Photochromic-dichroic article

专利摘要:
PHOTOCHROMIC-DICHROIC ARTICLE. Photochromic-dichroic articles are provided which include a substrate having a first surface, a polarized layer affixed to a first surface of the substrate, and a photochromic-dichroic layer on the first surface of the substrate. The attached polarized layer optionally includes an attached dye and has a first polarization axis. The photochromic-dichroic layer includes a photochromic-dichroic compound that is laterally aligned within the photochromic-dichroic layer, and that defines a second polarization axis. The first polarization axis and the second polarization axis are oriented relative to each other at an angle greater than 0° and less than or equal to 90°. Photochromic-dichroic articles can provide, for example, a combination of increased optical and kinetic density when exposed to a certain amount of actinic radiation.
公开号:BR112015005410B1
申请号:R112015005410-2
申请日:2013-09-13
公开日:2022-02-01
发明作者:Delwin S. Jackson；Henry Nguyen；Rachael L. Demeio；Truman Wilt；Anil Kumar；John S. Ligas
申请人:Transitions Optical, Inc；
IPC主号:

专利说明:

[0001] The present invention relates to a photochromic-dichroic article that includes a substrate, an attached polarized layer positioned on a first surface of the substrate, and a photochromic-dichroic layer positioned over the attached polarized layer, in which the axis of polarization of the aforementioned layers is oriented with respect to each other at an angle greater than 0° and less than or equal to 90°. Background of the invention
[0002] Conventional linearly polarizing elements, such as linearly polarizing lenses for sunglasses and linearly polarizing filters, are typically formed from unilaterally stretched polymeric sheets, which may optionally contain a dichroic material, such as a dichroic dye. Accordingly, conventional linearly polarizing elements are static elements having a single linearly polarizing state. Consequently, when a linearly polarizing element is exposed to either randomly polarized radiation or reflected radiation of the appropriate wavelength, some percentage of the radiation transmitted through the element will be linearly polarized.
[0003] Additionally, conventional linearly polarizing elements are typically dyed elements. Typically, conventional linearly polarizing elements contain a static or fixed coloring agent and have an absorption spectrum that does not vary in response to actinic radiation. The color of the conventional linearly polarizing element will depend on the color of the coloring agent used to form the element and is most commonly a neutral color (eg brown, blue or gray). Thus, while conventional linearly polarizing elements are useful for reducing reflected light glare, because of their static ink, they are not well suited for use under low or low light conditions. Furthermore, because conventional linearly polarizing elements have only a single tinted linearly polarizing state, they are limited in their ability to store or display information.
[0004] Conventional photochromic elements such as photochromic lenses that are formed using conventional thermally reversible photochromic materials are generally capable of converting from a first state, for example a “clear state”, to a second state, for example a “clear state”. colored state” in response to actinic radiation, and revert back to the first state in response to thermal energy. Thus, conventional photochromic elements are generally well suited for use in both low-light and high-light (bright) conditions. However, conventional photochromic elements that do not include linearly polarizing filters are generally not capable of linearly polarizing radiation. The absorption ratio of conventional photochromic elements, in any state, is generally less than two. Therefore, conventional photochromic elements are not able to reduce the brightness of reflected light to the same extent as conventional linearly polarizing elements. Additionally, conventional photochromic elements have a limited ability to store or display information.
[0005] Photochromic-dichroic compounds and materials were developed in order to provide both the photochromic properties and the dichroic properties, if properly and at least sufficiently aligned. When in a colored or darkened state, such as when exposed to actinic light, photochromic-dichroic compounds, however, typically have a higher percentage transmittance than conventional or non-polarizing photochromic compounds at equivalent concentrations and sample thickness. Although not intended to be bound by theory, and based on the evidence at hand, it is believed that the increased transmittance percentage of photochromic-dichroic materials in the darkened or colored state is due to the transmittance percentage being an average of the two polarized components in the orthogonal plane of polarized radiation. A photochromic-dichroic material will more strongly absorb one of the two orthogonal plane-polarized components of random incident radiation, resulting in one of the planes of transmitted polarized light (passing through and out of the sample) having a higher transmittance percentage than the other. component polarized in orthogonal plane. The average of two orthogonal plane-polarized components typically results in a higher-amplitude average transmittance percentage. In general, with linearly polarizing efficiency, the percentage of transmittance associated with these increases can be quantified in terms of the proportion of absorption, of photochromic-dichroic compounds that increases.
[0006] It would be desirable to develop novel polarizing photochromic articles that include photochromic-dichroic compounds, and which provide a combination of linear polarizing properties, and reduce the percentage of transmittance in a colored or darkened state, such as when exposed to actinic light. It would further be desirable for such newly developed polarizing photochromic articles to have an increased combination of increased optical density and increased kinetics, such as increased discoloration rates, when exposed to a given amount of actinic radiation. Summary of the invention
[0007] In accordance with the present invention, there is provided a photochromic-dichroic article comprising (a) a substrate having a first surface and a second surface. The photochromic-dichroic article also comprises (b) an attached polarized layer positioned over the first surface of the substrate. The polarized layer is attached having a first polarization axis. The photochromic-dichroic article further comprises (c) a photochromic-dichroic layer positioned on the first surface of said substrate. The photochromic-dichroic layer comprises a photochromic-dichroic compound, which is laterally aligned within the photochromic-dichroic layer, and which defines a second polarization axis of the photochromic-dichroic layer. The first polarization axis and the second polarization axis are oriented relative to each other at an angle greater than 0° and less than or equal to 90°.
[0008] In accordance with the present invention, there is additionally provided a photochromic-dichroic article as described above which comprises a birefringent layer comprising a polymer, in which the birefringent layer is interposed between the first photochromic-dichroic layer and the second photochromic layer. -dichroic.
[0009] In accordance with the present invention, there is further provided a photochromic-dichroic article comprising (a) a substrate having a first surface and a second surface, on which the substrate has a first axis of polarization. The photochromic-dichroic article additionally comprises (b) a photochromic-dichroic layer positioned on the first surface of the substrate. The photochromic-dichroic layer comprises a photochromic-dichroic compound, which is laterally aligned within the photochromic-dichroic layer, and which defines a second polarization axis of the photochromic-dichroic layer. The first polarization axis and the second polarization axis being oriented relative to each other at an angle greater than 0° and less than or equal to 90°.
[0010] In accordance with the present invention, there is further provided a photochromic-dichroic article as described above, which further comprises a birefringent layer comprising a polymer, in which the birefringent layer is interposed between the linearly polarizing substrate and the photochromic-dichroic. Brief description of drawings
[0011] Figure 1 is a representative exploded perspective view of a photochromic-dichroic article in accordance with some embodiments of the present invention that includes separate fixed polarized layers and photochromic-dichroic layers;
[0012] Figure 2 is a representative exploded perspective view of a photochromic-dichroic article according to some embodiments of the present invention that includes a birefringent layer interposed between the attached polarized layers and the photochromic-dichroic layer;
[0013] Figure 3 illustrates an exploded perspective view of a photochromic-dichroic article according to some embodiments of the present invention, which includes a substrate that is linearly polarizing and a photochromic-dichroic layer;
[0014] Figure 4 is a representative exploded perspective view of a photochromic-dichroic article according to some embodiments of the present invention that includes a birefringent layer interposed between a linearly polarized substrate and a photochromic-dichroic layer;
[0015] Figure 5 illustrates a graphical representation of an average delta absorbance as a function of wavelength (over a visible wavelength region after activation with actinic radiation), and represents two different average absorption spectra obtained in two orthogonal planes for a photochromic-dichroic layer that includes a photochromic-dichroic compound that can be included in the photochromic-dichroic layer of the photochromic-dichroic article in accordance with some embodiments of the present invention; and
[0016] Figure 6 illustrates a side elevational sectional view of a photochromic-dichroic article according to the present invention which additionally includes the alignment, primer layer, top layer, and hard coating layer.
[0017] From figure 1 to figure 6 the same characters refer to the same structural features and components, unless otherwise indicated. Detailed description of the invention
[0018] As used herein, the term "actinic radiation" and similar terms such as "actinic light" means electromagnetic radiation that is capable of causing a response in a material, such as, but not limited to, transforming a material photochromic from one shape or state to another, as will be discussed in further detail here.
[0019] As used herein, the term "photochromic" and related terms such as "photochromic compound" means an absorption spectrum for at least one visible radiation that varies in response to the absorption of at least one actinic radiation. Furthermore, as used herein, the term "photochromic material" means any substance that is adapted to exhibit photochromic properties (i.e., adapted to have an absorption spectrum for at least one visible radiation that varies in response to the absorption of at least one visible radiation). actinic) and which includes at least one photochromic compound.
[0020] As used herein, the term “photochromic compound” includes thermally reversible photochromic compound and non-thermally reversible photochromic compound. The term "thermally reversible photochromic compound/material" as used herein means a compound/material capable of converting from a first state, e.g., a "transparent state", to a second state, e.g., a "colored state", in response to actinic radiation, and revert back to the first state in response to thermal energy. The term “non-thermally reversible photochromic compound/material” as used herein means a compound/material capable of converting from a first state, e.g., a “transparent state”, to a second state, e.g., “a colored state”. , in response to actinic radiation, and revert back to the first state in response to actinic radiation of substantially the same wavelength as the absorption of the colored state (e.g., discontinuous exposure to said actinic radiation).
[0021] As used herein, the term "dichroic" means capable of absorbing one of two polarized components from orthogonal planes of at least one transmitted radiation more strongly than the other.
[0022] As used herein, the term “photochromic-dichroic” and similar terms such as “photochromic-dichroic materials” and “photochromic-dichroic compounds” mean materials and compounds that possess and/or provide both photochromic properties (i.e., having an absorption spectrum for at least one visible radiation that varies in response to at least one actinic radiation), and dichroic properties (i.e. capable of absorbing one of two orthogonal plane-polarized components of at least one transmitted radiation more strongly than than another).
[0023] As used here, As used here, the term "absorption ratio" refers to the ratio of absorption of linearly polarized radiation in a foreground to the absorption of radiation of the same wavelength linearly polarized in a plane orthogonal to the foreground , in which the foreground is taken as the plane with the highest absorption.
[0024] As used herein, to modify the term "state", the terms "first" and "second" are not intended to refer to any particular order or chronology, but rather refer to two different conditions or two different properties. . For the non-limiting purpose of illustration, the first state and second state of the photochromic-dichroic compound of the photochromic-dichroic layer may differ with respect to at least one optical property, such as, but not limited to, absorption or linear polarization of radiation. visible and/or UV radiation. Thus, in accordance with various non-limiting embodiments described herein, the photochromic-dichroic compound of the photochromic-dichroic layer may have a different absorption spectrum in each of the first and second states. For example, although not limiting here, the photochromic-dichroic compound of a photochromic-dichroic layer can be transparent in the first state and colored in the second state. Alternatively, the photochromic-dichroic compound of the photochromic-dichroic layer may have a first color in the first state and a second color in the second state. Furthermore, as discussed below in more detail, the photochromic-dichroic compound of the photochromic-dichroic layer can be non-linearly polarized (or “non-polarized”) in the first state, and linearly polarized in the second state.
[0025] As used herein, the term "optical" means pertaining to or associated with light and/or vision. For example, in accordance with various non-limiting embodiments described herein, the optical article or optical element or device may be chosen from ophthalmic articles, elements and devices, display articles, elements and devices, windows, mirrors, and cell-cell articles. active or passive liquid crystal, elements and devices.
[0026] As used herein, the term "ophthalmic" means pertaining to or associated with the eye and vision. Non-limiting examples of ophthalmic articles or elements include corrective lenses and non-corrective lenses, including single vision or multi-vision lenses, which can be either segmented or non-segmented multi-ocular lenses (such as , but not limited to bifocals, trifocals and progressive lenses), as well as other elements used to correct, protect or enhance (cosmetically or otherwise) vision, including without limitation contact lenses, intraocular lenses, magnifying lenses , and protective lenses or visors.
[0027] As used herein, the term "ophthalmic substrate" means lenses, partially formed lenses, and white lenses.
[0028] As used herein the term “display” means the representation of visible or machine-readable information in words, numbers, symbols, figures or drawings. Non-limiting examples of display articles, elements and devices include screens, monitors and security elements such as security markings.
[0029] As used herein, the term "window" means an opening adapted to allow the transmission of radiation through it. Non-limiting examples of windows include automotive and aircraft clear windows, filters, shutters, and optical switches.
[0030] As used here the term “mirror” means a surface that specifically reflects a large fraction of incident light.
[0031] As used herein the term "liquid crystal cell" refers to a structure containing a liquid crystal material that is capable of being ordered. Active liquid crystal cells are cells where the liquid crystal material is capable of being reversibly and controllably switched, or converted between ordered and disordered states, or between two ordered states through the application of an external force, such as electric fields. or magnetic. Passive liquid crystal cells are cells in which the liquid crystal material maintains an ordered state. A non-limiting example of an active liquid crystal cell element or device is a liquid crystal display.
[0032] As used herein, the term "coating" means a supported film derived from a fluid liquid or particulate solid composition, which may or may not be of uniform thickness and specifically exclude polymeric laminae. For the non-limiting purposes of illustration, an example of a particulate solid fluid composition is a powder coating composition. The first and second photochromic-dichroic layers and additional layers, such as a primer layer, and a topcoat layer of the photochromic-dichroic articles of the present invention may, in some embodiments, each independently be a coating or formed from a coating composition.
[0033] As used herein, the term "blade" means a preformed film having a generally uniform thickness and capable of supporting itself.
[0034] As used herein, the term “connected to” means a direct contact with an object or an indirect contact with an object through one or more other structures or materials, at least one of which is in direct contact with the object. . For the purpose of non-limiting illustration, the photochromic-dichroic layer, for example, may be in direct contact (e.g., adjacent/abutting contact) with at least a portion of the substrate, or it may be in indirect contact. with at least a portion of the substrate through one or more other intervening structures or materials, and may be in direct contact (e.g. adjacent contact) with at least a portion of the substrate or may be in indirect contact with at least a portion of the substrate through one or more other intervening materials or structures, such as a primer layer and/or a monomolecular layer of a coupling agent or adhesive. For example, while not limiting here, the first photochromic-dichroic layer may be in contact with one or more of other interposed coatings, polymeric sheets, or combinations thereof, at least one of which is in direct contact with at least a portion of the surface. substrate.
[0035] As used herein, the term "photosensitive material" means materials that respond physically or chemically to electromagnetic radiation, including, but not limited to, phosphorescent materials and fluorescent materials.
[0036] As used herein, the term "non-photosensitive materials" means materials that do not respond physically or chemically to electromagnetic radiation, including, but not limited to, static dyes.
[0037] As used herein, the term "fixed-polarized" and related terms, such as "fixed polarized layer", "fixed polarized film", and "fixed polarized sheet" means a structure, such as a layer, film, or lamina which at least: (i) is capable of absorbing one of two orthogonal plane-polarized components of at least one transmitted radiation more strongly than the other; (ii) having a polarization axis (such as a first polarization axis); (iii) not respond physically or chemically to, and not be physically or chemically altered by exposure to, actinic radiation, with respect to the absorption of one of two orthogonal plane-polarized components of at least one transmitted radiation more strongly than the other; and (iv) having a single linear polarization state.
[0038] As used herein, the term "fixed dye" and related terms such as "fixed dye", "static dye", "fixed dye", "static dye" mean dyes that are non-photosensitive materials, which do not respond to physically or chemically the electromagnetic radiation with respect to the visually observed color in them.
[0039] As used herein, molecular weight values of polymers, such as weight average molecular weight (Mw) and number average molecular weight (Mn), and z-average molecular weights (Mz) are determined through of gel permeation chromatography using appropriate standards, such as polystyrene standard.
[0040] As used herein, polydispersibility index (PDI) values represent a ratio of the number average molecular weight (Mw) to the number average molecular weight (Mn) of the polymer (ie, Mw/Mn).
[0041] As used herein, the term "polymer" means homopolymers (e.g. prepared from a single monomer species), copolymers (e.g. prepared from at least two monomer species), and polymeric graft, including, but not limited to, crested graft polymers, stellate graft polymers, and dendritic graft polymers.
[0042] As used herein, the term "(meth)acrylate" and similar terms such as "(meth)acrylic acid ester" mean methacrylates and/or acrylates. As used herein, the term "(meth)acrylic acid" means methacrylic acid and/or acrylic acid.
[0043] Unless otherwise noted, all ranges or ratios described herein are to be understood to encompass any and all subranges or sub-ratios subsumed herein. For example, a stated range or ratio of “1 to 10” should be considered to include any and all subranges between (and including) the minimum value of 1 and the maximum value of 10; that is, all sub-ranges or sub-ratios belonging to 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.
[0044] As used herein and in the claims, unless otherwise stated, left-to-right representations of linking groups, such as divalent linking groups, are inclusive of other appropriate orientations, such as, but not limited to, , right-to-left orientation. For the non-limiting purpose of the illustration, the left-to-right representation of the divalent bonding group:
or equivalently -C(O)O-, is even a right-to-left representation of it,
or equivalently -O(O)C- or -OC(O)-.
[0045] As used herein, the articles "a", "an", "the", "the" include reference to the plural unless otherwise expressly and unambiguously limited to a reference.
[0046] As used herein, the term "a fixed dye" means at least one fixed dye.
[0047] As used herein, the term "a photochromic-dichroic compound" means at least one photochromic-dichroic compound.
[0048] As used herein, and unless otherwise noted, "percent transmittance" may be determined using an instrument recognized in the art, such as an ULTRASCAN PRO spectrometer, commercially obtained from "HunterLab", in accordance with the instructions provided in the spectrometer user manual.
[0049] As used here, the term "linearly polarize" means to confine the electric vector vibrations of electromagnetic waves, such as light waves, to a direction or plane.
[0050] In addition to the operation examples, or where otherwise indicated, all numbers expressing amounts of ingredients, reaction conditions, and so on, used in the specification and claims must be supported, as modified in all examples by the term "about".
[0051] As used herein, spatial or directional terms such as “left”, “right”, “internal”, “external”, “above”, “below”, and the like, refer to the invention as it is. represented in the drawing figures. However, it is to be understood that the invention may assume various alternative orientations and, accordingly, such terms are not to be considered limiting.
[0052] As used herein, the terms “formed upon”, “deposited upon”, “provided upon”, “applied upon”, “residing upon”, or “positioned upon”, mean formed, deposited, provided for, applied, resident or positioned on, but not necessarily in direct contact with (or adjacent to) the base element, or surface of the base element. For example, a layer "positioned on" a substrate does not exclude the presence of one or more other layers, coatings, or films thereof or a composition located between the positioned or formed layer and the substrate.
[0053] All documents, such as, but not limited to, granted patents and patent applications, referred to herein, and unless otherwise indicated, shall be deemed to be “incorporated by reference” in their entirety.
[0054] The photochromic-dichroic articles of the present invention include a substrate. Substrates from which the substrate of the photochromic-dichroic articles of the present invention can be selected include, but are not limited to, substrates formed from organic materials, inorganic materials, or combinations thereof (e.g., composite materials). Non-limiting examples of substrates can be used in accordance with various non-limiting embodiments herein are described in more detail below.
[0055] Non-limiting examples of organic materials that can be used to form the substrate of the photochromic-dichroic articles of the present invention include polymeric materials, for example, homopolymers and copolymers, prepared from monomers and monomer mixtures described in the US patent. -American No. US 5,962,617 and U.S. Patent No. US 5,658,501 from column 15, line 28 through column 16, line 17, the disclosures of said patents being specifically incorporated herein by reference. For example, such polymeric materials can be thermoplastics or thermosetting polymeric materials, can be transparent or optically transparent, and can have any required refractive index. Non-limiting examples of said described monomers and polymers include: polyol(allyl carbonate) monomers, for example, allyl diglycol carbonates, such as diethylene glycol bis(allyl carbonate), which monomer is sold under the tradename CR-39 by PPG Industries Inc.; polyurea-polyurethane (polyurea-urethane) polymers, which are prepared, for example, by the reaction of a polyurethane prepolymer and a diamine curing agent, a composition for one of said polymers being sold under the TRIVEX trademark by PPG Industries Inc., polyol(meth)acryloyl terminated carbonate monomer; diethylene glycol dimethacrylate monomers; ethoxylated phenol methacrylate monomers; diisopropenyl benzene monomers; ethoxylated trimethylol propane triacrylate monomers; ethylene glycol bismethacrylate monomers; poly(ethylene glycol) bismethacrylate monomers; urethane acrylate monomers; poly(ethoxylated bisphenol A dimethacrylate); poly(vinyl acetate); poly(vinyl alcohol); polyvinyl chloride); poly(vinylidene chloride); polyethylene; polypropylene; polyurethanes; polythiourethanes; thermoplastic polycarbonates, such as carbonate-bound resin derived from Bisphenol A and phosgene, one of said materials being sold under the tradename LEXAN; polyester, such as the material sold under the tradename MILAR; poly(ethylene terephthalate); polyvinyl butyral; poly(methyl methacrylate), such as the material sold under the trade name PLEXIGLAS, and polymers prepared by reacting polyfunctional isocyanate with polythiols or polyepisulfide monomers, either homopolymerized or co- and/or terpolymerized with polythiols, polyisocyanates, polyisothiocyanates and optionally monomers ethylenically unsaturated or vinyl monomers containing aromatic halogens. Also contemplated are copolymers of said monomers and mixtures of the described polymers and copolymers with other polymers, for example to form block copolymers or interpenetrating network products.
[0056] The substrate may, with some embodiments, be an ophthalmic substrate. Non-limiting examples of organic materials suitable for use in forming ophthalmic substrates include, but are not limited to, art-recognized polymers that are useful as ophthalmic substrates, such as organic optical resins that are used to prepare optically clear melts for optical applications. , such as ophthalmic lenses.
[0057] Other non-limiting examples of organic materials suitable for use in forming substrates for the photochromic-dichroic articles of the present invention include both synthetic materials and natural organic materials, including without limitation: opaque or translucent polymeric materials, synthetic or natural textiles , and cellulosic materials such as paper and wood.
[0058] Non-limiting examples of organic materials suitable for use in forming substrates for the photochromic-dichroic articles of the present invention include glasses, minerals, ceramics, and metals. For example, in a non-limiting embodiment the substrate may include glass. In another non-limiting embodiment, the substrate may have a reflective surface, for example, a polished ceramic substrate, metallic substrates, or mineral substrates. In other non-limiting embodiments, a reflective coating or layer may be deposited or otherwise applied to a surface of an inorganic substrate or an organic substrate to make it reflective or to improve its reflectivity.
[0059] Furthermore, in accordance with a certain non-limiting embodiment described herein, the substrate may have a protective coating, such as, but not limited to, an abrasion-resistant coating, such as a "hard coating", on its outer surface. . For example, commercially available thermoplastic polycarbonate ophthalmic lens substrates are often sold with an abrasion resistant coating already applied to their outer surface, because these surfaces tend to be quickly scratched, scraped, or worn. An example of such lens substrates is the GENTEXTM polycarbonate lens (available from Gentex Optics). Therefore, as used herein, the term "substrate" includes a substrate having a protective coating, such as but not limited to an abrasion resistant coating, on its surface(s).
[0060] Additionally, the substrate of the photochromic-dichroic articles of the present invention may be selected from non-stained (undyed) substrates, dyed/stained substrates, linearly polarized, circularly polarized, elliptically polarized substrates, photochromic substrates, or photochromic-stained substrates. With some embodiments, and as will be discussed in greater detail, the substrate has a first polarization axis and optically includes a fixed dye, and as such is a linearly polarized substrate which optionally includes a fixed dye.
[0061] As used herein with reference to substrates, the term "unstained" means substrates that are essentially free from the addition of coloring agents (such as, but not limited to, conventional dyes) and have an absorption spectrum for visible radiation that does not vary significantly in response to actinic radiation. Furthermore, with reference to substrates, the term "stained/dyed" means substrates that have the addition of a coloring agent (such as, but not limited to, conventional dyes) and an absorption spectrum for visible radiation that does not vary significantly in response to actinic radiation.
[0062] As used herein, the term "linearly polarized" with respect to the substrate means a substrate that has been adapted for linearly polarized radiation. As used herein, the term "circularly polarized" with respect to substrate means substrates that are adapted for circularly polarized radiation. As used herein, the term "elliptically polarized" with respect to substrate means substrates which are adapted to polarize elliptically in radiation. As used herein, with the term "photochromic" with respect to a substrate, it means substrates having an absorption spectrum for visible radiation that varies in response to at least actinic radiation. Additionally, as used herein with respect to the substrate, the term "fixed color photochromic" means substrates containing a fixed coloring agent as well as a photochromic material, and having an absorption spectrum for visible radiation that varies in response to at least one radiation. actinic. Thus, for example, and without limitation, a fixed colored photochromic substrate may have a first color characteristic of the fixed coloring agent (or fixed dye) and a second color characteristic of the combination of the coloring agent of the photochromic material when exposed to radiation. actinic.
[0063] With reference to Figure 1, and for the purpose of non-limiting illustration, a photochromic-dichroic article 2 in accordance with the present invention is described. The photochromic-dichroic article 2 includes a substrate 12 having a first surface 15 and a second surface 18. The first surface 15 of the substrate 12, with some embodiments, shows incident actinic radiation represented by arrow 21. The photochromic-dichroic article 2 further includes an attached polarized layer 24 which is positioned over the first surface 15 of the substrate 12. The polarized layer 24 is a linearly polarized layer and as such has a first polarization axis represented by two points of arrows 27.
[0064] The photochromic-dichroic article 2 additionally includes a photochromic-dichroic layer 30 which is positioned above the first surface 15 of the substrate 12. With some embodiments, the photochromic-dichroic layer 30 is interposed between the first surface 15 of the substrate 12 and the attached polarized layer 24 (not shown in Figure 1). With some additional embodiments, the attached polarized layer is interposed between the first surface 15 of the substrate and the photochromic dichroic layer. For the purpose of non-limiting illustration and as depicted in Figure 1, the affixed polarized layer 24 is interposed between the first surface 15 of the substrate 12, and the photochromic-dichroic layer 30.
[0065] With some embodiments, the attached polarized layer 24 abuts the first surface 15 of the substrate 12. According to further embodiments, one or more additional layers, such as a primary layer (not shown), are interposed between the first surface 15 of the substrate 12 and the attached polarized layer 24. With some additional embodiments, the dichroic photochromic layer 30 abuts the first surface 15 of the substrate 12. With some additional embodiments, one or more additional layers, such as the first layer (not shown) and/or or a first alignment layer (not shown), are interposed between the first surface 15 of the substrate 12 and the photochromic-dichroic layer 30.
[0066] The photochromic-dichroic layer includes at least one photochromic-dichroic compound. The photochromic-dichroic compound is laterally aligned within the photochromic-dichroic layer. By laterally aligned it is meant that the photochromic-dichroic compound is laterally aligned through at least a portion of the width or length of the photochromic-dichroic layer. The photochromic-dichroic compound may be laterally aligned along the top and/or bottom surface of the photochromic-dichroic layer, within at least a portion of the interior of the second photochromic-dichroic layer, or any combination thereof. The lateral alignment of the photochromic-dichroic compound within the photochromic-dichroic layer serves to define a second polarization axis of the second photochromic-dichroic layer. With non-limiting reference to Figure 1, the photochromic-dichroic layer 30 has a second polarization axis as represented by the double arrows 33.
[0067] With the photochromic-dichroic articles of the present invention, the first polarization axis of the first photochromic-dichroic layer and the second polarization axis of the second photochromic-dichroic layer are oriented relative to each other at an angle greater than 0° and less than or equal to 90°, such as from 0.1° to 90°, or from 1° to 90°, or from 10° to 90°, or from 25° to 90°, or from 45° to 90° , or from 60° to 90°, including the quoted values. With some embodiments, when the first and second polarization axes are oriented relative to each other at a 90° angle, the photochromic-dichroic articles of the present invention have a minimal level of transmittance of incident actinic radiation, providing that the first and second photochromic dichroic compounds undergo both photochromic activation (eg, being converted to a colored state) and dichroic activation when exposed to incident actinic radiation, such as when exposed to direct southern light.
[0068] Depending on the wavelength or wavelength range, and/or energy (or intensity) of the incident electromagnetic radiation, and the relative positioning of the fixed polarized layer and the photochromic-dichroic layer, the photochromic-dichroic articles of the The present invention can provide a variety of photochromic and/or dichroic responses, resulting in a variety of observable colors, color intensities, polarization effects, and/or at least partially cross polarization effects. The photochromic-dichroic compound of the photochromic-dichroic layer can, with some embodiments, undergo any combination of photochromic activation (e.g., conversion to a colored state) and/or dichroic activation (resulting in at least partially linear polarization of the incident electromagnetic radiation). With some additional embodiments, the photochromic-dichroic compound of the photochromic-dichroic layer may undergo substantially no photochromic activation and substantially no dichroic activation, such as when the photochromic-dichroic article is exposed to ambient indoor light, such as fluorescent light.
[0069] With some embodiments, the photochromic-dichroic layer is interposed between the first surface of the substrate and the fixed polarized layer, in this case, the superimposed polarized layer fixed can absorb certain wavelengths of and/or a certain amount of energy of the incident electromagnetic radiation, resulting in the photochromic-dichroic compound, of the sustained photochromic-dichroic layer, undergoing: any combination of photochromic activation (e.g., it is converted to a colored state) and/or dichroic activation (resulting in a linear polarization by the less partial of the incident electromagnetic radiation); or substantially no photochromic activation and substantially no dichroic activation
[0070] According to some embodiments, the fixed polarized layer may be adapted to have a first polarization axis. Such adaptations include, but are not limited to: (i) the presence of one or more dichroic materials or compounds that are aligned together in a first lateral direction within the attached polarized layer; (ii) the attached polarized layer includes a polymer that is laterally aligned along a first direction within the attached polarized layer; (iii) the presence of the aligned nanoscale structures on at least one surface of the attached polarized layer which are aligned together in a first lateral direction; (iv) the polarization (or Brewster) angle of the material from which the fixed polarized layer is manufactured; (v) the attached polarized layer including, at least in part, a lyotropic liquid crystal matrix that acts as a host for a template, which are aligned together in a first lateral direction; and (vi) combinations of two or more of such adaptations (i) through (v).
[0071] With some embodiments, the fixed polarized layer includes a dichroic material or compound, such as one or more conventional dichroic compounds, which is aligned together in a first lateral direction within the fixed polarized layer and thus defines the first axis of polarization of the fixed polarized layer. The dichroic material can be aligned by methods known in the art, such as, but not limited to, shear forces and/or alignment with a polymer matrix of the attached polarized layer.
[0072] With some embodiments of the present invention, the attached polarized layer may comprise a polymer, the polymer being laterally aligned along a first lateral direction within the attached polarized layer and defining the first polarization axis of the attached polarized layer. The polymer of the attached polarized layer may be laterally aligned according to methods known in the art, such as, but not limited to, unilateral stretching of the attached polarized layer.
[0073] With some embodiments, the attached polarized layer additionally includes one or more attached dyes such as conventional dyes. In accordance with some embodiments, the attached polarized layer includes a polymer that is laterally aligned along a first lateral direction within the attached polarized layer so as to define the first polarization axis thereof, and the attached polarized layer further includes at least one of a dichroic compound and, optionally, a fixed dye. The dichroic compound can be laterally aligned with the polymer along the first lateral direction. The fixed polarized layer according to some embodiments is free of photochromic compounds. The optional fixed dye of the fixed polarized layer, with some embodiments of the present invention, comprises a fixed dye selected from azo dyes, anthraquinone dyes, xanthene dyes, azime dyes, iodine , iodide salts, polyazo dyes, stilbene dyes, pyrazolone dyes, thiphenylmethane dye, quinoline dye, oxazine dye, thiazine dye, polyene dye, and mixtures thereof.
[0074] The fixed dye, with some embodiments, may be present in the fixed polarized layer in amounts sufficient to provide a desired color and percentage transmittance of actinic radiation, such as visible light. The types and amounts of fixed dye can be selected, with some embodiments, to provide the photochromic-dichroic article with a base color and a percentage of base transmittance, when the photochromic-dichroic compound of the photochromic-dichroic layer does not even undergo photochromic activation. nor by dichroic activation. The types and amounts of fixed dye can be selected, with some embodiments, to provide the photochromic-dichroic article with one or more colors and one or more values of activated transmittance percentage, when the photochromic-dichroic compound of the photochromic-dichroic layer undergoes photochromic activation and/or dichroic activation. The fixed dye may be present in the fixed polarized layer in varying amounts to provide the desired effect as is done with other conventional additives.
[0075] Classes of dichroic compounds, such as conventional dichroic compounds, that may be included, with some embodiments, in the fixed polarized layer of the photochromic-dichroic articles of the present invention may include, but are not limited to, azomethine, indigoids, thioindigoids , merocyanines, indans, quinophthalonic dyes, perylene, phthaloprines, triphendiaxozines, indoloquinoxalines, imidazo-triazines, tetrazines, azo and (poly)azo dyes, benzoquinones, naphthoquinones, anthroquinone and (poly)anthroquinones, anthropyrimidinones, iodine and iodates.
[0076] The dichroic compounds can be present in the fixed polarized layer, with some embodiments, in an amount of at least 0.001 weight percent and less than or equal to 99.0 weight percent, such as from 0.1 to 50 weight percent, or from 1.0 to 20 weight percent, in which case the weight percentages are in each case based on the total weight of the attached polarized layer.
[0077] The polarized bonded layer may additionally include at least one additive that may facilitate one or more of the processing, properties, or performance of the polarized bonded layer. Non-limiting examples of such conventional additives include solvents, light stabilizers (such as, but not limited to, ultraviolet light absorbers and light stabilizers such as hindered amine light stabilizers (HALS)), heat stabilizers, release agents molds, rheology control agents, leveling agents (such as, but not limited to, surfactants), free radical scavengers, and adhesion promoters (such as diacrylate and hexanediol and coupling agents).
[0078] According to some embodiments, the attached polarized layer may be adapted to have a first axis of polarization by the presence of a plurality of nanoscale structures aligned on at least one surface of the attached polarized layer. The plurality of aligned nanoscale structures define the first polarization axis of the attached polarized layer. With some embodiments, nanoscale structures include a plurality of substantially parallel ribs (such as raised rib), in which each rib is laterally spaced from an adjacent rib. The lateral spacing between the ribs is, with some embodiments, nanoscale to provide a polarization effect.
[0079] Reinforcements may be manufactured from a non-organic material including, but not limited to, one or more metals, metal alloys, inorganic materials such as metal oxides, and combinations thereof. Examples of metals from which reinforcements can be made include, but are not limited to, Al, Ti, Zn, Cu, Cr, Ta, Nb, mixtures of two or more of the same, combinations of two or more of the same, and alloys of two or more of them. Examples of metal oxides from which reinforcements can be made include, but are not limited to, oxides of Si, Al, Zr, Ti, Ge, SN, In, Zn, SB, Ta, Nb, V, Y, mixtures of two or more of the same, and combinations of two or more of the same.
[0080] Nanoscale structures can be prepared by methods known in the prior art, such as deposition of an inorganic material (such as a metal or metal oxide) on a surface of the fixed polarization layer, and etching the material. inorganic material deposited to form the structure. Recording may be conducted in accordance with art-recognized methods, such as, but not limited to, chemical recording, physical recording, and actinic radiation recording (such as electron beam recording). The deposited material has a thickness, with some embodiments, that is at least sufficient to allow the formation of parallel grooves and reinforcements therein. With some embodiments, the deposited material has a thickness greater than 0 micrometers (μ m) and less than or equal to 10 μ m, or less than or equal to 5 μ m, or less than or equal to 1 μ m.
[0081] To improve the adhesion of nanoscale structures to the surface of the fixed polarized layer, and with some embodiments, an underlayer (with some embodiments, composed of a metal, such as metallic chromium, or a metal oxide) is first deposited on the surface of the fixed polarized layer. The underlayer, with some embodiments, is thinner than the layer subsequently deposited (within which the grooves and reinforcement are formed). With some embodiments, the sublayer has a thickness greater than 0 nm and less than or equal to 300 nm, or less than or equal to 100 nm, or less than or equal to 20 nm. Examples of linear polarizers that include aligned nanoscale structures include, but are not limited to, PROFLUX® polarizers (including visible light polarizers) which are commercially available from MOXTEK Incorporated.
[0082] With some embodiments, the first polarization axis of the fixed polarized layer is defined by the polarization (or Brewster) angle of the material from which the fixed polarized layer is manufactured. The Brewster angle can be determined according to art-recognized methods, such as from the following equation: θB = arctan(n2/n1)
[0083] In the above equation, θB is the Brewster angle of the material from which the fixed polarized layer is manufactured; n1 is the refractive index of the initial medium through which electromagnetic radiation (such as visible light) propagates; and n2 is the refractive index of the material from which the fixed polarized layer is made. The polarization/Brewster angle is determined with respect to the surface of the fixed polarized layer that confronts the incident electromagnetic radiation.
[0084] According to some embodiments, the first polarization axis of the fixed polarized layer is defined by (or is the result of) the fixed polarized layer including, at least in part, a guest host system, which includes a crystal matrix lyotropic liquid that acts as a host for a dye, such as a non-dichroic dye, that is disposed within the lyotropic liquid crystal matrix. The dye is oriented through the orientation of the lyotropic liquid crystal matrix. The visiting host system can be formed by art-recognized methods, such as by coating an underlying material or substrate with a coating composition that includes a lyotropic liquid crystal matrix material and a dye.
[0085] Orientation of the visiting host system may be accomplished through art-recognized methods during and/or after formation of the visiting host system, such as through interaction with an external force including, but not limited to, a magnetic field, an electric field, linearly polarized infrared radiation, linearly polarized ultraviolet radiation, linearly polarized visible radiation, and/or shear forces. During and/or after application of the composition and coating, and with some embodiments, the liquid crystal matrix material is unilaterally oriented, and correspondingly the dye is also unilaterally oriented along with the liquid crystal matrix material.
[0086] The visitor host system dye can be selected from the dyes known from the prior art, such as, but not limited to, acid dyes, basic dyes, direct dyes, reactive dyes, and combinations of two or more of the same . With some embodiments, the dye is selected from one or more pleochroic dyes. A pleochroic dye, and in particular a pleochroic dye molecule, is a molecule that has a light absorption spectrum that varies as a function of the orientation of the molecule with respect to incident light polarization.
[0087] The lyotropic liquid crystal matrix material of the visiting host system may be selected from one or more prior art recognized materials, such as liquid crystal compounds, including but not limited to, those composed of liquid crystals described further herein with respect to the optional anisotropic material of the photochromic-dichroic layer, and/or the optional alignment layer. With some embodiments, the lyotropic liquid crystal matrix material includes one or more liquid crystal compounds that include at least one triazine group per molecule. Examples of suitable guest host systems include, but are not limited to, those described in column 2, line 65 through column 13, line 41 of U.S. Patent No. US 6,245,399 B1, the disclosure of which is incorporated herein by reference.
[0088] The dichroic photochromic layer may, with some embodiments, of the dichroic photochromic articles of the present invention, be non-polarizing in a first state (i.e., the layer will not confine electrical vector vibrations of light waves to one direction), and be linearly polarized in a second state with respect to the transmitted radiation. As used herein, the term "transmitted radiation" refers to radiation that is passed through at least a portion of an object. Although not limiting, the transmitted radiation can be ultraviolet radiation, visible radiation, infrared radiation, or a combination thereof. Thus, in accordance with various non-limiting embodiments described herein, the photochromic-dichroic layer can be non-polarizing in the first state and linearly polarized in the second state, thereby transmitting linearly polarizing transmitted ultraviolet radiation, transmitting linearly polarized visible radiation. , or a combination thereof in the second state.
[0089] In accordance with further non-limiting embodiments, the photochromic-dichroic layer may have a first absorption spectrum in the first state, a second absorption spectrum in the second state, and may be linearly polarizing in both the first and second states. state.
[0090] With some embodiments, the photochromic-dichroic layer independently has an average absorption ratio of at least 1.5 and at least one state. With some additional embodiments, the photochromic-dichroic layer may independently have an average absorption ratio ranging from at least 1.5 to 50 (or greater) in at least one state. The term “absorption ratio” refers to the ratio of the absorbance of linearly polarized radiation in a foreground to the absorbance of linearly polarized radiation in a plane orthogonal to the foreground, in which the foreground is taken as the plane with the most high absorbance. Thus, the absorption ratio (and the average absorption ratio which is described below) is an indication of how strongly one of the two orthogonal plane-polarized components of radiation is absorbed by an object or material.
[0091] The average absorption ratio of a photochromic-dichroic layer that includes a photochromic-dichroic compound can be determined as shown below. For example, to determine the average absorption ratio of a photochromic-dichroic layer that includes a photochromic-dichroic compound, a substrate having a layer is placed on an optical bench and the layer is placed in a linearly polarizing state through activation of the compound. photochromic-dichroic. Activation is achieved by exposing the layer to UV radiation for a time sufficient to reach a saturated or close to saturated state (i.e., a state where the absorption properties of the layer do not change substantially over the time interval during which measurements are made). Absorption measurements are taken over a period of time (typically 10 to 300 seconds) at 3 second intervals for light that is linearly polarized in a plane perpendicular to the optical bench (referred to as the O° plane or direction of polarization) and the light that is linearly polarized in a plane that is parallel to the optical bench (referred to as the plane or direction and 90° polarization) in the following sequence; 0°, 90°, 90°, 0°, etc. The absorbance of linearly polarized light across the layer is measured at each time interval for all wavelengths tested and the inactivated absorbance (i.e., the absorbance of the coating in an inactivated state) over the same wavelength range that is subtracted to obtain the absorption spectrum for the layer in an activated state in each of the 0° and 90° polarization planes to obtain a different average absorption spectrum in each polarization plane for the layer in the saturated state or close to saturated state.
[0092] For example, with reference to figure 5, the different average absorption spectrum (generally indicated 36) in a polarization plane that was obtained for a photochromic-dichroic layer according to a non-limiting embodiment described here is shown. The average absorption spectrum (generally indicated 395) is the different average absorption spectrum obtained for the same photochromic-dichroic layer in the orthogonal polarization plane.
[0093] Based on the different average absorption spectrum obtained for the photochromic-dichroic layer, the average absorption ratio for the photochromic-dichroic layer is obtained as follows. The absorption ratio of the photochromic-dichroic layer at each wavelength in a predetermined wavelength range corresponding to Δmax-vis+/-5 nanometers (generally indicated as 42 in Figure 5), where Δmax-vis is the wavelength in which the coating had the highest average absorbance in any plane, is calculated according to Equation (Eq.1) below:

