Curable photochromic compositions comprising segmented polymers

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 vinyl fluoride 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 invention also relates to an article comprising: a substrate; and a photochromic layer on at least one surface of the substrate, wherein the photochromic layer is formed from the curable photochromic composition of the present invention.

Description

Technical Field

[0001] The present invention relates to a curable photochromic composition comprising a photochromic compound, a 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 Art

[0002] In response to certain wavelengths of electromagnetic radiation (or "actinic radiation"), photochromic compounds such as indeno-fused naphthopyrans typically undergo a transition from one form or state to another, wherein each form has a characteristic or distinguishable absorption spectrum associated therewith. Typically, upon exposure to actinic radiation, many photochromic compounds transition from a closed form corresponding to an unactivated (or bleached, e.g., substantially colorless) state of the photochromic compound to an open form corresponding to an activated (or colored) state of the photochromic compound. Such photochromic compounds can reversibly transition from an activated (or colored) state back to an unactivated (or bleached) state without exposure to actinic radiation. Compositions and articles (such as optical lenses) containing photochromic compounds or having photochromic compounds applied thereto (e.g., in the form of photochromic coating compositions) typically display colorless (e.g., transparent) and colored states corresponding to the colorless and colored states of the photochromic compounds contained therein or applied thereto.

[0003] Photochromic compounds can be used in curable compositions to form, for example, a photochromic cured layer, such as a cured film or sheet. For cured photochromic films (such as cured photochromic coatings), it is typically desirable that they provide a combination of hardness and photochromic properties. Typically, the kinetics associated with the reversible transition between a closed form (unactivated / colorless) and an open form (activated / colored) of a photochromic compound are faster in a soft matrix (of the cured film in which the photochromic compound resides), but slower in a hard matrix (of the cured film in which the photochromic compound resides). Cured photochromic films with a soft matrix typically have a reduced hardness, while those with a hard matrix typically have an increased hardness.

[0004] It would be desirable to develop curable photochromic compositions that provide cured photochromic layers having improved hardness without degrading the photochromic properties. Summary of the invention

[0005] According to the present invention, a curable photochromic composition is provided, which comprises: (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, wherein the photochromic layer is formed from the curable photochromic composition of the present invention as described above.

[0007] The features that characterize the present invention are pointed out with particularity in the claims, which are attached to and form a part of this disclosure. These and other features of the present invention, its operating advantages and specific objects obtained by its use will be more fully understood from the following detailed description, in which non-limiting embodiments of the present invention are shown and described. DETAILED DESCRIPTION

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

[0009] Unless otherwise indicated, all ranges or ratios disclosed herein should be understood to include any and all values ​​and subranges or subratios contained therein. For example, the range or ratio of "1 to 10" should be deemed to include: any and all values ​​therebetween, including the end values ​​(such as 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10); and the subranges between the minimum value 1 and the maximum value 10 (and including the end values), that is, all subranges or subratios starting with a minimum value of 1 or greater and ending with a maximum value of 10 or less, such as but not limited to 1 to 6.1, 3.5 to 7.8, and 5.5 to 10.

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

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

[0012] As used herein, molecular weight values ​​of polymers, such as weight average molecular weight (Mw) and number average molecular weight (Mn), are determined by gel permeation chromatography (GPC) 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" means homopolymers (eg, prepared from a single monomer species), copolymers (eg, prepared from at least two monomer species), and grafted polymers.

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

[0016] As used herein, the term "photochromic" and similar terms (such as "photochromic compound") means having an absorption spectrum for at least visible radiation that changes in response to the absorption of at least actinic radiation. Further, as used herein, the term "photochromic material" means any substance suitable for displaying photochromic properties (such as suitable for having an absorption spectrum for at least visible radiation that changes in response to the absorption of at least actinic radiation) and containing at least one photochromic compound.

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

[0018] As used herein, the term "percent transmittance" and related terms such as "percent transmission" and "%T" refer to photopic transmission, and more specifically refer to the fraction of incident electromagnetic power (or radiation) in the visible spectrum (wavelengths of 390 nm to 700 nm) that is transmitted through a subject such as an optical element (e.g., a display element) multiplied by 100 (so as to provide a percentage). For non-limiting illustrative purposes, and in accordance with some embodiments, the percent transmittance is determined by passing light from a light source through a subject and recording a first intensity value using a spectrophotometer; passing light from the same light source through a blank (e.g., in the absence of a subject) and recording a second intensity value using the same spectrophotometer; and dividing the first intensity value by the second intensity value and multiplying the fractional result by 100. The percent transmittance (%T) may be represented by the following equation 1 (Eq. 1): %T=(P / P 0 ) x 100 (Eq. 1) Referring to Eq.1, P is the intensity of light after passing through the subject, and P 0 is the intensity of the same light after passing through a blank. As further provided herein, the Examples describe a method for measuring percent transmittance.

[0019] As used herein, the term "photochromic material" includes both thermoreversible photochromic materials and compounds and non-thermoreversible photochromic materials and compounds. As used herein, the term "thermoreversible photochromic compound / material" means a compound / material that can be converted 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 return to the first state in response to thermal energy. As used herein, the term "non-thermoreversible photochromic compound / material" means a compound / material that can be converted 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 return to the first state in response to actinic radiation of substantially the same wavelength as the absorption of the colored state.

[0020] As used herein, the terms "first" and "second" are not intended to refer to any particular order or timing, but rather to two different conditions or properties, for purposes of non-limiting illustration. For purposes of non-limiting illustration, the first state and the second state of the photochromic compound may differ in at least one optical property, such as, but not limited to, the absorption of visible radiation and / or UV radiation. Thus, according to various non-limiting embodiments disclosed herein, the photochromic compounds of the present invention may have different absorption spectra in each of the first and second states. For example, although not limited herein, the photochromic compounds of the present invention may be transparent in the first state and colored in the second state. Alternatively, the photochromic compounds of the present invention may have a first color in the first state and a second color in the second state.

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

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

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

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

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

[0026] As used herein, the term "liquid crystal cell" refers to a structure containing liquid crystal material that is capable of being ordered. A non-limiting example of a liquid crystal cell element is a liquid crystal display.

[0027] As used herein, spatial or directional terms, such as "left", "right", "inner", "outer", "above", "below", etc., relate to various orientations of the invention as may be further described herein, such as articles and multilayer articles of the invention. However, it should be understood that the invention may assume various alternative orientations to those described herein, and therefore, such terms should not be considered limiting.

[0028] As used herein, the terms "formed over", "deposited over", "provided over", "applied over", "residing over", or "positioned over" mean formed, deposited, provided, applied, applied, present, or positioned on an underlying element, or on a surface of an underlying element, but not necessarily in direct (or adjacent) contact therewith. For example, a layer "placed 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 placed or formed layer and the substrate.

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

[0030] As used herein, the description of a "straight or branched" group (such as a straight or branched alkyl group) is understood to include: methylene or methyl; straight chain groups, such as a straight chain C 2 -C 20 Alkyl; and appropriately branched groups, such as branched C 3 -C 20 alkyl.

[0031] As used herein, the term "alkyl" refers to a linear or branched, cyclic or non-cyclic C 1 -C 25 Alkyl. A straight chain or branched chain alkyl group may include C 1 -C 25 Alkyl, such as C 1 -C 20 Alkyl, such as C 2 -C 10 Alkyl, such as C 1 -C 12 Alkyl, such as C 1 -C 6Alkyl. Examples of alkyl groups from which the various alkyl groups of the present invention may be selected include, but are not limited to, those further listed herein. Alkyl groups may include "cycloalkyl". As used herein, the term "cycloalkyl" means a suitable cyclic group, such as, but not limited to, C 3 -C 12 Cycloalkyl (including but not limited to cyclic C 3 -C 10 Alkyl or cyclic C 5 -C 7 Alkyl). Examples of cycloalkyl include, but are not limited to, those further listed herein. As used herein, the term "cycloalkyl" also includes: bridged ring polycycloalkyl group (or bridged ring polycyclic alkyl group), such as but not limited to bicyclo[2.2.1]heptyl (or norbornyl) and bicyclo[2.2.2]octyl; and condensed ring polycycloalkyl (or condensed ring polycycloalkyl (polycyclic alkyl)), such as but not limited to octahydro-1H-indenyl and decahydronaphthyl.

[0032] As used herein, the term "heterocycloalkyl" refers to a suitable cyclic group such as but not limited to C 2 -C 12 Heterocycloalkyl, such as C 2 -C 10 Heterocycloalkyl, such as C 5 -C 7 Heterocycloalkyl, and it has at least one heteroatom in the cyclic ring, such as but not limited to O, S, N, P, and combinations thereof. Examples of heterocycloalkyl include, but are not limited to, imidazolyl, tetrahydrofuranyl, tetrahydropyranyl, and piperidinyl. As used herein, the term "heterocycloalkyl" also includes: bridged polycyclic heterocycloalkyl, such as but not limited to 7-oxabicyclo[2.2.1]heptyl; and fused polycyclic heterocycloalkyl, such as but not limited to octahydrocyclopenta[b]pyranyl and octahydro-1H-isochromenyl.

[0033] The descriptions, species and examples provided herein for alkyl, cycloalkyl, heterocycloalkyl, haloalkyl, etc. also apply to alkane groups, cycloalkane groups, heterocycloalkane groups, haloalkane groups, etc., such as but not limited to multivalent alkane groups, such as multivalent alkane linking groups, such as divalent alkane linking groups.

