Curable photochromic compositions containing segmented polymers - Patents.com

Abstract

The present invention relates to a curable photochromic composition comprising a photochromic compound, a trialkoxysilane functional material having at least two trialkoxysilane groups, and a segmented polymer comprising at least one first segment and at least one second segment. Each first segment of the segmented polymer independently comprises a (meth)acrylic polymer segment and / or a fluoroethylene vinyl ether polymer segment. Each second segment of the segmented polymer independently comprises a polycarbonate segment, a polyester segment, a polyether segment, a polyurethane segment, or a combination thereof. The present invention also relates to an article comprising a substrate; and a photochromic layer on at least one surface of the substrate, the photochromic layer being 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 trialkoxysilane functional material having at least two trialkoxysilane groups, and a segmented polymer comprising at least one first segment and at least one second segment. [Background technology]

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

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

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

[0005] According to the present invention, there is provided a curable photochromic composition comprising: (a) a photochromic compound; (b) a trialkoxysilane functional material having at least two trialkoxysilane groups; and (c) a segmented polymer comprising at least one first segment and at least one second segment. Each first segment of the segmented polymer independently comprises at least one of a (meth)acrylic polymer segment or a fluoroethylene vinyl ether polymer segment. Each second segment of the segmented polymer independently comprises at least one of a polycarbonate segment, a polyester segment, a polyether segment, or a polyurethane segment.

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

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

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

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

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

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

[0012] As used herein, values ​​for molecular weight of polymers, such as weight average molecular weight (Mw) and number average molecular weight (Mn), are determined by gel permeation chromatography (GPC) using appropriate standards, such as polystyrene standards.

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

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

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

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

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

[0018] As used herein, the terms "transmittance percentage" and "transmission percentage" and related terms such as "%T" refer to photopic transmission, and more specifically mean the fraction, multiplied by 100 (to give a percentage), of incident electromagnetic power (or radiation) in the visible spectrum (wavelengths between 390 nm and 700 nm) that is transmitted through an object, such as an optical element (e.g., a display element). By way of non-limiting illustration and according to some embodiments, the transmission percentage is determined by passing light from a light source through an object and recording a first intensity value using a spectrophotometer; passing light from the same light source through a blank (e.g., no object present) and recording a second intensity value using the same spectrophotometer; and dividing the first intensity value by the second intensity value and multiplying the resulting fraction by 100. The transmission percentage, %T, may be represented by the following Equation 1 (Equation 1): %T=(P / P0)×100 (Formula 1) In terms of Equation 1, P is the intensity of the light after passing through the object and P0 is the intensity of the same light after passing through a blank. The examples provided further herein explain how to measure the transmission percentage.

[0019] As used herein, the term "photochromic material" includes thermally reversible photochromic materials and compounds as well as non-thermally reversible photochromic materials and compounds. As used herein, the term "thermally reversible photochromic compound / material" refers to a compound / material that can be transformed from a first state, e.g., a "transparent state", to a second state, e.g., a "colored state", in response to actinic radiation and can be restored to the first state in response to thermal energy. As used herein, the term "non-thermally reversible photochromic compound / material" refers to a compound / material that can be transformed from a first state, e.g., a "transparent state", to a second state, e.g., a "colored state", in response to actinic radiation and can be restored to the first state in response to actinic radiation of substantially the same wavelength as the absorption of the colored state.

[0020] When used herein to modify the term "state," the terms "first" and "second" are not intended to refer to any particular order or chronological sequence, but rather to two different states or properties. For non-limiting illustrative purposes, the first and second states of the photochromic compound may differ with respect to at least one optical property, such as, but not limited to, the absorption of visible light and / or UV radiation. Thus, according to various non-limiting embodiments disclosed herein, the photochromic compound of the present invention may have different absorption spectra in each of the first and second states. For example, but not limited to, the photochromic compound of the present invention may be clear in the first state and colored in the second state. Alternatively, the photochromic compound of the present invention may have a first color in the first state and a second color in the second state.

[0021] The term "optical" as used herein means relating to or associated with light and / or vision. For example, according to various non-limiting embodiments disclosed herein, optical articles or elements or devices can be selected from ophthalmic articles, elements and devices, display articles, elements and devices, windows, mirrors, and active and passive liquid crystal cell articles, elements and devices.

[0022] The term "ophthalmic" as used herein means relating to or associated with the eye and vision. Non-limiting examples of ophthalmic articles or elements include corrective and non-corrective lenses, including multivision lenses (such as, but not limited to, bifocal, trifocal and progressive lenses), which may be single vision or segmented or non-segmented multivision lenses, as well as other elements used to correct, protect or enhance vision (cosmetic or otherwise), such as, but not limited to, contact lenses, intraocular lenses, magnifying lenses and protective lenses or visors.

[0023] The term "display" as used herein means a visible or machine-readable representation of information in words, numbers, symbols, designs or drawings. Non-limiting examples of display elements include screens, monitors and security elements such as security marks.

[0024] As used herein, the term "window" means an opening adapted to allow the transmission of radiation. Non-limiting examples of windows include automobile and aircraft transparencies, windshields, filters, shutters, and optical switches.

[0025] As used herein, the term "mirror" means a surface that specularly reflects a large portion of incident light.

[0026] As used herein, the term "liquid crystal cell" refers to a structure that contains liquid crystal material that can be aligned. A non-limiting example of a liquid crystal cell element is a liquid crystal display.

[0027] As used herein, spatial or directional terms such as "left", "right", "inner", "outer", "upper", "lower", and the like, refer to various orientations of the present invention, including the articles and multi-layer articles of the present invention, which may be further described herein. However, it should be understood that the present invention may assume various alternative orientations to those described herein, and thus such terms should not be considered limiting.

[0028] As used herein, the terms "formed on," "deposited on," "provided on," "coated on," "present on," or "disposed on" mean formed, deposited, provided, applied, present, or disposed on, but not necessarily in direct (or adjacent) contact with, an underlying element or a surface of an underlying element. For example, a layer "disposed on" a substrate does not exclude the presence of one or more other layers, coatings, or films of the same or different composition located between the disposed or formed layer and the substrate.

[0029] All documents, including but not limited to issued patents and patent applications, mentioned herein are to be deemed "incorporated by reference" in their entirety, unless otherwise indicated.

[0030] As used herein, references to a "straight or branched chain" group, such as straight or branched chain alkyl, are understood herein to include: methylene or methyl groups; straight chain C-C alkyl groups; 20 Straight-chain groups such as alkyl groups; and branched C3-C 20 Suitably branched groups such as alkyl groups.

[0031] As used herein, the term "alkyl" refers to any linear or branched, cyclic or non-cyclic C1-C 25 The straight or branched alkyl group is C1 to C 25 Alkyl, e.g. C1-C 20 Alkyl, e.g. C2-C 10 Alkyl, e.g. C1-C 12Examples of alkyl groups from which the various alkyl groups of the present invention can be selected include, but are not limited to, those further listed herein. The alkyl group can include a "cycloalkyl" group. The term "cycloalkyl" as used herein includes, but is not limited to, C3 to C6 alkyl groups. 12 Cycloalkyl (including but not limited to cyclic C3-C 10 "cycloalkyl" refers to a group that is suitably cyclic, such as an alkyl or cyclic C5-C7 alkyl group. Examples of cycloalkyl groups include, but are not limited to, those further listed herein. The term "cycloalkyl" as used herein also includes, but is not limited to, bridged-ring polycycloalkyl groups (or bridged-ring polycyclic alkyl groups), such as bicyclo[2.2.1]heptyl (or norbornyl) and bicyclo[2.2.2]octyl, and fused-ring polycycloalkyl groups (or fused-ring polycyclic alkyl groups), such as, but not limited to, octahydro-1H-indenyl and decahydronaphthalenyl.

[0032] As used herein, the term "heterocycloalkyl" refers to any C2-C heterocycloalkyl group, including, but not limited to, a C5-C7 heterocycloalkyl group. 10 C2-C such as heterocycloalkyl groups 12 Heterocycloalkyl groups, as appropriate, refer to groups having at least one heteroatom in the cyclic ring, such as, but not limited to, O, S, N, P, and combinations thereof. Examples of heterocycloalkyl groups include, but are not limited to, imidazolyl, tetrahydrofuranyl, tetrahydropyranyl, and piperidinyl. As used herein, the term "heterocycloalkyl" also includes, but is not limited to, bridged-ring polycyclic heterocycloalkyl groups, such as, but not limited to, 7-oxabicyclo[2.2.1]heptanyl; and fused-ring polycyclic heterocycloalkyl groups, such as, but not limited to, octahydrocyclopenta[b]pyranyl and octahydro-1H-isochromenyl.

[0033] The descriptions, classes and examples given herein for alkyl groups, cycloalkyl groups, heterocycloalkyl groups, haloalkyl groups, and the like also apply, without limitation, to alkane groups, cycloalkane groups, heterocycloalkane groups, haloalkane groups, and the like, such as polyvalent alkane groups, such as polyvalent alkane linking groups, such as divalent alkane linking groups.

[0034] As used herein, the term "aryl" and related terms such as "aryl group" refer to an aromatic cyclic monovalent hydrocarbon group. As used herein, the term "aromatic" and related terms such as "aromatic group" refer to a cyclic conjugated hydrocarbon that has significantly greater stability (due to delocalization of π electrons) than hypothetical localized structures. Examples of aryl groups include, but are not limited to, C6-C aryl groups, such as phenyl, naphthyl, phenanthryl, and anthracenyl. 14 Examples of such groups include aryl groups.

[0035] As used herein, the term "heteroaryl" includes, but is not limited to, C-C 10 C3-C heteroaryl (condensed ring polycyclic heteroaryl groups, etc.) 18 Heteroaryl includes, but is not limited to, aryl groups having at least one heteroatom in an aromatic ring or, in the case of fused ring polycyclic heteroaryl groups, in at least one aromatic ring. Examples of heteroaryl groups include, but are not limited to, furanyl, pyranyl, pyridinyl, quinolinyl, isoquinolinyl, and pyrimidinyl.

[0036] As used herein, the term "aralkyl" includes, but is not limited to, C6-C 10 C6-C such as aralkyl 24 "Aralkyl" refers to an alkyl group substituted with an aryl group, including but not limited to, "aralkyl." Examples of aralkyl groups include, but are not limited to, benzyl and phenethyl.

[0037] 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.

[0038] As used herein, the term "nitrogen-containing heterocycle", such as "nitrogen-containing heterocyclic group" or "nitrogen-containing heterocyclic substituent", includes, but is not limited to, a nitrogen-containing ring bonded through a ring nitrogen. Examples of nitrogen-containing heterocycles include, but are not limited to, aliphatic cyclic amino (or alicyclic amino) such as morpholino, piperidino, pyrrolidino, and decahydroisoquinolino; and heteroaromatics such as imidazole, pyrrole, indole, and carbazole.

[0039] As used herein, the term "halo" and related terms such as "halo group," "halo substituent," "halogen group" and "halogen substituent" refer to a single-bonded halogen radical, such as -F, -Cl, -Br, and -I.

[0040] As used herein, the recitation of "halo-substituted" and related terms (including but not limited to haloalkyl, haloalkenyl, haloalkynyl, haloaryl and halo-heteroaryl) refers to a group in which at least one and up to all of its available hydrogen radicals are replaced by a halo radical, such as but not limited to F, Cl or Br. The term "halo-substituted" includes "perhalo-substituted". As used herein, the term perhalo-substituted and related terms (including but not limited to perhaloalkyl, perhaloalkenyl, perhaloalkynyl, perhaloaryl or perhalo-heteroaryl) refers to a group in which all of its available hydrogen radicals are replaced by a halo radical. For non-limiting illustrative purposes, perhalomethyl is -CX; perhalophenyl is -CX, where X represents one or more halo radicals, such as but not limited to F, Cl, Br or I.

