A curable photochromic composition containing an isocyanate and an imine functional component

Abstract

The present invention relates to a curable photochromic composition comprising: (a) a photochromic compound; (b) a polyisocyanate containing at least two isocyanate groups; and (c) a reactive component having at least two reactive groups that are each reactive with the isocyanate groups of the polyisocyanate. Each reactive group of the reactive component is independently selected from primary amines and imines, provided that at least one reactive group of the reactive component is selected from imines. The curable photochromic composition further comprises (d) a non-reactive component that does not contain a functional group reactive with the polyisocyanate and the reactive component. The present invention also relates to an article comprising a substrate and a photochromic layer on at least one surface of the substrate, wherein the photochromic layer is formed from the curable photochromic composition of the present invention.

Description

Technical Field

[0001] The present invention relates to a curable photochromic composition comprising a photochromic compound, a polyisocyanate, a reactive component having an imine group and optionally a primary amine group, and a non-reactive component that does not contain a functional group reactive with the polyisocyanate and the reactive component.

Background Art

[0002] In response to a specific wavelength of electromagnetic radiation (or "actinic radiation"), photochromic compounds such as indeno-fused naphthopyrans typically undergo a conversion from one form or state to another, with each form having a characteristic or distinguishable absorption spectrum corresponding thereto. Typically, when exposed to actinic radiation, many photochromic compounds are converted from a closed form corresponding to the unactivated (or faded, e.g., substantially colorless) state of the photochromic compound to an open form corresponding to the activated (or colored) state of the photochromic compound. In the absence of exposure to actinic radiation, such photochromic compounds revert reversibly from the activated (or colored) state to the unactivated (or faded) state. Compositions containing or having applied thereto a photochromic compound (e.g., in the form of a photochromic coating composition) and articles such as optical lenses typically exhibit colorless (e.g., transparent) and colored states corresponding to the colorless and colored states of the photochromic compound contained therein or applied thereto.

[0003] A photochromic compound can be used in a curable composition to form a cured layer such as a cured film or sheet that is photochromic, for example. In a cured photochromic film such as a cured photochromic coating, it is typically desirable to provide a combination of hardness and photochromic performance. Generally, the reaction rate for the reversible conversion of a photochromic compound between a closed form (deactivated / colorless) and an open form (activated / colored) is faster in a soft matrix but slower in a hard matrix (of the cured film in which the photochromic compound is present). A cured photochromic film having a soft matrix typically has a reduced hardness, while those having a hard matrix typically have an increased hardness.

Summary of the Invention

Problems to be Solved by the Invention

[0004] It would be desirable to develop a curable photochromic composition that provides a cured photochromic layer having improved hardness without a decrease in photochromic performance.

Means for Solving the Problems

[0005] According to the present invention, there is provided a curable photochromic composition comprising: (a) a photochromic compound; (b) a polyisocyanate containing at least two isocyanate groups; (c) a reactive component containing at least two reactive groups each reactive with an isocyanate group, wherein each reactive group of the reactive component is independently selected from a primary amine and an imine; and (d) a non-reactive component. The non-reactive component does not contain a functional group reactive with the polyisocyanate and the reactive component.

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

[0007] The features that characterize the present invention are pointed out in detail in the claims, which are appended to and form a part of the present disclosure. These and other features of the present invention, the advantages of its operation, and the particular objects obtained by its use will be more particularly understood from the following detailed description in which non-limiting embodiments of the present invention are illustrated and described.

DETAILED DESCRIPTION OF THE INVENTION

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

[0009] Unless otherwise indicated, all ranges or ratios disclosed herein are to be understood to encompass any and all values and subranges or subratios subsumed therein. For example, a stated range or ratio of "1 to 10" encompasses any value between the stated end values (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10); as well as subranges (and including) between the lowest value of 1 and the highest value of 10, i.e., without limitation, 1 to 6.1, 3.5 to 7.8, and 5.5 to 10, etc., all subranges or subratios starting with a lowest value of 1 or more and ending with a highest value of 10 or less are to be considered to be included.

[0010] As used herein, unless otherwise indicated, the left-to-right representation of a linking group, such as a divalent linking group, encompasses other suitable directions, such as, for example, but not limited to, a right-to-left direction. For purposes of non-limiting illustration, the left-to-right representation of a divalent linking group

Chemical Formula

Chemical formula

[0011] Unless otherwise indicated in the examples, it should be understood that all numbers representing amounts of components, reaction conditions, etc. used in this specification and the claims are modified by the term "about" in all cases.

[0012] As used herein, values of polymer molecular weights such as weight-average molecular weight (Mw) and number-average molecular weight (Mn) are determined by gel permeation chromatography (GPC) using an appropriate standard such as polystyrene standard.

[0013] As used herein, the value of the polydispersity index (PDI) represents the ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn) of the polymer (i.e., Mw / Mn).

[0014] As used herein, the term "polymer" means a homopolymer (e.g., prepared from a single monomer species), a copolymer (e.g., prepared from at least two monomer species), and a graft polymer.

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

[0016] As used herein, the term "photochromic" and similar terms such as "photochromic compound" mean having an absorption spectrum of at least visible light that changes in response to at least the absorption of actinic radiation. Further, as used herein, the term "photochromic material" means any material that is adapted to exhibit photochromic properties (such as being adapted to have an absorption spectrum of at least visible light that changes in response to at least the absorption of actinic radiation) and includes at least one photochromic compound.

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

[0018] As used herein, the term "photochromic material" includes thermally reversible photochromic materials and compounds and non-thermally reversible photochromic materials and compounds. As used herein, the term "thermally reversible photochromic compound / material" means a compound / material capable of converting from a first state, such as a "transparent state", to a second state, such as a "colored state", in response to actinic radiation and reverting to the first state in response to thermal energy. As used herein, the term "non-thermally reversible photochromic compound / material" means a compound / material capable of converting from a first state, such as a "transparent state", to a second state, such as a "colored state", in response to actinic radiation and reverting to the first state in response to actinic radiation having a wavelength (or wavelengths) substantially the same as the absorption(s) of the colored state.

[0019] As used herein to modify the term "state", the terms "first" and "second" are not intended to refer to any particular order or time series, but rather to refer to two different states or properties. For purposes of non-limiting illustration, the first and second states of a photochromic compound may differ with respect to at least one optical property, e.g., but not limited to, absorption of visible light and / or UV irradiation. Thus, according to various non-limiting embodiments disclosed herein, the photochromic compounds of the present invention may have different absorption spectra in each of the first and second states. For example, but not limiting the present disclosure, the photochromic compounds of the present invention may be transparent in the first state and colored in the second state. Alternatively, the photochromic compounds of the compositions of the present invention may have a first color in the first state and a second color in the second state.

[0020] As used herein, the term "optical" means related to or associated with light and / or vision. For example, according to various non-limiting embodiments disclosed herein, an optical article or element or device can be selected from ophthalmic articles, elements and devices, display articles, elements and devices, windows, mirrors and active and passive liquid crystal cell articles, elements and devices.

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

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

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

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

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

[0026] As used herein, spatial or directional terms such as "left," "right," "inner," "outer," "upper," "lower," etc. relate to various orientations of the present invention, such as articles and multilayer articles of the present invention, which may be further described herein. However, it should be understood that the present invention can assume various alternative orientations other than those described herein, and thus such terms should not be considered limiting.

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

[0028] Without limitation, all documents such as issued patents and patent applications referred to herein shall be considered to be "incorporated by reference" in their entirety, unless otherwise indicated.

[0029] As used herein, the description of a "linear or branched" group, such as a linear or branched alkyl, herein refers to a methylene group or a methyl group; a linear group, such as a linear C2-C 20 alkyl group; and a properly branched group, such as a branched C3-C 20 alkyl group, etc.

[0030] As used herein, the term "alkyl" means a linear or branched, cyclic or acyclic C1-C 25 alkyl. Examples of linear or branched alkyl include C1-C 25 alkyl, such as C1-C 20 alkyl, such as C2-C 10 alkyl, such as C1-C 12 alkyl, such as C1-C6 alkyl. Examples of alkyl groups from which various alkyl groups of the present invention can be selected include, but are not limited to, those further listed herein. The alkyl group may include a "cycloalkyl" group. As used herein, the term "cycloalkyl" means a properly cyclic group, such as, but not limited to, C3-C 12 cycloalkyl (including, but not limited to, cyclic C3-C10 It means a group including an alkyl or cyclic C5-C7 alkyl, etc. Examples of the cycloalkyl group include, but are not limited to, those further listed in this specification. As used herein, the term "cycloalkyl" refers to a bridged-ring polycycloalkyl group (or bridged-ring polycyclic alkyl group), such as, but not limited to, bicyclo[2.2.1]heptyl (or norbornyl) and bicyclo[2.2.2]octyl, etc., and a fused-ring polycycloalkyl group (or fused-ring polycyclic alkyl group), such as, but not limited to, octahydro-1H-indenyl and decahydronaphthalenyl, etc.