[0034] As used herein, the term "aryl" and related terms, such as "aryl group", means an aromatic cyclic monovalent hydrocarbon radical. As used herein, the term "aromatic" and related terms, such as "aromatic group", means a cyclic conjugated hydrocarbon having a stability (due to the delocalization of π electrons) that is significantly greater than the stability of the assumed localized structure. Examples of aryl groups include C 6 -C 14 Aryl groups such as, but not limited to, phenyl, naphthyl, phenanthrenyl, and anthracenyl.

[0035] As used herein, the term "heteroaryl" includes, but is not limited to, C 3 -C 18 Heteroaryl, such as but not limited to C 3 -C 10 Heteroaryl (including fused polycyclic heteroaryl) and means an aryl having at least one heteroatom in an aromatic ring or in at least one aromatic ring in the case of a fused polycyclic heteroaryl. Examples of heteroaryl include, but are not limited to, furanyl, pyranyl, pyridyl, quinolyl, isoquinolyl, and pyrimidinyl.

[0036] As used herein, the term "aralkyl" includes, but is not limited to, C 6 -C 24 Arylalkyl, such as but not limited to C 6 -C 10 Aralkyl refers to an alkyl group substituted by an aryl group. Examples of aralkyl groups include, but are not limited to, benzyl and phenethyl.

[0037] Representative alkyl includes but is not limited to methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl and decyl. Representative alkenyl includes but is not limited to vinyl, allyl and propenyl. Representative alkynyl includes but is not limited to ethynyl, 1-propynyl, 2-propynyl, 1-butynyl and 2-butynyl. Representative cycloalkyl includes but is 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 nitrogen-containing rings in which the nitrogen-containing ring is bonded through a ring nitrogen. Examples of nitrogen-containing heterocycles include but are not limited to aliphatic cyclic amino groups (or alicyclic amino groups), such as morpholinyl, piperidinyl, pyrrolidinyl, and decahydroisoquinolinyl; and heteroaromatic compounds, 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 singly bonded halogen groups, such as -F, -Cl, -Br, and -I.

[0040] As used herein, the description of "halogen-substituted" and related terms (such as but not limited to haloalkyl, haloalkenyl, haloalkynyl, halogenated aryl and halogenated heteroaryl) means a group in which at least one, and at most and including all available hydrogen groups are replaced by halogen groups (such as but not limited to F, Cl or Br). The term "halogen-substituted" includes "perhalogen-substituted". As used herein, the term perhalogen-substituted group and related terms (such as but not limited to perhaloalkyl, perhaloalkenyl, perhaloalkynyl, perhaloaryl or perhalogenated heteroaryl) means a group in which all available hydrogen groups are replaced by halogen groups. For non-limiting purposes: Perhalomethyl is -CX 3 ; and the perhalogenated phenyl group is -C 6 X 5 , wherein X represents one or more halogen groups, 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," whether the elements are listed in conjunction or separately. For example, the phrases "at least one of A, B, and C" and "at least one of A, B, or C" each mean any one of A, B, or C, or any combination of any two or more of A, B, or C. For example, A alone; or B alone; or C alone; or A and B; or A and C; or B and C; or all of A, B, and C.

[0042] As used herein, "selected from" is synonymous with "chosen from", regardless of whether the elements are listed in combination or separately. Further, the phrases "selected from A, B, and C" and "selected from A, B, or C" each mean any one of A, B, or C, or any combination of any two or more of A, B, or C. For example, A alone; or B alone; or C alone; or A and B; or A and C; or B and C; or all of A, B, and C.

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

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

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

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

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

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

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

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

[0051] As used herein, and according to some embodiments, the term "silyloxy" (as with respect to the compounds and components of the present invention and substituents of various groups) and related terms such as "silyloxy" and "silyloxy substituents" include radicals consisting of -O-Si(R) 3 A material represented by wherein each R is independently selected from those groups other than hydrogen as described below.

[0052] As used herein, and according to some embodiments, the term "alkoxysilane" (as with respect to the compounds and components of the present invention and substituents of various groups) and related terms such as "alkoxysilane group" and "alkoxysilane substituent" include alkoxysilanes consisting of -Si(OR") w (R) t A material represented by wherein w is 1 to 3 and t is 0 to 2, with the proviso that the sum of w and t is 3; R" is independently selected for each w from an alkyl group; and R is independently selected for each t from those groups other than hydrogen as described below.

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

[0054] Reference formula (A): t' is greater than or equal to 2, such as from 2 to 200; R f and R gFor each t', each is independently selected from the group R other than hydrogen as described below; and R h Independently is a group R as described below.

[0055] Unless otherwise indicated, each R group of each of the above-described ketones, esters (carboxylic acid esters), carboxylates, amides, carbonates, urethanes, ureas, siloxanes, alkoxysilane groups, and polysiloxane groups is independently selected at each occurrence from hydrogen, alkyl, haloalkyl, perhaloalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and combinations thereof (including those species and examples thereof as previously listed herein).

[0056] The photochromic composition of the present invention comprises a trialkoxysilane functional material having at least two trialkoxysilane groups. For some embodiments, the trialkoxysilane functional material has from 2 to 7 trialkoxysilane groups, or from 2 to 5 trialkoxysilane groups, or from 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 contain aromatic groups. For some other embodiments, the trialkoxysilane functional material comprises one or more of the following linkages: an ether linkage (—O—); a thioether linkage (—S—); a urea linkage (—N(R)—C(O)—N(R)—, wherein each R is independently as described above); a carbonate linkage (—OC(O)—O—); a carboxylate linkage (—OC(O)—); a carbamate linkage (—N(H)—C(O)—O—); a thiocarbamate linkage (—SC(O)—N(H)—); a thiourea linkage (—N(R)—C(S)—N(R)—, wherein each R is independently as described above); and an amide linkage (—C(O)—N(R)—, wherein R is as described above).

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

[0059] With reference to formula (I), n is at least 2, such as from 2 to 7, or from 2 to 6, or from 2 to 5, or from 2 to 4, or from 2 to 3, in each case including the recited values. Also with reference to formula (I), R 2 is independently methyl or ethyl in each occurrence. 1At least one of the following items is included: a polyvalent aliphatic hydrocarbon residue; a polyvalent aliphatic ether residue; a polyvalent aliphatic carbamate residue; a polyvalent aliphatic carboxylate 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 carbamate residue, the polyvalent aliphatic carboxylate residue and the polyvalent aliphatic carbonate residue independently have a valence of n (or a valence equal to n) in each case.

[0060] As used herein, the term "aliphatic hydrocarbon" means a hydrocarbon that may be linear or branched and / or cyclic and that does not contain an aromatic group. For some embodiments, the polyvalent aliphatic hydrocarbon residue is selected from a linear or branched alkyl group, such as a linear or branched C 1 -C 20 Alkyl or cycloalkyl, such as C 3 -C 10 Cycloalkyl.

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

[0062] As used herein, the term "aliphatic ether" means an ether containing at least one ether linkage (-O-), which may be linear or branched and / or cyclic, and which does not contain an aromatic group. For some embodiments, the polyvalent aliphatic ether residue 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 other embodiments, the polyvalent aliphatic ether residue contains linear or branched C 2-hydroxy- ... 1 -C 20 Alkyl linker and / or C 3 -C 10 Cycloalkyl linker.

[0063] As used herein, the term "aliphatic carbamate" means a carbamate containing at least one carbamate linkage (-OC(O)-N(H)-), which may be linear or branched and / or cyclic, and does not contain aromatic groups. For some embodiments, the polyvalent aliphatic carbamate residue 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 carbamate linkages. For some other embodiments, the polyvalent aliphatic carbamate residue contains linear or branched C 2-H ... 1 -C 20 Alkyl linker and / or C3 -C 10 Cycloalkyl linker.

[0064] As used herein, the term "aliphatic carboxylate" means a carboxylate containing at least one carboxylate linkage (-C(O)-O-), which may be linear or branched and / or cyclic, and does not contain aromatic groups. For some embodiments, the polyvalent aliphatic carboxylate residue 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 carboxylate linkages. For some other embodiments, the polyvalent aliphatic carboxylate residue contains linear or branched C(O)-O- independently extending between and / or from each carboxylate linkage. 1 -C 20 Alkyl linker and / or C 3 -C 10 Cycloalkyl linker.

[0065] As used herein, the term "aliphatic carbonate" means a carbonate comprising at least one carbonate link (-OC(O)-O-), which may be linear or branched and / or cyclic, and does not contain an aromatic group. For some embodiments, the polyvalent aliphatic carbonate residue comprises 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 links. For some other embodiments, the polyvalent aliphatic carbonate residue comprises independently between each carbonate link and / or extending from each carbonate link. 1 -C 20 Alkyl linker and / or C 3 -C 10 Cycloalkyl linker.

[0066] Examples of trialkoxysilane functional materials having at least two trialkoxysilane groups that can be used in the curable photochromic composition 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)tetramethyldisiloxanepropyloxy]methyl}methane; and combinations of two or more thereof.

[0067] The trialkoxy functional material of the curable photochromic composition of the present invention can be prepared according to methods recognized in the art. For some embodiments, the trialkoxy functional material can be prepared by the reaction of an isocyanate functional trialkoxy silane reactant (such as isocyanato alkyl trialkoxy silane) 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 weight less than or equal to 500 grams / mole. Examples of isocyanate functional trialkoxy silane reactants include, but are not limited to: 3-isocyanato propyl trimethoxy silane; 3-isocyanato propyl triethoxy silane; isocyanato methyl trimethoxy silane; and isocyanato methyl triethoxy silicon.

