Composition

Abstract

The present invention relates to compositions comprising: (a) polyvalent metal oxyanions or oxyacids, or hydrates thereof; (b) redox buffers; and (c) antioxidants, wherein the redox buffer is a polyvalent metal salt. The present invention also relates to the formation of substrates on which the compositions are coated, and substrates on which marks or images are displayed.

Description

Technical Field

[0001] The present invention relates to a composition capable of displaying a mark or image with improved optical density.

Background Art

[0002] It is known in the art to use compositions for variable information printing that generate human and / or machine-readable elements on substrates. After applying such a composition to a substrate, the composition can be exposed to suitable radiation to form a mark or image.

[0003] Oxyanions of polyvalent metals, or oxyacids, or hydrates thereof are color-forming compounds used in such compositions. Oxyanions of polyvalent metals, or oxyacids, or hydrates thereof decompose upon application of radiation to the composition to form a color, thus generating a mark or image. However, these currently known compositions have the problem that the formed marks or images are not sufficiently sharp and distinct.

[0004] Attempts to address this problem have involved the use of components that accelerate the decomposition of oxyanions of polyvalent metals, or oxyacids, or hydrates thereof. However, these attempts have not resulted in sharper, more distinct marks or images, have resulted in inadequate color formation, and have hindered the formation of any mark or image.

[0005] Accordingly, it is desirable to provide a solution that enables the effective formation of sharp and distinct marks or images with improved optical density using a composition comprising an oxyanion of a polyvalent metal, or an oxyacid, or a hydrate thereof.

Summary of Invention

[0006] According to a first aspect of the present invention: (a) an oxyanion of a polyvalent metal, or an oxyacid, or a hydrate thereof; (b) Redox buffers; and (c) Antioxidants; Includes, A composition is provided in which the redox buffer is a polyvalent metal salt.

[0007] According to a second aspect of the present invention: (a) polyvalent metal oxyanions, or oxyacids, or hydrates thereof; and (b) Redox buffers; Includes, A composition is provided in which the redox buffer is a polyvalent metal salt selected from manganese or iron gluconate, polyvalent metal acetate, polyvalent metal carbonate, polyvalent metal sulfate, and polyvalent metal oxide.

[0008] A third aspect of the present invention provides a substrate on which a composition is coated or incorporated therein, wherein the composition is: (a) Polyvalent metal oxyanions, or oxyacids, or hydrates thereof; (b) Redox buffers; and (c) Antioxidants; Includes, Redox buffers are polyvalent metal salts.

[0009] A fourth aspect of the present invention provides a substrate on which a composition is coated or incorporated therein, wherein the composition is: (a) polyvalent metal oxyanions, or oxyacids, or hydrates thereof; and (b) Redox buffers; Includes, Redox buffers include polyvalent metal salts selected from manganese or iron gluconates, polyvalent metal acetates, polyvalent metal carbonates, polyvalent metal sulfates, and polyvalent metal oxides.

[0010] A fifth aspect of the present invention provides a method for forming a substrate according to a third aspect of the present invention, the method comprising applying or incorporating a composition according to a first aspect of the present invention onto a substrate.

[0011] A sixth aspect of the present invention provides a method for forming a substrate according to a fourth aspect of the present invention, the method comprising applying or incorporating a composition according to a second aspect of the present invention onto a substrate.

[0012] A seventh aspect of the present invention provides a method for forming a mark or image on a substrate according to a third or fourth aspect, the method comprising exposing a composition to radiation to form a mark or image.

[0013] An eighth aspect of the present invention provides the use of a redox buffer in forming a mark or image with improved optical density on a substrate on which a composition is coated or incorporated therein, wherein the composition comprises a redox buffer and a polyvalent metal oxyanion or oxy acid, or hydrates thereof, the redox buffer being a polyvalent metal salt and polyvalent metal oxide selected from manganese or iron gluconates, polyvalent metal acetates, polyvalent metal carbonates, and polyvalent metal sulfates.

