Photochromic-dichroic article

Abstract

There is provided a photochromic optical article that includes an optical substrate and at least a partially anisotropic layer disposed on at least a portion of a surface of the substrate. The anisotropic layer comprises: an anisotropic polymer; a photochromic-dichroic dye, a photochromic dye, or a combination thereof; a mesogenic hindered amine light stabilizer; and a mesogenic antioxidant. There is provided a coated photochromic article that includes a substrate and an anisotropic coating on at least a portion of a surface of the substrate. The anisotropic coating is formed from a polymerizable composition that comprises: a polymerizable anisotropic material; a photochromic-dichroic dye, a photochromic dye, or a combination thereof; a mesogenic hindered amine light stabilizer; and a mesogenic antioxidant.

Description

Technical Field

[0001] The present invention relates to a photochromic article that employs an anisotropic layer comprising an anisotropic polymer, a photochromic-dichroic dye and / or a photochromic dye, a mesogenic hindered amine light stabilizer, and a mesogenic antioxidant. Background Art

[0002] Photochromic coatings (including photochromic-dichroic coatings) for various optical elements are well known. These photochromic coatings have an absorption spectrum for at least visible radiation that varies in response to actinic radiation and can have a first state and a second state. In response to actinic radiation, the photochromic coating can transition from the first state (e.g., "transparent state") to the second state (e.g., "colored state") and return to the first state in response to actinic radiation having a wavelength substantially the same as that absorbed in the second state. The photochromic coating can also be thermally reversible, where the coating transitions from the first state (e.g., "transparent state") to the second state (e.g., "colored state") in response to actinic radiation. Upon exposure to thermal energy, the photochromic coating can return from the second "colored state" to the first "transparent state".

[0003] Photochromic-dichroic materials can be used in photochromic coatings to form such coatings that simultaneously have photochromic properties (such as having an absorption spectrum for at least visible radiation that varies in response to actinic radiation) and dichroic properties (such as being able to absorb one of two orthogonally polarized components of at least transmitted radiation more strongly than the other), which also vary in response to at least actinic radiation. While being able to absorb one of the two orthogonally polarized components of transmitted radiation, the dichroic material requires proper positioning or arrangement to achieve net linear polarization. If the dichroic compound is not properly positioned or arranged, net linear polarization will not be achieved. Therefore, the compound having dichroic properties must be properly positioned or arranged to achieve net linear polarization, and these compounds can be aligned by using anisotropic materials (such as liquid crystal materials) such that the long axes of the molecules generally adopt an orientation parallel to a common axis.

[0004] When a photochromic material and / or a photochromic-dichroic material undergoes a change from one state to another (e.g., from a first "transparent state" to a second "colored state"), the photochromic and / or photochromic-dichroic material undergoes a conformational change from a first conformation to a second conformation. The change from the first conformation to the second conformation results in a change in the amount of physical space occupied by the material. Accordingly, the photochromic and / or photochromic-dichroic material requires a chemically flexible enough environment to allow the compound to transition from the first conformational state to the second conformational state at a rate sufficient to provide the desired response within an acceptable time frame. Such an environment can be provided by an anisotropic material such as a liquid crystal material. Liquid crystal materials are generally capable of ordering and aligning due to their structure, e.g., by interacting with an external force or another structure, so as to be able to adopt an overall orientation.

[0005] Prolonged exposure to ultraviolet light or heat energy may cause a reduction in the ability of the photochromic and / or photochromic-dichroic material to change from the first conformational state to the second conformational state and back to the first conformational state. This reduction in ability is believed to be the result of irreversible decomposition of the photochromic and / or photochromic-dichroic compound and is referred to as fatigue or photofatigue. Prolonged exposure to ultraviolet light may further cause yellowing of the photochromic and / or photochromic-dichroic coating. To reduce fatigue and yellowing, photochromic and photochromic-dichroic coatings typically contain additional organic materials, such as stabilizers (i.e., heat stabilizers and / or ultraviolet light stabilizers), which limit and / or delay the deterioration of the coating composition due to exposure to high temperature and / or ultraviolet light. Inclusion of these stabilizers in a coating (such as a photochromic and / or photochromic-dichroic coating) may interfere with the alignment of the anisotropic material as well as the dichroic material in the photochromic-dichroic coating.

[0006] In view of the foregoing, it is desirable to provide photochromic and / or photochromic-dichroic coatings (especially those containing anisotropic materials) that have reduced fatigue and yellowing with minimal or no interference with the alignment of the anisotropic material. SUMMARY OF THE INVENTION

[0007] The present invention relates to a photochromic optical article. The photochromic optical article includes an optical substrate. At least a portion of an anisotropic layer is disposed on at least a portion of the surface of the substrate. The anisotropic layer comprises: an anisotropic polymer; a photochromic-dichroic dye, a photochromic dye, or a combination thereof; a mesogenic hindered amine light stabilizer; and a mesogenic antioxidant.

[0008] The present invention relates to a photochromic coated article. The photochromic coated article includes a substrate. An anisotropic coating is disposed on at least a portion of the surface of the substrate. The anisotropic coating is formed from a polymerizable composition. The polymerizable composition comprises: a polymerizable anisotropic material; a photochromic-dichroic dye, a photochromic dye, or a combination thereof; a mesogenic hindered amine light stabilizer; and a mesogenic antioxidant. Detailed Description

[0009] As used herein, unless the context clearly dictates otherwise, the singular forms of "a / an" and "the" include plural referents.

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

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

[0012] As used herein, the term "actinic radiation" means electromagnetic radiation capable of inducing a response in a material, such as but not limited to converting a photochromic material from one form or state to another form or state, as will be discussed in further detail herein.

[0013] As used herein, the term "photochromic material" includes both thermally reversible and non-thermally reversible (or photoreversible) photochromic compounds. Generally, although not limited herein, when two or more photochromic materials are used in combination with each other or in combination with photochromic-dichroic compounds (such as those described above), various materials can be selected to complement each other to produce a desired color or hue. For example, as disclosed herein, mixtures of photochromic compounds can be used to obtain certain activated colors, such as near-neutral gray or near-neutral brown. See, for example, U.S. Patent No. 5,645,767, columns 12, line 66 to column 13, line 19, the disclosure of which is incorporated herein by reference and which describes the parameters defining neutral gray and brown.

[0014] The photochromic material can include any one of a variety of organic and inorganic photochromic materials. One or more photochromic materials can include, but are not limited to, materials of the following classes: chromenes, such as naphthopyrans, benzopyrans, indeno-fused naphthopyrans, phenanthropyrans, or mixtures thereof; spiropyrans, such as spiro(benzindoline)naphthopyran, spiro(indoline)benzopyran, spiro(indoline)naphthopyran, spiro(indoline)quinolinopyran, and spiro(indoline)pyran; oxazines, such as spiro(indoline)naphthoxazine, spiro(indoline)pyridinobenzoxazine, spiro(benzindoline)pyridinobenzoxazine, spiro(benzindoline)naphthoxazine, and spiro(indoline)benzoxazine; mercuric dithizonate, fulgides, fulgimides, and mixtures of such photochromic compounds.

[0015] Such photochromic materials and complementary photochromic materials are described in U.S. Patent Nos. 4,931,220, column 8, line 52 to column 22, line 40; 5,645,767, column 1, line 10 to column 12, line 57; 5,658,501, column 1, line 64 to column 13, line 17; 6,153,126, column 2, line 18 to column 8, line 60; 6,296,785, column 2, line 47 to column 31, line 5; 6,348,604, column 3, line 26 to column 17, line 15; and 6,353,102, column 1, line 62 to column 11, line 64, the disclosures of the foregoing patents being incorporated herein by reference. Spiropyrans are also described in: Techniques in Chemistry , Volume III, “Photochromism”, Chapter 3, edited by Glenn H. Brown, John Wiley and Sons, Inc., New York, 1971.

[0016] Suitable photochromic materials may also include polymerizable photochromic materials, such as polymerizable naphthoxazines disclosed in column 3, line 36 to column 14, line 3 of U.S. Patent No. 5,166,345; polymerizable spirobenzopyrans disclosed in column 1, line 45 to column 6, line 65 of U.S. Patent No. 5,236,958; polymerizable spirobenzopyrans and spirobenzothiopyrans disclosed in column 1, line 45 to column 6, line 65 of U.S. Patent No. 5,252,742; polymerizable fulgides disclosed in column 5, line 25 to column 19, line 55 of U.S. Patent No. 5,359,085; polymerizable naphthoquinones disclosed in column 1, line 29 to column 7, line 65 of U.S. Patent No. 5,488,119; polymerizable spirooxazines disclosed in column 3, line 5 to column 11, line 39 of U.S. Patent No. 5,821,287; polymerizable polyalkoxylated naphthopyrans disclosed in column 2, line 23 to column 23, line 29 of U.S. Patent No. 6,113,814; and polymerizable photochromic compounds disclosed in WO 97 / 05213 and column 1, line 16 to column 24, line 56 of U.S. Patent No. 6,555,028. The disclosures of the foregoing patents regarding polymerizable photochromic materials are incorporated herein by reference.

[0017] Other suitable photochromic materials can include organo-metal dithizonates, such as (arylazo)-thioformic acid arylhydrazonates, such as mercuric dithizonate described in, for example, column 2, line 27 to column 8, line 43 of U.S. Patent No. 3,361,706; and fulgides and fulgimides, such as 3-furyl and 3-thienyl fulgides and fulgimides described in column 1, line 39 to column 22, line 41 of U.S. Patent No. 4,931,220, the disclosures of these patents being incorporated herein by reference.

[0018] As used herein, the term "linearly polarized" or similar terms mean that the vibration of the electric vector of a light wave is confined to one direction or plane.

[0019] As used herein, the term "dichroic" means capable of absorbing one of at least two orthogonally plane-polarized components of transmitted radiation more strongly than the other. Thus, while a dichroic material can preferentially absorb one of the two orthogonally plane-polarized components of transmitted radiation, if the molecules of the dichroic material are not properly positioned or arranged, a net linear polarization of the transmitted radiation will not be achieved. That is, due to the random positioning of the molecules of the dichroic material, the selective absorption of individual molecules will cancel each other out, such that no net or overall linear polarization effect will be achieved. Therefore, it is generally necessary to properly position or arrange the molecules of the dichroic material by alignment with another material in order to achieve net linear polarization.

[0020] As used herein, the terms "photochromic-dichroic" and like terms such as "photochromic-dichroic material", "photochromic-dichroic dye", and "photochromic-dichroic compound" mean having and / or providing simultaneously a photochromic property (i.e., having an absorption spectrum for at least visible radiation that varies in response to at least actinic radiation) and a dichroic property (i.e., being capable of absorbing one of two orthogonally plane-polarized components of at least transmitted radiation more strongly than the other), which also varies in response to at least actinic radiation. It should be understood that a photochromic-dichroic material, a photochromic-dichroic dye, or a photochromic-dichroic compound can be a single compound having and / or providing simultaneously a photochromic property and a dichroic property.

[0021] As used herein, for purposes of modifying the term "state", the terms "first" and "second" are not intended to refer to any particular order or chronology, but rather to two different conditions or properties. For purposes of non-limiting illustration, the first and second states of a photochromic compound can differ in at least one optical property, such as but not limited to absorption of visible radiation and / or UV radiation. Thus, the photochromic compounds of the present invention can 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 can be transparent in a first state and colored in a second state. Alternatively, the photochromic compounds of the present invention can have a first color in a first state and a second color in a second state.

[0022] As used herein, the term "polymer" means a homopolymer (e.g., prepared from a single monomer species), a copolymer (e.g., prepared from at least two monomer species), and a graft polymer.

[0023] 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 using suitable standards (such as polystyrene standards).

[0024] As used herein, the term "(meth)acrylate" and like terms (such as "(meth)acrylic acid ester") mean methacrylate and / or acrylate. For example, unless otherwise specified herein, the term "(meth)acrylic acid" includes methacrylic acid and / or acrylic acid.

[0025] 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 (i.e., Mw / Mn).

[0026] As used herein, the term "optical" means related to or associated with light and / or vision. For example, as disclosed herein, an optical article or component or device can be selected from: ophthalmic articles, components and devices, display articles, components and devices, windows, mirrors, and active and passive liquid crystal cell articles, components and devices.

[0027] As used herein, the term "ophthalmic" means related to or associated with the eye and vision. Non-limiting examples of ophthalmic articles or components include corrective and non-corrective lenses (which include single-vision or multi-vision lenses, and multi-vision lenses can be segmented or non-segmented multi-vision lenses (such as but not limited to bifocal lenses, trifocal lenses, and progressive lenses)), and other components for correcting, protecting, or enhancing (cosmetically or otherwise) vision (which include but are not limited to contact lenses, intraocular lenses, magnifying lenses, and protective lenses or goggles).

[0028] As used herein, the term "display" means a visible or machine-readable representation of information in the form of letters, numbers, symbols, designs, or pictures. Non-limiting examples of display components include screens, monitors, and security components, such as security markings.

[0029] As used herein, the term "window" means an aperture adapted to allow radiation to pass therethrough. Non-limiting examples of windows include transparencies, windshields, filters, shutters, and optical switches for automobiles and airplanes.

[0030] As used herein, the term "mirror" means a surface that specularly reflects a large portion of the incident light.

[0031] As used herein, the term "liquid crystal cell" refers to a structure containing a liquid crystal material that can be ordered. A non-limiting example of a liquid crystal cell component is a liquid crystal display.

[0032] As used herein, spatial or directional terms, such as "left", "right", "in", "out", "above", "below", etc. relate to the various orientations of the present invention that may be further described herein, such as the articles and multi-layer articles of the present invention. However, it should be understood that the present invention can assume various alternative orientations to those described herein, and thus, such terms should not be considered restrictive.

[0033] As used herein, the terms "formed over", "deposited over", "provided over", "applied over", "residing over", or "positioned over" mean formed, deposited, provided, applied, residing, or positioned on the underlying element, or on the surface of the underlying element, but not necessarily in direct (or contiguous) contact therewith. For example, a layer "positioned over 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 positioned or formed layer and the substrate.