[0068] Examples of polyols from which the active hydrogen functional reactant may be selected include, but are not limited to, aliphatic polyols and / or alicyclic 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; Sorbitol; 1,4-cyclohexanediol; 1,3-cyclohexanediol; or 1,2-cyclohexanediol; cyclohexanetriol, such as 1,3,5-cyclohexanetriol or 1,2,3-cyclohexanetriol; cyclohexanetetraol; cyclohexanepentaol; cyclohexanehexaol; cyclopentanediol, such as 1,3-cyclopentanediol or 1,2-cyclopentanediol; and heterocyclic aliphatic polyols, such as 1,3,5-tris(2-hydroxyethyl)isocyanurate. For some embodiments, the polyol reactant has a hydroxyl equivalent weight of less than or equal to 500 g / mole.

[0069] For some embodiments, the active hydrogen functional reactant includes one or more of: an aliphatic polyether polyol; an aliphatic polyester polyol; an aliphatic polycarbonate polyol; and an aliphatic polycarbonate-polyester polyol.

[0070] Examples of polyamines from which active hydrogen functional reactants may be selected include, but are not limited to, linear or branched C 2 -C 6 Alkane diamine; diethylene triamine; branched polyethylene imine; polyether diamine; and polyether triamine. Polyether diamine and polyether triamine are commercially available under the trade name 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 reactant may be selected include, but are not limited to: 1,2-ethanedithiol; 1,2-propanedithiol; 1,3-propanedithiol; 1,2,3-propanetriol; bis(2-mercaptoethyl)sulfide; trimethylolpropane tris(3-mercaptopropionate); and pentaerythritol tetrakis(3-mercaptopropionate).

[0072] For some embodiments, the trialkoxysilane functional material is prepared by 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, those 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-(2-aminoethyl)-3-aminopropyltrimethoxysilane; N-(2-aminoethyl)-3-aminopropyltriethoxysilane; N-(6-aminohexyl)aminopropyltrimethoxysilane.

[0073] For some embodiments, the trialkoxysilane functional material is prepared by the reaction of a polyisocyanate reactant having at least two isocyanate groups with a thiol (or mercaptan; -SH) functional trialkoxysilane such as a thioalkyltrialkoxysilane (or mercaptoalkyltrialkoxysilane). Examples of polyisocyanate reactants include, but are not limited to, those 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] For some embodiments, the trialkoxysilane functional material is prepared by a Michael addition / reaction involving: an amine functional trialkoxysilane reactant or a thiol functional trialkoxysilane reactant; and an acrylate functional reactant having at least two acrylate groups. Types and examples of amine functional trialkoxysilane and thiol functional trialkoxysilane reactants include those previously listed herein. Examples of acrylate functional reactants include, but are not limited to: alkylene glycol diacrylates, such as ethylene glycol diacrylate and neopentyl glycol diacrylate; and trimethylol triacrylate.

[0075] For some embodiments, the trialkoxysilane functional material is prepared by a Michael addition / reaction involving: 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. Types and examples of polyamine and polythiol reactants include those previously listed herein. Non-limiting types of acrylate functional trialkoxysilane reactants include alkyl (trialkoxysilane) acrylates, such as 3-(trimethoxysilyl)propyl acrylate.

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

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

[0078] According to some embodiments, the trialkoxysilane-functional material contains Si in an amount of from 5.0 to 16.0 weight percent, or from 6.0 to 14.0 weight percent, or from 7.0 to 13.0 weight percent, the weight percents being in each case based on the solid weight of the trialkoxysilane-functional material. For some embodiments, the amount of Si is determined by NMR analysis or mass spectrometry analysis of the trialkoxysilane-functional material, or by calculation of 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 composition of the present invention comprises a segmented polymer, wherein the segmented polymer comprises (i) at least one first segment, and (ii) at least one second segment. Each first segment 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 each first segment of the (meth)acrylic polymer segment can be independently prepared include, but are not limited to, (meth)acrylic acid C 1 -C 20 ester and optionally having at least one active hydrogen group selected from hydroxyl, thiol, primary amine and secondary amine (meth) acrylic acid C 1 -C 20 Ester. The C of the (meth)acrylate 1 -C 20 The group may be selected from, for example, C 1 -C 20 Straight chain alkyl, C 3 -C 20 Branched alkyl, C 3 -C 20 Cycloalkyl, C 3 -C 20 Condensed-ring polycyclic alkyl, C 5 -C 20 Aryl, and C 10 -C 20 Fused ring aromatic group.

[0082] Each (meth)acrylic acid C of each (meth)acrylic polymer segment of each first segment can be independently prepared therefrom. 1 -C 20 Examples of esters (containing no functional groups such as hydroxyl, thiol, primary 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, the (meth)acrylic acid C having at least one active hydrogen group 1 -C 20 The esters are each independently selected from (meth)acrylic acid C having at least one hydroxyl group 1 -C 20 Each (meth)acrylic acid C having at least one active hydrogen group selected from hydroxyl groups of each (meth)acrylic polymer segment of each first segment can be independently prepared therefrom.1 -C 20 Examples of esters 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, after the first segment is formed, a hydroxyl group is introduced into the (meth) acrylic polymer segment of the first segment. For non-limiting purposes, the (meth) acrylic polymer segment of the first segment can be prepared from monomers including (meth) acrylic monomers having ethylene oxide functionality. The ethylene oxide functional (meth) acrylic monomer residues or units can be hydrolyzed or reacted with a monofunctional alcohol after polymerization to form hydroxyl functional (meth) acrylic monomer residues or units. Examples of ethylene oxide functional (meth) acrylic esters 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-epoxycyclohexyl methyl (meth) acrylate, and 2-(3,4-epoxycyclohexyl) ethyl (meth) acrylate.

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

[0086] Examples of vinyl aromatic monomers that can 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 free radical polymerizable ethylenically unsaturated monomers 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 methyl ester of undecylenic acid; and diesters of ethylenically unsaturated dibasic acids, such as diethyl maleate.

[0089] For some embodiments, each first segment of the (meth)acrylic polymer segment is prepared from a free radical polymerizable monomer selected from only (meth)acrylate monomers, such as (meth)acrylic acid C 1 -C 20 ester and optionally having at least one active hydrogen group selected from hydroxyl, thiol, primary amine and secondary amine (meth) acrylic acid C 1 -C 20 esters; and optionally (meth)acrylic acid.

[0090] The (meth)acrylic polymer segment of each first segment can be prepared by polymerization methods recognized in the art, 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 main chain) 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 thus may be selected from, for example, linear (meth)acrylic polymer segments and / or branched (meth)acrylic polymer segments. For some embodiments, the (meth)acrylic polymer segment of each first segment is a linear (meth)acrylic polymer segment.

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

[0094] For some embodiments, each first segment 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. For some embodiments, the fluoroethylene monomer used to prepare the fluoroethylene vinyl ether polymer segment includes chlorotrifluoroethylene and / or tetrafluoroethylene. For some embodiments, the vinyl ether monomer used to prepare the fluoroethylene vinyl ether polymer segment includes one or more alkyl vinyl monomers, the alkyl vinyl monomers including, for example, linear or branched C 2 -C 8 Alkyl vinyl ether, linear or branched C 2 -C 4Alkyl vinyl ether. For some embodiments, in addition to vinyl fluoride monomers and alkyl vinyl monomers, the vinyl fluoride vinyl ether polymer segments are prepared using one or more optional comonomers, such as: olefins, such as ethylene, propylene, and isobutylene; halogenated olefins, such as vinyl chloride and vinylidene chloride; unsaturated carboxylic acid esters, such as alkyl (meth)acrylates and carboxylic acid vinyl esters, 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 fluorinated polymer segments may be prepared or derived include fluoroethylene-alkyl vinyl ether alternating copolymers (such as those described in US Pat. No. 4,345,057), examples of which include but are not limited to Vinyl fluoride copolymers, commercially 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, wherein each second segment independently comprises 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 segmented polymer can be prepared independently according to art-recognized methods.For some embodiments, and for the purpose of non-limiting illustration, each polycarbonate segment can be independently by the reaction of aliphatic polyol (such as glycol) and carbonyl dihalide (such as carbonyl dichloride), and remove the obtained halide acid (such as HCl) to prepare.For the purpose of further non-limiting illustration, each polycarbonate segment can be independently by the transesterification reaction of polyol (such as glycol) and dialkyl carbonate (such as diphenyl carbonate), and remove the obtained hydroxyl-functional alkyl (such as phenol) to prepare.

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

[0099] Each polycarbonate segment of each second segment may independently be free of active hydrogen functionality, or contain one or more active hydrogen functional groups independently selected from hydroxyl, thiol, primary amine and secondary amine. According to methods recognized in the art, active hydrogen functionality can be independently introduced into each polycarbonate segment during or after the formation of each polycarbonate segment. For some embodiments, at least some of the polycarbonate segments have hydroxyl functionality. For some embodiments, the polycarbonate segments with hydroxyl functionality can be prepared from polycarbonate polyols (such as polycarbonate diols). For some other embodiments, polycarbonate polyols (such as polycarbonate diols) can be selected from commercially available polycarbonate polyols, such as but not limited to polycarbonate polyols from UBE Industries, Ltd. Polycarbonate diol and DURANOL polycarbonate diol from Asahi Kasei.

[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 an Mw of less than 45,000, such as from 3,000 to 40,000.