[0041] As used herein, "at least one of" is synonymous with "one or more of," regardless of whether the elements are listed in a conjunctive or non-conjunctive manner. For example, the phrases "at least one of A, B, and C" and "at least one of A, B, or C" mean any one of A, B, or C, respectively, or any combination of any two or more of A, B, or C. For example, A only, or B only, or C only, or A and B, or A and C, or B and C, or all of A, B, and C.

[0042] As used herein, "selected from" is synonymous with "selected from," regardless of whether the elements are listed in a conjunctive or non-conjunctive manner. Additionally, the phrases "selected from A, B, and C" and "selected from A, B, or C" mean any one of A, B, or C, respectively, or any combination of any two or more of A, B, or C. For example, A only, or B only, or C only, or A and B, or A and C, or B and C, or all of A, B, and C.

[0043] As used herein, and according to some embodiments, the term "ketone" and related terms such as "ketone group" and "ketone substituent", as used herein with respect to groups and substituents of various groups of the compounds and components of the invention, refer to a substance represented by -C(O)R, where R is selected from the groups described below, other than hydrogen.

[0044] As used herein, and according to some embodiments, the term "carboxylic acid" and related terms such as "carboxylic acid group" and "carboxylic acid substituent," as they relate to groups and substituents of various groups of the compounds and components of the invention, include substances represented by -C(O)OH.

[0045] As used herein, and according to some embodiments, the term "ester" and related terms such as "ester group" and "ester substituent", as used with respect to groups and substituents of various groups of the compounds and components of the invention, refer to a carboxylic acid ester group represented by -C(O)OR, where R is selected from the groups described below, other than hydrogen.

[0046] As used herein, and according to some embodiments, the term "carboxylate" and related terms such as "carboxylate group" and "carboxylate substituent," as used herein with respect to groups and substituents of various groups of the compounds and components of the invention, include materials represented by -OC(O)R, where R is selected from the groups described below.

[0047] As used herein, and according to some embodiments, the term "amide" and related terms such as "amide group" and "amide substituent," as they relate to groups and substituents of various groups of the compounds and components of the invention, include entities represented by -C(O)N(R)(R) or -N(R)C(O)R, where each R is independently selected from the groups described below.

[0048] As used herein, and according to some embodiments, the term "carbonate" and related terms such as "carbonate group" and "carbonate substituents", as they relate to groups and substituents of various groups of the compounds and components of the invention, include substances represented by -OC(O)OR, where R is selected from the groups described below, other than hydrogen.

[0049] As used herein, and according to some embodiments, the terms "carbamate" and related terms such as "urethane" and related terms such as "carbamate group," "carbamate substituent," "urethane group" and "urethane substituent," as they relate to groups and substituents of various groups of the compounds and components of the invention, include materials represented by -OC(O)N(R)(H) or -N(H)C(O)OR, where R in each instance is independently selected from the groups described below other than hydrogen.

[0050] As used herein, and according to some embodiments, the term "urea" and related terms such as "urea group" and "urea substituents," as they relate to groups and substituents of various groups of the compounds and components of the invention, include substances represented by -N(R)C(O)N(R)(R), where each R is independently selected from the groups described below.

[0051] As used herein, and according to some embodiments, the term "siloxy" and related terms such as "siloxy group" and "siloxy substituents", as they relate to groups and substituents of various groups of the compounds and components of the invention, include materials represented by -O-Si(R)3, where each R is independently selected from the groups described below, other than hydrogen.

[0052] As used herein, and according to some embodiments, the term "alkoxysilane" and related terms such as "alkoxysilane group" and "alkoxysilane substituent" refer to groups and substituents of various groups of the compounds and components of the present invention and include -Si(OR'') w (R) twherein w is 1 to 3, t is 0 to 2, and R″ for each w is independently selected from alkyl, and R for each t is independently selected from the groups described below other than hydrogen, provided that the sum of w and t is 3.

[0053] As used herein, and according to some embodiments, the term "polysiloxane" and related terms such as "polysiloxane group" and "polysiloxane substituent," as they relate to groups and various group substituents of the compounds and components of the present invention, include materials represented by the following formula (A): [ka]

[0054] With respect to formula (A), t' is 2 or greater, such as 2 to 200; R for each t' is f and R g are each independently selected from the groups R described below other than hydrogen; R h are independently a group R described below.

[0055] Unless otherwise specified, each R group in each of the above-mentioned ketone, ester (carboxylic acid ester), carboxylate, amide, carbonate, carbamate, urea, siloxane, alkoxysilane groups, and polysiloxane groups is independently selected at each occurrence from hydrogen, alkyl, haloalkyl, perhaloalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and combinations thereof, including the classes and examples enumerated herein above.

[0056] The photochromic compositions of the present invention include a trialkoxysilane-functional material having at least two trialkoxysilane groups. The trialkoxysilane-functional material, for some embodiments, has 2 to 7 trialkoxysilane groups, or 2 to 5 trialkoxysilane groups, or 2 to 4 trialkoxysilane groups. The trialkoxysilane groups can each independently be a trimethoxysilane group or a triethoxysilane group.

[0057] For some embodiments, the trialkoxysilane functional material does not include aromatic groups. For some further embodiments, the trialkoxysilane functional material includes one or more of the following bonds: ether bond (-O-); thioether bond (-S-); urea bond (-N(R)-C(O)-N(R)-, where each R is independently as described above); carbonate bond (-OC(O)-O-); carboxylic acid ester bond (-OC(O)-); urethane bond (-N(H)-C(O)-O-); thiourethane bond (-SC(O)-N(H)-); thiourea bond (-N(R)-C(S)-N(R)-, where each R is independently as described above); and amide bond (-C(O)-N(R)-, where R is as described above).

[0058] For some embodiments, the trialkoxysilane functional material is represented by the following formula (I): [ka]

[0059] With respect to formula (I), n is at least 2, such as 2 to 7, or 2 to 6, or 2 to 5, or 2 to 4, or 2 to 3, inclusive of the values ​​recited in each instance. 2 is, in each occurrence, independently methyl or ethyl. Further with respect to formula (I), R 1 comprises at least one of the following: a polyvalent aliphatic hydrocarbon residue; a polyvalent aliphatic ether residue; a polyvalent aliphatic urethane residue; a polyvalent aliphatic carboxylic acid ester residue; a polyvalent aliphatic carbonate residue; or a combination of two or more thereof. The polyvalent aliphatic hydrocarbon residue, the polyvalent aliphatic ether residue, the polyvalent aliphatic urethane residue, the polyvalent aliphatic carboxylic acid ester residue, and the polyvalent aliphatic carbonate residue, in each instance, independently, have a valence of n (or a valence equal to n).

[0060] As used herein, the term "aliphatic hydrocarbon" refers to a hydrocarbon that may be linear or branched and / or cyclic and does not contain aromatic groups. For some embodiments, the polyvalent aliphatic hydrocarbon residue is a linear or branched C1-C 20 Alkyl, straight or branched chain alkyl, or CC3-C 10 It is selected from cycloalkyl, such as cycloalkyl.

[0061] For some embodiments, R of formula (I) 1 comprises at least one of a polyvalent aliphatic hydrocarbon residue, a polyvalent aliphatic urethane residue, a polyvalent aliphatic carbonate residue, or a combination of two or more thereof.

[0062] As used herein, the term "aliphatic ether" refers to an ether containing at least one ether linkage (-O-), which may be linear or branched and / or cyclic, and does not contain an aromatic group. The polyvalent aliphatic ether residue, for some embodiments, contains 1 to 20, or 1 to 15, or 1 to 10, or 1 to 8, or 1 to 5, or 1 to 4, or 1 to 3 ether linkages. For some further embodiments, the polyvalent aliphatic ether residue contains linear or branched C1 to C6 alkyl groups, independently extending between and / or from each ether linkage. 20 Alkyl bonds and / or C3-C 10 Contains a cycloalkyl bond.

[0063] As used herein, the term "aliphatic urethane" refers to a urethane containing at least one urethane bond (-OC(O)-N(H)-), which may be linear or branched and / or cyclic, and does not contain aromatic groups. The polyvalent aliphatic urethane residue, for some embodiments, contains 1 to 20, or 1 to 15, or 1 to 10, or 1 to 8, or 1 to 5, or 1 to 4, or 1 to 3 urethane bonds. For some further embodiments, the polyvalent aliphatic urethane residue contains linear or branched C1-C cyclic alkyl groups extending between and / or from each urethane bond. 20 Alkyl bonds and / or C3-C 10 Contains a cycloalkyl bond.

[0064] As used herein, the term "aliphatic carboxylic acid ester" refers to a carboxylic acid ester that includes at least one carboxylic acid ester bond (-C(O)-O-), which may be linear or branched and / or cyclic, and does not include aromatic groups. The polyvalent aliphatic carboxylic acid ester residue, for some embodiments, includes 1 to 20, or 1 to 15, or 1 to 10, or 1 to 8, or 1 to 5, or 1 to 4, or 1 to 3 carboxylic acid ester bonds. For some further embodiments, the polyvalent aliphatic carboxylic acid ester residue includes linear or branched C1-C alkyl groups extending independently between and / or from each carboxylic acid ester bond. 20 Alkyl bonds and / or C3-C 10 Contains a cycloalkyl bond.

[0065] As used herein, the term "aliphatic carbonate" refers to a carbonate that includes at least one carbonate linkage (-OC(O)-O-), which may be linear or branched and / or cyclic, and does not include aromatic groups. The polyvalent aliphatic carbonate residue, for some embodiments, includes 1 to 20, or 1 to 15, or 1 to 10, or 1 to 8, or 1 to 5, or 1 to 4, or 1 to 3 carbonate linkages. For some further embodiments, the polyvalent aliphatic carbonate residue includes independently 1 to 5 C1 to C2 carbon atoms extending between and / or from each carbonate linkage. 20 Alkyl bonds and / or C3-C 10 Contains a cycloalkyl bond.

[0066] Examples of trialkoxysilane functional materials having at least two trialkoxysilane groups that may be used in the curable photochromic compositions of the present invention include, but are not limited to, 1,1-bis(trimethoxysilylmethyl)ethylene; 1,6-bis(trimethoxysilyl)hexane; 1,8-bis(trimethoxysilyl)octane, 1,10-bis(trimethoxysilyl)decane; 1,6-bis(trimethoxysilyl)2,5-dimethylhexane; N,N'-bis[(3-trimethoxysilyl)propyl)ethylenediamine. bis(3-trimethoxysilylpropyl)amine; bis(3-trimethoxysilylpropyl)-N-methylamine; N-(hydroxyethyl)-N,N-bis(trimethoxysilylpropyl)amine; tris(3-trimethoxysilylpropyl)isocyanurate; bis(3-trimethoxysilylpropyl)fumarate; N,N'-bis(3-trimethoxysilylpropyl)thiourea; tetrakis-{3-[2-trimethoxysilylethyl)tetramethyldisiloxanylpropoxy]methyl}methane; and combinations of two or more thereof.

[0067] The trialkoxy-functional material of the curable photochromic composition of the present invention may be prepared according to art-recognized methods. For some embodiments, the trialkoxy-functional material may be prepared from the reaction of an isocyanate-functional trialkoxysilane reactant, such as an isocyanatoalkyltrialkoxysilane, with an active hydrogen-functional reactant having at least two active hydrogen groups, such as hydroxyl, thiol, and / or primary amine groups. For some embodiments, the active hydrogen-functional reactant has an active hydrogen equivalent of 500 g / mole or less. Examples of isocyanate-functional trialkoxysilane reactants include, but are not limited to, 3-isocyanatopropyltrimethoxysilane; 3-isocyanatopropyltriethoxysilane; isocyanatomethyltrimethoxysilane; and isocyanatomethyltriethoxysilane.

