Multilayer exposed substrate and methods of making and using the multilayer substrate

Abstract

Disclosed are multi-layer exposed substrates and methods of making and / or using the substrates, the substrate including: a first layer comprising a first opacifying material; a first color material applied to a first side of the first layer comprising the first opacifying material, the first layer comprising the first opacifying material being positioned to cover the first color material; and a second layer comprising a second opacifying material applied to a side of the first color material opposite the first layer comprising the first opacifying material, the second layer comprising a second opacifying material being configured to change from an opaque state to a transparent state upon application of a first predetermined energy to expose the first color material underlying the first opacifying material, and the second opacifying material being configured to change from an opaque state to a transparent state upon application of a second predetermined energy.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This non-provisional application claims priority to U.S. Provisional Patent Application No. 63 / 382,807, filed November 8, 2022, and U.S. Provisional Patent Application No. 63 / 537,287, filed September 8, 2023, which are incorporated herein by reference. [Background technology]

[0002] The present invention relates to the field of printing and printable multilayer substrates and improves upon the printing substrates and methods described in U.S. Patent No. 8,054,323 and U.S. Patent Application Publication No. 2021 / 0086542, both of which are incorporated herein by reference in their entireties. More specifically, the present disclosure is directed to novel multilayer printing substrates, methods of making and / or using the multilayer printing substrates, and at least two opaque layers of the substrate, the opacifying layer being disposed over at least two coloring materials or layers and provided by one or more opaque polymers or polymeric materials that are sensitive to the application of at least one selected from heat, pressure, light, and / or laser energy, or a combination thereof. One or more of the opaque polymers or polymeric materials of the at least two opacifying layers can be induced to become transparent to expose the coloring material (e.g., ink) or underlying material. For example, the print head may transmit first light / laser energy and / or heat energy to a portion of the multilayer substrate to cause at least one opaque polymer or polymer material of at least one of the at least two opacifying layers to become transparent in those portions, thereby exposing a first color material or layer underlying the at least one opacifying layer in those portions. The print head may also transmit second light / laser energy and / or heat energy to a portion of the multilayer substrate to cause one or more opaque polymers or polymer materials of the at least two opacifying layers to become transparent in those portions, thereby exposing at least one second color material or layer underlying the at least two opacifying layers in those portions. As a result of the transmission of the first and second light / laser energy and / or heat energy to the portion of the multilayer substrate, a blended color of the first color material or layer and at least one second color material or layer is exposed and displayed in the portion of the multilayer substrate. In an embodiment, the first color material or layer may be blue, the at least one second color material or layer may be yellow, and the blended color may be green.The multilayer substrates and methods disclosed herein may achieve improved color imaging and printhead alignment, adjustment, registration, and / or re-registration by utilizing or implementing one or more of the systems and / or methods described in U.S. Pat. No. 10,427,440 (hereinafter "the '440 patent"), the entirety of which is incorporated herein by reference. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] U.S. Patent No. 8,054,323 [Patent Document 2] U.S. Patent Application Publication No. 2021 / 008654 [Patent Document 3] U.S. Patent No. 10,427,440 Summary of the Invention [Means for solving the problem]

[0004] The present disclosure relates to multilayer exposed substrates and methods for making and / or using such multilayer substrates. The present disclosure also relates to a multilayer exposed substrate having at least two opaque or opacifying layers comprising one or more opaque polymers or polymeric materials, which can be induced to transition from an opaque state to a transparent state, thereby exposing one or more color materials and / or one or more pigmented layers underlying the opaque polymer or polymeric material of one or more of the at least two opaque or opacifying layers. One or more of the opaque polymer or polymeric materials of the at least two opaque or opacifying layers can be induced to become transparent by heat, pressure, light / laser energy, and / or chemical reaction, thereby exposing the underlying color material (e.g., ink) or pigmented layer. One or more of the opaque polymer or polymeric materials of the at least two opaque or opacifying layers can be sensitive to light and / or laser energy, thermal energy or heat, chemicals, and / or pressure, thereby forming at least two light- and / or laser-sensitive, heat-sensitive, chemical-sensitive, and / or pressure-sensitive substrates. One or more opaque polymers or polymeric materials of the at least two opaque or opacifying layers may be induced to become transparent by exposure to predetermined light and / or laser energy (e.g., light and / or laser energy having one or more predetermined frequencies, intensities, and / or amounts, hereinafter referred to as "light / laser energy"), heating at elevated or high temperatures (e.g., above ambient or other thresholds), application of pressure (e.g., above atmospheric pressure), chemical reaction or change, and / or other transparency-inducing methods. As a result of application of predetermined and / or sufficient light / laser energy, heating, pressure, and / or chemical change, one or more of the at least two opaque or opacifying layers may become or change to a transparent state and / or expose the underlying color material or color layer.More specifically, one or more opaque polymers or polymeric materials of the at least two opaque or opacifying layers comprise at least one plurality of spherical polymer particles, at least one plurality of irregular or irregularly shaped polymer particles, or a mixture thereof, which are or can be transformed from an opaque state to a transparent state, wherein upon transformation the structure of the at least two opaque or opacifying layers is at least partially disrupted, changed, modified, and / or altered, such that the at least two opaque or opacifying layers transmit incident light instead of internally reflecting the incident light.

[0005] In some configurations, the first side surface of the multilayer exposed substrate has a color material, such as ink, and / or color layer that substantially outlines and / or covers the first side surface, either entirely or at least partially. The color material (e.g., ink) and / or color layer can be any single color and / or multiple colors desired for printing or imaging. In one or more embodiments, the color material and / or ink disclosed herein can be, include, or consist of one or more opaque inks, one or more semi-transparent and / or transparent inks, one or more colored opaque inks, one or more colored semi-transparent and / or transparent inks, or at least one combination thereof. In at least one embodiment, the color material and / or color layer can include a plurality of different or similar colors, wherein at least one of the different or similar colors is exposed when one or more opaque or opacifying layers (i.e., one or more opaque polymers or polymeric materials) change from an opaque state to a transparent state. Additionally, the multilayer exposed substrate may have at least two opaque materials and / or layers (hereinafter referred to as "opacifying layers") that cover, obscure, and / or block the color material (e.g., ink) and / or color layer on the first side surface of the multilayer exposed substrate. As a result, the opacifying layer obscures, blocks, and / or covers the color material (e.g., ink) and / or color layer on the first side surface when viewed prior to any induced transparency. The opacifying layer provides the second side surface of the multilayer exposed substrate with or appears to exhibit at least one opaque color, e.g., white and / or one opaque color. Only upon application of a predetermined amount of heat, pressure, and / or light / laser energy does the color material (e.g., ink) and / or color layer on the first side surface become exposed and / or visible. Each opacifying layer comprises at least one opaque polymer or polymeric material. In some embodiments, the opacifying layer comprises one or more spherical and / or non-spherical polymer particles that may or may not have an opaque color. In some such embodiments, the one or more spherical and / or non-spherical polymer particles may have an opaque color that can be induced to become transparent.In other embodiments, the one or more spherical and / or non-spherical polymer particles may be, or may include, one or more spherical particles, one or more rod-shaped particles, one or more flake-shaped particles, or a combination thereof, and may be induced to be transparent.

[0006] In one or more embodiments, the one or more opaque polymer or polymeric materials (i.e., spherical polymer particles, non-spherical polymer particles, irregular and / or irregularly shaped polymeric particles, or mixtures thereof) are sensitive to the application of predetermined light / laser energy, heat, pressure, and / or chemical change, such that upon exposure to at least one of light / laser energy (i.e., a predetermined amount, frequency, and / or intensity), heating to a predetermined temperature, application of a predetermined pressure, and / or chemical change, at least one opacifying layer or both opacifying layers can become transparent and / or clear. As a result of becoming transparent and / or clear, at least one opacifying layer or both opacifying layers transmit incident light to expose a color material (e.g., ink) and / or pigmented layer disposed on a first side surface beneath the opacifying layer and one or more opaque polymer or polymeric materials.

[0007] In one or more embodiments, a multilayer exposed substrate includes a first layer including a first opacifying material, a first color material applied to a first side of the first layer including the first opacifying material, the first layer including the first opacifying material being positioned to cover the first color material, and a second layer including a second opacifying material applied to a side of the first color material opposite the first layer including the first opacifying material with respect to the first color material, the first opacifying material being configured to change from an opaque state to a transparent state upon application of a first predetermined energy to expose the first color material underlying the first opacifying material, and the second opacifying material being configured to change from an opaque state to a transparent state upon application of a second predetermined energy, the first predetermined energy being different from the second predetermined energy.