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

[0102] Examples of polyfunctional carboxylic acids that can be used to prepare each polyester segment include, but are not limited to, tetrahydrophthalic acid, hexahydrophthalic acid, endobicyclo-2,2,1,5-heptyne-2,3-dicarboxylic acid, cyclohexane diacid, succinic acid, azelaic acid, maleic acid, adipic acid, sebacic acid, and similar polyfunctional carboxylic acids (optionally including appropriate cyclic anhydrides and / or esters thereof).

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

[0104] Each polyester segment of each second segment may independently be free of active hydrogen functionality or contain one or more active hydrogen functional groups each independently selected from hydroxyl, thiol, primary amine and secondary amine. Active hydrogen functionality may be independently introduced into each polyester segment during or after its formation according to methods recognized in the art.

[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 an 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 independently prepared according to methods recognized in the art. 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 be free of active hydrogen functionality or contain 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 polyether segment during or after its formation according to methods recognized in the art.

[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 an 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 independently prepared according to methods recognized in the art. For some embodiments, and for non-limiting purposes, each polyurethane segment can be independently prepared by the reaction of a polyisocyanate having at least two isocyanate groups with a polyol having at least two hydroxyl groups, wherein there is: an appropriate molar excess of hydroxyl groups to form a hydroxyl-functional polyurethane having at least 2 hydroxyl groups; or an appropriate molar excess of isocyanate groups to form a polyurethane having at least 2 isocyanate groups. For some embodiments, examples of polyisocyanates that can be used to prepare polyurethane segments include aliphatic, alicyclic and heterocyclic polyisocyanates, and mixtures of such polyisocyanates.

[0110] Additional examples of polyisocyanates that can be used to prepare polyurethane segments include, but are not limited to, tetramethylene-1,4-diisocyanate; hexamethylene-1,6-diisocyanate; 2,2,4-trimethylhexane-1,6-diisocyanate; 2,4,4-trimethylhexane-1,6-diisocyanate; lysine methyl ester diisocyanate; bis(isocyanatoethyl)fumarate; isophorone diisocyanate; ethylene diisocyanate; dodecane-1,12-diisocyanate; cyclobutane- 1,3-diisocyanate; cyclohexane-1,3-diisocyanate; cyclohexane-1,4-diisocyanate; methylcyclohexyl diisocyanate; hexahydrotoluene-2,4-diisocyanate; hexahydrotoluene-2,6-diisocyanate; hexahydrophenylene-1,3-diisocyanate; hexahydrophenylene-1,4-diisocyanate; perhydrodiphenylmethane-2,4'-diisocyanate; perhydrodiphenylmethane-4,4'-diisocyanate; norbornane diisocyanate; and mixtures thereof.

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

[0112] Each polyurethane segment of each second segment may independently be free of active hydrogen functionality or contain one or more active hydrogen functional groups each independently selected from hydroxyl, thiol, primary amine and secondary amine. Active hydrogen functionality may be independently introduced into each polyurethane segment during or after its formation according to methods recognized in the art.

[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 an Mw of less than 45,000, such as from 3,000 to 40,000.

[0114] For some embodiments, each second segment of the segmented polymer of the curable composition of the present invention 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 segmented polymer can be independently prepared according to methods recognized in the art. For some embodiments, and for the purpose of non-limiting illustration, each polycarbonate-polyester segment can be independently prepared according to the description provided for the preparation of polyester segments previously herein, wherein at least some of the polyols are polycarbonate polyols. Polycarbonate polyols can be prepared according to the description provided for the preparation of polycarbonate segments previously herein, wherein the molar ratio of the reactants is regulated so that the resulting polycarbonate has hydroxy functionality, and correspondingly is a polycarbonate polyol with a desired molecular weight. For some embodiments, the polycarbonate polyol (such as polycarbonate diol) prepared by it has a Mw range of from 500 to 20,000, or from 500 to 10,000, or from 500 to 5,000. 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 an Mw of less than 45,000, such as from 3,000 to 40,000.

[0116] Each polycarbonate-polyurethane segment of each second segment of segmented polymer can be independently prepared according to methods recognized in the art. For some embodiments, and for the purpose of non-limiting illustration, each polycarbonate-polyurethane segment can be independently prepared according to the description provided for the preparation of polyurethane segments previously herein, wherein at least some of the polyols are polycarbonate polyols. Polycarbonate polyols can be prepared according to the description provided for the preparation of polycarbonate segments previously herein, wherein the molar ratio of the reactants is adjusted so that the resulting polycarbonate has hydroxyl functionality, and correspondingly the polycarbonate polyols with the desired molecular weight. For some embodiments, the polycarbonate polyol (such as polycarbonate diol) prepared by it has a Mw range of from 500 to 20,000, or from 500 to 10,000, or from 500 to 5,000. According to some embodiments, each polycarbonate-polyurethane segment of each second segment independently has a Mw less than 45,000, such as from 3,000 to 40,000.

[0117] Each polycarbonate-polyester-polyurethane segment of each second segment of segmented polymer can be independently prepared according to methods recognized in the art. For some embodiments, and for the purpose of non-limiting illustration, each polycarbonate-polyester-polyurethane segment can be independently prepared according to the description provided for the preparation of polyurethane segments previously herein, wherein at least some of the polyols are polycarbonate-polyester polyols. Polycarbonate-polyester polyols can be prepared according to the description previously provided as herein, wherein the molar ratio of the reactants is regulated so that the resulting polymer has hydroxyl functionality, and correspondingly are polycarbonate-polyester polyols with a desired molecular weight. For some embodiments, the polycarbonate-polyester polyol (such as polycarbonate-polyester diol) prepared by it has a Mw range of from 1,000 to 20,000, or from 1,000 to 10,000, or from 500 to 5,000. According to some embodiments, each polycarbonate-polyester-polyurethane segment of each second segment independently has an 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 segmented polymer are formed separately. Subsequently, the first segment previously formed and the second segment previously formed are combined together (such as reacting together to form a covalent bond between them), so as to form the segmented polymer of the curable photochromic composition of the present invention. For some other embodiments, the reactive group present in the second segment end previously formed can react with the complementary reactive group on the first segment previously formed. The non-limiting examples of complementary reactive groups include active hydrogen, such as reacting with isocyanate to form hydroxyl, mercaptan or amine of carbamate, thiocarbamate or urea group respectively. In the case where the first and second segments previously formed all include active hydrogen groups, the bifunctional material including complementary reactive groups (such as isocyanate) can be used for covalently bonding the first segment and the second segment. In certain embodiments, the part of the terminal reactive group on the second segment previously formed can be protected with a protection (or end-blocking) group recognized in the art to prevent gelation (such as blocked isocyanate).

[0119] For some further embodiments, each first segment is formed first, and subsequently, each second segment is formed by polymerization from (or off of) 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 polyester second segment directly attached to the first segment.

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

[0121] For some embodiments, the segmented polymers of the curable photochromic composition of the present invention optionally include active hydrogen groups. For some embodiments, each active hydrogen group of the segmented polymer is independently selected from hydroxyl (-OH), thiol (-SH), primary amine (-NH 2 ) and a secondary amine (-NHR'), wherein each R' is independently selected from any suitable organic group, such as a linear or branched C 1 -C 20 Alkyl, and cycloalkyl, including those species and examples thereof previously listed herein. 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 is free of functional groups, such as hydroxyl, thiol, primary amine, and secondary amine groups.

[0123] For some embodiments, 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 other embodiments, at least one first segment of the segmented polymer comprises a hydroxyl group, and each second segment of the segmented polymer does not contain a hydroxyl group. According to some other embodiments, each first segment of the segmented polymer comprises a hydroxyl group, and each second segment of the segmented polymer does not contain a hydroxyl group.

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

[0125] For 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 each other via a linking group. Examples of such linking groups include, but are not limited to, carboxylate linking groups (—C(O)O—), thioester linking groups (—C(O)—S—), amide linking groups (—C(O)—N(R—), and thioester linking groups (—C(O)—S—). a)-), carbamate linking group (-N(H)-C(O)-O-), thiocarbamate linking group (-N(H)-C(O)-S-), urea linking group (-N(R a )-C(O)-N(R a )-), thiourea linker (-N(R a )-C(S)-N(R a )-), carbonate linking group (-OC(O)-O-), ether linking group (-O-), and thioether linking group (-S-). Each R in the above-listed linking groups a The groups may be independently selected from hydrogen and any suitable organic group, such as a straight or branched chain C 1 -C 20 Alkyl groups, and cycloalkyl groups, include those species and examples thereof previously listed herein.

[0126] For some embodiments of the present invention, each second segment is covalently bonded to at least one first segment. For some embodiments, the segmented polymers of the curable photochromic composition of the present invention are not gelled (ungelled).

[0127] For some embodiments, the staged polymer has an Mw of 35,000 to 250,000, or from 40,000 to 200,000, or from 50,000 to 150,000.