[0094] With reference to equation Eq.1, ARÀi is the proportion of absorption at wavelength À, Abi is the average absorption at wavelength Ài in the polarization direction (ie, 0° and 90°) having the largest absorbance, and Ab2Ài is the average absorbance at wavelength Ài, in the remaining polarization direction. As previously discussed, the "absorption ratio" refers to the ratio of absorbance of linearly polarized radiation in a foreground to the absorbance of the same wavelength of radiation linearly polarized in a plane orthogonal to the foreground, where the foreground is taken as the plane with the highest absorbance.
[0095] The average absorbance ratio (“AR”) for the photochromic-dichroic layer is then calculated by averaging the individual proportions over the predetermined range of wavelengths (i.e. Àmax-vis +/- 5 nanometers) according to with the equation (Eq. 2) below:

[0096] With reference to equation Eq.2, AR is the average absorption ratio for the coating, ARÀ1 is the individual ratios (as determined above in Eq. 1) for each wavelength within the predetermined wavelength range, and ni is the number of individual absorption ratios averaged. A more detailed description of this method of determining the average absorption ratio is provided in Examples of U.S. Patent No. US 7,256,921, at column 102, line 38 through column 103, line 15, the description of which is specifically incorporated herein by reference.
[0097] With some embodiments, the photochromic-dichroic compound of the photochromic-dichroic layer can be at least partially aligned. As previously discussed, the term "photochromic-dichroic" means participating in both photochromic and dichroic (ie, linearly polarizing) properties under certain conditions, in which the properties are at least detectable by instrumentation. Consequently, "photochromic-dichroic compounds" are compounds exhibiting both photochromic and dichroic (ie linearly polarizing) properties under certain conditions, whose properties are at least detectable by instrumentation. Thus, photochromic-dichroic compounds have an absorption spectrum for at least one visible radiation that varies in response to at least one actinic radiation and are capable of absorbing one of two orthogonal plane-polarized components of at least one transmitted radiation more strongly than than the other. Additionally, when with the conventional photochromic compounds discussed herein, they may be thermally reversible. That is, the photochromic-dichroic compound can change from a first state to a second state in response to actinic radiation and revert back to the first state in response to thermal energy. As used herein with some embodiments, the term "compound" means a substance formed by the union of two or more elements, components, ingredients, or parts and includes, without limitation, molecules and macromolecules (e.g., polymers and oligomers) formed by the union of two or more elements, components, ingredients, or parts.
[0098] For example, the photochromic-dichroic layer can have a first state having a first absorption spectrum, a second state having a second absorption spectrum that is different from the first absorption spectrum, and can be adapted to change from a first absorption spectrum. state to the second state in response to at least one actinic radiation and revert back to the first state in response to thermal energy. Furthermore, the photochromic-dichroic compound can be dichroic (ie linearly polarizing) in one or both of the first and second states. For example, although not required, the photochromic-dichroic compound can be linearly polarizing in an activated state and non-polarizing in a bleaching or fading state (ie, non-activated or inactivated state). As used herein, the term "activated state" refers to the photochromic-dichroic compound when exposed to sufficient actinic radiation to induce at least a portion of the photochromic-dichroic compound to change from a first state to a second state. Furthermore, although not required, the photochromic-dichroic compound can be dichroic in both the first and second states. While not limiting here, for example, the photochromic-dichroic compound can be linearly polarized in visible radiation in both the activated state and the bleaching state. Furthermore, the photochromic-dichroic compound can linearly polarize on visible radiation in an activated state, and can linearly polarize on UV radiation in the bleaching state.
[0099] Although not required, in accordance with various non-limiting embodiments described herein, the photochromic-dichroic compound, of the photochromic-dichroic layer may each independently have an average absorption ratio of at least 1.5 in an activated state. as determined in accordance with the CELL METHOD. In accordance with other non-limiting embodiments described herein, the photochromic-dichroic compound may have an average absorption ratio greater than 2.3 in an activated state as determined in accordance with the CELL METHOD. In accordance with yet another non-limiting, at least partially aligned, embodiment, the photochromic-dichroic compound of the photochromic-dichroic layer may have an average absorption ratio ranging from 1.5 to 50 in an activated state as determined in accordance with the CELL METHOD According to another non-limiting, at least partially aligned, embodiment, the photochromic-dichroic compound of the photochromic-dichroic layer may have an average absorption ratio ranging from 4 to 20, or an average absorption ratio ranging from 3 to 30, or an average absorption ratio ranging from 2.5 to 50 in an activated state as determined in accordance with the CELL METHOD. More typically, however, the average absorption ratio of at least partially of the photochromic-dichroic compound may have any average absorption ratio that is sufficient to impart the desired properties to the photochromic-dichroic article of the present invention. Non-limiting examples of the photochromic-dichroic compounds each independently to be selected, with some embodiments, are described in detail here below.
[0100] THE CELL METHOD for determining the average absorption ratio of a photochromic-dichroic compound (such as the first and second photochromic compounds) is essentially the same as the method used to determine the average absorption ratio of the photochromic layer - dichroic containing said photochromic-dichroic compound, except that, rather than mediating the absorbance of a coated substrate, a cell array containing an aligned liquid crystal material and the particular photochromic-dichroic compound is tested.
[0101] With some embodiments, and for non-limiting purposes of illustration, the cell array includes two opposing glass substrates that are spaced apart by 20 microns +/- 1 micron. The substrates are sealed along two opposing edges to form a cell. The inner surface of each of the glass substrates is coated with a polyimide coating, the surface thereof being at least partially friction-ordered. Alignment of the photochromic-dichroic compound is achieved by introducing the photochromic-dichroic compound and the liquid crystal medium into the cell array, and allowing the liquid crystal medium and the photochromic-dichroic compound to align with the rubbed polyimide surface. . Once the liquid crystal medium and the photochromic-dichroic compound are aligned, the cell array is placed on an optical bench (which is described in detail in the Examples) and the average absorption ratio is determined in the manner previously described for the substrates. coated, except that the inactivated absorbance of the cell array is subtracted from the activated absorbance to obtain the average difference in the absorption spectrum.
[0102] Although dichroic compounds are able to potentially absorb one of two orthogonal components of plane-polarized light, an appropriate position or arrangement of the molecules of a dichroic compound would generally be required in order to achieve a net polarization effect. Similarly, it would generally be necessary to properly position or arrange the molecules of a photochromic-dichroic compound to achieve a net linear depolarization effect. That is, it would generally be necessary to align the photochromic-dichroic compound molecules so that the long axes of the photochromic-dichroic compound molecules in an activated state are generally parallel to each other. Therefore, and in accordance with various non-limiting embodiments described herein, the first and second photochromic-dichroic compounds are each independently at least partially aligned. Furthermore, if the activated state of the photochromic-dichroic compound corresponds to a dichroic state of the material in which it resides, the photochromic-dichroic compound can be at least partially aligned so that the long axis of the photochromic-dichroic compound molecules in the activated is aligned. As used herein, the term "align" means to bring into an appropriate arrangement or position appropriate for interaction with another material, composite or structure.
[0103] Furthermore, although not limiting here, the first and second photochromic-dichroic layers may include a plurality of photochromic-dichroic compounds. While not limiting here, when two or more photochromic-dichroic compounds are used in combination, the photochromic-dichroic compound may be chosen to complement the other to produce a desired color or a desired shade. For example, mixtures of photochromic-dichroic compounds can be used, in accordance with certain non-limiting embodiments herein, to bind certain activated colors, such as a near neutral gray or near neutral brown. See, for example, U.S. Patent No. US 5,645,767, column 12, line 66 through column 13, line 19, the description of which is specifically incorporated by reference herein, which describes parameters defining neutral gray and brown colors. Additionally or alternatively, each of the photochromic-dichroic layers of the photochromic-dichroic articles of the present invention will each independently include mixtures of photochromic-dichroic compounds having complementary linear polarization states. For example, photochromic-dichroic compounds of a photochromic-dichroic layer can be chosen to have complementary linear polarization states over the desired wavelength range to produce an optical element that is capable of polarizing light with respect to the desired wavelength range. desired wavelength. Furthermore, mixtures of complementary photochromic-dichroic compounds having essentially the same polarization states at the same wavelength can be chosen to enhance or improve the overall linear polarization achieved. For example, according to a non-limiting embodiment, each photochromic-dichroic layer of the photochromic-dichroic articles of the present invention may independently include at least two at least partially aligned photochromic-dichroic compounds, in which each of the compounds is at least partially aligned. aligned has: complementary colors; and/or complementary linear polarization states.
[0104] The photochromic-dichroic layer may further include at least one additive that may facilitate one or more processing steps, properties, or performance, of said layer. Non-limiting examples of such additives include dyes, alignment enhancers, horizontal alignment agents, kinetic enhancing additives, photoinitiators, thermal initiators, polarization inhibitors, solvents, light stabilizers (such as, but not limited to, light absorbers). ultraviolet and light stabilizers such as hindered amine light stabilizers (HALS), heat stabilizers, mold release agents, rheology control agents, leveling agents (such as but not limited to surfactants), scavengers free radicals, and adhesion promoters (such as hexanediol diacrylate and coupling agents).
[0105] Examples of dyes that may be present in the first and/or second photochromic-dichroic layer include, but are not limited to, dyes that are capable of imparting a desired color or other optical property to the first and/or second layer. photochromic-dichroic.
[0106] As used herein, the term "alignment enhancer" means an additive that can facilitate at least one of a rate and uniformity of alignment of a material to which it is added. Non-limiting examples of alignment promoters that may be present in the first and/or second photochromic-dichroic layers include, but are not limited to, those described in U.S. Patent No.: U.S. 6,338,808 and in the U.S. patent application publication. No. 2002/0039627, which are specifically incorporated herein by reference herein.
[0107] The horizontal alignment (or orientation) agents that may be used with some embodiments of the present invention assist in aligning the longitudinal axis of a photochromic-dichroic compound substantially parallel to a horizontal plane of the photochromic-dichroic layer. Examples of horizontal alignment agents that can be used with some embodiments of the present invention include, but are not limited to, those described in column 13, line 58 through column 23, line 2 of U.S. Patent No. US 7,315,341 B2 which describes is incorporated herein by reference.
[0108] Non-limiting examples of kinetic-enhancing additives that may be present in various layers of the photochromic-dichroic article of the present invention, such as the first and/or second photochromic-dichroic layer, include epoxy-containing compounds, organic polyols, and /or plasticizers. More specific examples of said kinetic-enhancing additives are described in US patent US 6,433,043 and patent application publication 2003/0045612, which are specifically incorporated herein by reference.
[0109] Non-limiting examples of photoinitiators that may be present in multiple layers of the photochromic-dichroic article of the present invention, such as the photochromic-dichroic layer include, but are not limited to, cleavage-type photoinitiators and abstraction-type photoinitiators. Non-limiting examples of cleavage-type photoinitiators include acetophenones, α-aminoalkylphenones, benzoin ethers, benzoyl oximes, acylphosphine oxides and bisacylphosphine oxides or mixtures of such initiators. A commercial example of such a photoinitiator is DAROCURE® 4265, which is available from Ciba Chemicals, Inc. Non-limiting examples of abstraction-type photoinitiators include benzophenones, Michler's ketone, thioxanthone, anthraquinone, camphorquinone, fluorone, ketocoumarin or mixtures of such initiators.
[0110] Another non-limiting example of a photoinitiator that may be present in one or more layers of the photochromic-dichroic article of the present invention, such as in the photochromic-dichroic beloved is a visible light photoinitiator. Non-limiting examples of suitable visible light photoinitiators are described in column 12, line 11 through column 13, line 21 of the U.S. patent. 6,602,603, which is specifically incorporated by reference herein.
[0111] Examples of thermal initiators include, but are not limited to, organic peroxy compounds and azobis(organonitrile) compounds. Examples of organic peroxy compounds that are useful as thermal initiators include, but are not limited to, peroxymonocarbonate esters, such as tertiary butylperoxy isopropyl carbonate; peroxydicarbonate esters such as di(2-ethylhexyl) peroxydicarbonate, di(secondary butyl) peroxydicarbonate and diisopropyl peroxydicarbonate; diacyperoxides such as 2,4-dichlorobenzoyl peroxide, isobutyryl peroxide, decanoyl peroxide, lauroyl peroxide, propionyl peroxide, acetyl peroxide, benzoyl peroxide and p-chlorobenzoyl peroxide; peroxyesters such as t-butylperoxy pivalate, t-butylperoxy octylate and t-butyl peroxyisobutyrate; methyl ethyl ketone peroxide, and acetylcyclohexane sulfonyl peroxide. In a non-limiting configuration, the thermal initiators used are those that do not discolor the resulting polymer. Non-limiting examples of azobis(organonitrile) compounds that can be used as the thermal initiators include azobis(isobutyronitrile), azobis(2,4-dimethylvaleronitrile) or a mixture thereof.
[0112] Examples of solvents that may be present in the formation of multiple layers of the photochromic-dichroic articles of the present invention, such as the photochromic-dichroic layer include, but are not limited to, those that will dissolve coating components that are compatible with the coating and elements and substrates and/or can ensure uniform coverage of the external surface to which the coating is applied. Examples of solvent include, but are not limited to, the following: propylene glycol acetate monomethyl ether and its derivatives (sold as DOWANOL® industrial solvents), acetone, amyl propionate, anisole, benzene, butyl acetate, cyclohexane, dialkyl ethers of ethylene glycol, e.g. diethylene glycol dimethyl ether and its derivatives (sold as CELLOSOLVE® industrial solvents), diethylene glycol dibenzoate, dimethyl sulfoxide, dimethyl formamide, dimethoxybenzene, ethyl acetate, isopropyl alcohol, methyl cyclohexanone, cyclopentanone, methyl ethyl ketone, methyl isobutyl ketone, methyl propionate, propylene carbonate, tetrahydrofuran, toluene, xylene, 2-methoxyethyl ether, 3-propylene glycol methyl ether, and mixtures thereof.
[0113] In another non-limiting embodiment, the photochromic-dichroic layer may include at least one conventional dichroic compound. Examples of suitable conventional dichroic compounds include, but are not limited to, azomethines, indigoids, thioindigoids, merocyanines, indans, quinophthalonic dyes, perylene, phthaloprines, triphenodiaxozines, indoloquinoxalines, imidazo-triazines, tetrazines, azo and (poly)azo dyes, benzoquinones , naphthoquinones, anthroquinone and (poly)anthroquinones, anthropyrimidinones, iodine and iodates. In another non-limiting embodiment, the dichroic material may include at least one reactive functional group that is capable of forming at least one covalent bond with other materials. With some embodiments, the dichroic material can be a polymerizable dichroic compound. Correspondingly, the dichroic material may include at least one group that is capable of being polymerized (i.e., "polymerizable group"). For example, while not limiting here, in a non-limiting embodiment, the dichroic compound may have at least one alkoxy group, a polyalkoxy group, alkyl, or polyalkyl substituent terminated with at least one polymerizable group.
[0114] If present and in accordance with some embodiments, the conventional dichroic compound may be present, in the photochromic-dichroic layer, in an amount of at least 0.001 weight percent and less than or equal to 5 (or 5.0 ) weight percent, such as from 0.01 weight percent to 4 (or 4.0) weight percent, from 0.1 weight percent to 1 (or 1.0) weight percent, wherein the weight percentages are in each case based on the total weight of the photochromic-dichroic layer.
[0115] With some embodiments, the photochromic-dichroic layer may include at least one conventional photochromic compound. As used herein, the term "conventional photochromic compound" includes both thermally reversible and non-thermally reversible photochromic compounds (such as actinic light, such as photoreversibles). Generally, although not limiting here, when two or more conventional photochromic materials are used in combination with each other or with a photochromic-dichroic compound, the various materials can be chosen to complement each other to produce a desired color or hue. For example, mixtures of photochromic compounds can be used in accordance with certain non-limiting embodiments herein to bind certain activated colors, such as one close to neutral gray or one close to neutral brown. See, for example, U.S. Patent No. US 5,645,767, column 12, line 66 through column 13, line 19, the description of which is specifically incorporated herein by reference, which describes the parameters defining neutral gray and neutral brown colors.
[0116] If present and in accordance with some embodiments, the conventional photochromic compound may be present, in the photochromic-dichroic layer, in an amount of at least 0.001 weight percent and less than or equal to 10.0 weight percent, such as from 0.01 weight percent to 5.0 weight percent, from 0.1 weight percent to 2.5 weight percent, in which case the weight percent are in each case on a weight basis total photochromic-dichroic layer.
[0117] According to some embodiments, the photochromic-dichroic layer is free of conventional photochromic compounds and/or conventional dichroic compounds.
[0118] The photochromic-dichroic layer may include one or more appropriate photochromic-dichroic compounds. Examples of photochromic-dichroic compounds from which the photochromic-dichroic compound can be selected include, but are not limited to those defined below:(PCDC-1) 3-phenyl-3-(4-(4-(3-piperidin) -4-yl-propyl)piperidino)phenyl)-13,13-dimethyl-3H,13-indeno[2',3':3,4]-naphtho[1,2-b]pyran; (PCDC-2) 3-phenyl-3-(4-(4-(3-(1-(2-hydroxyethyl)piperidin-4-yl)propyl)piperidine)phenyl)-13,13-dimethyl-3H,13H - indeno[2', 3':3,4]naphtho[1,2-b]pyran; (PCDC-3) 3-phenyl-3-(4-(4-(4-butyl-phenylcarbamoyl)-piperidin-1-yl)phenyl)-13,13-dimethyl-6-methoxy-7-(4-phenyl) -piperazin-1-yl)-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-4) 3-phenyl-3-(4-([1,4']bipiperidinyl-1'-yl)phenyl)-13,13-dimethyl-6-methoxy-7-([1,4'] bipiperidinyl-1'-yl)-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-5) 3-phenyl-3-(4-(4-phenyl-piperazin-1-yl)phenyl)-13,13-dimethyl-6-methoxy-7-(4-(4-hexylbenzoyloxy)-piperidin -1-yl)-3H, 13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-6) 3-phenyl-3-(4-(4-phenyl-piperazin-1-yl)phenyl)-13,13-dimethyl-6-methoxy-7-(4-(4'-octyloxy-biphenyl) -4-carbonyloxy)-piperidin-1-yl)-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-7) 3-phenyl-3-(4-(4-phenyl-piperazin-1-yl)phenyl)-13,13-dimethyl-6-methoxy-7-{4-[17-(1,5 -dimethylhexyl)-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren- 3-yloxycarbonyloxy]-piperidin-1-yl}-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-8) 3-phenyl-3-(4-{4-[17-(1,5-dimethylhexyl)-10,13-dimethyl-2,3,4,7,8,9,10, 11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yloxycarbonyloxy]-piperidin-1-yl}-phenyl)-13,13-dimethyl-6-methoxy-7 -{4-[17-(1,5-dimethylhexyl)-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17 - tetradecahydro-1H-cyclopenta[a]phenanthren-3-yloxycarbonyloxy]-piperidin-1-yl}-3H,13H-)indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-9) 3-phenyl-3-(4-(4-phenylpiperazin-1-yl)phenyl)-13,13-dimethyl-6-methoxy-7-(4-(4-(4'-octyloxy- biphenyl-4-carbonyloxy)phenyl)piperazin-1-yl)-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-10) 3-phenyl-3-(4-(4-phenyl-piperazin-1-yl)phenyl)-13,13-dimethyl-6-methoxy-7-(4-(4-(4-hexyloxyphenylcarbonyloxy) )phenyl)piperazin-1-yl)-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-11) 3-phenyl-3-(4-(4-phenyl-piperazin-1-yl)phenyl)-13,13-dimethyl-6-methoxy-7-(4-(4-(4-( 2-fluorobenzoyloxy)benzoyloxy)phenyl)piperazin-1-yl)-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-12) 3-phenyl-3-(4-(pyrrolidin-1-yl)phenyl)-13-hydroxy-13-ethyl-6-methoxy-7-(4-(4-(4-hexylbenzoyloxy)phenyl) )piperazin-1-yl)-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-13) 3-phenyl-3-(4-(pyrrolidin-1-yl)phenyl)-13,13-dimethyl-6-methoxy-7-(4-(4-hexylbenzoyloxy)benzoyloxy)-3H,13H -indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-14) 3-phenyl-3-(4-(pyrrolidin-1-yl)phenyl)-13,13-dimethyl-6-methoxy-7-(4-(4-(4-hexylbenzoyloxy)benzoyloxy)benzoyloxy )-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-15) 3-phenyl-3-(4-(4-methoxyphenyl)-piperazin-1-yl))phenyl)-13,13-dimethyl-6-methoxy-7-(4-(4-(3) -phenylprop-2-inoyloxy)phenyl)piperazin-1-yl)-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-16) 3-(4-Methoxyphenyl)-3-(4-(4-methoxyphenyl)piperazin-1-yl)phenyl)-13-ethyl-13-hydroxy-6-methoxy-7-(4-( 4-(4-hexylbenzoyloxy)phenyl)piperazin-1-yl)3H,13H-indene[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-17) 3-phenyl-3-{4-(pyrrolidin-1-yl)phenyl)-13-[17-(1,5-dimethylhexyl)-10,13-dimethyl-2,3,4 ,7,8,9,10,11,12,13,14,15, 16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yloxy]-13-ethyl-6-methoxy-7-(4 -[17-(1,5-dimethylhexyl)-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro- 1H-cyclopenta[a]phenanthren-3-yloxycarbonyloxy]-piperadin-1-yl)-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-18) 3-phenyl-3-(4-{4-[17-(1,5-dimethylhexyl)-10,13-dimethyl-2,3,4,7,8,9,10, 11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yloxycarbonyloxy]-piperidin-1-yl}-phenyl)-13-ethyl-13-hydroxy-6-methoxy -7-{4-[17-(1,5-dimethylhexyl)-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16 ,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yloxycarbonyloxy]-piperidin-1-yl}-)-3H,13H-indeno[2',3':3,4]naphtho[1,2-b ]pyran; (PCDC-19) 3-phenyl-3-{4-(pyrrolidin-1-yl)phenyl)-13,13-dimethyl-6-methoxy-7-(4-(4-(4-(3-phenyl-) 3-{4-(pyrrolidin-1-yl)phenyl}-13,13-dimethyl-6-methoxy-indeno[2',3':3,4]naphtho[1,2-b]pyran-7-yl )-piperadin-1-yl)oxycarbonyl)phenyl)phenyl)cabonyloxy)-3H,13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-20) 3-{2-Methylphenyl}-3-phenyl-5-(4-(4'-(trans-4-pentylcyclohexyl)-[1,1'-biphenyl]-4-ylcarboxamido)phenyl)- 3H-naphtho[2,1-b]pyran; (PCDC-21) 3-{4-[4-(4-Methoxy-phenyl)-piperazin-1-yl]-phenyl}-3-phenyl-7-(4,(4'-(trans-pentylcyclohexyl)- [1,1'-biphenyl]-4-ylcarboxamido)phenyl)-3H-naphtho[2,1-b]pyran; (PCDC-22) 3-{4-[4-(4-methoxy-phenyl)-piperazin-1-yl]-phenyl}-3-phenyl-7-(4-phenyl-(phen-1-oxy)carbonyl )-3H-naphtho[2,1-b]pyran; (PCDC-23) 3-{4-[4-(4-methoxy-phenyl)-piperazin-1-yl]-phenyl}-3-phenyl-7-(N-(4-((4-dimethylamino)phenyl) ) diazenyl)phenyl)carbamoyl-3H-naphtho[2,1-b]pyran; (PCDC-24) 2-phenyl-2-{4-[4-(4-methoxy-phenyl)-piperazin-1-yl]-phenyl}-benzofuro[3',2':7.8]benzo[b] ]pyran; (PCDC-25) 2-phenyl-2-{4-[4-(4-methoxy-phenyl)-piperazin-1-yl]-phenyl}-7-(4-(4'-trans-4-pentylcyclohexyl) -[1,1'-biphenyl]-4-ylcarboxamido)phenyl)-benzothieno[3',2':7.8]benzo[b]pyran; (PCDC-26) 7-{17-(1,5-dimethylhexyl)-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15, 16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yloxycarbonyloxy}-2-phenyl-2-(4-pyrrolidin-1-yl-phenyl)-6-methoxycarbonyl-2H-benzo[b]pyran; (PCDC-27) 2-phenyl-2-{4-[4-(4-methoxy-phenyl)-piperazin-1-yl]-phenyl}-9-hydroxy-8-methoxycarbonyl-2H-naphtho[1,2 -b]pyran; (PCDC-28) 2-phenyl-2-{4-[4-(4-methoxy-phenyl)-piperazin-1-yl]-phenyl}-9-hydroxy-8-(N-(4-butyl-phenyl) ))carbamoyl-2H-naphtho[1,2-b]pyran; (PCDC-29) 2-phenyl-2-{4-[4-(4-methoxy-phenyl)-piperazin-1-yl]-phenyl}-9-hydroxy-8-(4-(4'-(trans) -4-pentylcyclohexyl)-[1,1'-biphenyl]-4-ylcarboxamido)phenyl)-2H-naphtho[1,2-b]pyran; (PCDC-30) 1,3,3-Trimethyl-6'-(4-ethoxycarbonyl)-piperidin-1-yl)-spiro[indoline-2,3'-3H-naphtho[2,1-b][1 ,4]oxazine]; (PCDC-31) 1,3,3-Trimethyl-6'-(4-[N-(4-butylphenyl)carbamoyl]-piperidin-1-yl)-spiro[indoline-2,3'-3H-naphtho[ 2,1-b][1,4]oxazine]; (PCDC-32) 1,3,3-Trimethyl-6'-(4-(4-methoxyphenyl)piperazin-1-yl)-spiro[indoline-2,3'-3H-naphtho[2,1-b] [1,4]oxazine]; (PCDC-33) 1,3,3-Trimethyl-6'-(4-(4-(trans-4-pentylcyclohexyl)-[1,1'-biphenyl]-4-ylcarboxamido)phenyl)-spiro[indoline- 2,3'-3H-naphtho[2,1-b][1,4]oxazine]; (PCDC-34) 1,3,3,5,6-pentamethyl-7'-(4-(4'-(trans-4-pentylcyclohexyl)-[1,1'-biphenyl]-4-ylcarboxamido)phenyl- spiro[indoline-2,3'-3H-naphtho[2,1-b][1,4]oxazine]; (PCDC-35) 1,3-diethyl-3-methyl-5-methoxy-6'-( 4-(4'-Hexyloxy-biphenyl-4-carbonyloxy)-piperidin-1-yl)-spiro[indoline-2,3'-3H-naphtho[2,1-b][1,4]oxazine]; ( PCDC-36) 1,3-Diethyl-3-methyl-5-[4-(4-pentadeca-fluoroheptyloxy-phenylcarbamoyl)-benzyloxy]-6'-(4-(4'-hexyloxy-biphenyl-4-carbonyloxy) -piperidin-1-yl)-spiro[indoline-2,3'-3H-naphtho[2,1-b][1,4]oxazine]; (PCDC-37) 2-phenyl-2-{4-[ 4-(4-methoxy-phenyl)-piperazin-1-yl]-phenyl}-5-carbomethoxy-8-(N-(4-phenyl)phenyl)carbamoyl-2H-naphtho[1,2-b]pyran; (PCDC-38) 2-phenyl-2-{4-[4-(4-methoxy-phenyl)-piperazin-1-yl]-phenyl}-5-carbomethoxy-8-(N-(4-phenyl)phenyl ) carbamoyl-2H-fluoantheno[1,2-b]pyran; (PCDC-39) 2-phenyl-2-{4-[4-(4-methoxy-phenyl)-piperazin-1-yl]-phenyl}- 5-carbomethoxy-11-(4-{17-(1,5-dimethylhexyl)-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14, 15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yloxycar bonyloxy}phenyl)-2H-fluoanthene[1,2-b]pyran; (PCDC-40) 1-(4-carboxybutyl)-6-(4-(4-propylphenyl)carbonyloxy)phenyl)-3,3-dimethyl-6'-(4-ethoxycarbonyl)-piperidin-1-yl)- spiro[(1,2-dihydro-9H-dioxolane [4',5':6,7]indoline-2,3'-3H-naphtho[2,1-b][1,4]oxazine]; (PCDC -41) 1-(4-carboxybutyl)-6-(4-(4-propylphenyl)carbonyloxy)phenyl)-3,3-dimethyl-7'-(4-ethoxycarbonyl)-piperidin-1-yl)-spiro[ (1,2-dihydro-9H-dioxolane [4',5':6,7]indoline-2,3'-3H-naphtho[1,2-b][1,4]oxazine]; (PCDC-42 ) 1,3-diethyl-3-methyl-5-(4-{17-(1,5-dimethylhexyl)-10,13-dimethyl-2,3,4,7,8,9,10,11 ,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yloxycarbonyloxy}phenyl)-6'-(4-(4'-hexyloxy-biphenyl-4-carbonyloxy)-piperidin -1-yl)-spiro[indoline-2,3'-3H-naphtho[2,1-b][1,4]oxazine]; (PCDC-43) 1-butyl-3-ethyl-3-methyl- 5-methoxy-7'-(4-(4'-Hexyloxy-biphenyl-4-carbonyloxy)-piperidin-1-yl)-spiro[indoline-2,3'-3H-naphtho[1,2-b][ 1,4]oxazine]; (PCDC-44) 2-phenyl-2-{4-[4-(4-methoxy-phenyl)-piperazin-1-yl]-phenyl}-5-methoxycarbonyl-6-methyl- 2H-9-(4-(4-propylphenyl)carbonyloxy)phenyl)(1,2-dihydroxy) dro-9H-dioxolane[4',5':6,7]naphtho[1,2-b]pyran; (PCDC-45) 3-(4-Methoxyphenyl)-3-(4-(4-methoxyphenyl)piperazin-1-yl)phenyl)-13-ethyl-13-hydroxy-6-methoxy-7-(4-( 4-propylphenyl)carbonyloxy)phenyl)-3H, 13H-[1,2-dihydro-9H-dioxolane[4”,5”:6.7][indeno[2',3':3.4]]naphtho[ 1,2-b]pyran; (PCDC-46) 3-phenyl-3-(4-(4-methoxyphenyl)piperazin-1-yl)phenyl)-13-ethyl-13-hydroxy-6-methoxy-7-(4-(4-hexylphenyl) carbonyloxy)phenyl)-3H,13H-[1,2-dihydro-9H-dioxolane [4”,5”:5.6][indeno[2',3':3.4]]naphtho[1,2- b]pyran; (PCDC-47) 4-(4-((4-cyclohexylidene-1-ethyl-2,5-dioxopyrrolin-3-ylidene)ethyl)-2-thienyl)phenyl-(4-propyl)benzoate; (PCDC-48) 4-(4-((4-adamantan-2-ylidene-1-(4-(4-hexylphenyl)carbonyloxy)phenyl)-2,5-dioxopyrrolin-3-ylidene)ethyl)-2- thienyl)phenyl-(4-propyl)benzoate; (PCDC-49) 4-(4-((4-adamantan-2-ylidene-2,5-dioxo-1-(4-(4-(4-propylphenyl)piperazinyl)phenyl)pyrrolin-3-ylidene)ethyl )-2-thienyl)phenyl(4-propyl)benzoate; (PCDC-50) 4-(4-((4-adamantan-2-ylidene-2,5-dioxo-1-(4-(4-(4-propylphenyl)piperazinyl)phenyl)pyrrolin-3-ylidene)ethyl )-1-methylpyrrol-2-yl)phenyl(4-propyl)benzoate; (PCDC-51) 4-(4-((4-adamantan-2-ylidene-2,5-dioxo-1-(4-{17-(1,5-dimethyl-hexyl)-10,13-dimethyl- 2,3,4,7,8,9,10,11,12,13,14, 15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yloxycarbonyloxy}phenyl)pyrrolin-3-ylidene) ethyl)-1-methylpyrrol-2-yl)phenyl(4-propyl)benzoate; (PCDC-52) 4-(4-Methyl-5,7-dioxo-6-(4-(4-(4-propylphenyl)piperazinyl)phenyl)spiro[8,7a-dihydrothiafeno[4,5-f]isoindole - 8,2'-adamentane]-2-yl)phenyl(4-propyl)phenyl benzoate; (PCDC-53) N-(4-{17-(1,5-dimethylhexyl)-10,13-dimethyl-2,3,4,7, 8,9,10,11,12,13,14 ,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yloxycarbonyloxy}phenyl-6,7-dihydro-4-methyl-2-phenylspiro(5,6-benzo[b]thiophenedicarboxyimide-7,2 -tricyclo[3.3.1.1]decane); (PCDC-54) N-cyanomethyl-6,7-dihydro-2-(4-(4-(4-propylphenyl)piperazinyl)phenyl)-4-methylspiro(5,6) - benzo[b]thiophenedicarboxyimide-7,2-tricyclo[3.3.1.1]decane); (PCDC-55) N-phenylethyl-6,7-dihydro-2-(4-(4-(4-hexylbenzoyloxy)phenyl) piperazin-1-yl)phenyl-4-methylspiro(5,6-benzo[b]thiophenedicarboxyimide-7,2-tricyclo[3.3.1.1]decane); (PCDC-56) N-phenylethyl-6,7-dihydro- 2-(4-(4-(4-hexylbenzoyloxy)phenyl)piperazin-1-yl)phenyl-4-cyclopropyl spiro(5,6-benzo[b]thiophenedicarboxyimide-7,2-tricyclo[3.3.1.1]decane) ; (PCDC-57) N-phenylethyl-6,7-dihydro-2-(4-(4-(4-hexylbenzoyloxy)phenyl)piperazin-1-yl)phenyl-4-cyclopropyl spiro(5,6-benzo[ b] furodicarboxyimide-7,2-tricyclo[3.3.1.1]decane); (PCDC-58) N-cyanomethyl-6,7-dihydro-4-(4-(4-(4-hexylbenzoyloxy)fe nyl)piperazin-1-yl)phenyl-2-phenylspiro(5,6-benzo[b]thiophenedicarboxyimide-7,2-tricyclo[3.3.1.1]decane); (PCDC-59) N-[17-(1,5-dimethylhexyl)-10,13-dimethyl-2,3,4,7,8, 9,10,11,12,13,14,15, 16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yloxycarbonyl-6,7-dihydro-2-(4-methoxyphenyl)phenyl-4-methylspiro(5,6-benzo[b]thiophenedicarboxyimide-7,2 - tricyclo[3.3.1.1] decane); (PCDC-60) N-cyanomethyl-2-(4-(6-(4-butylphenyl)carbonyloxy-(4,8-dioxabicyclo[3.3.0]oct-2-yl))oxycarbonyl)phenyl-6,7- dihydro-4-cyclopropylspiro(5,6-benzo[b]thiophenedicarboxyimide-7,2-tricyclo[3.3.1.1]decane); (PCDC-61) 6,7-Dihydro-N-methoxycarbonylmethyl-4-(4-(6-(4-butylphenyl)carbonyloxy-(4,8-dioxabicyclo[3.3.0]oct-2-yl))oxycarbonyl) phenyl-2-phenylspiro(5,6-benzo[b]thiophenedicarboxyimide-7,2-tricyclo[3.3.1.1]decane); and (PCDC-62) 3-phenyl-3-(4-pyrrolidinylphenyl)-13,13-dimethyl-6-methoxy-7-(4-(4-(4-(4-(6-(4-(4)) -(4-onylphenylcabonyloxy)phenyl)oxycarbonyl)phenoxy)hexyloxy)phenyl)piperazin-1-yl)indeno[2',3':3,4]naphtho[1,2-b]pyran.