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

[0032] The descriptions, types and examples given herein for an alkyl group, cycloalkyl group, heterocycloalkyl group, haloalkyl group, etc. are also applicable to an alkane group, cycloalkane group, heterocycloalkane group, haloalkane group, etc., such as, but not limited to, a polyvalent alkane group, such as a polyvalent alkane linking group like a divalent alkane linking group, etc.

[0033] As used herein, the terms "aryl" and related terms such as "aryl group" mean aromatic cyclic monovalent hydrocarbon groups. As used herein, the terms "aromatic" and related terms, such as "aromatic group", mean cyclic conjugated hydrocarbons having significantly higher stability than the hypothetical delocalized structure (due to delocalization of π electrons). Examples of aryl groups include C6-C 14 aryl groups such as, but not limited to, phenyl, naphthyl, phenanthryl, and anthracenyl.

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

[0035] As used herein, the term "aralkyl" means, but is not limited to, C6-C 24 aralkyl such as, for example, C6-C 10 aralkyl, etc., including but not limited to, alkyl groups substituted by an aryl group. Examples of aralkyl groups include, but are not limited to, benzyl and phenethyl.

[0036] Representative alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, and decyl. Representative alkenyl groups include, but are not limited to, vinyl, allyl, and propenyl. Representative alkynyl groups include, but are not limited to, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, and 2-butynyl. Representative cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl.

[0037] As used herein, the terms "halo" and related terms such as "halo group", "halo substituent", "halogen group", and "halogen substituent" mean a singly-bonded halogen group such as -F, -Cl, -Br, and -I.

[0038] As used herein, the description of "halo-substituted" and related terms (e.g., but not limited to, haloalkyl group, haloalkenyl group, haloalkynyl group, haloaryl group, and halo-heteroaryl group, etc.) means that at least one and up to all of the available hydrogen groups are substituted by a halo group, e.g., but not limited to, F, Cl, or Br, etc. The term "halo-substituted" includes "perhalo-substituted".

[0039] As used herein, "at least one of" is synonymous with "one or more of" regardless of whether the elements are listed conjunctively or disjunctively. 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, only A, or only B, or only C, or A and B, or A and C, or B and C, or all of A, B, and C.

[0040] As used herein, "selected from" is synonymous with "chosen from", whether the elements are listed conjunctively or disjunctively. 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, only A, or only B, or only C, or A and B, or A and C, or B and C, or all of A, B, and C.

[0041] As used herein, and according to some embodiments, the terms "ester" and related terms such as "ester group" and "ester substituent" with respect to the compounds and components of the invention and the groups and substituents of various groups mean a carboxylic acid ester group represented by -C(O)OR, where R is selected from the groups described below other than hydrogen.

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

[0043] As used herein, and according to some embodiments, the terms "urethane" and related terms such as "urethane group" and "urethane substituent" with respect to the compounds and components of the invention and the groups and substituents of various groups include a substance represented by -OC(O)N(R)(H) or -N(H)C(O)OR, wherein in each case R is independently selected from the groups described below other than hydrogen.

[0044] Unless otherwise specified, each R group of the aforementioned ketone, ester (carboxylic acid ester), carbonate, and urethane group is independently selected in each case from hydrogen, alkyl, haloalkyl, perhaloalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and combinations thereof (including the types and examples listed earlier in this specification).

[0045] The curable photochromic composition of the present invention contains a polyisocyanate having at least two isocyanate groups. In some embodiments, the polyisocyanate contains 2 to 10 isocyanate groups, or 2 to 8 isocyanate groups, or 2 to 6 isocyanate groups, or 2 to 5 isocyanate groups, or 2 to 4 isocyanate groups. In some embodiments, the polyisocyanate contains at least one of a linear or branched aliphatic polyisocyanate, an alicyclic polyisocyanate, their biurets, their allophanates, their isocyanurates, and combinations thereof.

[0046] Examples of linear or branched aliphatic polyisocyanates from which the polyisocyanate of the curable photochromic composition can be selected include, but are not limited to, 1,2 - diisocyanatoethane (ethylene diisocyanate); tetramethylene - 1,4 - diisocyanate; hexamethylene - 1,6 - diisocyanate; 2,2,4 - trimethylhexane - 1,6 - diisocyanate; 2,4,4 - trimethylhexane - 1,6 - diisocyanate; and dodecane - 1,12 - diisocyanate.

[0047] Examples of alicyclic polyisocyanates from which the polyisocyanate of the curable photochromic composition can be selected include, but are not limited to, cyclobutane-1,3-diisocyanate; cyclohexane-1,3-diisocyanate; cyclohexane-1,4-diisocyanate; methylcyclohexyldiisocyanate; hexahydrotoluene-2,4-diisocyanate; hexahydrotoluene-2,6-diisocyanate; hexahydrophenylene-1,3-diisocyanate; hexahydrophenylene-1,4-diisocyanate; perhydrodiphenylmethane-2,4'-diisocyanate; perhydrodiphenylmethane-4,4'-diisocyanate; and norbornene diisocyanate.

[0048] The polyisocyanate of the curable photochromic composition, in some embodiments, has an isocyanate equivalent weight of 95 to 500 g / mol, or 150 to 400 g / mol, or 150 to 350 g / mol.

[0049] According to some embodiments, at least some of the isocyanate groups of the polyisocyanate are reversibly blocked (or capped) with a blocking agent (or capping agent).

[0050] As used herein, the term "reversibly blocked" with respect to the isocyanate groups of a polyisocyanate and related terms such as "reversibly capped" mean that isocyanate group is blocked or capped with a blocking or capping agent. For example, under controlled conditions such as exposure to elevated temperatures, the blocking / capping agent separates (or de-blocks or decaps) from the blocked isocyanate group, enabling the free / uncapped isocyanate group to react with the reactive groups of reactive components to form covalent bonds. After de-blocking or decapping from the blocked isocyanate groups of the polyisocyanate, the blocking / capping agent can volatilize from the curable photochromic composition (before the composition becomes glassy) and / or can remain in the curable photochromic composition, for example, in a plasticizer. In some embodiments, it is desirable that the blocking / capping agent does not form bubbles or voids in the curable photochromic composition and / or does not overly plasticize the curable photochromic composition after de-blocking / decapping.

[0051] As used herein and according to some embodiments, "at least some of the isocyanate groups of the polyisocyanate are independently and reversibly blocked with a blocking agent" means that at least 10%, or at least 20%, or at least 25%, or at least 50%, or at least 75%, or at least 90%, or at least 95%, or 100% of the isocyanate groups are reversibly blocked.

[0052] The blocking / capping groups for the blocked isocyanate groups of the polyisocyanate can, in some embodiments, be selected from hydroxy-functional compounds, 1H-azoles, lactams, ketoximes, and mixtures thereof. The types of hydroxy-functional compounds include, but are not limited to, aliphatic, alicyclic, or aromatic alkyl monoalcohols or phenols. Specific examples of hydroxy-functional compounds useful as blocking / capping agents include, but are not limited to, lower aliphatic alcohols such as methanol, ethanol, and n-butanol; alicyclic alcohols such as cyclohexanol and tetrahydrofuran; aromatic-alkyl alcohols such as phenylcarbinol and methylphenylcarbinol; and glycol ethers such as ethylene glycol butyl ether, diethylene glycol butyl ether, ethylene glycol methyl ether, and propylene glycol methyl ether. In some embodiments, the hydroxy-functional blocking / capping groups include, but are not limited to, phenols, examples of which include phenol itself, as well as substituted phenols such as cresol, nitrophenol, and p-hydroxymethylbenzoate.

[0053] Examples of 1H-azoles useful as blocking / capping groups include, but are not limited to, 1H-imidazole, 1H-pyrazole, 1H-dialkylpyrazoles (e.g., 1H-3,5-dimethylpyrazole and 1H-2,5-dimethylpyrazole), 1H-1,2,3-triazole, 1H-1,2,3-benzotriazole, 1H-1,2,4-triazole, 1H-5-methyl-1,2,4-triazole, and 1H-3-amino-1,2,4-triazole.