[0128] For some embodiments, the curable photochromic composition includes a catalyst that catalyzes the formation of siloxane linkages. Non-limiting types 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. For some embodiments, the catalyst is present in the curable photochromic composition in an effective amount, such as, but not limited to, from 0.05 to 5 weight percent based on the total weight of the resin solids. Commercially available catalysts are 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 includes a 3-dimensional network of siloxane units (-Si-O-Si-) formed by the condensation (or self-condensation) of trialkoxysilane functional materials, and further includes a domain consisting essentially of segmented polymers, which further includes a domain formed by the second segment of the segmented polymer, referred to herein as the "second segment domain". It is further believed that, without intending to be bound by any theory, at least some (and in some embodiments, at least a large amount) of the photochromic compounds of the curable photochromic composition of the present invention reside in the second segment domain of the cured article. It is also believed that, without intending to be bound by any theory, the photochromic compounds residing in the second segment domain have an enhanced molecular degree of freedom / range of motion, which makes it easier and faster for the photochromic compounds to transition between an open form and a closed form, such as in response to exposure to an actinic radiation source and removal of the actinic radiation source, thereby enhancing the photochromic performance characteristics 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 weight percent to 90 weight percent, or from 60 weight percent to 85 weight percent, the weight percent being based on the total weight of the segmented polymer (and including the recited values).

[0131] For some embodiments, the curable photochromic composition includes a total amount of second segments 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, the weight percents being in each case based on the total weight of resin solids of the curable photochromic composition (and in each case inclusive of the recited values).

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

[0133] The curable photochromic compound of the present invention comprises a photochromic compound. The photochromic compound may be selected from known types and examples of photochromic compounds, and may include combinations or mixtures thereof.

[0134] For example, although not limiting herein, mixtures of photochromic compounds can be used to obtain certain activated colors, such as near neutral gray or near neutral brown. See, for example, U.S. Pat. No. 5,645,767 at column 12, line 66 to column 13, line 19, which describes parameters defining neutral gray and brown and whose disclosure 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 naphthopyran, benzopyran, phenanthropyran, indenonaphthopyran, spiro(indoline)phenoxazine, spiro(indoline)pyridobenzoxazine, spiro(benzoindoline)pyridobenzoxazine, spiro(benzoindoline)phenoxazine, spiro(indoline)-benzoxazine, fulgide, fulgimide, diarylethene, and mixtures of such photochromic compounds.

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

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

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

[0139] For some embodiments, the curable photochromic composition of the present invention may further include one or more fixed-tint dyes. As used herein, the term "fixed-tint dye" and related terms (such as "fixed colorant", "static colorant", "fixed dye" and "static dye") means such a dye: a non-photosensitive material that has no physical or chemical response to electromagnetic radiation in terms of its visually observed color. As used herein, the term "fixed-tint dye" and related terms do not include photochromic compounds and can be distinguished from photochromic compounds. As used herein, the term "non-photosensitive material" means a material that has no physical or chemical response to electromagnetic radiation in terms of its visually observed color, which includes but is not limited to fixed-tint dyes.

[0140] One or more fixed hue dyes may be present in the curable photochromic composition of the present invention for purposes including, but not limited to, providing a cured article prepared from the curable photochromic composition with at least one primary (or first) color characteristic of the fixed hue dye when the photochromic compound is not activated; and optionally, a second color characteristic of the combination of the fixed hue dye and the photochromic compound when activated (e.g., by exposure to actinic radiation).

[0141] For some embodiments, the optional fixed hue dye of the curable photochromic composition includes at least one of an azo dye, an anthraquinone dye, a xanthene dye, an azime dye, iodine, an iodide salt, a polyazo dye, a stilbene dye, a pyrazolone dye, a triphenylmethane dye, a quinoline dye, an oxazine dye, a thiazine dye, and a polyene dye.

[0142] The fixed hue dye can be present in the curable photochromic composition in different amounts to provide the desired effect in the cured article prepared therefrom. For some embodiments, the fixed hue dye is present in the curable photochromic composition in an amount from 0.001 to 15 weight percent, or from 0.01 to 10 weight percent, or from 0.1 to 2.5 weight percent, the weight percent being 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. Non-limiting types of water scavengers include orthoformates, such as trialkyl orthoformates, such as tri(straight or branched) orthoformates. 1 -C 6For some embodiments, the water scavenger is present in the curable photochromic composition in an effective amount, such as from 0.5 to 15 weight percent, or from 5 to 15 weight percent, based on the total resin solids weight of the curable photochromic composition. Additional non-limiting types of water scavengers include multiphase water scavengers, such as magnesium sulfate and molecular sieves, which are typically separated from the curable photochromic composition, such as by filtration.

[0144] For some embodiments, the curable photochromic composition of the present invention may include a solvent selected from water, an organic solvent, and combinations thereof.

[0145] The types of organic solvents that may be present in the curable photochromic composition of the present invention include, but are not limited to: alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, isobutanol, furfuryl alcohol, and tetrahydrofurfuryl alcohol; ketones or ketone alcohols such as acetone, methyl ethyl ketone, and diacetone alcohol; ethers such as dimethyl ether and methyl ethyl ether; cyclic ethers such as tetrahydrofuran and dioxane; esters such as ethyl acetate, ethyl lactate, ethylene carbonate, and propylene carbonate; hydroxyl groups of alkylene glycols; Functional ethers such as butyl-2-hydroxyethyl ether, methyl-2-hydroxypropyl ether, and phenyl-2-hydroxypropyl ether; nitrogen-containing cyclic compounds such as pyrrolidone, N-methyl-2-pyrrolidone, 1-butyl-pyrrolidone, and 1,3-dimethyl-2-imidazolidinone; sulfur-containing compounds such as dimethyl sulfoxide and tetramethylene sulfone; aromatic compounds such as toluene, xylene, anisole, and butyl benzoate; and mixtures of aromatic compounds such as, but not limited to, Aromatic 100 Fluid (which is commercially available as C 9 -C 10 A mixture of dialkyl-benzenes and trialkyl-benzenes), and Aromatic 150 Fluid (which is a commercially available C 10 -C 12 mixture of alkylbenzenes and alkylnaphthalenes).

[0146] The solvent may be present in the curable photochromic composition of the present invention in an amount from 5 to 95 weight percent, or from 15 to 80 weight percent, from 30 to 70 weight percent, or from 30 to 60 weight percent, the weight percents being 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 and in particular photochromic articles prepared from the curable photochromic compositions of the present invention as previously described herein.For some embodiments, the photochromic article is selected from a layer (including a film and / or a sheet) and a 3-dimensional article.

[0148] Types of 3-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 composition of the present invention is used to prepare a photochromic layer, such as a photochromic film and a photochromic sheet. As used herein, the term "film" means a non-self-supporting layer, such as, but not limited to, a coating. As used herein, the term "sheet" means a self-supporting layer.

[0150] The curable photochromic composition of the present invention can be cured by any suitable method that causes the condensation (or self-condensation) of the alkoxysilane groups of the trialkoxysilane functional material. For some other embodiments, the curable photochromic composition is cured at ambient conditions, such as at room temperature of about 25°C for up to one week. For some other embodiments, the curable photochromic composition is cured by exposure to high temperature (exceeding ambient room temperature). As used herein, "curing" means forming a three-dimensional cross-linked network by covalent bond formation, such as siloxane linkages or units (-Si-O-Si-) generated by the condensation (or self-condensation) of the alkoxysilane groups of the trialkoxysilane functional material or the condensation (or self-condensation) between the alkoxysilane groups of the trialkoxysilane functional material. When cured at high temperature, the curable photochromic composition can be referred to as a thermosetting curable photochromic composition in this article. The temperature at which the thermosetting curable photochromic composition of the present invention is cured is variable and depends in part on the amount of time during which the curing is performed. For some embodiments, the curable photochromic composition is cured at an elevated temperature of from 35°C to 175°C, or from 40°C to 150°C, or from 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 the curable photochromic composition of the present invention.

[0152] For some embodiments, the article comprising a substrate and a photochromic layer (formed by the curable photochromic composition of the present invention) on at least one surface of the substrate can be selected from ophthalmic articles, display articles, windows, and mirrors. Accordingly, the substrate of the article can be selected from ophthalmic substrates, displays, windows, and mirrors. The substrate can be composed of one or more suitable materials, including but not limited to: organic materials, such as organic polymer materials, such as but not limited to thermoplastic polycarbonates, cross-linked polycarbonates, poly (meth) acrylates, and combinations thereof; glass, such as silica-based glass; metals; ceramic materials; and combinations thereof. Examples of substrates that can be included in the articles (including optical elements) of the present invention include but are not limited to those described in US8,628,685 B2 (the disclosure of which is incorporated herein by reference) at column 35, line 5 to column 36, line 57.

[0153] For some embodiments, the substrate may optionally contain a photochromic material and / or a fixed hue dye, each of which may be selected from those classes and examples of photochromic materials and fixed hue dyes as previously described herein. The optional photochromic material / compound present in the substrate may be the same or different from the photochromic compound of the photochromic layer. The optional fixed hue dye may be the same or different from the optional fixed hue 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 can be applied to the substrate according to methods recognized in the art, including but not limited to spraying application methods, curtain coating application methods, doctor blade (or rod) application methods, dip coating application methods, spin coating application methods, jet printing methods (such as inkjet printing methods, wherein "ink" is replaced by the curable photochromic composition according to the present invention), and combinations thereof.

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

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

[0158] The present invention further relates to a photochromic multilayer article, which includes at least one photochromic layer formed by a 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. For some embodiments, the photochromic multilayer article can include two or more layers formed by 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, such as, but not limited to: an adhesive layer; a protective layer (e.g., a hard coat); a polarizing layer; a birefringent layer; an antireflective layer; and / or an additional photochromic layer prepared from a composition other than the curable photochromic composition of the present invention.

[0160] The multilayer articles of the present invention may have any suitable thickness, such as from 10 microns to 1000 microns, or from 15 microns to 750 microns, or from 25 to 100 microns.

