Polychromatic photochromic optical article

Abstract

A photochromic optical article is provided. The photochromic optical article includes: an optical substrate comprising a first surface and a second surface opposite the first surface. The photochromic optical article reversibly transitions from an unactivated state to an activated state in response to actinic radiation. The activated state includes: a first color; and at least one image over at least a portion of the optical substrate, wherein the at least one image includes at least one second color that is visually distinct from the first color, and wherein the at least one image is visually indiscernible in the unactivated state. A method of making a photochromic optical article is also provided.

Description

POLYCHROMATIC PHOTOCHROMIC OPTICAL ARTICLEBACKGROUND OF THE INVENTIONField of the Invention

[0001] The present invention relates to photochromic optical articles. In particular, the present invention relates to photochromic optical articles that reversibly transition from an unactivated state to an activated state in response to actinic radiation, where the activated state includes a first color and at least one image over at least a portion of the optical substrate. The at least one image includes at least one second color that is visually distinct from the first color, and the at least one image is visually indiscernible in the unactivated state.Description of Related Art

[0002] In response to certain wavelengths of electromagnetic radiation (e.g., actinic radiation), photochromic compounds typically undergo a transformation from one form or state to another form, with each form having a characteristic or distinguishable absorption spectrum associated therewith. Typically, upon exposure to actinic radiation, many photochromic compounds transform from a closed-form, which corresponds to an unactivated or bleached state (e.g., substantially colorless) to an open-form, which corresponds to an activated or colored state. When the actinic radiation is removed, the photochromic compounds reversibly transform from the activated or colored state back to the unactivated or bleached state.

[0003] Compositions and articles, such as eyewear lenses, that contain photochromic materials or have photochromic materials applied thereto, such as in form of a photochromic coating composition, typically display colorless (or clear) and colored states that correspond to the bleached and colored states of the photochromic materials contained therein and / or applied thereto. However, these commercially-sold photochromic articles, such as eyewear lenses, are only available in a wide variety of monochromatic colors.

[0004] It would be desirable for a photochromic optical article to include two or more distinct colors to create a polychromatic effect, represented by patterns, shapes, logos, monograms (and the like) on the optical article, when in the activated state.SUMMARY

[0005] In some non-limiting examples or aspects of the present disclosure, provided herein is a photochromic optical article. The photochromic optical article includes: an optical substrate including a first surface and a second surface opposite the first surface, wherein the photochromic optical article reversibly transitions from an unactivated state to an activated state in response to actinic radiation, wherein the activated state includes: a first color; and at least one image over at least a portion of the optical substrate, wherein the at least one image includes at least one second color that is visually distinct from the first color, and wherein the at least one image is visually indiscernible in the unactivated state.

[0006] In some non-limiting examples or aspects of the present disclosure, provided herein is a method of making a photochromic optical article. The method of making a photochromic optical article includes: providing an optical substrate including an at least one first photochromic material, wherein the optical substrate includes a first surface and a second surface opposite the first surface; and forming an at least one image, wherein forming the at least one image includes: forming a pattern for the at least one image; applying an at least one second photochromic material or an ultraviolet light absorbing material to the pattern for the at least one image; heating the optical substrate to diffuse at least a portion of the at least one second photochromic material or the ultraviolet light absorbing material into the optical substrate including the at least one first photochromic material, wherein the photochromic optical article reversibly transitions from an unactivated state to an activated state in response to actinic radiation, wherein the activated state includes: a first color formed from the at least one first photochromic material; and the at least one image over at least a portion of the optical substrate, wherein the at least one image includes an at least one second color that is visually distinct from the first color, wherein the at least one second color is formed from the at least one second photochromic material or the ultraviolet light absorbing material; and wherein the at least one image is visually indiscernible in the unactivated state.

[0007] A photochromic optical article and a method of making a photochromic optical article may be characterized by one or more of the following aspects.

[0008] A photochromic optical article may be characterized by one or more of the following aspects.

[0009] In a first aspect, a photochromic optical article, includes: an optical substrate comprising a first surface and a second surface opposite the first surface; wherein the photochromic optical article reversibly transitions from an unactivated state to an activated state in response to actinic radiation, wherein the activated state includes: a first color; and at least one image over at least a portion of the optical substrate, wherein the at least one image includes at least one second color that is visually distinct from the first color, and wherein the at least one image is visually indiscernible in the unactivated state.

[0010] In a second aspect, in the photochromic optical article in accordance with the first aspect, the at least one image is selected from the group consisting of shapes, patterns, symbols, logos, monograms, text, pictures, and combinations thereof.[OH] In a third aspect, in the photochromic optical article in accordance with the first aspect or the second aspect, the photochromic optical article includes: at least one first photochromic material that forms the first color; and at least one second photochromic material or an ultraviolet light absorbing material that forms the at least one second color.

[0012] In a fourth aspect, in the photochromic optical article in accordance with the third aspect, the at least one second photochromic material forms the at least one second color.

[0013] In a fifth aspect, in the photochromic optical article in accordance with the third aspect, the ultraviolet light absorbing material forms the at least one second color.

[0014] In a sixth aspect, in the photochromic optical article in accordance with the third or fifth aspect, the at least one second photochromic material is different from the first photochromic material.

[0015] In a seventh aspect, in the photochromic optical article in accordance with the third or fifth aspect, the at least one second photochromic material is the same as the at least one first photochromic material.

[0016] In an eighth aspect, in the photochromic optical article in accordance with the third aspect or the fourth aspect, the photochromic optical article includes at least one first photochromic material and an ultraviolet light absorbing material that forms the at least one second color.

[0017] In a ninth aspect, in the photochromic optical article in accordance with any one of the third aspect to the eighth aspect, the at least one first photochromic material, the at least onesecond photochromic material, and the ultraviolet light absorbing material, when present, are imbibed into the first surface of the optical substrate.

[0018] In a tenth aspect, in the photochromic optical article in accordance with any one of the first aspect to the ninth aspect, the photochromic article includes at least one photochromic layer positioned over at least a portion of the first surface of the substrate.

[0019] In an eleventh aspect, in the photochromic optical article in accordance with the tenth aspect, the at least one photochromic layer includes a photochromic coating.

[0020] In a twelfth aspect, in the photochromic optical article in accordance with the tenth aspect or the eleventh aspect, further including one or more additional layers positioned over at least a portion of the at least one photochromic layer, wherein the one or more additional layers preferably are selected from the group consisting of barrier coatings and films, alignment coatings and films, transitional coatings and films, primer coatings and films, protective coatings and films, anti -reflective coatings and films, polarizing coatings and films and combinations thereof.

[0021] In a thirteenth aspect, in the photochromic optical article in accordance with any one of the first aspect to the twelfth aspect, the at least one image includes two or more second colors that are visually distinct from the first color, and wherein the two or more second colors are visually distinct from one another.

[0022] In a fourteenth aspect, in the photochromic optical article in accordance with any one of the first aspect to the thirteenth aspect, the activated state includes two or more images over at least a portion of the optical substrate.

[0023] In a fifteenth aspect, in the photochromic optical article in accordance with the fourteenth aspect, the two or more images include at least one second color that is visually distinct from the first color.

[0024] In a sixteenth aspect, in the photochromic optical article in accordance with the fourteenth aspect, the two or more images each independently include at least one second color that is visually distinct from the first color and visually distinct from one another.

[0025] In an seventeenth aspect, in the photochromic optical article in accordance with the fourteenth aspect, the two or more images include two or more second colors that are visually distinct from the first color and are visually distinct from one another.

[0026] In an eighteenth aspect, in the photochromic optical article in accordance with any one of the first aspect to the seventeenth aspect, the photochromic optical article is selected from the group consisting of ophthalmic articles, display articles, windows, mirrors, active liquid crystal cell articles, and passive liquid crystal cell articles.

[0027] In a nineteenth aspect, in the photochromic optical article in accordance with any one of the first aspect to the eighteenth aspect, the photochromic optical article is a display article, and the display article is selected from the group consisting of screens, monitors, and security elements.

[0028] In a twentieth aspect, in the photochromic optical article in accordance with any one of the first aspect to the eighteenth aspect, the photochromic optical article is an ophthalmic article.

[0029] In a twenty-first aspect, in the photochromic optical article in accordance with the twentieth aspect, the ophthalmic article is selected from the group consisting of corrective lenses, non-corrective lenses, contact lenses, intra-ocular lenses, magnifying lenses, protective lenses, and visors.

[0030] In a twenty-second aspect, in the photochromic optical article in accordance with the twentieth or the twenty -first aspect, the ophthalmic article includes a peripheral zone and a line- of-sight zone.

[0031] In a twenty-third aspect, in the photochromic optical article in accordance with the twenty-second aspect, the at least one image is positioned in the peripheral zone, the light-of- sight zone, or combinations thereof.

[0032] In a twenty-fourth aspect, in the photochromic optical article in accordance with the twenty-second or the twenty-third aspect, the at least one image is positioned in the peripheral zone.

[0033] In a twenty-fifth aspect, a method of making a photochromic optical article includes: providing an optical substrate including an at least one first photochromic material, wherein the optical substrate includes a first surface and a second surface opposite the first surface; and forming an at least one image, wherein forming the at least one image includes: forming a pattern for the at least one image; applying an at least one second photochromic material or an ultraviolet light absorbing material to the pattern for the at least one image; heating the optical substrate to diffuse at least a portion of the at least one second photochromic material or the ultraviolet lightabsorbing material into the optical substrate including the at least one first photochromic material, wherein the photochromic optical article reversibly transitions from an unactivated state to an activated state in response to actinic radiation, wherein the activated state includes: a first color formed from the at least one first photochromic material; and the at least one image over at least a portion of the optical substrate, wherein the at least one image includes an at least one second color that is visually distinct from the first color, wherein the at least one second color is formed from the at least one second photochromic material or the ultraviolet light absorbing material; and wherein the at least one image is visually indiscernible in the unactivated state.

[0034] In a twenty-sixth aspect, in the method of making the photochromic optical article in accordance with the twenty-fifth aspect, the at least one photochromic material is in an at least one photochromic layer positioned over the first surface of the optical substrate, wherein at least a portion of the at least one second photochromic material or the ultraviolet light absorbing material diffuses into the at least one photochromic layer.

[0035] In a twenty-seventh aspect, in the method of making the photochromic optical article in accordance with the twenty-fifth aspect, the at least one photochromic material is incorporated into the optical substrate, wherein at least a portion of the at least one second photochromic material or the ultraviolet light absorbing material diffuses into the optical substrate.

[0036] In a twenty-eighth aspect, in the method of making the photochromic optical article in accordance with any one of the twenty-fifth aspect to the twenty-seventh aspect, further including applying a temporary etch layer over the optical substrate including the at least one first photochromic material, wherein when the at least one photochromic material is in an at least one photochromic layer positioned over the first surface of the optical substrate, the temporary etch layer is positioned over at least a portion of the at least one photochromic layer, or wherein when the at least one photochromic material is incorporated into the optical substrate, the temporary etch layer is positioned over at least a portion of the first surface of the optical substrate.