[0008] In at least one embodiment, at least one of the first predetermined energy and the second predetermined energy is a predetermined light and / or laser energy.

[0009] In some embodiments, both the first predetermined energy and the second predetermined energy are predetermined light and / or laser energies.

[0010] In an embodiment, the second predetermined energy is greater than the first predetermined energy.

[0011] In at least one embodiment, the multilayer exposed substrate further comprises a second color material applied to a first side of a second layer comprising the second opacifying material, the second layer comprising the second opacifying material being positioned to cover the second color material, and the second opacifying material being configured to change from an opaque state to a transparent state upon application of a second predetermined energy to expose the second color material underlying the second opacifying material.

[0012] In some embodiments, the second predetermined energy is greater than the first predetermined energy.

[0013] In an embodiment, the first and second predetermined energies comprise light and / or laser energy.

[0014] In at least one embodiment, the multilayer exposed substrate further comprises a base substrate, the base substrate being disposed behind the second color material, and the first and second color materials being disposed between the base substrate and a first layer comprising the first opacifying material.

[0015] In one or more embodiments, a method includes providing a first color material covered by a first layer including a first opacifying material in an opaque state such that the first opacifying material prevents visibility of the first color material through the first opacifying material; disposing a second layer including a second opacifying material on a side of the first color material opposite the first layer including the first opacifying material; applying a first predetermined energy to change at least a portion of the first layer including the first opacifying material from an opaque state to a transparent state to expose the first color material underlying the first opacifying material; and applying a second predetermined energy to change at least a portion of the second layer including the second opacifying material from an opaque state to a transparent state, wherein the first predetermined energy is approximately less than the second predetermined energy.

[0016] In at least one embodiment, the method further includes covering a second color material with a second layer including the second opacifying material such that when the second predetermined energy is applied to a portion of the second layer including the second opacifying material, the underlying second color material is exposed and becomes visible from a side of the first layer including the first opacifying material opposite the first color material.

[0017] In some embodiments, the method further includes modifying the exposed portion of the first color material with the exposed portion of the second color material to produce and expose an modified color.

[0018] In an embodiment, the altered color comprises a combination of a first color of a first color material and a second color of the second color material.

[0019] In at least one embodiment, the exposed first color material is or includes at least one machine-readable code that appears as a single color or a mixture of colors.

[0020] In some embodiments, the at least one machine-readable code is displayed as a single color and is at least one selected from a machine-readable barcode, a machine-readable QR code, and combinations thereof.

[0021] In an embodiment, the at least one machine-readable code is displayed as a mixture of colors and is at least one selected from a machine-readable barcode, a machine-readable QR code, and combinations thereof.

[0022] The present disclosure will be best understood from the following detailed description taken in conjunction with the accompanying drawings, in which: It is emphasized that, according to standard practice in the industry, various features have not been drawn to scale, and in fact the dimensions of various features may be arbitrarily increased or decreased for clarity of discussion. [Brief explanation of the drawings]

[0023] [Figure 1] 1 is a perspective view of a multi-layer exposed substrate according to one or more embodiments of the present disclosure. [Figure 2] 2 is a side plan view illustrating the application of a first predetermined energy onto the multilayer exposed substrate shown in FIG. 1 in accordance with one or more embodiments of the present disclosure. [Figure 3] 2 is a side plan view illustrating the application of a second predetermined energy onto the multilayer exposed substrate shown in FIG. 1 in accordance with one or more embodiments of the present disclosure. [Figure 4] FIG. 10 is a side plan view illustrating the application of a second predetermined energy on another multi-layer exposed substrate, according to one or more embodiments of the present disclosure. [Figure 5] 2 is a side plan view illustrating the application of a first predetermined energy onto another multi-layer exposed substrate similar to the substrate shown in FIG. 1 in accordance with one or more embodiments of the present disclosure. FIG. [Figure 6] FIG. 5 is a side plan view illustrating the application of a second predetermined energy on another multi-layer exposed substrate similar to the substrate shown in FIG. 4, in accordance with one or more embodiments of the present disclosure. [Figure 7]1 is a schematic diagram of a plurality of first machine-readable codes, each displaying a different solid color throughout the code, in accordance with one or more embodiments of the present disclosure; FIG. [Figure 8] 10A-10C are schematic diagrams of second and third machine-readable codes, each displaying a different mix of colors throughout the code, in accordance with one or more embodiments of the present disclosure; DETAILED DESCRIPTION OF THE INVENTION

[0024] Illustrative examples of the claimed subject matter are disclosed below. In the interest of clarity, not all features of an actual implementation are described herein. It is understood that the development of such an actual implementation will involve numerous implementation-specific decisions that will vary from implementation to implementation in order to achieve the developer's particular goals, including compliance with system-related and business-related constraints. It is further understood that such a development effort, even if complex and time-consuming, would be a routine undertaking for one of ordinary skill in the art having the benefit of this disclosure.

[0025] Additionally, as used herein, the article "a" is intended to have its ordinary meaning in the patent art, i.e., "one or more." As used herein, the term "about," when applied to a value, generally means within the tolerance of the device used to generate the value, and in some instances, unless expressly specified, means plus or minus 10%, or plus or minus 5%, or plus or minus 1%. Furthermore, as used herein, the term "substantially" means majority, or nearly all, or all, or an amount ranging from, for example, about 51% to about 100%. Additionally, the examples herein are intended for illustrative purposes only and are presented for discussion and not limitation.

[0026] Referring now to the drawings, in which like reference numerals indicate like parts / features, the multilayer exposed substrate, as shown in Figures 1-4, is generally referred to by reference numeral 10 and is at least one of a thermally exposed substrate, a light / laser energy exposed substrate, a chemically exposed substrate, a pressure exposed substrate, or a combination thereof. The multilayer exposed substrate 10 is a heat, light / laser energy, chemical, and / or pressure exposed substrate (hereinafter collectively referred to as "substrate 10") that includes a first light / laser energy, heat, pressure, and / or chemically sensitive substrate 12 (hereinafter referred to as "first sensitive substrate 12") having a first opacifying material or layer 14 (hereinafter referred to as "first opacifying material 14") that can be induced to become transparent, semi-transparent, translucent, semi-translucent, tinted-transparent, and / or tinted-translucent (i.e., change from an opaque state to a transparent state, semi-transparent state, translucent state, semi-translucent state, tinted-transparent state, tinted-translucent state, or combinations thereof (hereinafter collectively referred to as "transparent state"). Additionally, substrate 10 includes a second optical / laser energy, thermal, pressure, and / or chemically sensitive substrate 16 (hereinafter "second sensitive substrate 16") having a second opacifying material or layer 18 (hereinafter "second opacifying material 18") that can be induced to become transparent, semi-transparent, translucent, semi-translucent, tinted-transparent, and / or tinted-translucent (i.e., change from an opaque state to a transparent state). In some embodiments, first opacifying material 14 can be a different opacifying material than second opacifying material 18, and first opacifying material 14 and / or second opacifying material 18 (hereinafter collectively referred to as "first and second opacifying materials 14 and 18") have different change parameters and / or energy for change from the opaque state to the transparent state.In one or more embodiments, application of a first predetermined energy 15 (i.e., predetermined light / laser energy, heat, pressure, chemicals, or a combination thereof; hereinafter referred to as "first energy 15") to a first opaque material 14 causes the first opaque material 14 to change from an opaque state to a transparent state, while application of the first energy 15 to a second opaque material 18 may or may not cause the second opaque material 18 to change from an opaque state to a transparent state. However, application of a second predetermined energy 19 (i.e., predetermined light / laser energy, heat, pressure, chemicals, or a combination thereof; hereinafter referred to as "second energy 19") that is greater in amount, frequency, or intensity than the first energy 15 may cause both the first and second opaque materials 14, 18 to change from an opaque state to a transparent state. In embodiments, the first opacifying material 14 may be the same, substantially the same, similar, or substantially similar to the opaque and / or opaque material of the second opacifying material 18, and both the first and second opacifying materials 14, 18 may change from an opaque state to a transparent state upon application of the first energy 15 and / or the second energy 19.