[0161] The multilayer articles of the present invention may be used alone or in combination with another article, such as a substrate. The substrate may be selected from those types and examples of substrates as previously described herein for 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 polymer materials; glass, such as silica-based glass; metals; ceramic materials; and combinations thereof.

[0162] The multilayer articles of the present invention may be attached to the surface of the substrate by methods recognized in the art, such as, but not limited to: electrostatic adsorption, such as with static electricity; one or more interposed adhesive layers; melt bonding, such as hot melt bonding; and in-mold forming, such as where the multilayer article is placed in a mold and the substrate is formed against at least one surface of the multilayer article in the mold. For some embodiments, the multilayer articles of the present invention may be supported by one or more brackets that are retainedly engaged with 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] Item 1: A curable photochromic composition comprising: (a) photochromic compounds; (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, wherein (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] Item 2: The curable photochromic composition of Item 1, wherein the first segment comprises a hydroxyl group.

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

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

[0168] Item 5: The curable photochromic composition of any of Items 1-4, wherein the segmented polymer has an Mw of 35,000 to 250,000.

[0169] Item 6: The curable photochromic composition of any of Items 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] Item 7: A curable photochromic composition as described in any of Items 1-6, wherein the trialkoxysilane functional material comprises one or more of the following linkages: an ether linkage (—O—); a thioether linkage (—S—); a urea linkage (—N(R)—C(O)—N(R)—); a carbonate linkage (—OC(O)—O—); a carboxylate linkage (—OC(O)—); a carbamate linkage (—N(H)—C(O)—O—); a thiocarbamate linkage (—SC(O)—N(H)—); a thiourea linkage (—N(R)—C(S)—N(R)—); and an amide linkage (—C(O)N(R)—), wherein each R is independently selected from hydrogen, alkyl, haloalkyl, perhaloalkyl, cycloalkyl, heterocycloalkyl, and combinations thereof.

[0171] Clause 8: The curable photochromic composition of any one of clauses 1 to 7, wherein the trialkoxysilane functional material is represented by the following formula (I), where n is at least 2, Each R 2 are independently methyl or ethyl, and R 1 Include at least one of the following: polyvalent aliphatic hydrocarbon residue, Polyvalent aliphatic ether residues, polyvalent aliphatic carbamate residues, A polyvalent aliphatic carboxylic acid ester residue, or Polyvalent aliphatic carbonate residue.

[0172] Item 9: A curable photochromic composition as described in Item 8, wherein n of formula (I) is from 2 to 20, or from 2 to 15, or from 2 to 10, or from 2 to 8, or from 2 to 6, or from 2 to 5, or from 2 to 4, or from 2 to 3.

[0173] Item 10: The curable photochromic composition of Item 8 or Item 9, wherein R 1 The polyvalent aliphatic hydrocarbon residue, the polyvalent aliphatic carbamate residue, or the polyvalent aliphatic carbonate residue is included.

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

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

[0176] Item 13: The curable photochromic composition of any of Items 1-12, wherein the weight ratio of the trialkoxysilane-functional material to the 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, wherein the curable photochromic composition comprises the second segment in a total amount of from 10 weight percent to 45 weight percent based on the total solid weight of the curable photochromic composition.

[0178] Clause 15: The curable photochromic composition of any of Clauses 1-14, wherein the curable photochromic composition further comprises a water scavenger.

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

[0180] Clause 17: The curable photochromic composition of any of Clauses 1-16, wherein the curable photochromic composition further comprises a catalyst that catalyzes the formation of siloxane linkages.

[0181] Item 18: A curable photochromic composition as described in any of Items 1 to 17, wherein the photochromic compound comprises at least one of the following: naphthopyran, benzopyran, phenanthropyran, indenonaphthopyran, spiro(dihydroindole)naphthooxazines, spiro(dihydroindole)pyridobenzoxazines, spiro(benzodihydroindole)pyridobenzoxazines, spiro(benzodihydroindole)naphthooxazines, spiro(dihydroindole)-benzoxazines, fulgated anhydrides, fulgated imides, and mixtures of such photochromic compounds.

[0182] Clause 19: An article of manufacture comprising: (A) a substrate; and (B) a photochromic layer on at least one surface of the substrate, wherein the photochromic layer is formed from the curable photochromic composition according to any one of clauses 1 to 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 therein will be apparent to those skilled in the art. Unless otherwise indicated, all parts and all percentages are by weight. Examples

[0184] Unless otherwise stated, certain values ​​and terms related to physical properties as used in the following examples are determined according to the following description.

[0185] The acid value is determined according to the method of ASTM D 1639. The results are reported in mg KOH / g.

[0186] Hydroxyl value (OH value) is typically determined according to methods generally recognized in the art. As reported in the following examples, each hydroxyl value is the mg number of KOH equivalents of the hydroxyl group in 1g of the target material. According to methods generally recognized in the art, the target sample of known mass is accurately weighed into a flask and dissolved in 20mL of tetrahydrofuran. Then ten milliliters (10mL) of 0.1 molar concentration (0.1M) 4-(dimethylamino) pyridine in tetrahydrofuran and 5mL of acetic anhydride 9vol% solution in tetrahydrofuran are added to the mixture. After 5 minutes, 10mL of 80vol% tetrahydrofuran / water solution is added. After 15 minutes, 10mL of tetrahydrofuran is added, and the solution is titrated with 0.5M potassium hydroxide (KOH) ethanolic solution. A blank sample is also run, in which the target sample is omitted. The resulting hydroxyl number is expressed in mg KOH / g, and is calculated according to the following equation (Eq.A):

[0187] Referring to Eq. A: V2 is the amount of KOH solution required to titrate the blank (mL); V1 is the amount of KOH solution required to titrate the acetylated sample (mL); 56.1 is the formula weight of KOH; "Sample mass" is the mass of the target sample (grams). Unless otherwise specified, the OH values ​​listed in the following examples are determined according to the method described above and are not corrected for solids.

[0188] For all staged polymer examples, the theoretical hydroxyl value was calculated according to the following equation (Eq. B):

[0189] Referring to Eq. B, "theoretical OH equivalents" is the amount of theoretical hydroxyl equivalents remaining when all equivalents of isocyanate have 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 for aliphatic isocyanates commercially available from SKC Corporation. TM Pad. No color change (SWYPE TM pad) indicates that no isocyanate was detected and, accordingly, all equivalents of isocyanate had been reacted (or otherwise consumed).

[0190] In Section 1 of the Examples below, the preparation of a second segment that can be used to prepare a segmented polymer according to the present invention is described. In Section 2, the preparation of a segmented polymer according to the present invention is described. In Section 3, the preparation of a trialkoxysilane functional material according to the present invention is described. In Section 4, the preparation of a comparative curable photochromic composition and a curable photochromic composition according to the present invention is described. In Section 5, the preparation of a test sample is described. In Section 6, the test methods and the test results obtained from the test samples of Section 5 are described. Part 1: Preparation of the second segment.

[0191] The charges and ingredients used to prepare the second segment are summarized in Table 1 below. Referring to Table 1, and for each example, Charge 1 was introduced into a reactor equipped with mechanical stirring, a Dean-Stock trap, a nitrogen blanket (or purge), and a thermocouple-controlled heating jacket. The contents of the reactor were heated to 170°C to achieve strong reflux. Xylene and water were removed from the Dean-Stock trap as needed to maintain a strong reflux between 170°C and 180°C. The reaction was kept at reflux until the measured acid value was less than 1 mg KOH / g, at which time Charge 2 was added in the case of SS-A. When the acid value was again determined to be less than 1 mg KOH / g, Charge 3 was added in the case of SS-A. For each example except SS-A, once the acid value dropped below 1 mg KOH / g, the solution was cooled to 130°C and Charge 4 was added. For Example SS-A, the solution was cooled to 130°C and Charge 4 was added three hours after the addition of Charge 3. After each reaction was completed, the contents of the reactor (including the product second fragment) were removed and stored without post-processing or other modification. The resulting product mixture (including the product second fragment) was found to have the characteristics listed in Table 1. Table 1 _____________________ 1 Polycarbonate diol from Asahi Kasei Corporation, with an average OH value of 56 mg KOH / g. 2 Polycarbonate diol from Ube Corporation, reported OH value 56 mgKOH / g 3 % solids measured after 1.5 hours in 120°C oven 4 The OH number for this sample was calculated based on NMR and is based on the solid. Part 2: Preparation of segmented polymers. Part 2A: Preparation of segmented polymers having fluoroethylene vinyl ether first segments.

[0192] The charges and ingredients used in the preparation of segmented polymers having a first segment of fluoroethylene vinyl ether are summarized in Table 2 below. Referring to Table 2, and for each example, Charge 1 was added to a reactor having mechanical stirring, a thermocouple-controlled heating jacket, and a nitrogen blanket (or purge). In each case, the contents of the reactor were heated to a first temperature and maintained for a first holding time, as indicated in Table 2. Charge 2 was added, followed by Charge 3 (where indicated). The reaction mixture was adjusted to a second temperature and maintained for a second holding time, as indicated in Table 2. Charge 4 was added, and the reaction continued until isocyanate was no longer detected. After each reaction was completed, the contents of the reactor (including the product segmented polymer) were removed and stored without post-processing or other modifications. It was found that the resulting product mixture (including the product segmented polymer) had the characteristics listed in Table 2. Table 2 _______________ 5 A mixture of 2,2,4-trimethyl-hexamethylene diisocyanate and 2,4,4-trimethyl-hexamethylene diisocyanate obtained from Evonik Industries. 6 Fluoroethylene vinyl ether polyol was obtained from Asahi Glass with an OH number of 101 and a solids percentage of 99%. 7 Fluoroethylene vinyl ether polyol obtained from Asahi Glass Co., Ltd. had a measured OH value of 68 (based on solids) and a solids percentage of 65.9%. 8 Fluoroethylene vinyl ether polyol was obtained from Asahi Glass Co., Ltd. and had a measured OH number of 68 (based on solids) and a % solids of 66.2%. Part 2B: Preparation of segmented polymer having acrylic first segment.