[0037] In a twenty-ninth aspect, in the method of making the photochromic optical article in accordance with the twenty-eighth aspect, further including applying a removable buffer layer over at least a portion of the temporary etch layer.

[0038] In a thirtieth aspect, in the method of making the photochromic optical article in accordance with twenty-ninth aspect, further including etching at least a portion of the removablebuffer layer and at least a portion of the temporary etch layer to form the pattern for the at least one image.

[0039] In a thirty-first aspect, in the method of making the photochromic optical article in accordance with the thirtieth aspect, the at least a portion of the removable buffer layer and the at least a portion of the temporary etch layer are etched by a laser.

[0040] In a thirty-second aspect, in the method of making the photochromic optical article in accordance with any one of the twenty-eighth to the thirty-first aspect, the at least one second photochromic material or the ultraviolet light absorbing material is applied to the pattern for the at least one image in an imbibition composition or a dye transfer substrate.

[0041] In a thirty -third aspect, in the method of making the photochromic optical article in accordance with the thirty-second aspect, the at least one second photochromic material or the ultraviolet light absorbing material is applied to the pattern for the at least one image in the imbibition composition.

[0042] In a thirty -fourth aspect, in the method of making the photochromic optical article in accordance with the thirty-second aspect, the at least one second photochromic material or the ultraviolet light absorbing material is applied over the pattern for the at least one image in the dye transfer substrate.

[0043] In a thirty-fifth aspect, in the method of making the photochromic optical article in accordance with any one of the twenty -fifth to the thirty-fourth aspect, further including washing the optical substrate after applying the at least one second photochromic material or the ultraviolet light absorbing material to the pattern for the at least one image.

[0044] In a thirty-sixth aspect, in the method of making the photochromic optical article in accordance with the thirty -fifth aspect, the optical substrate is washed with an aqueous wash.

[0045] In a thirty-seventh aspect, in the method of making the photochromic optical article in accordance with the twenty-sixth or the twenty-seventh aspect, further including: applying a clear coating over at least a portion of the at least one photochromic layer; or applying a clear coating over at least a portion of the first surface of the optical substrate, wherein at least a portion of the at least one second photochromic material or the ultraviolet light absorbing material diffuses into the clear coating.

[0046] In a thirty-eighth aspect, in the method of making the photochromic optical article in accordance with the thirty-seventh aspect, the clear coating is a polyurethane coating.

[0047] In a thirty -ninth aspect, in the method of making the photochromic optical article in accordance with the thirty-seventh aspect or the thirty-eighth aspect, further including: applying a temporary etch layer over at least a portion of the clear coating; applying a removable buffer layer over at least a portion of the temporary etch layer; and etching at least a portion of the removable buffer layer and at least a portion of the temporary etch layer to form the pattern for the at least one image.

[0048] In a fortieth aspect in the method of making the photochromic optical article in accordance with any one of the thirty-seventh aspect to the thirty-ninth aspect, the at least one second photochromic material or the ultraviolet light absorbing material is applied to the pattern for the at least one image in an imbibition composition or a dye transfer substrate.

[0049] In a forty-first aspect, in the method of making the photochromic optical article in accordance with the twenty-sixth aspect, the at least one second photochromic material or the ultraviolet light absorbing material is applied to a dye transfer sheet in the pattern for the at least one image and the dye transfer sheet is contacted with the at least one photochromic layer.

[0050] In a forty-second aspect, in the method of making the photochromic optical article in accordance with the twenty -fifth aspect to the forty-first aspect, the at least one image is selected from the group consisting of shapes, patterns, symbols, logos, monograms, text, pictures, and combinations thereof.

[0051] In a forty-third aspect, in the method of making the photochromic optical article in accordance with the twenty-fifth aspect to the forty-second aspect, the at least one second photochromic material forms the at least one second color.

[0052] In a forty-fourth aspect, in the method of making the photochromic optical article in accordance with the twenty-fifth aspect to the forty-second aspect, the ultraviolet light absorbing material forms the at least one second color.

[0053] In a forty-fifth aspect, in the method of making the photochromic optical article in accordance with the twenty-fifth aspect to the forty-third aspect, the at least one second photochromic material is different from the first photochromic material.

[0054] In a forty-sixth aspect, in the method of making the photochromic optical article in accordance with the twenty-fifth aspect to the forty-third aspect, the at least one second photochromic material is the same as the at least one first photochromic material.

[0055] In a forty-seventh aspect, in the method of making the photochromic optical article in accordance with the twenty-fifth aspect to the forty-fourth aspect, the at least one first photochromic material and the ultraviolet light absorbing material forms the at least one second color.

[0056] In a forty-eighth aspect, in the method of making the photochromic optical article in accordance with the twenty-sixth aspect, the at least one photochromic layer includes a photochromic coating.

[0057] In a forty-ninth aspect, in the method of making the photochromic optical article in accordance with any one of the twenty -fifth aspect to the forty-eighth aspect, further including applying one or more additional layers over at least a portion of the optical substrate including the at least one first photochromic material, wherein the one or more additional layers preferably are selected from the group consisting of clear coatings and films, barrier coatings and films, alignment coatings and films, transitional coatings and films, primer coatings and films, protective coatings and films, anti -reflective coatings and films, polarizing coatings and films and combinations thereof.

[0058] In a fiftieth aspect, in the method of making the photochromic optical article in accordance with any one of the twenty-fifth aspect to the forty -ninth aspect, the at least one image includes two or more second colors that are visually distinct from the first color, and wherein the two or more second colors are visually distinct from one another.

[0059] In a fifty-first aspect, in the method of making the photochromic optical article in accordance with the fiftieth aspect, the activated state includes two or more images over at least a portion of the optical substrate.

[0060] In a fifty-second aspect, in the method of making the photochromic optical article in accordance with the fifty-first aspect, the two or more images include at least one second color that is visually distinct from the first color.

[0061] In a fifty-third aspect, in the method of making the photochromic optical article in accordance with the fifty -first aspect, the two or more images each independently include at least one second color that is visually distinct from the first color and visually distinct from one another.

[0062] In a fifty -fourth aspect, in the method of making the photochromic optical article in accordance with the fifty -first aspect, the two or more images include two or more second colors that are visually distinct from the first color and are visually distinct from one another.

[0063] In a fifty-fifth aspect, in the method of making the photochromic optical article in accordance with any one of the twenty-fifth to the fifty-fourth aspect, the photochromic optical article is selected from the group consisting of ophthalmic articles, display articles, windows, mirrors, active liquid crystal cell articles, and passive liquid crystal cell articles.

[0064] In a fifty-sixth aspect, in the method of making the photochromic optical article in accordance with any one of the twenty-fifth to the fifty-fifth aspect, the photochromic optical article is a display article, and the display article is selected from the group consisting of screens, monitors, and security elements.

[0065] In a fifty-seventh aspect, in the method of making the photochromic optical article in accordance with any one of the twenty-fifth to the fifty-fifth aspect, the photochromic optical article is an ophthalmic article.

[0066] In a fifty-eighth aspect, in the method of making the photochromic optical article in accordance with the fifty-seventh aspect, the ophthalmic article is selected from the group consisting of corrective lenses, non-corrective lenses, contact lenses, intra-ocular lenses, magnifying lenses, protective lenses, and visors.

[0067] In a fifty -ninth aspect, in the method of making the photochromic optical article in accordance with the fifty-seventh or the fifty-eighth aspect, the ophthalmic article includes a peripheral zone and a line-of-sight zone.

[0068] In a sixtieth aspect, in the method of making the photochromic optical article in accordance with the fifty-ninth aspect, the at least one image is positioned in the peripheral zone, the light-of-sight zone, or combinations thereof.

[0069] In a sixty-first aspect, in the method of making the photochromic optical article in accordance with the fifty-ninth aspect or the sixtieth aspect, the at least one image is positioned in the peripheral zone.BRIEF DESCRIPTION OF THE DRAWINGS

[0070] A complete understanding of the invention will be obtained from the following description when taken in connection with the accompanying drawing figures, wherein like reference numbers identify like parts throughout.

[0071] FIGS. 1A and IB are side views (not to scale) of photochromic optical articles in accordance with the present disclosure;

[0072] FIG. 2 is a front view (not to scale) of a photochromic optical article in the unactivated state;

[0073] FIG. 3 is a front view (not to scale) of a photochromic optical article in the activated state;

[0074] FIG. 4 is an exemplary photochromic optical article, in the form of photochromic eyewear, in the activated state;

[0075] FIG. 5 is an exemplary photochromic optical article, in the form of photochromic eyewear, in the activated state;

[0076] FIG. 6 is an exemplary photochromic optical article, in the form of photochromic eyewear, in the activated state;

[0077] FIG. 7 is an exemplary photochromic optical article, in the form of photochromic eyewear, in the activated state;

[0078] FIG. 8 is an exemplary photochromic optical article, in the form of photochromic eyewear, in the activated state;

[0079] FIG. 9 is an exemplary photochromic optical article, in the form of photochromic eyewear, in the activated state;

[0080] FIG. 10 is an exemplary photochromic optical article, in the form of photochromic eyewear, in the activated state;

[0081] FIG. 11 is an exemplary photochromic optical article, in the form of photochromic eyewear, in the activated state;

[0082] FIG. 12 is an exemplary photochromic optical article, in the form of photochromic eyewear, in the activated state;

[0083] FIG. 13 is an exemplary photochromic optical article, in the form of photochromic eyewear, in the activated state;

[0084] FIG. 14 is an exemplary photochromic optical article, in the form of photochromic eyewear, in the activated state;

[0085] FIGS. 15A and 15B are block diagrams illustrating methods for making the photochromic optical articles of the present invention;

[0086] FIGS. 16A and 16B are block diagrams illustrating methods for making the photochromic optical articles of the present invention;

[0087] FIGS. 17A and 17B are block diagrams illustrating methods for making the photochromic optical articles of the present invention;

[0088] FIGS. 18A and 18B are block diagrams illustrating methods for making the photochromic optical articles of the present invention; and

[0089] FIGS. 19A and 19B are block diagrams illustrating methods for making the photochromic optical articles of the present invention.DESCRIPTION OF THE INVENTION

[0090] As used herein, the singular form of “a”, “an”, and “the” include plural referents unless the context clearly dictates otherwise.

[0091] Spatial or directional terms, such as “left”, “right”, “inner”, “outer”, “above”, “below”, and the like, relate to the invention as shown in the drawing figures and are not to be considered as limiting as the invention can assume various alternative orientations.

[0092] Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as modified in all instances by the term “about”. By “about” is meant plus or minus ten percent of the stated value. However, this should not be considered as limiting to any analysis of the values under the doctrine of equivalents.