[0014] A ninth aspect of the present invention provides the use of a redox buffer to control reaction stability and achieve the formation of a mark or image, preferably with improved optical density, on a substrate on which the composition is coated or incorporated therein, wherein the composition comprises a redox buffer, an antioxidant, and a polyvalent metal oxyanion or oxyacid, or a hydrate thereof, the redox buffer being a polyvalent metal salt. [Modes for carrying out the invention]

[0015] Surprisingly and advantageously, it was found that by introducing a redox buffer into a composition containing polyvalent metal oxyanions, oxyacids, or hydrates thereof, it becomes possible to generate clear and distinct marks or images, i.e., marks or images with improved optical density, when radiation is applied to the composition.

[0016] Polyvalent metal oxyanions, or oxyacids, or hydrates thereof, may exhibit complex redox chemistry. Without being bound by theory, the present inventors believe that upon application of radiation, the polyvalent metal oxyanion, or oxyacid, or hydrate thereof decomposes, and in the course of its chemical decomposition, may undergo both oxidation and reduction processes (redox reactions as part of a disproportionation reaction). Accordingly, the present inventors consider that polyvalent metal oxyanions, or oxyacids, or hydrates thereof are "redox active" substances. In general, they are considered to be strong oxidizing substances due to thermal decomposition. Therefore, the present inventors believe that polyvalent metal oxyanions, or oxyacids, or hydrates thereof undergo net reduction during their chemical decomposition.

[0017] The present inventors believe that the redox buffer can act as a redox catalyst for the oxidation and reduction processes, that is, the redox reaction, of the polyvalent metal oxyanion, or oxyacid, or hydrate thereof during its decomposition. The present inventors believe that the redox buffer acts as a free radical propagator in the disproportionation reaction, does not necessarily itself undergo sustained oxidation or chemical decomposition to its equivalent oxide, and circulates between its most advantageous oxidation states ("redox cycling").

[0018] This evidence is further supported by the fact that, surprisingly and advantageously, the present inventors have found that in compositions comprising a polyvalent metal oxyanion, or oxyacid, or hydrate thereof, such as the composition according to the first aspect of the present invention, when present together with an antioxidant, the redox buffer detailed herein functions synergistically with the antioxidant, preferably enabling the formation of marks or images with improved optical density.

[0019] Antioxidants are introduced into compositions containing polyvalent metal oxyanions, oxyacids, or hydrates thereof to accelerate the chemical decomposition of the polyvalent metal oxyanions, oxyacids, or hydrates, which are highly oxidative. However, if the composition does not contain a redox control substance, the antioxidant and the polyvalent metal oxyanions, oxyacids, or hydrates may undergo a redox reaction—the antioxidant is oxidized and the polyvalent metal oxyanions, oxyacids, or hydrates are reduced, which can lead to undesirable color formation. This redox reaction may be particularly prevalent in non-oxidizing or partially oxidizing atmospheres, but it can also occur over time in oxidizing atmospheres. Such undesirable color formation means that the composition is already colored so early that it is undesirable to form a mark or image through the application of certain radiation, or that the composition (other than the mark or image) undergoes undesirable coloration over time after the application of radiation, resulting in an illegible mark or image, or a mark or image with reduced illegibility. The redox buffers detailed herein act as redox catalysts, providing a stabilizing effect to the composition and controlling reaction stability to prevent undesirable redox reactions between polyvalent metal oxyanions, oxyacids, or their hydrates and antioxidants. Therefore, the redox buffers can preferably ensure that the chemical decomposition (the mechanism by which color is formed) of polyvalent metal oxyanions, oxyacids, or their hydrates occurs only when the composition is exposed to specific radiation. Preferably, color formation occurs when the application of radiation to the composition overcomes the energy threshold required to initiate the redox decomposition process. Furthermore, preferably, the polyvalent metal oxyanions, oxyacids, or their hydrates exhibit enhanced reaction sensitivity to radiation exposure. Therefore, the redox buffers preferably act as redox catalysts, facilitating the formation of marks or images with enhanced optical density.

[0020] While not being bound by theory, the present inventors believe that the redox buffer can act as a free radical propagator, does not necessarily itself undergo persistent oxidation or chemical decomposition to become its equivalent oxide, and circulates between its most advantageous oxidation states ("redox cycle"). Accordingly, the redox buffer is preferably capable of catalyzing the decomposition of the oxyanion or oxyacid of a redox-active polyvalent metal, or a hydrate thereof, upon application of radiation, and likewise buffering both the oxyanion or oxyacid of a redox-active polyvalent metal, or a hydrate thereof, and the antioxidant, if present in the composition, to prevent their reaction under ambient conditions.