[0054] Useful ketoximes as blocking / capping groups include those prepared from aliphatic or alicyclic ketones. Examples of ketoxime capping groups include, but are not limited to, 2-propanone oxime (acetone oxime), 2-butanone oxime (also referred to as methyl ethyl ketoxime), 2-pentanone oxime, 3-pentanone oxime, 3-methyl-2-butanone oxime, 4-methyl-2-pentanone oxime, 3,3-dimethyl-2-butanone oxime, 2-heptanone oxime, 3-heptanone oxime, 4-heptanone oxime, 5-methyl-3-heptanone oxime, 2,6-dimethyl-4-heptanone oxime, cyclopentanone oxime, cyclohexanone oxime, 3-methylcyclohexanone oxime, 3,3,5-trimethylcyclohexanone oxime, and 3,5,5-trimethyl-2-cyclohexen-5-one oxime.

[0055] Examples of lactam capping groups include, but are not limited to, ε-caprolactam and 2-pyrrolidinone. Other suitable capping groups include morpholine, 3-aminopropylmorpholine, and N-hydroxyphthalimide.

[0056] In some embodiments of the present invention, the blocked isocyanate groups of the polyisocyanate are each independently blocked with a blocking / capping agent selected from methyl ethyl ketoxime, pyrazole (more specifically, 1H-pyrazole), and dialkylpyrazole (more specifically, 1H-dialkylpyrazole, such as 1H-3,5-dimethylpyrazole and 1H-2,5-dimethylpyrazole).

[0057] The polyisocyanate is present in some embodiments in the curable photochromic composition of the present invention in an amount of 40 weight percent to 90 weight percent, or 45 weight percent to 90 weight percent, or 50 weight percent to 85 weight percent, in each case based on the total resin solids weight.

[0058] As used herein, and with respect to the curable photochromic composition, the terms "total weight of resin solids", and similar terms such as "total resin solid weight" and "total resin solids", mean the total weight of the polyisocyanate, reactive components and non-reactive components, and unless otherwise stated, do not include the weight of the photochromic compound(s) and other optional additives.

[0059] In some embodiments of the curable photochromic composition of the present invention, the molar ratio of the number of moles of isocyanate groups of the polyisocyanate to the total number of moles of reactive groups of the reactive components is 1:1 to 20:1, or 1:1 to 18:1, or 1:1 to 17:1, or 1:1 to 16.5:1.

[0060] The curable photochromic composition of the present invention includes a reactive component having at least two reactive groups that are each reactive with the isocyanate groups of the polyisocyanate compound. The reactive groups of the reactive component are each independently selected from primary amines (-NH2) and imines in each case. At least one reactive group of the reactive component is selected from imines. In some embodiments, the reactive component has 2 to 25 reactive groups, or 3 to 20 reactive groups, or 4 to 15 reactive groups.

[0061] According to some embodiments, the imine group of the reactive component is represented by the following formula (B).

Chemical formula

[0062] Regarding formula (B), according to some embodiments, R 1 and R 2 are each independently selected from hydrogen (H), linear or branched C1-C 20 alkyl, and cyclic C3-C 10 alkyl, or R 1 and R 2 together form a cyclic alkyl group having 3 to 10 carbon atoms in the ring. In some embodiments, R1 and R 2 at least one of which is other than hydrogen (H). In some further embodiments, R 1 and R 2 in each case is independently other than hydrogen (H). Without intending to be bound by any theory, the reaction between the imine group of the reactive component and the isocyanate group of the polyisocyanate as represented by formula (B) is thought to result in the formation of a cyclic bond between the polyisocyanate and the reactive component.

[0063] The reactive component in some embodiments includes at least one of an aliphatic polyether, an aliphatic polyester, an aliphatic polycarbonate, an aliphatic polyethyleneimine, and / or an aliphatic polyurethane, each of which independently has at least two reactive groups selected independently from primary amines and imines in each case, provided that at least one reactive group is selected from imines.

[0064] The aliphatic polyether having at least two reactive groups contains a plurality of ether bonds (-O-) and does not contain an aromatic group. In some embodiments, the aliphatic polyether independently has a linear or branched C2-C 20 alkyl bond and / or a C3-C 10It contains a cycloalkyl bond. The aliphatic polyether having at least two reactive groups can be prepared according to methods recognized in the art. In some embodiments, by reacting a hydroxyl-functional polyether having at least two hydroxyl groups with aziridine, an amine-functional polyether intermediate having at least two primary amine groups is formed. Next, at least a part of the primary amines of the amine-functional polyether intermediate can be reacted with one or more ketones, thereby forming a polyether having an imine group and optionally a primary amine group. In some embodiments, the aliphatic polyether having at least two reactive groups has a Mn of 175 g / mol to 20,000 g / mol, or 200 g / mol to 15,000 g / mol, or 200 g / mol to 10,000 g / mol.

[0065] The aliphatic polyester having at least two reactive groups contains a plurality of carboxylic acid ester bonds (-C(O)-O-) and does not contain an aromatic group. In some embodiments, the aliphatic polyester independently has a linear or branched C2 to C between and / or extending from each carboxylic acid ester bond. 20 alkyl bond and / or C3 to C 10It contains a cycloalkyl bond. The aliphatic polyester having at least two reactive groups can be prepared according to methods recognized in the art. In some embodiments, by reacting a hydroxyl-functional polyester having at least two hydroxyl groups with aziridine, an amine-functional polyester intermediate having at least two primary amine groups is formed. Next, at least a part of the primary amines of the amine-functional polyester intermediate can be reacted with one or more ketones, thereby forming a polyester having an imine group and optionally a primary amine group. According to some further embodiments, as described in Bioconjugate Chemistry, 2002, 13(5), pp1159 - 1162, the hydroxyl-terminated aliphatic polyester undergoes a condensation reaction with an N-benzyloxycarbonyl amino acid in the first step, followed by catalytic hydrogenation in the second step, thereby forming a primary amine-functional aliphatic polyester intermediate. In the third step, at least a part of the primary amines of the primary amine-functional aliphatic polyester intermediate is reacted with one or more ketones to form an aliphatic polyester having an imine group and optionally a primary amine group. In some embodiments, the aliphatic polyester having at least two reactive groups has a Mn of 210 g / mol to 20,000 g / mol, or 250 g / mol to 15,000 g / mol, or 250 g / mol to 10,000 g / mol.

[0066] The aliphatic polycarbonate having at least two reactive groups contains a plurality of carbonate bonds (-O-C(O)-O-) and does not contain an aromatic group. In some embodiments, the aliphatic polycarbonate independently has a linear or branched C2 - C between and / or extending from each carbonate bond. 20 alkyl bond and / or C3 - C 10It contains a cycloalkyl bond. An aliphatic polycarbonate having at least two reactive groups can be prepared according to methods recognized in the art. In some embodiments, by reacting a hydroxyl-functional polycarbonate having at least two hydroxyl groups with aziridine, an amine-functional polycarbonate intermediate having at least two primary amine groups is formed. Next, at least a portion of the primary amines of the amine-functional polycarbonate intermediate can be reacted with one or more ketones, thereby forming a polycarbonate having imine groups and optionally primary amine groups. In some further embodiments, as described in Macromolecules, 1997, 30, 6074, an aliphatic polycarbonate having at least two reactive groups is prepared in a first step by ring-opening of trimethylene carbonate in the presence of a nitrophenyl-functional initiator, followed by a reduction reaction in a second step that results in the formation of primary amines. In a third step, at least a portion of the primary amine groups of the primary amine-functional aliphatic polycarbonate intermediate is reacted with one or more ketones to form an aliphatic polycarbonate having imine groups and optionally primary amine groups. In some embodiments, the aliphatic polycarbonate having at least two reactive groups has an Mn of 275 g / mol to 20,000 g / mol, or 300 g / mol to 15,000 g / mol, or 300 g / mol to 10,000 g / mol.

[0067] An aliphatic polyurethane polycarbonate having at least two reactive groups contains a plurality of urethane bonds (-O-C(O)-N(H)-) and does not contain an aromatic group. In some embodiments, the aliphatic polyurethane independently has a linear or branched C1-C 20 alkyl bond and / or C3-C 10It contains a cycloalkyl bond. An aliphatic polyurethane having at least two reactive groups can be prepared according to methods recognized in the art. In some embodiments, a hydroxyl-functional polyurethane having at least two hydroxyl groups is reacted with aziridine to form an amine-functional polyurethane intermediate having at least two primary amine groups. Next, at least a part of the primary amines of the amine-functional polyurethane intermediate can be reacted with one or more ketones, thereby forming a polyurethane having an imine group and optionally a primary amine group. In some embodiments, the aliphatic polyurethane having at least two reactive groups has a Mn of 350 g / mol to 20,000 g / mol, or 400 g / mol to 15,000 g / mol, or 400 g / mol to 10,000 g / mol.

