and wetting; flow control agents, such as poly(2-ethylhexyl)acrylate; surface additives, such as polyether-modified polydimethylsiloxane; rheology control agents; leveling agents; antioxidants; light stabilizers, such as hindered amine light stabilizers; ultraviolet (UV) light absorbers; heat stabilizers; singlet oxygen quenchers; fixed hue dyes; dichroic dyes; adhesion promoters; catalysts; and combinations of two or more thereof. Examples of useful antioxidants, hindered amine light stabilizers, and UV light absorbers include, but are not limited to, those commercially available from BASF under the trade names IRGANOX and TINUVIN. When used, these optional additives may be present in an amount of up to 20% by weight based on the total solid weight (excluding solvent) of the curable photochromic adhesive composition.

[0113] Optional additives that may be included in the curable photochromic adhesive compositions of the present invention include one or more fixed hue dyes. As used herein, the term "fixed-hue dye" and related terms, such as "fixed-colorant," "static colorant," "fixed dye," and "static dye" mean a dye that is a non-photosensitive material that does not physically or chemically respond to electromagnetic radiation with respect to its visually observed color. As used herein, the term "fixed-hue dye" and related terms do not include and can be distinguished from photochromic compounds. As used herein, the term "non-photosensitive material" means a material that does not physically or chemically respond to electromagnetic radiation with respect to its visually observed color, including but not limited to fixed hue dyes.

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

[0115] In some embodiments, the optional fixed tint dye of the curable photochromic adhesive composition includes at least one of an azo dye, an anthraquinone dye, a xanthene dye, an azine 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.

[0116] The fixed tint dye can be present in the curable photochromic adhesive composition in varying amounts to provide the desired effect in the cured article prepared therefrom. In some embodiments, the fixed tint dye is present in the curable photochromic adhesive composition in an amount from 0.001 wt% to 15 wt%, or from 0.01 wt% to 10 wt%, or from 0.1 wt% to 2.5 wt%, with the weight percent in each instance being based on the total solids weight of the curable photochromic adhesive composition (including the weight of the fixed tint dye, and including the recited values).

[0117] Optional additives that can be included in the curable photochromic adhesive compositions of the present application include one or more dichroic dyes. As used herein, the term “dichroism” and like terms, such as “dichroic,” mean the ability to absorb one of two orthogonal plane polarized components of radiation (including transmitted and / or reflected radiation) more strongly than the other.

[0118] Examples of dichroic dyes that can be included in the curable photochromic adhesive compositions of the present application include, but are not limited to, methine, indigoid, thioindigoid, merocyanines, indanes, quinophthalone dyes, perylenes, phthaloperines, triphenodioxazines, indoloquinoxalines, imidazole-triazines, tetrazines, azo and (poly)azo dyes, benzoquinones, naphthoquinones, anthraquinones and (poly)anthraquinones, anthrapyrimidinones, iodine, iodate salts, or combinations of two or more thereof. The dichroic dye can be present in the curable photochromic adhesive compositions of the present application in any suitable amount, such as from 0.001 to 10 wt%, or from 0.01 to 5 wt%, or from 0.1 to 2.5 wt%, with the weight percent in each instance being based on the total solids weight of the curable photochromic adhesive composition (including the weight of the dichroic dye; and including the recited values).

[0119] The curable photochromic adhesive composition of the present invention can be applied by any suitable application method to form, for example, an applied layer. The application method by which the curable photochromic adhesive composition of the present invention can be applied on or to a substrate includes, but is not limited to, a doctor blade (or rod) application method; a slot die application method; a spin coating application method; a curtain coating application method; a dip coating application method; and combinations of such application methods.

[0120] The curable photochromic adhesive composition of the present invention can be cured by any suitable method. In some other embodiments, the curable photochromic adhesive composition is cured by exposure to high temperature (exceeding ambient room temperature). As used herein, "curing" means forming a three-dimensional crosslinked network by covalent bond formation, such as between the oxazoline group of the oxazoline functional material and the carboxylic acid group of the carboxylic acid functional material, as represented by the above formula (C). When cured at high temperature, the curable photochromic adhesive composition can be referred to as a thermosetting curable photochromic adhesive composition in this article. The temperature at which the thermosetting curable photochromic adhesive composition of the present invention is cured is variable and depends in part on the amount of time during the curing process. For some embodiments, the curable photochromic adhesive composition is cured at a high temperature of from 65°C to 204°C, or from 70°C to 177°C, or from 75°C to 140°C for a period of 20 to 240 minutes.

[0121] The cured photochromic layer formed from the curable photochromic adhesive composition of the present invention can have any suitable thickness, such as from 5 micrometers to 300 micrometers, or from 10 micrometers to 200 micrometers.

[0122] As used herein, the term "layer" includes films and sheets. As used herein, and according to some embodiments, the term "film" means a non-self-supporting layer; and the term "sheet" means a self-supporting layer.

[0123] According to the present invention, an optical article is further provided, comprising: (A) a substrate; and (B) an adhesive layer on at least a portion of a surface of the substrate, wherein the adhesive layer is formed from a curable photochromic adhesive composition of the present invention. In some embodiments, the layer is a cured layer. The layer can be formed on the substrate from the curable photochromic adhesive composition of the present invention using one or more of the application and curing methods previously described herein.

[0124] In some embodiments, an optical article comprising a substrate and a layer on at least one surface of the substrate (formed from a curable photochromic adhesive composition of the present invention) can be selected from display elements, windows, mirrors, liquid crystal cell elements, and ophthalmic elements. Accordingly, the substrate of the optical article can be selected from displays, windows, mirrors, liquid crystal cell element substrates, and ophthalmic substrates. The substrate can be composed of one or more suitable materials, including but not limited to organic materials, such as organic polymer materials; glass, such as silica-based glass; metal; ceramic materials; and combinations thereof.

[0125] Non-limiting examples of organic materials that can be used to form the substrate of the optical article of the present invention include polymeric materials, such as homopolymers and copolymers, prepared from the monomers and monomer mixtures disclosed in U.S. Patent No. 5,962,617 and U.S. Patent No. 5,658,501 from column 15, line 28 to column 16, line 17, the disclosures of which are specifically incorporated herein by reference. For example, such polymeric materials can be thermoplastic or thermosetting polymeric materials, can be transparent or optically clear, and can have any refractive index desired. Non-limiting examples of such disclosed monomers and polymers include polyol (allyl carbonate) monomers, for example, allyl diglycol carbonate, such as diethylene glycol bis (allyl carbonate), which is available from PPG Industries (PPG). Industries, Inc.) under the trademark CR-39; polyurea-polyurethane (polyurea-urethane) polymers, prepared, for example, by the reaction of a polyurethane prepolymer with a diamine curing agent, a composition for which is sold by PPG Industries under the trademark TRIVEX; polyol (meth)acryloyl-terminated carbonate monomers; diethylene glycol dimethacrylate monomers; ethoxylated phenol methacrylate monomers; diisopropenylbenzene monomers; ethoxylated trimethylolpropane triacrylate monomers; ethylene glycol dimethacrylate monomers; poly(ethylene glycol) dimethacrylate monomers; urethane acrylate monomers; poly(ethoxylated bisphenol A dimethacrylate); poly(vinyl acetate) ; poly(vinyl alcohol); poly(vinyl chloride); poly(vinylidene chloride); polyethylene; polypropylene; polyurethane; polythiourethane; thermoplastic polycarbonates, such as the carbonate-linked resin derived from bisphenol A and phosgene, one such material sold under the trademark LEXAN; polyesters, such as the material sold under the trademark MYLAR; poly(ethylene terephthalate); polyvinyl butyral; poly(methyl methacrylate) (such as the material sold under the trademark PLEXIGLAS), and polymers prepared by the reaction of a polyfunctional isocyanate with a polythiol or polycyclosulfide monomer, homopolymerized or copolymerized and / or terpolymerized with polythiols, polyisocyanates, polyisothiocyanates, and optionally ethylenically unsaturated monomers or halogenated aromatic-containing vinyl monomers. Copolymers of such monomers and blends of the described polymers and copolymers with other polymers (e.g., to form block copolymers or interpenetrating network products) are also contemplated.