[0068] Examples of polyols from which the active hydrogen functional reactant may be selected include, but are not limited to, aliphatic and / or cycloaliphatic polyols such as: ethylene glycol; diethylene glycol; propylene glycol; 1,3-propanediol; 1,2-butanediol; 1,4-butanediol; neopentyl glycol; 2-methyl-1,3-propanediol; glycerol; trimethylolpropane; ditrimethylolpropane; pentaerythritol; dipentaerythritol; erythritol; meso-erythritol; xylitol; Heterocyclic aliphatic polyols such as butylitol, sorbitol, 1,4-cyclohexanediol, 1,3-cyclohexanediol, or 1,2-cyclohexanediol, cyclohexanetriol, such as 1,3,5-cyclohexanetriol or 1,2,3-cyclohexanetriol, cyclohexanetetrol, cyclohexanepentol, cyclohexanehexol, cyclopentanediol, such as 1,3-cyclopentanediol or 1,2-cyclopentanediol, and 1,3,5-tris(2-hydroxyethyl)isocyanurate. For some embodiments, the polyol reactant has a hydroxyl equivalent weight of 500 g / mole or less.

[0069] The active hydrogen functional reactants, for some embodiments, include one or more of the following: aliphatic polyether polyols; aliphatic polyester polyols; aliphatic polycarbonate polyols; and aliphatic polycarbonate-polyester polyols.

[0070] Examples of polyamines from which the active hydrogen functional reactant may be selected include, but are not limited to, linear or branched C2-C6 alkane diamines; diethylene triamines; branched polyethyleneimines; polyether diamines; and polyether triamines. Polyether diamines and polyether triamines are commercially available under the trademark JEFFAMINE polyether amines. For some embodiments, the polyamine reactant has an amine equivalent weight of 500 g / mole.

[0071] Examples of polythiols from which the active hydrogen functional reactants can be selected include, but are not limited to, 1,2-ethanedithiol; 1,2-propanedithiol; 1,3-propanedithiol; 1,2,3-propanetrithiol; bis(2-mercaptoethyl)sulfide; trimethylolpropane tris(3-mercaptopropionate); and pentaerythritol tetrakis(3-mercaptopropionate).

[0072] For some embodiments, the trialkoxysilane functional material is prepared from the reaction of a polyisocyanate reactant having at least two isocyanate groups with an amine-functional trialkoxysilane, such as an aminoalkyltrialkoxysilane. Examples of polyisocyanate reactants include, but are not limited to, the polyisocyanate materials further listed herein. Examples of amine-functional trialkoxysilane reactants include, but are not limited to: 3-aminopropyltrimethoxysilane; 4-amino-3,3-dimethylbutyltrimethoxysilane; N-(2aminoethyl)-3-aminopropyltrimethoxysilane; N-(2-aminoethyl)-3-aminopropyltriethoxysilane; N-(6-aminohexyl)aminopropyltrimethoxysilane.

[0073] For some embodiments, trialkoxysilane functional materials are prepared from the reaction of a polyisocyanate reactant having at least two isocyanate groups with a thiol (or mercapto; -SH) functional trialkoxysilane, such as a thioalkyltrialkoxysilane (or mercaptoalkyltrialkoxysilane). Examples of polyisocyanate reactants include, but are not limited to, the polyisocyanate materials further listed herein. Examples of thiol functional trialkoxysilane reactants include, but are not limited to: (3-mercaptopropyl)trimethoxysilane; and (3-mercaptopropyl)triethoxysilane.

[0074] Trialkoxysilane-functional materials, for some embodiments, are prepared by a Michael addition / reaction comprising an amine-functional trialkoxysilane reactant or a thiol-functional trialkoxysilane reactant; and an acrylate-functional reactant having at least two acrylate groups. Classes and examples of amine-functional trialkoxysilane and thiol-functional trialkoxysilane reactants include those listed herein above. Examples of acrylate-functional reactants include, but are not limited to, alkylene glycol diacrylates, such as ethylene glycol diacrylate and neopentyl glycol diacrylate; and dimethylol triacylate.

[0075] Trialkoxysilane functional materials, for some embodiments, are prepared by a Michael addition / reaction that includes: a polyamine reactant having at least two amine groups or a polythiol reactant having at least two thiol groups; and an acrylate-functional trialkoxysilane reactant. Classes and examples of polyamine and polythiol reactants include those listed herein above. A non-limiting class of acrylate-functional trialkoxysilane reactants includes (trialkoxysilane) alkyl acrylates, such as 3-(trimethoxysilyl)propyl acrylate.

[0076] The trialkoxysilane functional material having at least two trialkoxysilane groups is present in the curable photochromic composition of the present invention in an amount of from 50 to 85 weight percent, or from 50 to 80 weight percent, or from 60 to 75 weight percent, inclusive of the recited values, for some embodiments, in each case based on the total weight of the resin solids of the curable photochromic composition.

[0077] As used herein and with respect to the curable photochromic compositions, the terms "total weight of resin solids" and similar terms such as "total weight of resin solids" and "total resin solids" mean the total weight of the trialkoxysilane-functional material and the segmented polymer, and for some further embodiments, do not include the weight of the photochromic compound or other optional additives.

[0078] According to some embodiments, the trialkoxysilane-functional material comprises Si in an amount of 5.0 to 16.0 weight percent, or 6.0 to 14.0 weight percent, or 7.0 to 13.0 weight percent, in each case based on the solids weight of the trialkoxysilane-functional material, the amount of Si being determined for some embodiments by NMR analysis or mass spectroscopy analysis of the trialkoxysilane-functional material or calculation from the chemical formula.

[0079] According to some further embodiments, the weight ratio of trialkoxysilane functional material to segmented polymer is from 80:15 to 50:50, or from 80:20 to 50:50, or from 75:25 to 60:40.

[0080] The photochromic compositions of the present invention comprise a segmented polymer comprising (i) at least one first segment and (ii) at least one second segment, each of which independently comprises at least one of a (meth)acrylic polymer segment and / or a fluoroethylene vinyl ether polymer segment.

[0081] The (meth)acrylic monomers from which the (meth)acrylic polymer segments of each first segment can be independently prepared include C1 to C 20 (Meth)acrylate and optionally at least one active hydrogen group selected from hydroxyl, thiol, primary amine and secondary amine, 20 (Meth)acrylates include, but are not limited to, C1 to C2 of (meth)acrylates. 20 The group is, for example, C1-C 20Straight chain alkyl, C3-C 20 Branched chain alkyl, C3-C 20 Cycloalkyl, C3-C 20 Fused-ring polycycloalkyl, C5-C 20 Aryl and C 10 ~C 20 fused ring aryls.

[0082] Each (meth)acrylic polymer segment of each first segment can be prepared independently from C1 to C6. 20 Examples of (meth)acrylates (lacking functional groups such as hydroxyl, thiol, primary amine and secondary amine groups) 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.

[0083] For some embodiments, C1-C having at least one active hydrogen group 20 (Meth)acrylate is a C1-C acrylate having at least one hydroxyl group. 20 Each (meth)acrylic polymer segment of each first segment may be independently prepared from a C1 to C6 (meth)acrylate having at least one active hydrogen group selected from hydroxyl. 20 Examples of (meth)acrylates include, but are not limited to, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxycyclohexyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 12-hydroxydodecyl (meth)acrylate.

[0084] For some embodiments, the hydroxyl group is introduced into the (meth)acrylic polymer segment of the first segment after its formation. For non-limiting illustrative purposes, the (meth)acrylic polymer segment of the first segment can be prepared from monomers including (meth)acrylic monomers having oxirane functionality. The oxirane-functional (meth)acrylic monomer residues or units can be hydrolyzed or reacted with a monofunctional alcohol after polymerization to form hydroxy-functional (meth)acrylic monomer residues or units. Examples of oxirane-functional (meth)acrylates from which the (meth)acrylic polymer segment of the first segment can be prepared include, but are not limited to, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, and 2-(3,4-epoxycyclohexyl)ethyl (meth)acrylate.

[0085] For some embodiments, the (meth)acrylic polymer segment of each first segment is prepared from, in addition to (meth)acrylate monomers, additional ethylenically unsaturated radically polymerizable monomers (other than (meth)acrylate monomers), such as (meth)acrylic acid, vinyl aromatic monomers, vinyl esters of carboxylic acids, and / or other ethylenically unsaturated monomers that are radically polymerizable.

[0086] Examples of vinyl aromatic monomers that may be used to form the (meth)acrylic polymer segment of the first segment include, but are not limited to, styrene, p-chloromethylstyrene, divinylbenzene, vinylnaphthalene, and divinylnaphthalene.

[0087] Examples of vinyl esters of carboxylic acids that can be used to form the (meth)acrylic polymer segment of the first segment include, but are not limited to, vinyl acetate, vinyl butyrate, vinyl 3,4-dimethoxybenzoate, and vinyl benzoate.

[0088] Examples of other ethylenically unsaturated monomers that are radically polymerizable that can be used to form the (meth)acrylic polymer segment of the first segment include, but are not limited to, cyclic anhydrides such as maleic anhydride, 1-cyclopentene-1,2-dicarboxylic anhydride, and itaconic anhydride; esters of acids that are unsaturated but do not have α,β-ethylenic unsaturation, such as the methyl ester of undecylenic acid; and diesters of ethylenically unsaturated dibasic acids, such as diethyl maleate.

[0089] For some embodiments, the (meth)acrylic polymer segment of each first segment is prepared from radically polymerizable monomers selected only from: C1 to C 20 (Meth)acrylate and optionally C1-C having at least one active hydrogen group selected from hydroxyl, thiol, primary amine, and secondary amine 20 (Meth)acrylate monomers such as (meth)acrylate; and optionally (meth)acrylic acid.

[0090] The (meth)acrylic polymer segment of each first segment may be prepared by art-recognized polymerization methods, including, but not limited to, free radical polymerization methods and living radical polymerization methods, such as atom transfer radical polymerization methods.

[0091] The (meth)acrylic polymer segment of each first segment may have any suitable polymer chain (or backbone) structure, such as: a random polymer chain structure; a block polymer chain structure; an alternating polymer chain structure; and a gradient polymer chain structure.

[0092] The (meth)acrylic polymer segment of each first segment may have any suitable overall structure and may thus be selected, for example, from a linear (meth)acrylic polymer segment and / or a branched (meth)acrylic polymer segment. For some embodiments, the (meth)acrylic polymer segment of each first segment is a linear (meth)acrylic polymer segment.

[0093] The (meth)acrylic segment of each first segment can have any suitable molecular weight. For some embodiments, the (meth)acrylic segment of each first segment can independently have a Mn of at least 1000, such as a Mn of 1000 to 15,000; and a Mw of at least 2000, such as a Mw of 2000 to 30,000.

[0094] Each first segment, for some embodiments, independently comprises a fluoroethylene vinyl ether polymer segment. For some embodiments, each fluoroethylene vinyl ether polymer segment is a fluoroethylene-alkyl vinyl ether alternating polymer (or copolymer) segment. The fluoroethylene monomer used to prepare the fluoroethylene vinyl ether polymer segment comprises, for some embodiments, chlorotrifluoroethylene and / or tetrafluoroethylene. For some embodiments, the vinyl ether monomer used to prepare the fluoroethylene vinyl ether polymer segment comprises one or more alkyl vinyl monomers, including, for example, linear or branched C2-C8 alkyl vinyl ether or linear or branched C2-C4 alkyl vinyl ether. For some embodiments, in addition to the fluoroethylene monomer and the alkyl vinyl monomer, the fluoroethylene vinyl ether polymer segment is prepared using one or more optional comonomers, such as: olefins, such as ethylene, propylene, and isobutylene; haloolefins, such as vinyl chloride and vinylidine chloride; unsaturated carboxylic acid esters, such as alkyl (meth)acrylates, and vinyl carboxylates, such as vinyl acetate and vinyl butyrate; and hydroxyl-functional ethylenically unsaturated monomers, such as hydroxyalkyl vinyl ether monomers.

[0095] Non-limiting classes of fluorinated polymers from which the fluorinated polymer segments can be prepared or derived include alternating fluoroethylene-alkyl vinyl ether copolymers (such as those described in U.S. Pat. No. 4,345,057), examples of which include, but are not limited to, LUMIFLON® fluoroethylene copolymers available from AGC Chemicals Americas.