[0027] In one or more embodiments, the first and second opacifying materials 14 and 18 can be induced to become transparent by exposure to a first energy 15 and / or a second energy 19 (hereinafter collectively referred to as "first and second energies 15, 19"). In embodiments, the first and second energies 15, 19 can include or consist of exposure to at least one predetermined light energy and / or laser energy (hereinafter referred to as "light / laser energy"), heating above a predetermined temperature, application of a predetermined pressure, and / or a chemical reaction or change that causes a change from an opaque state to a transparent state. As a result, the first and second opacifying materials 14 and 18 become transparent and / or clear and / or change to expose the color material (e.g., ink) and / or one or more color layers depicted thereunder as at least one exposed region 20 (hereinafter referred to as "region 20"), as shown in FIGS. 1-4. In at least one embodiment, the color material, ink, and / or one or more colored layers may be, comprise, or consist of one or more opaque inks, one or more clear and / or transparent inks, one or more colored opaque inks, one or more colored clear and / or transparent inks, or at least one combination thereof.

[0028] In one or more embodiments, the first and second opacifying materials 14 and 18 may each comprise at least one opaque polymer or polymeric material, which may include a plurality of spherical polymer particles, a plurality of non-spherical polymer particles, a plurality of irregular and / or irregularly shaped polymer particles, or mixtures thereof (collectively referred to hereinafter as "polymeric particles"). In some embodiments, the at least one opaque polymer or polymeric material may have a melting point of at least about 37°C, between about 37 and 150°C, between about 80 and 150°C, or greater than about 150°C. In embodiments, the at least one opaque polymer or polymeric material may comprise more than one polymer or copolymer, such as, for example, a styrene-acrylic copolymer. In another embodiment, the opaque polymer may comprise hollow sphere pigments, which may appear opaque as a result of their light-scattering properties. In other embodiments, the at least one opaque polymer may have a physical and / or chemical structure that can be changed and / or altered by application of heat, pressure, light / laser energy (i.e., first and second energies 15, 19), and / or chemical exposure such that the at least one opaque polymer or polymeric material becomes transparent or at least substantially transparent. In one or more other or alternative embodiments, the at least one opaque polymer or polymeric material may conform to or substantially conform to one or more opaque polymers / opaque polymers described in U.S. Patent Publication No. 2017 / 0337851, which is incorporated herein by reference in its entirety.

[0029] In some embodiments, at least one opaque polymer or polymeric material of the first and second opacifying materials 14 and 18 may comprise hollow polymeric microspheres that appear white until disrupted by the first and second energies 15 and 19. Thus, the at least one opaque polymer or polymeric material only exhibits an opaque color, which may be white, for example. Only upon application of the first and second energies 15 and 19 does the hollow polymeric microsphere change from an opaque state to a transparent state. In at least one embodiment, the at least one opaque polymer or polymeric material may be hollow microspheres comprised of a styrene-acrylic copolymer that, when applied to a surface, appears white or opaque to the viewer's eye, causing the viewed surface to appear white, regardless of whether the applied surface is a colored or transparent surface. Upon application of the first and second energies 15 and 19, the hollow microspheres cease to be opaque, and the areas where the first and second energies were applied become transparent, thereby revealing the underlying color material (i.e., ink). In other embodiments, the at least one opaque polymer or polymeric material may include an opaque polymer containing a styrene-acrylic copolymer (or equivalent), which in a preferred form is generally in the form of microspheres, providing an opacifying polymeric material, which appears white due to the reflective properties in the opaque polymer.

[0030] The opacity of the first and second opacifying materials 14 and 18 and / or one or more opaque polymers or polymeric materials of the first and second opacifying materials 14 and 18 can depend on the spaces and / or voids located between and / or outside the polymer particles. The spaces and / or voids may be located between the peripheries and / or outer surfaces of the polymer particles, and / or the spaces and / or voids may not be located inside the polymer particles or inside the peripheries and / or outer surfaces of the polymer particles. In other words, the spaces and / or voids are located outside the polymer particles. The polymer particles may be non-spherical and / or have different shapes and / or different sizes. The first and second opacifying materials 14 and 18 and / or one or more opaque polymers or polymeric materials of the first and second opacifying materials 14 and 18 can be induced to become transparent by exposure to first and second energies 15, 19 (i.e., different light / laser energies, heating at different elevated temperatures, application of different pressures, and / or different chemical reactions or chemical changes). As a result, the polymer particles of the one or more opaque polymers or polymeric materials may melt and / or change shape such that the spaces and / or voids between the outer surfaces of the polymer particles are removed or lost, and the first and second opacifying materials 14 and 18 may become transparent and / or clear to expose the color material (i.e., ink) and / or one or more underlying colored layers.

[0031] In more than one embodiment, the first and second opacifying materials 14 and 18, or the polymer particles of one or more opaque polymers or polymeric materials, comprise at least one first portion of polymer particles and at least one second portion of polymer particles, each having a different size and / or shape. The at least one first portion of polymer particles can have a first size and / or a first shape, and the at least one second portion of polymer particles can have a second size and / or a second shape. In some configurations, the first size is similar to the second size and the first shape is different from the second shape; the first size is different from the second size and the first shape is similar to the second shape; or the first size is different from the second size and the first shape is different from the second shape. The spaces and / or voids between the polymer particles of at least one first portion can be the same as, different from, or substantially the same as the spaces and / or voids between the polymer particles of at least one second portion. In some embodiments, the surface area and / or mass ratio of the first portion to the second portion can be about 1:1, greater than about 1:1, or less than about 1:1, respectively. For example, the surface area or mass ratio of the first portion to the second portion can be from about 1:1 to about 10:1, from about 3:1 to about 8:1, or from about 4:1 to about 6:1, respectively.

[0032] In some embodiments, the polymer particles of the first and second opacifying materials 14 and 18, or one or more opaque polymers or polymeric materials of the first and second opacifying materials 14 and 18, may provide both improved laser and / or inkjet imaging and printing process and / or method enhancements. In at least one embodiment, the polymer particles may provide improved optical / laser and / or thermal imaging quality or clarity and improved laser and / or inkjet receptivity. Furthermore, the improved imaging quality provided by the polymer particles is advantageous over conventional thermal printing mechanisms. The polymer particles of the first and second opacifying materials 14 and 18 are advantageous because they do not require or do not require leuco dyes, sensitizers, and / or color developers, thereby allowing the first and second opacifying materials 14 and 18 of the present disclosure to comply with and / or comply with increasing health and / or environmental regulations. For example, embodiments of the first and second opacifying materials 14 and 18 may be completely free, or at least substantially free, of leuco dyes, sensitizers, and / or color developers.

[0033] In at least one embodiment, the average particle size of the polymer particles disclosed herein can be at least about 50 nm, at least about 100 nm, at least about 150 nm, at least about 250 nm, less than about 1000 nm, less than about 500 nm, less than about 450 nm, less than about 400 nm, or less than about 350 nm. In another embodiment, the polymer particles of the present invention can have an average particle size of up to about 1000 nm or up to about 1500 nm. In one or more embodiments, the polymer particles can have an average particle size between and / or including about 1000 nm and about 1500 nm.

[0034] In embodiments, the polymer particles, or one or more opaque polymers or polymer materials, of the first and second opacifying materials 14 and 18 can provide high or improved opacity, good or improved resolution, and / or good or improved water resistance and rub resistance to the substrate 10 (e.g., compared to spherical particles). The spaces and / or voids between the polymer particles can receive ink, printed colors, and / or printed indicia for inkjet color printing of the substrate 10. At least one portion or part of the layers of the first and second opacifying materials 14 and 18 can be made transparent to expose the color material (e.g., ink) or one or more color layers underlying the polymer particles, for example, for direct light / laser and / or thermal printing of the substrate 10. In some embodiments, one or more of the polymer particles can be aligned when in a transparent state or condition, such that the transparency clearly exposes the color material (i.e., ink) and / or one or more color layers underlying the first and second opacifying materials 14 and 18. As a result, optical / laser and / or thermal imaging of the substrate 10 can achieve enhanced image density and / or enhanced clarity for optical / laser and / or thermal printing or imaging of the substrate 10 .

[0035] In some embodiments, the first sensitive substrate 12 and / or the second sensitive substrate 16 (hereinafter collectively referred to as "first and second sensitive substrates 12, 16") may include one or more opacifying agents, such as particulate titanium dioxide having a particular morphology, as an opacifying agent and / or white pigment. Particulate titanium dioxide for use as an opacifying agent in polymer compositions and products formulated therefrom is widely available and may include titanium dioxide, calcium carbonate, white zinc, white lead, lithopone, alumina white, white carbon, zirconium oxide, tin oxide, barium sulfate, barium carbonate, or combinations thereof.