[0126] In some embodiments, the substrate can optionally include a photochromic material and / or a fixed tint dye, each of which can be selected from those classes and examples of photochromic materials and fixed tint dyes previously described herein. The optional photochromic material / compound present in the substrate can be the same as or different from the photochromic compound of the layer formed from the curable photochromic adhesive composition of the present application. The optional fixed tint dye can be the same as or different from the optional fixed tint dye of the layer formed from the curable photochromic adhesive composition of the present application.

[0127] The layer formed from the curable photochromic adhesive composition of the present application can be in the form of a single layer or multiple layers. When in the form of multiple layers, each layer can be prepared from a curable photochromic adhesive composition according to the present application (having the same or different composition, such as the same or different photochromic compound(s)).

[0128] In addition to the photochromic layer formed from the curable photochromic adhesive composition of the present application, the optical article can optionally include one or more additional layers, including art-recognized layers such as, but not limited to, a primer layer; an adhesive layer prepared from a composition different from the curable photochromic adhesive composition of the present application; a protective layer (such as a hard coat layer); a polarizing layer; a birefringent layer; an anti-reflective layer; a photochromic layer prepared from the curable photochromic coating composition of the present application; and / or another photochromic layer prepared from a composition different from the curable photochromic coating composition of the present application.

[0129] In some embodiments, the optical article including the layer formed from the curable photochromic adhesive composition of the present application is selected from a corrective lens, a non-corrective lens, a magnifying lens, a protective lens, and eyewear.

[0130] The adhesive layer formed from the curable photochromic adhesive composition of the present application can be interposed between a substrate surface and a cover layer; and / or interposed between a base layer and a cover layer.

[0131] In some additional embodiments, the adhesive layer formed from the curable photochromic adhesive composition of the present application is interposed between a first substrate and a second substrate and adheres the first substrate and the second substrate together.

[0132] The present application is also directed to a curable photochromic coating composition as previously described herein.

[0133] The oxazoline-functional material of the curable photochromic coating composition that includes at least two oxazoline groups is as previously described herein with respect to the oxazoline-functional material of the curable photochromic adhesive composition.

[0134] As previously described herein, the curable photochromic coating composition of the present invention includes a first carboxylic acid-functional material and a second carboxylic acid-functional material.

[0135] The first carboxylic acid-functional material of the curable photochromic coating composition of the present invention comprises at least two carboxylic acid groups and has an acid (carboxylic acid) equivalent weight greater than or equal to 600 g / mole. The first carboxylic acid-functional material of the curable photochromic coating composition of the present invention is as previously described herein with respect to the carboxylic acid-functional material of the curable photochromic adhesive composition of the present invention.

[0136] According to some embodiments, the first carboxylic acid-functional material of the curable photochromic coating composition is selected from carboxylic acid-functional polyesters; carboxylic acid-functional polycarbonates; carboxylic acid-functional polyethers; carboxylic acid-functional polyurethanes; carboxylic acid-functional polyureas; carboxylic acid-functional polyamides; carboxylic acid-functional poly(siloxanes); their respective carboxylates; copolymers thereof; or combinations thereof. The carboxylic acid-functional polyesters, carboxylic acid-functional polycarbonates, carboxylic acid-functional polyethers, carboxylic acid-functional polyurethanes, carboxylic acid-functional polyureas, carboxylic acid-functional polyamides, carboxylic acid-functional poly(siloxanes), and their respective carboxylates from which the first carboxylic acid-functional material of the curable photochromic coating composition of the present invention may be selected are each as previously described herein with respect to the curable photochromic adhesive composition.

[0137] The second carboxylic acid-functional material of the curable photochromic coating composition of the present invention comprises at least three carboxylic acid groups and has an acid (carboxylic acid) equivalent weight of less than or equal to 580 grams per mole.

[0138] In certain embodiments, the second carboxylic acid functional material of curable photochromic coating composition of the present invention has acid (carboxylic acid) equivalent weight that is less than or equal to 570 grams / mol, or is less than or equal to 565 grams / mol, or is less than or equal to 560 grams / mol.In some other embodiments, the second carboxylic acid functional material has the acid equivalent weight of at least 50 grams / mol, or at least 55 grams / mol, or at least 60 grams / mol, or at least 64 grams / mol, or at least 70 grams / mol.The acid equivalent weight of the second carboxylic acid functional material can be in the scope between any combination of the upper and lower limits (comprising the value of enumeration) of these enumerations.In some other embodiments, the second carboxylic acid functional material has the acid equivalent weight from 50 grams / mol to 580 grams / mol, or from 55 grams / mol to 570 grams / mol, or from 60 grams / mol to 565 grams / mol, or from 64 grams / mol to 560 grams / mol, all comprising the value of enumeration in each case.

[0139] In some embodiments, the second carboxylic acid-functional material comprises a carboxylic acid-functional polymer having at least three carboxylic acid groups, an Mn greater than or equal to 2000 g / mole, and an acid equivalent weight less than or equal to 580 g / mole. In some embodiments, the second carboxylic acid-functional material is a carboxylic acid-functional polymer having at least three carboxylic acid groups, an Mn greater than or equal to 2000 g / mole, and an acid equivalent weight less than or equal to 580 g / mole.

[0140] The carboxylic acid-functional polymer of the second carboxylic acid-functional material has an Mn greater than or equal to 2000 g / mole (e.g., at least 2500 g / mole or at least 3000 g / mole). In some embodiments, the carboxylic acid-functional polymer of the second carboxylic acid-functional material has an Mn less than or equal to 50,000 g / mole, or less than or equal to 20,000 g / mole, or less than or equal to 15,000 g / mole. In some further embodiments, the carboxylic acid-functional polymer of the second carboxylic acid-functional material has an Mn from 2000 g / mole to 50,000 g / mole, or from 2500 g / mole to 20,000 g / mole, or from 3000 g / mole to 15,000 g / mole, each inclusive of the recited values.

[0141] The carboxylic acid-functional polymer of the second carboxylic acid-functional material has an acid equivalent weight of less than or equal to 580 g / mole, and can have additional acid equivalent weight values ​​and ranges selected from those recited above for the second carboxylic acid-functional material. In some embodiments, the carboxylic acid-functional polymer of the second carboxylic acid-functional material has an acid equivalent weight of from 55 g / mole to 580 g / mole, or from 65 g / mole to 575 g / mole, or from 80 g / mole to 570 g / mole, or from 100 g / mole to 570 g / mole, in each case inclusive of the recited values.

[0142] In some embodiments, the carboxylic acid functional polymer of the second carboxylic acid functional material comprises residues (or monomer units) of carboxylic acid functional ethylenically unsaturated free radical polymerizable monomers, such as carboxylic acid functional (meth)acrylate monomers and / or carboxylic acid functional olefin monomers (including carboxylic acid functional vinyl monomers and / or carboxylic acid functional allyl monomers). Examples of carboxylic acid functional ethylenically unsaturated free radical polymerizable monomers from which the carboxylic acid functional polymer of the second carboxylic acid functional material can be formed include, but are not limited to, acrylic acid; methacrylic acid; 2-methacryloyloxyethylsuccinic acid; 3-butenoic acid; 6-heptenoic acid; 6-methyl 6-heptenoic acid; 2-methyl 6-heptenoic acid; 3-methyl 6-heptenoic acid; 3-ethyl 6-heptenoic acid; 5-methyl 6-heptenoic acid; 4-methyl 6-heptenoic acid; 6-octenoic acid; 2-propyl 6-heptenoic acid; and 2,4-dimethyl 6-heptenoic acid; and combinations of two or more thereof. In some embodiments, the carboxylic acid-functional polymer of the second carboxylic acid-functional material includes residues (or monomer units) of carboxylic acid-functional (meth)acrylate monomers, such as acrylic acid, methacrylic acid, 2-methacryloyloxyethylsuccinic acid, and combinations thereof.