[0068] The aliphatic polyethyleneimine having at least two reactive groups does not contain an aromatic group. The aliphatic polyethyleneimine can be described herein as a polyethyleneimine having at least two reactive groups. In some embodiments, the aliphatic polyethyleneimine is prepared by ring-opening polymerization of aziridine in the first step. The resulting polyethyleneimine intermediate is branched in some embodiments and contains a combination of primary amine groups, secondary amine groups, and tertiary amine groups. By reacting at least a part of the primary amines of the polyethyleneimine intermediate with one or more ketones, an aliphatic polyethyleneimine having an imine group and optionally a primary amine group is formed. In some embodiments, an aliphatic polyethyleneimine having an imine group and optionally a primary amine group is formed by reacting a commercially available polyethyleneimine having a primary amine group (such as EPOMIN polyethyleneimine) with one or more ketones. In some embodiments, the aliphatic polyethyleneimine having at least two reactive groups has a Mn of 140 g / mol to 5000 g / mol, or 150 g / mol to 2500 g / mol, or 200 g / mol to 2500 g / mol.

[0069] In some embodiments, the reactive component has a reactive group equivalent weight of from 70 g / mol to 2600 g / mol, or from 75 g / mol to 2000 g / mol, or from 80 g / mol to 1500 g / mol. The recited reactive group equivalent weight values and the associated ranges represent, in each case, the combination (or sum) of primary amine group equivalents and imine group equivalents.

[0070] In some embodiments, the reactive component is formed from the reaction of a polyamine containing at least two primary amine groups (—NH2) and at least one ketone (type of ketone). The reaction between the primary amine and the ketone forms an imine group as represented by formula (B) above. In some embodiments, each ketone reacting with the primary amine of the polyamine has a formula weight of less than 300 g / mol (such as from 58 g / mol to less than 300 g / mol). Examples of such ketones include, but are not limited to, dimethyl ketone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-propyl ketone, methyl isopropyl ketone, cyclopentanone, and acetophenone. In some further embodiments, at least 80 percent, or at least 85 percent, or at least 90 percent, or at least 95 percent, or 100 percent of the primary amine groups of the polyamine (their ranges such as 80 - 100%, or 85% - 100%, or 90% - 100%, or 95% - 100% are included, the primary amine groups) are reacted with the ketone, thereby being converted to imine groups.

[0071] In some embodiments, the reactive component, in each case, based on the total number of primary amine groups and imine groups, contains 0% to 20% primary amine groups and 80% to 100% imine groups; or 0% to 15% primary amine groups, and 85% to 100% imine groups; or 0% to 10% primary amine groups, and 90% to 100% imine groups; or 0% to 5% primary amine groups, and 95% to 100% imine groups.

[0072] In some embodiments, the reactive component is present in the curable photochromic composition in an amount of 1 wt% to 20 wt%, or 1 wt% to 15 wt%, or 2 wt% to 14 wt% in each case based on the total resin solids weight.

[0073] The curable photochromic composition of the present invention contains a non-reactive component that does not contain a functional group reactive with the above polyisocyanate or reactive component. More specifically, the non-reactive component does not contain a functional group reactive with the isocyanate group of the polyisocyanate or the reactive groups (primary amine group and imine group) of the reactive component.

[0074] The non-reactive component contains, in some embodiments, at least one of polyether, polyester, polycarbonate, polyurethane, and / or organic phosphate. Further, according to the present invention, the non-reactive component contains at least one of aliphatic polyether, aliphatic polyester, aliphatic polycarbonate, aliphatic polyurethane, and / or organic phosphate. According to some embodiments, the polyether, polyester, polycarbonate, and polyurethane from which the non-reactive component can be selected each independently have an Mn of 300 to 10,000 g / mol, or 300 to 8000 g / mol, or 300 to 7000 g / mol.

[0075] The polyether of the non-reactive component contains a plurality of ether bonds (-O-), and in the case of an aliphatic polyether, does not contain an aromatic group. In some embodiments, the polyether is an aliphatic polyether and independently has a linear or branched C2-C 20 alkyl bond and / or C3-C 10 cycloalkyl bond between and / or extending from each ether bond. The polyether of the non-reactive component can be prepared according to methods recognized in the art. The polyether of the non-reactive component has, in some embodiments, a terminal ether group such as a terminal -OR a group, where Ra In each case, independently, is a linear or branched C1-C 20 alkyl group or a C3-C 10 cycloalkyl group. In some further embodiments, the polyether of the non-reactive component has a terminal carboxylic acid ester group such as -OC(O)R a group, where R a is, in each case, independently, a linear or branched C1-C 20 alkyl group or a C3-C 10 cycloalkyl group.

[0076] The polyester of the non-reactive component contains a plurality of carboxylic acid ester bonds (-C(O)-O-), and in the case of an aliphatic polyester, does not contain an aromatic group. In some embodiments, the polyester of the non-reactive component is an aliphatic polyester and independently has linear or branched C2-C 20 alkyl bonds and / or C3-C 10 cycloalkyl bonds between and / or extending from each carboxylic acid ester bond. The polyester of the non-reactive component can be prepared according to methods recognized in the art. In some further embodiments, the polyester of the non-reactive component has terminal carboxylic acid ester groups such as -OC(O)R a groups and / or -C(O)OR a groups, where R a is, in each case, independently, a linear or branched C1-C 20 alkyl group or a C3-C 10 cycloalkyl group.

[0077] The polycarbonate of the non-reactive component contains a plurality of carbonate bonds (-O-C(O)-O-), and in the case of an aliphatic polycarbonate, does not contain an aromatic group. In some embodiments, the polycarbonate of the non-reactive component is an aliphatic polycarbonate and independently has linear or branched C2-C 20 alkyl bonds and / or C3-C10 It contains a cycloalkyl bond. The polycarbonate of the non-reactive component can be prepared according to methods recognized in the art. In some further embodiments, the polycarbonate of the non-reactive component has a terminal carbonate group such as -O-C(O)-O-R a group, where R a is, in each case, independently a linear or branched C1-C 20 alkyl group or a C3-C 10 cycloalkyl group.

[0078] The polyurethane of the non-reactive component contains a plurality of urethane bonds (-O-C(O)-N(H)-), and in the case of aliphatic polyurethane, it does not contain an aromatic group. In some embodiments, the polyurethane of the non-reactive component is an aliphatic polyurethane, and independently, linear or branched C2-C 20 alkyl bonds and / or C3-C 10 cycloalkyl bonds are included between and / or extending from each urethane bond. The polyurethane of the non-reactive component can be prepared according to methods recognized in the art. In some further embodiments, the polyurethane of the non-reactive component has a terminal urethane group such as -N(H)-C(O)-OR a group, where R a is, in each case, independently a linear or branched C5-C 20 alkyl group or a C6-C 10 cycloalkyl group.

[0079] The organic phosphate from which the non-reactive component can be selected is, in some embodiments, represented by the following formula (C). Formula (C) P(O)(OR’)3

[0080] Regarding formula (C), each R’ is, in each case, independently selected from alkyl, haloalkyl, perhaloalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and combinations thereof (including those types and their examples listed above herein). In some further embodiments, each R’ of formula (C) is, in each case, independently selected from alkyl, cycloalkyl, aryl, and combinations thereof. Further regarding formula (C), according to some further embodiments, each R’ is, in each case, independently, C1-C 20 linear alkyl, C3-C 20 branched alkyl, C3-C 20 cycloalkyl, C5-C 20 aryl, and combinations thereof. Further regarding formula (C), according to some further embodiments, each R’ is, in each case, independently phenyl; C1-C 20 linear alkyl, C3-C 20 branched alkyl, or phenyl substituted by at least one of C3-C 20 cycloalkyl; C1-C substituted by at least one phenyl 20 linear alkyl; C3-C substituted by at least one phenyl 20 branched alkyl; and C3-C substituted by at least one phenyl 20 cycloalkyl. Non-limiting examples of organic phosphates from which non-reactive components can be selected include tricresyl phosphate, tris(2-phenylethyl) phosphate, tris(2-chloroethyl) phosphate, tris(1,3-dichloro-2-propyl) phosphate, cresyl diphenyl phosphate, tris(2,3-dibromopropyl) phosphate, tris-(2-ethylhexyl) phosphate, and tris(2-methylphenyl) phosphate.

[0081] In some embodiments, the non-reactive components of the curable photochromic composition of the present invention have a viscosity (at 25 °C) of 1 cP to 60,000 cP, or 1 cP to 10,000 cP, or 1 cP to 7,500 cP (where cP in each case means centipoise). The viscosity can be measured according to methods recognized in the art. In some embodiments, the viscosity is measured using a rotational viscometer, such as a Brookfield CAP 2000+ viscometer available from AMETEK, Inc., in accordance with the manufacturer's instructions. Further methods for measuring viscosity include, but are not limited to, those described in ASTM D789 or ASTM D4878.