[0034] All documents mentioned herein (such as but not limited to issued patents and patent applications), and unless otherwise specified, are hereby incorporated by reference in their entirety.

[0035] As used herein, the recitation of an "optionally substituted" group means such a group that includes, but is not limited to, alkyl, cycloalkyl, heterocycloalkyl, aryl, and / or heteroaryl, wherein at least one hydrogen thereof has been optionally replaced or substituted by a group other than hydrogen, such as but not limited to halo groups (e.g., F, Cl, I, and Br), hydroxy, ether groups, thiol groups, thioether groups, carboxylic acid groups, carboxylic ester groups, phosphoric acid groups, phosphoric ester groups, sulfonic acid groups, sulfonic ester groups, nitro, cyano, hydrocarbon groups (including but not limited to alkyl; alkenyl; alkynyl; cycloalkyl, including polyfused cycloalkyl and polycycloalkyl; heterocycloalkyl; aryl, including hydroxy-substituted aryl such as phenol, and including polyfused aryl; heteroaryl, including polyfused heteroaryl; and aralkyl), and amine groups such as -N(R 14 ’)(R 15 ’) wherein R 14 ’ and R 15 ’ are each independently hydrogen, straight-chain or branched C1-C 20 alkyl, C3-C 12 cycloalkyl, C3-C 12 heterocycloalkyl, aryl, or heteroaryl.

[0036] As used herein, unless otherwise specified, the left-to-right representation of a linking group such as a divalent linking group includes other suitable orientations, such as but not limited to the right-to-left orientation. For purposes of non-limiting illustration, the following left-to-right representation of a divalent linking group (or equivalent to -C(O)O-)

[0037]

[0038] which includes its representation from right to left

[0039]

[0040] (or equivalent to -O(O)C- or -OC(O)-).

[0041] As used herein, the term "alkyl" and related terms (such as "alkyl group(s)") mean a group that includes at least one carbon atom, such as 1 to 20 carbon atoms, such as C1-C 20 alkyl, or C1-C 10 alkyl, or C1-C6 alkyl; is straight-chain or branched-chain; and is saturated (and accordingly does not contain alkenyl and alkynyl). Examples of alkyl include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, straight-chain or branched-chain pentyl, straight-chain or branched-chain hexyl, straight-chain or branched-chain heptyl, straight-chain or branched-chain octyl, straight-chain or branched-chain nonyl, straight-chain or branched-chain decyl, straight-chain or branched-chain undecyl, straight-chain or branched-chain dodecyl, straight-chain or branched-chain tridecyl, straight-chain or branched-chain tetradecyl, straight-chain or branched-chain pentadecyl, straight-chain or branched-chain hexadecyl, straight-chain or branched-chain heptadecyl, straight-chain or branched-chain octadecyl, straight-chain or branched-chain nonadecyl, and straight-chain or branched-chain eicosyl.

[0042] As used herein, the recitation of a "straight-chain or branched-chain" group (such as a straight-chain or branched-chain alkyl) should be understood herein to include: methylene or methyl; straight-chain groups, such as straight-chain C2-C 20 alkyl; and appropriately branched groups, such as branched-chain C3-C 20 alkyl.

[0043] As used herein, the term "cycloalkyl" means an appropriately cyclic group, such as but not limited to C3-C 12 cycloalkyl (including but not limited to cyclic C5-C7 alkyl). Examples of cycloalkyl include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl. 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 fused ring polycycloalkyl group (or fused ring polycyclic alkyl group), such as but not limited to octahydro-1H-indenyl, and decahydronaphthyl.

[0044] As used herein, the term "heterocycloalkyl" means a suitable cyclic group, such as but not limited to C3-C 12 heterocycloalkyl or C5-C7 heterocycloalkyl, and which 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 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]heptanyl; and fused polycyclic heterocycloalkyl, such as but not limited to octahydrocyclopenta[b]pyranyl and octahydro-1H-isoindenyl.

[0045] As used herein, the term "alkynyl" and related terms (such as "alkynyl group(s)") mean a group that includes at least two carbon atoms, such as 2 to 20 carbon atoms, such as C2-C 20 alkynyl, or C2-C 10 alkynyl, or C2-C6 alkynyl; is straight-chain or branched-chain; and includes one or more internal and / or terminal alkyne group (or alkynyl group). Examples of alkynyl include but are not limited to ethynyl, propynyl, butynyl, straight-chain or branched-chain pentynyl, straight-chain or branched-chain hexynyl, etc.

[0046] As used herein, the term "heteroaryl" and related terms (such as "heteroaryl group(s)") mean a cyclic aromatic group that includes at least 3 carbon atoms, such as C3-C 20 heteroaryl, or C5-C 14 heteroaryl; at least one heteroatom in the aromatic ring, such as -O-, -N-, and / or -S-; and optionally includes at least two fused rings, where at least one is a fused heteroaromatic ring. Examples of heteroaryl include but are not limited to pyrazolyl, imidazolyl, triazinyl, furanyl, thiophenyl, pyranyl, pyridinyl, isoquinolinyl, and pyrimidinyl.

[0047] As used herein, the term "alkoxy" and related terms (such as "alkoxy group(s)") mean a group represented by -OR, where R is a straight-chain or branched-chain alkyl including at least one carbon atom, such as 1 to 20 carbon atoms, such as C1-C 20 alkyl, or C1-C 10 alkyl, or C1-C6 alkyl, and accordingly the alkoxy is, for example, C1-C 20 alkoxy, or C1-C 10an alkoxy group, or a C1-C6 alkoxy group. Examples of alkoxy groups include, but are not limited to, those examples of alkyl groups listed previously herein, which include a terminal divalent oxygen bond or group (or a terminal ether bond or group), such as, but not limited to, methoxy (CH3-O-), ethoxy (CH3CH2-O-), n-propoxy (CH3CH2CH2-O-), isopropoxy, straight-chain or branched butoxy, straight-chain or branched pentyloxy, straight-chain or branched hexyloxy, and the like.

[0048] As used herein, the terms "halogen" and related terms (such as "halogen group" and / or "halo group") mean a halogen atom bonded by a single bond (such as fluorine (F), chlorine (Cl), bromine (Br), and / or iodine (I)).

[0049] As used herein, the term "amino" and related terms (such as "amino group") include a group represented by -N(R 14 )(R 15 ), where R 14 and R 15 are each independently selected from, for example, hydrogen, an aliphatic group, an alicyclic group, a heteroalicyclic group, an aryl group, and a heteroaryl group. As used herein, the term "primary amino" and related terms (such as "primary amino group") mean a group represented by -NH2.

[0050] As used herein, and unless otherwise expressly stated, the term "hydrogen" and related terms (such as "hydrogen group") mean a hydrogen (-H) bonded by a single bond.

[0051] As used herein, the term "alkenyl" and related terms (such as "alkenyl group") mean a group that includes at least two carbon atoms, such as 2 to 20 carbon atoms, such as C2-C 20 alkenyl, or C2-C 10 alkenyl, or C2-C6 alkenyl; is straight-chain or branched; and includes one or more internal and / or terminal alkene groups (or alkenyl groups). Examples of alkenyl groups include, but are not limited to, those examples of straight-chain or branched alkyl groups listed previously herein, which have at least two carbon atoms and at least one alkene group (or alkenyl group), such as, but not limited to, vinyl, straight-chain or branched propenyl, straight-chain or branched butenyl, straight-chain or branched pentenyl, straight-chain or branched hexenyl, and the like.

[0052] As used herein, the term "aryl" and related terms (such as "aryl group(s)") mean the following cyclic aromatic groups: which include at least 6 carbon atoms, such as C6-C 20 aryl, or C6-C 14 aryl; and optionally include at least two fused rings, where at least one is a fused aromatic ring. Examples of aryl include but are not limited to phenyl, naphthyl, anthracenyl, phenanthrenyl, triphenylenyl, 9,10-dihydroanthracenyl, 9,10-dihydrophenanthrenyl, and triptycenyl.

[0053] As used herein, the term "aralkyl" or "arylalkyl" means aryl-alkyl, where aryl and alkyl are as described previously. The bonding to the parent moiety is through the alkyl group. Non-limiting examples of suitable aralkyls include but are not limited to benzyl and phenethyl.

[0054] The photochromic optical article of the present invention includes an optical substrate. The photochromic optical article further includes at least a partially anisotropic layer disposed on at least a portion of the surface of the optical substrate. The at least partially anisotropic layer of the photochromic optical article contains an anisotropic polymer, a photochromic-dichroic dye, a photochromic dye, or a combination thereof, a mesogenic hindered amine light stabilizer, and a mesogenic antioxidant. The photochromic optical article includes other optional layers, which will be further described herein.

[0055] As used herein, the term "anisotropic" means having at least one property that is different in value when measured in at least one different direction. Accordingly, an "anisotropic material" is a material that has at least one property that is different in value when measured in at least one different direction. Non-limiting examples of polymerizable anisotropic materials that can be included in the anisotropic layer include but are not limited to those further described herein with respect to the optional alignment layer of the photochromic optical article of the present invention.

[0056] The anisotropic layer contains an anisotropic polymer formed from polymerizable anisotropic materials such as liquid crystal monomers and / or oligomers, as disclosed in Table 1 of columns 43-90 of U.S. Patent No. 7,910,019B2, the disclosure of which is incorporated herein by reference. Suitable commercially available polymerizable liquid crystal monomers include those available from Merck KGaA (Darmstadt, Germany) under the trade name Those obtained from reactive mesogens. Examples include but are not limited to RM-23, RM-82, RM-105, and RM-257. The polymerizable liquid crystal monomers can be bis-mesogenic reactive liquid crystal monomers such as those disclosed in Examples 12, 24-34, and CE-41 of International Patent Application Publication No. WO 2020 / 119877.

[0057] Examples of the photochromic-dichroic dyes in the anisotropic layer of the photochromic optical article suitable for the present invention can include but are not limited to those described in detail in column 5, line 12 to column 78, line 13 of U.S. Patent No. 7,342,112, the disclosure of which is incorporated herein by reference.

[0058] The photochromic-dichroic dyes and / or photochromic dyes are generally present in the anisotropic layer in an amount at least sufficient to provide the desired level of photochromic properties for the article prepared from the composition, and this amount is referred to as the photochromic amount. When used, the amount of one or more photochromic-dichroic dyes present in the anisotropic layer can range from 0.1 weight percent to 40 weight percent, or 1 weight percent to 30 weight percent, or 5 weight percent to 20 weight percent, or 10 weight percent to 15 weight percent based on the weight of the anisotropic polymer, photochromic dye, and photochromic-dichroic dye in the anisotropic layer.

[0059] The anisotropic layer of the photochromic optical article further comprises a mesogenic hindered amine light stabilizer. The mesogenic hindered amine light stabilizer is a compound represented by the following formula (I):

[0060]

[0061] The mesogenic hindered amine light stabilizer compounds (such as those represented by formula (I)) suitable for preparing the photochromic optical article of the present invention and their various groups will be described in further detail herein below.

[0062] R of the mesogenic hindered amine light stabilizer compound having formula (I) 1 is hydrogen, alkyl, alkoxy, acetyl, hydroxy, or oxide. In some examples, R of the mesogenic hindered amine light stabilizer compound having formula (I) 1 is hydrogen, alkyl, or alkoxy.

[0063] R of the mesogenic hindered amine light stabilizer compound having formula (I) 2 、R 3 、R 4 and R 5 are each independently hydrogen or alkyl, provided that R 2 、R 3 、R 4and R 5 Two or more of which are alkyl groups. In some instances, R of the mesogenic hindered amine light stabilizer compound having formula (I) 2 , R 3 , R 4 , and R 5 are each alkyl groups.

[0064] The divalent linking group L of the mesogenic hindered amine light stabilizer having formula (I) 1 is a double bond, or one of formula (IIa), (IIb), (IIc), (IId), (IIe), or (IIf),

[0065]

[0066] For the divalent linking group represented by formula (IIb), R 6 is a divalent alkyl or a divalent substituted alkyl. For the divalent linking group represented by formula (IId), R 7 is a divalent alkyl or a divalent substituted alkyl. For the divalent linking group represented by formula (IIe), R 8 is a divalent alkyl or a divalent substituted alkyl. For the divalent linking group represented by formula (IIf), R b is hydrogen, alkyl, or substituted alkyl. For the mesogenic hindered amine light stabilizer having formula (I), m is from 0 to 4.

[0067] For each m of the mesogenic hindered amine light stabilizer having formula (I), the L 2 segment is independently a divalent C1-C 25 alkyl or a divalent C2-C 25 alkenyl, optionally interrupted in each case by at least one of -O-, -C(O)-, -C(O)O-, or -OC(O)O-.

[0068] The mesogen of the mesogenic hindered amine light stabilizer having formula (I) is represented by the following formula III:

[0069]

[0070] For the mesogen represented by formula (III), Y is a divalent linking group as a double bond, -O-, or -S-.

[0071] For the mesogen represented by formula (III), v and u are each independently 0 to 4, provided that the sum of v and u is 2 to 4. In some instances, for the mesogen represented by formula (III), the sum of v and u is 3 to 4.

[0072] For a mesogen represented by formula (III), Z for each v is independently a divalent linking group that is a double bond, -O-, -S-, -C(O), -C(O)O-, -OC(O)O-, -N(R 9 )-C(O)-O-, or -C(O)-N(R 9 ). For a mesogen represented by formula (III), R 9 is hydrogen, alkyl, or substituted alkyl. In some instances, for a mesogen represented by formula (III), Z for each v is independently a divalent linking group that is a double bond or -C(O)O-.

[0073] For a mesogen represented by formula (III), for each v (for divalent ring -A) and each u (for divalent ring -B), the divalent rings

[0074]

[0075] are each independently phenylene-1,4-diyl, or substituted phenylene-1,4-diyl, or cyclohexane-1,4-diyl, or substituted cyclohexane-1,4-diyl. Optional substituents for divalent ring A and divalent ring B can be alkoxy, alkyl, or halogen.