[0119] With some additional embodiments, the photochromic-dichroic compound of the photochromic-dichroic articles of the present invention can be chosen from the following: (PCDC-a1) 3,3-Bis(4-methoxyphenyl)-10-[4 -(4-(trans-4-pentylcyclohexyl)benzamide)phenyl]-13,13-dimethyl-12-bromo-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2- b]pyran; (PCDC-a2) 3,3-Bis(4-methoxyphenyl)-10-[4-((4-(trans-4-pentylcyclohexyl)phenoxy)carbonyl)phenyl]-6,13,13-trimethyl-3,13 -dihydro-indene[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-a3) 3-(4-Fluorophenyl)-3-(4-piperidinephenyl)-10-[4-(4-(4-(trans-4-pentylcyclohexyl)phenyl)benzamide)phenyl]-6-trifluoromethyl- 11,13,13-trimethyl-3,13-dihydro-indeno[2',3': 3,4]naphtho[1,2-b]pyran; (PCDC-a4) 3,3-Bis(4-methoxyphenyl)-10-[4-(4-(trans-4-pentylcyclohexyl)benzamide)phenyl]-5,7-difluoro-13,13-dimethyl-3, 13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-a5) 3-(4-Methoxyphenyl)-3-(4-piperidinephenyl)-10-[4-(4-(4-(trans-4-pentylcyclohexyl)phenyl)benzamide)phenyl]-5,7- difluoro-13,13-dimethyl-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-a6) 3-(4-Methoxyphenyl)-3-(4-morpholinophenyl)-10-[4-(4-(4-(trans-4-pentylcyclohexyl)phenyl)benzamide)phenyl]-5,7- difluoro-13,13-dimethyl-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-a7) 3-(4-Fluorophenyl)-3-(4-piperidinephenyl)-10-[4-((4-(trans-4-pentylcyclohexyl)phenoxy)carbonyl)phenyl]-12-bromo-5, 7-difluoro-13,13-dimethyl-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-a8) 3-Phenyl-3-(4-piperidinophenyl)-10-[4-(4-(4-(trans-4-pentylcyclohexyl)phenyl)benzamide)phenyl]-12-bromo-5,7- difluoro-13,13-dimethyl-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-a9) 3-Phenyl-3-(4-piperidinophenyl)-10-[4-((4-(trans-4-pentylcyclohexyl)phenoxy)carbonyl)phenyl]-12-bromo-5,7-difluoro- 13,13-dimethyl-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-a10) 3-(4-Fluorophenyl)-3-(4-piperidinephenyl)-10-[4-(4-(4-(trans-4-pentylcyclohexyl)phenyl)benzamido)phenyl]-12-bromo- 13,13-dimethyl-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-a11) 3,3-Bis(4-methoxydinophenyl)-10-[4-(4-(4-(trans-4-pentylcyclohexyl)phenyl)benzamido)phenyl]-12-bromo-6,7-dimethoxy -11,13,13-trimethyl-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-a12) 3,3-Bis(4-methoxyphenyl)-10-[4-(4-(4-(trans-4-pentylcyclohexyl)phenyl)benzamido)phenyl]-6-trifluoromethyl-12-bromo-13 ,13-dimethyl-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-a13) 3,3-Bis(4-methoxyphenyl)-10,12-bis[4-(4-(4-(trans-4-pentylcyclohexyl)phenyl)benzamido)phenyl]-6-trifluoromethyl-13, 13-dimethyl-3,13-dihydro-indene[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-a14) 3,3-Bis(4-methoxyphenyl)-10-[4-(4-(4-(trans-4-pentylcyclohexyl)phenyl)benzamido)phenyl]-5,7-difluoro-13,13 - dimethyl-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-a15) 3,3-Bis(4-methoxyphenyl)-10-[4-(4-(4-(trans-4-pentylcyclohexyl)phenyl)benzamido)phenyl]-6-trifluoromethyl-13,13-dimethyl -3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-a16) 3,3-Bis(4-methoxyphenyl)-10-[4-(4-(4-(trans-4-pentylcyclohexyl)phenyl)benzamido)phenyl]-5,7-difluoro-12-bromo -13,13-dimethyl-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-a17) 3-(4-Fluorophenyl)-3-(4-morpholinophenyl)-10-[4-(4-(4-(trans-4-pentylcyclohexyl)phenyl)benzamido)phenyl]-6-trifluoromethyl- 13-methyl-13-butyl-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-a18) 3-(4-Fluorophenyl)-3-(4-morpholinophenyl)-10-[4-(4-(4-(trans-4-pentylcyclohexyl)phenyl)benzamido)phenyl]-5,7- difluoro-12-bromo-13,13-dimethyl-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-a19) 3-Phenyl-3-(4-methoxyphenyl)-10-[4-(4-(4-(trans-4-pentylcyclohexyl)phenyl)benzamido)phenyl]-6-trifluoromethyl-13,13- dimethyl-3,13-dihydro-indene[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-a20) 3-Phenyl-3-(4-morpholinophenyl)-10-[4-(4-(4-(trans-4-pentylcyclohexyl)phenyl)benzamido)phenyl]-6-trifluoromethyl-13,13- dimethyl-3,13-dihydro-indene[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-a21) 3,3-Bis(4-fluorophenyl)-10-[4-(4-(4-(trans-4-pentylcyclohexyl)phenyl)benzamido)phenyl]-6-trifluoromethyl-12-bromo-13 ,13-dimethyl-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-a22) 3,3-Bis(4-fluorophenyl)-10-[4-(4-(4-(trans-4-pentylcyclohexyl)phenyl)benzamido)phenyl]-6-trifluoromethyl-13,13-dimethyl -3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-a23) 3-(4-Methoxyphenyl)-3-(4-butoxyphenyl)-10-[4-(4-(4-(trans-4-pentylcyclohexyl)phenyl)benzamido)phenyl]-6-trifluoromethyl- 13,13-dimethyl-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-a24) 3-(4-Fluorophenyl)-13,13-dimethyl-3-(4-morpholinophenyl)-10-(4-(4'-(trans-4-pentylcyclohexyl)-[1,1'- biphenyl]-4-ylcarboxamido)phenyl)-6-(trifluoromethyl)-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-a25) 3-(4-Butoxyphenyl)-3-(4-fluorophenyl)-13,13-dimethyl-10-(4-(4'-(trans-4-pentylcyclohexyl)-[1,1'- biphenyl]-4-ylcarboxamido)phenyl)-6-(trifluoromethyl)-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-a26) 3-(4-(4-(4-Methoxyphenyl)piperazin-1-yl)phenyl)-13,13-dimethyl-10-(4-(4'-(trans-4-pentylcyclohexyl)- [1,1'-biphenyl]-4-ylcarboxamido)phenyl)-3-phenyl-6-(trifluoromethyl)-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2- b]pyran; (PCDC-a27) 3-(4-Butoxyphenyl)-3-(4-fluorophenyl)-13,13-dimethyl-10-(4-(((trans,trans-4'-pentyl-[1,1'- bi(cyclohexan)]-4-yl)oxy)carbonyl)phenyl)-6-(trifluoromethyl)-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran ; (PCDC-a28) 3-(4-Fluorophenyl)-13,13-dimethyl-10-(4-(4'-(trans-4-pentylcyclohexyl)-[1,1'-biphenyl]-4-ylcarboxamido)phenyl )-3-(4-butoxyphenyl)-6-(trifluoromethyl)-3,13-dihydro indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-a29) 3-(4-Methoxyphenyl)-13,13-dimethyl-10-(4-(4'-(trans-4-pentylcyclohexyl)-[1,1'-biphenyl]-4-ylcarboxamido)phenyl )-3-(4-(trifluoromethoxy)phenyl)-6-(trifluoromethyl)-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-a30) 3,3-Bis(4-hydroxyphenyl)-10-[4-(4-(4-(trans-4-pentylcyclohexyl)phenyl)benzamido)phenyl]-6-trifluoromethyl-13,13-dimethyl -3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-a31) 3-(4-morpholinophenyl)-3-phenyl-13,13-dimethyl-10-(4-(4'-(trans-4-pentylcyclohexyl)-[1,1'-biphenyl]-4 - ylcarboxamido)phenyl)-6-(trifluoromethyl)-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-a32) 3-(4-morpholinophenyl)-3-(4-fluorophenyl)-13,13-dimethyl-(4-(4'-(trans-4-pentylcyclohexyl)-[1,1'-biphenyl] -4-ylcarboxamido)phenyl)-6-(trifluoromethyl)-3,13-dihydro-indene[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-a40) 12-Bromo-3-(4-butoxyphenyl)-3-(4-fluorophenyl)-13,13-dimethyl-10-(4-((4'-(trans-4-pentylcyclohexyl)-[ 1,1'-biphenyl]-4-carbonyl)oxy)benzamido)-6-(trifluoromethyl)-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran ; (PCDC-a41) 3-(4-Butoxyphenyl)-5,7-dichloro-11-methoxy-3-(4-methoxyphenyl)-13,13-dimethyl-10-(4-(4'-(trans-4) - pentylcyclohexyl)-[1,1'-biphenyl]-4-ylcarboxamido)phenyl)-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-a42) 3-(4-Butoxyphenyl)-3-(4-fluorophenyl)-13,13-dimethyl-10-(4-((4'-(trans-4-pentylcyclohexyl)-[1,1') -biphenyl]-4-carbonyl)oxy)benzamido)-6-(trifluoromethyl)-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-a43) 5,7-Dichloro-3,3-bis(4-hydroxyphenyl)-11-methoxy-13,13-dimethyl-10-(4-(4'-(trans-4-pentylcyclohexyl)-[ 1,1'-biphenyl]-4-ylcarboxamido)phenyl)-3,13-dihydro-indene[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-a44) 6,8-Dichloro-3,3-bis(4-hydroxyphenyl)-11-methoxy-13,13-dimethyl-10-(4-(4'-(trans-4-pentylcyclohexyl)-[ 1,1'-biphenyl]-4-ylcarboxamido)phenyl)-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-a45) 3-(4-Butoxyphenyl)-5,8-difluoro-3-(4-fluorophenyl)-13,13-dimethyl-10-(4-(4'-(trans-4-pentylcyclohexyl)- [1,1'-biphenyl]-4-ylcarboxamido)phenyl)-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-a46) 3-(4-Butoxyphenyl)-3-(4-fluorophenyl)-13,13-dimethyl-10-(4-(4'-(trans-4-pentylcyclohexyl)-[1,1'- biphenyl]-4-carbonyl)piperazin-1-yl)-6-(trifluoromethyl)-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-a47) 3-(4-Morpholinophenyl)-3-(4-methoxyphenyl)-10,7-bis[4-(4-(4-(trans-4-pentylcyclohexyl)phenyl)benzamido)phenyl]-5 -fluoro-13,13-dimethyl-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-a48) 3-(4-Morpholinophenyl)-3-(4-methoxyphenyl)-10-[4-(4-(4-(trans-4-pentylcyclohexyl)phenyl)benzamido)-2-(trifluoromethyl)phenyl ]-13,13-dimethyl-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-a49) 3,3-Bis(4-methoxyphenyl)-10-[4-(4-(4-(trans-4-pentylcyclohexyl)phenyl)benzamido)-2-(trifluoromethyl)phenyl]-13,13 -dimethyl-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-a50) 3-(4-Morpholinophenyl)-3-(4-methoxyphenyl)-10-[4-(4-(4-(trans-4-pentylcyclohexyl)phenyl)benzamido)-2-(trifluoromethyl)phenyl ]-13,13-dimethyl-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-a51) 3,3-Bis(4-methoxyphenyl)-13,13-dimethyl-10-(2-methyl-4-(trans-4-((4'-((trans-4-pentylcyclohexyl)biphenyl) -4-yloxy)carbonyl)cyclohexanecarboxamido)phenyl)-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-a52) 3-(4- (4-(4-Butylphenyl)piperazin-1-yl)phenyl)-3-(4-methoxyphenyl)-13,13-dimethyl-10-(4-(4'-(trans-4-pentylcyclohexyl)biphenyl-4 -ylcarboxamido)-2-(trifluoromethyl)phenyl)-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-a53) 3-(4- (4-(4-Butylphenyl)piperazin-1-yl)phenyl)-3-(4-methoxyphenyl)-13,13-dimethyl-10-(2-methyl-4-(4'-(trans-4-pentylcyclohexyl) )biphenyl-4-ylcarboxamido)phenyl)-7-(4-(4-(trans-4-pentylcyclohexyl)benzamido)phenyl)-3,13-dihydro-indeno[2',3':3,4]naphtho[ 1,2-b]pyran; (PCDC-a54) 3-(4-Methoxyphenyl)-13,13-dimethyl-7,10-bis(4-(4'-(trans-4-pentylcyclohexyl)biphenyl-4- ylcarboxamido)phenyl)-3-phenyl-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-a55) 3-p-Tolyl-3- (4-methoxyphenyl)-6-methoxy-13,13-dimethyl-7-(4'-(trans,trans-4'-pentylbi(cyclohexane-4) - )carbonyloxy)biphenylcarbonyloxy)-10-(4-(4'-(trans-4-pentylcyclohexyl)biphenyl-4-ylcarboxamido)phenyl)-3,13-dihydro-indeno[2',3':3,4] naphtho[1,2-b]pyran; (PCDC-a56) 10-(4-(((3S,8S,9S,10R,13R,14S,17R)-10,13-Dimethyl-17-((R)-6-methylheptan-2-yl)- 2,3,4,7,8,9,10,11, 12,13,14, 15, 16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yloxy)carbonyl)piperazin-1-yl) -3-(4-methoxyphenyl)-13,13-dimethyl-3-(4-morpholinophenyl)-3,13-dihydro-indene[2',3':3,4]naphtho[1,2-b]pyran ; (PCDC-a57) 6-Methoxy-3-(4-methoxyphenyl)-13,13-dimethyl-3-(4-((S)-2-methylbutoxy)phenyl)-10-(4-(4'-( trans-4-pentylcyclohexyl)biphenyl-4-ylcarboxamido)phenyl)-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-a58) 6-Methoxy-3-(4-methoxyphenyl)-13,13-dimethyl-3-(4-((S)-2-methylbutoxy)phenyl)-7-(4'-(trans,trans -4'-pentylbi(cyclohexane-4-)carbonyloxy)biphenylcarbonyloxy)-10-(4-(4'-(trans-4-pentylcyclohexyl)biphenyl-4-ylcarboxamido)phenyl)-3,13-dihydro-indeno[2] ',3':3,4]naphtho[1,2-b]pyran; and (PCDC-a59) 6-Methoxy-3-(4-methoxyphenyl)-13,13-dimethyl-3-(4-((S)-2-methylbutoxy)phenyl)-10-(4-(((3R) ,3aS,6S,6aS)-6-(4'-(trans-4-pentylcyclohexyl)biphenylcarbonyloxy)hexahydrofuro[3,2-b]furan-3-yloxy)carbonyl)phenyl)-3,13-dihydro-indeno[ 2',3':3,4]naphtho[1,2-b]pyran.
[0120] With some additional embodiments, the photochromic-dichroic compounds of the photochromic-dichroic articles of the present invention can be chosen from the following: (PCDC-b1) 3-{4-fluorophenyl)-3-(4-(piperidin) -1yl)phenyl}-13-methoxy-13-ethyl-6-methoxy-7-(4'-((4-(trans-4-pentylcylohexyl)benzoyl)oxy)-[1,1'-biphenyl]-4 -carbonyloxy)-3,13-dihydro-indeno[2'm3':3,4]naphtho[1,2-b]pyran;(PCDC-b2) 3-(4-fluorophenyl)-3-(4-( piperidin-1-yl)phenyl)-13-methoxy-13-ethyl-6-methoxy-7-(4-(4'-(4-(trans-4-pentylcyclohexyl)-[1,1'-biphenyl]- 4-carbonyloxy)benzoyloxy))-3,13-dihydro-indeno[2',3,:3,4]naphtho[1,2-b]pyran; (PCDC-b3) 3,3-bis(4-methoxyphenyl)-13-methoxy-13-ethyl-6-methoxy-7-{4'-((4-(trans-4-pentylcyclohexyl)benzoyl)oxy)- (1,1-biphenyl]-4-carbonyloxy)-3,13-dihydro-indeno[2'3':3.4]naphtho[1,2-b]pyran; (PCDC-b4) 3,3-bis(4-methoxyphenyl)-13-methoxy-13-ethyl-6-methoxy-7-{4-(4'-(4-(trans-4-pentylcyclohexyl)-[1] ,1'-biphenyl]-4-carbonyloxy)benzoyloxy))-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-b5) 3-(4-fluorophenyl)-3-(4-(piperidin-1-yl)phenyl)-13-methoxy-13-ethyl-6-methoxy-7-(4'-(4-( trans-4-pentylcyclohexyl)-[1,1'-biphenyl]-4-carbonyloxy))-4-carbonyloxy))-3,13-dihydro-indeno[2',3':3,4]naphtho[1, 2-b]pyran; (PCDC-b6) 3,3-bis(4-methoxyphenyl)-13-methoxy-13-ethyl-6-methoxy-7-((trans,trans)-4'-pentyl-[1,1'-bi( cyclohexane)]-4-carbonyloxy)-3,13-dihydro-indene[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-b7) 3,3-bis(4-fluorophenyl)-13-methoxy-13-ethyl-6-methoxy-7-(4'-(4'-(trans-4-pentylcyclohexyl)-[1,1] '-biphenyl]-4-carbonyloxy)-[1,1'-biphenyl]-4-carbonyloxy)-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b] pyran; (PCDC-b8) 3-(4-Methoxyphenyl)-3-(4-(piperidin-1-yl)phenyl)-13-methoxy-13-ethyl-6-methoxy-7-(4'-(4'- (trans-4-pentylcyclohexyl)-[1,1'-biphenyl]-4-carbonyloxy)-[1,1'-biphenyl]-4-carbonyloxy)-3,13-dihydro-indeno[2',3'; 3,4]naphtho[1,2-b]pyran; (PCDC-b9) 3-(4-Methoxyphenyl)-3-(4-morpholinophenyl)-13-methoxy-13-ethyl-6-methoxy-7-(4'-(4'-(trans-4-pentylcyclohexyl) -{1,1'-biphenyl]-4-carbonyloxy)-[1,1'-biphenyl]-4-carbonyloxy)-3,13-dihydro-indeno[2',3':3,4]naphtho[1 ,2-b]pyran; (PCDC-b10) 3-{4-{4-Methoxyphenyl)piperazin-1-yl)-3-phenyl-13-methoxy-13-ethyl-6-methoxy-7-(4'(4'(2-hydroxyethoxy) )benzoyloxy}-[1,1'-biphenyl]-4-carbonyloxy)-[1,1'-biphenyl)-4-carbonyloxy)-3,13-dihydro-indeno[2',3:;3,4] naphtho[1,2-b]pyran; (PCDC-b11) 3,3-bis(4-methoxyphenyl}-13-methoxy-13-ethyl-8-methoxy-7-{3-phenylpropioloyloxy)-3,13-dihydro-indeno[2',3': 3;4]naphtho[1,2-b]pyran; (PCDC-b12) 3,3-bis(4-methoxyphenyl)-13-methoxy-13-ethyl-6-methoxy-7-(2-methyl-4-(4'-(trans-4-pentylcyclohexyl)-[ 1,1'-biphenyl]-4-ylcarboxamido)phenyl)-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-b13) 3,3-bis(4-methoxyphenyl)-6,13-dimethoxy-7-(4-{4-(trans,trans-4!-pen+yl-[1,1'-bi( cyclohexane)]-4-carbonyloxy)phenyl)piperazin-yl)-13-trifluoromethyl-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-b14) 3,3-bis(4-methoxyphenyl)-6-methoxy-7-{4-{4-{trans,trans-4'-pentyl-[1,1'-bi(cyclohexane)]4 - carbonyloxy)phenyl)piperazin-lyl)-13-hydroxy-13-trifluoromethyl-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-b15) 3,3-bis(4-methoxyphenyl)-6,7-di(4-(4-(trans,trans-4'-pentyl-[1,1'-bi(cyclohexane)}-4 -carbonyloxy)phenyl)piperazin-lyl)-13-methoxy-13-trifluoromethyl-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-b16) 3,3-bis(4-methoxyphenyl)-6-methoxy-7-{4-(4-((trans,trans)-4'-pentyl-[1,1'-bicyclohexane)]- 4-carbonyloxy)phenyl)piperazin-1-yl)-13-fluoro-13-trifluoromethyl-3,13-dihydro-indeno[2',3:3,4]naphtho[1,2-b]pyran; (PCDC-b17) 3-(4-fluorophenyl)-3-(4-(piperidin-1-yl)phenyl)-7-(2-methyl-4-(4'-(trans-4-pentylcyclohexyl)-[ 1,1'-biphenyl]-4-ylcarboxamido)phenyl)-11-trifluoromethyl-13,13-dimethyl-3,13-dihydro-indeno[2',3:3,4]naphtho[1,2-b] pyran; (PCDC-b18) 3-(4-Butoxyphenyl)-3-(4-methoxyphenyl)-7-(2-methyl-4-(4'-(trans-4-pentylcyclohexyl)-[1,1'-biphenyl] ~4-ylcarboxamido)phenyl)-11-trifluoromethyl-13,13-dimethyl-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-b19) 3-(4-(N-morpholinyl)phenyl)-3-phenyl-7-(4-(4'-(trans-4-pentylcyclohexyl)-[1,1'-biphenyl]-4- ylcarboxamido)phenyl)-10,12-difluoro-13,13-dimethyl-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-b20) 3-(4-Fluorophenyl)-3-{4-(piperidin-1-yl)phenyl)-7-(4-{4'-(trans-4-pentylcyclohexyl)-[1,1' -biphenyl]-4-ylcarboxamido)phenyl)-10,12-difluoro-13,13-dimethyl-3,13-dihydro-indene[2',3':3,4]naphtho[1,2-b]pyran ; (PCDC-b21) 3,3-bis(4-methoxyphenyl)-6-methoxy-7-(2-methyl-4-(4'-(trans-4-pentylcyclohexyl)-[1,1'-biphenyl]-4 - ylcarboxamido)phenyl)-10,12-di(trifluoromethyl)-13,13-dimethyl-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-b22) 3,3-bis(4-methoxyphenyl)-6-methoxy-7-(4-(4'-(trans-4-pentylcyclohexyl)-[1,1'-biphenyl]-4-ylcarboxamido) phenyl)-10,12-di(trifluoromethyl)-13,13-dimethyl-3,13-dihydro-indene[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-b23) 3,3-bis(4-methoxyphenyl)-6-methoxy-7-(2-methyl{-4-{4-(4-(trans-4-pentylcyclohexyl)benzamido)phenyl)phenyl)- 10,12-di(trifluoromethyl)-13,13-dimethyl-3,13-dihydro-indene [2',3':3,4]naphtho[1,2-b]pyran; (PCDC-b24) 3,3-bis(4-methoxyphenyl)-6-methoxy-7-(2-methyl-4-(4-(4-(trans-4-pentylcyclohexyl)benzamido)benzamido)phenyl}-10 ,12-di{trifluoromethyl}-13,13-dimethyl-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-b25) 3-( 4-methoxyphenyl)-3-phenyl-6-methoxy-7-(2-methyl-4-(4'-(trans-4-pentylcyclohexyl)-[1,1'-biphenyl]-4-ylcarboxamido}phenyl)- 10,12-di(trifluoromethyl)-13,13-dimethyl-3,13-dihydro-indeno[2',3':3,4}naphtho[1,2-b]pyran; (PCDC-b26) 3- (4-methoxyphenyl)-3-phenyl-6-methoxy-7-(2-methyl-4-{4-{4-(trans-4-pentylcyclohexyl)benzamido)phenyl)phenyl)-10,12-di(trifluoromethyl) )-13,13-dimethyl-3,13-dihydro-indene [2',3':3,4]naphtho[1,2-b]pyran; (PCDC-b27) 3-(4-Methoxyphenyl)-3-phenyl-6-methoxy-7-(2-methyl-4-(4-((trans,trans)-4'-pentyl-[1,1') -bi(cyclohexane)]-4-carboxamido]benzamido)phenyl)-10,12-di(trifluoromethyl)13,13-dimethyl-3,13-dihydro-indeno[2',3':3,4]naphtho[ 1,2-b]pyran; (PCDC-b28) 3-{4-methoxyphenyl)-3-phenyl-6-methoxy-7-(2-methyl-4-(trans-4-(((4'-( trans-4-pentylcyclohexyl)-[1,1'-biphenyl]-4-yl)oxy)carbonyl)cyclohexanecarboxamido)phenyl)-10,12-di(trifluoromethyl)-13,13-dimethyl-3,13-dihydro- indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-b29) 3-(4-N-morpholinylphenyl)-3-phenyl-6-methoxy-7-(2-methyl-4-(4'-(trans-4-pentylcyclohexyl)-[1,1'- biphenyl-4-ylcarboxamido)phenyl)-10,12-di[trifluoromethyl]-13,13-dimethyl-3,13-dihydro-indene[2',3':3,4]naphtho[1,2-b] pyran; (PCDC-b30) 3-(4-N-morpholinophenyl)-3-phenyl-6-methoxy-7-(2-methyl-4-{trans-4-(((4'-(trans-4-pentylcyclohexyl)) -[1,1'-biphenyl]-4-yl)oxy)carbonyl)cyclohexanecarboxamido(phenyl)-10,12-di(trifluoromethyl)-13,13-dimethyl-3,13-dihydro-indeno[2', 3': 3,4]naphtho[1,2-b]pyran; (PCDC-b31) 3-(4-N-morpholinophenyl)-3-phenyl-6-methoxy-7-{4-(4'-(trans-4-pentylcyclohexyl)-[1,1'-biphenyl]4- ylcarboxamido)phenyl)-10,12-di(trifluoromethyl)-13,13-dimethyl-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-b32) 3-(4-N-morpholinophenyl)-3-(4-methoxyphenyl)-6-methoxy-7-(2-methyl-4-(4,-{trans-4-pentylcyclohexyl)-[1 ,1'-biphenyl]-4-ylcarboxamido)phenyl)-10,12-di(trifluoromethyl)-13,13-dimethyl-3,13-dihydro-indene[2',3':3,4]naphtho[1 ,2-b]pyran; (PCDC-b33) 3-{4-N-morpholinophenyl)-3-(4-methoxyphenyl)-6-methoxy-7-(4-(4'-{trans-4-pentylcyclohexyl)-[1,1'- biphenyl]-4-ylcarboxamido)phenyl)-10,12-di(trifluoromethyl)-13,13-dimethyl-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b ] pyran; (PCDC-b34) 3-phenyl-3-{4-(piperidin-1-yl)phenyl-6-methoxy-7-(4-(4-(trans-4-pentylcyclohexyl)benzamido)-2-(trifluoromethyl) phenyl)-10,12-di(trifluoromethyl)-13,13-dimethyl-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-b35) 3,3-bis(4-fluorophenyl)-6-methoxy-7-(4-(4'-(trans-4-pentylcyclohexyl)[1,1'-biphenyl]-4-ylcarboxamido)- phenyl)-10,12-di(trifluoromethyl)-13,13-dimethyl-3,13-dihydro-indene[2',3,:3,4]naphtho{1,2-b]pyran; (PCDC-b36) 3,3-bis(4-fluorophenyl)-6-methoxy-7-(trans-4-(4'-(trans-4-pentylcyclohexyl)-[1,1'-biphenyl]-4- yloxycarbonyl)cyclohexanecarbonyloxy)-10,12-di(trifluoromethyl])-13,13-dimethyl-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDG-b37) 3-{4-(pipersdin-1-yl)phenyl)-3-phenyl-6-methoxy-7-{trans-4-{4'-{trans-4-pentylcyclohexyl)-[1, 1'-biphenyl]-4-yloxycarbonyl}cyclohexanecarbonyloxy)-10,12-di(trifluoromethyl)-13,13-dimethyl-3,13-dihydro-indene[2',3':3,4]naphtho[1, 2-b]pyran; (PCDC-b38) 3-(4-(N-morpholino)phenyl)-3-phenyl-6-methoxy-7-(trans-4-(4'-(trans-4-pentylcyclohexyl)-[1,1' -biphenyl]-4-yloxycarbonyl)cyclohexanecarbonyloxy)-10,12-di(trifluoromethyl)-13,13-dimethyl-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2- b]pyran; (PCDC-b39) 3-(4-(N-morpholino)phenyl)-3-phenyl-6-methoxy-7-{4-(4-(trans,trans)-4'-pentyl-[1,1' -bi(cyclohexane)]-4-carbonyloxy)phenyl)benzoyloxy)-10,12-di(trifluoromethyl)-13,13-dimethyl-3,13-dihydro-indeno[2',3':3,4]naphtho [1,2-b]pyran; (PCDC-b40) 313-Bis(4-methoxyphenyl)-6-methoxy-7-(4-(4-(trans, trans)-4'-pentyl-[1,1'-bi(cyclohexane)]-4 -carbonyloxy)phenyl)benzoyloxy)-10,12-di(trifluoromethyl)-13,13-dimethyl-3,13-dihydro-indeno[2',3':3,4]mphato[1,2-b]pyran ; (PCDC-b41 ) 3-(4-fluorophenyl)-3-(4-(piperidin-1-yl)phenyl)-6-methoxy-7-{4-(4-({trans,trans)-4'- pentyl-1,1'-bi(cyclohexane)]-4-carbonyloxy)phenyl)benzoyloxy)-10,12-di(trifluoromethyl)-13,13-dimethyl-3,13-dihydro-indene[2',3' :3,4}naphtho[1,2-b]pyran; (PCDC-b42) 3-(4-fluorophenyl)-3-(4-(piperidin-1-yl)phenyl)-6-methoxy-7-(trans-4-(4'-(trans-4-pentylcyclohexyl)) -[1,1'-biphenyl]-4-yloxycarbonyl)cyclohexanecarbonyloxy}-10,12-di(trifluoromethyl)-3,13-dimethyl-3,13-dihydro-indene [2',3':3,4] naphtho[1,2-b]pyran; (PCDC-b43) 3,3-bis(4-methoxyphenyl)-6,13-dimethoxy-7-(trans-4-(4'-(trans-4-pentylcyclohexyl)) -(1,1'-biphenyl]-4-yloxycarbonyl)cyclohexanecarbonyloxy}-13-ethyl-3,13-dihydro-indeno[2',3';3,4]naphtho[1,2-b]pyran; ( PCDC-b44) 3,3-bis(4-methoxyphenyl)-6-methoxy-7-(4-(4-(trans,trans-4'-pentyl-[1,1'-bi(cyclohexane)]-4 - carbonyloxy)phenyl)piperazin-1-yl)-10,12-di(trifluoromethyl)-13,13-dimethyl-3,13-dihydro-indene[2',3':3,4]naphtho[1,2] - b]pyran; (PCDC-b45) 3,3-bis(4-hydroxyphenyl)-6-methoxy-7-(4-(4-(trans, trans-4'-pentyl-[1,1'-bi (cyclohexane)]-4-carbonyloxy)phenyl)piperazin-1-yl)-10,12-di(trifluoromethyl)-13,13-dimethyl-3,13-dihydro-indeno[2',3':3,4 ]naphtho]1,2-b]pyran; (PCDC-b46) 3,3-bis(4-fluorophenyl)-6-methoxy-7-{4-(4-(trans, trans-4'-pentyl-[ 1.1'-bi( cyclohexane)]-4-carbonyloxy)phenyl)piperazin-1-yl)-10,12-di(trifluoromethyl)-1,313-dimethyl-3,13-dihydro-indene[2',3':3,4]naphtho[ 1,2-b]pyran; (PCDC-b47) 3-(4-Methoxyphenyl)-3-(4-N-morpholinophenyl)-6-methoxy-7-(4-(4-{trans,trans-4'-pentyl-[1,1' -bi(cyclohexane}]-4-carbonyloxy)phenyl)piperazin-1-yl}-10,12-di(trifluoromethyl)-13,13-dimethyl-3,13-dihydro-indene[2',3':3 :4]naphtho[1,2-b]pyran; (PCDC-b48) 3,3-bis(4-methoxyphenyl)-6-methoxy-7-(4-(4-(trans-4-(4-( trans-4-pentylcyclohexyl)-[1,1'-biphenyl]-4-yloxycarbonyl)cyclohexanecarbonyloxy}phenyl)piperazin-1-yl)-10,12-di(trifluoromethyl)-13,13-dimethyl-3,13- dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-b49) 3,3-bis(4-methoxyphenyl)-6-methoxy-7-(4-{ 4-(trans-4-(4-(trans-4-penylcyclohexyl)-phenyloxycarbonyl)-cyclohexanecarbonyloxy)phenyl)piperazin-1-yl)-10,12-di(trifluoromethyl)-13,13-dimethyl-3,13 -dihydro-indene[2',3,:3,4]naphtho[1,2-b]pyran; (PCDC-b50) 3,3-bis(4-methoxyphenyl)-7-(4-(4-( trans-4-pentylcyclohexyl)phenoxycarbonyl)phenyl)-11-methyl-13,13-dimethyl-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran; ( PCDC-b51) 3-(4-fluorophenyl)-3-(4-{piperidin-1-yl)phenyl)-6-methyl-7-(4-(4'-(trans-4-pe ntilcyclohexyl}-[1,1'-biphenyl]-4-ylcarboxamido)phenyl)-11-trifluoromethyl-13,13-dimethyl-3,13-dihydro-indene[2',3':3,4]naphtho[1] ,2-b]pyran; (PCDC-b52) 3,3-bis(4-hydroxyphenyl)-6-methyl-7-(4-(4'-(trans-4-pentylcyclohexyl)-[1,1'-biphenyl]-4-ylcarboxamido) phenyl)-11-trifluoromethyl-13,13-dimethyl-3,13-dihydro-indene[2',3':3,4]naphtho[1,2-b]pyran; (PCDC-b53) 3,3-bis(4-methoxyphenyl)-6-methoxy-7-(4-(4-(trans, trans-4'-pentyl-[1,1'-bi(cyclohexane}]- 4-carbonyloxy)phenyl)piperazin-1-yl)-11-trifluoromethyl-13,13-dimethyl-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran ; (PCDC-b54) 3-{4-{4-methoxyphenyl)piperazin-1-yl)-3-phenyl-6-methoxy-7-{4-((4-(trans-4-propylcyclohexyl)phenoxy)carbonyl phenyloxycarbonyl)-13,13-dimethyl-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran; and (PCDC-b55) 3,3-bis(4-methoxyphenyl)-7(4-([1,1':4',1”-terphenyl]4-ylcarbamoyl)piperazin-1-yl)-6-13 -dimethoxy-13-trifluoromethyl-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran.
[0121] More generally, the photochromic-dichroic compounds of the photochromic-dichroic articles of the present invention include: (a) at least one photochromic group (PC), which may be chosen from, for example, pyrans, oxazines, and fulgides , and (b) at least one extender or group attached to the photochromic group. Such photochromic-dichroic compounds are described in detail in US Patent No.: US 7,342,112 B1, column 5, line 35 through column 14, line 54; and Table 1, the cited portions being incorporated herein by reference. Other suitable photochromic compounds and reaction schemes for their preparation can be found in U.S. Patent No. 7,342,112 B1, at column 23, line 37 through column 78, line 13, the cited portions of said patent being incorporated herein by reference.
[0122] Non-limiting examples of thermally reversible photochromic pyrans from which the photochromic group (PC) of the photochromic-dichroic compound can be chosen include, benzopyrans, naphthopyrans, e.g. naphtho[1,2-b]pyrans, naphtho[2] ,1-b]pyrans, indene-fused naphthopyrans, such as those described in the US patent 5,645,767 and fused heterocyclic naphthopyrans such as those described in US Patent Nos.: US 5,723,072, US 5,698,141, US 6,153,126, and US 6,022,497, which are incorporated herein by reference; spirofluorene[1,2-b]pyran, such as spiro-9-fluorene[1,2-b]pyran; phenanthropyran, quinopyran, fluoroantenopyran, spiropyran, for example, spiro(benzindoline)naphthopyran, spiro(indoline)benzopyran, spiro(indoline)naphthopyran, spiro(indoline)quinopyran and spiro(indoline)pyran. More specific examples of naphthopyrans and the complementary organic photochromic substances are described in Patent No. US 5,658,501, which is incorporated herein by reference herein. Spiro(indoline)pyrans are also described in the text, “Techniques in Chemistry,” Volume III, “Photochromism,” Chapter 3, Glenn H. Brown, Editor, John Wilei and Sons, Inc., New York, 1971, which is incorporated herein by reference.
[0123] Non-limiting examples of photochromic oxazines from which the PC group may be chosen include benzoxazines, naphthoxaxins and spiro-oxazines, e.g. spiro(indoline)naphthoxazines, spiro(indoline)pyridobenzoxazines, spiro(benzindoline)pyridobenzoxazines, spiro(benzindoline )naphthoxazines, spiro(indoline)benzoxazines, spiro(indoline)fluoranthenoxazine, and spiro(indoline)quinoxazine. Non-limiting examples of photochromic fulgides from which PC can be chosen include: fulgimides, and the 3-furyl and 3-thienol fulgides and fulgimides, which are described in U.S. Patent No. US 4,931,220 (which are specifically incorporated herein by reference) and mixtures of any of the aforementioned photochromic materials/compounds.
[0124] According to some embodiments, the first and second photochromic-dichroic compounds can each independently include at least two photochromic compounds (PCs), in each case the PCs can be linked together via linking group substituents on the individual PCs. For example, PCs can be polymerizable photochromic groups or photochromic groups that are adapted to be compatible with a host material (“compatible photochromic group”). Non-limiting examples of polymerizable photochromic groups from which PC can be chosen and which are useful in conjunction with the various non-limiting configurations disclosed herein are described in US patent 6,113,814, which is specifically incorporated herein by reference herein. Non-limiting examples of compatibilized photochromic groups from which PC may be chosen and which are useful in conjunction with various non-limiting configurations disclosed herein in US Patent 6,555,028, which is hereby specifically incorporated by reference herein.
[0125] Other suitable photochromic groups and complementary photochromic groups are described in US Patent Nos.: US 6,080,338 in column 2, line 21 through column 14, line 43; US 6,136,968 in column 2, line 43 through column 20, line 67; US 6,296,785 in column 2, line 47 through column 31, line 5; US 6,348,604 in column 3, line 26 through column 17, line 15; US 6,353,102 in column 1, line 62 through column 11, line 64; and US 6,630,597 in column 2, line 16 through column 16, line 23; the aforementioned patent disclosures are incorporated herein by reference.
[0126] With some embodiments of the present invention, the first photochromic-dichroic compound includes at least a first photochromic portion (or first/the PC group/moiety) and the second photochromic-dichroic compound includes at least a second photochromic portion (or second /a group/PC portion) and each first photochromic portion and each second photochromic portion are in each case independently selected from indene-fused naphthopyrans, naphtho[1,2-b]pyrans, naphtho[2,1-b]pyrans, spirofluoroene [1,2-b]pyrans, phenanthropyrans, quinolinopyrans, fluoroantenopyrans, spiropyrans, benzoxazines, naphthoxazine, spiro(indoine)naphthoxaxins, spiro(indoline)pyridobenzoxazines, spiro(indoline)fluoranthenoxazines, spiro(indoline)quinoxazines, fulgides, fulgimides, diarylenes , diaryl alkylenes, diaryl alkenylenes, thermally reversible photochromic compounds, and non-thermally reversible photochromic compounds, and mixtures thereof.
[0127] The photochromic-dichroic compound can be present in the photochromic-dichroic layer in amounts (or proportions) such as the photochromic-dichroic article exhibits desired optical properties, such as a desired level of photochromic activity and a desired level of dichroic activity . The particular amounts of the photochromic-dichroic compound that are present in the photochromic-dichroic layer are not critical, with some embodiments providing that at least a sufficient amount in each case is present to produce the desired effect. For the purpose of non-illustrative illustration, the amounts of the photochromic-dichroic compound that are present in the photochromic-dichroic layer may depend on a variety of factors, such as, but not limited to, the absorption characteristics of the particular photochromic-dichroic compound, the color and intensity of the particular photochromic-dichroic compound during photochromic activation, the level of dichroic activity of the particular photochromic-dichroic compound during dichroic activation, and the method used to incorporate the particular photochromic-dichroic compound within the photochromic-dichroic layer private.