[0096] The segmented polymer of the curable photochromic composition of the present invention further comprises at least one second segment, each second segment independently comprising at least one of a polycarbonate segment, a polyester segment, a polyether segment, or a polyurethane segment.

[0097] Each polycarbonate segment of each second segment of the segmented polymer can be prepared independently according to art-recognized methods. For some embodiments and for non-limiting illustrative purposes, each polycarbonate segment can be prepared independently from the reaction of an aliphatic polyol, such as a diol, with a carbonyl dihalide, such as carbonyl dichloride, while removing the resulting halide acid, such as HCl. For further non-limiting illustrative purposes, each polycarbonate segment can be prepared independently from the transesterification of a polyol, such as a diol, with a dihydrocarbyl carbonate, such as diphenyl carbonate, while removing the resulting hydroxyl-functional hydrocarbyl, such as phenol.

[0098] Examples of polyols having at least two hydroxyl groups from which each polycarbonate segment may be independently prepared include, but are not limited to, glycerin, trimethylolpropane, trimethylolethane, trishydroxyethyl isocyanurate, pentaerythritol, ethylene glycol, propylene glycol, trimethylene glycol, 1,3-, 1,2-, and 1,4-butanediol, pentanediol (including but not limited to 1,5-pentanediol), heptanediol, hexanediol, octanediol, 4,4'-(propane-2,2-diyl)dicyclohexanol, 4,4'-methylenedicyclohexanol, neopentyl glycol, 2,2,3-trimethylpentane-1,3-diol, 1,4-dimethylolcyclohexane, 2,2,4-trimethylpentanediol, and similar polyols.

[0099] Each polycarbonate segment of each second segment may independently have no active hydrogen functionality or may include one or more active hydrogen functional groups each independently selected from hydroxyl, thiol, primary amine, and secondary amine. The active hydrogen functionality may be independently introduced into each polycarbonate segment during or after its formation according to art-recognized methods. According to some embodiments, at least a portion of the polycarbonate segments have hydroxyl functionality. The polycarbonate segments having hydroxyl functionality may be prepared from a polycarbonate polyol, such as a polycarbonate diol, for some embodiments. The polycarbonate polyol, such as a polycarbonate diol, may be selected from commercially available polycarbonate polyols, such as, but not limited to, ETERNACOLL® polycarbonate diol from Ube Industries, Ltd. and DURANOL polycarbonate diol from Asahi Kasei Corporation, for some further embodiments.

[0100] Each polycarbonate segment of each second segment can have any suitable molecular weight. For some embodiments, each polycarbonate segment of each second segment independently has a Mw of less than 45,000, such as 3,000 to 40,000.

[0101] Each polyester segment of the second segment of the segmented polymer can be prepared independently according to art-recognized methods. For some embodiments and for non-limiting illustrative purposes, each polyester segment can be prepared independently by reacting an aliphatic carboxylic acid functional material (and / or its cyclic anhydride and / or its ester) having a carboxylic acid functionality (or available carboxylic acid functionality, such as in the case of cyclic anhydrides and carboxylic acid esters) of at least 2 with a polyol having a hydroxy functionality of at least 2. The molar equivalent ratio of carboxylic acid groups to hydroxy groups of the reactants is selected so that the resulting polyester segment has hydroxyl and / or carboxylic acid functionality and the desired molecular weight.

[0102] Examples of polyfunctional carboxylic acids useful in preparing each polyester segment include, but are not limited to, tetrahydrophthalic acid, hexahydrophthalic acid, endo-bicyclo-2,2,1,5-heptyne-2,3-dicarboxylic acid, cyclohexanedioic acid, succinic acid, azelaic acid, maleic acid, adipic acid, sebacic acid, and similar polyfunctional carboxylic acids (optionally including the appropriate cyclic anhydrides and / or esters thereof).

[0103] Examples of polyols that may be used to prepare each polyester segment of the second segment include, but are not limited to, the examples of polyols listed previously herein.

[0104] Each polyester segment of each second segment may independently have no active hydrogen functionality or may include one or more active hydrogen functional groups each independently selected from hydroxyl, thiol, primary amine, and secondary amine. The active hydrogen functionality may be independently introduced into each polyester segment during or after its formation according to art-recognized methods.

[0105] Each polyester segment of each second segment can have any suitable molecular weight. For some embodiments, each polyester segment of each second segment independently has a Mw of less than 45,000, such as from 3,000 to 40,000.

[0106] Each polyether segment of each second segment of the segmented polymer can be prepared independently according to art-recognized methods. For some embodiments, the polyether segment is selected from polyalkylene glycols, such as, but not limited to, polyethylene glycol, polypropylene glycol, poly(1,2-butylene glycol), polyethylene glycol-polypropylene glycol copolymers, and polytetrahydrofuran.

[0107] Each polyether segment of each second segment may independently have no active hydrogen functionality or may include one or more active hydrogen functional groups each independently selected from hydroxyl, thiol, primary amine, and secondary amine. The active hydrogen functionality may be independently introduced into each polyether segment during or after its formation according to art-recognized methods.

[0108] Each polyether segment of each second segment can have any suitable molecular weight. For some embodiments, each polyether segment of each second segment independently has a Mw of less than 45,000, such as from 3,000 to 40,000.

[0109] Each polyurethane segment of each second segment of the segmented polymer can be prepared independently according to art-recognized methods.For some embodiments and for non-limiting illustrative purposes, each polyurethane segment can be prepared independently with a suitable molar excess of hydroxyl groups to form a hydroxyl-functional polyurethane with at least two hydroxyl groups from the reaction of a polyisocyanate having at least two isocyanate groups with a polyol having at least two hydroxyl groups; or with a suitable molar excess of isocyanate groups to form a polyurethane with at least two isocyanate groups.Examples of polyisocyanates useful in preparing polyurethane segments include, for some embodiments, aliphatic, cycloaliphatic and heterocyclic polyisocyanates and mixtures of such polyisocyanates.

[0110] Further examples of polyisocyanates useful in the preparation of polyurethane segments include tetramethylene-1,4-diisocyanate; hexamethylene-1,6-diisocyanate; 2,2,4-trimethylhexane-1,6-diisocyanate; 2,4,4-trimethylhexane-1,6-diisocyanate; lysine methyl ester diisocyanate; bis(isocyanatoethyl) fumarate; isophorone diisocyanate; ethylene diisocyanate; dodecane-1,12-diisocyanate; cyclobutane-1,3-diisocyanate; cyclohexamethylol diisocyanate; hexahydrotoluene-2,4-diisocyanate; hexahydrotoluene-2,6-diisocyanate; hexahydrophenylene-1,3-diisocyanate; hexahydrophenylene-1,4-diisocyanate; perhydrodiphenylmethane-2,4'-diisocyanate; perhydrodiphenylmethane-4,4'-diisocyanate; norbornane diisocyanate; and mixtures thereof.

[0111] Examples of polyols having at least two hydroxyl groups from which the polyurethane segment of the second segment may be prepared include, but are not limited to, the polyols listed herein above.

[0112] Each polyurethane segment of each second segment may independently have no active hydrogen functionality or may include one or more active hydrogen functional groups each independently selected from hydroxyl, thiol, primary amine, and secondary amine. Active hydrogen functionality may be independently introduced into each polyurethane segment during or after its formation according to art-recognized methods.

[0113] Each polyurethane segment of each second segment can have any suitable molecular weight. For some embodiments, each polyurethane segment of each second segment independently has a Mw of less than 45,000, such as from 3,000 to 40,000.

[0114] Each second segment of the segmented polymer of the curable composition of the present invention, for some embodiments, independently comprises at least one of a polycarbonate segment, a polycarbonate-polyester segment, a polycarbonate-polyurethane segment, and a polycarbonate-polyester-polyurethane segment.

[0115] Each polycarbonate-polyester segment of each second segment of the segmented polymer can be prepared independently according to art-recognized methods. For some embodiments and for non-limiting illustrative purposes, each polycarbonate-polyester segment can be prepared independently according to the description provided hereinabove for the preparation of polyester segments, where at least a portion of the polyol is a polycarbonate polyol. The polycarbonate polyol can be prepared according to the description provided hereinabove for the preparation of polycarbonate segments, adjusting the molar ratio of reactants so that the resulting polycarbonate has hydroxyl functionality and correspondingly a polycarbonate polyol having the desired molecular weight. The polycarbonate polyol, such as a polycarbonate diol, from which the polycarbonate-polyester segment is prepared has a Mw range of 500 to 20,000, or 500 to 10,000, or 500 to 5,000 for some embodiments. Each polycarbonate-polyester segment of each second segment can have any suitable molecular weight. According to some embodiments, each polycarbonate-polyester segment of each second segment independently has a Mw of less than 45,000, such as from 3,000 to 40,000.

[0116] Each polycarbonate-polyurethane segment of each second segment of the segmented polymer can be prepared independently according to art-recognized methods. For some embodiments and for non-limiting illustrative purposes, each polycarbonate-polyurethane segment can be prepared independently according to the description provided hereinabove for the preparation of polyurethane segments, where at least a portion of the polyol is a polycarbonate polyol. The polycarbonate polyol can be prepared according to the description provided hereinabove for the preparation of polycarbonate segments, adjusting the molar ratio of reactants so that the resulting polycarbonate has hydroxyl functionality and correspondingly a desired molecular weight. The polycarbonate polyol, such as the polycarbonate diol from which the polycarbonate-polyurethane segment is prepared, has a Mw range of 500 to 20,000, or 500 to 10,000, or 500 to 5,000 for some embodiments. According to some embodiments, each polycarbonate-polyurethane segment of each second segment independently has a Mw of less than 45,000, such as from 3,000 to 40,000.

[0117] Each polycarbonate-polyester-polyurethane segment of each second segment of the segmented polymer can be prepared independently according to art-recognized methods. For some embodiments and for non-limiting illustrative purposes, each polycarbonate-polyester-polyurethane segment can be prepared independently according to the description provided herein above for the preparation of polyurethane segments when at least a portion of the polyol is a polycarbonate-polyester polyol. The polycarbonate-polyester polyol can be prepared according to the description provided herein above when the mole ratio of reactants is adjusted so that the resulting polymer is a polycarbonate-polyester polyol having hydroxyl functionality and correspondingly the desired molecular weight. The polycarbonate-polyester polyol, such as a polycarbonate-polyester diol, from which the polycarbonate-polyester-polyurethane segment is prepared has a Mw range of 1,000 to 20,000, or 1,000 to 10,000, or 500 to 5,000 for some embodiments. According to some embodiments, each polycarbonate-polyester-polyurethane segment of each second segment independently has a Mw of less than 45,000, such as from 3,000 to 40,000.

[0118] For some embodiments, each first segment and each second segment of the segmented polymer are formed separately. The preformed first segment and the preformed second segment are then combined together (e.g., reacted together resulting in the formation of a covalent bond therebetween) to form the segmented polymer of the curable photochromic composition of the present invention. For some additional embodiments, the reactive group present at the end of the preformed second segment can react with a complementary reactive group on the preformed first segment. Non-limiting examples of complementary reactive groups include active hydrogens such as hydroxyls, thiols, or amines that react with isocyanates to form urethane, thiourethane, or urea groups, respectively. When the preformed first and second segments both contain active hydrogen groups, a bifunctional material containing a complementary reactive group, such as an isocyanate, can be used to covalently bond the first and second segments. In some embodiments, a portion of the terminal reactive groups on the preformed second segment can be protected by art-recognized protecting (or blocking) groups to prevent gelation, such as blocked isocyanates.

[0119] For some further embodiments, each first segment is formed first, and then each second segment is formed by polymerization from (or away from) the backbone of the previously formed first segment. A non-limiting example of such a reaction is the ring-opening polymerization of a cyclic ester to form a second segment of a polyester directly attached to the first segment.