[0076] As used herein, the term "divalent ring -A" means a divalent ring having the following representation:

[0077]

[0078] Additionally, as used herein, the term "divalent ring -B" means a divalent ring having the following representation:

[0079]

[0080] E of the mesogenic hindered amine light stabilizer having formula (I) is hydrogen, straight-chain or branched C1-C 25 alkyl, straight-chain or branched C2-C 25 alkenyl, straight-chain or branched C2-C 25 alkynyl, each optionally interrupted by at least one of -O-, -S-, -C(O)-, -C(O)O-, or -OC(O)O-. In some instances, E of the mesogenic hindered amine light stabilizer having formula (I) is alkyl.

[0081] For the mesogenic hindered amine light stabilizer having formula (I), when L 1 is directly connected to L 2 (and is equivalent to when L 2 is connected to L 1 ), the direct connection therebetween (e.g., each direct L 1 -L 2The connection) does not contain two heteroatoms connected (or bonded) together. For the mesogenic hindered amine light stabilizer having the formula (I), when L 1 is directly connected to the mesogen (and is equivalent to when the mesogen is connected to L 1 ), the direct connection between L 1 and Y (e.g., each direct L 1 -mesogen connection) does not contain two heteroatoms connected (or bonded) together. For the mesogenic hindered amine light stabilizer having the formula (I), when L 2 is directly connected to the mesogen (and is equivalent to when the mesogen is connected to L 2 ), the direct connection between L 2 and Y (e.g., each direct L 2 -mesogen connection) does not contain two heteroatoms connected (or bonded) together.

[0082] Mesogenic hindered amine light stabilizers that can be used in anisotropic layers include, but are not limited to, materials recognized in the art as described in U.S. Patent No. 8,349,210, the disclosure of which is incorporated herein by reference.

[0083] For example, mesogenic hindered amine light stabilizers for anisotropic layers can be represented by the following formulas (IVA) to (IVH):

[0084]

[0085] 1,2,2,6,6-Pentamethylpiperidin-4-yl (4'-(4-pentylcyclohexyl)-[1,1'-biphenyl]-4-yl) succinate,

[0086]

[0087] 1,2,2,6,6-Pentamethylpiperidin-4-yl 4-((4'-(4-pentylcyclohexyl)-[1,1'-biphenyl]-4-yl)oxy) butyrate,

[0088]

[0089] 2,2,6,6-Tetramethylpiperidin-4-yl 4'-(4-pentylcyclohexyl)-[1,1'-biphenyl]-4-carboxylate,

[0090]

[0091] 1-Ethoxy-2,2,6,6-tetramethylpiperidin-4-yl 4'-(4-pentylcyclohexyl)-[1,1'-biphenyl]-4-carboxylate,

[0092]

[0093] 1-Acetyl-2,2,6,6-tetramethylpiperidin-4-yl 4'-((1s,4r)-4-pentylcyclohexyl)-[1,1'-biphenyl]-4-carboxylate,

[0094]

[0095] 6-((4'-(4-Pentylcyclohexyl)-[1,1'-biphenyl]-4-yl)oxy)hexyl (2,2,6,6-tetramethylpiperidin-4-yl) succinate,

[0096]

[0097] 1,2,2,6,6-Pentamethylpiperidin-4-yl (8-(4-((4-((4'-pentyl-[1,1'-bicyclohexyl]-4-carbonyl)oxy)phenoxy)carbonyl)phenoxy)octyl) succinate, and

[0098]

[0099] 6,13,20,27,34,41-Hexaoxo-50-(4-((4-((4'-pentyl-[1,1'-bicyclohexyl]-4-carbonyl)oxy)phenoxy)carbonyl)phenoxy)-7,14,21,28,35,42-hexaoxapentacontyl (1,2,2,6,6-pentamethylpiperidin-4-yl) succinate.

[0100] Relative to the total moles of one or more photochromic-dichroic dyes present in the anisotropic layer, the amount of the mesogenic hindered amine light stabilizer in the anisotropic layer can range from 10 mole percent to 50 mole percent.

[0101] Mesogenic antioxidant compounds (such as those represented by formula (V)) suitable for preparing the photochromic optical articles of the present invention and their various groups will be described in further detail herein below.

[0102]

[0103] R of the mesogenic antioxidant compound having formula (V) 10 and R 11 are each independently hydrogen or a straight-chain or branched-chain alkyl group, provided that at least one of R 10 and R 11 is an alkyl group.

[0104] The divalent linking group L of the mesogenic antioxidant having formula (V) 3 is a double bond, or one of formula (VIa), (VIb), (VIc), (VId), (VIe), or (VIf),

[0105]

[0106] For the divalent linking groups represented by formulae (VIb), (VId), (VIe), and (VIf), R 6 ’, R 7 ’, R 8 ’, and R b ’ are each independently and respectively R 6 , R 7 , R 8 , and R b . For the mesogenic antioxidants having formula (V), m is from 0 to 4.

[0107] For each m of the mesogenic antioxidants having formula (V), the L 4 segment is independently a divalent C1-C 25 alkyl or a divalent C2-C 25 alkenyl, optionally interrupted in each case by at least one of -O-, -C(O)-, -C(O)O-, or -OC(O)O-.

[0108] The mesogen of the mesogenic antioxidants having formula (V) is represented by formula (III):

[0109]

[0110] For the mesogen represented by formula (III), Y is a divalent linking group as a double bond, -O-, or -S-.

[0111] For the mesogen represented by formula (III), v and u are each independently 0 to 4, provided that the sum of v and u is 2 to 4. For the mesogen represented by formula (III), the sum of v and u is 3 to 4.

[0112] For the mesogen represented by formula (III), for each v (for the divalent ring -A) and each u (for the divalent ring -B), the divalent ring 9 )-C(O)-O-, or -C(O)-N(R 9 )-. For the mesogen represented by formula (III), R 9 is hydrogen, alkyl, or substituted alkyl. For the mesogen represented by formula (III), for each v, Z is independently a divalent linking group as a double bond or -C(O)O-.

[0113] For the mesogen represented by formula (III), for each v (for the divalent ring -A) and each u (for the divalent ring -B), the divalent ring

[0114]

[0115] Each independently is phenylene-1,4-diyl, or substituted phenylene-1,4-diyl, or cyclohexane-1,4-diyl, or substituted cyclohexane-1,4-diyl. Optional substituents of the divalent ring A and the divalent ring B may be alkoxy, alkyl, or halogen.

[0116] E of the mesogenic antioxidant having the formula (V) is hydrogen, a straight-chain or branched C1-C 25 alkyl, a straight-chain or branched C2-C 25 alkenyl, a straight-chain or branched C2-C 25 alkynyl, each optionally inserted with at least one of -O-, -S-, -C(O)-, -C(O)O-, or -OC(O)O-. E of the mesogenic antioxidant stabilizer having the formula (V) is alkyl.

[0117] For the mesogenic antioxidant stabilizer having the formula (V), when L 3 is directly connected to L 4 (and is equivalent to when L 4 is connected to L 3 ), the direct connection therebetween (e.g., each direct L 3 -L 4 connection) does not contain two heteroatoms connected (or bonded) together. For the mesogenic antioxidant having the formula (V), when L 3 is directly connected to the mesogen (and is equivalent to when the mesogen is connected to L 3 ), the direct connection between L 3 and Y therebetween (e.g., each direct L 3 -mesogen connection) does not contain two heteroatoms connected (or bonded) together. For the mesogenic antioxidant having the formula (V), when L 4 is directly connected to the mesogen (and is equivalent to when the mesogen is connected to L 4 ), the direct connection between L 4 and Y therebetween (e.g., each direct L 4 -mesogen connection) does not contain two heteroatoms connected (or bonded) together.

[0118] Mesogenic antioxidants that can be used in the anisotropic layer include, but are not limited to, materials recognized in the art as described in U.S. Patent No. 8,613,868, the disclosure of which is incorporated herein by reference.

[0119] For example, mesogenic antioxidants suitable for the anisotropic layer can be represented by the following formulas (VIIA) to (VIIG):

[0120]

[0121] 6 - ((4'-(4 - pentylcyclohexyl)-[1,1'-biphenyl]-4 - yl)oxy)hexyl 3,5 - di - tert - butyl - 4 - hydroxybenzoate,

[0122]

[0123] 4 - ((4 - ((8 - ((3,5 - di - tert - butyl - 4 - hydroxybenzoyl)oxy)octyl)oxy)benzoyl)oxy)phenyl 4'-pentyl - [1,1'-biscyclohexane]-4 - carboxylate,

[0124]

[0125] 4 - ((4 - ((8 - ((3,5 - di - tert - butyl - 4 - hydroxybenzoyl)oxy)octyl)oxy)benzoyl)oxy)-3 - methylphenyl 4'-pentyl - [1,1'-biscyclohexane]-4 - carboxylate,

[0126]

[0127] 6 - ((4'-(4 - pentylcyclohexyl)-[1,1'-biphenyl]-4 - yl)oxy)hexyl 3-(3,5 - di - tert - butyl - 4 - hydroxyphenyl)propionate,

[0128]

[0129] 4 - ((4 - ((8 - ((4-(3-(tert - butyl)-4 - hydroxy - 5 - methylphenyl)-4 - oxobutanoyl)oxy)octyl)oxy)benzoyl)oxy)phenyl 4 - methylbenzoate,

[0130]

[0131] 4 - ((4 - ((1-(3,5 - di - tert - butyl - 4 - hydroxyphenyl)-1,8,15,22,29,36,43 - heptaoxo - 2,9,16,23,30,37,44 - heptaoxapentacontane - 52 - yl)oxy)benzoyl)oxy)phenyl 4'-pentyl - [1,1'-biscyclohexane]-4 - carboxylate, and

[0132]

[0133] 8-(4 - ((4 - ((4 - methylbenzoyl)oxy)phenoxy)carbonyl)phenoxy)octyl 3,5 - di - tert - butyl - 4 - hydroxybenzoate.

[0134] The amount of the mesogenic antioxidant in the anisotropic layer can range from 25 mole percent to 150 mole percent relative to the total moles of one or more photochromic-dichroic dyes present in the anisotropic layer. The moles of the mesogenic antioxidant are present in an amount greater than or equal to the moles of the mesogenic hindered amine light stabilizer.

[0135] The anisotropic layer can further comprise an ultraviolet light absorber. Non-limiting examples of suitable ultraviolet light absorbers for the anisotropic layer include benzotriazoles, benzophenones, and combinations thereof. For example, the anisotropic layer can comprise a benzotriazole ultraviolet light absorber represented by the following formula (VIII):

[0136]

[0137] The benzotriazole compounds (such as those represented by formula (VIII)) and their various groups suitable for preparing the photochromic optical article of the present invention will be described in further detail herein below.

[0138] R for each c of the benzotriazole ultraviolet light absorber 12 and R for each d 13 are each independently methyl, ethyl, hydroxy, or a halogen such as F or Cl. In the benzotriazole ultraviolet light absorber having formula (VIII), c is from 0 - 4. In the benzotriazole ultraviolet light absorber having formula (VIII), d is from 0 - 4.

[0139] Non-limiting examples of suitable benzotriazole ultraviolet light absorbers include 4-(2H-benzotriazol-2-yl)-1,3-benzenediol, 2-(2H-benzotriazol-2-yl)-1,3,5-benzenetriol, 4-(2H-benzotriazol-2-yl)-5-methyl-1,3-benzenediol, 4-(2H-benzotriazol-2-yl)-2-methyl-1,3-benzenediol, 2-(2H-benzotriazol-2-yl)-5-methoxyphenol, 4-(2H-benzotriazol-2-yl)-1,2,3-benzenetriol, 4-(5-methyl-2H-benzotriazol-2-yl)-1,3-benzenediol, 2-(2H-benzotriazol-2-yl)-4-methyl-1,3,5-benzenetriol, 5-(2H-benzotriazol-2-yl)-1,2,4-benzenetriol, 4-(5-hydroxy-2H-benzotriazol-2-yl)-1,3-benzenediol, 4-(2H-benzotriazol-2-yl)-1,2,3,5-benzenetetrol, 2-(5-hydroxy-2H-benzotriazol-2-yl)-1,3,5-benzenetriol, 4-(2H-benzotriazol-2-yl)-2-ethyl-1,3-benzenediol, 4-(5-methoxy-2H-benzotriazol-2-yl)-1,3-benzenediol, 4-(2H-benzotriazol-2-yl)-6-chloro-1,3-benzenediol, 4-(5-fluoro-2H-benzotriazol-2-yl)-1,3-benzenediol, 2-(5-methoxy-2H-benzotriazol-2-yl)-1,3,5-benzenetriol, 2-(2,4-dihydroxyphenyl)-2H-benzotriazole-4,6-diol, 4-[5-(trifluoromethyl)-2H-benzotriazol-2-yl]-1,3-benzenediol, and combinations thereof.

[0140] Non-limiting examples of suitable benzophenone ultraviolet light absorbers include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2′,4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, and combinations thereof.

[0141] The photochromic-dichroic dyes, mesogenic antioxidants, and mesogenic hindered amine light stabilizers of the anisotropic layer can be at least partially aligned by interacting with a polymerizable anisotropic material that is itself at least partially ordered. For example, although not limited herein, at least a portion of the photochromic-dichroic dye can be aligned such that the long axis of the photochromic-dichroic dye in the dichroic state is substantially parallel to the overall direction of the polymerizable anisotropic material. Additionally, although not necessary, the photochromic-dichroic dye, mesogenic antioxidant, or mesogenic hindered amine light stabilizer can be incorporated into or reacted with at least a portion of the at least partially ordered polymerizable anisotropic material.

[0142] An anisotropic coating can be applied to a substrate, or other optional layers, by methods well known in the art, including but not limited to spin coating, spraying, spray and spin coating, curtain coating, flow coating, dip coating, injection molding, casting, roll coating, wire coating, and overmolding.