[0128] The photochromic-dichroic layer of the photochromic-dichroic articles of the present invention may, with some embodiments, include one or more photochromic-dichroic compounds, in an amount of from 0.01 to 40 percent by weight, or from 0.05 to 15, or 0.1 to 5 percent by weight, based on the weight of the photochromic-dichroic layer.
[0129] The photochromic-dichroic compound of the photochromic-dichroic articles of the present invention can be prepared according to art-recognized methods. With some embodiments, the photochromic-dichroic compound can be prepared in accordance with the description provided in column 35, line 28 through column 66, line 60 of U.S. Patent No. US 7,256,921, the disclosure of which is incorporated herein by reference.
[0130] The photochromic-dichroic layer, with some embodiments, may include a single layer or multiple layers each including a photochromic-dichroic compound which may be the same or different. The photochromic-dichroic layer can be formed by art-recognized methods including, but not limited to: lamination, such as from one or more plastic sheets or films; in-mold forming, such as in-mold coating; film casting; and coating methods. With some embodiments, the photochromic-dichroic layer is formed from the photochromic-dichroic coating composition. The photochromic-dichroic coating composition may be a curable photochromic-dichroic coating composition, which is curable upon exposure to, for example, ambient temperature, as in the case of two-component coating compositions; elevated temperatures (e.g., 150°C to 190°C for 5 to 60 minutes), as in the case of thermally cured coating compositions; or actinic radiation, as in the case of ultraviolet light curable coating compositions.
[0131] The photochromic-dichroic layer typically includes an organic matrix, such as a thermoplastic organic matrix and/or a crosslinking organic matrix. At least a portion of the organic matrix of the photochromic-dichroic layer can in some embodiments include anisotropic materials, such as liquid crystal materials, additives, oligomers, and/or polymers, as will be discussed in detail below. In addition to or alternatively to an organic matrix, the photochromic-dichroic layer may include an inorganic matrix, including, for example, silane bonds, siloxane bonds, and/or titanate bonds. The organic matrix of the photochromic-dichroic layer includes, for example, acrylate residues (or monomer units) and/or methacrylate residues; vinyl waste; ether bonds, sulphide bonds, including monosulphide bonds and/or polysulphide bonds; carboxylic ester bonds, carbonate bonds (e.g. -O-C(O)-O-) urethane bonds (e.g. -N(H)-C(O)-O-); and/or thiourethane bonds (e.g. -N(H)-C(O)-S-).
[0132] The photochromic-dichroic layer can be of any suitable thickness. With some embodiments, the photochromic-dichroic layer is 0.5 to 50 microns thick, such as 1 to 45 microns, or 2 to 40 microns, or 5 to 30 microns, or 10 to 25 microns.
[0133] With some embodiments, the photochromic-dichroic layer of the photochromic-dichroic article additionally includes a phase-separated polymer that includes: a matrix phase that is at least partially ordered; and a guest phase that is at least partially ordered. The "guest" phase of the first photochromic-dichroic layer includes the photochromic-dichroic compound, and the photochromic-dichroic compound is at least partially aligned with at least a portion of the "guest" phase of said photochromic-dichroic layer.
[0134] In accordance with further embodiments of the present invention, the photochromic-dichroic layer further includes an interpenetrating polymer network that includes: an anisotropic material that is at least partially ordered, and a polymeric material. The anisotropic material of the photochromic-dichroic layer includes the photochromic-dichroic compound, and the photochromic-dichroic compound is at least partially aligned with at least a portion of the anisotropic material of the photochromic-dichroic layer.
[0135] With some embodiments of the present invention, the photochromic-dichroic layer further includes an anisotropic material. As used herein the term "anisotropic" means having at least one property that differs in value when measured in at least one different direction. Consequently, "anisotropic materials" are materials that have at least one property that differs in value when measured in at least one different direction. Non-limiting examples of anisotropic materials that may be included in the photochromic-dichroic layer include, but are not limited to, those such as liquid crystal materials as further described herein with respect to the optional alignment layer of the photochromic articles of the present invention.
[0136] With some embodiments, the anisotropic material of the photochromic-dichroic layer includes a liquid crystal material. Classes of liquid crystal materials include, but are not limited to, liquid crystal oligomers, liquid crystal polymers, mesogenic compounds, and combinations thereof.
[0137] With some embodiments, the photochromic-dichroic layer includes: (i) includes liquid crystal oligomers and/or polymers prepared at least in part from the monomeric mesogenic compounds; and/or (ii) mesogenic compounds, in each case as described in table 1 of U.S. Patent No. US 7,910,019 B2, at columns 4390 thereof, the disclosure of which is incorporated herein by reference.
[0138] In accordance with some embodiments of the present invention, the photochromic-dichroic compound of the photochromic-dichroic layer is at least partially aligned by interaction with the anisotropic material of (or present within) that layer, which itself partially ordered. . For the purpose of non-limiting example, at least a portion of the photochromic-dichroic compound may be aligned so that the long geometric axis of the photochromic-dichroic compound in the dichroic state is essentially parallel to the general direction of the anisotropic material of the photochromic-dichroic layer. Additionally, although not required, the photochromic-dichroic compound may be bonded to or reacted with at least a portion of at least one partially ordered anisotropic material from the photochromic-dichroic layer.
[0139] Methods of ordering, or order introduction, of the anisotropic material of the photochromic-dichroic layer include, but are not limited to, exposing the anisotropic material to at least one of a magnetic field, an electric field, a linearly polarized ultraviolet radiation , linearly polarized infrared radiation, linearly polarized visible radiation, and a shear force. Alternatively or additionally, the anisotropic material may be at least partially ordered by aligning at least a portion of the anisotropic material with another material or structure. For example, anisotropic material can be at least partially ordered by aligning the anisotropic material with an alignment layer (or an orientation facility) such as, but not limited to, those of the alignment layer as described in further detail here below. .
[0140] By ordering at least a portion of the anisotropic material, it is possible to align, at least partially, a portion of the photochromic-dichroic compound that is contained within or otherwise connected to the anisotropic material of the photochromic-dichroic layer. Although not required, the photochromic-dichroic compound can be at least partially aligned while in an activated state. With some embodiments, the ordering of the anisotropic material and/or the alignment of the photochromic-dichroic compound may occur before, during, or after application or formation of the photochromic-dichroic layer.
[0141] The photochromic-dichroic compound and related anisotropic material can each independently be aligned and ordered during the application or formation of the photochromic-dichroic layer. For the purpose of non-limiting illustration the photochromic-dichroic layer can be applied using a coating technique that introduces a shear force to the anisotropic material during application, such as the anisotropic material becomes at least partially ordered, generally parallel, to the direction of the applied shear force. For non-limiting purposes of illustration, a solution or mixture (optionally in a solvent or vehicle) including, for example, the photochromic-dichroic compound and the anisotropic material can be coated onto the substrate such that the shear forces are introduced to the materials being applied due to the relative movement of the substrate surface with respect to the materials being applied. An example of a coating process that can introduce at least sufficient shear force is a fabric coating process. Shear forces can induce at least a portion of the anisotropic material to be ordered in a general direction that is substantially parallel to the direction of surface movement. As discussed above, by ordering at least a portion of the anisotropic material in this way, at least a portion of the photochromic-dichroic compound can be aligned. In addition, and optionally, by exposing at least a portion of the photochromic-dichroic compound to actinic radiation during the screen coating process, so as to convert the photochromic-dichroic compound into an activated, at least partially aligned, state of the compound. photochromic-dichroic while in the activated state can also be achieved.
[0142] The photochromic-dichroic compound and the anisotropic material can be aligned and ordered after applying the respective photochromic-dichroic layer. For the purpose of non-limiting illustration, a solution or mixture of the photochromic-dichroic compound and the anisotropic material (optionally in a solvent or carrier) may be spin-coated on at least a portion of the substrate (or one or more substrates). more layers previously applied). Thereafter, at least a portion of the anisotropic material may be ordered, for example, by exposing the anisotropic material to a magnetic field, an electric field, linearly polarized ultraviolet radiation, linearly polarized infrared radiation, linearly polarized visible radiation, and/or a shear force. Alternatively or additionally, the anisotropic material may be at least partially ordered by aligning it with another material or structure, such as an alignment layer.
[0143] The photochromic-dichroic compound and related anisotropic material can each independently be aligned and ordered for application of the photochromic-dichroic layer. For the purpose of non-limiting illustration, a solution or mixture (optionally in a solvent or vehicle) of the photochromic-dichroic compound and the anisotropic material may be applied onto an ordered polymeric sheet to form a layer thereon. Thereafter, at least a portion of the anisotropic material may be aligned with the underlying ordered polymeric sheet. The polymer sheet may subsequently be applied onto the substrate of the photochromic-dichroic article, for example, by art recognized lamination or bonding methods. Alternatively, the ordered photochromic-dichroic layer may be transferred from the polymeric sheet to/on an adjacent structure (such as the substrate or one or more photochromic-dichroic layers) by art-recognized methods, such as hot stamping.
[0144] With some embodiments, the photochromic-dichroic layer may include a phase-separated polymer that includes: a matrix phase; and a guest phase distributed in a matrix phase. The matrix phase may independently include an at least partially ordered liquid crystal polymer. The invited phase can independently include the at least partially ordered anisotropic material and at least a portion of the photochromic-dichroic compound, which can be at least partially aligned through interaction with the at least partially ordered anisotropic material.
[0145] For the purpose of non-limiting illustration, with some embodiments, a phase-separating polymer system including, a matrix phase-forming material that includes the liquid crystal material, and a guest phase-forming material that includes the anisotropic material and the photochromic-dichroic compound, is applied over the substrate (or one or more previously applied layers). Upon application of the phase-separating polymer system, at least a portion of the matrix phase liquid crystal material and at least a portion of the guest phase anisotropic material are at least partially ordered, so that at least at least a portion of the photochromic-dichroic compound is aligned with at least a portion of at least one partially ordered anisotropic material from the guest phase. Methods of ordering the matrix phase-forming material and the invited phase-forming material of the phase-separating polymer system include, but are not limited to, exposing the applied layer to at least one of: a magnetic field, a field electric, a linearly polarized infrared radiation, linearly polarized ultraviolet radiation, linearly polarized visible radiation, and a shear force. Alternatively or additionally, ordering the matrix phase-forming material and the guest phase-forming material may include aligning the same through interaction with an underlying alignment layer, as described in further detail herein. The above non-limiting illustration is also applicable to the photochromic-dichroic layer.
[0146] After sorting the matrix phase forming material and the guest phase forming material, the guest phase forming material can be separated from the matrix phase forming material through polymerization-induced phase separation and/or separation solvent-induced phase. Although the separation of the matrix phase and guest phase forming materials are described herein in relation to the guest phase forming material separated from the matrix phase forming material, it should be the matrix phase forming material, it should be appreciated that this language is intended to cover any separation between the two phase-forming materials. That is, this language is intended to cover the separation of the guest phase-forming material from the matrix phase-forming material, and separation of the matrix-phase-forming material from the guest-phase-forming material, as well as, simultaneous separation of both phase-forming materials and any combination thereof.
[0147] According to some embodiments, the matrix phase-forming material may include a liquid crystal material chosen from liquid crystal monomers, liquid crystal prepolymers, and liquid crystal polymers. Each guest phase forming material may, with some embodiments, independently include a liquid crystal material chosen from liquid crystal mesogens, liquid crystal monomers, and liquid crystal polymers and prepolymers. Examples of said materials include, but are not limited to, those described above, and further described herein with respect to the optional alignment layer.
[0148] With some embodiments, the phase-separating polymer system may include, a mixture of a matrix phase-forming material that includes a liquid crystal monomer, an invited phase-forming material that includes the liquid crystal mesogens, and the photochromic-dichroic compound. With such a non-limiting embodiment, inducing the invited phase-forming material to separate from the matrix phase-forming material, may include polymerization-induced phase separation. Typically, the matrix phase liquid crystal monomer may be polymerized and thereby separated from at least a portion of the liquid crystal mesogens of the guest phase forming material. Examples of polymerization methods include, but are not limited to, photoinduced polymerization and thermally induced polymerization.
[0149] With some additional embodiments, each polymeric phase separation system may include, a mixture of a matrix phase forming material that includes a liquid crystal monomer, a guest phase forming material that includes a liquid crystal monomer of low viscosity having a different functionality from the matrix phase liquid crystal monomer, and the photochromic-dichroic compound. As used herein, the term "low viscosity liquid crystal monomer" refers to a liquid crystal monomer mixture or solution that is free-flowing at room temperature. Typically, inducing the guest phase-forming material to separate from the matrix phase-forming material includes polymerization-induced phase separation. For example, at least a portion of the matrix phase liquid crystal monomer may be polymerized under conditions that do not induce the invited phase liquid crystal monomer to polymerize. During polymerization of the matrix phase-forming material, the invited phase-forming material typically separates from the matrix phase-forming material. Then, the liquid crystal monomer of the guest phase forming material can be polymerized in a separate polymerization process.
[0150] The polymeric phase separation system may include, with some embodiments, a solution in at least one common solvent of a matrix phase-forming material that includes a liquid crystal polymer, a guest phase-forming material that includes a liquid crystal polymer which is different from the liquid crystal polymer of the matrix phase-forming material, and the photochromic-dichroic compound. Inducing the invited phase-forming material to separate from the matrix phase-forming material forming the material typically includes solvent-induced phase separation. Typically, at least a portion of the common solvent is evaporated from the mixture of the liquid crystal polymers, thereby inducing two phases to separate from each other.
[0151] With some additional embodiments, the first and second photochromic-dichroic layers can each independently include an interpenetrating polymer network. The at least partially ordered anisotropic material and a polymeric material may form an interpenetrating polymer network in which at least a portion of the polymeric material interpenetrates with at least a portion of the at least partially ordered anisotropic material. As used herein, the term "interpenetrating polymer network" means a captured combination of polymers, at least one of which is cross-linked, that are bonded together. Thus, as used herein, the term interpenetrating polymer network includes semi-interpenetrating polymer networks. For example, see L.H. Sperling, “Introduction to Physical Polymer Science”, John Wilei & Sons, New York (1986) on page 46. Additionally, at least a portion of at least one partially aligned photochromic-dichroic compound may be at least partially aligned with at least one partially aligned photochromic-dichroic compound. partially ordered anisotropic material. Furthermore, the polymeric material can be isotropic or anisotropic, providing that, in general, the first or second photochromic-dichroic layer is anisotropic. The methods of forming such first and second photochromic-dichroic layers are described in more detail here below.
[0152] According to some embodiments, the anisotropic material can be adapted to allow the photochromic-dichroic compound to switch from a first state to a second state at a desired rate. In general, conventional photochromic compounds can undergo a transformation from one isometric form to another in response to actinic radiation, with each of the isomeric forms having a characteristic absorption spectrum. The photochromic-dichroic compounds in the photochromic-dichroic articles of the present invention undergo a similar isomeric transformation. Without pretending to be bound by any theory, the rate or speed at which this isomeric transformation (and the reverse transformation) occurs depends in part on the properties of the local environment surrounding the particular photochromic-dichroic compound (which may be referred to as the “host ”). Although not limiting here, it is believed that based on manual evidence the transformation rate of the photochromic-dichroic compound depends, in part, on the flexibility of the host chain segments, and more particularly, on the mobility or viscosity of the host segments. host chain. Accordingly, it is believed, without wishing to be bound by any theory, that the rate of transformation of the photochromic-dichroic compound is generally rapid in hosts having more flexible chain segments in hosts having rigid or hard chain segments. As such, and in accordance with some embodiments, when the anisotropic material is a host, the anisotropic material can be adapted to allow the photochromic-dichroic compound to transform between various isomeric states at desired rates. For example, the anisotropic material can be adapted by adjusting the molecular weight and/or the crosslink density of the anisotropic material.
[0153] With some embodiments, the photochromic-dichroic layer includes a phase-separated polymer that includes a matrix phase including a liquid crystal polymer, and the guest phase distributed within the matrix phase. The invited phase may include the anisotropic material. Typically, a majority of the first or second photochromic-dichroic compound may be contained within the respective invited phase of the phase-separated polymer. As previously discussed, because the rate of transformation of the photochromic-dichroic compound depends, in part, on the host in which it is contained, the rate of transformation of the photochromic-dichroic compound substantially depends on the properties of the guest phase, with some embodiments.
[0154] With some embodiments, and as discussed in further detail here, the photochromic-dichroic articles of the present invention may include an alignment layer (also referred to as an alignment or orientation facility). With some additional embodiments, the photochromic-dichroic article may include an alignment layer interposed between the first surface of the substrate and the photochromic-dichroic layer, on which the alignment layer and the photochromic-dichroic layer at least partially abut (or contact) each other. The alignment layer may also be referred to here as an orientation facility. The photochromic-dichroic composite of the photochromic-dichroic layer can be at least partially aligned by interaction with the base alignment layer.
[0155] With some embodiments, the fixed polarized layer is interposed between the first surface of the substrate and the photochromic-dichroic layer, in this case, the optional alignment layer is interposed between the fixed polarized layer and the photochromic-dichroic layer, and the alignment layer and the photochromic-dichroic layer abut, at least partially, against each other. With some embodiments, the photochromic-dichroic layer is interposed between the first surface of the substrate and the fixed polarized layer, in which case, the alignment layer is optionally interposed between the first surface of the substrate and the photochromic-dichroic layer, and the layer of alignment and the photochromic-dichroic layer abuts, at least partially, against each other.
[0156] Referring to Figure 6, the photochromic-dichroic article 3 includes an alignment layer 45 that is interposed between the substrate 11 and the photochromic-dichroic layer 30. With a non-limiting embodiment of the present invention, represented by Figure 6, the fixed polarized layer 24 is interposed between the first surface 15 of the substrate 12, and the photochromic-dichroic layer 30 and, correspondingly, the alignment layer 45 is interposed between the polarized layer 24 and the photochromic-dichroic article 30. In addition , alignment layer 45 is in close relationship with at least an overlapping portion of photochromic-dichroic layer 30, and correspondingly, photochromic-dichroic layer 30 is in close relationship with at least a portion of underlying alignment layer 45 As shown in Figure 5, alignment layer 45 and attached polarized layer 24 are in at least partially close relationship. With some embodiments, one or more additional layers may be interposed between the attached polarized layer 24 and the alignment layer 45.
[0157] The photochromic-dichroic article 3 also includes a primary layer 48 which, with non-limiting embodiments shown in Figure 6, is interposed between the first surface 15 of the substrate 12 and the fixed polarized layer 24. The photochromic-dichroic article 3 6 also includes a topsheet 51 residing over the photochromic-dichroic layer 30. With some embodiments, one or more additional layers (not shown) may be interposed between the topsheet 51 and the photochromic-dichroic layer 30.
[0158] As used herein, the term "alignment layer" means a layer that can facilitate the placement of one or more other structures that are exposed, directly and/or indirectly, to at least a portion thereof. As used herein the term "order" means bringing about an appropriate arrangement or position, such as an alignment with another structure or material, or by some other force or effect. Thus, as used herein, the term "order" encompasses both contact methods of ordering a material, such as by alignment with another structure or material, and non-contacting methods of ordering a material, such as by exposure. to an external force or effect. The term order also encompasses combinations of contact and non-contact methods.
[0159] For example, the photochromic-dichroic compound that is at least partially aligned by interaction with the alignment layer can be at least partially aligned, such that the longitudinal geometric axis of the photochromic-dichroic compound in the activated state is essentially parallel in at least a first general direction of the alignment layer. With some embodiments, the photochromic-dichroic compound that is at least partially aligned by interacting with the alignment layer is bound to or reacted with the alignment layer. As used herein with reference to the order or alignment of a material or structure, the term "general direction" refers to the predominant arrangement or orientation of the material, compound or structure. Furthermore, it will be appreciated by those skilled in the art that a material, compound or structure may have a general direction even if there is some variation within the arrangement of the material, compound or structure, providing that the material, compound or structure has at least one predominant arrangement.
[0160] The alignment layer may, with some embodiments, have at least a first general direction. For example, an alignment layer may include a first ordered region having a first general direction and at least one second ordered region adjacent to the first ordered region having a second general direction that is different from the first general direction. Furthermore, an alignment layer may have a plurality of regions, each of which has an overall direction that is the same or different from the remaining regions so as to form a desired pattern or desired design. The alignment layer can include, for example, a coating including at least a partially ordered alignment means, an at least partially ordered polymer sheet, an at least partially treated surface, Langmuir-Blodgett films, and combinations thereof.
[0161] The alignment layer may include, with some embodiments, a coating that at least partially includes an ordered alignment means. Examples of suitable alignment means that can be used in conjunction with the first and second alignment layers include, but are not limited to, photo-orientation materials, slide-orientation materials, and liquid crystal materials. Methods of ordering at least a portion of the alignment means are described here below in further detail.
[0162] The alignment medium of an alignment layer may be a liquid crystal material, and the alignment layer may be referred to as a liquid crystal alignment layer. Liquid crystal materials, due to their structure, are generally capable of being ordered or aligned in a general direction. More specifically, because liquid crystal molecules have disk or rod-like structures, a rigid long axial axis, and strong dipoles, liquid crystal molecules can be ordered or aligned through interaction with an external force or other structure, such as the long axis of molecules taken in an orientation that is generally parallel to a common axis. For example, it is possible to align the molecules of a liquid crystal material with a magnetic field, an electric field, linearly polarized infrared radiation, linearly polarized ultraviolet radiation, linearly polarized visible radiation, or shear forces. It is also possible to align liquid crystal molecules with an oriented surface. For example, liquid crystal molecules can be applied to a surface that has been oriented, for example, by polishing, grooving, or photoalignment methods and subsequently aligned so that the long axis of each of the liquid crystal molecules takes an orientation that is generally parallel to the general orientation direction of the surface. Examples of suitable liquid crystal materials for use as an 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 partially polymerized materials.
[0163] Classes of liquid crystal monomers that are suitable for use in conjunction with the first and second alignment layers include, but are not limited to, mono- as well as multi-functional liquid crystal monomers. The liquid crystal monomers may, with some embodiments, be selected from cross-linked liquid crystal monomers, such as photocross-linked liquid crystal monomers. As used herein, the term "photocrosslinked" means a material, such as a monomer, a prepolymer, or a polymer, that can be crosslinked upon exposure to actinic radiation. For example, photocrosslinked liquid crystal monomers include, but are not limited to, those liquid crystal monomers that are crosslinkable on exposure to ultraviolet and/or visible radiation, either with or without the use of polymerization initiators.
[0164] Examples of cross-linked liquid crystal monomers that can be independently included in the first and second alignment layers include, but are not limited to, liquid crystal monomers having functional groups chosen from acrylate, methacrylates, allyl, ethers of allyl, alkynes, amino, anhydrides, epoxides, hydroxides, isocyanate, blocked isocyanate, siloxane, thiocyanates, thiols, urea, vinyl, vinyl ethers, and mixtures thereof. Examples of photocrosslinked liquid crystal monomers that may be included in the first and second alignment layers include, but are not limited to, liquid crystal monomers having functional groups chosen from acrylate, methacrylates, alkynes, epoxides, thiols, and mixtures. of the same.
[0165] 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 side chain and prepolymers and liquid crystal polymers. -polymers. With the main-chain liquid crystal polymers and prepolymers, the disk-like or rod-like liquid crystal mesogens are primarily located within the polymer backbone. Additionally, liquid crystal polymers or prepolymers can be cross-linked, and even photo-crosslinkable.
[0166] Examples of liquid crystal polymers or prepolymers that may be included in the alignment layer include, but are not limited to, main-chain or side-chain polymers or prepolymers having functional groups chosen from acrylate , methacrylates, allyl, allyl esters, alkynes, amino, anhydride, epoxides, hydroxides, isocyanate, blocked isocyanate, siloxanes, thiocyanates, thiols, urea, vinyl, divinyl ethers, and mixtures thereof. Examples of photocrosslinkable liquid crystal polymers and prepolymers which may be included in the alignment layer include, but are not limited to, polymers and prepolymers having functional groups chosen from acrylate, methacrylates, alkynes, epoxides, thiols, and mixtures thereof.