[0082] According to some embodiments of the curable photochromic composition of the present invention, the non-reactive components are present in an amount of 10 weight percent to 40 weight percent, or 15 weight percent to 35 weight percent, or 20 weight percent to 35 weight percent, by weight percent based on the total resin solids of the curable photochromic composition in each case.

[0083] The curable photochromic composition of the present invention contains a photochromic compound (s). The photochromic compound can be selected from known types and examples of photochromic compounds and can include combinations or mixtures thereof.

[0084] For example, without limitation herein, mixtures of photochromic compounds can be used to achieve certain activation colors, such as substantially neutral gray or substantially neutral brown. See, for example, U.S. Patent No. 5,645,767, column 12, line 66 to column 13, line 19, which describes the parameters defining neutral gray and brown colors. The disclosure is specifically incorporated herein by reference.

[0085] Regarding some embodiments, the photochromic compounds of the curable photochromic composition of the present invention are selected from the group consisting of naphthopyrans, benzopyrans, phenanthropyrans, indenonaphthopyrans, spiro(indoline)naphthoxazines, spiro(indoline)pyridobenzoxazines, spiro(benzindoline)pyridobenzoxazines, spiro(benzindoline)naphthoxazines, spiro(indoline)-benzoxazines, fulgides, fulgimides, diarylethenes, and mixtures of such photochromic compounds.

[0086] Further examples of other photochromic compounds that can be used in the curable photochromic composition of the present invention include, but are not limited to, those disclosed in columns 34, line 20 to column 35, line 13 of U.S. Patent No. 9,028,728B2. The above disclosure is specifically incorporated herein by reference.

[0087] The photochromic compound is present in the curable photochromic composition of the present invention in at least a sufficient amount to provide an article prepared from a composition having a desired level of photochromic properties, which is referred to as the photochromic amount in some embodiments. Regarding some embodiments, the amount of the photochromic compound(s) present in the curable photochromic composition is, in each case, a weight percentage based on the total resin solids weight, from 0.001 weight percent to 40 weight percent, or from 0.001 to 10 weight percent, or from 0.01 to 8 weight percent, or from 0.1 to 2.5 weight percent.

[0088] In some embodiments, the curable photochromic composition of the present invention optionally includes additives such as, but not limited to, the following: waxes, such as waxes for flow and wetting; flow modifiers such as poly(2-ethylhexyl) acrylate; antioxidants; adhesion promoters such as (3-glycidoxypropyl)trimethoxysilane; surfactants; and ultraviolet (UV) light absorbers. Examples of useful antioxidants and UV light absorbers include, but are not limited to, those commercially available from BASF under the trademarks IRGANOX and TINUVIN. A non-limiting type of antioxidant is a hindered amine light stabilizer (HALS), which can include one or more 2,2,6,6-tetraalkylpiperidin-4-yl groups, such as one or more 2,2,6,6-tetramethylpiperidin-4-yl groups. These optional additives, when used, can be present in amounts up to 20 weight percent based on the total resin solids content.

[0089] In some embodiments, the curable photochromic composition of the present invention can further include one or more fixed-tint dyes. As used herein, the terms "fixed-tint dyes" and related terms such as "fixed-colorant," "static colorant," "fixed dye," and "static dye" mean dyes that are non-photosensitive materials that do not physically or chemically react to electromagnetic radiation with respect to the color observed visually. The term "fixed-tint dyes" and related terms used herein do not include photochromic compounds and are distinguished from them. The term "non-photosensitive material" as used herein means a material that does not physically or chemically react to electromagnetic radiation with respect to the color observed visually, such as, but not limited to, fixed-tint dyes.

[0090] One or more dyes of a fixed hue are present in the curable photochromic composition of the present invention and impart to a cured article prepared from the curable photochromic composition at least a basic (or first) color characteristic of the dye of the fixed hue when the photochromic compound is not activated; and optionally, a second color characteristic of a combination of the dye of the fixed hue and the photochromic compound when activated, for example, by exposure to actinic radiation, and may be present for purposes including, but not limited to, these.

[0091] Optional dyes of a fixed hue in the curable photochromic composition, in some embodiments, include at least one of azo dyes, anthraquinone dyes, xanthene dyes, azime dyes, iodine, iodide salts, polyazo dyes, stilbene dyes, pyrazolone dyes, triphenylmethane dyes, quinoline dyes, oxazine dyes, thiazine dyes, and polyene dyes.

[0092] Dyes of a fixed hue are present in the curable photochromic composition in various amounts and can provide the intended effect to the cured article produced therefrom. For some embodiments, the dyes of a fixed hue are present in the curable photochromic composition in an amount of 0.001 to 15 weight percent, or 0.01 to 10 weight percent, or 0.1 to 2.5 weight percent, based on the total resin solids weight of the curable photochromic composition in each case.

[0093] The curable photochromic composition of the present invention can, in some embodiments, include one or more solvents, such as one or more organic solvents.

[0094] Examples of types of organic solvents that may be present in the curable photochromic composition of the present invention include, but are not limited to, the following: ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ethers such as dimethyl ether and methyl ethyl ether; cyclic ethers such as tetrahydrofuran and dioxane; esters such as ethyl acetate, ethyl lactate, ethylene carbonate, and propylene carbonate; nitrogen-containing cyclic compounds such as pyrrolidone, N-methyl-2-pyrrolidone, 1-butyl-pyrrolidinone, and 1,3-dimethyl-2-imidazolidinone; sulfur-containing compounds such as dimethyl sulfoxide and tetramethylene sulfone; aromatic compounds such as toluene, xylene, anisole, and butyl benzoate; and mixtures of aromatic compounds such as, but not limited to, Aromatic 100 Fluid, which is a commercially available mixture of dialkyl- and trialkylbenzenes, and 10 C 10 ~C 12 Aromatic 150 Fluid, which is a commercially available mixture of alkylbenzene and alkylnaphthalene.

[0095] The solvent(s) may be present in the curable photochromic composition of the present invention in an amount of 5 to 95 weight percent, or 15 to 80 weight percent, 30 to 70 weight percent, or 30 to 60 weight percent, based on the total weight of the curable photochromic composition (including the weight of the solvent) in each case.

[0096] In some embodiments, the curable photochromic composition of the present invention can include one or more curing catalysts for catalyzing the reaction between the unblocked and / or blocked isocyanate groups of the polyisocyanate component and the reactive groups of the reactive component. Examples of useful catalysts include, but are not limited to, metal compounds such as organotin compounds, organobismuth compounds, organozinc compounds, organozirconium compounds, organoaluminum compounds, organonickel compounds, organomercury compounds, and alkali metal compounds; amine compounds such as tertiary amine compounds, and quaternary ammonium compounds. Examples of organotin compounds include, but are not limited to, tin(II) salts of carboxylic acids such as tin(II) acetate, tin(II) octanoate, tin(II) ethylhexanoate, and tin(II) laurate; tin(IV) compounds such as dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, and dioctyltin diacetate. Examples of suitable tertiary amine catalysts include, but are not limited to, diazabicyclo[2.2.2]octane and 1,5-diazabicyclo[4,3,0]non-5-ene. Examples of organobismuth compounds include, but are not limited to, bismuth carboxylates. Examples of alkali metal compounds include, but are not limited to, alkali metal carboxylates such as potassium acetate and potassium 2-ethylhexanoate. Examples of quaternary ammonium compounds include, but are not limited to, N-hydroxyalkyl quaternary ammonium carboxylates. In some embodiments, the catalyst can be selected from tin(II) octanoate, dibutyltin(IV) dilaurate, and / or bismuth 2-ethylhexanoate.

[0097] In some embodiments of the present invention, the curable photochromic composition includes a curing catalyst that includes an organotin compound selected from a tin(II) salt of a carboxylic acid, a tin(IV) compound, or a combination thereof.

[0098] In some further embodiments of the present invention, the curable photochromic composition is selected from tin(II) acetate, tin(II) octanoate, tin(II) ethylhexanoate, tin(II) laurate, dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, dioctyltin diacetate, or combinations thereof

[0099] The curing catalyst is typically present in an amount of about 0.05 to about 5.0 weight percent, or about 0.25 to about 2.0 weight percent, based on the total weight of the resin solids in the curable photochromic composition.