[0143] Methods for at least partially aligning at least a portion of the polymerizable anisotropic material in the at least partially aligned anisotropic layer are described herein and in column 27, lines 17 to column 28, line 45 of U.S. Patent No. 7,097,303, which is incorporated herein by reference.

[0144] Methods for ordering or introducing order into the polymerizable anisotropic material of the anisotropic layer include but are not limited to exposing the polymerizable anisotropic material to at least one of a magnetic field, an electric field, linearly polarized ultraviolet radiation, linearly polarized infrared radiation, linearly polarized visible radiation, and shear forces. Alternatively or additionally, the polymerizable anisotropic material can be at least partially ordered by aligning at least a portion of the polymerizable anisotropic material with another material or structure. For example, the polymerizable anisotropic material can be at least partially ordered by aligning the polymerizable anisotropic material with an alignment layer (or alignment facility), such as but not limited to those alignment layers described in further detail below.

[0145] By ordering at least a portion of the polymerizable anisotropic material, at least a portion of the photochromic-dichroic dyes, mesogenic antioxidants, and mesogenic hindered amine light stabilizers contained within or otherwise attached to the polymerizable anisotropic material of the anisotropic layer can be at least partially aligned. Although not required, the photochromic-dichroic dyes can be at least partially aligned while in the activated state. Ordering the polymerizable anisotropic material and / or aligning the photochromic-dichroic dyes, mesogenic antioxidants, and mesogenic hindered amine light stabilizers can be performed before, during, or after applying the anisotropic layer over an optional primer layer or an optional alignment layer.

[0146] Photochromic-dichroic dyes, mesogenic antioxidants, mesogenic hindered amine light stabilizers, and polymerizable anisotropic materials can be aligned and ordered during the application of an anisotropic layer. For example, the anisotropic layer can be applied using a coating technique that introduces shear forces into the polymerizable anisotropic material during application such that the polymerizable anisotropic material becomes at least partially ordered substantially parallel to the direction of the applied shear force. For purposes of non-limiting illustration, a solution or mixture (optionally in a solvent or carrier) containing a photochromic-dichroic dye, a mesogenic antioxidant, a mesogenic hindered amine light stabilizer, and a polymerizable anisotropic material can be curtain-coated onto a substrate such that shear forces are introduced into the material being applied, which is attributed to the relative movement of the substrate surface with respect to the applied material. An example of a coating process that can introduce at least sufficient shear force is the curtain-coating process. The shear force can cause at least a portion of the anisotropic material to be ordered in a general direction substantially parallel to the surface movement direction. As discussed above, by ordering at least a portion of the polymerizable anisotropic material in this manner, at least a portion of the photochromic-dichroic dye, mesogenic antioxidant, and mesogenic hindered amine light stabilizer can be aligned. Additionally, and optionally, at least a portion of the photochromic-dichroic dye can be aligned while in an activated state by exposing at least a portion of the photochromic-dichroic dye to actinic radiation during the curtain-coating process to convert the photochromic-dichroic dye to an activated state.

[0147] Photochromic-dichroic dyes, mesogenic antioxidants, mesogenic hindered amine light stabilizers, and polymerizable anisotropic materials can be aligned and ordered after applying a polymerizable composition onto a substrate. For example, a solution or mixture (optionally in a solvent or carrier) of a photochromic-dichroic dye, a mesogenic antioxidant, a mesogenic hindered amine light stabilizer, and a polymerizable anisotropic material can be spin-coated onto at least a portion of the substrate. Thereafter, at least a portion of the polymerizable anisotropic material can be ordered, for example, by exposing the polymerizable anisotropic material to a magnetic field, an electric field, linearly polarized ultraviolet radiation, linearly polarized infrared radiation, linearly polarized visible radiation, and / or shear forces. Alternatively or additionally, the polymerizable anisotropic material can be at least partially ordered by its alignment with another material or structure, such as an alignment layer.

[0148] A photochromic-dichroic dye, a mesogenic antioxidant, a mesogenic hindered amine light stabilizer, and a polymerizable anisotropic material can be aligned and ordered before applying the polymerizable composition onto a substrate. For example, a solution or mixture (optionally in a solvent or carrier) of the photochromic-dichroic dye, the mesogenic antioxidant, the mesogenic hindered amine light stabilizer, and the polymerizable anisotropic material can be applied onto an ordered polymer sheet to form a layer thereon. Thereafter, at least a portion of the polymerizable anisotropic material can be allowed to align with the underlying ordered polymer sheet. The polymer sheet can then be applied onto the substrate by, for example, lamination or adhesion methods well known in the art. Alternatively, the ordered anisotropic layer can be transferred from the polymer sheet to the substrate / substrates by methods well known in the art such as hot stamping.

[0149] The polymerizable anisotropic material of the photochromic optical article can be at least partially cured or at least partially polymerized by any method known in the art, such as those disclosed in column 38, lines 24 to 38 of U.S. Patent No. 7,910,019, the disclosure of which is incorporated herein by reference. For example, the anisotropic polymer can comprise polymerized liquid crystal monomers. Non-limiting examples of suitable curing methods include exposing at least a portion of the coating to ultraviolet radiation, visible radiation, gamma radiation, microwave radiation, electron radiation, thermal energy, or a combination of any of these curing methods.

[0150] The polymerizable anisotropic material can also be cured by exposing to light-emitting diodes having a peak emission wavelength ranging from 385 to 460 nanometers, such as from 390 to 460 nanometers, or from 410 to 460 nanometers, to effect curing (i.e., polymerization) of the anisotropic layer, wherein the light-emitting diodes can include inorganic or organic light-emitting diodes. The light-emitting diode light source can be an organic light-emitting diode; and / or an inorganic light-emitting diode, e.g., those made of alloys using some or all of aluminum nitride, gallium nitride, and indium nitride. Commercially available light sources including suitable inorganic light-emitting diodes include the LB80-438P1-84 or JL3-395-G2-12 units from Clearstone Technologies, Inc. Commercially available light sources including suitable inorganic light-emitting diodes are also available from Heraeus Noblelight America LLC or Phoseon Technology.

[0151] As disclosed herein, the photochromic optical article includes one or more additional layers positioned between a substrate and at least a portion of an anisotropic layer. As disclosed herein, the photochromic article includes one or more additional layers positioned on at least a portion of the anisotropic layer. As disclosed herein, the one or more additional layers may further comprise a permanent tint dye, a dichroic dye, a photochromic-dichroic dye, a photochromic dye, or combinations thereof.

[0152] As used herein, the terms "permanent tint dye" and related terms such as "fixed-colorant", "static colorant", "fixed dye", and "static dye" mean dyes that are non-photosensitive materials that do not physically or chemically respond to electromagnetic radiation related to the color visually observed by them. As used herein, the terms "permanent 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 does not physically or chemically respond to electromagnetic radiation related to the color visually observed by it, which includes but is not limited to permanent tint dyes. One or more permanent tint dyes may be present in the one or more additional layers of the present invention for purposes including but not limited to providing for an article prepared from these compositions: at least the base (or first) color characteristics of the permanent tint dye (when the photochromic compound (if used) is not activated); and optionally, a second color characteristic of a combination of the permanent tint dye and the photochromic compound (when activated, such as by exposure to actinic radiation). Optional permanent tint dyes of the curable photochromic composition may include at least one of the following: azo dyes, anthraquinone dyes, xanthene dyes, azime dyes, iodine, iodide salts, polyazo dyes, stilbene dyes, pyrazolone dyes, triphenylmethane dyes, quinoline dyes, oxazine dyes, thiazine dyes, and polyene dyes.

[0153] Non-limiting examples of suitable conventional dichroic dyes include azomethine, indigo, thioindigo, merocyanine, indane, quinophthalone dyes, perylene, phthaloperine, tribenzodioxazine, indoloquinoxaline, imidazo-triazine, tetrazine, azo and (poly)azo dyes, benzoquinone, naphthoquinone, anthraquinone and (poly)anthraquinone, anthrapyrimidinone, iodine, and iodate.

[0154] The dichroic dye can be a polymerizable dichroic compound. That is, the dichroic dye can include at least one group capable of polymerization (i.e., a "polymerizable group"). For example, although not limited herein, the at least one dichroic compound can have at least one alkoxy, polyalkoxy, alkyl, or polyalkyl substituent capped with at least one polymerizable group.

[0155] As discussed further herein, the photochromic optical article of the present invention can include an alignment layer (also referred to as an alignment or orientation means) between the substrate or optional primer layer and the anisotropic layer.

[0156] As used herein, the term "alignment layer" means a layer that can facilitate the alignment of one or more other structures that are directly and / or indirectly exposed to at least a portion thereof. As used herein, the term "ordering" means bringing to a suitable arrangement or orientation, such as aligning with another structure or material or by some other force or effect. Thus, as used herein, the term "ordering" encompasses both contact methods of ordering a material, such as by aligning with another structure or material, and non-contact methods of ordering a material, such as by exposure to an external force or effect. The term ordering also encompasses combinations of contact and non-contact methods.

[0157] For example, a photochromic-dichroic dye that is at least partially aligned by interaction with an optional alignment layer can be at least partially aligned such that the long axis of the photochromic-dichroic dye in the activated state is substantially parallel to at least a first general direction of the alignment layer. The photochromic-dichroic dye that is at least partially aligned by interaction with the alignment layer is bound to or reacted with the alignment layer. As used herein with respect to the ordering or alignment of a material or structure, the term "general direction" refers to the main arrangement or orientation of the material, compound, or structure. Further, those skilled in the art will understand that a material, compound, or structure can have a general direction even if there are some variations in the arrangement of the material, compound, or structure, provided that the material, compound, or structure has at least one main arrangement.

[0158] The alignment layer can have at least a first overall direction. For example, the alignment layer can include a first ordered region having a first overall direction and at least one second ordered region adjacent to the first ordered region, the second ordered region having a second overall direction different from the first overall direction. Additionally, the alignment layer can have multiple regions, each having the same or a different overall direction from the remaining regions, so as to form a desired pattern or design. The alignment layer can include, for example, a coating containing at least partially ordered alignment medium, an at least partially ordered polymer sheet, an at least partially treated surface, a Langmuir-Blodgett (LB) film, and combinations thereof.

[0159] The alignment layer can include a coating containing at least partially ordered alignment medium. Examples of suitable alignment media that can be used in combination with the alignment layer include, but are not limited to, liquid crystal materials, photoalignment materials, and rubbing alignment materials.

[0160] The alignment medium of the alignment layer can be a liquid crystal material, and the alignment layer can be referred to as a liquid crystal alignment layer. Due to its structure, a liquid crystal material is generally capable of being ordered or aligned so as to adopt an overall direction. More specifically, since liquid crystal molecules have a rod-like or disc-like structure, a rigid long axis, and a strong dipole, the liquid crystal molecules can be ordered or aligned by interacting with an external force or another structure such that the long axes of the molecules adopt an orientation generally parallel to a common axis. For example, the molecules of a liquid crystal material can be aligned using a magnetic field, an electric field, linearly polarized infrared radiation, linearly polarized ultraviolet radiation, linearly polarized visible radiation, or a shear force. The liquid crystal molecules can also be aligned using an oriented surface. For example, liquid crystal molecules can be applied to a surface that has been oriented, for example, by rubbing, grooving, or photoalignment methods, and then aligned such that the long axis of each liquid crystal molecule adopts an orientation of an overall direction generally parallel to the orientation of the surface. Examples of liquid crystal materials suitable for use as the alignment medium include, but are not limited to, liquid crystal polymers, liquid crystal prepolymers, liquid crystal monomers, and liquid crystal mesogens. As used herein, the term "prepolymer" means a partially polymerized material.

[0161] The classes of liquid crystal monomers suitable for use in combination with the alignment layer include, but are not limited to, monofunctional liquid crystal monomers and polyfunctional liquid crystal monomers. The liquid crystal monomers can be crosslinkable liquid crystal monomers, such as photo-crosslinkable liquid crystal monomers. As used herein, the term "photo-crosslinkable" means a material that can be crosslinked or polymerized upon exposure to actinic radiation, such as a monomer, prepolymer, or polymer. For example, photo-crosslinkable liquid crystal monomers include, but are not limited to, those liquid crystal monomers that can be crosslinked upon exposure to ultraviolet radiation and / or visible radiation, with or without a polymerization initiator.

[0162] Examples of crosslinkable liquid crystal monomers that can be included in the alignment layer include, but are not limited to, liquid crystal monomers having functional groups selected from the following: acrylate, methacrylate, allyl, allyl ether, alkynyl, amino, anhydride, epoxide, hydroxide, isocyanate, blocked isocyanate, siloxane, thiocyanate, thiol, urea, vinyl, vinyl ether, and blends thereof. Examples of photocrosslinkable liquid crystal monomers that can be included in the alignment layer include, but are not limited to, liquid crystal monomers having functional groups selected from the following: acrylate, methacrylate, alkynyl, epoxide, thiol, and blends thereof.

[0163] Liquid crystal polymers and prepolymers that can be included in the alignment layer include, but are not limited to, main-chain liquid crystal polymers and prepolymers and side-chain liquid crystal polymers and prepolymers. For main-chain liquid crystal polymers and prepolymers, rod-like or disc-like liquid crystal mesogens are mainly located within the polymer backbone. For side-chain liquid crystal polymers and prepolymers, rod-like or disc-like liquid crystal mesogens are mainly located within the polymer side chains. Additionally, the liquid crystal polymer or prepolymer can be crosslinkable and further can be photocrosslinkable.

[0164] Examples of liquid crystal polymers and prepolymers that can be included in the alignment layer include, but are not limited to, main-chain and side-chain polymers and prepolymers having functional groups selected from the following: acrylate, methacrylate, allyl, allyl ether, alkynyl, amino, anhydride, epoxide, hydroxide, isocyanate, blocked isocyanate, siloxane, thiocyanate, thiol, urea, vinyl, vinyl ether, and blends thereof. Examples of photocrosslinkable liquid crystal polymers and prepolymers that can be included in the alignment layer include, but are not limited to, those polymers and prepolymers having functional groups selected from the following: acrylate, methacrylate, alkynyl, epoxide, thiol, and blends thereof.