[0036] The polymer particles of the first and second opacifying materials 14 and 18, or one or more opaque polymers or polymeric materials of the first and second opacifying materials 14 and 18, may have thermal melting and / or transition properties, or a suitable glass transition state (hereinafter referred to as "Tg"), which defines a pseudo-second-order phase transition in which a supercooled melt, upon cooling, assumes a glass-like structure and properties similar to a crystalline material, e.g., an isotropic solid material. Tg can apply to fully or partially amorphous solids (i.e., polymer particles), such as common glasses and plastics. The thermal melting temperature and / or Tg of the polymer particles of the first and second opacifying materials 14 and 18 may be less than about 120°C, less than about 110°C, less than about 105°C, less than about 95°C, and less than about 85°C. In some embodiments, the thermal melting temperature and / or Tg of the polymer particles may be in the range of about 80° C. to about 130° C., 90° C. to about 120° C., about 100° C. to about 110° C., or about 100° C. to about 105° C. In other embodiments, the thermal melting temperature and / or Tg of the polymer particles may be greater than about 70° C., greater than about 80° C., greater than about 95° C., or greater than about 100° C.

[0037] In embodiments, the polymer particles of the first and second opacifying materials 14 and 18, or one or more opaque polymers or polymeric materials of the first and second opacifying materials 14 and 18, may include at least one of a styrene and an acrylate, and / or may be provided in a suspension and / or with a carrier. The suspension may be in the form of an aqueous emulsion. In embodiments, the aqueous emulsion may be an acrylic emulsion or a styrene-acrylic emulsion. The aqueous emulsion may be a non-film-forming emulsion or a film-forming emulsion. The pH of the aqueous emulsion at 25° C. may be less than about 8.5, less than about 8.0, less than about 7.5, greater than about 6.5, greater than about 7.0, or about 7.5. The viscosity of the aqueous emulsion at 25°C may be less than about 100 cps, at least about 200 cps, at least about 300 cps, at least about 400 cps, about 2200 cps or less, about 2100 cps or less, or about 2000 cps or less. The molecular weight (hereinafter referred to as "Mw") of the aqueous emulsion may be greater than about 150,000, greater than about 175,000, greater than about 200,000, less than about 250,000, less than about 230,000, or less than about 210,000. The density of the aqueous emulsion at 25°C is about 1.12 g / cm 3 Less than 1.10 g / cm 3 Less than 1.06g / cm 3 Less than 1.02 g / cm 3 Exceeding 1.04g / cm 3 Exceeding 1.06g / cm 3 It may be more than that.

[0038] In addition to the polymer particles or one or more opaque polymers or polymeric materials, the first and second opacifying materials 14, 18 may further include at least one wax, at least one optional sensitizer, at least one optical brightener, at least one binder or resin, and / or at least one optional additive. In embodiments, the at least one optional additive may include one or more components selected from the group of components consisting of clay, antifoaming agent, surfactant, biocide, viscosity modifier, and / or rheology modifier. In other embodiments, the at least one optional additive may include at least one component selected from the group of components consisting of emulsifier, surfactant, lubricant, coalescing agent, plasticizer, antifreeze agent, hardener, buffer, neutralizer, thickener, rheology modifier, humectant, wetting agent, biocide, plasticizer, antifoaming agent, UV absorber, optical brightener, light or heat stabilizer, biocide, chelating agent, dispersant, colorant, water repellent, antioxidant, and one or more combinations thereof.

[0039] In embodiments, the polymer particles or one or more opaque polymers or polymeric materials may be present in the first and second opacifying materials 14, 18 at a concentration of at least about 5%, at least about 10%, at least about 20%, at least about 25%, at least about 40%, at least about 50%, or greater than about 50% by weight. In other embodiments, the polymer particles or one or more opaque polymers or polymeric materials may be present in the first and second opacifying materials 14, 18 at a concentration of less than about 55%, less than about 45%, less than about 30%, less than about 20%, less than about 15%, or less than about 8% by weight. All weight concentrations are calculated relative to the total weight of the first and second opacifying materials 14, 18.

[0040] The at least one wax may be provided in a suspension and / or with at least one carrier. In embodiments, the at least one wax may be at least one selected from paraffin wax, microcrystalline wax, carnauba wax, methylol stearamide, polyethylene wax, polystyrene wax, fatty acid amide-based wax, or a combination thereof. In other embodiments, the at least one wax may include at least one selected from erucamide, stearamide, palmitamide, ethylene-bis-stearamide, or a combination thereof.

[0041] The at least one optional sensitizer can be configured to lower the melting temperature and / or Tg temperature of the polymer particles. For example, the at least one optional sensitizer can be 2-benzyloxynaphthalene, dimethylbenzyl oxalate, m-terphenyl, ethylene glycol tolyl ether, p-benzylbiphenyl, 1,2-diphenoxymethylbenzene, 1,2-diphenoxyethane, diphenyl sulfone, aliphatic monoamides, aliphatic bisamides, stearyl urea, di(2-methylphenoxy)ethane, di(2-methoxyphenoxy)ethane, β-naphthol-(p-methylbenzyl)ether, α- The optional sensitizers may be selected from naphthyl benzyl ether, 1,4-butanediol-p-methylphenyl ether, 1,4-butanediol-p-isopropylphenyl ether, 1,4-butanediol-p-tert-octylphenyl ether, 1-phenoxy-2-(4-ethylphenoxy)ethane, 1-phenoxy-2-(chlorophenoxy)ethane, 1,4-butanediol phenyl ether, diethylene glycol bis(4-methoxyphenyl)ether, and 1,4-bis(phenoxymethyl)benzene. These optional sensitizers may be used alone or in combination of two or more. In embodiments, the first and second opacifying materials 14, 18 may be formulated, adapted, and / or configured to reduce or eliminate the content of any sensitizer. For example, some embodiments of the first and second opacifying materials 14, 18 may be completely free, or at least substantially free, of any sensitizer.

[0042] The at least one optional optical brightening agent may comprise one or more optical brightening agents, one or more optical brightening agents, one or more fluorescent whitening agents, or a combination thereof. In embodiments, the at least one optical brightening agent may absorb light in the ultraviolet and violet regions of the electromagnetic spectrum and / or re-emit light in the blue region by fluorescence. For example, the at least one optical brightening agent may comprise one or more stilbenes.

[0043] The at least one binder or resin may comprise one or more thermoplastic and / or crosslinkable resins. In embodiments, the at least one binder or resin may be one or more selected from polyvinyl alcohol, proteins such as casein, starch, gelatin, copolymers of acrylic or methacrylic acid esters, copolymers of styrene and acrylic or methacrylic acid esters, copolymers of styrene and acrylic acid, styrene-butadiene copolymers, copolymers of vinyl acetate and other acrylic or methacrylic acid esters, and combinations of one or more thereof.

[0044] In one or more embodiments, first and second opacifying materials 14, 18 comprising polymer particles or one or more opaque polymers or polymeric materials disclosed herein may be disposed on and / or utilized with a substrate 10 and / or utilized in the methods also disclosed herein. The substrate 10 may have a structural configuration and / or relationship such that a first sensitive substrate 12 comprising the first opacifying material 14 is disposed on the upper surface or uppermost layer of the substrate 10, as shown in Figures 1-4. A first colored substrate or layer 22 (hereinafter referred to as the "first colored layer 22") may be disposed below the first sensitive substrate 12, and a second sensitive substrate 16 comprising the second opacifying material 18 may be disposed below the first colored layer 22 such that the first colored layer 22 is disposed between the first and second sensitive layers 12, 16 and the first and second opacifying materials 14, 18. A second colored substrate or layer 24 (hereinafter referred to as the "second colored layer 24") may be disposed below the second sensitive layer 16, such that the second colored layer 16 is disposed between the first colored layer 22 and the second colored layer 24 (hereinafter referred to collectively as the "first and second colored layers 22, 24"). A base substrate 26 (hereinafter referred to as the "base 26") may be disposed below the second colored layer 24, such that the second colored layer 24 is disposed between the second sensitive substrate 16 and the base 26. In some embodiments, the base 26 may be, include, or consist of a paper-based substrate, a film-based substrate, a polymer-based substrate, a release film substrate, an adhesive-based layer or substrate, or a combination thereof.