[0120] According to some embodiments, at least a portion of the active hydrogen groups on the separately formed first segment are used to form bonds to the second segment, thereby consuming at least a portion of the active hydrogen of the first segment. According to some further embodiments, substantially all of the active hydrogen groups on the separately formed first segment are used to form bonds to the second segment, thereby consuming substantially all of the active hydrogen of the first segment.

[0121] The segmented polymer of the curable photochromic composition of the present invention, for some embodiments, optionally comprises active hydrogen groups. Each active hydrogen group of the segmented polymer, for some embodiments, is independently selected from hydroxyl (-OH), thiol (-SH), primary amine (-NH2), and secondary amine (-NHR'), where each R' includes the classes and examples thereof listed herein above, and may be a linear or branched C1-C 20 The active hydrogen groups are independently selected from any suitable organic group, such as alkyl groups and cycloalkyl groups. For some embodiments, each active hydrogen group of the segmented polymer is a hydroxyl group. According to some embodiments, at least one first segment and / or at least one second segment of each segmented polymer independently comprises one or more active hydrogen groups, such as hydroxyl groups.

[0122] For some embodiments, each first segment of the segmented polymer does not include functional groups such as hydroxyl, thiol, primary amine, and secondary amine groups.

[0123] At least one first segment of the segmented polymer comprises a hydroxyl group for some embodiments. Each first segment of the segmented polymer comprises a hydroxyl group for some embodiments. For some additional embodiments, at least one first segment of the segmented polymer comprises a hydroxyl group and each second segment of the segmented polymer does not comprise a hydroxyl group. According to some further embodiments, each first segment of the segmented polymer comprises a hydroxyl group and each second segment of the segmented polymer does not comprise a hydroxyl group.

[0124] According to some embodiments of the present invention, the segmented polymer has a hydroxyl number of less than 35, such as 30 or less, or 25 or less, or 20 or less, or 15 or less, or 10 or less.

[0125] With respect to the segmented polymer of the curable photochromic composition of the present invention, and according to some embodiments, at least one first segment and at least one second segment are covalently bonded to one another by a linking group. Examples of such linking groups include carboxylic acid ester linking groups (-C(O)O-), thioester linking groups (-C(O)-S-), amide linking groups (-C(O)-N(R a )-), urethane bond (-N(H)-C(O)-O-), thiourethane bond (-N(H)-C(O)-S-), urea bond (-N(R a )-C(O)-N(R a )-), thiourea linking group (-N(R a )-C(S)-N(R a )-), carbonate linking groups (-OC(O)-O-), ether linking groups (-O-), and thioether linking groups (-S-). a The groups each include hydrogen and any suitable organic group, such as the classes and examples thereof listed herein above, and may be linear or branched C1-C 20 The alkyl groups may be independently selected from alkyl groups, cycloalkyl groups, and the like.

[0126] For some embodiments of the present invention, each second segment is covalently bonded to at least one first segment. The segmented polymer of the curable photochromic composition of the present invention, for some embodiments, is gel-free (non-gelling).

[0127] The segmented polymer has a Mw of from 35,000 to 250,000, or from 40,000 to 200,000, or from 50,000 to 150,000 for some embodiments.

[0128] The curable photochromic composition, for some embodiments, includes a catalyst that catalyzes the formation of siloxane bonds. Non-limiting classes of siloxane catalysts include: acid catalysts, including inorganic or organic acids, such as hydrochloric acid, phosphorous acid, phosphoric acid, phytic acid, nitric acid, acetic acid, oxalic acid, malic acid, maleic acid, citric acid, formic acid, and benzoic acid; base catalysts, including inorganic and organic bases, such as sodium hydroxide, ammonium hydroxide, ethanolamine, quaternary amines, and tertiary amines, such as dimethylaminoethanol and diazabicyclo[2.2.2]octane; organotin compounds, such as dibutyltin dilaurate and dibutyltin bis(acetylacetonate); and zinc complexes, such as zinc carboxylates. The catalyst is present in the curable photochromic composition in an effective amount, such as, for some embodiments, but not limited to, 0.05 to 5 weight percent based on the total weight of resin solids. A commercially available catalyst is K-KAT® 670 zinc carbonate catalyst.

[0129] Without intending to be bound by any theory, it is believed that the cured article, such as a cured film, prepared from the curable photochromic composition of the present invention further comprises a domain substantially composed of a segmented polymer, including a three-dimensional network of siloxane units (-Si-O-Si-) formed by condensation (or self-condensation) of a trialkoxysilane functional material, and further comprising what is referred to herein as a "second segment domain" formed by a second segment of the segmented polymer. Without intending to be bound by any theory, it is further believed that at least a portion (and in some embodiments at least a majority) of the photochromic compound of the curable photochromic composition of the present invention is present within the second segment domain of the cured article. Without intending to be bound by any theory, it is further believed that the photochromic compound present within the second segment domain has an expanded range of molecular freedom / motion, which allows the photochromic compound to more easily and rapidly transition between open and closed forms, for example in response to exposure to a source of actinic radiation and its removal, thus resulting in expanded photochromic performance properties associated with the cured article.

[0130] According to some embodiments of the curable photochromic composition of the present invention, the second segment is present in the segmented polymer in an amount from 50 to 90 weight percent or from 60 to 85 weight percent (and inclusive of the recited values), based on the total weight of the segmented polymer.

[0131] The curable photochromic composition, for some embodiments, comprises the second segment in a total amount of from 10 weight percent to 45 weight percent, or from 10 weight percent to 35 weight percent, or from 12 weight percent to 30 weight percent, in each case based on the total weight of the resin solids of the curable photochromic composition (and in each case inclusive of the recited values).

[0132] The segmented polymer, for some embodiments, is present in the curable photochromic composition of the present invention in an amount of from 15 to 50 weight percent, or from 20 to 50 weight percent, or from 25 to 40 weight percent, in each case based on the total weight of the resin solids of the curable photochromic composition.

[0133] The curable photochromic compounds of the present invention include photochromic compounds that may be selected from known classes and examples of photochromic compounds and may include combinations or mixtures thereof.

[0134] For example, but not limited to, a mixture of photochromic compounds can be used to achieve a certain activated color, such as an approximately neutral gray or an approximately neutral brown. See, for example, U.S. Patent No. 5,645,767 at column 12, line 66 to column 13, line 19, which describes the parameters that define neutral gray and brown colors, the disclosure of which is specifically incorporated herein by reference.

[0135] For some embodiments, the photochromic compound of the curable photochromic composition of the present invention is selected from the group consisting of naphthopyrans, benzopyrans, phenanthropyrans, indenonaphthopyrans, spiro(indoline)naphthoxazines, spiro(indoline)pyridobenzoxazines, spiro(benzindoline)pyridobenzoxazines, spiro(benzindoline)naphthoxazines, spiro(indoline)-benzoxazines, fulgides, fulgimides, diarylethenes, and mixtures of such photochromic compounds.

[0136] Further examples of other photochromic compounds that may be used in the curable photochromic compositions of the present invention include, but are not limited to, those disclosed in U.S. Pat. No. 9,028,728 B2, column 34, line 20 to column 35, line 13, the disclosures of which are specifically incorporated herein by reference.

[0137] The photochromic compound is present in the curable photochromic composition in an amount at least sufficient to provide an article prepared from the composition with a desired level of photochromic properties, which in some embodiments is referred to as a photochromic amount. For some embodiments, the amount of photochromic compound present in the curable photochromic composition is 0.001 to 40 weight percent, or 0.001 to 10 weight percent, or 0.01 to 5 weight percent, or 0.1 to 2.5 weight percent, based on the total resin solids weight.

[0138] The curable photochromic composition of the present invention, for some embodiments, optionally includes additives such as, but not limited to, waxes for flow and wetting; flow control agents such as poly(2-ethylhexyl)acrylate; antioxidants; and ultraviolet (UV) light absorbers. Examples of useful antioxidants and UV absorbers include, but are not limited to, those available from BASF under the trademarks IRGANOX and TINUVIN. These optional additives, if used, may be present in amounts up to 20 percent by weight based on total resin solids.

[0139] The curable photochromic composition of the present invention further comprises one or more fixed color dyes for some embodiments. As used herein, the term "fixed color dye" and related terms such as "fixed colorant", "static colorant", "fixed pigment" and "static pigment" refer to a dye that is: a non-photosensitive material that does not react physically or chemically to electromagnetic radiation with respect to its color as observed by the eye. As used herein, the term "fixed color dye" and related terms do not include and are distinct from photochromic compounds. As used herein, the term "non-photosensitive material" refers to a material that does not react physically or chemically to electromagnetic radiation with respect to its color as observed by the eye, including but not limited to a fixed color dye.

[0140] One or more fixed color dyes may be present in the curable photochromic compositions of the present invention for the purpose of imparting to a cured article prepared from the curable photochromic composition, without limitation: at least a primary (or first) color characteristic of the fixed color dye when the photochromic compound is not activated; and, optionally, a second color characteristic of the combination of the fixed color dye and the photochromic compound when activated, such as by exposure to actinic radiation.

[0141] The optional fixed color dyes of the curable photochromic composition, for 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.

[0142] The fixed color dye can be present in the curable photochromic composition in various amounts to provide a desired effect in the cured article produced therefrom. For some embodiments, the fixed color dye is present in the curable photochromic composition in an amount of 0.001 to 15 weight percent, or 0.01 to 10 weight percent, or 0.1 to 2.5 weight percent, in each case based on the total resin solids weight of the curable photochromic composition.

[0143] For some embodiments, the curable photochromic composition further comprises a water (or moisture) scavenger. A non-limiting class of water scavengers includes orthoformates such as trialkyl orthoformates, such as tri(linear or branched C1-C6 alkyl) orthoformates. The water scavenger is present in the curable photochromic composition in an effective amount, such as, for some embodiments, 0.5 to 15 weight percent or 5 to 15 weight percent based on the total resin solids content of the curable photochromic composition. A further non-limiting class of water scavengers includes heterogeneous water scavengers such as magnesium sulfate and molecular sieves, which are typically separated from the curable photochromic composition by filtration or the like.

[0144] The curable photochromic composition of the present invention, for some embodiments, comprises a solvent selected from water, organic solvents, and combinations thereof.

[0145] Classes of organic solvents that may be present in the curable photochromic compositions of the present invention include, but are not limited to, alcohols, such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butyl alcohol, tert-butyl alcohol, iso-butyl alcohol, furfuryl alcohol, and tetrahydrofurfuryl alcohol; ketones or ketoalcohols, 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 acetic acid. hydroxy-functional ethers of alkylene glycols, such as butyl-2-hydroxyethyl ether, methylene-1,2-hydroxypropyl ether, and phenyl-2-hydroxypropyl ether; nitrogen-containing cyclic compounds, such as pyrrolidone, N-methyl-2-pyrrolidone, 1-butyl-pyrrolidinone, and 1,3-dimethyl-2-imidazolidinone; sulfur-containing compounds, such as dimethyl sulfoxide and tetramethylene sulfone; aromatic compounds, such as toluene, xylene, anisole, and butyl benzoate; and mixtures of aromatic compounds, such as, but not limited to, C9-C 10 Aromatic 100 Fluid and C, commercial mixtures of dialkylbenzenes and trialkylbenzenes. 10 ~C 12 Aromatic 150 Fluid, a commercially available mixture of alkylbenzenes and alkylnaphthalenes.

[0146] The solvent may be present in the curable photochromic composition of the present invention in an amount of 5 to 95 weight percent, or 15 to 80 weight percent, 30 to 70 weight percent, or 30 to 60 weight percent, in each case based on the total weight of the curable photochromic composition (including the weight of the solvent).

[0147] The present invention also relates to articles, particularly photochromic articles, prepared from the inventive curable photochromic compositions described hereinbefore. For some embodiments, the photochromic articles are selected from layers (including films and / or sheets) and three-dimensional articles.