[0143] In some embodiments, in addition to the residues of carboxylic acid-functional ethylenically unsaturated free-radically polymerizable monomers, the carboxylic acid-functional polymer of the second carboxylic acid-functional material further comprises the residues of one or more ethylenically unsaturated free-radically polymerizable monomers that do not contain carboxylic acid functional groups (or groups). Types of ethylenically unsaturated free-radically polymerizable monomers that do not contain carboxylic acid functional groups include, but are not limited to, (meth)acrylate monomers that do not contain carboxylic acid functional groups; olefin monomers that do not contain carboxylic acid functional groups (including vinyl monomers and / or allyl monomers); and combinations thereof. C1-C ... 20Examples of (meth)acrylates 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. Additional examples of ethylenically unsaturated free-radically polymerizable monomers that do not contain carboxylic acid functional groups include, but are not limited to, styrene; vinyl alcohol; allyl alcohol; vinyl chloride; allyl chloride; acrylonitrile; trimethyl(4-methyl-4-penten-1-yl)-silane; 1-octene; 1-undecene; 1-octadecene; 4-heptenal; 6-methyl-,9-decen-3-one; 5-methyl-1-heptene; vinylcyclopentane; bicyclo[2.2.1]hept-2-ene; vinylcyclohexane; 2-acrylate, cyclohexyl; 2-acrylate, bicyclo[2.2.1]hept-2-yl ester; 2-acrylate, 4-(1,1-dimethylethyl)cyclohexyl ester; 2-acrylate, tricyclo[3.3.1.1 3,7 ]dec-2-yl ester; and combinations of two or more thereof.

[0144] In some embodiments of the present invention, the second carboxylic acid-functional material is selected from (i) a carboxylic acid-functional polymer as described above having at least three carboxylic acid groups, an Mn greater than or equal to 2000 g / mole, and an acid equivalent weight less than or equal to 580 g / mole; and / or (ii) a carboxylic acid-functional material having 3 or 4 carboxylic acid groups and an acid equivalent weight less than or equal to 580 g / mole.

[0145] The carboxylic acid-functional material having 3 or 4 carboxylic acid groups and an acid equivalent weight of less than or equal to 580 g / mole from which the second carboxylic acid-functional material can be selected can have additional acid equivalent weight values ​​and ranges selected from those recited above for the second carboxylic acid-functional material, such as from 50 g / mole to 580 g / mole, or from 55 g / mole to 570 g / mole, or from 60 g / mole to 565 g / mole, or from 64 g / mole to 560 g / mole, in each case inclusive of the recited values.

[0146] Examples of carboxylic acid functional materials having 3 or 4 carboxylic acid groups and having an acid equivalent weight of less than or equal to 580 g / mol from which the second carboxylic acid functional material may be selected include, but are not limited to, citric acid; aconitic acid; homoaconitic acid; isocitric acid; homocitric acid; homoisocitric acid; hydroxycitric acid; mellitic acid; trimesic acid; agaric acid; collidinic acid; fluorocitric acid; oxalosuccinic acid; propane-1,2,3-tricarboxylic acid; 3-carboxy-cis, cis-muconic acid; N-(2-carboxyethyl)iminodiacetic acid; carboxyglutamic acid; pyrroloquinoline quinone; trachyspic acid; acid); cyclopentanetetracarboxylic acid; carboxylic acid-functional crown ethers, such as 18-crown-6-tetracarboxylic acid; furan tetracarboxylic acid; 3-hexyne-1,1,6,6-tetracarboxylic acid; cyclobutane-1,1,3,3,-tetracarboxylic acid; cyclopentane-1,2,3,4-tetracarboxylic acid; bis(cyclopropane)-2,2'-3,3'-tetracarboxylic acid; bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic acid; tricyclo[4.2.2.0(2,5)]dec-9-ene- 3,4,7,8,-tetracarboxylic acid; pentane-1,3,3,5-tetracarboxylic acid; biphenyl-3,3',5,5'-tetracarboxylic acid; 1,2,3,4-butanetetracarboxylic acid; 3,3',5,5'-tetracarboxydiphenylmethane; 1,2,3,4-butanetetracarboxylic acid; 1,2,3,4-cyclobutanetetracarboxylic acid; methanetricarboxylic acid; 1,1,1-ethanetricarboxylic acid; 1,1,2-ethanetricarboxylic acid; 2-hydroxy-1,1,1-ethanetricarboxylic acid; and combinations thereof.

[0147] In the curable photochromic coating composition of the present invention, the first carboxylic acid functional material and the second carboxylic acid functional material together provide a total carboxylic acid equivalent weight, which is the sum of the acid equivalent weight of the first carboxylic acid functional material and the acid equivalent weight of the second carboxylic acid functional material.

[0148] In some embodiments of the curable photochromic coating composition of the present invention, the second carboxylic acid-functional material provides 25% to 90% of the carboxylic acid equivalents based on the total carboxylic acid equivalents of the first carboxylic acid-functional material and the second carboxylic acid-functional material. Accordingly, and in accordance with some further embodiments of the present invention, the first carboxylic acid-functional material provides 10% to 75% of the carboxylic acid equivalents based on the total carboxylic acid equivalents of the first carboxylic acid-functional material and the second carboxylic acid-functional material.

[0149] According to some embodiments of the present invention, the curable photochromic coating composition has an equivalent ratio of (i) the oxazoline equivalents of the oxazoline-functional material to (ii) the total carboxylic acid equivalents of the first carboxylic acid-functional material and the second carboxylic acid-functional material from 0.5: 1 to 3: 1. In some further embodiments, the curable photochromic coating composition has an equivalent ratio of (i) the oxazoline equivalents of the oxazoline-functional material to (ii) the total carboxylic acid equivalents of the first carboxylic acid-functional material and the second carboxylic acid-functional material from 0.5: 1 to 3: 1, or from 0.5: 1 to 2: 1, or from 0.9: 1 to 2: 1, in each case inclusive of the recited ratios.

[0150] The curable photochromic coating composition of the present invention includes a photochromic compound, such as one or more photochromic compounds. Each photochromic compound of the curable photochromic coating composition can be selected from known classes and examples of photochromic compounds, and can include combinations or mixtures thereof, including those classes and examples of photochromic compounds as previously described herein with respect to the curable photochromic adhesive composition of the present invention. The photochromic compound can be present in the curable photochromic coating composition in a photochromic amount, including those amounts as previously described herein with respect to the curable photochromic adhesive composition of the present invention.

[0151] In some embodiments of the present invention, the curable photochromic coating composition optionally includes a solvent, such as an organic solvent. The types, examples, and amounts of organic solvents that may be optionally included in the curable photochromic composition of the present invention include, but are not limited to, those types, examples, and amounts of organic solvents previously described herein with respect to the curable photochromic adhesive composition of the present invention.

[0152] In some embodiments, the organic solvent optionally included in the curable photochromic coating composition of the present invention is selected from aprotic organic solvents, including those species and examples as previously described herein with respect to the curable photochromic adhesive composition of the present invention.

[0153] In some embodiments, the curable photochromic coating composition of the present invention optionally includes one or more additives, such as, but not limited to, waxes for flow and wetting; flow control agents, such as poly(2-ethylhexyl)acrylate; surface additives, such as polyether-modified polydimethylsiloxane; rheology control agents; leveling agents; antioxidants; light stabilizers, such as hindered amine light stabilizers; ultraviolet (UV) light absorbers; heat stabilizers; singlet oxygen quenchers; fixed hue dyes; dichroic dyes; adhesion promoters; catalysts; and combinations of two or more thereof. Examples of useful antioxidants, hindered amine light stabilizers, and UV light absorbers include, but are not limited to, those commercially available from BASF under the trade names IRGANOX and TINUVIN. When used, these optional additives may be present in an amount of up to 20% by weight based on the total solid weight (excluding solvent) of the curable photochromic coating composition.