[0045] In at least one embodiment, the first side surface of the first sensitive substrate 12 adjacent to the second sensitive substrate 16 may have or be coated with a first colored layer 22, which may include at least one colored ink, and the at least one colored ink may cover at least a portion of, or substantially the entire, the first side surface of the first sensitive substrate 12. In one or more embodiments, the at least one colored ink disclosed herein may be, include, or consist of one or more opaque inks, one or more semi-transparent and / or transparent inks, one or more colored opaque inks, one or more colored semi-transparent and / or transparent inks, or at least one combination thereof. The first colored layer 22 may have at least one first colored region 28 (hereinafter referred to as "first colored region 28") including one or more inks, which may be of any desired color or colors. In embodiments, the first colored region 28 of the first colored layer 22 may be or include any desired color or colors. In one or more embodiments, the first colored region 28 may be, include, or consist of one or more opaque inks, one or more translucent and / or transparent inks, one or more colored opaque inks, one or more colored translucent and / or transparent inks, or at least one combination thereof. The first sensitive substrate 12 includes the first opacifying material 14, such that the first colored region 28 is not visible when viewed from the second side surface opposite the first colored layer 22 prior to the application of any light / laser energy, heat, and / or pressure, such as the light / laser, heat, and / or pressure printhead 21 (hereinafter referred to as "printhead 21"). In embodiments, the first opacifying material 14 may be part of the physical configuration of the first sensitive substrate 12 or may be a separate and / or discrete layer or layers.In embodiments, this may be achieved by providing polymer particles or one or more opaque polymers or polymeric materials of the first and second opacifying materials 14, 18 disclosed herein that may appear white or opaque until application of at least one of light / laser energy, heat, pressure, or a combination thereof (i.e., application of first energy 15). In this manner, the second side surface of the first sensitive substrate 12 may exhibit only an opaque color, which may be, for example, white or at least one different opaque color. Only upon application of light / laser energy, elevated temperature heat, and / or pressure (i.e., application of first energy 15) is the black, gray, and / or one or more other colors of the first colored region 28 on the first side surface of the first sensitive substrate 12 revealed or visible.

[0046] In at least one embodiment, the first side surface of the second sensitive substrate 16 adjacent the base 26 may have or be coated with a second colored layer 24 including at least one colored ink covering at least a portion or substantially the entire first side surface of the second sensitive substrate 16. The second colored layer 24 may have at least one second colored region 30 (hereinafter referred to as "second colored region 30") including one or more inks, which may be of any desired color or colors. In embodiments, the second colored region 30 of the second colored layer 24 may be of any desired color or colors and may include any desired color or colors. In one or more embodiments, the second colored region 30 disclosed herein may be, include, or consist of one or more opaque inks, one or more semi-transparent and / or transparent inks, one or more colored opaque inks, one or more colored semi-transparent and / or transparent inks, or at least one combination thereof. The first and second sensitive substrates 12, 16 have first and second opacifying materials 14, 18, respectively, such that the first colored regions 28 and second colored regions 30 (hereinafter collectively referred to as "first and second colored regions 28, 30") are not visible when viewed from the second side surfaces of the first and second sensitive substrates 12, 16 opposite the base 26 prior to application of light / laser energy, heat, and / or pressure by the printhead 21. In embodiments, the second opacifying material 18 may be part of the physical configuration of the second sensitive substrate 16 or may be a separate and / or independent layer or layers. In some embodiments, this may be achieved by providing polymer particles disposed within the first and second sensitive substrates 12, 16 that may appear white or opaque until application of at least one of light / laser energy, heat, pressure, or a combination thereof (i.e., application of both the first and second energies 15, 19). In this manner, the second side surfaces of the first and second sensitive substrates 12, 16 may exhibit only an opaque color, which may be, for example, white or at least one different opaque color.Only upon application of light / laser energy, elevated temperature heat, and / or pressure (i.e., application of both the first and second energies 15, 19) is the black, gray, and / or one or more other colors of the first and second colored regions 28, 30 on the first side surfaces of the first and second sensitive substrates 12, 16 exposed or visible. In one or more configurations disclosed herein, the first side surfaces of the first and second sensitive substrates 12, 16 are adjacent the base 26, and the second side surfaces of the first and second substrates 12, 16 are adjacent the top surface of the substrate 10.

[0047] In one or more embodiments, the first and second opacifying materials 14, 18, including polymer particles or one or more opaque polymers or polymeric materials, appear white or another opaque color to the viewer's eye when applied to a surface, causing the viewed surface (the first side surfaces of the first and second sensitive substrates 12, 16) to appear white or at least one different opaque color, whether applied to a colored or transparent surface (i.e., the first and second colored layers 22, 24). Upon application of predetermined light / laser energy, predetermined pressure, and / or predetermined heat via the print head 21 (i.e., application of at least one or both of the first and second energies 15, 19), the polymer particles or one or more opaque polymers or polymeric materials become non-opaque, allowing the areas 20 to which such print head 21 was applied to become transparent, thereby revealing the underlying first colored region 28 (i.e., upon application of the first energy 15) or the underlying first and second colored regions 28, 30 (i.e., upon application of the second energy 19).

[0048] In some embodiments, each of the first and second colored regions 28, 30 may comprise a single color or at least two different colors, as shown in Figures 1-4. In at least one embodiment, at least one of the first and second colored regions 28, 30 may comprise at least two different colored regions, at least two different colors, and / or at least one two-dimensional matrix, as described and disclosed in the '440 patent and U.S. Pat. No. 9,757,968, the entire specifications of which are incorporated herein by reference. In at least one embodiment, each of the first and second colored regions 28, 30 may be formed by a plurality of color blocks, including at least one first color block 32a, at least one second color block 32b, and at least one third color block 32c (hereinafter referred to as "color blocks 32a, 32b, 32c"). Each of the color blocks 32a, 32b, 32c may have or display only one of at least two different colors, and / or the color blocks 32a, 32b, 32c may be arranged within the first and second color layers 22, 24 to have at least one repeating color pattern, design, and / or indicia. In embodiments, at least two of the color blocks 32a, 32b, 32c may have or display a single color. In other embodiments, one or more of the color blocks 32a, 32b, 32c disclosed herein may be, consist of, or consist of one or more opaque inks, one or more semi-transparent and / or transparent inks, one or more colored opaque inks, one or more colored semi-transparent and / or transparent inks, or at least one combination thereof.

[0049] In one or more embodiments, the color blocks 32 a, 32 b, 32 c of the first and second colored regions 28, 30 may have or include at least two colors of the CMYK color model, which is commonly used in printed color illustrations. The CMYK color model is a subtractive color model that uses the colors cyan, magenta, yellow, and / or key (black) and may include one or more overlapping regions of at least two of the colors cyan, magenta, yellow, and / or key (black). The CMYK color model is known to those skilled in the art and is discussed in detail, for example, in Tkalcic et al., “Color Spaces, Perceptual, Historical and Applicational Background,” University of Ljubljana, EUROCON 2003, pp. 304-308; and Jennings, S. Artist's Color Manual: The Complete Guide to Working with Color. Chronicle Books LLC. (2003). When each of the color blocks 32a, 32b, 32c includes each of the four colors of the CMYK color model, each of the color blocks 32a, 32b, 32c is divided or partitioned such that each of the four colors is within a quarter or quadrant of each of the color blocks 32a, 32b, 32c.

[0050] In some embodiments disclosed herein, the color blocks 32a, 32b, and 32c of the first and second colored regions 28 and 30 may include three colors of the CMYK color model. In at least one embodiment, each of the color blocks 32a, 32b, and 32c may be, comprise, or consist of cyan, magenta, and yellow. As a result of including three colors of the CMYK color model, each of the color blocks 32a, 32b, and 32c may be divided or separated into thirds, with each of the three colors being provided within each third or third of the color block 32a, 32b, and 32c. In this manner, utilizing only three colors of the CMYK color model instead of all four colors may improve color brightness, intensity, and / or orientation due to increased surface area for each of the three colors of the CMYK color model (i.e., 33% for each of the three colors versus 25% for each of the four colors). In one or more embodiments, the first sensitive substrate 12 may be or include a first single color, such as white, the color blocks 32a, 32b, 32c may each include three colors of the CMYK color model, and the second sensitive substrate 16 or base 26 may include a second single color, such as black or gray.

[0051] In at least one preferred embodiment, the first color layer 22 of the substrate 10 may be, include, or consist of three colors of the CMYK color model, and the second color layer 24 may be a single color, such as, for example, black, gray, or a combination thereof. In at least one embodiment, the first and second colors 12, 16 may be, include, or consist of a single color, such as, for example, white or another single color. In an embodiment, the three colors of the CMYK color model are, include, or consist of cyan, magenta, and yellow.

[0052] In alternative embodiments, the color blocks 32a, 32b, 32c of the first and second colored regions 28, 30 may have or include at least two colors of the RGB color model, which can also be used to print color illustrations. The RGB color model utilizes additive color mixing with the primary colors red, green, and blue. In yet another alternative embodiment, the color blocks 32a, 32b, 32c may have or include one or more colors of at least one known color system, such as the American Munsell Color System, the Swedish Natural Color System, the Optical Society of America's Uniform Color Space, the Hungarian Coloroid System, the American Pantone, and the German RAL Commercial Color Matching System. In alternative embodiments, it should be understood that the present disclosure is not limited to the specific embodiments of the color model and / or color system provided in the color blocks 32a, 32b, 32c and / or the first and second colored regions 28, 30.