[0093] Unless otherwise indicated, all ranges or ratios disclosed herein are to be understood to encompass the beginning and ending values and any and all subranges or subratios subsumed therein. For example, a stated range or ratio of “1 to 10” should be considered to include any and all subranges or subratios between (and inclusive of) the minimum value of 1 and the maximum value of 10; that is, all subranges or subratios beginning with a minimum value of 1 or more and ending with a maximum value of 10 or less. The ranges and / or ratios disclosed herein represent the average values over the specified range and / or ratio.

[0094] The terms “first”, “second”, and the like are not intended to refer to any particular order or chronology, but refer to different conditions, properties, or elements.

[0095] All documents referred to herein are “incorporated by reference” in their entirety.

[0096] The term “at least” is synonymous with “greater than or equal to”.

[0097] The term “not greater than” is synonymous with “less than or equal to”.

[0098] The term “adjacent” means proximate to and optionally, in direct contact with.

[0099] The term “includes” is synonymous with “comprises”.

[0100] As used herein, “at least one of’ is synonymous with “one or more of’. For example, the phrase “at least one of A, B, or C” means any one of A, B, or C, or any combination of any two or more of A, B, or C. For example, “at least one of A, B, or C” includes A alone; or B alone; or C alone; or A and B; or A and C; or B and C; or all of A, B, and C.

[0101] 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 graft polymers.

[0102] As used herein, the term “(meth)acrylate” and similar terms, such as “(meth)acrylic acid ester” means derivatives of acrylic acid and methacrylic acid, inclusive of acrylate esters, methacrylate esters, acrylamides, methacrylamides, acrylic acid and methacrylic acid. As used herein, the term “(meth)acrylic acid” means methacrylic acid and / or acrylic acid.

[0103] As used herein, the term “photochromic” and similar terms, such as “photochromic compound”, means having an absorption spectrum for at least visible radiation that varies in response to absorption of at least actinic radiation.

[0104] As used herein, the term “photochromic material” means any substance that is adapted to display photochromic properties (such as, adapted to have an absorption spectrum for at least visible radiation that varies in response to absorption of at least actinic radiation) and which includes at least one photochromic compound. Photochromic materials include thermally reversible photochromic materials and compounds and non-thermally reversible photochromic materials and compounds. The term “thermally reversible photochromic compounds / materials” as used herein means compounds / materials capable of converting from a first state, for example, an unactivated or bleached state, to second state, for example an activated or colored state, in response to actinic radiation, and reverting back to the first state in response to thermal energy. The term “non-thermally reversible photochromic compounds / materials” as used herein meanscompounds / materials capable of converting from an first state, for example an unactivated or bleached state, to a second state, for example an activated or colored state, in response to actinic radiation, and reverting back to the first state in response to actinic radiation of substantially the same wavelength(s) as the absorption(s) of the second state.

[0105] 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 instead refer to two different conditions or properties. For purposes of non-limiting illustration, the first state and the second state of a photochromic compound can differ with respect to at least one optical property, such as but not limited to the absorption of visible and / or UV radiation. Thus, according to various non-limiting embodiments disclosed herein, the photochromic materials of the present invention can have a different absorption spectrum in each of the first and second states. For example, while not limiting herein, a photochromic material of the present invention can be clear in the first state, for example, the unactivated or bleached state, and colored in the second state, for example the activated or bleached state.

[0106] As used herein, the term “photochromic optical article” means an optical substrate having at least one photochromic material located over at least a portion of the substrate and / or incorporated into the substrate.

[0107] The term “optical” means pertaining to or associated with light and / or vision. For example, an optical element, article, or device can be chosen from ophthalmic elements, articles, and devices; display elements, articles, and devices; visors; windows; and mirrors.

[0108] The term “ophthalmic” means pertaining to or associated with the eye and vision. Non-limiting examples of ophthalmic articles or elements include corrective and non-corrective lenses, including single vision or multi-vision lenses, which may be either segmented or nonsegmented multi-vision lenses (such as, but not limited to, bifocal lenses, trifocal lenses, and progressive lenses), as well as other elements used to correct, protect, or enhance (cosmetically or otherwise) vision, including without limitation, contact lenses, intra-ocular lenses, magnifying lenses, and protective lenses or visors.

[0109] As used herein, the terms “lens” and “lenses” mean and encompass at least individual lenses, lens pairs, partially formed (or semi-finished) lenses, fully formed (or finished) lenses, and lens blanks.

[0110] As used herein the term “display” means the visible or machine-readable representation of information in words, numbers, symbols, designs or drawings. Non-limiting examples of display elements include screens, monitors, and security elements, such as security marks.[OHl] As used herein, the term “transparent”, such as used in connection with a substrate, film, material, and / or coating, means that the indicated substrate, film, material, and / or coating has the property of transmitting visible light without appreciable scattering so that objects lying beyond are visibly observable.

[0112] As used herein, the term “actinic radiation” means electromagnetic radiation that is capable of causing a response in a material, such as, but not limited to, transforming a photochromic material from one form or state to another as will be discussed in further detail herein.

[0113] As used herein, the terms “ultraviolet”, “UV”, “ultraviolet light”, or “ultraviolet radiation” mean electromagnetic radiation having a wavelength in the range of 10 nm to 400 nm.

[0114] As used herein, the term “coating” means a supported film derived from a flowable coating material, which can optionally have a uniform thickness, and specifically excludes polymeric sheets. The terms “layer” and “film” each encompass both coatings (such as a coating layer or a coating film) and sheets, and a layer can include a combination of separate layers, including sub-layers and / or over-layers. The verb “coating” means, within appropriate context, the process of applying a coating material (or materials) to the substrate to form a coating (or coating layer).

[0115] As used herein, the terms “formed over”, “deposited over”, “provided over”, “applied over”, “residing over”, or “positioned over” mean formed, deposited, provided, applied, residing, or positioned on but not necessarily in direct (or abutting) contact with the underlying element, or surface of the underlying element. For example, a layer “positioned over” a substrate does not preclude the presence of one or more other layers, coatings, or films of the same or different composition located between the positioned or formed layer and the substrate.

[0116] As used herein, the terms “cure”, “cured”, and related terms, mean that at least a portion of the polymerizable and / or crosslinkable components that form a curable composition are at least partially polymerized and / or crosslinked. In accordance with some examples, the degree of crosslinking can range from 5% to 100% of complete crosslinking. In accordance withsome further examples, the degree of crosslinking can range from 30% to 95%, such as 35% to 95%, or 50% to 95%, or 50% to 85% of complete crosslinking. The degree of crosslinking can range between any combination of these recited lower and upper values, inclusive of the recited values.

[0117] The discussion of the invention may describe certain features as being “particularly” or “preferably” within certain limitations (e.g., “preferably”, “more preferably”, or “even more preferably”, within certain limitations). It is to be understood that the invention is not limited to these particular or preferred limitations but encompasses the entire scope of the disclosure.

[0118] The invention comprises, consists of, or consists essentially of the following examples of the invention, in any combination. Various examples of the invention may be discussed separately. However, it is to be understood that this is simply for ease of illustration and discussion. In the practice of the invention, one or more aspects of the invention described in one example can be combined with one or more aspects of the invention described in one or more of the other examples.

[0119] The invention is directed to a photochromic optical article 10. The photochromic optical article 10 comprises an optical substrate 12 comprising a first surface 14 and a second surface 16 opposite the first surface 14. The photochromic optical article 10 reversibly transitions from an unactivated state to an activated state in response to actinic radiation. The activated state comprises a first color and at least one image 18 over at least a portion of the optical substrate 12 (FIG. 3). The at least one image 18 comprises at least one second color that is visually distinct from the first color (FIG. 3). The at least one image 18 is visually indiscernible in the unactivated state (FIG. 2).

[0120] With reference to FIGS. 1-3, the photochromic optical article 10 comprises an optical substrate 12. The optical substrate 12 comprises a first surface 14 and a second surface 16 opposite the first surface. The optical substrate 12 can be of any desired material having any desired characteristics. In general, the optical substrate 12 can be made of various materials including, but not limited to, organic materials, inorganic materials, or combinations thereof (for example, composite materials).

[0121] Specific, non-limiting examples of organic materials that may be used to for the optical substrate 12 disclosed herein include polymeric materials, such as homopolymers and copolymers, prepared from the monomers and mixtures of monomers disclosed in U.S. PatentNo. 5,962,617 and in U.S. Patent No. 5,658,501 from column 15, line 28 to column 16, line 17. For example, such polymeric materials can be thermoplastic or thermoset polymeric materials, can be transparent or optically clear, and can have any refractive index required. Examples of such monomers and polymers include polyol(allyl carbonate) monomers, e.g., allyl di glycol carbonates such as diethylene glycol bis(allyl carbonate), which monomer is sold under the trademark 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 such polymer being sold under the trademark TRIVEX by PPG Industries, Inc.; polyol(meth)acryloyl terminated carbonate monomer; di ethylene 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); poly(vinyl chloride); poly(vinylidene chloride); polyethylene; polypropylene; polyurethanes; polythiourethanes; thermoplastic polycarbonates, such as the carbonate-linked resin derived from bisphenol A and phosgene, one such material being sold under the trademark LEXAN; polyesters, such as the material sold under the trademark MYLAR; poly(ethylene terephthalate); polyvinyl butyral; poly(methyl methacrylate), such as the material sold under the trademark PLEXIGLAS, and polymers prepared by reacting poly functional isocyanates with polythiols or polyepisulfide monomers, either homopolymerized or co-and / or terpolymerized with polythiols, polyisocyanates, and polyisothiocyanates; and optionally ethylenically unsaturated monomers or halogenated aromatic-containing vinyl monomers. Also contemplated are copolymers of such monomers and blends of the described polymers and copolymers with other polymers, for example, to form block copolymers or interpenetrating network products.

[0122] Non-limiting examples of inorganic materials suitable for use in forming the optical substrate 12 include glasses, minerals, ceramics, and metals. For example, the optical substrate 12 can comprise glass.

[0123] The optical substrates 12 can include untinted, tinted, linearly polarizing, circularly polarizing, or elliptically polarizing optical substrates. As used herein, with reference to optical substrates 12, the term “untinted” means optical substrates that are essentially free of coloring agent additions (such as, but not limited to, conventional dyes) and have an absorption spectrumfor visible radiation that does not vary significantly in response to actinic radiation. Further, with reference to optical substrates, the term “tinted” means optical substrates that have a coloring agent addition (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. As used herein, the term “linearly polarizing” with reference to optical substrates refers to optical substrates that are adapted to linearly polarize radiation (i.e., confine the vibrations of the electric vector of light waves to one direction). As used herein, the term “circularly polarizing” with reference to optical substrates refers to optical substrates that are adapted to circularly polarize radiation. As used herein, the term “elliptically polarizing” with reference to optical substrates refers to optical substrates that are adapted to elliptically polarize radiation.