[0167] 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 classes of liquid crystal mesogens that can be included in the alignment layer include, but are not limited to, columatic (or rod-like) liquid crystal mesogens and discotic (or disk-like) liquid crystal mesogens.
[0168] Examples of photo-orientation materials that can be included in the alignment layer include, but are not limited to, photo-oriented polymer network. More specific examples of photo-oriented polymer networks include, but are not aligned to, azobenzene derivatives, cinnamic acid derivatives, coumarin derivatives, ferulic acid derivatives, and polyimides. With some embodiments, the alignment layer may include at least one ordered partially photo-oriented polymer network chosen from azobenzene derivatives, cinnamic acid derivatives, coumarin derivatives, ferulic acid derivatives, and/or polyimides. Examples of cinnamic acid derivatives that can be independently included in the alignment layer include, but are not limited to, polyvinyl cinnamate and polyvinyl esters of paramethoxycinnamic acid.
[0169] As used herein, the term "polished orientation material" means a material that can be at least partially ordered by polishing at least a portion of a surface of the material with another appropriately textured material. For example, the polished guide material can be polished with a fabric of the appropriate texture or with a velvet brush. Examples of polished guide materials that may be included in the alignment layer include, but are not limited to, (poly)imidated, (poly)siloxane, (poly)acrylate, and (poly)coumarins. With some embodiments, the lining layer may include a polyimide, and the lining layer may be polished with a cotton or terry fabric so that it is at least partially arrayed on a portion of the surface of the lining layer.
[0170] With some embodiments, the alignment layer may include at least one partially ordered polymeric lamina. For example, a polyvinyl alcohol sheet can be at least partially ordered by stretching (e.g., uniaxial stretching) of the sheet, and then the stretched sheet can be bonded to or on at least a portion of a surface of the optical substrate. to form the orientation facility. Alternatively, the ordered polymer sheet may be made by a method which at least partially orders the polymer chains during manufacture, for example by extrusion. Furthermore, at least one partially ordered sheet of polymer may be formed by casting or otherwise forming a sheet of a liquid crystal material and then at least partially ordered of the sheet, for example, but exposing the sheet to a field magnetic field, an electric field, and/or a shear force. Still further, the at least partially ordered polymer sheet may be formed, for example, by casting and then at least partially ordered by exposure to linearly polarized ultraviolet radiation.
[0171] The alignment layer of the photochromic-dichroic articles of the present invention may include an at least partially treated surface. As used herein, the term "treated surface" refers to at least a portion of a surface that has been physically altered to create at least one ordered region over at least a portion of the surface. Examples of treated surfaces include, but are not limited to, polished surfaces, etched surfaces, and inlaid surfaces. Furthermore, the treated surfaces can be patterned, for example using a photolithography process or an interferography process. With some embodiments, the surface of the alignment layer may be a treated surface selected from, for example, chemically etched surfaces, plasma etched surfaces, nano-engraved surfaces (such as etched surfaces using a scanning tunnel microscope or an atomic force microscope), laser etch surface, and/or electron beam etch surface.
[0172] According to some embodiments, when the alignment layer includes a treated surface, the treated surface may be formed by deposition of a metal salt (such as a metal oxide or metal fluoride) on at least a portion of a surface. (for example, a surface of the alignment layer itself, or a surface of the primary layer), and then notching the deposit to form the treated surface. Art-recognized metal salt deposition methods include, but are not limited to, plasma vapor deposition, chemical vapor deposition, and sputtering. Polishing may be carried out in accordance with art-recognized methods, such as those previously described herein.
[0173] As used herein, the term "Langmuir-Blodgett film" means one or more molecular films at least partially ordered on a surface. Langmuir-Blodgett films can be formed, for example, by immersing a substrate in a liquid one or more times so that it is at least partially covered by a molecular film and then removed from the substrate from the liquid so that it is at least partially covered by a molecular film. so that, due to the relative surface tensions of the liquid and the substrate, the molecules of the molecular film are at least partially ordered in substantially a general (or a single) direction. As used herein, the term molecular film refers to monomolecular films (i.e., monolayers) as well as films comprising more than one monolayer.
[0174] With some embodiments, the phase-separating polymer of a particular photochromic-dichroic layer may include a matrix phase, at least a portion of which is at least partially aligned with the base alignment layer, and a guest phase , including an anisotropic material, in which the invited phase is dispersed within the matrix phase. At least a portion of the anisotropic guest phase material may be at least partially aligned with at least a portion of the base alignment layer, and the particular photochromic-dichroic compound may be at least partially aligned with at least a portion of the anisotropic material. In addition, the matrix phase of the phase-separating polymer may include a liquid crystal polymer, and the anisotropic material of the guest phase may be chosen from liquid crystal polymers and liquid crystal mesogens. Non-limiting examples of said materials are depicted in detail above. When including a phase separation polymer as described, the first and/or second photochromic-dichroic layer can be substantially free of haze (turbidity). Turbidity is defined as the percentage of transmitted light that deviates from the incident beam by more than 2.5 degrees from the mean according to “ASTM D 1003 Standard Test Method of Haze and Luminous Transmittance of Transparent Plastics”. An example of an instrument on which turbidity measurement according to ASTM D 1003 can be made is the Haze-Gard PlusTM made by BYK-Gardener.
[0175] The photochromic-dichroic articles of the present invention may, with some embodiments, additionally include an alignment transfer material interposed between the alignment layer and the photochromic-dichroic layer, and/or interposed between the alignment layer and the photochromic-dichroic layer. The alignment transfer material can be aligned by interacting with the alignment layer and correspondingly the photochromic-dichroic composite can be aligned by interacting with the respective alignment transfer material. Alignment transfer material may, with some embodiments, facilitate propagation or transfer of an appropriate arrangement or position of an alignment layer of the photochromic-dichroic compound of the base photochromic-dichroic layer.
[0176] Examples of alignment transfer materials include, but are not limited to, those liquid crystal materials described above in conjunction with the alignment means described herein. It is possible to align the molecules of a liquid crystal material with an oriented surface. For example, a liquid crystal material can be applied to a surface that has been oriented and subsequently aligned so that the longitudinal axis of the liquid crystal molecules adopts an orientation that is generally parallel to the same general direction as the surface. The liquid crystal material of the alignment transfer material may be at least partially ordered by alignment with the alignment layer, so that the longitudinal axis of the molecules of the liquid crystal material is generally parallel to, for example, a first direction. general ease of orientation. In this way, the general direction of the alignment layer can be transferred to the liquid crystal material, which can then transfer the general direction to another structure or material. Furthermore, if the alignment layer includes a plurality of regions having general directions that together form a design or pattern, which design or pattern can be transferred to the liquid crystal material by aligning the liquid crystal material with various regions of the layer of alignment. Additionally, although not required, in accordance with various non-limiting embodiments described herein, at least a portion of the liquid crystal material of the alignment transfer material may be exposed to at least one of, a magnetic field, an electric field, radiation linearly polarized infrared, linearly polarized ultraviolet, and linearly polarized visible radiation, while being at least partially aligned with at least a portion of the alignment layer.
[0177] According to some embodiments, the photochromic-dichroic compound can be encapsulated or coated with an anisotropic material having relatively flexible chain segments, such as a liquid crystal material, and then dispersed or distributed in another material having segments of relatively rigid chain. The anisotropic encapsulating material may be at least partially ordered. For example, the encapsulated photochromic-dichroic compound can be dispersed or distributed in a liquid crystal polymer having relatively rigid chain segments, and therefore the mixture can be applied to form the particular photochromic-dichroic layer.
[0178] With additional embodiments, the photochromic-dichroic layer is defined by a polymeric sheet, the polymeric sheet includes the photochromic-dichroic compound, the polymeric sheet is laterally aligned along the second lateral direction, and the photochromic-dichroic compound is substantially and laterally aligned with the second lateral direction. The polymeric sheet may be uniaxially stretched, with some embodiments. Stretching the polymeric sheet typically results in alignment and ordering of the photochromic-dichroic material on it. The photochromic-dichroic layer may, with some embodiments, include two or more polymeric sheets each containing a photochromic-dichroic compound which may be the same or a different one, in which each polymeric sheet may be stretched in the same direction.
[0179] Examples of polymeric sheets that can be used as or to form the first and second photochromic-dichroic layers include, but are not limited to: stretching (such as uniaxially stretched) polymeric sheets, ordered liquid crystal polymer sheets, and photo-oriented polymer sheets. Examples of polymeric materials in addition to liquid crystal material and photo-orientation materials that can be used in forming the polymeric lamina of the first and/or second photochromic-dichroic layer include, but are not limited to: polyvinyl alcohol, polyvinyl, polyurethane, polyacrylate, and polycaprolactam. Non-limiting examples of methods of at least partially ordering the polymeric sheets are described in greater detail below.
[0180] According to some embodiments, the photochromic-dichroic layer of the photochromic-dichroic articles of the present invention can be formed by applying at least one anisotropic material, embedded in the photochromic-dichroic compound within the previously applied anisotropic material, of the ordered anisotropic material, and alignment of the photochromic-dichroic composite with at least a portion of the ordered anisotropic material. The anisotropic material can be ordered before, during or after being soaked with the photochromic-dichroic compound. The photochromic-dichroic compound can be aligned while in an activated state, with some embodiments.
[0181]
[0182] Embedding a photochromic-dichroic compound within a previously applied anisotropic material may involve, with some embodiments, applying a solution or mixture of the photochromic-dichroic compound in a vehicle for the previously applied anisotropic material, and allowing the compound to photochromic-dichroic to diffuse into the anisotropic material, for example with or without heating. The pre-applied anisotropic material may, with some embodiments, be part of a phase-separating polymeric coating, as described above.
[0183] The photochromic-dichroic articles of the present invention may with some embodiments include a topcoat layer, which optionally includes an ultraviolet light absorber, and which resides on both the fixed polarized layer and the photochromic-dichroic. Referring to Figure 6, the top coat layer 51 resides on the photochromic-dichroic layer 30, and the fixed polarized layer 24 is interposed between the first surface 15 of the substrate 12 and the photochromic-dichroic layer 30. With some additional embodiments, the top coat layer resides over the fixed polarized layer, and the dichroic photochromic layer is interposed between the first substrate surface and the fixed polarized layer (not shown in Figure 6).
[0184] The top coat layer may include a single layer or multiple layers, at least one of which optionally includes an ultraviolet light absorber. The coating layer typically includes an organic matrix, such as a thermoplastic organic matrix and/or a cross-linked organic matrix. In addition to or alternatively to an organic matrix, the coating layer may include an inorganic matrix including, for example, silane bonds, siloxane bonds, and/or titanate bonds. The organic matrix can include, for example, acrylate residues (or monomeric units) and/or methacrylate residues, vinyl residues, ether bonds, sulfide bonds, including monosulfide, and/or polysulfide bonds, carboxylic ester bonds, carbonate (eg -OC(O)-O-), urethane linkages (eg -N(H)-C(O)-O-); and/or thiourethane bonds (e.g. -N(H)-C(O)-S).
[0185] The coating layer may be formed by art-recognized methods including, but not limited to: lamination, such as one or more plastic sheets or films; mold forming, such as mold coating, film casting; and coating methods. Typically, the primer layer is formed from a primer coating composition. The coating composition may be a curable primary coating composition that is curable by exposure to, for example, room temperature, as in the case of two-component coating compositions; elevated temperatures (e.g., 150°C to 190°C for 5 to 60 minutes), such as in the case of ultraviolet light curable coating compositions; or actinic radiation, as in the case of ultraviolet light curable coating compositions.
[0186] The coating layer can be of any suitable thickness. With some embodiments, the layer has a thickness of from 0.5 microns to 10 microns, such as from 1 to 8 microns, or from 2 to 5 microns, inclusive of the recited values.
[0187] With some embodiments, the topcoat layer includes an organic matrix formed from an acrylate-based composition and cured by radiation, and correspondingly, the topcoat layer can be described as a basecoat topcoat layer. of acrylate.
[0188] The acrylate-based coating layer can be prepared using (meth)acrylate monomers and/or (meth)acrylic acid monomers. (meth)acrylate monomers can include one, two, three, four, or five (meth)acrylate groups. Additional copolymerizable monomers, such as epoxy monomers, e.g. monomers containing an epoxy (or oxirane) functionality, monomers containing both (meth)acrylate and epoxy functionality, etc., may also be present in the formulation used to prepare the layer. topcoat based on (meth)acrylate. The monomers used to prepare the (meth)acrylate-based coating layer include a plurality of, for example, greater than 50 weight percent (meth)acrylate monomers; hence the designation “top coating layer based on (meth)acrylate”. The formulations used to prepare the (meth)acrylate-based coating layer may also contain components having at least one isocyanate (-NCO) group, for example, organic monoisocyanates, organic diisocyanates, and organic triisocyanates, thus, urethane bonds may be incorporated within the top coat layer.
[0189] The (meth)acrylate-based top coat layer typically has physical properties including, for example, transparency, adhesion to the underlying photochromic-dichroic layer, resistance to aqueous alkali metal hydroxide removal, compatibility with a coating Optional abrasion resistant, such as a hard coating applied to its surface, and stretch resistance. With some embodiments, the (meth)acrylate-based top coat layer has a hardness that is greater than that of the second photochromic-dichroic layer.
[0190] Radiation curing of (meth)acrylate-based polymeric systems can be achieved with, for example, electron curing (EB) and/or ultraviolet light (UV) radiation. Ultraviolet curing typically requires the presence of at least a photoinitiator, while EB curing techniques do not require a photoinitiator. With the exception of the presence or absence of the photoinitiator, (meth)acrylate based formulations, which are cured by either UV or EB radiation technology, may otherwise be identical.
[0191] Radiation curable (meth)acrylate-based polymeric systems are well known in the polymer art, and any such systems can be used to produce the (meth)acrylate-based top coat layer of the photochromic article. of the present invention. In accordance with some embodiments, the (meth)acrylate-based topcoat layer is formed from a composition that includes a miscible combination or mixture of one or more free radical-initiated (meth)acrylate monomers and/or oligomers. of (meth)acrylate, and one or more cationic initiated epoxy monomers. When this mixture of monomers is cured, a top coat layer based on (meth)acrylate, in the form of a polymerizate, is formed and includes an interpenetrating network of the polymeric components.
[0192] Examples of (meth)acrylate monomers that can be included in the compositions from which the (meth)acrylate-based top coat layer can be formed, include, but are not limited to, polyfunctional (meth)acrylates having, for example, 1, 2, 3, 4, or 5 mono-functional (meth)acrylate, and (meth)acrylate groups, for example, a monomer containing a single (meth)acrylate group, hydroxy substituted (meth)acrylate and alkoxysilyl alkylacrylates, such as trialkoxysilylpropyl methacrylate. Other reactive monomers/diluents, such as monomers containing an ethylene functional group (in addition to other (meth)acrylate monomers) may also be present.
[0193] The compositions from which the (meth)acrylate-based top coat layer can be formed, and methods of applying and curing said compositions, are described in column 16, line 14 through column 25, line 3 of the US patent No. US 7,452,611 B2, the disclosure of which is incorporated herein by reference.
[0194] The compositions from which the top coat layer is formed may include one or more additives, including, but not limited to, adhesion promoters, coupling agents, ultraviolet light absorbers, thermal stabilizers, catalysts, free radial, plasticizers, flow additives, and/or static inks or static dyes (ie inks or dyes that are not photochromic).
[0195] With some embodiments, the compositions from which the (meth)acrylate-based top coat layer can be formed may further include an adhesion promoter. The adhesion promoter can be selected from, for example, organosilanes, such as amino organosilanes, organic titanate coupling agents, organic zirconate coupling agents, and combinations thereof. Examples of adhesion promoters, which may be included in the compositions from which the acrylate-based topcoat layer may be formed, include, but are not limited to, those described in column 5, line 52 through column 8, line 19 of US patent No. US 7,410,691 B2, the disclosure of which is incorporated herein by reference.
[0196] The top coat layer, in some embodiments, includes an ultraviolet light absorber. The ultraviolet light absorber may be selected from one or more art-recognized classes of ultraviolet light absorbers, including, but not limited to: hindered amines, which may include, for example, one or more 2,2 N-substituted piperidine groups ,6,6-tetramethyl; benzophenones; and/or benzotriazole. The ultraviolet light absorber is typically present in at least an effective amount, such as 0.1 to 10 weight percent, or 0.2 to 5 weight percent, or 0.3 to 3 weight percent. , based on the total weight of solids of the coating composition from which the top coating layer is prepared.
[0197] The photochromic-dichroic articles of the present invention may, with some embodiments, include a hard coating layer residing on top of the top coating layer. Referring to Figure 6, the photochromic-dichroic article 3 includes a hard coating layer 54 residing on top of the coating layer 51. The hard coating layer may include a single layer or multiple layers.
[0198] The hard facing layer can be selected from abrasion resistant coatings including organosilanes, abrasion resistant coatings including thin films based on radiation cured acrylate, abrasion resistant coatings based on inorganic materials such as silica, titanite, and /or zirconia, organic abrasion resistant coatings of the type that are ultraviolet light curable, oxygen barrier coatings, UV protective coatings, and combinations thereof. With some embodiments, the hard coating layer may include a first coating of a radiation-cured acrylate-based thin film and a second coating including an organosilanes. Non-limiting examples of commercial hard coating products include SILVUE® 124 and HI-GARD® coatings, available from SDC Coatings, Inc., and PPG Industries, Inc., respectively.
[0199] The hardfacing layer may be selected from art-recognized hardfacing materials, such as organosilane abrasion resistant coatings. Organosilane abrasion resistant coatings, often referred to as hard coatings or silicone-based hard coatings, are well known in the art, and are commercially available from a number of manufacturers, such as SDC Coatins, Inc., and PPG Industries, Inc. . Reference is made to US Patent No. US 4,756,973 at column 5, lines 1-45; and in US patent 5,462,806 at column 1, lines 58 through column 2, line 8, and column 3, line 52 through column 5, line 50, the disclosure of which features organosilane hard coatings and the disclosure of which is incorporated herein by reference. Reference is also made to US Patent Nos.: US 4,731,264; US 5,134,191; US 5,231,156 and international application publication WO 94/20581 for the description of organosilanes hard coatings, the description of which is also incorporated herein by reference. The hard coating layer can be applied by those coating methods as described in the art, such as melt coating.
[0200] Other coatings that can be used to form the hardfacing layer include, but are not limited to, polyfunctional acrylic hardfacings, melamine-based hardfacings, urethane-based hardfacings, alkyd-based hardfacings, silica-sol base or other inorganic/organic or organic hybrid hard coatings.
[0201] The hardfacing layer, with some embodiments, is selected from organosilane-type hardfacings. The organosilane-type hard coatings from which the hard coating layer of the photochromic-dichroic articles of the present invention can be selected include, but are not limited to, those described in column 24, line 46 through column 28, line 11 of the northern patent. -American No. US 7,465,414 B2, the disclosure of which is incorporated herein by reference.
[0202] With some embodiments, the photochromic-dichroic articles of the present invention include a primer layer. With some embodiments, the primer layer is interposed between the first substrate surface and the photochromic-dichroic layer. With some additional embodiments, the primer layer is interposed between the first surface of the substrate and the attached polarized layer. For the purpose of non-limiting illustration and with reference to Figure 6, the primer layer 48 is interposed between the first surface 15 of the substrate 12 and the bonded polarized layer 24, and more particularly, the primer layer 48 abuts the first surface 15 of the substrate. 12 and abuts the fixed polarized layer 24.
[0203] The primary layer may include a single layer or multiple layers which may be the same or different. The primary layer typically includes an organic matrix, such as a thermoplastic organic matrix and/or a cross-linked organic matrix. Additionally or alternatively, in an organic matrix, the primary layer may include an inorganic matrix, including, for example, silane bonds, siloxane bonds, and/or titanate bonds. The organic matrix may include, for example, acrylate residues (or monomer units) and/or methacrylate residues; vinyl waste; ether bonds, sulfide bonds, including monosulphide bonds and/or polysulphide bonds; carboxylic ester bonds; carbonate bonds (e.g. -O-C(O)-O-), urethane bonds (e.g. -N(H)-C(O)-O-); and/or thiourethane bonds (e.g. -N(H)-C(O)-S-).
[0204] The primary layer may be formed by methods known in the art including, but not limited to: lamination, such as one or more plastic sheets or films; mold forming, such as mold coating, film casting; and coating methods. Typically, the primer layer is formed from a primer coating composition. The primer coating composition can be a curable primer coating composition that is curable by exposure to, for example, room temperature, as in the case of two-component coating compositions; elevated temperatures (e.g. 150°C to 190°C for 5 to 60 minutes), such as in the case of heat cured coating compositions; or actinic radiation, as in the case of ultraviolet light curable coating compositions.
[0205] The primer layer can be any appropriate thickness. With some embodiments, the primer layer has a thickness of 0.5 microns to 20 microns, such as 1 to 10 microns, or 2 to 8 microns, or 3 to 5 microns, inclusive of the recited values.
[0206] With some embodiments, the primary layer includes an organic matrix that includes urethane bonds. According to some embodiments, the primary layer containing the urethane linkages is formed from the curable coating composition that includes: a (meth)acrylate copolymer having active hydrogen functionality selected from hydroxyl, thiol, primary amine, secondary amine , and combinations thereof; blocked isocyanate, such as diisocyanate and/or triisocyanate blocked with an appropriate blocking or leaving group, such as 3,5-dimethyl pyrazole; and one or more additives, including but not limited to, adhesion promoters, coupling agents, ultraviolet light absorbers, thermal stabilizers, catalysts, free radical scavengers, plasticizers, flow additives, and/or static inks or static dyes ( i.e. inks or dyes that are non-photochromic).
[0207] Examples of (meth)acrylate monomers from which the functional active hydrogen of the (meth)acrylate copolymer can be prepared include, but are not limited to, C1-C20 (meth)acrylate, C1 (meth)acrylate -C20 having at least one active hydrogen group selected from hydroxyl, thiol, primary amine, and secondary amine. The C1-C20 groups of the (meth)acrylate can be selected from, for example, linear C1-C20 alkyl, branched C3-C20 alkyl, C3-C20 cycloalkyl, fused ring C3-C20 polycycloalkyl, C5-C20 aryl, and fused ring C10-C20 aryl.
[0208] Additional polyols that may be used in the primary coating compositions from which the primary layer is prepared include, but are not limited to, art-recognized materials such as described in U.S. Patent No. US 7,465,414, at column 15, line 22 through column 16, line 62, the description of which is incorporated herein by reference. Isocyanates that can be used in the primer coating compositions from which the primer layer is prepared include, but are not limited to, art-recognized materials, such as those described in U.S. Patent No. US 7,465,414, at column 16, line 63 through column 17, line 38, the description of which is incorporated herein by reference. Catalysts that can be used in the primer coating compositions from which the primer layer is prepared include, but are not limited to, art-recognized materials, as described in U.S. Patent No. US 7,465,414 at column 17, line 39-62, the description of which is incorporated herein by reference.
[0209] The primer coat may include additional additives that improve the performance of the first photochromic compound. Said additional additives may include, but are not limited to, ultraviolet light absorbers, stabilizers such as hindered lua amine stabilizers (HALS), antioxidant, e.g. polyphenolic antioxidants, asymmetric diaryloxalamide (oxanilide) compounds, isolated oxygen repressors , for example, a nickel ion complex with an organic binder, and mixtures and/or combinations of said photochromic performance-enhancing additive materials.
[0210] The primer coat can be applied over the substrate by art-recognized methods including, but not limited to, spray application, spindle coating, medical foil application (or lowering), and screen application.
[0211] The primary layer may include at least partially hydrolyzed coupling agents and mixtures thereof. As used herein "coupling agent" means a material having at least one group capable of reacting, binding and/or associating with a group on at least one surface. With some embodiments, a coupling agent may serve as a molecular bridge at the interface of at least two surfaces which may be similar or dissimilar surfaces. Coupling agents, with some additional embodiments, can be monomers, oligomers, prepolymers and/or polymers. Said materials include, but are not limited to, organometallics such as silanes, titanates, zirconates, aluminates, zirconium aluminates, hydrolysates thereof and mixtures thereof. As used herein, the phrase "at least partially hydrolyzed coupling agents" means at least some of all of the hydrolyzable groups on the coupling agent are hydrolyzed.
[0212] In addition to, or alternatively, the coupling agents and/or hydrolysates of the coupling agent, the primary layer may include other adhesion-enhancing ingredients. For example, while not limiting here, the primer layer may further include an adhesion-enhancing amount of an epoxy-containing material. Adhesion-enhancing amounts of an epoxy-containing material when included in the primer layer can improve the adhesion of a subsequently applied coating or layer. A class of an epoxy (or oxirane) functional adhesion promoter that may be included in the compositions from which the primer layer is formed includes, but is not limited to, oxirane functional alkyl trialkoxysilanes, such as gamma-glycidoxypropyltrimethoxysilane, such as gamma-glycidoxypropyltrimethoxysilane, and beta-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.
[0213] The photochromic-dichroic articles of the present invention may include additional coatings or layers, such as anti-reflective coatings. With some embodiments, an anti-reflective coating can be applied over the hard coating layer. Examples of anti-reflective coatings are described in U.S. Patent No. US 6,175,450 and in international publication No. WO 00/33111, the description of which are incorporated herein by reference.