[0148] Classes of three-dimensional articles that can be prepared from the curable photochromic compositions of the present invention include, but are not limited to, ophthalmic articles, display articles, windows and mirrors.

[0149] More typically, the curable photochromic compositions of the present invention are used to prepare photochromic layers, such as photochromic films and photochromic sheets. As used herein, the term "film" refers, without limitation, to a layer that is not self-supporting, such as a coating. As used herein, the term "sheet" refers to a layer that is self-supporting.

[0150] The curable photochromic composition of the present invention may be cured by any suitable method that results in condensation (or self-condensation) of the alkoxysilane groups of the trialkoxysilane functional material. For some further embodiments, the curable photochromic composition is cured at ambient conditions, such as room temperature of about 25° C., for up to one week. For some further embodiments, the curable photochromic composition is cured by exposure to elevated temperatures (above ambient room temperature). As used herein, "cured" means that a three-dimensional crosslinked network has been formed by covalent bond formation, such as siloxane bonds or units (-Si-O-Si-), resulting from condensation (or self-condensation) between or among the alkoxysilane groups of the trialkoxysilane functional material. When curing is performed at elevated temperatures, the curable photochromic composition may be referred to herein as a thermally curable photochromic composition. The temperature at which the thermally curable photochromic composition of the present invention cures may vary and depends in part on the amount of time that curing is performed. For some embodiments, the curable photochromic composition is cured at elevated temperatures of 35° C. to 175° C., or 40° C. to 150° C., or 80° C. to 130° C. for a period of 15 to 240 minutes.

[0151] The present invention also relates to an article, such as a photochromic article, comprising: (A) a substrate; and (B) a photochromic layer on at least one surface of the substrate, wherein the photochromic layer is formed from a curable photochromic composition of the present invention.

[0152] The article comprising a substrate and a photochromic layer (formed from the curable photochromic composition of the present invention) on at least one surface of the substrate may be selected from ophthalmic articles, display articles, windows and mirrors for some embodiments. Correspondingly, the substrate of the article may be selected from ophthalmic substrates, displays, windows and mirrors. The substrate may be composed of one or more suitable materials, including but not limited to: organic materials, such as organic polymeric materials, including but not limited to thermoplastic polycarbonates, crosslinked polycarbonates, poly(meth)acrylates and combinations thereof; glasses, such as silica-based glasses; metals; ceramic materials; and combinations thereof. Examples of substrates that may be included in the article (including optical elements) of the present invention include, but are not limited to, those described in U.S. Pat. No. 8,628,685 B2, column 35, line 5 to column 36, line 57, the disclosure of which is incorporated herein by reference.

[0153] The substrate, for some embodiments, may optionally include a photochromic material and / or a fixed color dye, each of which may be selected from the classes and examples of photochromic materials and fixed color dyes previously described herein. The optional photochromic material / compound present in the substrate may be the same or different from the photochromic compound of the photochromic layer. The optional fixed color dye may be the same or different from the optional fixed color dye of the photochromic layer.

[0154] The photochromic layer of the article can be a photochromic film or a photochromic sheet. For 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.

[0155] The curable photochromic coating composition may be applied to a substrate according to art-recognized methods, including, but not limited to, spray application, curtain coating application, drawdown blade (or bar) application, dip coating application, spin coating application, jet printing (such as inkjet printing where the "ink" is replaced with the curable photochromic composition according to the present invention), and combinations thereof.

[0156] After application of the curable photochromic composition on at least one surface of the substrate, the applied curable photochromic composition as described herein above is cured. The photochromic layer can be in the form of a single layer or multiple layers. When in the form of multiple layers, each layer of the photochromic layer can be prepared from the curable photochromic composition according to the present invention having the same or different composition, such as the same or different photochromic compounds. The photochromic layer can have any suitable thickness, for example, from 10 micrometers to 250 micrometers or from 15 micrometers to 75 micrometers.

[0157] In addition to the photochromic layer, the article may optionally include one or more additional art-recognized layers, including, but not limited to, the following: a primer layer; an adhesive layer; a protective layer (such as a hardcoat layer); a polarizing layer; a birefringent layer; an antireflective layer; and / or another photochromic layer prepared from a composition other than the curable photochromic composition of the present invention.

[0158] 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 be independently in the form of a film or sheet. The photochromic multilayer article can, for some embodiments, comprise two or more layers formed from the same or different curable photochromic compositions of the present invention.

[0159] The multilayer articles of the present invention may optionally include one or more additional art recognized layers, including, but not limited to, an adhesive layer; a protective layer (such as a hardcoat layer); a polarizing layer; a birefringent layer; an antireflective layer; and / or another photochromic layer prepared from a composition other than the curable photochromic composition of the present invention.

[0160] The multi-layer articles of the present invention can have any suitable thickness, such as from 10 micrometers to 1000 micrometers, or from 15 micrometers to 750 micrometers, or from 25 to 100 micrometers.

[0161] The multilayer articles of the present invention may be used alone or with another article, such as a substrate. The substrate may be selected from the classes and examples of substrates as described herein above with respect to the articles of the present invention, such as ophthalmic substrates, displays, windows and / or mirrors. The substrate may be composed of one or more suitable materials, including, but not limited to, organic materials, such as organic polymeric materials; glasses, such as silica-based glasses; metals; ceramic materials; and combinations thereof.

[0162] The multilayer articles of the present invention may be adhered to a surface of a substrate by art-recognized methods, including, but not limited to, electrostatic attachment, such as by static electricity; one or more intervening adhesive layers; fusion, such as heat sealing; and in-mold forming, such as when the multilayer article is placed in a mold and the substrate is formed against at least one surface of the multilayer article within the mold. The multilayer articles of the present invention, for some embodiments, may be supported by one or more brackets that retainingly engage one or more peripheral regions of the multilayer article.

[0163] The present invention may be further characterized by one or more of the following non-limiting clauses.

[0164] Clause 1:(a) Photochromic compound; (b) a trialkoxysilane-functional material having at least two trialkoxysilane groups; and (c) a segmented polymer comprising at least one first segment and at least one second segment. A curable photochromic composition comprising: (i) each first segment independently comprises at least one of a (meth)acrylic polymer segment or a fluoroethylene vinyl ether polymer segment; and (ii) each second segment independently comprises at least one of a polycarbonate segment, a polyester segment, a polyether segment, or a polyurethane segment;

[0165] Clause 2: The curable photochromic composition of clause 1, wherein the first segment comprises a hydroxyl group.

[0166] Clause 3: The curable photochromic composition of clause 1 or clause 2, wherein the segmented polymer has a hydroxyl number of less than 35.

[0167] Clause 4: The curable photochromic composition of any one of clauses 1-3, wherein the second segment is present in the segmented polymer in an amount of 50 weight percent to 90 weight percent, based on the total weight of the segmented polymer.

[0168] Clause 5: The curable photochromic composition of any one of clauses 1-4, wherein the segmented polymer has a Mw of 35,000 to 250,000.

[0169] Clause 6: The curable photochromic composition of any one of clauses 1-5, wherein each second segment independently comprises a polycarbonate segment, a polycarbonate-polyester segment, a polycarbonate-polyurethane segment, and a polycarbonate-polyester-polyurethane segment.

[0170] Clause 7: The curable photochromic composition of any one of clauses 1-6, wherein the trialkoxysilane functional material includes one or more of the following bonds: an ether bond (-O-); a thioether bond (-S-); a urea bond (-N(R)-C(O)-N(R)-; a carbonate bond (-OC(O)-O-); a carboxylic acid ester bond (-OC(O)-); a urethane bond (-N(H)-C(O)-O-); a thiourethane bond (-SC(O)-N(H)-); a thiourea bond (-N(R)-C(S)-N(R)-); and an amide bond (-C(O)N(R)-), where each R, at each occurrence, is independently selected from hydrogen, alkyl, haloalkyl, perhaloalkyl, cycloalkyl, heterocycloalkyl, and combinations thereof.

[0171] Clause 8: The trialkoxysilane functional material is represented by the following formula (I): [ka] wherein n is at least 2; Each R 2 is independently methyl or ethyl; and R 1 teeth, polyvalent aliphatic hydrocarbon residues, polyvalent aliphatic ether residues, Polyaliphatic urethane residues, a polyvalent aliphatic carboxylic acid ester residue, or (containing at least one polyaliphatic carbonate residue) The curable photochromic composition of any one of clauses 1 to 7, represented by:

[0172] Clause 9: The curable photochromic composition of clause 8, wherein n in formula (I) is 2 to 20, or 2 to 15, or 2 to 10, or 2 to 8, or 2 to 6, or 2 to 5, or 2 to 4, or 2 to 3.

[0173] Article 10:R 110. The curable photochromic composition of clause 8 or clause 9, comprising at least one of a polyvalent aliphatic hydrocarbon residue, a polyvalent aliphatic urethane residue, or a polyvalent aliphatic carbonate residue.

[0174] Clause 11: The curable photochromic composition of any one of clauses 8-10, wherein the trialkoxysilane functional material comprises Si in an amount of 5.0 to 16.0 weight percent based on the solids weight of the trialkoxysilane functional material.

[0175] Clause 12. The curable photochromic composition of any one of clauses 1 to 11, wherein the weight ratio of trialkoxysilane functional material to segmented polymer is from 80:20 to 50:50.

[0176] Clause 13. The curable photochromic composition of any one of clauses 1 to 12, wherein the weight ratio of trialkoxysilane functional material to segmented polymer is from 70:30 to 60:40 or from 75:25 to 60:40.

[0177] Clause 14: The curable photochromic composition of any one of clauses 1 to 13, comprising a total amount of the second segment of from 10 weight percent to 45 weight percent based on the total solids weight of the curable photochromic composition.

[0178] Clause 15: The curable photochromic composition of any one of clauses 1 to 14, further comprising a water scavenger.

[0179] Clause 16: The curable photochromic composition of clause 15, wherein the water scavenger comprises one or more trialkyl orthoformates.

[0180] Clause 17: The curable photochromic composition of any one of clauses 1 to 16, further comprising a catalyst that catalyzes the formation of siloxane bonds.

[0181] Clause 18: The curable photochromic composition of any one of clauses 1 to 17, wherein the photochromic compound comprises at least one of naphthopyran, benzopyran, phenanthropyran, indenonaphthopyran, spiro(indoline)naphthoxazine, spiro(indoline)pyridobenzoxazine, spiro(benzindoline)pyridobenzoxazine, spiro(benzindoline)naphthoxazine, spiro(indoline)-benzoxazine, fulgide, fulgimide, or a mixture of such photochromic compounds.

[0182] Clause 19:(A) Substrate; and (B) a photochromic layer on at least one surface of the substrate. 19. An article comprising: wherein the photochromic layer is formed from the curable photochromic composition of any one of clauses 1-18.

[0183] The present invention is more particularly described in the following examples, which are intended to be illustrative only, since numerous modifications and variations thereto will be apparent to those skilled in the art. Unless otherwise specified, all parts and all percentages are by weight. EXAMPLES

[0184] As used in the following examples, specific values ​​and terms relating to physical properties were measured according to the following descriptions unless otherwise specified.

[0185] Acid number was measured according to the method of ASTM D1639 and the results are reported in mg KOH / g.

[0186] Hydroxyl values ​​(OH values) are typically measured according to art-recognized methods. As reported in the examples below, each hydroxyl value is mg of KOH equivalents per gram of hydroxyl groups in the material of interest. Following art-recognized methods, a known mass of the sample of interest is accurately weighed into a flask and dissolved in 20 mL of tetrahydrofuran. Ten milliliters (10 mL) of 0.1 molar (0.1 M) 4-(dimethylamino)pyridine in tetrahydrofuran and 5 mL of a 9% by volume solution of acetic anhydride in tetrahydrofuran are then added to the mixture. After 5 minutes, 10 mL of an 80% by volume tetrahydrofuran / water solution is added. After 15 minutes, 10 mL of tetrahydrofuran is added and the solution is titrated with 0.5 M ethanolic potassium hydroxide (KOH). A blank sample is also run in which the sample of interest is omitted. The resulting hydroxyl value is expressed in mg KOH / g and is calculated according to the following formula (Formula A):

number

[0187] For formula A, V2 is the amount (mL) of KOH solution required to titrate the blank; V1 is the amount (mL) of KOH solution required to titrate the acetylated sample; 56.1 is the formula weight of KOH; and "Sample Mass" is the mass (grams) of the sample of interest. Unless otherwise noted, the OH numbers listed in the following examples were calculated according to the method described above and were not corrected for solids content.