[0154] Optional additives that may be included in the curable photochromic coating composition of the present invention include one or more fixed hue dyes, including those types, examples, and amounts as previously described herein with respect to the curable photochromic adhesive composition of the present invention.

[0155] Optional additives that may be included in the curable photochromic coating composition of the present invention include one or more dichroic dyes, including those types, examples, and amounts as previously described herein with respect to the curable photochromic adhesive composition of the present invention.

[0156] The curable photochromic coating composition of the present invention can be applied to form, for example, an applied layer by any suitable application method. The curable photochromic coating composition of the present invention can be applied to or onto a substrate by an application method including, but not limited to, a spray application method; a dip coating method; a curtain coating method; a doctor blade (or rod) application method; a spin coating application method; a jet printing method (such as an inkjet printing method, wherein the curable photochromic coating composition of the present invention is used instead of "ink"); and a combination of two or more such application methods.

[0157] The curable photochromic coating composition of the present application can be cured by any suitable method. In some additional embodiments, the curable photochromic coating composition is cured by exposure to elevated temperature (above ambient room temperature). As used herein, "cured" means formation of a three-dimensional crosslinked network through covalent bond formation, such as between the oxazoline groups of the oxazoline-functional material and the carboxylic acid groups of the first and second carboxylic acid-functional materials, as represented by the above formula (C). When cured at elevated temperature, the curable photochromic coating composition can be referred to herein as a thermoset curable photochromic coating composition. The temperature at which the thermoset curable photochromic coating composition of the present application is cured is variable and depends in part on the amount of time during which curing is performed. For some embodiments, the curable photochromic coating composition is cured at an elevated temperature from 65 °C to 204 °C, or from 70 °C to 177 °C, or from 75 °C to 140 °C for a period of time from 20 to 240 minutes.

[0158] The cured photochromic layer formed from the curable photochromic coating composition of the present application can have any suitable thickness, such as from 10 micrometers to 250 micrometers, or from 10 micrometers to 75 micrometers.

[0159] In some embodiments of the present application, the cured layer of the curable photochromic coating composition has a Fischer microhardness of at least 10 N / mm 2 (10 N / mm 2 to 110 N / mm 2 , or from 15 N / mm 2 to 105 N / mm 2 , or from 15 N / mm 2 to 100 N / mm 2 , in each case including the recited values).

[0160] According to the present application, there is further provided an optical article comprising: (A) a substrate; and (B) a layer on at least a portion of a surface of the substrate, wherein the layer is formed from the curable photochromic coating composition of the present application. In some embodiments, the layer is a cured layer. The layer can be formed from the curable photochromic coating composition of the present application on the substrate by one or more of the application and curing methods previously described herein.

[0161] In some embodiments, an optical article comprising a substrate and a layer on at least one surface of the substrate (formed from a curable photochromic coating composition of the present invention) can be selected from a display element, a window, a mirror, a liquid crystal cell element, and an ophthalmic element. Accordingly, the substrate of the optical article can be selected from a display, a window, a mirror, a liquid crystal cell element substrate, and an ophthalmic substrate. The substrate can be composed of one or more suitable materials, including but not limited to organic materials, such as organic polymer materials; glass, such as silica-based glass; metal; ceramic materials; and combinations thereof.

[0162] Non-limiting examples of organic materials useful in forming the substrates of the optical articles of the present invention include those polymeric materials as previously described herein with respect to optical articles including a layer formed from the curable photochromic adhesive composition of the present invention.

[0163] In some embodiments, the substrate may optionally include a photochromic material and / or a fixed hue dye, each of which may be selected from those classes and examples of photochromic materials and fixed hue dyes as previously described herein. The optional photochromic material / compound present in the substrate may be the same as or different from the photochromic compound of the layer formed from the curable photochromic coating composition of the present invention. The optional fixed hue dye may be the same as or different from the optional fixed hue dye of the layer formed from the curable photochromic coating composition of the present invention.

[0164] The layer formed by the curable photochromic coating composition of the present invention can be in the form of a single layer or multiple layers. When in the form of multiple layers, each layer can be prepared by a curable photochromic coating composition according to the present invention (having the same or different compositions, such as the same or different one or more photochromic compounds).

[0165] In addition to the photochromic layer formed from the curable photochromic coating composition of the present invention, the optical article may optionally include one or more additional layers, including layers recognized in the art, such as, but not limited to, a primer layer; an adhesive layer prepared from the curable photochromic adhesive composition of the present invention; an adhesive layer prepared from a composition other than the curable photochromic adhesive composition of the present invention; a protective layer (such as a hard coat); a polarizing layer; a birefringent layer; an antireflective layer; and / or another photochromic layer prepared from a composition other than the curable photochromic coating composition of the present invention.

[0166] In some embodiments, the optical article comprising a layer formed from the curable photochromic coating composition of the present invention is selected from the group consisting of corrective lenses, non-corrective lenses, magnifying lenses, protection lenses, and goggles.

[0167] The present invention may be further characterized by one or more of the following non-limiting clauses.

[0168] Item 1: A curable photochromic adhesive composition comprising:

[0169] (a) an oxazoline-functional material comprising at least two oxazoline groups;

[0170] (b) a carboxylic acid-functional material having at least two carboxylic acid groups and having an acid equivalent weight greater than or equal to 600 g / mole; and

[0171] (c) a photochromic compound,

[0172] The equivalent ratio of the oxazoline equivalent of the oxazoline functional material to the carboxylic acid equivalent of the carboxylic acid functional material is from 0.5:1 to 10:1.

[0173] Item 2: The curable photochromic adhesive composition of Item 1, wherein the oxazoline-functional material comprises the residue of a free-radically polymerizable monomer having an oxazoline functional group.

[0174] Item 3: The curable photochromic adhesive composition of Item 1 or 2, wherein the oxazoline-functional material comprises an average of at least three oxazoline groups.

[0175] Item 4: The curable photochromic adhesive composition of any of Items 1 to 3, wherein the oxazoline-functional material has an oxazoline equivalent weight of at least 70 g / mole, or at least 90 g / mole, or at least 100 g / mole, or at least 110 g / mole.

[0176] Item 5: A curable photochromic adhesive composition as described in any of Items 1 to 4, wherein the carboxylic acid is selected from carboxylic acid functional polyesters; carboxylic acid functional polycarbonates; carboxylic acid functional polyethers; carboxylic acid functional polyurethanes; carboxylic acid functional polyureas; carboxylic acid functional polyamides; carboxylic acid functional poly(siloxanes); their respective carboxylates; their copolymers; or combinations thereof.

[0177] Item 6: The curable photochromic adhesive composition of any one of Items 1 to 5, further comprising at least one additive selected from the group consisting of a flow control agent, a surface additive, a rheology control agent, a leveling agent, an antioxidant, a light stabilizer, an ultraviolet light absorber, a heat stabilizer, a singlet oxygen quencher, a fixed hue dye, a dichroic dye, an adhesion promoter, a catalyst, and a combination of two or more thereof.

[0178] Item 7: The curable photochromic adhesive composition of any of Items 1 to 6, wherein the carboxylic acid functional material (b) has an acid equivalent weight from 600 g / mole to 40,000 g / mole, or from 650 g / mole to 40,000 g / mole, or from 700 g / mole to 40,000 g / mole, or from 600 g / mole to 20,000 g / mole, or from 600 g / mole to 10,000 g / mole, in each case inclusive of the recited values.