[0021] As used herein, "oxidation" or "reduction" means the transfer of one or more electrons to or from a molecular entity. Reduction is the gain of one or more electrons, and oxidation is the removal of one or more electrons.

[0022] The composition according to the first or second aspect of the present invention comprises an oxyanion or oxyacid of a polyvalent metal, or a hydrate thereof.

[0023] The polyvalent metal oxyanions, or oxyacids, or hydrates thereof, may be any suitable polyvalent metal oxyanions, or oxyacids, or hydrates thereof (anionic components) present in association with a cationic counterion. The hydrates may be polyvalent metal oxyanions or hydrates of the corresponding polyvalent metal oxyacids. The polyvalent metal oxyanions or their oxyacids may also be anhydrous. The use of polyvalent metal oxyanions, or oxyacids, or hydrates thereof in compositions is disclosed in U.S. Patent No. 7,485,403, the contents of which are incorporated herein by reference. The anionic components may be inorganic metal oxyanion compounds, such as molybdates, tungstates, chromates, or similar transition metal compounds, including di-, tri-, hexa-, hepta-, octa-, and deca-molybdates, and may also be mixed inorganic metal oxyanions with mixed oxidation states and trace elements or in any higher concentration ratios. The accompanying cationic component is preferably an alkali metal, alkaline earth metal, or ammonium. An example of a polyvalent metal oxyanion is sodium molybdate. Preferred polyvalent metal oxyanions are ammonium salts of inorganic metal oxyanion compounds. For example, ammonium paratungstate (APT). Particularly preferred as polyvalent metal oxyanions, oxyacids, or hydrates thereof are ammonium salts of polyvalent metal oxyanions. Particularly preferred polyvalent metal oxyanions, oxyacids, or hydrates thereof is ammonium octamolybdate (NH4)4Mo8O 26 Alternatively, it may be "AOM," which is a commercially available molybdenum composition having CAS number 12411-64-2.

[0024] The polyvalent metal oxyanion, oxyacid, or hydrate thereof is preferably an ammonium salt of a polyvalent metal oxyanion, such as an ammonium salt of molybdenum oxyanion. More preferably, the polyvalent metal oxyanion, oxyacid, or hydrate thereof is ammonium octamolybdate (AOM).

[0025] A composition according to a first or second aspect of the present invention comprises a redox buffer.

[0026] In a composition according to a first aspect of the present invention, the redox buffer is a polyvalent metal salt.

[0027] The polyvalent metal salt may be provided in the form of a hydrate or anhydrous substance.

[0028] The polyvalent metal salt may be a polyvalent metal salt of an organic acid or an inorganic acid, i.e., a polyvalent metal salt of an organic acid or an inorganic acid, or a polyvalent metal oxide. The polyvalent metal salt is a polyvalent metal salt of an organic acid or an inorganic acid, and more preferably a polyvalent metal salt of an organic acid.

[0029] Suitable organic acids include, but are not limited to, carboxylic acids such as gluconic acid and acetic acid; oxalic acid; and carbonic acid. Suitable inorganic acids include, but are not limited to, sulfuric acid; and phosphoric acid. The polyvalent metal salt is preferably a polyvalent metal salt of an organic acid.

[0030] With respect to compositions according to the first aspect of the present invention, the redox buffer is preferably selected from polyvalent metal carboxylates, polyvalent metal oxalates, polyvalent metal carbonates, and polyvalent metal sulfates.

[0031] With respect to compositions according to the first aspect of the present invention, the redox buffer is more preferably selected from polyvalent metal carboxylates, polyvalent metal oxalates, and polyvalent metal carbonates. The redox buffer in the composition according to the first aspect of the present invention is more preferably a polyvalent metal carboxylate. Carboxylates improve the redox cycling properties of polyvalent metals due to their electron delocalization properties.

[0032] Preferred examples of polyvalent metal carboxylates referred to herein include, but are not limited to, polyvalent metal gluconates and polyvalent metal acetates. Accordingly, with respect to compositions according to a first aspect of the present invention, the redox buffer can be selected from polyvalent metal gluconates, polyvalent metal acetates, polyvalent metal oxalates and polyvalent metal carbonates, preferably polyvalent metal gluconates and polyvalent metal acetates.