[0053] In some embodiments, one or more of the color arrangements provided on the first and second color layers 22, 24 may be in the form of or configured as at least one grid. The portions and / or squares of the at least one grid forming the two-dimensional matrix may be aligned with one another, or the portions and / or squares may be offset with respect to one another. It will be apparent to those skilled in the art that the boundaries of the color blocks 32a, 32b, 32c may not be physically or visually present on the top surfaces of the first and second color layers 22, 24. Furthermore, the color blocks 32a, 32b, 32c may form or provide one or more overlapping regions on the grid or matrix, where at least two different colors overlap each other to form additional or different colors thereon.

[0054] In at least one embodiment, an adhesive material (not shown), such as a pressure-sensitive adhesive, can be applied to the side of the second color layer 24 or the base 26 that is opposite the second sensitive substrate 16. In embodiments, the adhesive material can adhere the substrate 10 to another surface, such as product packaging, and a release substrate (not shown) can be applied to the adhesive material. Optionally, instead of a release substrate, a paper-based substrate (not shown) can be applied to the adhesive material, thereby forming a composite heat-sensitive and / or pressure-sensitive exposed substrate for the substrate 10. The paper-based substrate can be mated to the second sensitive substrate 16 or base 26 as a part thereof. A PSA or other adhesive material can be employed to effect the bond between the release substrate or paper substrate and the second sensitive substrate 16 or base 26. In embodiments, the paper-based substrate can include color paper, film, board, or a combination thereof.

[0055] The first and second sensitive substrates 12, 16 can also include polymer particles or one or more opaque polymers or polymeric materials disclosed herein, which can provide an additional white appearance due to the light scattering properties of the polymer particles and / or the light scattering properties provided by the first and second opacifying materials 14, 18. The first and second sensitive substrates 12, 16 can have a thermal melting temperature or Tg in the range of about 80°C to about 120°C, suitable for one or more printing methods and / or applications disclosed herein. For example, in certain embodiments, the polymer particles or one or more opaque polymers or polymeric materials have a melting temperature or glass transition of about 80°C to 120°C, 90°C to 110°C, or 95°C to 105°C.

[0056] Additionally, the first sensitive substrate 12 may include another coating (not shown), such as a varnish (a so-called overprint lacquer), as a protective element to protect the first opacifying material 14. The coating may be a polymeric material, such as a modified styrene acrylic polymer, that is essentially transparent or clear and has a higher melting point than the polymer particles of the first opacifying material 14. Thus, it functions as a protective barrier for the underlying first opacifying material 14 against normal user handling and exposure to the sun and heat elements, while allowing the polymer particles of the first and second opacifying materials 14, 18 to be exposed to light, laser, melted, and / or pressure for effective imaging and / or printing, as described herein.

[0057] The print head 21 can apply light / laser energy (i.e., at least one or both of the first and second energies 15, 19), melting, or pressure to selected portions of the first and second sensitive substrates 12, 16 to cause the polymer particles of the first and second opacifying materials 14, 18 to change from opaque to translucent. The print head 21 can be equipped to apply sufficient or predetermined light / laser energy, temperature, and / or pressure to the first and second sensitive substrates 12, 16 to cause the light / laser, melting, and / or pressure change. Depending on the application, it may be more suitable to provide the first and second sensitive substrates 12, 16 with at least one low change state by employing at least one low crosslinking technology. By appropriately selecting the polymer particles or one or more opaque polymers or polymeric materials, the melting point can be less than about 110°C, less than about 105°C, less than about 100°C, less than about 90°C, or less than about 80°C. The polymer particles or one or more opaque polymers or grades of polymeric material may be chemically resistant such that they do not melt at room temperature.

[0058] In some embodiments, the first and second sensitive substrates 12, 16 may appear white and comprise a material having an appropriate melting point for safe application with the printhead 21. Thus, when viewed from the top, the substrate 10 may appear white or a pale color that obstructs the view of the first and second colored regions 28, 30, color blocks 32a, 32b, 32c, and / or base 26. A glass-like appearance is achieved when heated to affect a change state of the polymer particles or one or more opaque polymers or polymeric materials of the first and second opacifying materials 14, 18, and the opacifying material is adjusted in an amount to usably expose the first and second colored regions 28, 30, color blocks 32a, 32b, 32c, and / or base 26.

[0059] Unlike other prior art heat-activated papers, the polymer particles or one or more opaque polymers or polymer materials of the present invention may be less sensitive to subsequent exposure to ultraviolet light, fluorescent lamps, hand and finger sweat, and slight rubbing or other solvent applications. In contrast, the substrate 10 disclosed herein is a superior substrate that can solve one or more of the above-mentioned difficulties. The exposed image viewable through the substrate 10 may be any of a variety of colors, such as black, red, dark purple, blue, and / or one or more of such colors. While it is contemplated that conventional color-responsive materials may be employed in the present disclosure, the substrate 10 disclosed herein provides a more reliable, simpler, and less expensive product. In some embodiments, the product provided, produced, and / or manufactured by or from the substrate 10 may be a direct light / laser and / or thermal imaging product and / or a pressure-sensitive product. For example, the substrate 10 may be a pressure-sensitive label, tag, ticket, point-of-sale document, or receipt, or one or more combinations thereof. In other embodiments, substrate 10 may be or include one or more thin layers, one or more films, or a combination thereof.

[0060] In addition to the resulting product being more stable at typical ambient temperatures, the substrate 10 disclosed herein can also provide a quick and easy means for destroying confidential information printed thereon, such as in the case of HIPAA labels. In this regard, the label can be simply passed through a laser printhead and / or a heated plate or pressure roller nip, rendering the confidential information unreadable. When forming the label, for example, an adhesive can be applied directly onto the second color layer 30, or an adhesive can be applied to the backside of the base 26.

[0061] The substrate 10 disclosed herein may exhibit and / or have easy handling and a good appearance and feel. According to a further feature of the substrate 10, the first and second sensitive substrates 12, 16 resist aging, provide high stability over time, and improve the contrast of thermally exposed images, eliminating the difficulty of reading such images.

[0062] Thus, even when a highly transparent substrate, such as a completely transparent polyethylene film, is used, the coated product has a white appearance that contrasts clearly with the thermally exposed image. The amount of first and second opacifying materials 14, 18 must be such that a translucent effect is achieved upon application of heat or pressure, while still allowing the first and second colored regions 28, 30 and / or color blocks 32a, 32b, 32c to be pre-masked using a laser and / or heat and / or pressure printhead 21. Thus, the substrate 10 disclosed herein successfully improves upon conventional thermal sheet materials, which naturally develop (discolor) in the background, for one or more of the reasons previously mentioned. Furthermore, the substrate 10 provides excellent color contrast with the first and second opacifying materials 14, 18 of the first and second sensitive substrates 12, 16, allowing for a clear image throughout the region 13.

[0063] An illustrative, non-limiting example includes a coating on a color paper substrate of approximately 25% by weight of polymer particles or one or more opaque polymers or polymeric materials in the polymer particles of the first and second opacifying materials 14, 18. In some embodiments, a more heat-resistant styrene-acrylic protective overprint varnish can be employed that has a melting point range above the melting point of the polymer particles or one or more opaque polymers or polymeric materials of the first and second opacifying materials 14, 18, allowing heat to radiate through the varnish without melting into the printhead 21.

[0064] 1-4, the substrate 10 may include first and second sensitive substrates 12, 16, first and second opacifying materials 14, 18, first and second colored layers, a base 26, first and second colored regions 28, 30, color blocks 32a, 32b, 32c, or at least one combination thereof. In some embodiments, the print head 21 can apply first and second energies 15, 19 onto one or more regions (i.e., at least region 20) of the substrate 10, as shown in FIG. 1; can apply the first energy 15 onto one or more regions (i.e., at least region 20) of the substrate 10, as shown in FIG. 2; and / or can provide the second energy 19 onto one or more regions (i.e., at least region 20) of the substrate 10, as shown in FIGS. 3 and 4. As a result, the first opacifying material 14 of the first sensitive substrate 12 can change from an opaque state to a transparent state via the first energy 15, as shown in FIGS. 1 and 2. This causes the first color layer 22, the first color region 28, and / or at least one of the color blocks 32a, 32b, 32c (of the first color region 28) to be exposed and visible from the top side of the substrate 10 and / or displayed on the top side of the substrate 10. As shown in Figures 2 and 3, the second color region 30 of the second color layer 24 may be a single color and / or may exclude the color blocks 32a, 32b, 32c.