[0179] Item 8: The curable photochromic adhesive composition of any of Items 1 to 7, wherein the carboxylic acid functional material (b) has an Mn from 1200 g / mole to 80,000 g / mole, or from 1200 g / mole to 40,000 g / mole, or from 1200 g / mole to 20,000 g / mole, in each case inclusive of the recited values.

[0180] Item 9: The curable photochromic adhesive composition according to any one of Items 1 to 8, wherein the curable photochromic adhesive composition further comprises an organic solvent.

[0181] Item 10: The curable photochromic adhesive composition of any one of Items 1 to 8, wherein the curable photochromic adhesive composition further comprises an aprotic organic solvent.

[0182] Item 11: An optical article comprising:

[0183] substrate; and

[0184] An adhesive layer on at least a portion of the surface of the substrate, wherein the adhesive layer is formed from the curable photochromic adhesive composition of any one of items 1 to 10.

[0185] Item 12: The optical article of Item 11, wherein the optical element is selected from the group consisting of a display element, a window, a mirror, a liquid crystal cell element, and an ophthalmic element.

[0186] Item 13: The optical article of Item 12, wherein the ophthalmic element is selected from the group consisting of corrective lenses, non-corrective lenses, magnifying lenses, protective lenses, and goggles.

[0187] Item 14: A curable photochromic coating composition comprising:

[0188] (a) an oxazoline-functional material comprising at least two oxazoline groups;

[0189] (b) a first carboxylic acid-functional material having at least two carboxylic acid groups and having an acid equivalent weight greater than or equal to 600 g / mole;

[0190] (c) a second carboxylic acid functional material having at least three carboxylic acid groups and having an acid equivalent weight of less than or equal to 580 grams per mole; and

[0191] (d) a photochromic compound,

[0192] wherein the equivalent ratio of oxazoline equivalents of the oxazoline functional material to the total carboxylic acid equivalents of the first and second carboxylic acid functional materials is from 0.5: 1 to 3: 1.

[0193] Clause 15: The curable photochromic coating composition of clause 14, wherein the oxazoline functional material comprises residues of a free-radically polymerizable monomer having an oxazoline functional group.

[0194] Clause 16: The curable photochromic coating composition of clause 14 or 15, wherein the oxazoline functional material comprises, on average, at least three oxazoline groups.

[0195] Clause 17: The curable photochromic coating composition of any one of clauses 14 to 16, wherein the oxazoline functional material has an oxazoline equivalent weight of at least 70 grams per mole, or at least 90 grams per mole, or at least 100 grams per mole, or at least 110 grams per mole.

[0196] Clause 18: The curable photochromic coating composition of any one of clauses 14 to 17, wherein the first carboxylic acid functional material is selected from a carboxylic acid functional polyester; a carboxylic acid functional polycarbonate; a carboxylic acid functional polyether; a carboxylic acid functional polyurethane; a carboxylic acid functional polyurea; a carboxylic acid functional polyamide; a carboxylic acid functional poly(siloxane); a carboxylic acid salt of each thereof; a copolymer thereof; or a combination thereof.

[0197] Clause 19: The curable photochromic coating composition of any one of clauses 14 or 18, wherein the second carboxylic acid functional material is selected from (i) a carboxylic acid functional polymer having at least three carboxylic acid groups, a Mn greater than or equal to 2000 grams per mole, and an acid equivalent weight less than or equal to 580 grams per mole; and / or (ii) a carboxylic acid functional material having 3 or 4 carboxylic acid groups and having an acid equivalent weight less than or equal to 580 grams per mole.

[0198] Clause 20: The curable photochromic coating composition of any one of clauses 14 to 19, wherein the second carboxylic acid functional material comprises a carboxylic acid functional polymer having at least three carboxylic acid groups, a Mn greater than or equal to 2000 grams per mole, and an acid equivalent weight less than or equal to 580 grams per mole.

[0199] Item 21: The curable photochromic coating composition of Item 20, wherein the second carboxylic acid functional polymer of the second carboxylic acid functional material comprises the residue of a carboxylic acid functional (meth)acrylate monomer.

[0200] Item 22: The curable photochromic coating composition of any of Items 14 to 21, wherein the second carboxylic acid functional material provides 25% to 90% of the carboxylic acid equivalents based on the total carboxylic acid equivalents of the first carboxylic acid functional material and the second carboxylic acid functional material.

[0201] Item 23: The curable photochromic coating composition of any one of Items 14 to 22, wherein the cured layer of the curable photochromic coating composition of any one of Items 12 to 20 has a hardness of at least 10 Newtons per square meter (N / mm 2 ) of Fisher microhardness.

[0202] Item 24: The curable photochromic coating composition of any one of Items 14 to 23, further comprising at least one additive selected from the group consisting of a flow control agent, a surface additive, a rheology control agent, a leveling agent, an antioxidant, a light stabilizer, an ultraviolet light absorber, a heat stabilizer, a singlet oxygen quencher, a fixed hue dye, a dichroic dye, an adhesion promoter, a catalyst, and a combination of two or more thereof.

[0203] Item 25: The curable photochromic coating composition of any of Items 14 to 24, wherein the first carboxylic acid functional material has an acid equivalent weight from 600 g / mole to 40,000 g / mole, or from 650 g / mole to 40,000 g / mole, or from 700 g / mole to 40,000 g / mole, or from 600 g / mole to 20,000 g / mole, or from 600 g / mole to 10,000 g / mole, in each case inclusive of the recited values.

[0204] Item 26: The curable photochromic coating composition of any of Items 14 to 25, wherein the second carboxylic acid functional material has an acid equivalent weight from 50 g / mole to 580 g / mole, or from 55 g / mole to 570 g / mole, or from 60 g / mole to 565 g / mole, or from 64 g / mole to 560 g / mole, in each case inclusive of the recited values.

[0205] Item 27: The curable photochromic coating composition of any one of Items 14 to 26, further comprising an organic solvent.

[0206] Item 28: The curable photochromic coating composition of any one of Items 14 to 26, further comprising an aprotic organic solvent.

[0207] Clause 29: An optical article comprising:

[0208] substrate; and

[0209] A layer on at least a portion of the surface of the substrate, wherein the layer is formed from the curable photochromic coating composition of any one of items 14 to 28.

[0210] Item 30: The optical article of Item 29, wherein the optical element is selected from the group consisting of a display element, a window, a mirror, a liquid crystal cell element, and an ophthalmic element.

[0211] Item 31. The optical article of Item 30, wherein the ophthalmic element is selected from the group consisting of corrective lenses, non-corrective lenses, magnifying lenses, protective lenses, and goggles.

[0212] The present invention is more particularly described in the following examples, which are intended to be illustrative only, as many modifications and variations therein will be apparent to those skilled in the art. Unless otherwise indicated, all parts and all percentages are by weight.

[0213] Examples

[0214] In Section 1 of the Examples below, the synthesis of the formulation components is provided. In Section 2, instructions for preparing a photochromic adhesive composition according to the present invention, a photochromic coating composition according to the present invention, and a comparative photochromic coating composition are provided. In Section 3, instructions for preparing multilayer photochromic adhesive samples made using the photochromic adhesive composition of Section 2 and photochromic coating samples made using the photochromic coating composition of Section 2 are provided. In Section 4, an evaluation of the properties of the samples prepared in Section 3 is provided.

[0215] Part 1: Preparation of formulation components.

[0216] Example 1

[0217] The poly(caprolactone) tetraacid material was prepared as follows.

[0218] Step-1: Preparation of poly(caprolactone)tetraol.

[0219] Pentaerythritol (6 g) and ε-caprolactone (126 g) are combined in a three-necked flask under nitrogen and heated to 150 degrees Celsius (° C.) until uniform. Tin (II) octoate (1 g) is added within 5 minutes, resulting in a temperature rise to 180° C. The flask is evacuated and purged with nitrogen three times, then stirred at 150° C. for 24 hours under nitrogen. Hexane (3×300 mL) is added to the cooled reaction mixture, and the supernatant is decanted after each addition. The resulting viscous liquid is vacuum dried at 40° C. to obtain a low melting point white solid (yield: 107 g), which is used in step 2.