[0214] With some embodiments of the present invention, the additional photochromic-dichroic article includes a birefringent layer that includes a polymer. The birefringent layer is interposed between the fixed polarized layer and the photochromic-dichroic layer. Referring to Figure 2, the dichroic photochromic article 4 includes a birefringent layer 57 which is interposed between the fixed polarized layer 24 and the photochromic-dichroic layer 30. The birefringent layer may also be referred to herein as a compensation layer or a dichroic layer. delay. The birefringent layer can be composed of a single layer or multiple layers. When the birefringent layer is composed of multiple layers, each may be the same, or at least two layers of the multiple layers may be different. The birefringent layer may be formed from one or more polymeric laminae, one or more coating compositions, and combinations thereof.
[0215] With some embodiments, the birefringent layer is included for the purpose of providing the photochromic-dichroic articles of the present invention with improved color properties and/or spectral filtering properties. According to some embodiments, the properties of the birefringent layer, such as improved color grade, spectral filtering, circular polarization, and/or elliptical polarization, thus provided, can be selected by modifying one or more of the thickness, refractive index, and anisotropic order level of the birefringent layer. The anisotropic order level of the birefringent layer can, with some embodiments, be adjusted by unilateral stretching of the birefringent layer and/or anisotropic ordering of one or more liquid crystal materials within the birefringent layer, in accordance with methods recognized by the prior art. .
[0216] According to some embodiments of the present invention, the birefringent layer is operable for circularly polarized transmitted radiation or elliptically polarized transmitted radiation. As used herein, and with some embodiments, the term "transmitted radiation" with respect to the birefringent layer means radiation that is transmitted through the birefringent layer. With some embodiments, the birefringent layer includes a quarter-wave plate or layer. In accordance with some additional embodiments, the birefringent layer defines a quarter-wave plate.
[0217] The birefringent layer, with some embodiments, includes a first ordered region having a first general direction, and at least one second ordered region adjacent to the first ordered region having a second general direction that is the same or different from the first general direction so as to form a desired pattern in the birefringent layer. The desired pattern includes, but is not limited to, symbols, such as alphanumeric, and designs.
[0218] Materials from which the birefringent layer can be prepared, with some embodiments, include birefringent materials which are known in the art. For example, a polymeric film, a liquid crystal film, self-arranged materials, or a film on which a liquid crystal material is aligned can be used as or form the birefringent layer. Examples of birefringent layer include, but are not limited to, those described in U.S. Patent Nos.: US 6,864,932 at column 3, line 60 to column 4, line 64; US 5,550,561 in column 4, line 30 through column 7, line 2; US 5,948,487 at column 7, line 1 through column 10, line 10, said description thereof, in each case, being incorporated herein by reference.
[0219] With some embodiments, the birefringent layer includes a polymeric coating (or is formed from the polymeric composition and coating). With some additional embodiments, the polymeric coating (or polymeric coating composition) may include self-arranging materials and/or film-forming materials.
[0220] Examples of commercially available birefringent films or sheets from which the birefringent layer can be formed include: Model No. NFR-140, a positive spritz, uniaxial film available from Nitto Corporation, Japan, or Nitto Denko America, Inc., New Brunswick, New Jersey; and OPTIGRAFIX circular polarizing films; available from GRAFIX Plastics, a division of GRAFIX, Inc., Cleveland Ohio.
[0221] The birefringent layer includes one or more polymers. Examples of polymers that can be included in the birefringent layer, and/or from which the birefringent layer can be prepared, include, but are not limited to, polyacrylate, polymethacrylates, poly(C1-C12alkyl)methacrylates, polyoxy(alkylenemethacrylates) , poly(phenol alkoxylated methacrylates), cellulose acetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, poly(vinyl acetate), poly(vinyl alcohol), poly(vinyl chloride), poly( vinylidene chloride), poly(vinylpyrrolidone), poly(meth)acrylamide), poly(dimethyl acrylamide), poly(hydroxyethyl methacrylate), poly(meth)acrylic acid), thermoplastic polycarbonates, polyesters, polyurethanes, polythiourethanes, poly(ethylene terephthalate) ethylene), polystyrene, poly(alpha methylstyrene), copoly(styrene-methylmethacrylate), copoly(styrene-acrylonitrile), polyvinylbutyral and polymers of members of the group consisting of polyol(allyl carbonate) monomers, monofunctional acrylate monomers, mono monofunctional methacrylate monomers, polyfunctional acrylate monomers, monofunctional methacrylate monomers, polyfunctional acrylate monomers, polyfunctional methacrylate monomers, diethylene glycol dimethacrylate monomers, benzene diisopropenyl monomers, alkoxylated polyhydric alcohol monomers and dialylidene pentaerythritol monomers, and in in particular, self-assembled materials, polycarbonate, polyamide, polyimide, poly(meth)acrylate, polycalcium alkene, polyurethane, poly(urea)urethane, polythiourethanes, polythio(urea)urethane, polyol(allyl carbonate), cellulose acetate, diacetate of cellulose, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, polyalkene, polyalkylene-vinyl acetate, poly(vinylacetate), poly(vinyl alcohol), poly(vinyl chloride), poly(vinylformal), poly (vinyl acetal), poly(vinylidene chloride), poly(ethylene terephthalate), polyester, polysulfone, polyolefin, copolymers thereof, and/or mixtures thereof themselves. With some embodiments, the birefringent layer is formed from one or more polymeric laminae with each including one or more polymers, such as, but not limited to, those examples cited with respect to the polymer that can be included in the birefringent layer, and/or from which the birefringent layer can be prepared.
[0222] According to some embodiments, the birefringent layer includes a polymeric sheet comprising, self-arranging materials, polycarbonate, polyamide, polyimide, poly(meth)acrylate, polycyclic alkene, polyurethane, poly(urea)urethane, polythiourethanes, polythio( urea)urethane, polyol(allyl carbonate), cellulose acetate, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, polyalkene, polyalkylene-vinyl acetate, poly9vinylacetate), poly(vinyl alcohol ), poly(vinyl chloride), poly(vinylformal), poly(vinylacetal), poly(vinylidene chloride), poly(ethylene terephthalate), polyester, polysulfone, polyolefin, copolymers thereof, and/or mixtures thereof, and/or mixtures thereof.
[0223] The birefringent layer can, with some embodiments, be positioned such that a slower axis direction (direction where a refractory index is much higher in one plane) of the birefringent layer is oriented with respect to an alignment direction of the birefringent layer. photochromic-dichroic layer so as to result in the desired resulting polarization, such as circular polarization or elliptical polarization. For example, a quarter-wave plate, with some embodiments, would be oriented at an angle of 45°+/5° or 45°+/-3° to a photochromic-dichroic composite alignment direction of the photochromic- dichroic.
[0224] In accordance with some embodiments of the photochromic-dichroic articles of the present invention, the substrate includes a first polarization axis and may be referred to herein as a linearly polarizing substrate. A photochromic-dichroic layer that includes a photochromic-dichroic compound and has a second polarization axis, as previously described here, is positioned over the substrate. The substrate's first polarization axis and the photochromic-dichroic layer's second polarization axis are oriented relative to each other at an angle greater than 0° and less than or equal to 90°. With some embodiments, the linearly polarized substrate optionally includes a fixed dye.
[0225] For the purpose of non-limiting illustration and with reference to Figure 3, the photochromic-dichroic article 3 includes a substrate 60 having a first surface 63 and a second surface 66. The first surface 66 of substrate 60, with some embodiments, with respect to incident actinic radiation represented by arrow 21. Substrate 66 also has a first polarization axis represented by double headed arrows 69. Photochromic-dichroic article 5 additionally includes a photochromic-dichroic layer 30 which is positioned above the first surface 63 of substrate 60, and which includes a photochromic-dichroic compound that is laterally aligned within the layer, and that defines a second polarization axis represented by double-headed arrows 33. The photochromic-dichroic layer and the photochromic-dichroic compound thereof are each as previously described here.
[0226] The optional fixed dye of the linearly polarizing substrate, such as substrate 60 is, with some embodiments, as previously herein with respect to the fixed polarized layer, such as the fixed polarized layer 24. The linearly polarizing substrate, such as substrate 60, may, with some embodiments, be selected from those classes and examples of substrates, and may include one or more optional additives, as described previously herein, for example, with respect to substrate 12. The linearizing properties of the linear polarizing substrate may be obtained according to art-recognized methods including, but not limited to, those methods and procedures as previously described herein with respect to the attached polarized layer, such as attached polarized layer 24. The linearly polarizing substrate may include one or more additives as previously described herein with with respect to the fixed polarized layer, such as, but not limited to, dichroic compounds, coran dichroic fixatives, solvents, light stabilizers (such as, but not limited to, ultraviolet light absorbers and light stabilizers such as hindered amine light stabilizers (HALS)), heat stabilizers, mold release agents, rheology control agents, leveling agents (such as, but not limited to, surfactants), free radical scavengers, and adhesion promoters (such as hexanediol diacrylate and coupling agents).
[0227] The first polarization axis of the linearly polarizing substrate and the second polarization axis of the photochromic-dichroic layer are oriented relative to each other at an angle greater than 0° and less than or equal to 90°, such as from 0, 1° to 90°, or from 1° to 90°, or from 10° to 90°, or from 25° to 90°, or from 45° to 90°, or from 60° to 90°, including the aforementioned values . With some embodiments, when the first polarization axis of the linearly polarizing substrate and the second polarization axis of the photochromic-dichroic layer are oriented relative to each other at a 90° angle, the photochromic-dichroic articles of the present invention have a minimum level actinic radiation transmittance, providing that the photochromic-dichroic compound undergoes both photochromic activation (e.g. being converted to a colored state) and dichroic activation when exposed to incident actinic radiation, such as when exposed to southern light directly. For the purpose of illustration, and with non-limiting reference to Figure 3, the first polarization axis 69 of the linearly polarizing substrate 60 and the second polarization axis 33 of the photochromic-dichroic layer 30 are oriented relative to each other at an angle of substantially 90°.
[0228] In accordance with some embodiments, the photochromic-dichroic articles of the present invention additionally include a birefringent layer that includes a polymer, wherein the birefringent layer is interposed between the substrate (such as the linearly polarizing substrate) and the photochromic-dichroic layer. . For purposes of illustration and with non-limiting reference to Figure 4, the photochromic-dichroic article 6 includes a birefringent layer 72 interposed between the substrate 60 (which may be referred to herein as a linearly polarizing substrate) and the photochromic-dichroic layer 30. With some embodiments, the birefringent layer, such as the birefringent layer 72, is as described previously herein, such as with respect to the birefringent layer 57.
[0229] Photochromic-dichroic articles of the present invention that include a linearly polarizing substrate, such as substrate 60, may include one or more additional layers as described previously herein, such as alignment layers, primer, topcoat, hardcoat, and/or anti-reflective coatings (not shown in figures 3 and 4).
[0230] According to further embodiments, the photochromic-dichroic articles of the present invention can be selected from ophthalmic articles or elements, display articles or elements, windows, mirror, packaging material, such as shrinkwrap and active and passive liquid crystal cell items or elements.
[0231] Examples of ophthalmic articles or elements include, but are not limited to, corrective lenses, non-corrective lenses, including monofocal or multifocal vision lenses, which can be either segmented or non-segmented multifocal lenses (such as, but not limited to, bifocals, trifocals and progressive lenses), as well as other elements used to correct, protect, or improve (cosmetically or otherwise) vision, including, without limitation, contact lenses, intraocular lenses, magnifying lenses, protective lenses or viewers.
[0232] Examples of display items, elements, and devices include, but are not limited to, screens, monitors, and security elements, including without limitation security marks and authentication marks.
[0233] Examples of windows include, but are not limited to, automotive and aircraft transparencies, filters, shutters, and optical switches.
[0234] With some embodiments, the photochromic article can be a security element. Examples of security elements include, but are not limited to, security tags and authentication tags that are attached to at least a portion of a substrate, such as: access cards and passes, e.g., tickets, badges, identification or membership, eg, notes, checks, bonds, notes, certificates of deposit, stock certificates, etc.; government documents, eg currency, licenses, ID cards, benefit cards, visas, passports, official certificates, deeds, etc.; consumer goods, eg software, compact discs (“CDs”), digital video discs (“DVDs”), household items, consumer electronics, sporting goods, cars, etc.; credit cards; and tags, labels and packaging for goods.
[0235] With additional embodiments, the security element may be connected to at least a portion of a substrate chosen from a transparent substrate and a reflective substrate. Alternatively, according to additional embodiments in which a reflective substrate is required, if the substrate is not reflective or sufficiently reflective for the intended application, a reflective material may first be applied to at least a portion of the substrate before the security marking is applied. applied to the same. For example, a reflective aluminum coating can be applied to at least a portion of the substrate before forming the security element thereon. Additionally or alternatively, the security element may be attached to at least a portion of a substrate chosen from uncolored substrates, colored substrates, photochromic substrates, colored photochromic substrates, linearly polarized substrates and circularly polarized substrates, and elliptically polarized substrates.
[0236] In addition, security elements according to the aforementioned embodiments may further include one or more of other coatings or films or foils to form a multi-layered reflective security element with viewing angle dependent characteristics, as described in Patent No. US 6,641,874.
[0237] The present invention is more particularly described in the following examples, which are intended as illustrative only, as numerous modifications and variations herein will be apparent to those skilled in the art. Unless otherwise specified, all parts and all percentages are by weight. EXAMPLES
[0238] The preparation of coating #1 is described in parts 1A & 1B and coating #2 in Part 2. The cleaning procedure for the substrate is described in part 3 and the coating procedure for the photo-alignment layers as well as coatings #1 and #2 are described in Parts 4A to 4D. The preparation of the transitional coating solution (Top Coat) and the coating application procedure are described in Part 5. The protective coating (hard coating) preparation and the coating application procedure are described in Part 6. Photochromic Performance Testing - dichroic is described in Part 7. The results for Examples 1, 1A & 1B to 3, 3A & 3B and Comparative Example 1, 1A and 1B are included in Table 1. Part 1: Preparation of anisotropic materials solution:
[0239] In a suitable bottle, containing a mixture of anisole (3.990 g) and the additive BYK®-322 (0.004g) reported to be an aralkyl-modified poly-methyl-alkyl-siloxane, available from BYK Chemie, USA, was added to RM-257 liquid crystal monomers (3,000g), reported to have the molecular formula of C33H32O10; and RM-105 (3,000g), reported to have the molecular formula of C23H26O6; both are available from EMD Chemicals, Inc., 4-methoxyphenol (0.006g), and IRGACURE® 819 (0.090g) a photoinitiator available from Ciba-Geigy Corporation. The resulting mixture was stirred for 2 hours at 60°C until the solids dissolved as determined by visual observation and cooled to about 26°C for 60 minutes and then cooled to about 26°C. Part 2 - Preparation of coating #2 of anisotropic materials and photochromic-dichroic materials:
[0240] In an appropriate bottle containing a mixture of anisole (3,990 g) and BYK®-322 additive 0.004 g, RM-257 (1,500g), RM-105 (1,500g), RM-82 (1,500g) was added. , was reported to have the molecular formula of C33H32O10; LCM-1 (1500g) described below, photochromic-dichroic dye combination Gray (0.720 grams of mixture in the following weight percentage of the dyes: 20% of photochromic-dichroic #1, an indene-naphthopyran that demonstrates an activated brown color yellowish; 15% photochromic-dichroic #2, an indenone-naphthopyran that demonstrates a blue-green activated color; and 65% photochromic-dichroic #3, an indene-naphthopyran that demonstrates a cyan activated color; which has been heated to 80° C for 60 minutes and then cooled to about 26°C), 4-methoxyphenol (0.006g), and IRGACURE® 819 (0.090G). The resulting mixture was stirred for 2 hours at 60°C and cooled to about 26°C.
[0241] LCM-1 is 1-(6-(6-(6-(6-(6-(6-(6-(6-(8-(4-{4-(4-(8-acryloylcyhrcilloxy)) benzoyloxy)phenyloxycarbonyl)phenoxy)octioxy)-6-oxohexyloxy)-6-oxohexyloxy)-6-oxohexyloxy)-6-oxohexyloxy}-6-oxohexyloxy)-6-oxohexyloxy)-6-oxohexyloxy)-6-oxohexan-1- ol, which was prepared according to the procedure described in Example 17 of Patent Publication No. US 2009/0323011, the description of which of the liquid crystal monomer is incorporated herein by reference. Part 3 - Substrate Cleaning:
[0242] Square substrates measuring 5.08cm by 5.08cm by 0.318cm (2 inches(in.) by 2 inches by 0.125 inches) prepared from CR-39® monomer were obtained from Homalite, Inc.. Each substrate was cleaned by drying with an acetone soaked tissue, dried with an air stream and corona treated by passing over a conveyor belt in Tantec EST Systems Series No. 020270 - HV2000 power generator - corona series treatment equipment with a high voltage transformer. The substrates were exposed to corona generated by 53.99 KV, 500 Watts while traveling on a conveyor belt at a speed of 3 feet/minute. Part 4A - Coating procedure for the first photoalignment layer:
[0243] Photoalignment material, Staralign™ 2200 CP2, from Vantico, Inc., was applied to test substrates by melt coating over a portion of the test substrate surface by dispersing approximately 1.0 mL of the solution and substrate spinning at 800 revolutions per minute (rpm) for 3 seconds, followed by 1000 rpm for 7 seconds, followed by 2500 rpm for 4 seconds. A spindle processor from Laurell Technologies Corp. (WS-400B-6NPP/LITE) was used for melt coating. Then, the coated substrates were placed in an oven maintained at 120°C for 30 minutes. The coated substrates were cooled to about 26°C.
[0244] The dry photo-alignment layer on each of the substrates was at least partially ordered by exposure to linearly polarized ultraviolet radiation using a DYMAX® UVC-6 UV/carrier system by DYMAX Corp., having a power supply of 400 Watt. The light source was oriented so that the radiation was linearly polarized in a plane perpendicular to the substrate surface. The amount of ultraviolet radiation that each photoalignment layer was exposed to was measured using an EIT Inc (Serial No. 2066) high energy UV Power Puck™ radiometer and was as follows: UVA 0.126W/cm2 and 5.962 J/cm2; UVB 0.017 W/cm and 0.078 J/cm 2 ; UVC 0 W/cm2 and 0 J/cm2; and UW 0.046 W/cm 2 and 2150 J/cm 2 . After ordering at least a portion of the photo-oriented polymer network, the substrates were cooled to about 26°C and kept covered. Part 4B - Coating Procedure for Coating #1:
[0245] Coating #1 (approximately 2.0 mL) was applied to each substrate by melt coating at a rate of 2000 revolutions per minute (rpm) for 10 seconds over the at least partially ordered photoalignment materials. Each coated substrate was placed in an oven at 60°C for 30 minutes. Then, the substrates were cured under two ultraviolet lamps in a UV curing machine designed and built by “Belcan Engineering”, in a nitrogen atmosphere, while running on a conveyor belt at 2 ft/minute at a peak speed of intensity of 0.445 Watts/cm2 UVA and 0.179 Watts/cm2 UVV and UV dosage of 2,753 Joules/cm2 UVA and 1.191 Joules/cm2 UVV. Each of the cured layers was exposed to corona generated by 53.00 KV, 500 Watts while traveling over the conveyor belt at a speed of 3 feet/minute. Part 4C - Coating procedure for the second photo-alignment layer:
[0246] A second application of the photo-alignment material was applied following the procedure in part 4A. The second photoalignment layer was dried and at least partially ordered in a 0°, 30°, 60° or 90° orientation to the first alignment layer by rotating the substrate to an appropriate angle and exposing it to ultraviolet radiation. linearly polarized as described in Part 4A. Part 4D - Coating Procedure for Coating #2:
[0247] Coating #2 (approximately 2.0 mL) was applied over the at least partially ordered photo-alignment layer prepared in Part 4C by melt coating at a rate of 2000 revolutions per minute (rpm) for 3 seconds, followed by 1000 rpm for 7 seconds, followed by 2500 rpm for 4 seconds. Each coated substrate was placed in an oven at 60°C for 30 minutes. Next, the substrates were cured under two ultraviolet lamps in a UV curing machine designed and built by “Belcan Engineering”, in a nitrogen atmosphere, as described in Part 4B. The cured layers were exposed to corona generated by 53.00 KV, 500 Watts, while traveling on a conveyor belt at a speed of 3 feet/minute, if a subsequent coating layer was applied. On the other hand, the samples were post-baked for 3 hours at 105°C. Substrates having coating #2 in a 30° orientation for coating #1 were from Example 1; coating #2 in a 60° orientation to coating #1 were from Example 2; coating #2 in a 90° orientation to coating #1 were from Example 3; coating #2 in a 0° orientation for coating 1 were from Comparative Example (CE)1. Part 5 - Coating Procedure for Transition Coating (TC):
[0248] The transition coating solution was prepared as follows: in a 50 mL amber glass bottle equipped with a magnetic stir rod, where the following materials were added: Hydroxy methacrylate (1.242 g) from Sigma- Aldrich; Diacrylate and Neopentyl Glycol (13.7175 g) SR247 from Sartomer; Trimethylolpropane trimethacrylate (2.5825 g) SR350 from Sartomer; DESMODUR® PL 340 (5.02 g) from Bayer Material Science; IRGACURE®-819 (0.0628g) from Ciba Specialty Chemicals; DAROCUR® TPO (0.0628 g); from Ciba Specialty Chemicals; Polybutyl acrylate (0.125g), 3-aminopropylpropyltrimethoxylsilane (1.4570g) A-1100 from Momentive Performance Materials; Absolute anhydrous ethanol test 200 (1.4570 g) from Pharmaco-Aaper; and stirred at room temperature for 2 hours.
[0249] The transition coating (approximately 4.0 mL) was melt coated at a rate of 1,400 revolutions per minute (rpm) for 7 seconds on the cured coated substrates. The substrates were then cured under two ultraviolet lamps in a UV curing machine designed and built by “Belcan Engineering”, in a nitrogen atmosphere, while traveling on a conveyor belt at a speed of 6 ft/minute at peak. intensity of 1.887 Watts/cm2 of UVA and 0.694 Watts/cm2 of UVV and UV dosage of 4,699 Joules/cm2 of UVA and 1.787 Joules/cm2 of UVV. The cured transition layers were exposed to corona generated by 53.00 KV, 500 Watts while traveling over the conveyor belt at a speed of 3 feet/minute. Part 6 - Coating procedure for protective coating (PC):
[0250] The protective coating was prepared as follows: Charge 1 was added to a clear dry beaker and placed in an ice bath at 5°C with stirring. Charge 2 was added and an exothermic rise of the reaction temperature of the mixture to 50°C. The temperature of the resulting reaction mixture was cooled to 20-25°C and Charge 3 was added with stirring. Charge 4 was added to adjust the pH from about 3 to about 5.5. Charge 5 was added and the solution was mixed for half an hour. The resulting solution was filtered through a nominal 0.45 micron capsule filter and stored at 4°C until use. Charge 1 Glycidoxypropyltrimethoxysilane 32.4 grams Methyltrimethoxysilane 345.5 grams Charge 2 Deionized (DI) water solution with nitric acid (1g/7000g nitric acid) 292 grams Charge 3 DOWANOL® PM Solvent 228 grams Charge 4 TMAOH (25% sodium hydroxide) tetramethylammonium in methanol) 0.45 grams Charge 5 BYK®-306 Surfactant 2.0 grams
[0251] The resulting protective coating solution (approximately 4.0 mL) was melt coated at a rate of 2000 revolutions per minute (rpm) for 10 seconds onto the cured transition layer coated substrates. Post curing of the coated substrates will be completed at 105°C for 3 hours. Part 7 - Photochromic-Dichroic Performance Test:
[0252] Each of the coated substrates prepared above was tested in duplicate for photochromic-dichroic response on the photochromic measurement bench (“BMP”), optical bench made by Essilor, Ltd. France. The optical bench was maintained at a constant temperature of 73.4°F (23°C) during the test.
[0253] Prior to the optical bench test, each of the coated substrates was exposed to ultraviolet light at 365 nanometers for about 10 minutes at a distance of about 14 centimeters to activate the photochromic-dichroic materials. The UVA irradiation (315 to 380 nm) on the substrates was measured with a LICOR® Model Li-1800 spectroradiometer and observed at 22.2 Watts per square meter. The substrate was then placed under a halogen lamp with 500 Watts of intensity for about 10 minutes at a distance of about 36 centimeters to the bench (inactive) the photochromic-dichroic material. Substrate illuminance was measured with a LICOR® spectroradiometer and observed at 21.4 Klux. The substrates were then kept in a dark medium at room temperature (70 to 75°F, or 21 to 24°C) for at least 1 hour before testing on an optical bench. Prior to measurement on the optical bench, the substrates were measured for ultraviolet absorbance at 390 nanometers.
[0254] The BMP optical bench was filtered with two ORIEL® Model #66057 150-Watt Xenon Arc Lamps at right angles to each other. The light path from lamp 1 was directed through a 3 mm SCHOTT® KG-2 bandpass filter and appropriate neutral density filters that contributed to the required UV and partial visible light irradiation level. The light path from lamp 2 was directed through a 3mm SCHOTT® KG-2 bandpass filter, a 400 nm SCHOTT® short-band cut-off filter and appropriate neutral density filters in order to provide the illuminance of supplementary visible light. A 2-inch x 2-inch 50% beam splitter (“polka dot bean splitter”), at 45° for each lamp was used to mix the two beams. A combination of neutral density filters and Xenon lamp voltage control were used to adjust the irradiation intensity. Proprietary software was used on top of the BMP to control time, irradiance, air cell and sample temperature, shutter, filter selection, and response measurement. A ZEISS® spectrophotometer, model MCS501, with fiber optic cables to deliver light through the substrates was used to measure response and color. Photopic response measurements, as well as the response at four selected wavelengths, were collected on each substrate.
[0255] The output power of the optical bench, i.e. the dose of light that the substrate was exposed to, was adjusted to 6.7 Watts per square meter (W/m2) UVA, integrated from 315-380 nm and 50 Klus of illuminance, integrated from 380-780 nm. The output energy measurement was done using the optometer and software contained within the BMP.
[0256] The average response, in terms of a change in optical density (ΔOD) from the non-activated or bleached state to the activated or colored state was determined by establishing the initial inactivated transmittance, opening the Xenon lamp shutter and measuring transmittance by activating at selected time intervals. The change in optical density was determined according to the formula: ΔOD = log (10(%tb/%Ta), where % Tb is the percentage of transmittance in the discolored state, % Ta is the percentage of transmittance in the uncolored state. On Optical density measurement was based on photopic optical density.
[0257] The results of this test are presented in Table 1, where the ΔOD at saturation is after 15 minutes of activation and the value of the Fade half-life ("T ^") is the time interval in seconds for the ΔOD in the activated form of the photochromic-dichroic material in the coating to achieve half of the fifteen minutes of ΔOD at 73.4°F (23°C) after removal of the activating light source. Results reported are an arithmetic mean of the duplicate test substrates for each Example and Comparative Example.
[0258] In Table 1, Example 1 has coating #2 in a 30° orientation to coating #1; Example 1A has a transition coating (TC) applied to Example 1; and Example 1B has a protective coating (PC) applied to Example 1A; Example 2 has coating #2 in a 60° orientation to coating #1; Example 2A has a TC applied to Example 2: and Example 2B has a PC applied to Example 2A; Example 3 has coating #2 in a 90° orientation to coating #1; Example 3A has a TC applied to Example 3; and Example 3B has a PC applied to Example 3A; Comparative Example (CE) 1 has coating #2 in a 0° orientation to coating #1; CE 1A has a CT applied to CE 1; and CE 1B has a PC applied to CE 1A. Table 1 Photochromic-Dichroic Performance of Examples and Comparative Example