[0100] The curable photochromic composition of the present invention can be cured by any suitable method that results in the formation of covalent bonds between the isocyanate groups of the polyisocyanate and the reactive groups (primary amine groups and imine groups) of the reactive component. In some embodiments, the curable photochromic composition is cured by exposure to elevated temperature (above ambient room temperature, e.g., higher than 25 °C). In some embodiments, exposure to elevated temperature results in the deblocking of blocked isocyanate groups of the polyisocyanate (if it contains blocked isocyanate groups). As used herein, "curing" means the formation of a three-dimensional cross-linked network by the formation of covalent bonds resulting from the reaction between the isocyanate groups of the polyisocyanate and the reactive groups (primary amine groups and imine groups) of the reactive component. When curing is carried out at elevated temperature, the curable photochromic composition can be referred to herein as a thermosetting photochromic composition. The temperature at which the thermosetting photochromic composition of the present invention cures varies and depends to some extent on the amount of time for which curing is carried out. In some embodiments, the curable photochromic composition is cured at an elevated temperature of 80 °C to 175 °C, or 85 °C to 150 °C, or 90 °C to 130 °C for a period of 15 to 240 minutes.

[0101] The present invention also relates to an article prepared from the curable photochromic composition of the present invention described earlier herein, particularly a photochromic article. In some embodiments, the photochromic article is selected from a layer (including a film and / or a sheet) and a three-dimensional article.

[0102] Examples of three-dimensional articles that can be prepared from the curable photochromic composition of the present invention include, but are not limited to, ophthalmic articles, display articles, windows, and mirrors.

[0103] More typically, the curable photochromic composition of the present invention is used to prepare photochromic layers such as photochromic films and photochromic sheets. As used herein, the term "film" means a non-self-supporting layer such as a coating, although not limited thereto. As used herein, the term "sheet" means a self-supporting layer such as an extruded sheet, although not limited thereto.

[0104] The present invention also relates to an article, such as a photochromic article, comprising (A) a substrate and (B) a photochromic layer on at least one surface of the substrate, wherein the photochromic layer is formed from the curable photochromic composition of the present invention.

[0105] An article comprising a substrate and a photochromic layer (formed from the curable photochromic composition of the present invention) on at least one surface of the substrate can, in some embodiments, be selected from ophthalmic articles, display articles, windows, and mirrors. Correspondingly, the substrate of the article can be selected from ophthalmic substrates, displays, windows, and mirrors. The substrate can be composed of one or more suitable materials including, but not limited to, organic materials such as organic polymer materials, such as, but not limited to, thermoplastic polycarbonate, cross-linked polycarbonate, poly(meth)acrylate, and combinations thereof; glass such as silica-based glass; metals; ceramic materials; and combinations thereof. Examples of substrates that can be included in the articles (including optical elements) of the present invention include, but are not limited to, those described in columns 35, line 5 to column 36, line 57 of U.S. Patent No. 8,628,685B2, the disclosure of which is incorporated herein by reference.

[0106] In some embodiments, the substrate can optionally include a photochromic material and / or a fixed-color dye, each selected from the types and examples of photochromic materials and fixed-color dyes previously described herein. The optional photochromic material(s) / compound(s) present in the substrate can be the same as or different from the photochromic compound(s) of the photochromic layer. The optional fixed-color dye(s) can be the same as or different from the optional fixed-color dye(s) of the photochromic layer.

[0107] The photochromic layer of the article can be a photochromic film or a photochromic sheet. In some embodiments, the photochromic film of the article is a photochromic coating, and the curable photochromic composition of the present invention is a curable photochromic coating composition.

[0108] The curable photochromic coating composition can be applied to a substrate according to methods recognized in the art, including, but not limited to, spray coating, curtain coating, drawdown blade (or bar) coating, dip coating, spin coating, inkjet printing (such as an inkjet printing method where the "ink" is replaced with the curable photochromic composition according to the present invention), and combinations thereof.

[0109] After applying the curable photochromic composition onto at least one surface of the substrate, as previously described herein, the applied curable photochromic composition is cured. The photochromic layer can be in the form of a single layer or multiple layers. In the case of multiple layers, each layer of the photochromic layer can be prepared from the curable photochromic composition of the present invention having the same or different compositions, for example, having the same or different photochromic compound(s) (one or more). The photochromic layer can have any suitable thickness, for example, from 10 micrometers to 250 micrometers or from 15 micrometers to 75 micrometers.

[0110] In addition to the photochromic layer, the article can optionally include one or more additional layers recognized in the art, including, but not limited to, for example, primer layer(s); adhesive layer(s); protective layer(s) (such as a hard coat layer); polarizing layer(s); birefringent layer(s); anti-reflection layer(s); and / or another photochromic layer(s) prepared from a composition other than the curable photochromic composition of the present invention.

[0111] The present invention further relates to a photochromic multilayer article comprising at least one photochromic layer formed from the curable photochromic composition of the present invention. Each layer of the photochromic multilayer article can independently be in the form of a film or sheet. The photochromic multilayer article can, in some embodiments, include two or more layers formed from the same or different curable photochromic compositions of the present invention.

[0112] The multilayer article of the present invention may optionally include one or more additional layers recognized in the art, such as, but not limited to, an adhesive layer(s); a protective layer(s) (such as a hard coat layer); a polarizing layer(s); a birefringent layer(s); an anti-reflection layer(s); and / or another photochromic layer(s) prepared from a composition other than the curable photochromic composition of the present invention.

[0113] The multilayer article of the present invention can have any suitable thickness, for example, from 10 micrometers to 1000 micrometers, or from 15 micrometers to 750 micrometers, or from 25 to 100 micrometers.

[0114] The multilayer article of the present invention can be used alone or with another article such as a substrate. The substrate can be selected from the types and examples of substrates described hereinabove with respect to the articles of the present invention, such as ophthalmic substrates, displays, windows, and / or mirrors. The substrate can be composed of one or more suitable materials including, but not limited to, organic materials such as organic polymeric materials; glass such as silica-based glass; metals; ceramic materials; and combinations thereof.

[0115] The multilayer article of the present invention can be adhered to the surface of the substrate by methods recognized in the art, such as, but not limited to, electrostatic adhesion such as by static electricity; one or more intervening adhesive layers; fusion such as heat fusion; and in-mold formation such as when the multilayer article is placed in a mold and the substrate is formed against at least one surface of the multilayer article within the mold. The multilayer article of the present invention can, in some embodiments, be supported by one or more brackets that engage and hold one or more peripheral regions of the multilayer article.

[0116] The present invention can be further characterized by one or more of the following non-limiting clauses.

[0117] Clause 1: (a) a photochromic compound; (b) a polyisocyanate containing at least two isocyanate groups; (c) a reactive component containing at least two reactive groups each reactive with an isocyanate group of the polyisocyanate, each reactive group of the reactive component being independently selected from primary amines and imines, provided that at least one reactive group of the reactive component is selected from imines; (d) a non-reactive component containing no functional groups reactive with the polyisocyanate and the reactive component; A curable photochromic composition comprising the same.

[0118] Clause 2: The curable photochromic composition according to Clause 1, wherein the molar ratio of the number of moles of the isocyanate groups of the polyisocyanate to the total number of moles of the reactive groups of the reactive component is 1:1 to 20:1, or 1:1 to 18:1, or 1:1 to 17:1, or 1:1 to 16.5:1.

[0119] Clause 3: The curable photochromic composition according to Clause 1 or Clause 2, wherein the polyisocyanate contains at least one of linear or branched aliphatic polyisocyanates, alicyclic polyisocyanates, their biurets, their allophanates, their isocyanurates, and combinations thereof.

[0120] Clause 4: The curable photochromic composition according to any one of Clauses 1 to 3, wherein the polyisocyanate has an isocyanate equivalent of 95 to 500 g / mol, or 150 to 400 g / mol, or 150 to 350 g / mol.

[0121] Clause 5: The curable photochromic composition according to any one of Clauses 1 to 4, wherein at least some of the isocyanate groups of the polyisocyanate are reversibly blocked with a blocking agent.

[0122] Clause 6: The curable photochromic composition according to any one of Clauses 1 to 5, wherein the polyisocyanate is present in an amount of 40% to 90% by weight, or 45% to 90% by weight, or 50% to 85% by weight, based on the total resin solid content weight in each case.

[0123] Clause 7: The curable photochromic composition according to any one of Clauses 1 to 6, wherein the reactive component independently contains at least one of an aliphatic polyether, an aliphatic polyester, an aliphatic polycarbonate, an aliphatic polyethyleneimine, or an aliphatic polyurethane, each having at least two reactive groups.

[0124] Clause 8: The curable photochromic composition according to any one of Clauses 1 to 7, wherein the reactive component has a reactive group equivalent weight of 70 g / mol to 2600 g / mol, or 75 g / mol to 2000 g / mol, or 80 g / mol to 1500 g / mol.

[0125] Clause 9: The curable photochromic composition according to any one of Clauses 1 to 8, wherein the reactive component is formed from the reaction of a polyamine containing a primary amine group and at least one ketone.

[0126] Clause 10: The curable photochromic composition according to Clause 9, wherein each ketone independently has a formula weight of less than 300 g / mol.