[0220] Step-2: Preparation of poly(caprolactone) tetraacid.

[0221] Toluene (250 mL) and triethylamine (EtN, 5.0 mL) were added to a single-necked round-bottom flask containing the product of step 1 (107 g) and succinic anhydride (18.1 g). The suspension was heated to 80° C. and stirred for 16 hours or overnight. The reaction mixture was cooled and poured into hexane (0.5 L) over 5 minutes under stirring. The resulting solution was allowed to cool to room temperature and allowed to stand for one hour. The upper hexane layer was decanted and the crude product was vacuum dried for 4 hours to obtain a low melting point white solid (yield 125 g). 1 H NMR data confirmed the structure and determined a molecular weight of 2954 g / mol. Based on this, the product had an acid equivalent weight of 738.5 g / mol.

[0222] Example 2

[0223] The poly(caprolactone) diacid material was prepared as follows.

[0224] In a round-bottom flask, 100 grams (g) of poly (caprolactone) diol (available from Millipore Sigma, with a reported Mn of approximately 2000 g / mol), 10.51 g of succinic anhydride, 250 mL of toluene, and 5 mL of triethylamine were added. The mixture was heated to 80° C. for 16 hours. Under stirring, 250 mL of hexane was added to the cooled mixture, resulting in the formation of a precipitate. The liquid was decanted. The remaining precipitate was dissolved in 450 mL of ethyl acetate, washed twice with 50 mL of 1 N HCl, washed twice with 50 mL of brine, and concentrated under vacuum. The concentrated material was dissolved in 250 mL of ethyl acetate, washed twice with 50 mL of deionized water, and then concentrated on a rotary evaporator. 2-propanol was mixed twice and the material was concentrated again. The material was then dried under vacuum overnight to obtain 91.1 g of a white solid. 1 H NMR data were used to confirm conversion of the poly(caprolactone) diol to the diacid and to determine an Mn of approximately 2633 g / mol and an acid equivalent weight of 1316.5 g / mol for the isolated product.

[0225] Example 3

[0226] UH-100D polycarbonate diacid was prepared as follows.

[0227] Example 3 was carried out according to step 2 of Example 1 using the following reagents: UH-100D polycarbonate diol (100 g), succinic anhydride (25 g), EtN (5 ml), and toluene (250 mL). After recovery from the mixture with hexane, the product was redissolved in DCM and washed twice with 1N aqueous HCl, twice with brine, dried over anhydrous MgSO, and filtered through a short pad of celite. The concentration step yielded a low melting point white solid (120 g). Based on the acid number, the product had an acid equivalent weight of 621 g / mol.

[0228] Example 4

[0229] PH-300D polycarbonate diacid was prepared as follows.

[0230] 90g of PH-300D (a polycarbonate diol available from Ube Corporation), 6.30g of succinic anhydride, 250mL of toluene and 5mL of triethylamine were added to a round-bottom flask. The mixture was heated to 80°C for 16 hours. 250mL of hexane was added to the cooled mixture under stirring. After sedimentation under stirring was stopped, the upper layer was decanted. Another 250mL of hexane was added under stirring. The solution was allowed to settle again and the upper layer was decanted. Next, the remaining bottom layer was diluted with 250mL of ethyl acetate, washed twice with 50mL of 1NHCl, washed twice with 50mL of water, and then concentrated on a rotary evaporator. 2-propanol was mixed in and the material was concentrated again. The material was then dried under vacuum at approximately 50°C-60°C until a near constant weight was reached to obtain 88.5g of a viscous, transparent liquid. 1 H NMR data confirmed the formation of the diacid product. Based on the measured acid number, the Mn was determined to be approximately 3364 g / mol, and the acid equivalent weight was approximately 1682 g / mol.

[0231] Example 5

[0232] The di(trimethylolpropane) tetraacid material was prepared as follows.

[0233] To a round bottom flask was added 25.03 g of di(trimethylolpropane), 42.03 g of succinic anhydride, 250 mL of toluene, and 5 mL of Et3N. The mixture was heated to 80 °C for 16 hours. To the cooled mixture was added 350 mL of ethyl acetate and 150 mL of 1 N HC1. After mixing and settling, the aqueous layer was discarded. The organic layer was washed with an additional 150 mL of 1 N HC1 and then washed twice with 150 mL of deionized water. The organic layer was then concentrated on a rotary evaporator. The concentrated low melting solid was dried under vacuum at about 60 °C for 6 hours (yield 67 g with some residual solvent). Based on the acid value, the calculated acid equivalent weight was 162.66 g / mole. 1 Based on structure determination via H NMR, the di(trimethylolpropane) tetraacid compound was determined to have an acid equivalent weight of 162.66 g / mole.

[0234] Example 6

[0235] An acrylic poly(acid) material was prepared as follows.

[0236] Dipropylene glycol methyl ether acetate (“DPMA”, 65 g) was bubbled with nitrogen for 15 minutes and then heated to 125 °C. A solution of 2-methacryloyloxyethyl succinate (80.9 g), n-butyl methacrylate (50 g), 2,2’-azobis(2-methylbutyronitrile) (7.8 g), triphenylphosphite (0.65 g), and tert-dodecyl mercaptan (1.30 g) was added dropwise over 30 minutes. After stirring for 30 min, 0.3 g of 2,2’-azobis(2-methylbutyronitrile) in 5 ml DPMA was added and the solution was stirred for an additional 30 minutes. The solution was then cooled to 50 °C and slowly added to hexanes (0.5 L) with stirring. The combined solution was cooled to room temperature. The solvent was decanted to yield a viscous liquid. The crude solid product was dried under vacuum at 50 °C for 3 hours. Yield: 140 g. The weight average molecular weight (Mw) was 10,800 g / mol and the number average molecular weight (Mn) was 4800 g / mol as determined by GPC with tetrahydrofuran eluent and relative to polystyrene standards. The calculated acid equivalent weight was 559 g / mole based on the acid value.

[0237] Example 7

[0238] An acrylic poly(oxazoline-co-butyl acrylate) copolymer was prepared as follows.

[0239] Dipropylene glycol methyl ether acetate (" DPMA ", 31g) was bubbled with nitrogen for 15 minutes and then heated to 130°C. A solution of 2-isopropenyl-2-oxazoline (25g), n-butyl methacrylate (32g), 2,2'-azobis(2-methylbutyronitrile) (5.2g), triphenyl phosphite (0.29g) and tert-dodecyl mercaptan (0.57g) was added dropwise over 30 minutes. After stirring for 30min, 0.5g 2,2'-azobis(2-methylbutyronitrile) in 5ml DPMA was added and the solution was stirred for another 30 minutes. Another 0.5g 2,2'-azobis(2-methylbutyronitrile) in 5ml of DPMA was added and the solution was stirred for another 30 minutes. The solution was then cooled to 50°C and slowly added to hexane (0.5L) under stirring. The combined solution was cooled to room temperature. The solvent was decanted to produce a viscous liquid. The product was added to hexane (0.5 L) and decanted again. The crude solid product was dried under vacuum at 50°C. Yield: 45 g. Mw was 3610 g / mol and Mn was 2120 g / mol as determined by GPC using tetrahydrofuran eluent and relative to polystyrene standards. Based on 1 H NMR, calculated oxazoline equivalent weight was 292 g / mol.

[0240] Example 8

[0241] Acrylic acid poly(oxazoline-styrene) copolymer was prepared as follows.