[0065] As a result of applying second energy 19 to the top surface of substrate 10 via printhead 21, first and second opacifying materials 14, 18 of first and second sensitive substrates 12, 16 may change from an opaque state to a transparent state, as shown in Figures 3 and 4. This may cause second colored region 30 of second colored layer 24 to be exposed and visible from the top side of substrate 10 and / or displayed on the top surface of substrate 10, as shown in Figure 3; or at least one of color blocks 32a, 32b, 32c (of second colored region 30) to be exposed and visible from the top side of substrate 10 and / or displayed on the top surface of substrate 10, as shown in Figure 4. In addition to exposing second color region 30 and / or one or more color blocks 32a, 32b, 32c of second color region 30, application of second energy 19 onto at least one region (i.e., at least region 20) exposes first color region 28 and / or one or more color blocks 32a, 32b, 32c of first color region 28, as shown in Figures 3 and 4. In at least one embodiment, first color region 28 of first color layer 24 may be a single color and / or may exclude color blocks 32a, 32b, 32c.

[0066] In one or more embodiments, print head 21 may apply first energy 15 onto at least one first region of substrate 10 (i.e., region 20 in FIG. 2 ) and second energy 19 onto at least one second region of substrate 10 (i.e., region 20 in FIG. 3 or FIG. 4 ). As a result, first colored region 28 and / or one or more color blocks 32 a, 32 b, 32 c of first colored region 28 may be exposed and / or made visible in at least one first region of substrate 10, and second colored region 30 and / or one or more color blocks 32 a, 32 b, 32 c of second colored region 30 may be exposed and / or made visible in at least one second region of substrate 10. In this manner, application of first and second energies 15, 19 may expose and make visible and display at least one color in at least one first region and / or at least one second region of substrate 10. As a result of the application of first energy 15 and second energy 19 to substrate 10, a blended color of the first color material or layer exposed by the application of first energy 15 and the at least one second color material or layer exposed by the application of second energy 19 may be exposed and displayed in portions of substrate 10. In embodiments, the first color material or layer may be blue, the at least one second color material or layer may be yellow, and the blended color may be green.

[0067] In some embodiments, at least one color or colors exposed in or by first color layer 22 via first energy 15 may be improved, modified, enhanced, and / or changed by at least one color or colors exposed in or by second color layer 24 via second energy 19. For example, at least one color or colors exposed by first color layer 22 in region 20 via first energy 15 may be darkened or lightened by at least one color or colors exposed by second color layer 24 in region 20 via second energy 19, as shown in FIGS. Alternatively, as shown in FIG. 2 , the at least one color or colors exposed by the first color layer 22 in the region 20 via the first energy are not altered (i.e., not darkened or lightened) by the at least one color or colors of the second color layer 24 in the region 20 when the second opacifying material 18 of the second sensitive substrate 16 is not changed from an opaque state to a transparent state or is not changed in whole or in whole (i.e., when the second energy 19 is not applied).

[0068] In one or more embodiments, each of the layers, substrates, and / or materials selected from the following group: first and second sensitive substrates 12, 16, first and second opacifying materials 14, 18, first and second colored layers 22, 24, and / or base 26, can have either a first thickness or at least one second thickness. The first thickness can be greater than, less than, or equal to the at least one second thickness, and / or the at least one second thickness can include multiple second thicknesses that can be different from each other and / or from the first thickness. The first and second energies 15, 19 required, needed, and / or desired to transition / change one or more of the first and second sensitive substrates 12, 16 from an opaque or colored state to a transparent state can depend on the first thickness and / or at least one second thickness of each of the identified layers, the substrate, and / or the material, respectively. For example, the energy of at least one of the first and second energies 15, 19 may be greater or lesser based on the first thickness and / or one or more second thicknesses of the first and second sensitive substrates 12, 16, the first and second opacifying materials 14, 18, the first and second color layers 22, 24, and / or the base 26. Furthermore, the first thickness and / or one or more second thicknesses of the first and second sensitive substrates 12, 16, the first and second opacifying materials 14, 18, the first and second color layers 22, 24, and / or the base 26 may provide the systems and methods disclosed herein with improved color printing and / or imaging achievable solely based on the greater or lesser energy associated with the first and second energies 15, 19.

[0069] In at least one embodiment, as shown in FIG. 5, the first colored layer 22 of the substrate 10 may include a first colored region 28, which may have no partitions, blocks, or partitions and may include at least one colored ink of any desired color or colors disclosed herein. In some embodiments, the first colored region 28 of the first colored layer 22 may be, include, or consist of a single or separate opaque ink, a single or separate translucent ink, a single or separate colored opaque ink, a single or separate colored translucent and / or transparent ink, or at least one combination thereof. In FIG. 5, the first colored region 28 of the first colored layer 22 may include, for example, at least one of at least one first color block 32a, at least one second color block 32b, at least one third color block 32c, and combinations thereof.

[0070] In one or more embodiments, as shown in FIG. 6 , the second colored layer of the substrate 10 may include a second colored region 30, which may have no partitions, blocks, or partitions and may include at least one colored ink of any desired color or colors disclosed herein. In some embodiments, the second colored region 30 of the second colored layer 24 may be, include, or consist of a single or separate opaque ink, a single or separate translucent ink, a single or separate colored opaque ink, a single or separate colored translucent and / or transparent ink, or at least one combination thereof. In FIG. 6 , the first colored region 28 of the first colored layer 22 may include, for example, at least one of at least one first color block 32 a, at least one second color block 32 b, at least one third color block 32 c, and combinations thereof. Also, the second colored region 30 of the second colored layer 24 may include, for example, at least one of at least one first color block 32a, at least one second color block 32b, at least one third color block 32c, and combinations thereof.

[0071] In one or more embodiments, the color exposed image, thermal image, thermal exposed image, clear image, and / or at least one thermal / thermally exposable image (collectively referred to herein as "exposable / exposable images") associated with the substrate 10 may be, include, or consist of at least one first machine-readable code 50 (hereinafter referred to as "first code 50"), as shown in FIG. 7, and may be, include, or consist of at least one second machine-readable code 60 (hereinafter referred to as "second code 60") and / or at least one third machine-readable code 62 (hereinafter referred to as "third code 62"), as shown in FIG. 8. The first code 50, the second code 60, and / or the third code 62 (hereinafter collectively referred to as "codes 50, 60, 62") may be, include, or consist of at least one machine-readable barcode, which may be at least one linear barcode, at least one matrix two-dimensional barcode, or a combination thereof. In some embodiments, the at least one linear barcode may be, include, or consist of at least one of the following linear barcodes: postal barcode, code bar, "Code 25", "Code 11", "Code 32", "Code 39", "Code 49", "Code 93", "Code 128", CPC binary code, film barcode, "EAN2 code", "EAN5 code", and "EAN8 code" or "EAN13 code", face identification mark code, "GS1-128 code", mail code, "ITF-14 code", "ITF-6 code", JAN code, MSI code, Pharma code, Plessy code, post barcode, UPC-A code, UPC-E code, or combinations thereof.In an embodiment, the at least one matrix two-dimensional barcode may be, include, or consist of at least one of the following matrix two-dimensional barcodes: AR Code, Aztec Code, b Code, BEEtag Code, BEETagg Code, Bokode Code, Boxing Code, "Code 1", "Code 16K", Color Code, Color Config Code, Cronto Visual Cryptography Code, Cyber ​​Code, d Touch Code, Data Glyph Code, Data Matrix Code, Data Strip Code, Digimark Barcode, Digital Paper Code, Dot Code, DW Code, EZ Code, High Capacity Color Barcode, Hue Code, Inter Code, JAB Code, Maxi Code, m Code, MMCC Code, Nex Code, "ODF417 Code", Q Code, QR Code, Screen Code, Shot Code, Snap Code, Snowflake Code, SPARQ Code, Trill Code, Voice Eye Code, or a combination thereof.