[0259] The present invention has been described with reference to the specific details of particular embodiments thereof. These details are not intended to limit the scope of protection of the invention, except to the extent and extend those limitations which are included in the claims accompanying the proceeding.

权利要求:
Claims (26)
[0001]
1. Photochromic-dichroic article, characterized in that it comprises: (a) a substrate (12) having a first surface (15) and a second surface (18); (b) a first fixed polarized layer (24) positioned on said first surface (15) of said substrate (12), said fixed polarized layer (24) having a first polarization axis (27); (c) a photochromic-dichroic layer (30) positioned on said first surface (15) of said substrate (12), said photochromic-dichroic layer (30) comprising a photochromic-dichroic compound, said photochromic-dichroic compound being laterally aligned within said photochromic-dichroic layer (30) and defining a second polarization axis (33) of said photochromic-dichroic layer (30); wherein said first polarization axis (27) and said second polarization axis (33) are oriented relative to each other at an angle of from 25° to 90°.
[0002]
2. Photochromic-dichroic article, characterized in that it comprises: (a) a substrate (60) having a first surface (63) and a second surface (66), and said substrate (60) having a first polarization axis (69) ); (b) a photochromic-dichroic layer (30) positioned on said first surface (63) of said substrate (60), said photochromic-dichroic layer (30) comprising a photochromic-dichroic compound, said photochromic-dichroic compound being laterally aligned within said photochromic-dichroic layer (30) and defining a second polarization axis (33) of said photochromic-dichroic layer (30); wherein said first polarization axis (69) and said second polarization axis (33) are oriented relative to each other at an angle of from 25° to 90°.
[0003]
3. Photochromic-dichroic article, according to claim 2, characterized in that it additionally comprises a birefringent layer (72) comprising a polymer, said birefringent layer (72) being interposed between said substrate (60) and said photochromic layer -dichroic (30).
[0004]
4. Photochromic-dichroic article, according to any one of claims 1 or 2, characterized in that it comprises a fixed dye.
[0005]
5. Photochromic-dichroic article, according to claim 4, characterized in that said fixed dye, from said fixed polarized layer, is selected from azo dyes, anthraquinone dyes, xanthene dyes, azime dyes, iodine, iodide salts, polyazo dyes, stilbene dyes, pyrazolone dyes, thiphenylmethane dye, quinoline dye, oxazine dye, thiazine dye, polyene dye, and mixtures thereof.
[0006]
6. Photochromic-dichroic article, according to claim 1, characterized in that said photochromic-dichroic layer (24) comprises a polymer, said polymer being laterally aligned along with a first lateral direction within said fixed polarized layer (24) and defining said first polarization axis (27) of said fixed polarized layer (24).
[0007]
7. Photochromic-dichroic article, according to claim 1, characterized in that said fixed polarized layer (24) is defined by a polymeric sheet, said polymeric sheet comprising said dichroic photochromic compound, said polymeric sheet being laterally aligned to the along a second lateral direction, and said photochromic-dichroic compound being laterally aligned along said second lateral direction.
[0008]
8. Photochromic-dichroic article, according to claim 1, characterized in that said photochromic-dichroic layer (30) additionally comprises: - an anisotropic material, wherein the anisotropic material of said photochromic-dichroic layer (30) comprises a liquid crystal material.
[0009]
9. Photochromic-dichroic article according to claim 1, characterized in that said photochromic-dichroic layer (30) further comprises a phase-separated polymer comprising a matrix phase that is at least partially ordered; and a guest phase that is at least partially ordered; said invited phase comprising said photochromic-dichroic compound, and said photochromic-dichroic compound being at least partially aligned with at least a portion of said invited phase of said photochromic-dichroic layer (30).
[0010]
10. Photochromic-dichroic article, according to claim 1, characterized in that said photochromic-dichroic layer (30) further comprises a polymeric interpenetrating network comprising an anisotropic material that is at least partially ordered, and a polymeric material; wherein said anisotropic material of said photochromic-dichroic layer (30) comprises said photochromic-dichroic compound, and said photochromic-dichroic compound being at least partially aligned with at least a portion of said anisotropic material of said photochromic-dichroic layer (30).
[0011]
11. Photochromic-dichroic article, according to claim 1, characterized in that said photochromic-dichroic layer (30) comprises at least one additive selected from dyes, alignment promoters, horizontal alignment agents, kinetic-enhancing additives, photoinitiators, thermal initiators, polymerization inhibitors, solvents, light stabilizers, heat stabilizers, mold release agents, rheology controlling agents, leveling agents, free radical scavengers, and adhesion promoters.
[0012]
12. Photochromic-dichroic article, according to claim 1, characterized in that the photochromic-dichroic layer (30) further comprises at least one dichroic material chosen from azomethine, indigoids, thioindigoids, merocyanines, indans, quinophthalonic dyes, perylene, phthaloprines, triphenodiaxozines, indoloquinoxalines, imidazo-triazines, tetrazines, azo and (poly)azo dyes, benzoquinones, naphthoquinones, anthroquinone and (poly)anthroquinones, anthropyrimidinones, iodine and iodates.
[0013]
13. Photochromic-dichroic article, according to claim 1, characterized in that said photochromic-dichroic compound comprises at least one photochromic portion, and each photochromic portion is independently selected from indeno-fused naphthopyrans, naphtho[1, 2-b]pyrans, naphtho[2,1-b]pyrans, spirofluoroene[1,2-b]pyrans, phenanthropyrans, quinolinopyrans, fluoroantenopyrans, spiropyrans, benzoxazines, naphthoxazine, spiro(indoine)naphthoxaxins, spiro(indoline)pyridobenzoxazines, spiro(indoline)fluoranthenoxazines, spiro(indoline)quinoxazines, fulgids, fulgimides, diarylethenes, diarylalkylethylenes, diarylkenylethenes, thermally reversible photochromic compounds, and non-thermally reversible photochromic compounds, and mixtures thereof.
[0014]
14. Photochromic-dichroic article, according to claim 1, characterized in that it comprises a photochromic-dichroic layer (30), wherein said alignment layer and said photochromic-dichroic layer (30) abuts at least partially a in the other.
[0015]
15. Photochromic-dichroic article, according to claim 1, characterized in that it further comprises a top cover (51) comprising an ultraviolet light absorber, and said top cover layer (51) resides on both, said first fixed polarized layer (24) and said photochromic-dichroic layer (30).
[0016]
16. Photochromic-dichroic article, according to claim 15, characterized in that the top cover (51) comprises a hard coating layer (54), wherein the hard coating layer (54) resides on said layer of top cover (51).
[0017]
17. Photochromic-dichroic article, according to claim 1, characterized in that it additionally comprises a birefringent layer (57) comprising a polymer, said birefringent layer (57) being interposed between said fixed polarized layer (24) and said layer photochromic-dichroic (30).
[0018]
18. Photochromic-dichroic article, according to claim 17, characterized in that said birefringent layer (57) is operable for transmitted radiation of circular polarization or transmitted radiation of elliptical polarization.
[0019]
19. A photochromic-dichroic article according to claim 17, characterized in that said birefringent layer (57) comprises a first ordered region having a first general direction, and at least one adjacent second ordered region, the first ordered region having a second general direction which is the same or different from the first general direction so as to form a desired pattern in said birefringent layer (57).
[0020]
20. Photochromic-dichroic article, according to claim 17, characterized in that said birefringent layer (57) comprises a polymeric coating comprising self-arranging materials or film-forming materials.
[0021]
21. Photochromic-dichroic article, according to claim 17, characterized in that said birefringent layer (57) comprises a polymeric sheet comprising self-arranged materials, polycarbonate, polyamide, polyimide, poly(meth)acrylate, polycyclic alkene, polyurethane , poly(urea)urethane, polythiourethane, polythio(urea)urethane, poly(allyl carbonate), cellulose acetate, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, polyalkene, polyalkylene- vinyl acetate, poly(vinylacetate), poly(vinyl alcohol), poly(vinyl chloride), poly(vinylformal), poly(vinyl acetal), poly(vinylidene chloride), poly(ethylene terephthalate), polyester, polysulfone, polyolefin, copolymers thereof, and/or mixtures thereof.
[0022]
22. Photochromic-dichroic article, according to claim 17, characterized in that the birefringent layer (57) defines a quarter-wave plate.
[0023]
23. Photochromic-dichroic article, according to claim 1, characterized in that said photochromic-dichroic article (2) is selected from ophthalmic articles, display articles, windows, mirrors, and active liquid crystal cell articles , and passive liquid crystal cell article.
[0024]
24. Photochromic-dichroic article, according to any one of claims 18 to 22, characterized in that said photochromic-dichroic article is selected from the ophthalmic article, the ophthalmic articles being selected from: corrective lenses, non-corrective, contact lenses, intraocular lenses, magnifying lenses, protective lenses, and visors.
[0025]
25. Photochromic-dichroic article, according to claim 23, characterized in that said photochromic-dichroic article is selected from display articles, the display articles being selected from elements of screens, monitors, and security elements.
[0026]
26. Photochromic-dichroic article, according to claim 1, characterized in that the substrates are selected from undyed substrates, dyed substrates, photochromic substrates, and dyed photochromic substrates.