[0242] Dipropylene glycol methyl ether acetate ("DPMA", 20g) was bubbled with nitrogen for 15 minutes and then heated to 130°C. A solution of 2-isopropenyl-2-oxazoline (25g), styrene (23.4g), 2,2'-azobis(2-methylbutyronitrile) (5.2g), triphenyl phosphite (0.25g) and tert-dodecyl mercaptan (0.5g) was added dropwise over 1 hour (the reaction was slightly exothermic). After stirring for 30 minutes, 0.5g of 2,2'-azobis(2-methylbutyronitrile) in 3ml of DPMA was added and the solution was stirred for another 30 minutes. Another 0.5g of 2,2'-azobis(2-methylbutyronitrile) in 3ml of DPMA was added and the solution was stirred for another 30 minutes. The solution was then cooled to 50°C and slowly added to hexane (0.5L) over 5 minutes under stirring. The precipitated suspension was cooled to room temperature. The solvent was decanted to produce a white solid. The resulting white solid was dried under vacuum at 50° C. for 6 hours. Yield: 56 g. Mw was 4280 g / mol and Mn was 2100 g / mol as determined by GPC using tetrahydrofuran eluent and relative to polystyrene standards. Based on 1 H NMR, calculated oxazoline equivalent weight was 294 g / mol.

[0243] Part-2

[0244] Part 2a: Preparation of Photochromic Adhesive Composition.

[0245] Examples 9-12

[0246] Photochromic Composition A was prepared using the materials listed in Table 1 by combining the materials (in the order listed) and stirring at 200 rpm at room temperature for at least 30 minutes until all materials were dissolved.

[0247] Table 1 Photochromic composition A

[0248]

[0249] _______________________

[0250] 1 The formulated blend of photochromic indenonaphthopyran dyes yields a grey color upon activation.

[0251] 2 Hindered amine light stabilizers, commercially available from BASF.

[0252] 3 Antioxidant, commercially available from BASF.

[0253] Photochromic adhesive compositions were prepared using the components listed in Table 2. For each composition, the components were combined (in the order listed) and stirred at 60 rpm at room temperature for at least 16 hours until all materials were observed to have dissolved.

[0254] Table 2

[0255] Photochromic adhesive composition

[0256]

[0257] Part 2b: Preparation of Photochromic Coating Composition.

[0258] Examples 13-16

[0259] Photochromic coating compositions using a poly(oxazoline) functional crosslinker were prepared using the components listed in Table 3. All components are listed in parts by weight. For each coating composition shown in Table 3, the components of Charge 1 were combined and heated to 50°C for a minimum of 30 minutes, or until the solids dissolved. Charge 2 was added and stirring continued at 60°C for 1-2 hours, or until the solids dissolved. The solution was cooled to room temperature, and then Charge 3 was added. The mixture was stirred at room temperature or at 40°C (if necessary) for one hour to dissolve all materials. All compositions were formulated to 58% theoretical solids.

[0260] Table 3

[0261]

[0262]

[0263] ____________________

[0264] 4 Polyether-modified dimethylpolysiloxane copolymer available from BYK-Chemie.

[0265] Comparative Examples CE17-CE20

[0266] The components used to prepare Comparative Examples CE17 through CE20 are summarized in Table 4 below. Comparative Examples CE-17 and CE-18 do not include a second carboxylic acid functional material having an acid equivalent weight less than or equal to 580 g / mole. CE-17 and CE-18 were prepared as described for Examples 13 through 16 using equimolar amounts of the carboxylic acid equivalent of the first carboxylic acid functional material and the oxazoline equivalent of the oxazoline functional material. Comparative Examples CE-19 and CE-20 do not include a first carboxylic acid functional material having an acid equivalent weight greater than or equal to 600 g / mole. CE-19 and CE-20 were prepared as described for Examples 13 through 16 using equimolar amounts of the carboxylic acid equivalent of the second carboxylic acid functional material and the oxazoline equivalent of the oxazoline functional material.

[0267] Table 4

[0268]

[0269]

[0270] Part-3

[0271] Part 3a: Preparation of Multilayer Photochromic Adhesive Specimens.

[0272] The photochromic adhesive compositions of Examples 9 to 12 are each applied to a separate transparent polyester sheet (available from Transcendia) by a pull-down technique using a 10 mil (254 micron) gap of a square metal pull-down applicator with a 3-inch (7.6 cm) coating width, which results in the formation of an intermediate adhesive layered polyester sheet. After application, these intermediate adhesive layered polyester sheets were allowed to stand at room temperature for thirty minutes. Next, these intermediate adhesive layered polyester sheets were placed in a forced-air oven at 125°C for 30 minutes. Next, a four-inch wide benchtop rubber roller (product model 4121) from Speedball was used to cover and adhere a transparent polyester sheet (from Transcendia) to the adhesive layer of each intermediate adhesive layered polyester sheet, resulting in the formation of three intermediate samples. Each three intermediate sample was then placed in a 125°C forced-air oven between two thin metal sheets for thirty minutes, then cooled to room temperature, resulting in the formation of a cured three-layer sample. The cured three-layer samples were cut into 2 inch x 2 inch (5.1 cm x 5.1 cm) multilayer photochromic adhesive coupons for photochromic performance evaluation as described below.

[0273] Part 3b: Preparation of Photochromic Coating Samples

[0274] The compositions of Examples 13 to 16 and Comparative Examples 17 to 20 were applied to Coated Polycarbonate flat lenses, each having a diameter of 76 mm. Prior to coating, each lens was corona treated using a Tantec device with 70 kV and 1000 W settings. Approximately 1-2 mL of each composition was dispensed onto the substrate and then spun for 8 seconds (for all Examples 13 to 16 and Comparative Examples CE17 to CE20) at a speed sufficient to deposit 0.3-0.35 g of wet coating (58% solids) onto the lens.

[0275] Part-4

[0276] Part 4a. Photochromic Performance Testing of Multilayer Photochromic Adhesive Samples.

[0277] The photochromic properties of the multilayer photochromic adhesive samples prepared as described in Section 3a were measured on the optical bench of the Advanced Platform for Measuring Photochromism ("A-BMP"). The multilayer photochromic adhesive samples were first exposed to light with a maximum intensity near 365 nm for 5 minutes at a distance of 10 cm. The integrated UVA irradiance of this light was measured to be 7.7 watts per square meter using a Goosch & Housego OL 756 spectroradiometer with an OL 86-T cosine receiver. Next, the multilayer photochromic adhesive samples were heated to 70°C and maintained at that temperature while the samples were exposed to an F17T8 yellow fluorescent lamp at a distance of 10 cm for 25 minutes to deactivate the photochromic material. The fluorescent lamp irradiance on the sample was measured to be 9 Klux using the OL 756. The multilayer photochromic adhesive samples were then kept in a dark environment at 21°C to 24°C for at least one hour before being tested on the optical bench.

[0278] The optical bench was equipped with two 150W Newport Model #66902 xenon arc lamps, positioned at right angles to each other, with associated Newport 69907 digital controllers. The first lamp was directed through a 3mm SCHOTT KG-2 bandpass filter and appropriate neutral density filters to obtain the desired UV and visible light spectra. The second lamp was directed through a 3mm SCHOTT KG-2 bandpass filter, a SCHOTT GG400 short-wavelength cutoff filter, and appropriate neutral density filters to provide supplemental visible light. A 2-inch × 2-inch (5.1 cm × 5.1 cm) 50% polka-dot beamsplitter was placed at a 45° angle relative to each lamp to mix the two beams. The intensity of the beams was adjusted using neutral density filters and the voltage to the xenon arc lamps. Proprietary software (PTSoft Version 5.3) was used to control timing, irradiance, gas cell and sample temperature, shutter, filter selection, and response measurement. During the test, the optical bench was maintained at 23°C. The combined beam from the xenon arc lamp used to activate the specimen was adjusted to 6.7 watts / m² UVA integrated at 315-380 nm and 50 Klux illuminance integrated at 380-780 nm. The sample cell was equipped with a quartz window and the specimen was located in the center of the holder. The temperature in the cell was controlled by proprietary software with an AirJet XE custom-connected to a bubbling water bath to deliver air at 23°C ± 0.1°C with 50% relative humidity. The photochromic response of the specimen is measured using a Model MCS601 spectrophotometer equipped with a fiber optic cable for transmitting light from a tungsten-halogen lamp. A collimated light beam from the lamp is positioned perpendicular to the specimen, passing through the sample and into a receiving fiber optic cable connected to the spectrophotometer. An activating beam from a xenon arc lamp is incident on the specimen at a 30° angle and positioned to overlap with the monitoring light to form two concentric circles.