[0033] The redox buffer in the composition according to the first aspect of the present invention is preferably a polyvalent metal gluconate salt.

[0034] The polyvalent metal in all the polyvalent metal salts detailed above may be any suitable polyvalent metal. Suitable examples include, but are not limited to, manganese or iron, preferably manganese. In the context of the present invention, the polyvalent metal may have a suitable oxidation state. Such polyvalent metals have advantageous redox cycling properties. With respect to manganese and iron, this is preferably the oxidation state of manganese(II) or iron(II).

[0035] Accordingly, with respect to compositions according to the first aspect of the present invention, the redox buffering agent can be selected from organic or inorganic salts of manganese or iron, or from manganese oxide or iron oxide, and preferably from manganese or iron carboxylates, manganese or iron oxalates, manganese or iron carbonates, and manganese or iron sulfates.

[0036] With respect to compositions according to the first aspect of the present invention, the redox buffer is more preferably selected from organic salts of manganese or iron, such as manganese or iron carboxylates, manganese or iron oxalates, and manganese or iron carbonates.

[0037] With respect to compositions according to the first aspect of the present invention, the redox buffer is more preferably a manganese or iron carboxylate. Carboxylates improve the redox cycling properties of polyvalent metals due to their electron delocalization properties.

[0038] As stated above, manganese or iron carboxylates include, but are not limited to, manganese or iron gluconates and manganese or iron acetates.

[0039] With respect to compositions according to the first aspect of the present invention, the redox buffer is more preferably selected from organic or inorganic salts of manganese, or manganese oxide, such as manganese carboxylate, manganese oxalate, manganese carbonate, and manganese sulfate.

[0040] With respect to compositions according to the first aspect of the present invention, the redox buffer is more preferably selected from manganese carboxylate, manganese oxalate, and manganese carbonate.

[0041] With respect to the composition according to the first aspect of the present invention, the redox buffer is more preferably manganese carboxylate.

[0042] In a composition according to a second aspect of the present invention, the redox buffer is a polyvalent metal salt selected from manganese or iron gluconate, polyvalent metal acetate, polyvalent metal carbonate, polyvalent metal sulfate, and polyvalent metal oxide.

[0043] The polyvalent metal salt may be provided in the form of a hydrate or anhydrous substance.

[0044] With respect to compositions according to a second aspect of the present invention, the redox buffer is preferably a polyvalent metal salt selected from manganese or iron gluconate, polyvalent metal acetate, and polyvalent metal carbonate.

[0045] With respect to the first aspect of the present invention, in the compositions according to the second aspect of the present invention, the polyvalent metal of the polyvalent metal salt in the options detailed above may be any suitable polyvalent metal. Suitable examples include, but are not limited to, manganese or iron, preferably manganese. In the context of the present invention, the polyvalent metal may have a suitable oxidation state. Such polyvalent metals have advantageous redox cycling properties. With respect to manganese and iron, this is preferably the oxidation state of manganese(II) or iron(II).

[0046] Therefore, with respect to compositions according to a second aspect of the present invention, the redox buffer is preferably selected from manganese or iron gluconate, manganese or iron metal acetate, manganese or iron carbonate, manganese or iron sulfate, and manganese oxide or iron oxide, for example, manganese or iron gluconate, manganese or iron metal acetate, and manganese or iron carbonate.

[0047] With respect to compositions according to a second aspect of the present invention, the redox buffer is more preferably a manganese gluconate, a metal acetate of manganese, a manganese carbonate, a manganese sulfate, and manganese oxide, for example, a manganese gluconate, a metal acetate of manganese, and a manganese carbonate.

[0048] With respect to both the composition according to the first aspect of the present invention and the composition according to the second aspect of the present invention, the redox buffer is more preferably a manganese or iron gluconate, such as manganese(II) gluconate or iron(II) gluconate, and most preferably a manganese gluconate, such as manganese(II) gluconate.

[0049] Manganese gluconates, such as manganese(II) gluconate, are available in anhydrous or hydrated form (C 12 H 22 MnO 14 It may also be provided as (x2H2O).

[0050] A composition according to a first aspect of the present invention contains an antioxidant.