[0165] Liquid crystal mesogens that can be included in the alignment layer include, but are not limited to, thermotropic liquid crystal mesogens and lyotropic liquid crystal mesogens. Additional categories of liquid crystal mesogens that can be included in the alignment layer include, but are not limited to, columnar (or rod-like) liquid crystal mesogens and discotic (or disc-like) liquid crystal mesogens.

[0166] Examples of photoalignment materials that can be included in the alignment layer include, but are not limited to, those disclosed in column 15, lines 15 to 32 of U.S. Patent No. 7,097,303 B2, the disclosure of which is incorporated by reference.

[0167] As used herein, the term "rubbed alignment material" means a material that can be at least partially ordered by rubbing at least a portion of the surface of the material with another appropriately textured material. Examples of suitable materials and methods for at least partially ordering a rubbed alignment material include, but are not limited to, those disclosed in column 15, lines 33 to 49 of U.S. Patent No. 7,097,303B2, the disclosure of which is incorporated herein by reference.

[0168] The alignment layer can include a polymer sheet that is at least partially ordered. Examples of suitable polymer sheets that are at least partially ordered and methods for at least partially ordering a polymer sheet include, but are not limited to, those disclosed in column 70, lines 1 to 23 of U.S. Patent No. 7,256,921B2, the disclosure of which is incorporated herein by reference.

[0169] The alignment layer of the photochromic article of the present invention can include a surface that has been at least partially treated. As used herein, the term "treated surface" means that at least a portion of the surface has been physically altered to create at least one ordered region on at least a portion of the surface. Examples of suitable treated surfaces include, but are not limited to, those disclosed in column 70, lines 24 to 51 of U.S. Patent No. 7,256,921B2, the disclosure of which is incorporated herein by reference.

[0170] As used herein, the term "Langmuir-Blodgett film" means one or more molecular films on a surface that are at least partially ordered. Methods for forming a Langmuir-Blodgett film include, but are not limited to, those disclosed in column 70, lines 52 to 63 of U.S. Patent No. 7,256,921B2, the disclosure of which is incorporated herein by reference.

[0171] The photochromic optical article of the present invention can further include an alignment transfer material disposed between the alignment layer and the anisotropic layer. The alignment transfer material can be aligned by interacting with the alignment layer, and accordingly, a polymerizable anisotropic material, a photochromic-dichroic dye, a mesogenic hindered amine light stabilizer, and a mesogenic antioxidant can be aligned by interacting with the alignment transfer material. The alignment transfer material can facilitate the transfer or conveyance of a polymerizable anisotropic material, a photochromic-dichroic dye, a mesogenic hindered amine light stabilizer, and a mesogenic antioxidant from the alignment layer to the anisotropic layer in a suitable arrangement or orientation.

[0172] Examples of alignment transfer materials and methods for aligning an alignment transfer material include, but are not limited to, those disclosed in column 17, lines 23 to 27 to column 18, lines 1 to 10 of U.S. Patent No. 7,097,303B2, the disclosure of which is incorporated by reference.

[0173] The photochromic article of the present invention may include a primer layer between the substrate and the anisotropic layer. Examples of suitable primer layers include, but are not limited to, those disclosed in column 43, line 38 to column 47, line 67 of U.S. Patent No. 8,545,015B2, the disclosure of which is incorporated herein by reference.

[0174] The primer layer may include a single layer or multiple layers each containing a hue dye, a photochromic dye, or a combination thereof, which may be the same or different.

[0175] For example, the photochromic dye of the primer layer may be certain indeno-fused naphthopyran compounds, such as those described in column 3, line 66 to column 10, line 51 of U.S. Patent No. 6,296,785, the disclosure of which is incorporated herein by reference.

[0176] The photochromic optical article of the present invention may include a topcoat layer on the anisotropic layer. Examples of suitable topcoat layers include, but are not limited to, those described in column 48, line 1 to column 51, line 42 of U.S. Patent No. 8,545,015B2, the disclosure of which is incorporated herein by reference.

[0177] The topcoat layer may include a single layer or multiple layers each containing a hue dye, a photochromic dye, or a combination thereof, which may be the same or different.

[0178] The composition for forming the topcoat layer may contain one or more additives, including but not limited to, adhesion promoters, coupling agents, ultraviolet light absorbers, heat stabilizers, catalysts, radical scavengers, plasticizers, flow additives, and / or static tints or static dyes (i.e., tints or dyes that are not photochromic tints or dyes).

[0179] The topcoat layer may contain an ultraviolet light absorber and be free of a hue dye, a dichroic dye, a photochromic-dichroic dye, a photochromic dye, or a combination thereof. The topcoat layer may contain an ultraviolet light absorber and a hue dye, a photochromic dye, or a combination thereof. The topcoat layer may contain a hue dye, a photochromic dye, or a combination thereof and be free of an ultraviolet light absorber. The ultraviolet light absorber may be one or more ultraviolet light absorbers of recognized types in the art, including but not limited to: benzophenone; and / or benzotriazole. The ultraviolet light absorber may be any ultraviolet light absorber as described above. The ultraviolet light absorber is typically present in an amount effective based on the total solids weight of the coating composition for preparing the topcoat layer, such as from 0.1 to 10 weight percent, or 0.2 to 5 weight percent, or from 0.3 to 3 weight percent.

[0180] The topcoat layer may contain a photochromic dye, such as any of those described above.

[0181] The photochromic article of the present invention may further include a hard coat present on the top coat. Examples of suitable hard coats include, but are not limited to, those described in column 55, line 49 to column 56, line 31 of U.S. Patent No. 8,545,015B2, the disclosure of which is incorporated herein by reference. The hard coat may include a single layer or multiple layers.

[0182] The photochromic article of the present invention may include additional coatings, such as an anti-reflection coating. For example, the anti-reflection coating may be applied on the hard coat. Examples of anti-reflection coatings are described in U.S. Patent No. 6,175,450 and International Patent Application Publication No. WO 00 / 33111, the disclosures of which are incorporated herein by reference.

[0183] Examples of solvents that may be present in the various layers (such as the anisotropic layer) forming the photochromic optical article of the present invention may include solvents such as water, organic solvents common in the art, and combinations thereof.

[0184] Substrates from which the substrate of the photochromic article of the present invention can be selected include, but are not limited to, substrates formed of organic materials, inorganic materials, or combinations thereof (e.g., composite materials).

[0185] Non-limiting examples of organic materials for the substrate that can be used to form the photochromic article of the present invention include polymeric materials, such as those described in column 5, lines 12 to 56 of U.S. Patent No. 7,097,303B2. Suitable polymeric materials for the substrate that can be used to form the photochromic article of the present invention are polycarbonate, polycyclic olefin, polyurethane, poly(urea)urethane, polythiourethane, polythi(urea)urethane, polyol (allyl carbonate), cellulose acetate, diacetate cellulose, triacetate cellulose, cellulose acetate propionate, cellulose acetate butyrate, poly(vinyl acetate), poly(vinyl alcohol), poly(vinyl chloride), poly(vinylidene chloride), poly(ethylene terephthalate), polyester, polysulfone, polyolefin, copolymers thereof, or mixtures thereof.

[0186] The substrate may be an ophthalmic substrate. Non-limiting examples of organic materials suitable for forming an ophthalmic substrate include, but are not limited to, polymers recognized in the art as being useful as ophthalmic substrates, such as organic optical resins for preparing optically transparent castings for optical applications (such as ophthalmic lenses).

[0187] Other non-limiting examples of organic materials for the substrate that can be used to form the photochromic article of the present invention include both synthetic and natural organic materials, including but not limited to: opaque or translucent polymeric materials, natural and synthetic fabrics, and cellulose materials such as paper and wood.

[0188] Non-limiting examples of inorganic materials for substrates suitable for forming the photochromic articles of the present invention include glass, minerals, ceramics, and metals. For example, the substrate can include glass. For example, the substrate can have a reflective surface, e.g., a polished ceramic substrate, a metal substrate, or a mineral substrate. A reflective coating or layer can be deposited or otherwise applied to the surface of an inorganic or organic substrate to make it reflective or enhance its reflectivity.

[0189] In addition, the substrate can have a protective coating on its outer surface, such as but not limited to an abrasion-resistant coating, such as a "hard coat". For example, commercially available thermoplastic polycarbonate ophthalmic lens substrates are typically sold with an abrasion-resistant coating applied to their outer surfaces because these surfaces tend to be easily scratched, abraded, or scuffed. An example of such a lens substrate is GENTEX TM polycarbonate lenses (available from Gentex Optics). Thus, as used herein, the term "substrate" includes such substrates that have a protective coating, such as but not limited to an abrasion-resistant coating, on one or more of their surfaces.

[0190] Furthermore, the substrate of the photochromic article of the present invention can be an uncolored substrate, a colored substrate, a linearly polarized substrate, a circularly polarized substrate, an elliptically polarized substrate, a photochromic substrate, or a colored-photochromic substrate. As used herein with respect to a substrate, the term "uncolored" means a substrate that is substantially free of colorant additives (such as but not limited to conventional dyes) and has an absorption spectrum for visible radiation that does not change significantly in response to actinic radiation. In addition, the term "colored" with respect to a substrate means a substrate that has a colorant additive (such as but not limited to conventional dyes) and an absorption spectrum for visible radiation that does not change significantly in response to actinic radiation.

[0191] As used herein, the term "linearly polarized" with respect to a substrate means a substrate that is adapted for linearly polarized radiation. As used herein, the term "circularly polarized" with respect to a substrate means a substrate that is adapted for circularly polarized radiation. As used herein, the term "elliptically polarized" with respect to a substrate means a substrate that is adapted for elliptically polarized radiation. In addition, as used herein with respect to a substrate, the term "colored-photochromic" means a substrate that contains a colorant additive and a photochromic material and has an absorption spectrum for visible radiation that changes in response to at least actinic radiation. Thus, for example and without limitation, a colored-photochromic substrate can have a first color characteristic of the colorant and a second color characteristic of a combination of the colorant and the photochromic material when exposed to actinic radiation.

[0192] One or more layers suitable for preparing the photochromic articles of the present invention can be applied to a substrate by methods well known in the art, including but not limited to spin coating, spraying, spray and spin coating, curtain coating, flow coating, dip coating, injection molding, casting, roll coating, wire coating, and overmolding.

[0193] The one or more layers of the photochromic optical article can be at least partially cured or at least partially polymerized by any of the methods described above for the anisotropic layer.

[0194] Photochromic coated articles can be prepared according to the present invention. The photochromic coated articles include a substrate. The photochromic coated articles further include an anisotropic coating disposed on at least a portion of the surface of the substrate. The anisotropic coating of the photochromic coated article is formed from a polymerizable composition. The polymerizable composition comprises a polymerizable anisotropic material, a photochromic-dichroic dye, a photochromic dye, or a combination thereof, a mesogenic hindered amine light stabilizer, and a mesogenic antioxidant.

[0195] The substrate of the photochromic coated article can be any substrate as described for the photochromic optical article.

[0196] The polymerizable anisotropic material, mesogenic hindered amine light stabilizer, and mesogenic antioxidant of the polymerizable composition of the photochromic coated article can be any of the polymerizable anisotropic materials, mesogenic hindered amine light stabilizers, and mesogenic antioxidants described above for the photochromic optical article.

[0197] The photochromic-dichroic dye and / or photochromic dye of the polymerizable composition can be any of the photochromic-dichroic dyes or photochromic dyes described for the photochromic optical article.

[0198] The polymerizable composition of the photochromic coated article can further comprise an ultraviolet light absorber selected from the group consisting of benzotriazole, benzophenone, and combinations thereof.

[0199] The polymerizable anisotropic material, mesogenic antioxidant, mesogenic hindered amine light stabilizer, and photochromic-dichroic dye, photochromic dye, or combination thereof of the polymerizable composition of the anisotropic coating are at least partially aligned. The mesogenic antioxidant, mesogenic hindered amine light stabilizer, and photochromic-dichroic dye, photochromic dye, or combination thereof of the polymerizable composition of the anisotropic coating can be aligned using any suitable method as described above.

[0200] As disclosed above, the photochromic coated article includes one or more additional layers positioned between the substrate and the anisotropic coating. As disclosed above, the photochromic coated article includes one or more additional layers positioned on at least a portion of at least a portion of the anisotropic coating. As disclosed above, the one or more additional layers may further include a fixed-tint dye, a dichroic dye, a photochromic-dichroic dye, a photochromic dye, or a combination thereof.

[0201] The present invention relates to, for example but not limited to, the following aspects.

[0202] In a first aspect, the present invention may relate to a photochromic optical article comprising: an optical substrate; and at least a partially anisotropic layer disposed on at least a portion of the surface of the substrate, wherein the anisotropic layer comprises: an anisotropic polymer; a photochromic-dichroic dye, a photochromic dye, or a combination thereof; a mesogenic hindered amine light stabilizer; and a mesogenic antioxidant.

[0203] In a second aspect of the present invention, in the photochromic optical article as described above for the first aspect, the anisotropic layer further comprises an ultraviolet light absorber selected from the group consisting of benzotriazole, benzophenone, and combinations thereof.

[0204] In a third aspect of the present invention, in the photochromic optical article as described above for the second aspect, the ultraviolet light absorber is a benzotriazole represented by the following formula (VIII):

[0205]

[0206] wherein each c's R 12 and each d's R 13 are each independently methyl, ethyl, hydroxy, or halogen; c is 0 - 4; and d is 0 - 4.

[0207] In a fourth aspect of the present invention, in the photochromic optical article as described above for any one of the first to third aspects, the anisotropic polymer comprises a polymerized liquid crystal monomer.