[0127] Clause 11: The curable photochromic composition according to Clause 9 or Clause 10, wherein each ketone independently has a formula weight of 58 g / mol to less than 300 g / mol.

[0128] Clause 12: A curable photochromic composition according to any one of Clauses 9 to 11, wherein at least 80%, or at least 85%, or at least 90%, or at least 95%, or 100% of the primary amine groups of the polyamine are converted to imine groups by reaction with a ketone.

[0129] Clause 13: A curable photochromic composition according to any one of Clauses 1 to 12, wherein the reactive component is present in an amount of 1 wt% to 20 wt%, or 1 wt% to 15 wt%, or 2 wt% to 14 wt% by weight percent based on the total resin solids weight in each case.

[0130] Clause 14: A curable photochromic composition according to any one of Clauses 1 to 13, wherein the non-reactive component has a viscosity of 1 cP to 60,000 cP, or 1 cP to 10,000 cP, or 1 cP to 7500 cP at 25°C.

[0131] Clause 15: A curable photochromic composition according to any one of Clauses 1 to 14, wherein the non-reactive component contains at least one of polyether, polyester, polycarbonate, polyurethane, and / or organic phosphate.

[0132] Clause 16: A curable photochromic composition according to any one of Clauses 1 to 15, wherein the non-reactive component contains at least one of polyether, polyester, polycarbonate, and / or polyurethane, and these each independently have an Mn of 300 to 10,000 g / mol, or 300 to 8000 g / mol, or 300 to 7000 g / mol.

[0133] Clause 17: The curable photochromic composition of any one of Clauses 1 to 16, wherein the non-reactive component contains at least one of aliphatic polyethers, aliphatic polyesters, aliphatic polycarbonates, and / or aliphatic polyurethanes, and in each case independently has an Mn of 300 to 10,000 g / mol, or 300 to 8000 g / mol, or 300 to 7000 g / mol.

[0134] Clause 18: The curable photochromic composition of any one of Clauses 1 to 17, wherein the non-reactive component contains an organic phosphate represented by the following formula (C) Formula (C) P(O)(OR’)3 (wherein, in each case, R’ is independently selected from alkyl, haloalkyl, perhaloalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and combinations thereof).

[0135] Clause 19: The curable photochromic composition of Clause 18, wherein in each case, R’ is independently phenyl; phenyl substituted by at least one of C1-C 20 linear alkyl and / or C3-C 20 branched alkyl; C1-C substituted by at least one phenyl 20 linear alkyl; and C3-C substituted by at least one phenyl 20 branched alkyl.

[0136] Clause 20: The curable photochromic composition of any one of Clauses 1 to 19, wherein the non-reactive component is present in an amount of 10 wt% to 40 wt%, or 15 wt% to 35 wt%, or 20 wt% to 35 wt% by weight percent based on the total resin solids of the curable photochromic composition in each case.

[0137] Clause 21: The curable photochromic composition according to any one of Clauses 1 to 20, wherein the photochromic compound (a) contains at least one of naphthopyrans, benzopyrans, phenanthropyrans, indenonaphthopyrans, spiro(indoline)naphthoxazines, spiro(indoline)pyridobenzoxazines, spiro(benzindoline)pyridobenzoxazines, spiro(benzindoline)naphthoxazines, spiro(indoline)-benzoxazines, fulgides, fulgimides, and / or diarylethene.

[0138] Clause 22: The curable photochromic composition according to any one of Clauses 1 to 21, further comprising an additive selected from wax, flow control agent, antioxidant, surfactant, adhesion promoter, ultraviolet absorber, and combinations thereof.

[0139] Clause 23: The curable photochromic composition according to any one of Clauses 1 to 22, further comprising a curing catalyst selected from metal compounds, amine compounds, and combinations thereof.

[0140] Clause 24: (A) A substrate; (B) A photochromic layer on at least one surface of the substrate An article comprising, wherein the photochromic layer is formed from the curable photochromic composition according to any one of Clauses 1 to 23.

[0141] The present invention is more specifically described in the following examples, which are intended to be illustrative only, since numerous modifications and variations will become apparent to those skilled in the art. Unless otherwise specified, all parts and all percentages are by weight.

Examples

[0142] In Part 1 of the following examples, the preparation of polyethyleneimine having a primary amine group and an imine group (Example 1) is described. In Part 2, the preparation of comparative curable photochromic compositions (CE-2, CE-3, and CE-4) is described. In Part 3, the preparation of curable photochromic compositions according to the present invention (Examples 5 to 12) is described. In Part 3, the preparation of photochromic test pieces is described. In Part 4, the physical tests and evaluations of test pieces prepared using the comparative and curable photochromic compositions of the present invention are described and summarized.

[0143] Part 1. Preparation of polyethyleneimine having a primary amine group and an imine group. Example 1 EPOMIN (trademark) SP006 polyethyleneimine (10 g; branched polyethyleneimine having a reported number average molecular weight of 600 g / mol and a calculated primary amine equivalent of 142.8 g / mol, available from Nippon Shokubai Co., Ltd.) and methyl ethyl ketone (21.63 g) were combined in a sealed 100 ml amber vial and stirred at 60 °C for 1 hour using a magnetic stir bar. From NMR analysis, the estimated conversion rate from primary amine to imine was determined to be approximately 82% based on the calculated equivalent of reactive groups of 178.5 g / mol (total of primary amine groups and imine groups). The resulting solution having a 69 wt% solids content was used in the following compositions without further purification or modification.

[0144] Part 2. Preparation of comparative curable photochromic compositions. Comparative Examples CE-2 to CE-4 Comparative Examples (CE) CE-2, CE-3, and CE-4 were prepared using the components listed in Table 1 shown in parts by weight. The components of Input 1 were combined, heated to 70 °C, and stirred for at least 1 hour until it was observed that the solids were completely dissolved. After cooling to room temperature, the components of Input 2 were added and the solution was stirred for 1 hour. The components of Input 3 were added and the solution was stirred for at least 1 hour before use.

[0145]

Table 1

[0146] Examples 5 - 7 Examples 5 - 7, which are curable photochromic compositions according to the present invention, were prepared according to the explanations provided above for Comparative Examples 2 - 4 using the components listed in Table 2 below (shown in parts by weight). In Examples 5 - 7 below, the ratio of isocyanate to the reactive groups (total of primary amine groups and imine groups) was increased, and the level of non-reactive components was the same in Examples 5 - 6 and decreased in Example 7.

[0147]

Table 2

[0148] Examples 8 - 12 Examples 8 - 12, which are curable photochromic compositions according to the present invention, were prepared according to the explanations provided above for Comparative Examples 2 - 4 using the components listed in Table 3 below (shown in parts by weight). In Examples 8 - 12 below, the ratio of isocyanate to the reactive groups (total of primary amine groups and imine groups) was maintained at 5:1 while varying the amount and / or type of non-reactive components in each case.

[0149]

Table 3

[0150] Part 3. Preparation of photochromic test pieces. The curable photochromic compositions of Comparative Examples 2-4 and Examples 5-12 were each separately applied by spin coating onto Gentex (registered trademark) polycarbonate plano lenses coated with PDQ (registered trademark) having a diameter of 76 millimeters. Prior to spin coating, each lens was corona treated using a Tantec apparatus set at 70 kV and 1000 W. Approximately 2 mL of each composition was dispensed onto the substrate and then rotated at a spin speed sufficient to deposit this for 6 seconds: a wet coating of 0.28 - 0.35 g on the lens of each curable photochromic composition (the wet weight depends on the % nonvolatile solids). Test specimens of CE-2, CE-3, CE-4, and Examples 5-12 were prepared in duplicate and then cured at 125 °C for 1 hour in a forced air electric oven.

[0151] Part 4. Evaluation of test specimens. Part 4a. Microhardness evaluation. A duplicate set of test specimens was subjected to an additional heat cure at 105 °C for 3 hours and reserved for microhardness measurement. Then, these test specimens were subjected to a microhardness test using a Fischerscope HCV, Model H100SMC available from Fischer Technology, Inc. Hardness was measured at a penetration depth of 2 microns after applying a load of 100 Newtons for 15 seconds. Each test specimen was measured at least twice. The obtained data was averaged. The microhardness results are further tabulated in Tables 4 - 6 herein.

[0152] Part 4b. Photochromic performance. A second duplicate set of test specimens was further treated with corona as described above and spin coated with a protective coating according to the formulation reported in Table 1 of Example 1 of U.S. Patent No. 7,410,691 B2. The test specimens were cured in a UV oven equipped with a D bulb. Thereafter, each test specimen was heat cured at 105 °C for 3 hours.