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引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

US6245399B1|1998-10-14|2001-06-12|3M Innovative Properties Company|Guest-host polarizers|

---

US6316570B1|1999-06-23|2001-11-13|Ppg Industries Ohio, Inc.|Polymerizable composition of aliphatic polyol |

---

TWI230275B|2000-05-12|2005-04-01|Kuraray Co|Polyvinyl alcohol film and polarization film|

---

TW534869B|2000-06-09|2003-06-01|Mitsubishi Gas Chemical Co|Synthetic resin laminate having both polarization characteristic and photochromism characteristic, and molded article obtained therefrom|

---

US6926405B2|2003-06-06|2005-08-09|Younger Mfg. Co.|Eyewear lens having selective spectral response|

---

US7256921B2|2003-07-01|2007-08-14|Transitions Optical, Inc.|Polarizing, photochromic devices and methods of making the same|

---

US8545984B2|2003-07-01|2013-10-01|Transitions Optical, Inc.|Photochromic compounds and compositions|

---

US9096014B2|2003-07-01|2015-08-04|Transitions Optical, Inc.|Oriented polymeric sheets exhibiting dichroism and articles containing the same|

---

US7632540B2|2003-07-01|2009-12-15|Transitions Optical, Inc.|Alignment facilities for optical dyes|

---

US8089678B2|2003-07-01|2012-01-03|Transitions Optical, Inc|Clear to circular polarizing photochromic devices and methods of making the same|

---

US8545015B2|2003-07-01|2013-10-01|Transitions Optical, Inc.|Polarizing photochromic articles|

---

US7315341B2|2003-11-18|2008-01-01|Fujifilm Corporation|Liquid crystal display device with retardation layer with different relative humidity|

---

US7504054B2|2003-12-11|2009-03-17|Bayer Materialscience Llc|Method of treating a plastic article|

---

KR101237182B1|2004-12-21|2013-03-04|코닝 인코포레이티드|Light polarizing products and method of making same|

---

JP2008122485A|2006-11-09|2008-05-29|Nitto Denko Corp|Polarizer, polarizing plate, circular polarization filter, image display device, and manufacturing method of polarizer|

---

JP5183165B2|2006-11-21|2013-04-17|富士フイルム株式会社|Method for producing article having birefringence pattern|

---

US20080187749A1|2007-01-11|2008-08-07|Ppg Industries Ohio, Inc.|Optical element having light influencing property|

---

US8177358B2|2008-10-09|2012-05-15|SOL-Grid, LLC.|Polarized eyewear|

---

US20100014010A1|2008-06-27|2010-01-21|Transitions Optical, Inc.|Formulations comprising mesogen containing compounds|

---

JP2010072516A|2008-09-22|2010-04-02|Fujifilm Corp|Optical film, polarizing plate, and liquid crystal display device|

---

JP5481250B2|2010-03-26|2014-04-23|富士フイルム株式会社|Article with birefringence pattern|

---

US8649081B1|2012-09-14|2014-02-11|Transitions Optical, Inc.|Photochromic article having two at least partially crossed photochromic-dichroic layers|US20140264979A1|2013-03-13|2014-09-18|Transitions Opticals, Inc.|Method of preparing photochromic-dichroic films having reduced optical distortion|

---

JP6211488B2|2014-08-25|2017-10-11|富士フイルム株式会社|Liquid crystal display device and method for producing polarizing plate|

---

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---

CN106154358A|2015-03-24|2016-11-23|陈国樑|Tool filters and reduces the eyeglass composition of blue light penetrance and according to the eyeglass made by this composition|

---

CN104898300B|2015-06-30|2017-06-13|厦门天马微电子有限公司|Polaroid glasses|

---

WO2017090725A1|2015-11-27|2017-06-01|三井化学株式会社|Polymerizable composition for optical material, and optical material and plastic lens obtained from same|

---

CN105807359B|2016-05-30|2017-04-05|京东方科技集团股份有限公司|Line polarisation layer, rotatory polarization layer, flexible display apparatus and preparation method thereof|

---

CN105866977B|2016-05-30|2019-04-30|视悦光学有限公司|It is a kind of to become tea aspheric base sheet and preparation method thereof fastly|

---

CN110114703B|2016-12-30|2022-01-11|光学转变有限公司|Polarized article and method of forming a polarized article|

---

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---

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---

US10866455B2|2017-10-19|2020-12-15|Ppg Industries Ohio, Inc.|Display devices including photochromic-dichroic compounds and dichroic compounds|

---

EP3502768A1|2017-12-20|2019-06-26|Essilor International|Polarized eyewear with selective blocking|

---

US11003016B2|2018-09-21|2021-05-11|Coopervision International Limited|Flexible, adjustable lens power liquid crystal cells and lenses|

---

JP2021179605A|2020-05-08|2021-11-18|日東電工株式会社|Polarization film laminated body|

法律状态:
2018-11-21| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2020-06-09| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-11-23| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2022-02-01| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 13/09/2013, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US13/616,591|2012-09-14|

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US13/616,591|US9030740B2|2012-09-14|2012-09-14|Photochromic article having at least partially crossed polarized photochromic-dichroic and fixed-polarized layers|

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PCT/US2013/059774|WO2014043546A1|2012-09-14|2013-09-13|A photochromic article having at least partially crossed polarized photochromic-dichroic and fixed-polarized layers|

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