[0124] The photochromic optical article 10 reversibly transitions from an unactivated state to an activated state in response to actinic radiation. The activated state of the photochromic optical article 10 comprises a first color and at least one image 18 over at least a portion of the optical substrate 12 (FIG. 3). The at least one image 18 comprises at least one second color that is visually distinct from the first color.

[0125] As used herein, “visually distinct” means that the first color and the at least one second color are visually different and can be easily distinguished by the eye as being different from one another. There is a distinct boundary between the first color and the at least one second color that is visible to the eye.

[0126] The first color may include, but is not limited, to gray, brown, green, blue, purple, orange, yellow, pink, red, and hues thereof. The term “hue” as used herein means a gradation or variety of a color.

[0127] The at least one second color may include, but is not limited, to gray, brown, green, blue, purple, orange, yellow, pink, red, and hues thereof.

[0128] In the activated state, the at least one second color of the at least one image 18 may be the same color as the first color, but the at least one second color has a different hue or level of saturation such that at least one second color is visually distinct from the first color. The “level of saturation” as used herein means the intensity of a color. As an example, the first color and the at least one second color may both be gray, but the gray of the at least one second color may be a lighter or darker gray than the gray of the first color.

[0129] In the activated state, the at least one second color of the at least one image 18 may be a different color from the first color. As an example, the first color may be brown and the at least one second color may be yellow.

[0130] The at least one image 18 over at least a portion of the optical substrate 12 becomes visible when the photochromic optical article 10 is in the activated state. In the unactivated state, the at least one image is visually indiscernible. As used herein “visually indiscernible” means that the at least one image 18 cannot be recognized or clearly perceived to a viewer.

[0131] FIGS. 4-14 illustrate exemplary photochromic optical articles in form of an ophthalmic article, specifically photochromic eyewear 100. However, it is to be understood that the invention is not limited to photochromic eyewear 100 but could be practiced with various ophthalmic articles or elements, display articles or elements, visors, windows, mirrors, active liquid crystal cell articles, and passive liquid crystal cell articles.

[0132] The photochromic eyewear 100 includes a frame 50 having a first opening 52 and a second opening 54. The first opening 52 and second opening 54 include an optical substrate 112 having an outer surface 114 and an inner surface opposite the outer surface. The optical substrate 112 can be any of the optical substrates described herein. The frame 50 may be provided in various shapes and may be made of any suitable material, such as polymers, plastics, or metals.

[0133] In FIGS. 2 and 4, the photochromic optical article 10, 100 is in the unactivated state and the at least one image 118 is visually indiscernible.

[0134] In FIGS. 3, 5 and 6, the at least one image 18, 118 over at least a portion of the optical substrate 12, 112 becomes visible once the photochromic optical article 10, 100 is in the activated state. In the activated state, the photochromic optical article 10, 100 comprises a first color and at least one image 18, 118 that comprises at least one second color that is visually distinct from the first color.

[0135] The at least one image 18, 118 may include, but is not limited to shapes, patterns, symbols, logos, monograms, text, pictures, and combinations thereof. The term “pattern” as used herein with reference to the at least one image means a repeated decorative design.

[0136] For example, the at least one image 18, 118 visible in the activated state may be a shape, such as a circle, square, rectangle, star, heart, diamond, pentagon, hexagon, triangle, and the like.

[0137] For example, the at least one image 18, 118 visible in the activated state may be a logo, such as a corporate logo.

[0138] In the activated state, the at least one image 18, 118 may comprise two or more second colors that are visually distinct from the first color and are visually distinct from one another (FIGS. 7 and 8). The two or more second colors may comprise a single hue, a single level of saturation, a gradient hue, and / or a gradient level of saturation. As used herein “gradient hue and / or gradient level of saturation” refers to an increase or decrease in the magnitude or degree of a color.

[0139] In the activated state, the at least one image 18, 118 may comprise three second colors, four second colors, five second colors, six colors, or up to 20 second colors that are visually distinct from the first color and are visually distinct from one another.

[0140] For example, in the activated state, the at least one image 18, 118 may comprise two colors, e.g. second color A and second color B. Second color A and second color B may both be the same color as the first color, but second color A and second color B have different hues or levels of saturation such that second color A and second color B are visually distinct from the first color and second color A is visually distinct from second color B. As a non-limiting example, the first color, second color A, and second color B may all be gray, but the gray of the first color may be darker than the gray of second color A and the gray of second color B may be lighter than both the first color and second color A.

[0141] Alternatively, in the activated state, the at least one image 18, 118 may comprise two colors, e.g. second color A and second color B, where second color A, second color B, and the first color may different from one another. For example, in the activated state, brown may be the first color, red may be second color A, and green may be second color B.

[0142] In the activated state, the photochromic optical article 10, 100 may comprise two or more images 18, 118 over at least a portion of the optical substrate 12, 112 (FIGS. 9-14). The two or more images 18, 118 over at least a portion of the optical substrate 12, 112 may be the same image 18, 118. The two or more images 18, 118 over at least a portion of the optical substrate 12, 112 may be different images.

[0143] For example, in the activated state, the photochromic optical article 10, 100 may comprise at least two logos that are the same or different.

[0144] For example, in the activated state, the photochromic optical article 10, 100 may comprise at least two shapes that are the same or different.

[0145] The two or more images 18, 118 may each comprise at least one second color that is visually distinct from the first color (FIGS. 9 and 10). Alternatively, the two or more images 18, 118 may each independently comprise at least one second color that is visually distinct from the first color and visually distinct from one another (FIGS. 11 and 12). Alternatively, the two or more images 18, 118 may comprise two or more second colors that are visually distinct from the first color and are visually distinct from one another (FIGS. 13 and 14).

[0146] The photochromic optical article 10, 100 comprises at least one first photochromic material that forms the first color. The photochromic optical article 10, 100 comprises at least one second photochromic material that forms the at least one second color. Alternatively, the photochromic optical article 10, 100 comprises an ultraviolet light absorbing material that forms the at least one second color, where it is the combination of the first photochromic material and the ultraviolet light absorbing material that forms the at least one second color. The presence of the ultraviolet light absorbing material attenuates the radiation reaching the underlying at least one first photochromic material, reducing the amount of activation, which forms the second color having a lighter shade of the same color / hue.

[0147] The at least one first photochromic material and the at least one second photochromic material may each independently comprise one or more non-thermally reversible photochromic compounds and / or one or more thermally reversible photochromic compounds.

[0148] The at least one first photochromic material and / or the at least one second photochromic material may each independently comprise a “conventional photochromic compound”. As used herein, the term “conventional photochromic compound” includes both thermally reversible and non-thermally reversible (or photo-reversible) photochromic compounds. Generally, although not limiting herein, when two or more photochromic compounds are used in combination with each other, the various compounds can be chosen to complement one another to produce a desired color or hue. For example, mixtures of photochromic compounds can be used to attain certain activated colors, such as a near neutral gray or near neutral brown. See, for example, U.S. Patent No. 5,645,767, particularly at column 12, line 66 to column 13, line 19.

[0149] Examples of photochromic compounds that can be used include, but are not limited to, indeno-fused naphthopyrans, naphthofl, 2-b]pyrans, naphtho[2,l-b]pyrans, spirofluoroeno[l,2-b]pyrans, phenanthropyrans, quinolinopyrans, fluoroanthenopyrans, spiropyrans, benzoxazines, naphthoxazines, spiro(indoline)naphthoxazines, spiro(indoline)pyridobenzoxazines, spiro(indoline)fluoranthenoxazines, spiro(indoline)quinoxazines, fulgides, fulgimides, diarylethenes, diarylalkylethenes, diarylalkenylethenes, thermally reversible photochromic compounds, non-thermally reversible photochromic compounds, and mixtures thereof.

[0150] Further examples of photochromic compounds can be selected from certain indeno- fused naphthopyran compounds, such as described in U.S. Patent No. 6,296,785, particularly at column 3, lines 66 through column 10, line 51.

[0151] Examples of non-thermally reversible photochromic materials include fulgide compounds, diaryl ethene compounds, and mixtures thereof. Examples of fulgide compounds include dimethylaminoindolyl fulgide, furyl fulgide, and thienyl fulgide. Examples of diaryl ethene compounds are disclosed in U.S. Patent No. 8,444,450 at column 3, line 63 to column 12, line 63. A specific non-limiting example of a diaryl ethene compound is l,2-bis(2,4-dimethyl- 5-phenyl-3-thi enyl)-3, 3, 4, 4, 5, 5, -hexafluoro- 1 -cyclopentane.

[0152] Other examples of non-thermally reversible photochromic materials are described in WO 2004003107A, US 20040049040, JP 2004277416A, JP 2003082340A, JP 8134063 A, and the article entitled “Design of Mesomorphic Diarylethene-Based Photochromes” by Frigoli et al., J. AM. CHEM. SOC., Vol 126, No. 47, 2004, pages 15382-15383.

[0153] Suitable ultraviolet light absorbing materials include, but are not limited to, TINUVIN® ultraviolet light absorbers, commercially available from BASF Corporation. Other examples of commercially available ultraviolet light absorbing materials include the BLS family of ultraviolet light absorbing materials commercially available from Mayzo, Inc. and the HOSTAVIN® family of ultraviolet light absorbing materials commercially available from Clariant Inc. Other ultraviolet light absorbing materials include benzophenones, benzotriazoles, oxanilides, triazines, cinnamates, and bisphenylenes. Other examples of ultraviolet light absorbing materials are disclosed in U.S. Patent No. 8,444,450, particularly at column 14, line 44 to column 15, line 42.

[0154] The at least one second photochromic material may be different from the at least one first photochromic material.

[0155] The at least one second photochromic material may be the same as the at least one first photochromic material.

[0156] When the at least one second photochromic material is the same as the at least one first photochromic material, in order to form the at least one second color, the at least one second photochromic material may be present in an amount that is greater than the amount of the at least one first photochromic material used to form the at least one first color. The first color and the at least one second color are the same colors, but the at least one second color would have a darker hue or level of saturation than the first color such that the at least one second color is visually distinct from the first color.

[0157] When the at least one second photochromic material is the same as the at least one first photochromic material, in order to form the at least one second color, the at least one second photochromic material may be present in an amount that is lower than the amount of the at least one first photochromic material used to form the at least one first color. The first color and the at least one second color are the same colors, but the at least one second color would have a lighter hue or level of saturation than the first color such that the at least one second color is visually distinct from the first color.