[0072] In some embodiments, codes 50, 60, 62 may be, include, or consist of one or more machine-readable images, data, and / or information, which may be surrounded by or contained within white space or quiet zones, as shown in FIG. 8. For example, codes 50, 60, 62 may be, include, or consist of one or more quick response codes (hereinafter referred to as "QR codes"). In embodiments, codes 50, 60, 62 may be, include, consist of, and / or have at least one "Model 1 QR code," at least one Micro QR code, at least one IQR code, at least one Secure QR code, at least one Frame QR code, at least one HCC2D code, at least one JAB code, or a combination thereof. In embodiments, codes 50, 60, 62 may be square, rectangular, triangular, circular, oval, or a combination thereof. The codes 50, 60, 62 may include and / or consist of one or more code structure elements, such as, for example, a position detection pattern and / or a data region, which may be surrounded by or enclosed by white space. In some embodiments, the position detection pattern and / or the data region may include at least one selected from version information, format information, and / or an error correction key, and / or a required pattern. In embodiments, the required pattern may include at least one of a physical element, an alignment element, a timing element, or a combination thereof. The code structure element may be and / or include one or more position detection markers, one or more alignment markings, one or more timing patterns, version information, format information, one or more data and error correction keys, at least one quiet zone (i.e., margin), or a combination thereof.Furthermore, the code structure element may be and / or include at least one static QR code type, at least one dynamic QR code type, or a combination thereof. In an embodiment, the at least one static QR code type may be or include at least one QR code selected from at least one Wi-Fi QR code, at least one cryptocurrency address QR code, at least one plain text QR code, at least one email QR code, at least one online login QR code, at least one online promotion QR code, or a combination thereof. The at least one dynamic QR code type may be or include at least one QR code selected from at least one AppStore QR code, at least one PDF QR code, at least one social media QR code, at least one coupon QR code, at least one reward QR code, at least one promotion QR code, at least one gift QR code, at least one discount QR code, at least one business page QR code, at least one vCard Plus QR code, at least one video QR code, at least one dynamic URL QR code, at least one image gallery QR code, at least one event QR code, at least one MP3 QR code, at least one feedback QR code, at least one rating QR code, or any combination thereof.

[0073] In one or more embodiments, the first code 50 may be, include, consist of, and / or display a single or separate solid color throughout the first code 50. As shown in FIG. 7 , the first code 50 may be, include, consist of, and / or display, for example, a first color 52, a second color 54, a third color 56, or a fourth color 58. Furthermore, the first color 52, the second color 54, the third color 56, and the fourth color 58 are each solid colors that are different from one another. In embodiments, the solid colors may be any known colors. For example, as shown in FIG. 7 , the first color 52 may be black, the second color 54 may be green, the third color 56 may be blue, and / or the fourth color 58 may be white.

[0074] In some embodiments, the second code 60 and the third code 62 may be, include, consist of, and / or display a mixture of different colors throughout the second code 60 and the third code 62, respectively, as shown in FIG. 8 . In at least one embodiment, the second code 60 may be a machine-readable barcode and / or the third code 62 may be a machine-readable QR code. Each of the mixture of different colors in the second code and / or the third code 62 may be, include, consist of, and / or display a first color 52, a second color 54, a third color 56, and / or a fourth color 58 (collectively referred to herein as “colors 52, 54, 56, 58”). In some embodiments, the mixture of different colors may include one or more additional different colors beyond or in addition to colors 52, 54, 56, 58. The number of different colors in the different color mixture can be any number of different colors (ie, more or less than colors 52, 54, 56, 58) as known to those skilled in the art.

[0075] In one or more embodiments, one or more benefits and / or advantages of direct thermal printing color on demand using the methods / processes disclosed herein and in U.S. Provisional Patent Application No. 63 / 382,807 are achieved and / or provided by imaging barcodes and / or QR codes (i.e., codes 50, 60, 62) with one or more images (i.e., codes 50, 60, 62) of various colors (i.e., colors 52, 54, 56, 58) and shades, solid color differentiation, all of which are the same in code 50, or a mixture of different colors (i.e., colors 52, 54, 56, 58), as shown in FIG. 7 , in the barcodes and / or QR codes (i.e., codes 50, 60, 62) disclosed herein.

[0076] In some embodiments, the different solid colors (i.e., colors 52, 54, 56, 58) may enable or provide easy recognition not only by machine-readable scanners but also by the human eye. The different solid colors may, for example, represent or indicate another means of differentiation. In at least one example, a conference attendee may have a scannable exposed barcode or QR code on their badge for admission to a particular hall or conference space or location, and the visible color difference may inform the conference organizer of the level of access actually granted to the individual. For example, a first color 52 may represent or indicate level 1 and / or initial, minimum, or standard accessibility, a second color 54 may represent or indicate level 2 and / or first intermediate or silver service accessibility, a third color 56 may represent or indicate level 3 or second intermediate or gold service accessibility, and / or a fourth color 58 may represent or indicate level 4 and / or final, maximum, or platinum service accessibility.

[0077] As shown in Figure 8, by mixing different colors for the lines (of a barcode) and the rectangular blocks (of a QR code), it may be possible to obtain more additional information than known barcodes and / or QR codes. For example, not only may the width of a line or the position of a rectangle be related to additional information, but the color may also provide, have, contain, constitute, or indicate additional information. As a result of the colors 52, 54, 56, 58, many more combinations of line spacing and / or line color (in the case of a barcode), and / or both rectangle position and rectangle color (in the case of a QR code) are provided by the codes 50, 60, 62.

[0078] It has therefore been determined that the addition of three colors (i.e., three colors selected from colors 52, 54, 56, and 58) could increase the number of possible different QR codes by approximately a factor of four. Such an increase by approximately a factor of four could be relevant and important as the increased use of these codes may be reaching capacity in known barcodes and QR codes.

[0079] Prior to the present disclosure of multi-color thermal imaging anywhere on a substrate 10, such multi-color barcodes and QR codes were limited to more traditional processes such as inkjet, laser, or flexographic, screen, or gravure printing. However, the materials and / or printer or imaging device disclosed herein enable on-demand multi-color thermal imaging on the substrate 10 disclosed herein without the need for inks and / or toners, allowing for portable, fast, and easy digital printing on demand. In one or more embodiments, a substrate 10 configured for multi-color thermal imaging may be, include, and / or consist of at least one labeling item, at least one ticketing item, and / or at least one sales receipt. Known scanners traditionally read only contrast between two colors: black and white. However, with the use of optical color sensors, such as the optical color sensors and sensing methods disclosed in the '440 patent, to improve color imaging and printhead alignment, adjustment, registration, and / or re-registration, the current solid and mixed colors disclosed herein allow for much more additional information in roughly the same or substantially the same amount of space associated with barcodes and QR codes.

[0080] In the foregoing disclosure, for purposes of explanation, specific nomenclature was used to provide a thorough understanding of the disclosure. However, it will be apparent to those skilled in the art that specific details are not required to practice the systems and methods described herein. The foregoing descriptions of specific examples have been presented for purposes of illustration and description. They are not intended to be exhaustive or to limit the disclosure to the precise forms described. Obviously, many modifications and variations are possible in light of the above teachings. The examples are shown and described to best explain the principles and practical application of the disclosure, and to thereby enable those skilled in the art to best utilize the disclosure and various embodiments, with various modifications as may be suitable for the particular uses intended. It is intended that the scope of the present disclosure be defined by the following claims and their equivalents.

Claims

1. A multilayer exposed substrate, a first layer comprising a first opacifying material; a first color material applied to a first side of the first layer comprising the first opacifying material, the first layer comprising the first opacifying material being disposed to cover the first color material; and a second layer including a second opacifying material applied to a side of the first color material opposite the first layer including the first opacifying material relative to the first color material; the first opacifying material is configured to change from an opaque state to a transparent state upon application of a first predetermined energy to expose the first color material underlying the first opacifying material; the second opacifying material is configured to change from an opaque state to a transparent state upon application of a second predetermined energy; the first predetermined energy is different from the second predetermined energy; Multilayer exposed substrate.

2. 10. The multilayer exposed substrate of claim 1, At least one of the first predetermined energy and the second predetermined energy is a predetermined light and / or laser energy. Multilayer exposed substrate.

3. 10. The multilayer exposed substrate of claim 1, both the first predetermined energy and the second predetermined energy are predetermined light and / or laser energy; Multilayer exposed substrate.

4. 10. The multilayer exposed substrate of claim 1, the second predetermined energy is greater than the first predetermined energy; Multilayer exposed substrate.

5. 5. The multilayer exposed substrate of claim 4, the first and second predetermined energies comprise light and / or laser energy; Multilayer exposed substrate.

6. 10. The multilayer exposed substrate of claim 1, further comprising a base substrate, the base substrate being disposed behind the second color material, and the first and second color materials being disposed between the base substrate and a first layer comprising the first opacifying material. Multilayer exposed substrate.

Images