[0279] Measure the initial, unactivated transmittance with the xenon arc lamp shutter closed. Then open the shutter and monitor the change at selected time intervals. Determine the change in optical density of the specimen using the following formula:

[0280] ΔOD=log 10 (T b / T a ),

[0281] Where T b is the percent transmittance in the whitish state, and T a is the percent transmittance in the activated state. ΔOD measurements are based on photopic optical density. In the test, the shutter to the activating light was opened for 15 minutes and then closed to observe the activation and deactivation of the multilayer photochromic adhesive sample. 1 / 2 is the time (in seconds) for ΔOD to reach half of the activated ΔOD value after the shutter closes after 15 minutes of activation. 1 / 2 The time between two recorded data points, then the value is given by T 1 / 2 Determined by linear interpolation between the nearest data points on each side of time.

[0282] Part 4b. Photochromic Performance Testing of Photochromic Coating Samples.

[0283] A set of samples from Examples 13 to 16 and Comparative Examples CE17 to CE20 were further corona treated as described above and spin-coated with a protective coating: Hi-Gard 1080S from PPG Industries. Each sample was then heat cured at 105° C. for 3 hours. The samples were then tested for photochromic properties on a photochromic measurement platform (“BMP”) manufactured by Essilor, Ltd. France, as described above for the multilayer photochromic adhesive samples in Section 4a.

[0284] Part 4c: Microhardness testing of photochromic coating specimens.

[0285] A second set of specimens from Examples 13 to 16 and Comparative Examples CE17 to CE20 were subjected to an additional heat cure at 105° C. for 3 hours and hardness was measured using a Fischerscope HCV, Model H100SMC (available from Fischer Technology, Inc.). Hardness was measured at a penetration depth of 2 μm after a 100 millinewton load for 15 seconds. Each specimen was measured at least twice, and the resulting data were averaged and reported in Table 6.

[0286] Part 4d. Photochromic performance test results of multilayer photochromic adhesive samples.

[0287] The photochromic performance test results of the multilayer photochromic adhesive samples are summarized in Table 5.

[0288] Table 5

[0289]

[0290] Fifteen minutes after activation, all adhesive compositions showed good activated darkness of 0.76 to 0.81 ΔOD. All adhesive compositions also showed fast fading speed, T 1 / 2 29 to 47 seconds.

[0291] Section 4e. Test results of photochromic coating samples.

[0292] The microhardness and photochromic performance results of the photochromic coating samples are summarized in Table 6.

[0293] Table 6

[0294]

[0295] As shown in Table 6, the photochromic coating compositions of the present invention having both the first and second carboxylic acid materials (Examples 13 to 16) exhibited good photochromic performance and acceptable hardness. In contrast, comparative photochromic coating compositions that did not include a first carboxylic acid functional material having an acid equivalent weight greater than or equal to 600 g / mole provided very hard films, but faded very slowly (CE-19 and CE-20). Comparative photochromic coating compositions that did not include a second carboxylic acid functional material having an acid equivalent weight less than or equal to 580 g / mole showed good fading speed, but at the expense of coating hardness (CE-17 and CE-18).

[0296] While the present invention has been described with reference to specific details of particular embodiments thereof, it is not intended that these details be considered limitations on the scope of the invention except to the extent that they are included in the appended claims.

Claims

1. A curable photochromic adhesive composition comprising: (a) an oxazoline-functional material comprising at least two oxazoline groups, wherein the oxazoline-functional material comprises the residue of a free-radically polymerizable monomer having an oxazoline-functional group; (b) a carboxylic acid-functional material having at least two carboxylic acid groups and having an acid equivalent weight greater than or equal to 600 g / mole; and (c) a photochromic compound, wherein the equivalent ratio of the oxazoline equivalents of the oxazoline functional material to the carboxylic acid equivalents of the carboxylic acid functional material is from 0.5:1 to 10:

1.

2. The curable photochromic adhesive composition according to claim 1, wherein The oxazoline-functional material comprises an average of at least three oxazoline groups.

3. The curable photochromic adhesive composition according to claim 1, wherein The carboxylic acid is selected from: Carboxylic acid functional polyesters, Carboxylic acid functional polycarbonate, Carboxylic acid functional polyether, Carboxylic acid functional polyurethane, Carboxylic acid functional polyurea, Carboxylic acid functional polyamide, Carboxylic acid functional poly(siloxane), their respective carboxylates, its copolymers, or Its combination.

4. An optical product comprising: substrate; as well as An adhesive layer on at least a portion of the surface of the substrate, wherein the adhesive layer is formed from the curable photochromic adhesive composition according to any one of claims 1 to 3.

5. A curable photochromic coating composition comprising: (a) an oxazoline-functional material comprising at least two oxazoline groups, wherein the oxazoline-functional material comprises the residue of a free-radically polymerizable monomer having an oxazoline-functional group; (b) a first carboxylic acid-functional material having at least two carboxylic acid groups and having an acid equivalent weight greater than or equal to 600 g / mole; (c) a second carboxylic acid-functional material having at least three carboxylic acid groups and having an acid equivalent weight less than or equal to 580 g / mole; as well as (d) a photochromic compound, wherein the equivalent ratio of the oxazoline equivalents of the oxazoline functional material to the total carboxylic acid equivalents of the first carboxylic acid functional material and the second carboxylic acid functional material is from 0.5:1 to 3:

1.

6. The curable photochromic coating composition according to claim 5, wherein The oxazoline-functional material comprises an average of at least three oxazoline groups.

7. The curable photochromic coating composition according to claim 5, wherein The first carboxylic acid functional material is selected from: Carboxylic acid functional polyesters, Carboxylic acid functional polycarbonate, Carboxylic acid functional polyether, Carboxylic acid functional polyurethane, Carboxylic acid functional polyurea, Carboxylic acid functional polyamide, Carboxylic acid functional poly(siloxane), their respective carboxylates, its copolymers, or Its combination.

8. The curable photochromic coating composition according to claim 5, wherein: The second carboxylic acid-functional material comprises a carboxylic acid-functional polymer having at least three carboxylic acid groups, an Mn greater than or equal to 2000 g / mole, and an acid equivalent weight less than or equal to 580 g / mole.

9. The curable photochromic coating composition according to claim 8, wherein The second carboxylic acid-functional polymer of the second carboxylic acid-functional material comprises the residue of a carboxylic acid-functional (meth)acrylate monomer.

10. The curable photochromic coating composition according to claim 5, wherein The second carboxylic acid-functional material provides 25% to 90% of the carboxylic acid equivalents based on the total carboxylic acid equivalents of the first carboxylic acid-functional material and the second carboxylic acid-functional material.

11. The curable photochromic coating composition according to claim 5, wherein: The cured layer of the curable photochromic coating composition has a thermal conductivity of at least 10 N / mm 2 Fisher microhardness.

12. An optical product comprising: substrate; as well as A layer on at least a portion of the surface of the substrate, wherein the layer is formed from the curable photochromic coating composition of any one of claims 5 to 11.

13. The optical article according to claim 12, wherein: The optical article is selected from the group consisting of display elements, windows, mirrors, liquid crystal cell elements, and ophthalmic elements.

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