[0158] The at least one second color may be formed from an ultraviolet light absorbing material, where it is the combination of the at least one first photochromic material and the ultraviolet light absorbing material that forms the at least one second color. For example, the ultraviolet light absorbing material may be applied over a photochromic layer 20 comprising the at least one first photochromic material. The ultraviolet light absorbing material may be applied over an optical substrate 12, 112 that comprises the at least one first photochromic material. The ultraviolet light absorbing material may be imbibed into an at least one photochromic layer 20 comprising the at least one first photochromic material. The ultraviolet light absorbing material may be imbibed into an optical substrate 12, 112 that comprises the at least one first photochromic material.

[0159] The at least one first photochromic material, the at least one second photochromic material, and / or the ultraviolet light absorbing material, when present, may be incorporated intothe optical substrate 12, 112 and / or may be present in an at least one photochromic layer 20 positioned over at least a portion of the first surface 14, 114 of the optical substrate 12, 112.

[0160] To form the first color, the at least one first photochromic material may be imbibed into the first surface 14, 114 of the optical substrate 12, 112 to become incorporated into the optical substrate 12, 112.

[0161] As used herein, the term “imbibition” refers to the process of diffusing or permeating the materials into the optical substrate or a layer, solvent assisted transfer of such materials into a porous polymer, vapor phase transfer, heat transfer, and the like.

[0162] Alternatively, to form the first color, the at least one first photochromic material may be cast-in-place to become incorporated into the optical substrate 12, 112. In a cast-in-place method, the at least one first photochromic material may be mixed with: a polymer and / or oligomer composition in solution or melt form; or monomer composition in liquid form, so as to form a castable photochromic composition. The castable photochromic composition is then typically introduced into the cavity of a mold (e.g., a lens mold). The castable photochromic composition is then set within the mold so as to form a photochromic optical substrate.

[0163] The at least one first photochromic material, the at least one second photochromic material, and the ultraviolet light absorbing material, when present, may be present in at least one photochromic layer 20 positioned over at least a portion of the first surface 14, 114 of the optical substrate 12, 112 (FIG. IB). For example, the at least one first photochromic material, the at least one second photochromic material, and the ultraviolet light absorbing material may be present in at least one photochromic layer positioned over the first surface 14, 114 of the optical substrate 12, 112 (FIG. IB).

[0164] The at least one photochromic layer 20, when present, is formed over at least a portion of the first surface 14, 114 of the optical substrate 12, 112. Alternatively, the at least one photochromic layer 20 may be formed over the entire surface, e.g., the first surface 14, 114 of the optical substrate 12, 112.

[0165] The at least one photochromic layer 20 may comprise a single photochromic layer. For example, the at least one first photochromic material and the at least one second photochromic material may be present in a photochromic layer 20 positioned over at least a portion of the first surface 14, 114 of the optical substrate 12, 112. Alternatively, the at least one first photochromic material and the ultraviolet light absorbing material, may be present in aphotochromic layer 20 positioned over at least a portion of the first surface 14, 114 of the optical substrate 12, 112. Alternatively, the at least one first photochromic material, the at least one second photochromic material, and the ultraviolet light absorbing material, may be present in a photochromic layer 20 positioned over at least a portion of the first surface 14, 114 of the optical substrate 12, 112.

[0166] The at least one photochromic layer 20 may comprise a plurality of photochromic layers. For example, the at least one first photochromic material may be present in a first photochromic layer that is positioned over at least a portion of the first surface 14 of the optical substrate 12 and the at least one second photochromic material may be present in a second photochromic layer that is positioned over at least a portion of the first photochromic layer.

[0167] The at least one photochromic layer 20 may be a photochromic coating.

[0168] When the photochromic layer 20 is a photochromic coating, the photochromic coating may include a resin. The resin of the photochromic coating can include, but is not limited to: thermoset or UV curable resins, such as polyurethanes, polyisocyanurates, poly acrylates, or combinations of two or more thereof. A thermoplastic resin composition, such as a thermoplastic polyurethane composition, may be used. Anisotropic materials may optionally be present in the photochromic coating. The photochromic coating may be positioned over at least a portion of the first surface 14, 114 of the optical substrate 12, 112. Alternatively, the photochromic coating may be positioned over the entire first surface 14, 114 of the optical substrate 12, 112.

[0169] The photochromic coating may be formed from a photochromic coating composition. The at least one first photochromic material and / or the at least one second photochromic material may be present in the photochromic coating composition in a range of from 0.005 to 20% by weight. For example, the at least one first photochromic material can be present in the range of from 0.01 to 10% by weight.

[0170] The photochromic optical article may comprise one or more additional layers, in addition to the at least one photochromic layer 20. Examples of such additional layers include, but are not limited to, clear coatings and films; barrier coatings and films; alignment coatings and films; primer coatings and films; protective coatings and films, including transitional coatings and films and abrasion resistant coatings and films; anti -reflective coatings and films; polarizing coatings and films; and combinations thereof.

[0171] The photochromic optical article may comprise a clear coating or film over at least a portion of the first surface 14, 114 of the optical substrate 12, 112, when the optical substrate 12, 112 comprises the at least one first photochromic material (e.g., the at least one first photochromic material is imbibed into the optical substrate 12, 112 or the at least one first photochromic material is cast-in-place). The at least one second photochromic material or the ultraviolet light absorbing material may be imbibed into this clear coating or film that is present over the optical substrate 12, 112.

[0172] Alternatively, the photochromic optical article may comprise a clear coating or film over the at least one photochromic layer 20. The at least one second photochromic material or the ultraviolet light absorbing material may be imbibed into this clear coating or film that is present over the at least one photochromic layer 20.

[0173] The clear coating or film may be a polyurethane coating formed from a polyurethane composition.

[0174] As used herein, the term “protective coating or film” refers to coatings or films that can prevent wear or abrasion, provide a transition in properties from one coating or film to another, protect against the effects of polymerization reaction chemicals, and / or protect against deterioration due to environmental conditions such as moisture, heat, ultraviolet light, oxygen, etc.

[0175] As used herein, the term “transitional coating and film” means a coating or film that aids in creating a gradient in properties between two coatings or films, or a coating and a film. For example, although not limiting herein, a transitional coating can aid in creating a gradient in hardness between a relatively hard coating and a relatively soft coating. Non-limiting examples of transitional coatings include radiation-cured, acrylate-based thin films as described in U.S. Patent No. 7,452,611 B2.

[0176] As used herein, the term “abrasion resistant coating and film” refers to a protective polymeric material that demonstrates a resistance to abrasion that is greater than a standard reference material, e.g., a polymer made of CR-39® monomer available from PPG Industries, Inc., as tested in a method comparable to ASTM F-735 Standard Test Method for Abrasion Resistance of Transparent Plastics and Coatings Using the Oscillating Sand Method. Nonlimiting examples of abrasion resistant coatings include, for example, abrasion-resistant coatings comprising organosilanes, organosiloxanes, abrasion-resistant coatings based on inorganicmaterials such as silica, titania and / or zirconia, organic abrasion-resistant coatings of the type that are ultraviolet light curable, oxygen barrier-coatings, UV-shielding coatings, and combinations thereof. Non-limiting examples of commercial hard coating products include CRYSTALCOAT™ 124 and HI-GARD® coatings, available from SDC Coatings, Inc. and PPG Industries, Inc., respectively.

[0177] The abrasion resistant coating or film (or hard coat layer) can be selected from art- recognized hard coat materials, such as organo-silane abrasion-resistant coatings. Organo-silane abrasion-resistant coatings, often referred to as hard coats or silicone-based hard coatings, are well known in the art, and are commercially available from various manufacturers, such as SDC Coatings, Inc. and PPG Industries, Inc. Reference is made to U.S. Patent No. 4,756,973, particularly at column 5, lines 1-45; and to U.S. Patent No. 5,462,806, particularly at column 1, lines 58 through column 2, line 8, and column 3, line 52 through column 5, line 50, which disclosures describe organo-silane hard coatings. Reference is also made to U.S. Patent Nos. 4,731,264, 5,134,191, 5,231,156, and International Patent Publication WO 94 / 20581 for disclosures of organo-silane hard coatings. The hard coat layer can be applied by art-recognized coating methods such as, but not limited to, roll coating, spray coating, curtain coating, and spin coating.

[0178] Non-limiting examples of antireflective coatings and films include a monolayer, multilayer or film of metal oxides, metal fluorides, or other such materials, which can be deposited onto the articles disclosed herein (or onto films that are applied to the articles), for example, through vacuum deposition, sputtering, etc.

[0179] The photochromic optical article may include ophthalmic articles or elements, display articles or elements, visors, windows, mirrors, active liquid crystal cell articles, and passive liquid crystal cell articles. Examples of ophthalmic articles or elements include corrective and noncorrective lenses, including single vision or multi-vision lenses, which can be either segmented or non-segmented multi-vision lenses (such as, but not limited to, bifocal lenses, trifocal lenses, and progressive lenses), as well as other elements used to correct, protect, or enhance (cosmetically or otherwise) vision, including without limitation, clip-on lenses, contact lenses, intra-ocular lenses, magnifying lenses, protective lenses, and visors. Examples of display articles, elements and devices include screens, monitors, and security elements, including without limitation, security marks and authentication marks. Examples of windows includeautomotive and aircraft transparencies, filters, shutters, and optical switches. For example, the photochromic optical article can be selected from eyewear, contact lenses, and clip-on lenses.

[0180] The exemplary ophthalmic articles of FIGS. 4-14, in the form of photochromic eyewear, comprise a peripheral zone and a line-of-sight zone.

[0181] The at least one image 18, 118 or the two or more images 18, 118 may be positioned in the line-of-sight zone (FIGS. 5, 7, 9, 11, and 13).

[0182] The at least one image 18, 118 or the two or more images 18, 118 may be positioned in the peripheral zone (FIGS. 4, 8, 10, 12, and 14).

[0183] The at least one image 18, 118 or the two or more images 18, 118 may be positioned in both the light-of-sight zone and the peripheral zone. Preferably, the at least one image 18, 118 or the two or more images 18, 118 are positioned in the peripheral zone.

[0184] The invention is also directed to a method of making a photochromic optical article. The method includes providing an optical substrate including an at least one first photochromic material, wherein the optical substrate includes a first surface and a second surface opposite the first surface; and forming an at least one image, wherein forming the at least one image includes: forming a pattern for the at least one image; applying an at least one second photochromic material or an ultraviolet light absorbing material to a pattern for an at least one image; heating the optical substrate to diffuse at least a portion of the at least one second photochromic material or the ultraviolet light absorbing material into the optical substrate including the at least one first photochromic material, wherein the photochromic optical article reversibly transitions from an unactivated state to an activated state in response to actinic radiation, wherein the activated state includes: a first color formed from the at least one first photochromic material; and the at least one image over at least a portion of the optical substrate, wherein the at least one image includes an at least one second color that is visually distinct from the first color, wherein the at least one second color is formed from the at least one second photochromic material or the ultraviolet light absorbing material; and wherein the at least one image is visually indiscernible in the unactivated state.