[0193] The charges and ingredients used in the preparation of the segmented polymer (SP-7) having an acrylic first segment are summarized in Table 3 below. Referring to Table 3, Charge 1 was added to a reactor with mechanical stirring, a thermocouple-controlled heating mantle, and a nitrogen blanket (or purge). The contents of the reactor were heated to 80°C for 120 minutes. Charge 2 was added. After 30 minutes, Charges 3 and 4 were added, and the contents of the reactor were maintained at 80°C for 5 hours. Charge 5 was added to quench any remaining isocyanate. After the reaction was complete, the contents of the reactor (including the product segmented polymer) were removed and stored without post-treatment or other modification. The resulting product mixture (including the product segmented polymer) was found to have the properties listed in Table 3. Table 3 Segmented polymer SP-7 _________________ 9 Prepared by free radical polymerization of hydroxypropyl methacrylate (40.4%), butyl methacrylate (57.6%), and acrylic acid (2.0%), and having: 61.5% total solids by weight; a weight average molecular weight (Mw) of 5500; a polydispersity index of 1.96; and a theoretical hydroxyl equivalent weight (based on solids) of 360. Part 3: Preparation of trialkoxysilane materials.

[0194] Four different trialkoxysilane materials (Examples A through D) were prepared according to the following description. Example A

[0195] Under nitrogen, trimethylolpropane (96.88 g), 3-isocyanatopropyltrimethoxysilane (444.67 g) and anisole (125.5 g) were combined in a 1L 4-neck round bottom flask equipped with a mechanical stirrer and a condenser. Under continuous stirring, the contents of the flask were heated to 70° C. over 2 hours. After one hour at 70° C., the contents of the flask were cooled to room temperature and 0.05 g of K-KAT 348 (a bismuth carboxylate catalyst obtained from King Industries) was added. The contents of the flask were heated to 70° C. over a period of one hour and then maintained until no isocyanate was detected (approximately 6 hours). The contents of the flask (including the product trialkoxysilane functional material) were removed without post-treatment or other modifications and stored at 79.4% total solids under nitrogen. The product trialkoxysilane functional material was calculated to have a molecular weight of 750 g / mole and 11.23% Si by weight on a solids basis. The following formula (Ex-A) is a representative structural formula for the product trialkoxysilane functional material of Example A. Formula(Ex-A) Example B

[0196] Under nitrogen purge, pentaerythritol (15.87 g), 3-isocyanatopropyltrimethoxysilane (95.72 g), 348 (0.01 g, bismuth carboxylate catalyst, obtained from King's Industries) and tetrahydrofuran (40.0 g) were combined in a 250 mL 3-necked round bottom flask with a mechanical stirrer and condenser. The mixture was stirred and heated to 70° C. over 30 minutes and then maintained at 70° C. until no isocyanate was detected (5 hours). The contents of the flask (including the product trialkoxysilane functional material) were cooled to room temperature, removed from the flask without post-treatment or other modification, and stored in a glass jar at 78.9% total solids under nitrogen. 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. Formula (Ex-B) Example C

[0197] Will N 3200 (40.37 g, hexamethylene diisocyanate biuret, commercially 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 two hours, at which time no isocyanate was detected. The contents of the glass jar were retained 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% silicon by weight on a solids basis. The following formula (Ex-C) is a representative structural formula for the product trialkoxysilane-functional material of Example C. Formula (Ex-C) Example D

[0198] Neopentyl glycol diacrylate (21.89 g) and (3-aminopropyl) trimethoxysilane (36.98 g) were combined in a 100 mL 3-neck round bottom flask with magnetic stirring and a 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 to 80° C. over a period of 1.5 hours under nitrogen. After keeping the reaction at 80° C. for 6 hours, less than 0.1% neopentyl glycol diacrylate by weight 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 post-treatment or other modifications. The resulting product, a trialkoxysilane functional material, was calculated to have a molecular weight of 570.8 g / mol and 9.84% silicon by weight. The following formula (Ex-D) is a representative structural formula of the product trialkoxysilane functional material of Example D. Formula(Ex-D) Part 4: Preparation of curable photochromic composition.

[0199] In this section 4, the preparation of comparative curable photochromic compositions (CE-1 and CE-2) and curable photochromic compositions according to the invention (Examples 3 to 8) is described. Comparative example CE-1:

[0200] The curable photochromic composition of Comparative Example CE-1 comprises a second segment SS-B (polycarbonate polyester second segment) in the absence (or in place of) of a segmented polymer. The charges and ingredients used in preparing the curable photochromic composition of Comparative Example CE-1 are summarized in Table 4 below.

[0201] Referring to Table 4, the ingredients of Charge 1 were combined and mixed in a suitable container at 40°C to 60°C until the contents of the container were observed to be uniform. The polycarbonate-polyester second segment SS-B of Charge 2 was added and the resulting contents of the container were mixed for at least 30 minutes while heating to 40°C. The ingredients of Charge 3 were added to the container and the contents of the container were mixed for another 30 minutes. Finally, the catalyst of Charge 4 was added to the container and the resulting contents were mixed for 30 minutes. The container with the curable photochromic composition of Comparative Example CE-1 therein was then placed on a benchtop roller mixer overnight. Table 4 _____________________ 10A blend of 5 parts of a photochromic indeno-fused naphthopyran dye selected to provide a green-grey color upon activation, 2 parts of a hindered amine light stabilizer, and 2 parts of a hindered phenol antioxidant. 11 Zinc complex catalyst from King Industries. Comparative example CE-2:

[0202] The curable photochromic composition of Comparative Example CE-2 comprises a polyisocyanate in the absence of (or in place of) a trialkoxysilane functional material. The segmented polymer (SP-1) of Comparative Example CE-2 is prepared using and comprises the polycarbonate polyester second block SS-B used in Comparative Example CE-1.

[0203] The charges and ingredients used in preparing the curable photochromic composition of Comparative Example CE-2 are summarized in Table 5 below. Referring to Table 5, the ingredients of Charge 1 were combined and mixed in a suitable container at 40°C to 60°C until the contents of the container were observed to be uniform. The segmented polymer SP-1 of Charge 2 was added to the container and its 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 another 30 minutes. The container with the curable photochromic composition of Comparative Example CE-2 therein was then placed on a benchtop roller mixer overnight. Table 5 _____________________ 10 A blend of 5 parts of a photochromic indeno-fused naphthopyran dye selected to provide a green-grey color upon activation, 2 parts of a hindered amine light stabilizer, and 2 parts of a hindered phenol antioxidant. 12 Dipolar aprotic solvent obtained from Eastman. 13 Hexamethylene diisocyanate biuret terminated with 3,5-dimethylpyrazole was obtained from Baxenden Chemical Co. 14 Polyether-modified polydimethylsiloxane from BYK-Chemie, USA. 15 Bismuth carboxylate catalyst from King Industries. Examples of curable photochromic compositions according to the present invention (3-11):

[0204] The charges and ingredients used in the preparation of the curable photochromic compositions according to the present invention are summarized in Tables 6 and 7 below. For the curable photochromic compositions according to the present invention of Examples 3-8 (Table 6), the same trialkoxysilane functional material (Example A) was used. For the curable photochromic compositions according to the present invention of Examples 9-11 (Table 7), different trialkoxysilane functional materials (Examples B, C and D) were used. A summary of the various formulation details (e.g., weight ratio of alkoxysilane to segmented polymer) of the curable photochromic compositions according to the present invention of Examples 3-11 is provided in Table 8.

[0205] For each of Examples 3-8 of Table 6 and each of Examples 9-11 of Table 7, the components of Charge 1 were combined and mixed in a suitable container at 40°C to 60°C until the contents of the container were observed to be uniform. Charge 2 was then added to each container (as indicated) and the contents of each container were mixed at 40°C for at least 30 minutes. 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 benchtop roller mixer overnight. Table 6 ____________________ 10 A blend of 5 parts of a photochromic indeno-fused naphthopyran dye selected to provide a green-grey color upon activation, 2 parts of a hindered amine light stabilizer, and 2 parts of a hindered phenol antioxidant. 11 Zinc complex catalyst from King Industries. Table 7 _______________ 10 A blend of 5 parts of a photochromic indeno-fused naphthopyran dye selected to provide a green-grey color upon activation, 2 parts of a hindered amine light stabilizer, and 2 parts of a hindered phenol antioxidant. 11 Zinc complex catalyst from King Industries.

[0206] The weight percentage of the second segment based on (or relative to) the total curable composition is calculated based on the total mass of the second segment directly as in the first comparative example CE-1 or as a component of a segmented polymer as in the inventive examples. Part 5: Preparation of test samples.

[0207] The test substrate used to prepare the test specimens was in each case 76 mm in diameter. Coated Polycarbonate flat lenses (commercially available from Gentex Optics, Inc.) were each surface treated with oxygen plasma at an oxygen flow rate of 100 milliliters (mL) / minute at a power of 100 W for 3 minutes.