[0188] The theoretical hydroxyl numbers for all segmented polymer examples were calculated according to the following formula (Equation B):

number

[0189] With respect to formula B, "theoretical OH equivalents" is the amount of theoretical hydroxyl equivalents remaining if all equivalents of isocyanate are reacted, and is calculated by subtracting the known equivalents of hydroxyl functionality from the total equivalents of isocyanate functionality. The equivalents of hydroxyl functionality introduced into the reaction are the sum of the first segment, the second segment, and each additional octanol and / or butanol. To determine if and when all equivalents of isocyanate have reacted, a drop of the reaction solution is placed on a colorimetric SWYPE™ pad for aliphatic isocyanates available from SKC, Inc. The absence of a color change (of the SWYPE™ pad) indicates that no isocyanate is detectable and, correspondingly, all equivalents of isocyanate have reacted (or otherwise been consumed).

[0190] Part 1 of the following examples describes the preparation of a second segment that can be used to prepare a segmented polymer according to the invention. Part 2 describes the preparation of a segmented polymer according to the invention. Part 3 describes the preparation of a trialkoxysilane functional material according to the invention. Part 4 describes the preparation of a comparative curable photochromic composition and a curable photochromic composition according to the invention. Part 5 describes the preparation of test specimens. Part 6 describes the test methods and test results obtained from the test specimens of Part 5.

[0191] Part 1: Preparation of the second segment. The charges and ingredients used in the preparation of the second segment are summarized in Table 1 below. With reference to Table 1 and for each example, Charge 1 was introduced into a reactor equipped with mechanical stirring, a Dean-Stark trap, a nitrogen blanket (or sweep), and a thermocouple controlled heating mantle. The reactor contents were heated to 170° C. to obtain a strong reflux. Xylene and water were removed from the Dean-Stark trap as necessary to maintain a strong reflux at 170° C.-180° C. The reaction was maintained at reflux until the measured acid number was less than 1 mg KOH / g, at which point Charge 2 was added in the case of SS-A. The acid number was again measured and found to be less than 1 mg KOH / g, at which point Charge 3 was added in the case of SS-A. For each example except SS-A, once the acid number had fallen below 1 mg KOH / g, the solution was cooled to 130° C. and Charge 4 was added. In Example SS-A, the solution was cooled to 130° C. and Charge 4 was added 3 hours after the addition of Charge 3. After completion of each reaction, the reactor contents containing the second segment of product were removed and stored without workup or other modification. The resulting product mixture containing the second segment of product was found to have the properties listed in Table 1.

[0192] [Table 1]

[0193] Part 2: Preparation of segmented polymers. Part 2A: Preparation of segmented polymers with fluoroethylene vinyl ether first segments The charges and ingredients used in the preparation of segmented polymers having a fluoroethylene vinyl ether first segment are summarized in Table 2 below. With reference to Table 2 and for each example, Charge 1 was added to a reactor having mechanical stirring, a thermocouple controlled heating mantle and a nitrogen blanket (or sweep). The reactor contents were heated in each case to a first temperature as shown in Table 2 and maintained for a first hold time. Charge 2 was added, followed by Charge 3 (if indicated). The reaction mixture was adjusted to a second temperature as shown in Table 2 and maintained for a second hold time. Charge 4 was added and the reaction continued until no isocyanate was detected. After the completion of each reaction, the reactor contents containing the product segmented polymer were removed and stored without workup or other modification. The resulting product mixtures containing the product segmented polymer were found to have the properties listed in Table 2.

[0194] [Table 2]

[0195] Part 2B: Preparation of a segmented polymer with acrylic first segments. The charges and ingredients used to prepare the segmented polymer having an acrylic first segment (SP-7) are summarized in Table 3 below. With reference to Table 3, Charge 1 was added to a reactor having mechanical stirring, a thermocouple controlled heating mantle and a nitrogen blanket (or sweep). The reactor contents were heated to 80° C. for 120 minutes. Charge 2 was added. After 30 minutes, Charges 3 and 4 were added and the reactor contents were maintained at 80° C. for 5 hours. Charge 5 was added to quench the remaining isocyanate. After completion of the reaction, the reactor contents containing the product segmented polymer were removed and stored without workup or other modification. The resulting product mixture containing the product segmented polymer was found to have the properties listed in Table 3.

[0196] [Table 3]

[0197] Part 3: Preparation of trialkoxysilane materials. Four different trialkoxysilane materials (Examples A through D) were prepared according to the following description.

[0198] Example A Trimethylolpropane (96.88 g), 3-isocyanatopropyltrimethoxysilane (444.67 g) and anisole (125.5 g) were combined under nitrogen in a 1 L 4-neck round bottom flask equipped with a mechanical stirrer and condenser. The contents of the flask were heated to 70° C. with continuous stirring for 2 hours. After 1 hour at 70° C., the contents of the flask were cooled to room temperature and 0.05 g K-KAT 348 (a bismuth carboxylate catalyst available from King Industries) was added. The contents of the flask were heated to 70° C. for 1 hour and then maintained until no isocyanate was detected (approximately 6 hours). The contents of the flask containing the product trialkoxysilane functional material were removed without workup or other modification and stored under nitrogen at 79.4% total solids. The product trialkoxysilane functional material was calculated to have a molecular weight of 750 g / mole and 11.23 wt % Si based on solids. The following formula (Ex-A) is a representative structural formula of the product trialkoxysilane functional material of Example A. [ka]

[0199] Example B Pentaerythritol (15.87 g), 3-isocyanatopropyltrimethoxysilane (95.72 g), K-KAT® 348 (0.01 g, a bismuth carboxylate catalyst available from King Industries) and tetrahydrofuran (40.0 g) were combined under nitrogen sweep in a 250 mL three-neck round bottom flask with mechanical stirrer and condenser. The mixture was stirred and heated to 70° C. over 30 minutes and maintained at 70° C. until no isocyanate was detected (5 hours). The contents of the flask containing the product trialkoxysilane-functional material were cooled to room temperature, removed from the flask without workup or other modification, and stored under nitrogen in a glass jar at 78.9% total solids. The resulting product trialkoxysilane-functional material was calculated to have a molecular weight of 957.3 g / mole and 11.7% silicon by weight based on solids. The following formula (Ex-B) is a representative structural formula of the product trialkoxysilane functional material of Example B. [ka]

[0200] Example C DESMODUR® N 3200 (40.37 g, hexamethylene diisocyanate biuret available from Covestro), (3-mercaptopropyl)trimethoxysilane (45.48 g) and triethylamine (0.086 g) were combined in a glass jar with a magnetic stir bar. The contents of the glass jar were stirred at room temperature for 2 hours, at which point no isocyanate was detected. The contents of the glass jar were kept therein without post-treatment or other modification and stored under nitrogen. The resulting product trialkoxysilane-functional material had a calculated molecular weight of 1067.6 g / mole and 7.89 wt. % silicon based on solids. The following formula (Ex-C) is a representative structural formula of the product trialkoxysilane-functional material of Example C. [ka]

[0201] Example D Neopentyl glycol diacrylate (21.89 g) and (3-aminopropyl)trimethoxysilane (36.98 g) were combined in a 100 mL three-neck round bottom flask with magnetic stirring and condenser. The contents of the flask were stirred at room temperature for 30 minutes, followed by the addition of dibutyltin dilaurate (0.06 g). The contents of the flask were then heated under nitrogen to 80° C. over 1.5 hours. After the reaction was maintained at 80° C. for 6 hours, less than 0.1 wt. % neopentyl glycol diacrylate was detected by GC (gas chromatography). The contents of the flask were cooled to room temperature, removed from the flask, and stored under nitrogen without workup or other modification. The resulting product trialkoxysilane functional material was calculated to have a molecular weight of 570.8 g / mole and 9.84 wt. % silicon. The following formula (Ex-D) is a representative structural formula of the product trialkoxysilane functional material of Example D. [ka]

[0202] Part 4: Preparation of the curable photochromic composition. This Part 4 describes the preparation of comparative curable photochromic compositions (CE-1 and CE-2) and curable photochromic compositions according to the invention (Examples 3-8).

[0203] Comparative example CE-1: The curable photochromic composition of Comparative Example CE-1 includes a second segment SS-B (a polycarbonate polyester second segment) in the absence (or in place of) a segmented polymer. The charges and ingredients used to prepare the curable photochromic composition of Comparative Example CE-1 are summarized in Table 4 below.

[0204] With reference to Table 4, the ingredients of Charge 1 were combined in a suitable vessel and mixed at 40°C-60°C until the contents of the vessel were observed to be homogenous. The polycarbonate-polyester second segment SS-B of Charge 2 was added and the resulting contents of the vessel were mixed for at least 30 minutes while heating to 40°C. The ingredients of Charge 3 were added to the vessel and the contents of the vessel were mixed for an additional 30 minutes. Finally, the catalyst of Charge 4 was added to the vessel and the resulting contents were mixed for 30 minutes. The vessel with the curable photochromic composition of Comparative Example CE-1 therein was then placed on a bench top roller mixer overnight.

[0205] [Table 4]

[0206] Comparative example CE-2: The curable photochromic composition of Comparative Example CE-2 includes polyisocyanate in the absence (or in place of) trialkoxysilane-functional material. The segmented polymer (SP-1) of Comparative Example CE-2 was prepared and includes the second segment SS-B of the polycarbonate polyester used in Comparative Example CE-1.

[0207] The charges and ingredients used in preparing the curable photochromic composition of Comparative Example CE-2 are summarized in Table 5 below. With reference to Table 5, the ingredients of Charge 1 were combined in a suitable container and mixed at 40° C.-60° C. until the contents of the container were observed to be homogenous. The segmented polymer SP-1 of Charge 2 was added to the container and the contents were mixed for at least 30 minutes while heating to 40° C. The ingredients of Charge 3 were added and the contents of the container were mixed for an additional 30 minutes. The container with the curable photochromic composition of Comparative Example CE-2 therein was then placed on a bench top roller mixer overnight.

[0208] [Table 5]

[0209] Curable photochromic composition examples according to the present invention (3-11): The charges and ingredients used in preparing the curable photochromic compositions according to the invention are summarized in Tables 6 and 7 below. The same trialkoxysilane functional material (of Example A) was used with the curable photochromic compositions according to the invention of Examples 3-8 (Table 6). Different trialkoxysilane functional materials (Examples B, C, and D) were used with the curable photochromic compositions according to the invention of Examples 9-11 (Table 7). A summary of the various formulation details (e.g., weight ratio of alkoxysilane to segmented polymer) of the curable photochromic compositions according to the invention of Examples 3-11 is provided in Table 8.

[0210] For each of Examples 3-8 in Table 6 and each of Examples 9-11 in Table 7, the ingredients of Charge 1 were combined in a suitable container and mixed at 40° C.-60° C. until the contents of the container were observed to be homogenous. Charge 2 was then added to each container (as shown) and the contents of each container were mixed for at least 30 minutes at 40° C. The ingredients of Charge 3 were then added and the resulting contents were mixed for a minimum of 30 minutes. Finally, Charge 4 was added to each container and the contents were mixed for a minimum of 30 minutes. Each container with the curable photochromic composition of Examples 3-11 therein was then placed on a bench top roller mixer overnight.

[0211] [Table 6]

[0212] [Table 7]

[0213] [Table 8]

[0214] The weight percent of the second segment based on (or relative to) the total curable composition was calculated based on the total mass of the second segment, either directly, as in the first comparative example CE-1, or as a component of the segmented polymer, as in the inventive examples.