[0185] For example, the polychromatic photochromic optical articles of the present invention may be formed according to the following non-limiting method, as shown in FIGS. 15A and 15B. An optical substrate 12, 112 comprising the at least one first photochromic material is provided. For example, the at least one photochromic material may be present in at least one photochromiclayer 20, such as a photochromic coating, positioned over at least a portion of the first surface 14, 114 of the optical substrate 12, 112. The at least one first photochromic material may be any of the photochromic materials described herein. A temporary etch layer is applied over and in direct contact with the at least one photochromic layer 20 positioned over at least a portion of the first surface 14, 114 of the optical substrate 12, 112. The optical substrate 12, 112 comprising the at least one photochromic layer 20 and the temporary etch layer may be heated. A removable buffer layer comprising a buffer material is applied over and in direct contact with at least a portion of the temporary etch layer. The removable buffer layer and the temporary etch layer are etched to form a pattern for the at least one image 18, 118. The at least one image 18, 118 can be any of the images 18, 118 described herein. An imbibition composition comprising the at least one second photochromic material may be applied over the pattern for the at least one image 18, 118. Alternatively, a dye transfer substrate comprising the at least one second photochromic material may be contacted with the pattern for the at least one image 18, 118. Alternatively, an imbibition composition comprising the ultraviolet light absorbing material may be applied over the pattern for the at least one image 18, 118. Alternatively, a dye transfer substrate comprising the ultraviolet light absorbing material may be contacted with the pattern for the at least one image 18, 118. The optical substrate 12, 112, which includes the at least one photochromic layer 20, the temporary etch layer, the removable buffer layer, and the imbibition composition or the dye transfer substrate, may then be heated such that the at least one second photochromic material or the ultraviolet light absorbing material diffuses into the at least one photochromic layer 20. If a dye transfer substrate was used, the dye transfer substrate may then be removed from the optical substrate 12, 112. The optical substrate 12, 112 may then be washed to remove any residual imbibition composition (when used), the removable buffer layer, and the temporary etch layer. This process may be completed for additional images 18, 118 and / or additional second colors. After the removal of the residual imbibition composition, the removable buffer layer, and the temporary etch layer, one or more additional coatings may optionally be applied over the optical substrate 12, 112, including, but not limited to: barrier coatings and films; alignment coatings and films; primer coatings and films; protective coatings and films, including transitional coatings and films and abrasion resistant coatings and films; anti -reflective coatings and films; polarizing coatings and films; and combinations thereof.

[0186] For example, the polychromatic photochromic optical articles of the present invention may be formed according to the following non -limiting method, as shown in FIGS. 16A and 16B. An optical substrate 12, 112 comprising the at least one first photochromic material is provided. For example, the at least one first photochromic material may be incorporated into the optical substrate 12, 112, such as through imbibition. Alternatively, the at least one first photochromic material may be cast-in-place such that the at least one first photochromic material is incorporated into the optical substrate 12, 112. A clear coating, such as a polyurethane coating, may be applied over the first surface 14, 114 of the optical substrate 12, 112. A temporary etch layer is applied over and in direct contact with the clear coating. The optical substrate 12, 112 comprising the clear coating and the temporary etch layer may be heated. A removable buffer layer comprising a buffer material is applied over and in direct contact with at least a portion of the temporary etch layer. The removable buffer layer and the temporary etch layer are etched to form a pattern for the at least one image 18, 118. The at least one image 18, 118 can be any of the images 18, 118 described herein. An imbibition composition comprising the at least one second photochromic material may be applied over the pattern for the at least one image 18, 118. Alternatively, a dye transfer substrate comprising the at least one second photochromic material may be contacted with the pattern for the at least one image 18, 118. Alternatively, an imbibition composition comprising the ultraviolet light absorbing material may be applied over the pattern for the at least one image 18, 118. Alternatively, a dye transfer substrate comprising the ultraviolet light absorbing material may be contacted with the pattern for the at least one image 18, 118. The optical substrate 12, 112, which includes the clear coating, the temporary etch layer, the removable buffer layer, and the imbibition composition or the dye transfer substrate, may then be heated such that the at least one second photochromic material or the ultraviolet light absorbing material diffuse into the clear coating. If a dye transfer substrate was used, the dye transfer substrate may then be removed from the optical substrate 12, 112. The optical substrate 12, 112 may then be washed to remove any residual imbibition composition, the removable buffer layer, and the temporary etch layer. This process may be completed for additional images 18, 118 and / or additional second colors. After the removal of the residual imbibition composition, the removable buffer layer, and the temporary etch layer, one or more additional coatings may optionally be applied over the optical substrate 12, 112, including, but not limited to: barrier coatings and films; alignment coatings and films; primer coatings and films; protectivecoatings and films, including transitional coatings and films and abrasion resistant coatings and films; anti -reflective coatings and films; polarizing coatings and films; and combinations thereof.

[0187] For example, the polychromatic photochromic optical articles of the present invention may be formed according to the following non-limiting method, as shown in FIGS. 17A and 17B. An optical substrate 12, 112 comprising the at least one first photochromic material is provided. For example, the at least one photochromic material may be present in at least one photochromic layer 20, such as a photochromic coating, positioned over at least a portion of the first surface 14, 114 of the optical substrate 12, 112. A clear coating, such as a polyurethane coating, may be applied over the at least one photochromic layer. A temporary etch layer is applied over and in direct contact with the clear coating. The optical substrate 12, 112 comprising the clear coating and the temporary etch layer may be heated. A removable buffer layer comprising a buffer material is applied over and in direct contact with at least a portion of the temporary etch layer. The removable buffer layer and the temporary etch layer are etched to form a pattern for the at least one image 18, 118. The at least one image 18, 118 can be any of the images 18, 118 described herein. An imbibition composition comprising the at least one second photochromic material may be applied over the pattern for the at least one image 18, 118. Alternatively, a dye transfer substrate comprising the at least one second photochromic material may be contacted with the pattern for the at least one image 18, 118. Alternatively, an imbibition composition comprising the ultraviolet light absorbing material may be applied over the pattern for the at least one image 18, 118. Alternatively, a dye transfer substrate comprising the ultraviolet light absorbing material may be contacted with the pattern for the at least one image 18, 118. The optical substrate 12, 112, which includes the clear coating, the temporary etch layer, the removable buffer layer, and the imbibition composition or the dye transfer substrate, may then be heated such that the at least one second photochromic material or the ultraviolet light absorbing material diffuse into the clear coating. If a dye transfer substrate was used, the dye transfer substrate may then be removed from the optical substrate 12, 112. The optical substrate 12, 112 may then be washed to remove any residual imbibition composition, the removable buffer layer, and the temporary etch layer. This process may be completed for additional images 18, 118 and / or additional second colors. After the removal of the residual imbibition composition, the removable buffer layer, and the temporary etch layer, one or more additional coatings may optionally be applied over the optical substrate 12, 112, including, but not limitedto: barrier coatings and films; alignment coatings and films; primer coatings and films; protective coatings and films, including transitional coatings and films and abrasion resistant coatings and films; anti -reflective coatings and films; polarizing coatings and films; and combinations thereof.

[0188] For example, the polychromatic photochromic optical articles of the present invention may be formed according to the following non -limiting method, as shown in FIGS. 18A and 18B. An optical substrate 12, 112 comprising the at least one first photochromic material is provided. For example, the at least one first photochromic material may be imbibed into the first surface 14, 114 of the optical substrate 12, 112. Alternatively, the at least one first photochromic material may be cast-in-place such that the at least one first photochromic material is incorporated into the optical substrate 12, 112. A temporary etch layer is applied over and in direct contact with the first surface 14, 114 of the optical substrate 12, 112. The optical substrate 12, 112 comprising the temporary etch layer may be heated. A removable buffer layer comprising a buffer material is applied over and in direct contact with at least a portion of the temporary etch layer. The removable buffer layer and the temporary etch layer are etched to form a pattern for the at least one image 18, 118. The at least one image 18, 118 can be any of the images 18, 118 described herein. An imbibition composition comprising the at least one second photochromic material may be applied over the pattern for the at least one image 18, 118. Alternatively, a dye transfer substrate comprising the at least one second photochromic material may be contacted with the pattern for the at least one image 18, 118. Alternatively, an imbibition composition comprising the ultraviolet light absorbing material may be applied over the pattern for the at least one image 18, 118. Alternatively, a dye transfer substrate comprising the ultraviolet light absorbing material may be contacted with the pattern for the at least one image 18, 118. The optical substrate 12, 112, which includes the temporary etch layer, the removable buffer layer, and the imbibition composition or the dye transfer substrate, may then be heated so that the at least one second photochromic material or the ultraviolet light absorbing material diffuse into the optical substrate 12, 112. If a dye transfer substrate was used, the dye transfer substrate may then be removed from the optical substrate 12, 112. The optical substrate 12, 112 may then be washed to remove any residual imbibition composition, the removable buffer layer, and the temporary etch layer. This process may be completed for additional images 18, 118 and / or additional second colors. After the removal of remove residual imbibition composition, the removable buffer layer, and the temporary etch layer, one or more additional coatings may optionally be applied over theoptical substrate 12, 112, including, but not limited to: barrier coatings and films; alignment coatings and films; primer coatings and films; protective coatings and films, including transitional coatings and films and abrasion resistant coatings and films; anti-reflective coatings and films; polarizing coatings and films; and combinations thereof.

[0189] The temporary etch layer comprises a temporary etch material. The temporary etch material may include but is not limited to a water miscible / dispersible hydroxy-functional polymer, such as a partially hydrolyzed polyvinyl alcohol with an average molecular weight from about 10,000 to 50,000 grams per mole (g / mole). To form the temporary etch layer, an aqueous solution of the temporary etch material, such as the polyvinyl alcohol (PVA), may be applied over the optical substrate 12, 112 comprising the at least one first photochromic material. For example, to form the temporary etch layer, an aqueous solution of the temporary etch material, such as polyvinyl alcohol may be applied over the first surface 14, 114 of the optical substrate 12, 112 that comprises the at least one first photochromic material (e.g., the at least one first photochromic material is imbibed into the optical substrate 12, 112 or the at least one first photochromic material is cast-in-place). Alternatively, to form the temporary etch layer, an aqueous solution of the temporary etch material, such as polyvinyl alcohol may be applied over the at least one photochromic layer 20 present over at least a portion of the first surface 14, 114 of the optical substrate 12, 112. Alternatively, to form the temporary etch layer, an aqueous solution of the temporary etch material, such as polyvinyl alcohol may be applied over a clear coating, such as polyurethane coating, when present. The aqueous solution of the temporary etch material may comprise at least 2% temporary etch material, such as at least 5% temporary etch material, such as at least 10% temporary etch material, or such as up to 25%. The temporary etch layer may be applied by spin coating.