[0208] The test substrates were coated with each of the curable photochromic compositions of CE-1, CE-2, and Examples 3-11 by spin coating. About 1 mL to 2 mL of each curable photochromic composition was dispensed onto the test substrate, which was then spun for 8-32 seconds at a spin speed sufficient to deposit a sufficient wet coating onto the test substrate to produce similar activated optical densities (0.298 g to 0.508 g for the examples described herein).

[0209] A replica of each coated test substrate is prepared for use and evaluation in multiple tests. The coated test substrates are then placed in a 40°C oven until all coated test substrates are accumulated. The coated test substrates of comparative example CE-2 treated at 40°C are then cured in a forced-air oven at 125°C for one hour and then cooled to room temperature. In each case, the coated test substrates of all other examples are cured in a forced-air oven at 40°C for one hour and then cooled to room temperature; then further cured at 125°C in a forced-air oven for fifteen minutes and then cooled to room temperature. The repeated test samples are then divided into two groups. The first group is subjected to additional heat curing at 105°C for three hours and is set aside for evaluation of surface hardness. Before applying a protective coating thereon as described in the following paragraph, a HunterLab commercially available from Hunter Associates Laboratory, Inc. The second set of test samples were evaluated on the PRO for % haze. % haze was measured using D65 as the standard illuminant and a 10° viewing angle.

[0210] After the % haze measurement was completed, the second set of test samples were then further surface treated with oxygen plasma as previously described with respect to the above test substrates, and spin coated with a protective coating according to the formulation reported in Table 1 of Example 1 in US 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 three hours. The second set of protective coated test samples were then evaluated for photochromic properties. Part 6: Test methods and test results of test samples.

[0211] After 30 seconds under a load of 100 Newtons, at a penetration depth of 2 microns, using The first set of test samples were subjected to microhardness testing using a HM2000S apparatus (commercially available from Fischer Technology, Inc.) Each test sample was measured at least twice and the microhardness results were averaged.

[0212] The photochromic properties of the second set of protective coated test samples were determined using a photochromic measurement station ("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 test samples was exposed to 365 nm ultraviolet light at a distance of about 14 cm for about 10 minutes to activate the photochromic material. The UVA (315nm to 380nm) irradiance of the test sample was measured by a model Li-1800 spectroradiometer and found to be 22.2W / m 2 Each test sample was then placed under a 500W high intensity halogen lamp at a distance of about 36 cm for about 10 minutes to cause the photochromic material to turn white (not activated). The spectroradiometer measures the illuminance at the test sample and finds it to be 21.9 Klux. Each test sample is then kept in a dark environment at room temperature (from 21°C to 24°C) for at least one hour before testing on BMP. Prior to measurement, the UV absorbance of each test sample at 390nm is measured.

[0213] The BMP is equipped with two 150W Newport Model #6255 Xenon Arc Lamps set at right angles to each other. The light path from lamp 1 is directed through a 3mm KG-2 bandpass filters and appropriate neutral density filters, which contribute to the required UV and partial visible light irradiance levels. The light path from lamp 2 is directed through a 3mm KG-2 bandpass filter, A short-band 400 nm cutoff filter and appropriate neutral density filters were used to provide supplemental visible light illumination. A 2 inch x 2 inch (5.1 cm x 5.1 cm) 50% polka dot beam splitter set at 45° to each lamp was used to mix the two beams. The intensity of the irradiance was adjusted using a combination of neutral density filters and xenon arc lamp voltage control. Software (BMPSoft version 2.1e) was used on the BMP to control timing, irradiance, gas chamber and sample temperature, shading, filter selection, and response measurement. A 100 mm x 200 mm optical microscope was used with a fiber optic cable for light transmission through the lens. Response and color measurements were made using a spectrophotometer (Model MCS 601).Photopic response measurements were collected on each of the protective coated test samples of the second set.

[0214] The power output of the BMP (i.e., the dose of light to which the test sample is exposed) was adjusted to 6.7 W / m 2 UVA, integrated from 315-380nm and 50Klux illuminance, integrated from 380-780nm. Use an irradiance probe and a calibrated The spectrophotometer makes measurements at this power set point. The test sample cell was equipped with a quartz window and an auto-centering sample holder. The temperature in the cell was controlled at 23°C via software using a modified Facis, Model FX-10 environmental simulator. The dynamic photochromic response and color of the test samples were measured using the same The spectrophotometer is performed with a fiber optic cable for transmitting light from a tungsten halogen lamp through the sample. The collimated monitoring beam from the fiber optic cable is kept perpendicular to the test sample while passing through the test sample and being directed into a receiving fiber optic cable assembly attached to the spectrophotometer. The exact placement point of the test sample in the sample cell is where the activation xenon arc beam and the monitoring beam intersect to form two concentric circles of light. The incident angle of the xenon arc beam at the test sample placement point is about 30° relative to the vertical line.

[0215] The response measurement, in terms of the change in optical density (ΔOD) from the unactivated (blanched) state to the activated (colored) state, is determined by establishing an initial unactivated transmittance, then opening the shutter of the xenon arc lamp and measuring the transmittance through activation at selected time intervals. The change in optical density is determined according to the following equation (Eq. C): Eq.C ΔOD=log10(%Tb / %Ta) Referring to Eq. C, %Tb is the percent transmittance in the bleached state and %Ta is the percent transmittance in the activated state. Optical density measurements are based on photopic optical density.

[0216] Microhardness, haze, fading half-life (T 1 / 2), the third half-life of fading (T 7 / 8 ), fading fourth half-life (T 15 / 16 The results of the ΔOD at saturation and ΔOD at saturation tests are summarized in Tables 9 to 11. The ΔOD at saturation values ​​(as listed) are each after 15 minutes of activation.

[0217] Fading half-life (T 1 / 2 ) value is the time interval (seconds) for the ΔOD of the activated form of the photochromic material in the coating to reach half of the saturated ΔOD at 23° C. after removal of the activating light source in each case. Fading third half-life (T 7 / 8 ) value is the time interval (seconds) in 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 the activating light source is removed in each case. Fading fourth half-life (T 15 / 16 ) value is the time interval (seconds) for the ΔOD of the activated form of the photochromic material in the coating to reach one sixteenth of the saturated ΔOD at 23° C. in each case after removal of the activating light source. Table 9

[0218] Referring to Table 9, comparative example CE-1 is directly comparable to inventive example 3, where the second segment is present in the same amount, but in CE-1, the second segment is present in place of the segmented polymer of example 3 (or in the absence of the segmented polymer of example 3). The resulting CE-1 coating using the same trialkoxysilane functional material is significantly softer and more turbid. Likewise, CE-2 is directly comparable to example 3, as the same segmented polymer is used at comparable levels in both, but a trifunctional isocyanate matrix (CE-2) is compared to a trifunctional trialkoxysilane matrix (example 3). Although haze is acceptable for both CE-2 and example 3, the trialkoxysilane coating has a higher hardness and faster fading. This is particularly evident by the late (T 7 / 8 and T 15 / 16 ) fade rate. In fact, as shown in Example 4, the segmented polymer, when present in much lower amounts (as the second segment of the segmented polymer), provides a significantly harder coating when compared to the trifunctional isocyanate matrix (CE-2), but at a comparable fade rate using the same segmented polymer. Table 10 ________________ 16 Where visible haze is not specified, the haze value is considered to be less than 0.5. Typically, a haze value less than 0.5 is not visually observable.

[0219] The results listed in Table 10 demonstrate the effect of varying the characteristics of the segmented polymer on the hydroxyl value and molecular weight (Mw) and total amount of the segmented polymer and / or second segment. It is shown that hard, non-fogging coatings are obtained over a wide range of segmented polymer Mw while maintaining good photochromic performance. Examples 3 to 7 comprise fluorinated first segments, while Example 8 comprises an acrylic first segment. Table 11 _____________________ 16 Where visible haze is not specified, the haze value is considered to be less than 0.5. Typically, a haze value less than 0.5 is not visually observable.

[0220] The results summarized in Table 11 provide a comparison of coatings prepared from curable photochromic compositions according to the present invention comprising different trialkoxysilane functional materials. Each such curable photochromic coating composition of the present invention provides a haze-free coating having good hardness and photochromic properties.

[0221] The invention has been described with reference to specific details of particular embodiments of the invention. It is not intended that such details be considered limitations on the scope of the invention except to the extent they are included in the appended claims.

Claims

1. A curable photochromic composition comprising: (a) photochromic compounds; (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, wherein (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 according to claim 1, wherein The first segment comprises a hydroxyl group.

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

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

5. The curable photochromic composition according to claim 1, wherein The staged polymer has a Mw of 35,000 to 250,000.

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

7. The curable photochromic composition according to claim 1, wherein The trialkoxysilane functional material is represented by the following formula (I), where n is at least 2, Each R 2 are independently methyl or ethyl, and R 1 Include at least one of the following: polyvalent aliphatic hydrocarbon residue, Polyvalent aliphatic ether residues, polyvalent aliphatic carbamate residues, A polyvalent aliphatic carboxylic acid ester residue, or Polyvalent aliphatic carbonate residue.

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

9. The curable photochromic composition according to claim 7, wherein: R 1 The polyvalent aliphatic hydrocarbon residue, the polyvalent aliphatic carbamate residue, or the polyvalent aliphatic carbonate residue is included.

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

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

50.

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

40.

13. The curable photochromic composition according to claim 1, wherein: The curable photochromic composition comprises the second segment in a total amount of from 10 weight percent to 45 weight percent based on the total solid weight of the curable photochromic composition.

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

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

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