[0215] Part 5: Preparation of test specimens. The test substrates used to prepare the test specimens were in each case 76 mm diameter PDQ® coated GENTEX® polycarbonate plano lenses (commercially available from Gentex Optic, Inc.), each of which had been surface treated with oxygen plasma at a power of 100 W for 3 minutes with a flow rate of 100 milliliters (mL) of oxygen per minute.

[0216] Test substrates were coated by spin coating with each of the curable photochromic compositions of CE-1, CE-2, and Examples 3-11. Approximately 1 mL to 2 mL of each curable photochromic composition was dispensed onto the test substrate, which was then spun for 8 to 32 seconds at a spin speed sufficient to deposit a sufficient wet coating on the test substrate to result in a similar activated optical density (0.298 g to 0.508 g for the examples described herein).

[0217] Duplicate coated test substrates were prepared for use and evaluation in multiple tests. The coated test substrates were placed in a 40°C oven until all coated test substrates were stacked. The 40°C treated coated test substrates of Comparative Example CE-2 were then cured in a 125°C forced air oven for 1 hour and then cooled to room temperature. The coated test substrates of all other examples were cured in a 40°C forced air oven for 1 hour in each case and then cooled to room temperature; followed by an additional cure in a 125°C forced air oven for 15 minutes and then cooled to room temperature. The duplicate specimens were then divided into two groups. The first group was subjected to an additional heat cure at 105°C for 3 hours and reserved for evaluation of surface hardness. The second group of specimens was evaluated for haze % with a HunterLab UltraScan® PRO available from Hunter Associates Laboratory, Inc. before applying a protective coating thereon as described in the next paragraph. The % haze was measured using D65 as the standard illuminant and a 10° viewing angle.

[0218] After completing the haze % measurements, the second group of specimens were then further surface treated with oxygen plasma as described above for the test substrates 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. The applied protective coating was UV cured in an EyeUV oven equipped with a D bulb, and then further cured at 105° C. for 3 hours. The second group of protectively coated specimens were then evaluated for photochromic properties.

[0219] Part 6: Test specimen test methods and test results. The first group of specimens were subjected to microhardness testing using a Fischerscope HCV, Model H100SMC instrument (available from Fischer Technology, Inc.) at a penetration of 2 microns after a load of 100 Newtons for 30 seconds. Each specimen was measured at least twice and the microhardness results were averaged.

[0220] The photochromic performance of the second group of protectively coated specimens was measured using a bench for photochromic measurements ("BMP") manufactured by Essilor, Ltd. France. During testing, the BMP was maintained at a constant temperature of 23°C. Prior to testing on the BMP, each of the specimens was exposed to 365 nm UV light for approximately 10 minutes at a distance of approximately 14 centimeters to activate the photochromic material. The UVA (315 nm to 380 nm) irradiance of the specimens was measured by a LICOR® Model Li-1800 spectroradiometer and was found to be 22.2 W / m 2 Each test strip was then placed under a 500W high intensity halogen lamp at a distance of about 36 centimeters for about 10 minutes to bleach (deactivate) the photochromic material. The illuminance of the test strip was measured by a LICOR® spectroradiometer and found to be 21.9 Klux. Each test strip was then kept in a dark environment at room temperature (21°C-24°C) for at least 1 hour before testing with the BMP. Prior to the measurements, each test strip was measured for UV absorbance at 390 nm.

[0221] The BMP was fitted with two 150W Newport Model 6255 xenon arc lamps set at right angles to each other. The light path from lamp 1 was directed through a 3 mm SCHOTT® KG-2 bandpass filter and appropriate neutral density filters to contribute the required UV and partial visible irradiance levels. The light path from lamp 2 was directed through a 3 mm SCHOTT® KG-2 bandpass filter, a SCHOTT® shortwave 400 nm cutoff filter and appropriate neutral density filters to provide supplemental visible irradiance. A 2" x 2" (5.1 cm x 5.1 cm) 50% polka dot beam splitter set at 45° to each lamp was used to mix the two beams. A combination of neutral density filters and voltage control of the xenon arc lamps was used to regulate the intensity of the irradiance. Software (BMPSoft version 2.1e) was used on the BMP to control the timing, irradiance, air cell and sample temperatures, shutters, filter selection and response measurements. A ZEISS® spectrophotometer, model MCS 601, with a fiber optic cable to transmit light through the lens was used for response and color measurements. Photopic response measurements were collected on each protective coated specimen in the second group.

[0222] The output of the BMP (i.e. the amount of light the specimen was exposed to) was 6.7 W / m2 integrated from 315 to 380 nm. 2The irradiance was adjusted to 50 Klux integrated over 380-780 nm and 1000 nm UVA. Measurements of this power setting were made using an irradiance probe and a calibrated ZEISS® spectrophotometer. The specimen sample cell was fitted with a quartz window and a self-centering sample holder. The temperature in the sample cell was controlled at 23°C by software with a modified Facis model FX-10 environmental simulator. Measurements of the dynamic photochromic response and color of the specimens were made using the same ZEISS® spectrophotometer with a fiber optic cable to transmit light from a tungsten halogen lamp through the specimen. A collimated monitor light beam from the fiber optic cable was maintained perpendicular to the test sample while passing through the specimen and was directed to a receiving fiber optic cable assembly attached to the spectrophotometer. The exact placement location of the specimen in the sample cell was where the activating xenon arc beam and the monitor light beam intersected to form two concentric circles of light. The angle of incidence of the xenon arc beam at the specimen placement point was approximately 30° from normal.

[0223] Response measurements of the change in optical density (ΔOD) from the unactivated (bleached) state to the activated (colored) state were determined by establishing an initial unactivated transmittance and then opening a shutter from the xenon arc lamp and measuring the activation-induced transmittance at selected time intervals. The change in optical density was determined according to the following equation (Equation C): formula C ΔOD=Log 10 (%Tb / %Ta) For formula C, %Tb is the percent transmission of the bleached state and %Ta is the percent transmission of the activated state. Optical density measurements were based on photopic optical density.

[0224] Microhardness, haze, fading half-life (T 1 / 2 ), and the third half-life (T 7 / 8 ), and the fourth half-life (T 15 / 16 The results of the ΔOD for the activation and saturation tests are summarized in Tables 9 to 11. The ΔOD for the saturation values ​​listed is after 15 minutes of activation, respectively.

[0225] Fading half-life (T 1 / 2 The fading half-life (T ) value is in each case the time interval, expressed in seconds, at which the ΔOD of the activated form of the photochromic material in the coating reaches half of the saturated ΔOD at 23° C. after removal of the activating light source. 7 / 8 The fading half-life (T ) value is in each case the time interval, expressed in seconds, at which the ΔOD of the activated form of the photochromic material in the coating reaches one-eighth of the saturated ΔOD at 23° C. after removal of the activating light source. 15 / 16 ) value is in each case the time interval, expressed in seconds, at which the ΔOD of the activated form of the photochromic material in the coating reaches one-sixteenth of the saturated ΔOD at 23° C. after removal of the activating light source.

[0226] [Table 9]

[0227] Referring to Table 9, Comparative Example CE-1 is directly comparable to Example 3 of the invention, where the second segment is present in the same amount, but in CE-1, the second segment is present in place of (or in the absence of) the segmented polymer of Example 3. The resulting CE-1 coating, which uses the same trialkoxysilane functional material, is significantly softer and hazy. Similarly, CE-2 is directly comparable to Example 3 in that the same segmented polymer is used at comparable levels in both, but compares a trifunctional isocyanate matrix (CE-2) to a trifunctional trialkoxysilane matrix (Example 3). Haze is acceptable in both CE-2 and Example 3, but the trialkoxysilane coating has a higher hardness combined with a faster fade. This is due to the slower stage (T 7 / 8 and T 15 / 16) fade rates. Indeed, as shown by Example 4, the segmented polymer, when present in much lower amounts (as the second segment of the segmented polymer) compared to the trifunctional isocyanate matrix (CE-2), gives significantly harder coatings, while at the same time having comparable fade rates using the same segmented polymer.

[0228] [Table 10]

[0229] The results, tabulated in Table 10, demonstrate the properties of the segmented polymer in terms of hydroxyl number and molecular weight (Mw) and the effect of varying the total amount of segmented polymer and / or second segment. It is shown that hard, haze-free coatings can be obtained within a wide range of segmented polymer Mw while maintaining good photochromic performance. Examples 3-7 contain a fluorinated first segment and Example 8 contains an acrylic first segment.

[0230] [Table 11]

[0231] The results summarized in Table 11 provide a comparison of coatings prepared from curable photochromic compositions according to the present invention that contain different trialkoxysilane-functional materials. Each such curable photochromic coating composition of the present invention provides haze-free coatings with good hardness and photochromic performance.

[0232] The invention has been described with reference to specific details of specific embodiments thereof, and it is not intended that such details be considered limitations on the scope of the invention except insofar as they are included in the appended claims.

Claims

1. (a) a photochromic compound; (b) a trialkoxysilane-functional material having at least two trialkoxysilane groups; and (c) a segmented polymer comprising at least one first segment and at least one second segment. A curable photochromic composition comprising: (i) each first segment independently comprises at least one of a (meth)acrylic polymer segment or a fluoroethylene vinyl ether polymer segment; and (ii) each second segment independently comprises at least one of a polycarbonate segment, a polyester segment, a polyether segment, or a polyurethane segment;

2. The curable photochromic composition of claim 1 , wherein the first segment comprises a hydroxyl group.

3. The curable photochromic composition of claim 1 , wherein the segmented polymer has a hydroxyl number of less than 35.

4. 10. The curable photochromic composition of claim 1, wherein the second segment is present in the segmented polymer in an amount of 50 to 90 weight percent, based on the total weight of the segmented polymer.

5. 10. The curable photochromic composition of claim 1, wherein said segmented polymer has a Mw of 35,000 to 250,000.

6. 2. The curable photochromic composition of claim 1, wherein each second segment independently comprises the polycarbonate segment, the polycarbonate-polyester segment, the polycarbonate-polyurethane segment, and the polycarbonate-polyester-polyurethane segment.

7. The trialkoxysilane functional material has the following formula (I): 【Chemistry 10】 wherein n is at least 2; Each R ２ is independently methyl or ethyl; and R １ teeth, polyvalent aliphatic hydrocarbon residues, polyvalent aliphatic ether residues, Polyaliphatic urethane residues, a polyvalent aliphatic carboxylic acid ester residue, or Polyaliphatic carbonate residue (including at least one of the following) 2. The curable photochromic composition of claim 1, represented by:

8. The curable photochromic composition according to claim 7, wherein n in formula (I) is 2 to 4.

9. R １ The curable photochromic composition of claim 7, wherein comprises at least one of a polyvalent aliphatic hydrocarbon residue, a polyvalent aliphatic urethane residue, or a polyvalent aliphatic carbonate residue.

10. 10. The curable photochromic composition of claim 1, wherein the trialkoxysilane-functional material comprises Si in an amount of 5.0 to 16.0 weight percent based on the solids weight of the trialkoxysilane-functional material.

11. 10. The curable photochromic composition of claim 1, wherein the weight ratio of said trialkoxysilane functional material to said segmented polymer is from 80:20 to 50:

50.

12. 12. The curable photochromic composition of claim 11, wherein the weight ratio of said trialkoxysilane functional material to said segmented polymer is from 75:25 to 60:

40.

13. 10. The curable photochromic composition of claim 1 comprising a total amount of the second segment of from 10 weight percent to 45 weight percent based on the total solids weight of the curable photochromic composition.

14. 10. The curable photochromic composition of claim 1 further comprising a catalyst that catalyzes the formation of siloxane bonds.

15. (A) a substrate; and (B) a photochromic layer on at least one surface of the substrate.

13. An article comprising: a photochromic layer formed from the curable photochromic composition of claim 1.

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