[0190] The optical substrate 12, 112 comprising the temporary etch material may be heated to a temperature ranging from 75°C to 135°C, such as 125°C, to form the temporary etch layer. The optical substrate 12, 112 comprising the temporary etch material may be heated for at least 15 minutes, such as at least 20 minutes, such as at least 30 minutes, or such as at least 45 minutes to remove any residual water.

[0191] The temporary etch layer is capable of being etched by a laser. In addition, the temporary etch layer is impermeable to the photochromic materials and the ultraviolet light absorbing material and prevents the migration (i.e., imbibition) of the photochromic materialsand the ultraviolet light absorbing material into areas of underlying photochromic layers or the substrate where etching did not occur. The temporary etch layer is easily removable and may be removed from the optical substrate 12, 112 through an aqueous wash.

[0192] The removable buffer layer comprises a removable buffer material. The removable buffer material may include, but is not limited to a water-dispersible hydroxy-functional cellulosic material. The removable buffer resin material may include, but is not limited to nonionic water-soluble cellulose ethers, such as hydroxypropyl cellulose. The removable buffer material may be dissolved in suitable solvents to form a removable buffer material solution. Suitable solvents include but are not limited to protic or aprotic solvents, such as ethers and alcohols. For example, suitable solvents may include diglyme, propylene glycol n-butyl ether, tetrahydrofurfuryl alcohol, and combinations thereof. Silica may be included in the removable buffer material solution.

[0193] The removable buffer material solution is applied over and in direct contact with at least a portion of the temporary etch layer that is present over the optical substrate 12, 112. After application, the removable buffer material is dried to form the removable buffer layer. For example, the optical substrate 12, 112 comprising the removable buffer material may be heated to a temperature ranging from 75°C to 130°C, such as 105°C, to form the removable buffer layer. The optical substrate 12, 112 comprising the removable buffer material may be heated for at least 5 minutes, such as at least 10 minutes or such as at least 20 minutes to remove residual solvent and form the removable buffer layer.

[0194] The purpose of the removable buffer layer is to absorb a portion of the laser energy to protect the underlying photochromic layer 20 or the underlying clear coating, and inhibit damage to the photochromic layer 20 or the underlying clear coating, during laser etching of the temporary etch layer. The removable buffer layer is easily removable and may be removed from the optical substrate 12, 112 through an aqueous wash.

[0195] The removable buffer layer and the temporary etch layer present on the optical substrate 12, 112 are etched to form a pattern for the at least one image 18, 118. The at least one image 18, 118 may be etched using a laser, such as an ultraviolet radiation emitting laser or a visible light emitting laser. For example, the laser may be a 405 nanometer (nm) blue / violet diode laser. The laser may be a portable laser, such as a portable laser available from LaserPecker®. The power and depth of the laser may be selected such that the optical substrate12, 112, the at least one photochromic layer, or the one or more additional layers, when present, below the temporary etch layer are not damaged. For example, a power output of approximately 160 milliWatts (mW) may be used. The etching process removes both the removable buffer layer and the temporary etch layer to provide a pattern for the at least one image 18, 118.

[0196] After etching, an imbibition solution comprising the at least one second photochromic material or the ultraviolet light absorbing material, is applied over the pattern for the at least one image 18, 118. The at least one second photochromic material may be any of the photochromic materials described herein. The ultraviolet light absorbing material may be any of the ultraviolet light absorbing materials described herein. This solution may further comprise an imbibition resin and / or one or more solvents. The imbibition resin, which is similar to the removable buffer material, may include but is not limited to the nonionic water-soluble cellulose ethers as described above. The one or more solvents may include but are not limited to diglyme, propylene glycol n-butyl ether, tetrahydrofurfuryl alcohol, N-Methyl-2-Pyrrolidone, and combinations thereof.

[0197] The imbibition solution comprising the at least one second photochromic material, the imbibition resin, and the one or more solvents may be heated such that the at least one second photochromic is diffused or imbibed into optical substrate 12, 112 comprising the at least one first photochromic material, the at least one photochromic layer 20 comprising the at least one first photochromic material, or the clear coating applied over the at least one photochromic layer 20.

[0198] The imbibition solution comprising the ultraviolet light absorbing material, the imbibition resin, and the one or more solvents may be heated such that the ultraviolet light absorbing material is diffused or imbibed into optical substrate 12, 112 comprising the at least one first photochromic material, the at least one photochromic layer 20 comprising the at least one first photochromic material, or the clear coating applied over the at least one photochromic layer 20.

[0199] The optical substrate 12, 112 that includes the imbibition solution, the temporary etch layer, and the removable buffer layer may be heated to a temperature ranging from 50°C to 140°C, such as 125°C. The optical substrate 12, 112 that includes the imbibition solution, the temporary etch layer, and the removable buffer layer may be heated for at least at least 30 minutes, such as at least 45 minutes, or such as at least 60 minutes to imbibe the at least onesecond photochromic material or the ultraviolet light absorbing material into the optical substrate 12, 112 comprising the at least one first photochromic material, the at least one photochromic layer 20 comprising the at least one first photochromic material, or the clear coating applied over the at least one photochromic layer 20.

[0200] The imbibing of the at least one second photochromic material or the ultraviolet light absorbing material can also utilize a dye transfer substrate. As used herein, a “dye transfer substrate” refers to a component that can absorb and release photochromic materials under certain conditions. The dye transfer substrate can release the at least one second photochromic material or the ultraviolet light absorbing material under heat and / or pressure into the pattern for the at least one image 18, 118.

[0201] The dye transfer substrate can absorb and release the at least one second photochromic material or the ultraviolet light absorbing material into the optical substrate 12, 112 comprising the at least one first photochromic material, the at least one photochromic layer 20 comprising the at least one first photochromic material, or the one or more layers applied over the optical substrate 12, 112 comprising the at least one photochromic material, or the one or more layers applied over the at least one photochromic layer 20.

[0202] The optical substrate 12, 112 that includes the dye transfer substrate, the temporary etch layer, and the removable buffer layer may be heated to a temperature ranging from 50°C to 140°C, such as 125°C. The optical substrate 12, 112 that includes the dye transfer substrate, the temporary etch layer, and the removable buffer layer may be heated for at least at least 30 minutes, such as at least 45 minutes, or such as at least 60 minutes to imbibe the at least one second photochromic material or the ultraviolet light absorbing material into the optical substrate 12, 112 comprising the at least one first photochromic material, the at least one photochromic layer 20 comprising the at least one first photochromic material, or the clear coating applied over the at least one photochromic layer 20.

[0203] The remaining imbibing resins, the remaining at least one second photochromic material or the remaining ultraviolet light absorbing material, the removable buffer layer, and the temporary etch layer may be washed from the surface of the optical substrate 12, 112 after heating. This washing process removes the remaining imbibing resins, other residual materials, the removable buffer layer, and the temporary etch layer from the optical substrate 12, 112.

[0204] Alternatively, the polychromatic photochromic optical articles of the present invention may be formed according to the following non-limiting method, as shown in FIGS. 19A and 19B. An optical substrate 12, 112 comprising the at least one first photochromic material is provided. For example, the at least one photochromic material may be present in at least one photochromic layer 20 positioned over at least a portion of the first surface 14, 114 of the optical substrate 12, 112. The pattern for the at least one image 18, 118 may be printed, as a mirror image, onto a dye transfer sheet. The at least one image 18, 118 may be printed onto the dye transfer sheet using the at least one second photochromic material. Alternatively, the at least one image 18, 118 may be printed onto the dye transfer sheet using the ultraviolet light absorbing material. The dye transfer sheet having the at least one second photochromic material or the ultraviolet light material may be contacted with the at least one photochromic layer 20 on the optical substrate 12, 112 and the optical substrate 12, 112 may be heated. This process may be completed for additional images 18, 118 and / or additional second colors. Following removal of the dye transfer sheet, the optical substrate 12, 112 comprising the at least one photochromic layer 20 may be optionally washed and one or more additional coatings may optionally be applied over the optical substrate 12, 112, including, but, not limited to: barrier coatings and films; alignment coatings and films; primer coatings and films; protective coatings and films, including transitional coatings and films and abrasion resistant coatings and films; anti-reflective coatings and films; polarizing coatings and films; and combinations thereof.

[0205] Alternatively, the polychromatic photochromic optical articles of the present invention may be formed according to the following non-limiting method. An optical substrate 12, 112 comprising the at least one first photochromic material is provided. For example, the at least one first photochromic material may be incorporated into the optical substrate 12, 112, such as through imbibition. Alternatively, the at least one first photochromic material may be cast-in- place such that the at least one first photochromic material is incorporated into the optical substrate 12, 112. The pattern for the at least one image 18, 118 may be printed, as a mirror image, onto a dye transfer sheet. The at least one image 18, 118 may be printed onto the dye transfer sheet using the at least one second photochromic material. Alternatively, the at least one image 18, 118 may be printed onto the dye transfer sheet using the ultraviolet light absorbing material. The dye transfer sheet having the at least one second photochromic material or the ultraviolet light material may be contacted with the optical substrate 12, 112 and the opticalsubstrate 12, 112 may be heated. This process may be completed for additional images 18, 118 and / or additional second colors. Following removal of the dye transfer sheet, the optical substrate 12, 112 may be optionally washed and one or more additional coatings may optionally be applied over the optical substrate 12, 112, including, but not limited to: barrier coatings and films; alignment coatings and films; primer coatings and films; protective coatings and films, including transitional coatings and films and abrasion resistant coatings and films; anti -reflective coatings and films; polarizing coatings and films; and combinations thereof.

[0206] Alternatively, the polychromatic photochromic optical articles of the present invention may be formed according to the following non-limiting method. An optical substrate 12, 112 comprising the at least one first photochromic material is provided. For example, the at least one photochromic material may be present in at least one photochromic layer 20, such as a photochromic coating, positioned over at least a portion of the first surface 14, 114 of the optical substrate 12, 112. A clear coating, such as a polyurethane coating, may be applied over the at least one photochromic layer. The pattern for the at least one image 18, 118 may be printed, as a mirror image, onto a dye transfer sheet. The at least one image 18, 118 may be printed onto the dye transfer sheet using the at least one second photochromic material. Alternatively, the at least one image 18, 118 may be printed onto the dye transfer sheet using the ultraviolet light absorbing material. The dye transfer sheet having the at least one second photochromic material or the ultraviolet light material may be contacted with the optical substrate 12, 112 and the optical substrate 12, 112 may be heated. This process may be completed for additional images 18, 118 and / or additional second colors. Following removal of the dye transfer sheet, the optical substrate 12, 112 comprising the at least one photochromic layer 20 and the clear coating may be optionally washed and one or more additional coatings may optionally be applied over the optical substrate 12, 112, including, but not limited to: barrier coatings and films; alignment coatings and films; primer coatings and films; protective coatings and films, including transitional coatings and films and abrasion resistant coatings and films; anti -reflective coatings and films; polarizing coatings and films; and combinations thereof.