[0051] As used herein, “antioxidant” means a component that promotes a reduction process in a redox chemical system having a substance that inhibits oxidation or an oxidation process and therefore has a higher reduction potential than the antioxidant. In the context of the present invention, polyvalent metal oxyanions, or oxyacids, or hydrates thereof preferably have a higher reduction potential than the antioxidant. In the context of the present invention, the antioxidant is preferably a component that undergoes a redox reaction with a strongly oxidizing polyvalent metal oxyanion, or oxyacid, or hydrate thereof. The antioxidant is present in the composition according to a first aspect of the present invention and preferably accelerates the chemical decomposition of polyvalent metal oxyanions, or oxyacids, or hydrates thereof through a redox reaction: oxidation of the antioxidant and reduction of the polyvalent metal oxyanion, or oxyacid, or hydrate thereof.

[0052] In the context of the present invention, the antioxidant and the redox buffer preferably do not have the same functionality in the composition according to the first aspect of the present invention. It is preferable that these different functionalities cannot be provided by the same component. Therefore, it is preferable that the antioxidant and the redox buffer are not the same component.

[0053] With respect to compositions according to the first aspect of the present invention, any suitable antioxidant may be used. Suitable antioxidants include, but are not limited to, organic acids, organic alcohols, and esters of organic acids.

[0054] Examples of organic acids include, but are not limited to, tartaric acid, glycolic acid, mandelic acid, oxalic acid, malic acid, malonic acid, tannic acid, citric acid, and ascorbic acid.

[0055] Examples of organic alcohols include, but are not limited to, erythritol and pentaerythritol.

[0056] Examples of organic acid esters include, but are not limited to, ascorbyl palmitate, propyl gallate, octyl gallate, and octadecyl gallate.

[0057] With respect to the composition according to the first aspect of the present invention, the antioxidant is preferably an organic acid. With respect to the composition according to the first aspect of the present invention, the antioxidant is more preferably selected from tartaric acid, glycolic acid, mandelic acid, oxalic acid, malic acid, malonic acid, tannic acid, citric acid, and ascorbic acid. With respect to the composition according to the first aspect of the present invention, the antioxidant is more preferably selected from tartaric acid, glycolic acid, and mandelic acid, and most preferably selected from tartaric acid and glycolic acid.

[0058] A composition according to a second aspect of the present invention may not contain an antioxidant. Preferably, a composition according to a second aspect of the present invention does not contain an antioxidant as described herein.

[0059] Polyvalent metal oxyanions or oxyacids, or hydrates thereof, may be present in a composition according to a first or second aspect of the present invention in an amount of 1 to 70 wt%, for example, 5 to 40 wt%, or further 10 to 40 wt% of the composition.

[0060] Polyvalent metal oxyanions or oxyacids, or hydrates thereof, may be present in the composition according to the first or second aspect of the present invention in an amount of 1 wt% or more, or 5 wt% or more, for example, 10 wt% or more of the composition.

[0061] A redox buffer may be present in a composition according to the first or second aspect of the present invention in an amount of 0.1 to 35 wt%, for example, 0.25 to 35 wt%, or 0.5 to 35 wt%, or 0.75 to 35 wt%, or 1 to 10 wt%, or 2 to 10 wt% of the composition.

[0062] A redox buffer may be present in the composition according to the first or second embodiment of the present invention in an amount of 0.1 wt% or more, or 0.25 wt% or more, for example 0.5 wt% or more, or 0.75 wt% or more, for example 1 wt% or more, or 2 wt% or more of the composition.

[0063] The antioxidant may be present in the composition according to the first aspect of the present invention in an amount of 0.1 to 17.5 wt%, for example 0.25 to 17.5 wt%, or 0.5 to 17.5 wt%, for example 0.75 to 5 wt%, or 1 to 5 wt% of the composition.

[0064] The antioxidant may be present in the composition according to the first aspect of the present invention in an amount of 0.1 wt% or more, or 0.25 wt% or more, or 0.5 wt% or more, for example, 0.75 wt% or more, or 1 wt% or more, or 2 wt% or more of the composition.

[0065] A composition according to the first or second aspect of the present invention is not a pharmaceutical product and / or pharmaceutical composition.

[0066] With respect to a composition according to the first aspect of the present invention, the redox buffer and the antioxidant may be present in a ratio of 5:1 to 1:1, for example, 2:1 (redox buffer:antioxidant).