[0208] In a fifth aspect of the present invention, in the photochromic optical article of any one of the first to fourth aspects, the mesogenic hindered amine light stabilizer is a compound represented by the following formula (I):

[0209]

[0210] wherein R 1 is hydrogen, alkyl, alkoxy, acetyl, hydroxy or oxide, R 2 , R 3 , R 4 , and R 5Each independently is hydrogen or an alkyl group, provided that R 2 , R 3 , R 4 , and R 5 in two or more of them are alkyl groups, L 1 is a divalent linking group as a double bond or one of the following formulas (IIa), (IIb), (IIc), (IId), (IIe), or (IIf),

[0211]

[0212] wherein R 6 is a divalent alkyl group or a divalent substituted alkyl group,

[0213]

[0214] wherein R 7 is a divalent alkyl group or a divalent substituted alkyl group,

[0215]

[0216] wherein R 8 is a divalent alkyl group or a divalent substituted alkyl group, or

[0217]

[0218] wherein R b is hydrogen, an alkyl group or a substituted alkyl group, m is from 0 to 4, and each m of L 2 is independently a divalent C1-C 25 alkyl group or a divalent C2-C 25 alkenyl group, optionally inserted with at least one of -O-, -C(O)-, -C(O)O-, or -OC(O)O- in each case, and the mesogen is represented by the following formula (III),

[0219]

[0220] wherein Y is a divalent linking group as a double bond, -O-, or -S-, v and u are each independently from 0 to 4, provided that the sum of v and u is 2 to 4, and each v of Z is independently a divalent linking group as a double bond, -O-, -S-, -C(O)-, -C(O)O-, -OC(O)O-, -N(R 9 )-C(O)-O-, or -C(O)-N(R 9 )-, wherein R 9 is hydrogen, an alkyl group or a substituted alkyl group, and for each v and each u, the divalent ring,

[0221]

[0222] Each is independently a phenylene-1,4-diyl, or a substituted phenylene-1,4-diyl, or a cyclohexane-1,4-diyl, or a substituted cyclohexane-1,4-diyl, and E is hydrogen, a straight-chain or branched C1-C 25 alkyl, a straight-chain or branched C2-C 25 alkenyl, a straight-chain or branched C2-C 25 alkynyl, each optionally interrupted by at least one of -O-, -S-, -C(O)-, -C(O)O-, or -OC(O)O-, provided that the direct L 1 between L 2 and L 1 -L 2 connection does not contain two heteroatoms linked together, and the direct L 1 between L and Y 1 -mesogenic connection does not contain two heteroatoms linked together, and in each direct L 2 between L and Y 2 -mesogenic connection does not contain two heteroatoms linked together.

[0223] In a sixth aspect of the present invention, in the photochromic optical article as described above for the fifth aspect, for the mesogenic hindered amine light stabilizer represented by formula (I), R 1 is hydrogen, alkyl, or alkoxy; R 2 , R 3 , R 4 , and R 5 are each alkyl; the sum of v and u is 3 to 4; each Z of v is independently a divalent linking group as a double bond and -C(O)O-; and E is alkyl.

[0224] In a seventh aspect of the present invention, in the photochromic optical article of the fifth or sixth aspect, the mesogenic antioxidant is a compound represented by the following formula (V):

[0225]

[0226] wherein R 10 and R 11 are each independently hydrogen or alkyl, provided that at least one of R 10 and R 11 is alkyl, L 3 is a divalent linking group as a double bond or one of the following formulas (VIa), (VIb), (VIc), (VId), (VIe), or (VIf)

[0227]

[0228] wherein R 6’ , R 7’ , R8’ and R b’ are each independently R 6 , R 7 , R 8 , and R b , where m is from 0 to 4, and each L of each m 4 is independently a divalent C1-C 25 alkyl or a divalent C2-C 25 alkenyl, optionally interrupted in each case by at least one of -O-, -C(O)-, -C(O)O-, or -OC(O)O-, the mesogen is represented by formula (III), and E is hydrogen, a straight-chain or branched C1-C 25 alkyl, a straight-chain or branched C2-C 25 alkenyl, a straight-chain or branched C2-C 25 alkynyl, each optionally interrupted by at least one of -O-, -S-, -C(O)-, -C(O)O-, or -OC(O)O-; provided that the direct L 3 between L 4 and the direct L 3 -L 4 connection does not contain two heteroatoms linked together, and the direct L 3 between L 3 and Y does not contain two heteroatoms linked together, and each direct L 4 between each direct L 4 and Y does not contain two heteroatoms linked together.

[0229] In an eighth aspect of the present invention, in the photochromic optical article as described in the seventh aspect above, for the mesogenic antioxidant represented by formula (V), R 10 and R 11 are each independently an alkyl group, provided that at least one of R 10 and R 11 is a branched alkyl group; the sum of v and u is 3 to 4; each Z of each v is independently a divalent linking group as a double bond or -C(O)O-; and E is an alkyl group.

[0230] In a ninth aspect of the present invention, in the photochromic optical article according to any one of the foregoing first to eighth aspects, the mesogenic antioxidant, the mesogenic hindered amine light stabilizer; and the photochromic-dichroic dye, the photochromic dye, or a combination thereof of the at least partially anisotropic layer are at least partially aligned.

[0231] In a tenth aspect of the present invention, in the photochromic optical article as described in any one of the foregoing first to ninth aspects, the photochromic optical article further includes one or more layers positioned between the substrate and the at least partially anisotropic layer.

[0232] In an eleventh aspect of the present invention, in the photochromic optical article according to any one of the first to tenth aspects above, the photochromic optical article further comprises one or more layers positioned on at least a portion of at least part of the anisotropic layer.

[0233] In a twelfth aspect of the present invention, in the photochromic optical article according to any one of the foregoing tenth or eleventh aspects, the one or more layers may further comprise a fixed-tint dye, a dichroic dye, a photochromic-dichroic dye, a photochromic dye, or a combination thereof.

[0234] In a thirteenth aspect of the present invention, in the photochromic optical article according to any one of the first to twelfth aspects above, the substrate comprises a polymeric material selected from the group consisting of: polycarbonate, polycyclic olefin, polyurethane, poly(urea)urethane, polythiourethane, polythi(urea)urethane, polyol (allyl carbonate), cellulose acetate, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, poly(vinyl acetate), poly(vinyl alcohol), poly(vinyl chloride), poly(vinylidene chloride), poly(ethylene terephthalate), polyester, polysulfone, polyolefin, copolymers thereof, and mixtures thereof.

[0235] In a fourteenth aspect of the present invention, in the photochromic optical article according to any one of the first to thirteenth aspects above, the article is an optical element selected from the group consisting of: ophthalmic articles, display articles, windows, and mirrors.

[0236] In a fifteenth aspect of the present invention, in the photochromic optical article according to the fourteenth aspect above, the ophthalmic article is selected from the group consisting of: corrective lenses, non-corrective lenses, contact lenses, and protective lenses.

[0237] In a sixteenth aspect, the present invention may relate to a photochromic coated article comprising: a substrate; and an anisotropic coating on at least a portion of the surface of the substrate, wherein the anisotropic coating is formed from a polymerizable composition comprising: a polymerizable anisotropic material; a photochromic-dichroic dye, a photochromic dye, or a combination thereof; a mesogenic hindered amine light stabilizer; and a mesogenic antioxidant.

[0238] In a seventeenth aspect of the present invention, in the photochromic coated article as described above for the sixteenth aspect, the polymerizable composition further comprises an ultraviolet light absorber selected from the group consisting of: benzotriazole, benzophenone, and combinations thereof.

[0239] In an eighteenth aspect of the present invention, in the photochromic coated article as described above for the seventeenth aspect, the ultraviolet light absorber is a benzotriazole represented by the following formula (VIII):

[0240]

[0241] wherein R for each c 12 and R for each d 13 are each independently methyl, ethyl, hydroxy, or halogen; c is 0 - 4; and d is 0 - 4.

[0242] In a nineteenth aspect of the present invention, in the photochromic coated article of any one of the sixteenth to eighteenth aspects, the mesogenic hindered amine light stabilizer is a compound represented by the following formula (I):

[0243]

[0244] wherein R 1 is hydrogen, alkyl, alkoxy, acetyl, hydroxy or oxide, and R 2 , R 3 , R 4 and R 5 are each independently hydrogen or alkyl, provided that two or more of R 2 , R 3 , R 4 and R 5 are alkyl, L 1 is a divalent linking group as one of a double bond or the following formula (IIa), (IIb), (IIc), (IId), (IIe), or (IIf),

[0245]

[0246] wherein R 6 is a divalent alkyl or a divalent substituted alkyl,

[0247]

[0248] wherein R 7 is a divalent alkyl or a divalent substituted alkyl,

[0249]

[0250] wherein R 8 is a divalent alkyl or a divalent substituted alkyl, or

[0251]

[0252] wherein R b is hydrogen, alkyl or substituted alkyl, m is from 0 to 4, and L for each m2 independently is a divalent C1-C 25 alkyl or a divalent C2-C 25 alkenyl, optionally interrupted in each case by at least one of -O-, -C(O)-, -C(O)O-, or -OC(O)O-, the mesogen being represented by formula III,

[0253]

[0254] wherein Y is a divalent linking group as a double bond, -O-, or -S-, v and u are each independently 0 to 4, provided that the sum of v and u is 2 to 4, each Z for v is independently a divalent linking group as a double bond, -O-, -S-, -C(O)-, -C(O)O-, -OC(O)O-, -N(R 9 )-C(O)-O-, or -C(O)-N(R 9 ), wherein R 9 is hydrogen, alkyl or substituted alkyl, for each v and each u, the divalent ring,

[0255]

[0256] each independently is phenylene-1,4-diyl, or substituted phenylene-1,4-diyl, or cyclohexane-1,4-diyl, or substituted cyclohexane-1,4-diyl, and E is hydrogen, straight-chain or branched C1-C 25 alkyl, straight-chain or branched C2-C 25 alkenyl, straight-chain or branched C2-C 25 alkynyl, each optionally interrupted by at least one of -O-, -S-, -C(O)-, -C(O)O-, or -OC(O)O-, provided that the direct L 1 between L 2 and L 1 -L 2 linkage does not contain two heteroatoms linked together, the direct L 1 between L 1 and the mesogen does not contain two heteroatoms linked together, and each direct L 2 between each direct L 2 and the mesogen does not contain two heteroatoms linked together.

[0257] In a twentieth aspect of the present invention, in the photochromic coated article as described above for the nineteenth aspect, for the mesogenic hindered amine light stabilizer represented by formula (I), R 1 is hydrogen, alkyl, or alkoxy; R 2 , R 3 , R 4 , and R5 Each is an alkyl group; the sum of v and u is 3 to 4; each Z of v is independently a divalent linking group as a double bond or -C(O)O-; and E is an alkyl group.

[0258] In the twenty - first aspect of the present invention, in the photochromic coated article of the nineteenth or twentieth aspect, the mesogenic antioxidant is a compound represented by the following formula (V):

[0259]

[0260] Wherein R 10 and R 11 are each independently hydrogen or an alkyl group, provided that at least one of R 10 and R 11 is an alkyl group, L 3 is a divalent linking group as a double bond or one of the following formulas (VIa), (VIb), (VIc), (VId), (VIe), or (VIf):

[0261]

[0262] Wherein R 6’ , R 7’ , R 8’ , and R b’ are each independently respectively R 6 , R 7 , R 8 , and R b , m is from 0 to 4, each L of m 4 is independently a divalent C1 - C 25 alkyl group or a divalent C2 - C 25 alkenyl group, optionally inserted with at least one of -O-, -C(O)-, -C(O)O-, or -OC(O)O- in each case, the mesogen is as represented by formula (III), and E is hydrogen, a straight - chain or branched - chain C1 - C 25 alkyl group, a straight - chain or branched - chain C2 - C 25 alkenyl group, a straight - chain or branched - chain C2 - C 25 alkynyl group, each optionally inserted with at least one of -O-, -S-, -C(O)-, -C(O)O-, or -OC(O)O-; provided that the direct L 3 between L 4 and L 3 -L 4 linkage does not contain two heteroatoms linked together, the direct L 3 between L 3 and Y in the mesogen - linkage does not contain two heteroatoms linked together, and in each direct L 4 between each direct L4 - The mesogenic linkage does not contain two heteroatoms linked together.

[0263] In a twenty-second aspect of the present invention, in the photochromic coated article as described in the above twenty-first aspect, for the mesogenic antioxidant represented by formula (V), R 10 and R 11 are each independently an alkyl group, provided that at least one of R 10 and R 11 is a branched alkyl group; the sum of v and u is from 3 to 4; each Z of v is independently a divalent linking group as a double bond or -C(O)O-; and E is an alkyl group.

[0264] In a twenty-third aspect of the present invention, in the photochromic coated article according to any one of the foregoing sixteenth to twenty-second aspects, the mesogenic antioxidant, the mesogenic hindered amine light stabilizer, and the photochromic-dichroic dye, the photochromic dye, or a combination thereof of the anisotropic coating are at least partially aligned.

[0265] In a twenty-fourth aspect of the present invention, in the photochromic coated article as described in any one of the above sixteenth to twenty-third aspects, the photochromic coated article further comprises one or more layers positioned between the substrate and the anisotropic coating.

[0266] In a twenty-fifth aspect of the present invention, in the photochromic coated article as described in any one of the above sixteenth to twenty-fourth aspects, the photochromic coated article further comprises one or more layers positioned on at least a portion of the anisotropic coating.

[0267] In a twenty-sixth aspect of the present invention, in the photochromic coated article according to any one of the foregoing twenty-fourth or twenty-fifth aspects, the one or more layers further comprise a fixed-tone dye, a dichroic dye, a photochromic-dichroic dye, a photochromic dye, or a combination thereof.

[0268] In a twenty-seventh aspect of the present invention, in the photochromic coated article according to any one of the foregoing sixteenth to twenty-sixth aspects, the substrate comprises a polymeric material selected from the group consisting of polycarbonate, polycyclic olefin, polyurethane, poly(urea)urethane, polythiourethane, polythi(urea)urethane, polyol(allyl carbonate), cellulose acetate, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, poly(vinyl acetate), poly(vinyl alcohol), poly(vinyl chloride), poly(vinylidene chloride), poly(ethylene terephthalate), polyester, polysulfone, polyolefin, copolymers thereof, and mixtures thereof.