[0207] The at least one first photochromic material, the at least one photochromic layer, the at least one second photochromic material, the ultraviolet light absorbing material, and the optional one or more additional layers as described above, such as barrier coatings and films; alignment coatings and films; primer coatings and films; protective coatings and films, includingtransitional coatings and films and abrasion resistant coatings and films; anti-reflective coatings and films; polarizing coatings and films; and combinations thereof, the temporary etch layer, the removable buffer layer, and the imbibition solution, can be applied to (or formed over) the optical substrate in accordance with art-recognized methods, which include, but are not limited to, extrusion methods; spray application methods; curtain coating application methods; draw-down blade (or bar) application methods; dip-coating application methods; spin-coating application methods; in-mold coating or application methods; and combinations thereof.

[0208] The present invention is described in the following illustrative, non-limiting examples. Numerous possible modifications and variations will be apparent to those skilled in the art.EXAMPLESPart 1 - Preparation of compositions

[0209] Curable Photochromic Composition: A curable photochromic composition was prepared according to the procedure described in Example 8 of United States Patent No. 10,954,397 B2 comprising a mixture of indeno-fused naphthopyran dyes formulated to give a gray color on activation.

[0210] Temporary Etch Material Solution: A temporary etch solution was prepared by diluting Selvol™ 24-203 (88% hydrolyzed PVA solution at 24% solids available from Sekisui Specialty Chemicals) with deionized (DI) water to yield a formulation with 5% solids on total solution. Alternatively, other grades of PVA (having super, fully, intermediate hydrolysis) with varying viscosity types (having low, medium, high viscosity) can be dissolved with water to give formulations with a desirable solids range and used in the process described in Part 3. Moreover, other additives, such as defoamers and biocides, can be added to provide better processing and / or longevity to the final formulation.

[0211] Removable Buffer Material Solution: A removable hydroxy-propyl cellulose buffer solution was prepared by blending the components shown in Table 1 to give a solution with an opaque appearance and 16% total solids.Table 1 : Removable Buffer Material Solution1A nonionic water-soluble cellulose ether available from Ashland Inc.2A precipitated silica available from PPG Industries, Inc.

[0212] Imbibition Solution: A photochromic imbibition solution was prepared by blending the components shown in Table 2 to give a solution with an opaque orange appearance and 18.6% total solids.Table 2: Photochromic Imbibition Solution3An indeno-fused napthopyran that activates to an orange colorPart 2 - Preparing article with photochromic pattern

[0213] Step 1. Substrate Preparation

[0214] Polycarbonate “Plano” lenses (76mm diameter) were obtained from Gentex Optical. Each lens was corona treated by passing on a conveyor belt in a Tantec EST Systems Serial No. 020270 Power Generator HV 2000 series corona treatment equipment with a high voltage transformer. The lens substrates were exposed to corona generated at 70.00 kiloVolts (KV) and 1000 Watts while traveling on a conveyor at a belt speed 3 feet per minute (ft / min) (0.01524 meters per second (m / s)). Afterwards, the lens samples were cleaned by wiping with a nonwoven wiper soaked with isopropanol and dried with a stream of air.

[0215] Step 2. Application of first photochromic coating to form the first color

[0216] The curable photochromic composition described above was applied to the corona- treated polycarbonate lenses by spin coating to achieve a final wet weight of 0.300 grams (g) on each lens sample. Afterwards, the coated polycarbonate lenses were placed in a forced-air oven maintained at 125 °C for 60 minutes, then cooled to room temperature.

[0217] Step 3. Application of temporary etch layer

[0218] The coated polycarbonate lens were again corona treated as described above. The temporary etch material solution (PVA) was applied to the lenses by dispensing approximately 3.0 milliliters (mL) onto the surface and spinning at 1650 revolutions per minute (rpm) for 9 seconds. Afterwards, the lenses were placed in a forced-air oven maintained at 125°C for 15 minutes and cooled to room temperature.

[0219] Step 4. Application of removable buffer layer

[0220] The removable buffer material solution was applied to the cooled PVA-coated lenses by dispensing approximately 3.0 mL onto the surface and spinning at 2000 rpm for 9 seconds. Afterwards, the lenses were placed in a forced-air oven maintained at 125°C for 5 minutes and cooled to room temperature.

[0221] Step 5. Laser Engraving

[0222] A LaserPecker 1 Pro Deluxe (a portable laser engraver available from Shenzhen Hingin Technology Co., Ltd.) with a 405 nanometer (nm) blue / violet beam and a 0.15 millimeter (mm) light spot was used for engraving. This class Illb / IV laser with variable power / depth profile options was attached to the auto-focus supporting stand accessory. The device was solely operated through the downloadable LaserPecker App. A lens prepared abovewas placed on the base of the stand under the laser engraver. After automatic height adjustment, the LaserPecker App was operated from a smart phone. An image of a 5 -point star with dimensions of 10.00 mm by 9.55 mm was selected and the coated lens (i.e., the lens having the photochromic coating, the temporary etch layer, and the removable buffer layer) was placed below the engraver such that the image would be produced in a desired position by using the preview function. After the lens was in the desired position, a power of 15%, a depth of 15% and cycle pass of 1 were selected. These selections allowed for engraving through the removable / temporary layers while preserving the photochromic coating layer. No material selection was made in the LaserPecker App. The engraving process was initiated via the LaserPecker App. After the engraving process was completed, the sample was removed from the laser stage and the equipment was powered off.

[0223] Step 6. Imbibition of second photochromic material to form a second color

[0224] The photochromic imbibition solution was applied to the laser-engraved lens by dispensing approximately 3.0 mL of the solution onto the surface of the lens and spinning the lens at 1650 rpm for 9 seconds. Afterwards, the lens was placed in a forced-air oven maintained at 125°C for 30 minutes, then cooled to room temperature. Residual photochromic imbibition solution, the removable buffer layer, and the temporary etch layer were then removed by gently washing the lens with DI water and a soft foam sponge.

[0225] Photochromic image Evaluation

[0226] Lens quality was evaluated by exposing the clean, dried lens from Step 6 to a source of actinic radiation, such as auvBeast™ Black light UV flashlight with 385-395nm light. A well- defined image corresponding to the etched shape appeared as a yellow star on a gray lens. In the unactivated state, the star pattern was not apparent on the colorless lensPart 3 - Subsequent processing

[0227] Step 7. Process Ultraviolet (UV) curable layer

[0228] The photochromic optical article from Step 6 was further coated with a UV- curable protective layer. A UV-curable composition was prepared according to Example 1 in United States Patent No. 7,410,691 B2. The washed lens from Step 6 was corona treated as described above, then the UV-curable protective layer was applied by spin coating. The coated lens was then cured under 4 UV lamps in a UV Curing Oven Machine designed and built by Belcan Engineering in nitrogen atmosphere while running on a conveyor belt at 6 ft / min (0.03048 m / s)at peak intensity of 1.50 Watts per square centimeter (W / cm2) of UV-A and UV dosage of 4.5- 5.0 Joules per square centimeter (J / cm2) of UV-A.

[0229] Step 8. Application of an abrasion resistant layer

[0230] The photochromic optical article from Step 7 was further coated with Hi Gard® 1080 (a siloxane hard coat available from PPG Industries, Inc.). After corona treatment as described above, the siloxane composition was applied by spin coating. Afterwards, the coated lens was placed in a forced-air oven maintained at 125°C for 60 minutes and cooled to room temperature.

[0231] Upon irradiation with UV light, it was confirmed that the photochromic appearance of the etched and imbibed pattern was unaltered by the additional coatings.

[0232] The present invention has been described with reference to specific details of particular embodiments thereof. It is not intended that such details be regarded as limitations upon the scope of the invention except insofar as to the extent that they are included in the accompanying claims.

Claims

THE INVENTION CLAIMED IS:

1. A photochromic optical article comprising: an optical substrate comprising a first surface and a second surface opposite the first surface; wherein the photochromic optical article reversibly transitions from an unactivated state to an activated state in response to actinic radiation, wherein the activated state comprises: a first color; and at least one image over at least a portion of the optical substrate, wherein the at least one image comprises at least one second color that is visually distinct from the first color, and wherein the at least one image is visually indiscernible in the unactivated state.

2. The photochromic optical article of claim 1 , wherein the at least one image is selected from the group consisting of shapes, patterns, symbols, logos, monograms, text, pictures, and combinations thereof.

3. The photochromic optical article of claim 1 or 2, wherein the photochromic optical article comprises: at least one first photochromic material that forms the first color; and at least one second photochromic material or an ultraviolet light absorbing material that forms the at least one second color.

4. The photochromic optical article of claim 3, wherein the at least one second photochromic material is different from the first photochromic material.

5. The photochromic optical article of claim 3, wherein the at least one second photochromic material is the same as the at least one first photochromic material.

6. The photochromic optical article of claim 3, wherein the photochromic optical article comprises at least one first photochromic material and an ultraviolet light absorbing material that forms the at least one second color.

7. The photochromic optical article of any one of claims 3 to 6, wherein the at least one first photochromic material, the at least one second photochromic material, and the ultraviolet light absorbing material, when present, are imbibed into the first surface of the optical substrate.

8. The photochromic optical article of any one of claims 1 to 6, wherein the photochromic article comprises at least one photochromic layer positioned over at least a portion of the first surface of the substrate.

9. The photochromic optical article of any one of claims 1 to 9, wherein the at least one image comprises two or more second colors that are visually distinct from the first color, and wherein the two or more second colors are visually distinct from one another.

10. The photochromic optical article of any one of claims 1 to 8, wherein the activated state comprises two or more images over at least a portion of the optical substrate, wherein the two or more images comprise at least one second color that is visually distinct from the first color; or wherein the two or more images each independently comprise at least one second color that is visually distinct from the first color and visually distinct from one another; or wherein the two or more images comprise two or more second colors that are visually distinct from the first color and visually distinct from one another.

11. The photochromic optical article of any one of claims 1 to 10, wherein the photochromic optical article is selected from the group consisting of ophthalmic articles, display articles, windows, mirrors, active liquid crystal cell articles, and passive liquid crystal cell articles.

12. The photochromic optical article of any one of claims 1 to 11, wherein the photochromic optical article is a display article, and the display article is selected from the group consisting of screens, monitors, and security elements.

13. The photochromic optical article of any one of claims 1 to 13, wherein the photochromic optical article is an ophthalmic article, and the ophthalmic article is selected from the group consisting of corrective lenses, non-corrective lenses, contact lenses, intra-ocular lenses, magnifying lenses, protective lenses, and visors.

14. The photochromic optical article of claim 13, wherein the ophthalmic article comprises a peripheral zone and a line-of-sight zone.

15. The photochromic optical article of claim 14, wherein the at least one image is positioned in the peripheral zone of the ophthalmic article.

Images