[0153] The photochromic performance of the test pieces was tested on a bench for photochromic measurement (the "BMP") manufactured by Essilor, Ltd., France. During the test, the BMP was maintained at a constant temperature of 73.4°F (23°C). Before the test, each coated test piece was exposed to ultraviolet light of 365 nanometers at a distance of about 14 centimeters for about 10 minutes to activate the photochromic material. The UVA (315 - 380 nm) irradiance in the lens, as measured with a LICOR® model Li-1800 spectroradiometer, was found to be 22.2 watts per square meter. Subsequently, each test piece was placed under a 500-watt high-intensity halogen lamp at a distance of about 36 centimeters for about 10 minutes to decolorize (deactivate) the photochromic material. The illuminance of the test piece, as measured with a LICOR® spectroradiometer, was found to be 21.9 Klux. Then, each test piece was held in a dark environment at room temperature (70 - 75°F, or 21 - 24°C) for at least 1 hour before being tested on the BMP. Before the measurement, the ultraviolet absorbance at 390 nanometers (Abs390nm) was measured for each lens.

[0154] The BMP optical bench had two 150 watt Newport Model #6255 xenon arc lamps set at right angles to each other. The optical path from Lamp 1 was directed to pass through a 3 mm SCHOTT® KG-2 bandpass filter and an appropriate neutral density filter that contribute to the required UV and partial visible irradiance levels. The optical path from Lamp 2 was directed to pass through a 3 mm SCHOTT® KG-2 bandpass filter, a SCHOTT® shortwave 400 nm cut-off filter, and an appropriate neutral density filter to provide auxiliary visible irradiance. A 2-inch x 2-inch 50% polka dot beam splitter set at 45° to each lamp was used to mix the two beams. The intensity of the irradiance was adjusted using a combination of neutral density filters and voltage control of the xenon arc lamps. Software, namely BMPSoft version 2.1e, was used in the BMP to control the timing, irradiance, air cell and sample temperature, shutter, filter selection, and response measurements. A ZEISS® spectrophotometer, model MCS601, equipped with an optical fiber cable for sending light through the lens was used for response and color measurements. Measurements of the photopic response were collected at each lens.

[0155] The output of the optical bench, i.e., the amount of light to which the lens was exposed, was adjusted to 6.7 watts per square meter (W / m2) of UVA integrated at 315 - 380 nm and an illuminance of 50 Klux integrated at 380 - 780 nm. The measurement of the set point of this output was performed using a radiance probe and a calibrated Zeiss spectrophotometer. The lens sample cell was equipped with a quartz window and a self - centering sample holder. The temperature inside the sample cell was controlled at 23 °C by software with a modified Facis model FX - 10 environmental simulator. The measurement of the dynamic photochromic response and color of the sample was performed using the same Zeiss spectrophotometer equipped with an optical fiber cable for sending light through the sample from a tungsten halogen lamp. The parallel monitoring light beam from the optical fiber cable was maintained perpendicular to the test sample while passing through the sample and directed towards the receiving optical fiber cable assembly attached to the spectrophotometer. The exact placement location of the sample inside the sample cell was where the activated xenon arc beam and the monitoring light beam intersected to form two concentric circles of light. The incident angle of the xenon arc beam at the sample placement point was approximately 30° from the vertical.

[0156] Response measurements regarding the change in optical density (ΔOD) from the non - activated or decolored state to the activated or colored state were determined by confirming the initial non - activated transmittance, opening the shutter from the xenon lamp(s), and measuring the transmittance due to activation at selected time intervals. The change in optical density was determined according to the following formula: ΔOD = log 10 (%Tb / %Ta), where %Tb is the percent transmittance in the faded state and %Ta is the percent transmittance in the activated state. The measurement of optical density was based on the photopic optical density.

[0157] The results of microhardness and photochromic performance for CE-2, CE-3, CE-4, and Examples 5 to 12 are summarized in Tables 4 to 6 below. The ΔOD at saturation was measured 15 minutes after activation, and the fade half-life (“T1 / 2”) value is the time in seconds for the ΔOD of the activated form of the photochromic material in the coating to reach half of the ΔOD at 15 minutes at 73.4°F (23°C) after removal of the activation light source.

[0158] Comparative Examples 2 to 4 The microhardness values and photochromic performance of CE-2, CE-3, and CE-4 are summarized in Table 4 below.

[0159] [Table 4]

[0160] The coating made from CE-2 cured as a result of the self-reaction of the isocyanate groups of the polyisocyanate alone and was turbid, and thus was not suitable for use as part of an optical element. The coating made from CE-3 cured as a result of the reaction between the reactive groups of the polyimine / amine of Example 1 and the isocyanate groups of the polyisocyanate and had a desirable hardness, but was very slow and had an undesirable fade half-life (T 1 / 2 ). The coating made from CE-4 cured as a result of the reaction between the hydroxyl groups of the polycarbonate diol (which can be characterized as a reactive soft material), the reactive groups of the polyimine / amine of Example 1, and the isocyanate groups of the polyisocyanate, had sufficient hardness, but had unacceptable photochromic performance characteristics.

[0161] Examples 5 to 7 (NCO):(Reactive group) ratio change The test results of Examples 5 to 7 are summarized in Table 5 below.

[0162] [Table 5]

[0163] The results summarized in Table 5 demonstrate that by increasing the (NCO):(reactive group) ratio while maintaining the same amount of non-reactive components (Examples 5 and 6), an increase in hardness and desirable levels of photochromic performance can be obtained. Example 7, having a higher (NCO):(reactive group) ratio and a smaller amount of non-reactive components (compared to Examples 5 and 6), had further improved hardness and desirable levels of photochromic performance.

[0164] Examples 8 - 12 Variation in the amount and type of non-reactive components The test results of Examples 8 - 12 are summarized in Table 6 below.

[0165]

Table 6

[0166] The test results summarized in Table 6 demonstrate that by maintaining the same (NCO):(reactive group) ratio while increasing the amount of non-reactive groups (Examples 8 - 10), an acceptable decrease in hardness can be obtained while maintaining an acceptable level of photochromic performance. As summarized in Table 6, the test results of Examples 10 - 12 demonstrate that by maintaining the same (NCO):(reactive group) ratio while varying the type of non-reactive components, an increase in hardness can be obtained while maintaining an acceptable level of photochromic performance.

[0167] The present invention has been described with reference to specific details of its specific embodiments. Such details are not intended to be construed as limitations on the scope of the present invention, except insofar as they are included in the appended claims.

Claims

Claim 1 (a) a photochromic compound; (b) a polyisocyanate containing at least two isocyanate groups; (c) a reactive component containing at least two reactive groups each reactive with an isocyanate group, each reactive group of the reactive component being independently selected from primary amines and imines, provided that at least one reactive group of the reactive component is selected from imines; (d) a curable photochromic composition comprising the polyisocyanate and a non-reactive component free of functional groups reactive with the polyisocyanate and the reactive component. Claim 2 The curable photochromic composition according to claim 1, wherein the molar ratio of the number of moles of the isocyanate groups of the polyisocyanate to the total number of moles of the reactive groups of the reactive component is from 1:1 to 20:

1. Claim 3 The curable photochromic composition according to claim 1, wherein the polyisocyanate comprises at least one of a linear or branched aliphatic polyisocyanate, an alicyclic polyisocyanate, their biurets, their allophanates, their isocyanurates, and combinations thereof. Claim 4 The curable photochromic composition according to claim 1, wherein the polyisocyanate has an isocyanate equivalent weight of 95 to 500 g / mol. Claim 5 The curable photochromic composition according to claim 1, wherein at least some of the isocyanate groups of the polyisocyanate are reversibly blocked with a blocking agent. Claim 6 The curable photochromic composition according to claim 1, wherein the polyisocyanate is present in an amount of 40 weight percent to 90 weight percent based on the total resin solids weight. Claim 7 The curable photochromic composition according to claim 1, wherein the reactive component comprises at least one of an aliphatic polyether, an aliphatic polyester, an aliphatic polycarbonate, an aliphatic polyethyleneimine, or an aliphatic polyurethane, each independently having at least two reactive groups. Claim 8 The curable photochromic composition according to claim 1, wherein the reactive component has a reactive group equivalent weight of 70 g / mol to 2600 g / mol. Claim 9 The reactive component is formed from the reaction of a polyamine containing a primary amine group and at least one ketone, each ketone independently having a formula weight of less than 300 g / mol, and at least 80 percent of the primary amine groups of the polyamine being converted to imine groups by reaction with the ketone, the curable photochromic composition according to claim 1.

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

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

12. The non-reactive component contains at least one of polyethers, polyesters, polycarbonates, polyurethanes, or organic phosphates, the curable photochromic composition according to claim 11.

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

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

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

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