[0269] In a twenty-eighth aspect of the present invention, in a photochromic coated article according to any one of the sixteenth to twenty-seventh aspects, the article is selected from the group consisting of: ophthalmic articles, display articles, windows, and mirrors.

[0270] In a twenty-ninth aspect of the present invention, in a photochromic coated article according to the twenty-eighth aspect, the coated article is an ophthalmic article selected from the group consisting of: corrective lenses, non-corrective lenses, contact lenses, and protective lenses.

[0271] The present invention will be described in the following illustrative, non-limiting examples. Many possible modifications and variations will be apparent to those skilled in the art.

[0272] Examples

[0273] Part 1: Preparation of a Photopolymerizable Coating Composition

[0274] A photopolymerizable coating composition comprising a photopolymerizable anisotropic material, a photochromic-dichroic dye, and a photoinitiator was prepared using the materials in Table 1 to prepare a liquid crystal coating formulation (“LCCF”) stock solution, which was then used in the preparation of coating Examples A-K. The amounts listed are in parts by weight.

[0275] For the LCCF stock solution, the materials of Charge 1 were combined in an amber bottle equipped with a magnetic stir bar and stirred at room temperature for at least one hour until the composition appeared homogeneous. Next, the materials of Charge 2 were added, and the combined materials were stirred on a hot plate set to 90 °C for one hour. Next, Charge 3 was added, and the combined materials were stirred on a hot plate set to 90 °C for one hour. Charge 4 was added, and the combined materials were stirred on a hot plate set to 65 °C for thirty minutes.

[0276] Table 1. LCCF Stock Solution

[0277]

[0278]

[0279] 1 Aromatic alkyl-modified polymethylalkylsiloxane available from BYK Chemie, USA.

[0280] 2 A mixture of three photochromic-dichroic indeno-fused naphthopyran dyes formulated to give a gray color upon activation.

[0281] 3The liquid crystal monomer 4-(3-acryloyloxypropoxy)-benzoic acid 2-methyl-1,4-phenylene ester, which is commercially available from Merck KGaA, Darmstadt, Germany.

[0282] 4 4-((4-((8-((6-((6-((6-((6-((6-((6-((6-(methacryloyloxy)hexanoyl)oxy)hexanoyl)oxy)hexanoyl)oxy)hexanoyl)oxy)hexanoyl)oxy)hexanoyl)oxy)hexanoyl)oxy)octyl)oxy)benzoyl)oxy)phenyl 4'-pentyl-[1,1'-bi(cyclohexane)]-4-carboxylate, which is prepared according to the procedure described in U.S. Patent No. 7,910,019 B2.

[0283] 5 The liquid crystal monomer corresponding to Example 17 in U.S. Patent No. 7,910,019 B2.

[0284] 6 3-methyl-4-((4-pentylcyclohexane-1-carbonyl)oxy)phenyl 4-((6-(acryloyloxy)hexyl)oxy)benzoate.

[0285] The above LCCF stock solution was divided into eleven portions and added to amber vials with magnetic stir bars. To each vial, the hindered amine light stabilizer ("HALS"), antioxidant, and ultraviolet ("UV") light absorber ("UVA") materials indicated in Tables 2, 3, and 4 below were added, and the mixture was stirred on a hot plate set to 65 °C for thirty minutes. After cooling, MgSO4 was added, and the mixture was stirred at room temperature for at least thirty minutes. Then, before use, the resulting solution was passed through a polyvinylidene fluoride filter with a pore size of 5.0 microns.

[0286] Table 2. Coating Examples A to D

[0287]

[0288]

[0289] 7 1,2,2,6,6-pentamethyl-4-((4-oxo-4-((4'-(trans-4-pentylcyclohexyl)-[1,1'-biphenyl]-4-yl)oxy)butanoyl)oxy)piperidine, which is prepared according to the procedure described in U.S. Patent No. 8,349,210 B2.

[0290] 8 8-(4-((4-((4-methylbenzoyl)oxy)phenoxy)carbonyl)phenoxy)octyl 3,5-di-tert-butyl-4-hydroxybenzoate

[0291] Table 3. Comparative coating examples E to H, each having a single mesogenic HALS or antioxidant component

[0292]

[0293] Table 4. Comparative coating examples I to K, having non-mesogenic HALS and antioxidant components

[0294]

[0295]

[0296] 9 A mixture of bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate hindered amine light stabilizer, which is commercially available from BASF Corporation.

[0297] 10 Ethylene bis(oxyethylene) bis-(3-(5-tert-butyl-4-hydroxy-m-tolyl) propionate) antioxidant, which is commercially available from BASF Corporation.

[0298] The following Table 5 describes the molar ratios of the added HALS, antioxidant, and ultraviolet light absorber materials, respectively, relative to the total moles of the photochromic-dichroic dye in each of the above-prepared coating examples.

[0299] Table 5. Molar ratios of components relative to the total moles of the photochromic-dichroic dye

[0300]

[0301] Part 2: Preparation of the coated article

[0302] A finished plano lens (6 substrates, 65 mm diameter) made of monomers is used as the substrate for all coated articles. The lens is cleaned by wiping with a paper cloth moistened with isopropyl alcohol and then dried in air. Next, each lens is corona treated with a Power Generator HV 2000 (serial number 020270) from Tantec EST Inc. set at 70 kV and 1000 W with a belt speed of 3 ft / min.

[0303] ​After corona treatment, an optically aligned coating corresponding to Example 1 of U.S. Patent No. 9,475,901 was applied to each lens via a spin coating process. Approximately 1.5 milliliters (mL) of the solution was applied to a portion of the lens surface. The lens was rotated for two seconds at 800 revolutions per minute (rpm), then for seven seconds at 1,000 rpm, and then for four seconds at 2,500 rpm using a spin processor (WS-650-MZ-23NPPB) from Laurell Technologies Corp. Next, each coated lens was placed in a forced air convection oven set at 80 °C for approximately thirteen minutes.

[0304] After the lens cooled, each lens was exposed to linearly polarized ultraviolet light. The light source was positioned such that the light was polarized in a plane perpendicular to the top surface of the lens. A UVPower Puck TM II high-energy radiometer (S / N: 18938) from Uvitron International, Inc. was used to measure the energy density to which each optically aligned coating was exposed. The measured energy densities were as follows: UV-V: 1.5 J / cm 2 , UV-A: 3.1 J / cm 2 , UV-B: 0.4 J / cm 2 , and UV-C: 0.01 J / cm 2 .

[0305] Next, coating examples were applied to each lens via a spin coating process. The coatings for each example and counterexample are given in Table 6. Approximately 1.5 mL of the coating was applied to a portion of the lens surface. The lens was rotated for 6 seconds at 400 rpm, then for 4 seconds at 900 rpm using a spin processor (WS-650-MZ-23NPPB) from Laurell Technologies Corp. Next, each coated lens was placed in a forced air convection oven set at 65 °C for thirty minutes.

[0306] Table 6. Coatings Applied to Prepare Coated Articles

[0307]

[0308]

[0309] The coated lenses were cooled for two minutes. Then, the lenses were passed through a nitrogen-purged chamber using a conveyor belt system. The chamber was equipped with a series of D-type and V-type bulbs located above the top glass window of the chamber. The glass window had a high transmittance for ultraviolet and visible light. A UV Power Puck from Uvitron International, Inc. TMII The high-energy radiometer (S / N: 18938) measures the energy density to which each coating is exposed as follows: UV-V: 13.0 J / cm 2 , UV-A: 13.8 J / cm 2 , UV-B: 0.6 J / cm 2 , and UV-C: 0.1 J / cm 2 .

[0310] Finally, a hard coat is applied to each lens using a spin-coating process. Each lens is corona-treated using a Power Generator HV 2000 (serial number 020270) from Tantech EST set at 70 kV and 1000 W with a belt speed of 3 ft / min. Approximately 1.5 mL of the hard coat is applied to a portion of the lens surface. The lens is rotated for 4.3 seconds at 350 rpm and then for 1 second at 1300 rpm using a spin processor (WS-650-MZ-23NPPB) from Laurell Technologies Corporation.

[0311] The lens is placed in a forced-air convection oven set to 105 °C for three hours.

[0312] Part 3: Measurement

[0313] The photochromic performance tests include absorption ratio, optical response measurement, and fatigue.

[0314] Before the response test is performed on the optical bench, the specimen is adjusted in a multi-step custom adjustment unit. First, it is exposed to 365 nanometer (nm) ultraviolet light at a distance of approximately 10 centimeters (cm) from the electromagnetic radiation source for 10 minutes to pre-activate the photochromic compound. The ultraviolet-A (UV-A) irradiance at the sample is measured to be 7.7 watts per square meter (W / m 2 ). Next, the specimen is heated to and held at 70 °F (21.1 °C) for 10 minutes. Finally, the heating element is turned off and an F17T8 yellow halogen lamp is turned on for 30 minutes to fade or deactivate the photochromic compound in the specimen. The illuminance from the yellow halogen lamp at the specimen is measured to be 9.0 Klux. Then the specimen is held in a dark environment for at least 1 hour before testing to cool and continue to fade back to the ground state.

[0315] The optical properties of the specimen are measured using an optical bench and the absorption ratio and photochromic properties are determined. Each specimen is placed on an optical bench with an activation light source positioned at an incident angle of 35 ° + / - 1 ° to the test sample surface. The activation light source used is a xenon arc lamp powered by a Newport / Oriel 69911 type 300 watt power supply, which is equipped with VS-25 high-speed computer-controlled shutter, which is temporarily closed during data collection so that stray light will not interfere with the data collection process; removing short-wavelength radiation 3-millimeter (mm) KG-2 heat-absorbing filter; one or more neutral density filters for intensity attenuation; and a condenser lens for beam collimation. The arc lamp is equipped with a digital exposure controller and a sensor (Newport / Oriel model 68945) to maintain fine control of the output over time.

[0316] The broadband light source for monitoring response measurements is positioned perpendicular to the specimen surface. By collecting and combining light filtered separately from a 100-watt (W) tungsten-halogen lamp (controlled by a ZUP60-14 constant voltage power supply) with a split-end, bifurcated fiber optic cable, an enhanced signal at shorter visible wavelengths is obtained. The light from one side of the tungsten-halogen lamp is filtered with a KG1 filter to absorb heat and filtered with a B-440 filter to allow shorter wavelengths to pass through. The other side of the light is either filtered or unfiltered with a KG1 filter. The light is collected by focusing the light from each side of the lamp onto separate ends of the split-end, bifurcated fiber optic cable and then combining it into a single light source that emerges from a single end of the cable. A 4- to 6-inch (10.2 cm to 15.25 cm) light pipe is attached to the single end of the cable to ensure proper mixing. The broadband light source is equipped with a VS-25 high-speed computer-controlled shutter that is temporarily opened during data collection.

[0317] The polarization of the light source is achieved by passing the light from the single end of the cable through a Moxtek polarizer (model M-061.PD, M660, U651 or equivalent from Physik Instrumente) held on a computer-driven (analyzer polarizer), motorized rotating stage. The monitoring beam is set such that one polarization plane (0°) is perpendicular to the plane of the optical table and the second polarization plane (90°) is parallel to the plane of the optical table. The specimen is run in air at 23 °C ± 0.1 °C (this temperature is maintained by a temperature-controlled air chamber). The polarization of the light source is achieved by passing the light from the single end of the cable through a Moxtek polarizer (model M-061.PD, M660, U651 or equivalent from Physik Instrumente) held on a computer-driven (analyzer polarizer), motorized rotating stage. The monitoring beam is set such that one polarization plane (0°) is perpendicular to the plane of the optical table and the second polarization plane (90°) is parallel to the plane of the optical table. The specimen is run in air at 23 °C ± 0.1 °C (this temperature is maintained by a temperature-controlled air chamber).

[0318] To align the specimens, a second polarizer was added to the optical path (a research grade film polarizer such as polarizer SPF-50C-32 from OptoSigma). The second polarizer was set to 90° (+ / - 0.1°) from the first analyzer polarizer. The sample was placed in an air cell in a self-centering holder mounted on a rotary stage (type M-061.PD, M660, U651 or equivalent from Physik Instrumente). The laser beam (Coherent - ULN 635 diode laser) was directed through the crossed polarizers and the sample. The signal intensity of the laser beam was measured in relative counts by a spectrophotometer. The specimen was rotated 120° in 3° increments to locate the minimum transmitted light intensity of the laser beam. The specimen was then positioned near the minimum transmitted light intensity and then the specimen was rotated 12° in 0.1° steps to position the minimum transmission to + / - 0.1° depending on the sample quality. The specimen was then finally positioned at the minimum transmission angle. At this point, the specimen was aligned parallel or perpendicular to the Moxtek analyzer polarizer. The second polarizer and the diode laser beam were removed from the optical path. Using this procedure, the specimens were aligned to ±0.1° before any activation.

[0319] For measurements, each specimen was exposed to UV-A from an activation light source at approximately 6.7 W / m 2 for 15 minutes to activate the photochromic compound. An International Light Research Spectroradiometer (ILT950 or ILT950FC type) was used to verify the exposure at the start of each day. Then light from a monitoring source polarized to the 0° polarization plane was passed through the sample and focused onto a 1-inch (2.54 cm) integrating sphere which was connected to an OCEAN S2000 (or equivalent) spectrophotometer using a single function fiber optic cable. Ocean Optics drivers combined with proprietary software (from Transitions Optical, Ltd) were used to collect spectral information after the light passed through the sample. When activating the photochromic material, the position of the analyzer polarizer was rotated back and forth to polarize the light from the monitoring light source to the 90° polarization plane and back. Data was collected at 5-second intervals for approximately 900 seconds during activation. For each test, the rotation of the polarizer was adjusted to collect data in the following polarization plane sequence: 0°, 90°, 90°, 0°, etc.

[0320] Absorption spectra were obtained and each test sample was analyzed using Igor Pro software (available from WaveMetrics). The change in absorbance for each test sample in each polarization direction was calculated by subtracting the absorption measurement at 0 time (i.e., non-activated) of the sample at each test wavelength. For each sample, the average absorbance value was obtained in the activation profile region (where the photochromic response of the photochromic compound is saturated or near saturated (i.e., the region where the measured absorbance does not increase or does not increase significantly over time)) by averaging the absorbance at each time interval in this region. For 0° and 90° polarizations, the average absorbance values corresponding to the predetermined wavelength range of λ 最大-可见 ±5 nm were extracted, and the absorption ratio at each wavelength in this range was calculated by dividing the larger average absorbance by the smaller average absorbance. For each extracted wavelength, 5 to 100 data points were averaged. Then the average absorption ratio (AR) of the photochromic compound was calculated by averaging these individual absorption ratios.

[0321] The change in optical density (ΔOD) was determined as follows: The initial transmittance was established, and then the shutter from the xenon lamp was opened to provide ultraviolet radiation to change the specimen from the faded state to the activated state. Data were collected at selected time intervals, the transmittance in the activated state was measured, and the change in optical density was calculated according to the formula: ΔOD = log(%Tb / %Ta), where %Tb is the percentage transmittance in the faded state, %Ta is the percentage transmittance in the activated state, and the logarithm is base 10. Measurements were made using a D65 light source and a 10° observer under the weighted wavelength range corresponding to CIE Y (described in CIE Technical Report, Colorimetry, CIE 15:2018).

[0322] The Atlas Ci4000 aging tester was used to conduct simulated solar radiation accelerated aging, i.e., fatigue. The samples were exposed to a one-hour dark cycle and then a 65-hour light cycle using a xenon arc lamp filtered with boron / borosilicate (with an output of 0.25 watts per square meter at 340 nm). The temperature in the Atlas Ci4000 aging tester was maintained at 45 °C during the light cycle, and the relative humidity was controlled at 70% humidity. The temperature of the black panel with a thermometer attached thereto and representing the test sample was maintained at 55 °C.

[0323] After the samples had undergone this UV exposure fatigue cycle, they were pre-treated and measured on an optical bench to obtain the final photopic response (ΔOD) under the same conditions as described for the initial test最终 )。Percentage fatigue is determined by measuring the difference between the ΔOD of the test sample before and after accelerated aging according to the following formula: % fatigue = (ΔOD 初始 - ΔOD 最终 ) / ΔOD 初始 × 100. The Δb* value is also determined. The Δb* value is the measured b* on the Hunter UltraScan Pro device before exposure in the Atlas Ci4000 aging tester 初始 minus the b* value measured for the faded state of the lens after this 65-hour UV exposure fatigue cycle 最终 The measured difference in the b* value of the faded state. The Δb* value represents the amount of yellowing that occurs in the lens during fatigue.

[0324] Finally, the ΔAR value is determined. The ΔAR value is measured as the AR 初始 value measured before exposure in the Atlas Ci4000 aging tester minus the AR 最终 value measured after this 65-hour UV exposure fatigue cycle. ΔAR represents the amount of AR reduction that occurs in the photochromic coating during fatigue.

[0325] The average optical density, absorption ratio, along with percentage fatigue, and Δb* for Examples 1 and CE-4 to CE-8 are shown in Table 7. The average optical density, absorption ratio, along with percentage fatigue, Δb*, and ΔAR for Examples 2 and 3 and CE-9 to CE-11 are shown in Table 8. All test results are the arithmetic mean of repeated tests.

[0326] Table 7. Combined effect of mesogenic HALS and mesogenic antioxidants

[0327]

[0328] Table 8. Comparison of articles containing mesogenic HALS, mesogenic antioxidants, and UV light absorbers with articles containing non-mesogenic HALS and non-mesogenic antioxidants

[0329]

[0330]

[0331] Part 4: Discussion

[0332] For the prepared photochromic-dichroic lenses, Table 7 shows that the use of a combination of mesogenic HALS and mesogenic antioxidants at a specific molar ratio (Ex.1) improves % fatigue and Δb* compared to not using a stabilizer (CE-4), using only HALS (CE-5), or using only an antioxidant (CE-6). Additionally, CE-7 and CE-8 show that when using a molar ratio of 5 moles of stabilizer to 1 mole of photochromic-dichroic dye (PCDD), only mesogenic HALS can reduce Δb*, and only mesogenic antioxidants can reduce % fatigue. However, based on the individual results of only mesogenic HALS and mesogenic antioxidants (Ex.2), when mesogenic HALS and mesogenic antioxidants are used together, the reduction in both % fatigue and Δb* is much greater than expected.

[0333] Table 8 shows that various types of UV light absorbers can be used (specifically, benzotriazole (Ex.2) and benzophenone (Ex.3)) to further enhance fatigue resistance (as indicated by low % fatigue and Δb* values) without significantly affecting AR. Also, as confirmed by negative ΔAR values, when compared to Ex.2 and Ex.3 where mesogenic HALS and mesogenic antioxidants are used, the separate use of two UVAs (i.e., benzotriazole and benzophenone) together with non-mesogenic HALS and non-mesogenic antioxidants in CE-10 and CE-11 shows that the low pre-fatigue AR value is further reduced after fatigue cycling. Additionally, Table 8 shows that the use of mesogenic stabilizers is necessary to ensure a high AR for the coating. In two examples using mesogenic stabilizers (Ex.2 and Ex.3), the AR is sufficiently greater than 5.0, while in CE-9 - 11 (where non-mesogenic HALS and non-mesogenic antioxidants are used), the AR is less than 5.0.

[0334] These data indicate that in order to sufficiently stabilize these photochromic-dichroic coatings, a combination of mesogenic HALS and mesogenic antioxidants is necessary. This combination is superior to only mesogenic HALS or only mesogenic antioxidants. UVAs can be added to further stabilize the coating.

[0335] Although the present invention has been described with reference to specific details of certain embodiments thereof, it is not intended that such details be regarded as limitations on the scope of the invention, unless they are included in the appended claims.

Claims

1. A photochromic optical article, comprising: an optical substrate; and at least a partially anisotropic layer disposed on at least a portion of the surface of the substrate, wherein the anisotropic layer comprises: an anisotropic polymer; a photochromic-dichroic dye, a photochromic dye, or a combination thereof; a mesogenic hindered amine light stabilizer in an amount of 10 mole percent (mol%) to 50 mol% relative to the total moles of the photochromic-dichroic dye, photochromic dye, or combination thereof; and a mesogenic antioxidant in an amount of 25 mol% to 150 mol% relative to the total moles of the photochromic-dichroic dye, photochromic dye, or combination thereof, wherein the mesogenic antioxidant is present in moles in an amount greater than the moles of the mesogenic hindered amine light stabilizer, wherein the mesogenic hindered amine light stabilizer is a compound represented by the following formula (I): wherein R 1 is hydrogen, alkyl, alkoxy or acetyl, R 2 , R 3 , R 4 , and R 5 are each independently an alkyl group, L 1 is a divalent linking group that is a double bond or one of the following formulas (IIa) or (IId), wherein R 7 is a divalent alkyl group, m is from 0 to 4, L for each m 2 is independently a divalent C1-C 25 alkyl group, optionally inserted with at least one of -O- or -C(O)- in each case the mesogen is represented by the following formula (III), wherein Y is a divalent linking group as a double bond, v and u are each independently 0 to 4, provided that the sum of v and u is 3 to 4, each Z of v is independently a divalent linking group as a double bond or -C(O)O-, for each v and each u, a divalent ring, each independently is phenylene-1,4-diyl, or cyclohexane-1,4-diyl, and E is a straight-chain or branched C1-C 25 alkyl group, Provided that L 1 and L 2 the direct L between 1 -L 2 connection does not contain two heteroatoms connected together, L 1 the direct L between L and Y 1 -mesogenic connection does not contain two heteroatoms connected together, and in each direct L 2 each direct L between L and Y 2 -mesogenic connection does not contain two heteroatoms connected together; and wherein the mesogenic antioxidant is a compound represented by the following formula (V): wherein R 10 and R 11 are each independently an alkyl group, L 3 is a divalent linking group that is a double bond or one of the following formulas (VIb) or (VIe) wherein R 6’ and R 8’ are each independently a divalent alkyl group, m is from 0 to 4, L for each m 4 is independently a divalent C1-C 25 alkyl group, optionally interrupted in each case by at least one of -O- or -C(O)- the mesogen is as represented in formula III, and E is a straight-chain or branched C1-C 25 alkyl group; Provided that L 3 and L 4 the direct L between 3 -L 4 connection does not contain two heteroatoms connected together, L 3 the direct L between L and Y 3 -mesogenic connection does not contain two heteroatoms connected together, and in each direct connection of L 4 each direct L between L and Y 4 -mesogenic connection does not contain two heteroatoms connected together.

2. The photochromic optical article according to claim 1, wherein the anisotropic layer further comprises an ultraviolet light absorber selected from the group consisting of benzotriazole, benzophenone, and combinations thereof.

3. The photochromic optical article according to claim 2, wherein, The ultraviolet light absorber is a benzotriazole represented by the following formula (VIII): wherein the R of each c 12 and the R of each d 13 are each independently methyl, ethyl, hydroxy, or halogen; c is 0 - 4; and d is 0 - 4.

4. The photochromic optical article according to claim 1, wherein, The anisotropic polymer comprises a polymerized liquid crystal monomer.

5. The photochromic optical article according to claim 1, wherein, R 1 is hydrogen, an alkyl group, or an alkoxy group.

6. The photochromic optical article according to claim 1, wherein, R 10 and R 11 each independently is an alkyl group, wherein at least one of R 10 and R 11 is a branched alkyl group.

7. The photochromic optical article according to any one of claims 1 to 6, wherein, the mesogenic antioxidant of the at least a partially anisotropic layer; the mesogenic hindered amine light stabilizer; and the photochromic-dichroic dye, the photochromic dye, or a combination thereof are at least partially aligned.

8. The photochromic optical article according to claim 7, wherein, one or more layers are positioned between the substrate and the at least a partially anisotropic layer, and / or wherein one or more layers are positioned on at least a portion of the at least a partially anisotropic layer.

9. The photochromic optical article according to claim 8, wherein, The one or more layers may further comprise a fixed-tint dye, a dichroic dye, a photochromic-dichroic dye, a photochromic dye, or a combination thereof.

10. The photochromic optical article according to claim 1, wherein, The substrate comprises a polymeric material selected from the group consisting of polycarbonate, polycyclic olefin, polyurethane, poly(urea)urethane, polythiourethane, polythi(urea)urethane, polyol(allyl carbonate), cellulose acetate, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, poly(vinyl acetate), poly(vinyl alcohol), poly(vinyl chloride), poly(vinylidene chloride), poly(ethylene terephthalate), polyester, polysulfone, polyolefin, copolymers thereof, and mixtures thereof.

11. The photochromic optical article according to claim 1, wherein, The article is an optical element selected from the group consisting of: ophthalmic articles, display articles, windows, and mirrors.

12. The photochromic optical article according to claim 11, wherein, The optical element is an ophthalmic article selected from the group consisting of: corrective lenses, non-corrective lenses, contact lenses, and protective lenses.

13. A photochromic coated article, wherein, The coated article comprises: a substrate; and an anisotropic coating on at least a portion of the surface of the substrate, wherein the anisotropic coating is formed from a polymerizable composition comprising: a polymerizable anisotropic material; a photochromic-dichroic dye, a photochromic dye, or a combination thereof; a mesogenic hindered amine light stabilizer in an amount of 10 mole percent (mol%) to 50 mol% relative to the total moles of the photochromic-dichroic dye, photochromic dye, or combination thereof; and a mesogenic antioxidant in an amount of 25 mol% to 150 mol% relative to the total moles of the photochromic-dichroic dye, photochromic dye, or combination thereof, wherein the moles of the mesogenic antioxidant are present in an amount greater than the moles of the mesogenic hindered amine light stabilizer, wherein the mesogenic hindered amine light stabilizer is a compound represented by the following formula (I): wherein R 1 is hydrogen, alkyl, alkoxy or acetyl, R 2 、R 3 、R 4 、and R 5 are each independently an alkyl group, L 1 is a divalent linking group which is a double bond or one of the following formulas (IIa) or (IId), wherein R 7 is a divalent alkyl group, m is from 0 to 4, L for each m 2 is independently a divalent C1-C 25 alkyl group, optionally interrupted in each case by at least one of -O- or -C(O)- the mesogen is represented by the following formula (III), wherein Y is a divalent linking group as a double bond, v and u are each independently 0 to 4, provided that the sum of v and u is 3 to 4, for each v, Z is independently a divalent linking group as a double bond or -C(O)O-, for each v and each u, a divalent ring, each independently is phenylene-1,4-diyl, or cyclohexane-1,4-diyl, and E is a straight-chain or branched C1-C 25 alkyl group, Provided that L 1 with L 2 the direct L 1 -L 2 connection does not contain two heteroatoms connected together, L 1 the direct L 1 -mesogenic connection between L and Y does not contain two heteroatoms connected together, and in each direct connection of L 2 each direct L 2 -mesogenic connection between L and Y does not contain two heteroatoms connected together; and wherein the mesogenic antioxidant is a compound represented by the following formula (V): wherein R 10 and R 11 are each independently an alkyl group, L 3 is a divalent linking group that is a double bond or one of the following formulas (VIb) or (VIe) wherein R 6’ and R 8’ are each independently a divalent alkyl group, m is from 0 to 4, L for each m 4 is independently a divalent C1-C 25 alkyl group, optionally interrupted in each case by at least one of -O- or -C(O)- the mesogen is as represented in formula III, and E is a straight-chain or branched C1-C 25 alkyl group; Provided that L 3 and L 4 the direct L 3 -L 4 connection does not contain two heteroatoms connected together, and the direct L 3 connection between L and Y 3 -mesogenic connection does not contain two heteroatoms connected together, and in each direct L 4 connection between L and Y 4 -mesogenic connection does not contain two heteroatoms connected together.

Images