[0067] A composition according to the first or second aspect of the present invention may further contain a binder. Suitable binders are well known to those skilled in the art. Examples of suitable binders include, but are not limited to, polymer binders, e.g., acrylic copolymers, styrene copolymers, styrene-acrylic copolymers, styrene-maleic acid copolymers and their hydrogenation products; vinyl polymers; polyvinyl butyral polyolefins and their hydrogenation or epoxidation products; aldehyde-containing polymers; epoxide-containing polymers; polyamides; polyesters; polyurethanes; sulfone-containing polymers; natural products and their derivatives; and combinations thereof. The binder may be selected to complement other components present in the compositions according to the first and second aspects of the present invention.

[0068] The binder may be present in any suitable amount in the composition according to the first or second aspect of the present invention. The composition according to the first or second aspect of the present invention may contain 1 to 70 wt%, for example 5 to 50 wt%, more preferably 8 to 40 wt%, of the binder.

[0069] A composition according to a first or second aspect of the present invention may further comprise a near-infrared absorbing compound. The near-infrared absorbing compound may be any suitable compound capable of absorbing near-infrared (NIR) or mid-infrared, preferably near-infrared. The near-infrared absorbing compound is typically included when near-infrared or mid-infrared, preferably near-infrared, can be used to form a mark or image. Two or more near-infrared absorbing compounds may be present in a composition according to a first or second aspect of the present invention. Suitable examples of near-infrared absorbing compounds include, but are not limited to, inorganic copper salts such as hydroxyl copper(II) phosphate; organic NIR dyes and pigments such as N,N,N',N'-tetrakis(4-dibutylaminophenyl)-p-benzoquinone bis(iminium hexafluoroantimonate); non-stoichiometric, reduced or doped inorganic compounds, such as reduced indium tin oxide, reduced zinc oxide, reduced tungsten oxide, and compounds of the following formula MxWyOz (wherein M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al The inorganic compounds include reduced, doped tungsten oxide, reduced antimony tin oxide, or doped metal oxides, such as aluminum-doped zinc oxide (AZO) and fluorine-doped tin oxide (FTO); conductive polymers such as polypolystyrene sulfonate (PEDOT); and combinations thereof. Near-infrared absorbing compounds may be inorganic copper salts such as hydroxyl copper(II) phosphate.

[0070] Near-infrared absorbing compounds may be present in any suitable amount in the composition according to the first or second aspect of the present invention. The composition according to the first or second aspect of the present invention may contain 0.01 to 25 wt%, for example 0.1 to 15 wt%, more preferably 0.25 to 5 wt%, of the near-infrared absorbing compound.

[0071] A composition according to a first or second aspect of the present invention may further contain a solvent. A composition according to a first or second aspect of the present invention may contain a single solvent or a mixture of solvents. The solvent may be selected from water, an organic solvent, a mixture of water and an organic solvent, or a mixture of organic solvents. Suitable organic solvents include, but are not limited to, alcohols such as ethanol, n-propanol, isopropanol, and n-butanol; esters such as ethyl acetate, butyl acetate, propyl acetate, and n-hexyl acetate; aromatic hydrocarbons such as benzene, toluene, xylene, and solvent naphtha 100, 150, 200; ketones such as acetone, cyclohexanone, methyl isobutyl ketone, and methyl ethyl ketone; glycols such as butyl glycol; glycol ethers such as methoxypropanol, ethylene glycol monomethyl ether, and ethylene glycol monobutyl ether; and combinations thereof. A composition according to a first or second aspect of the present invention may be "aqueous" (containing only water and no organic solvent) or "organic solvent" (containing only organic solvents and no water). The solvent may be present in the composition according to the first or second aspect of the present invention in an amount of 20 to 70 wt%. The amount of solvent includes all solvents present in the composition according to the first or second aspect of the present invention, i.e., all solvents of the component materials used to form the composition.

[0072] A composition according to a first or second aspect of the present invention may further include additives or combinations of additives. Suitable additives are well known to those skilled in the art. Examples of suitable additives include, but are not limited to, polymers; light absorbers or energy absorbers; UV absorbers; surfactants; wetting agents; drying accelerators; colorants such as pigments; colorants; fluorescent agents; plasticizers; fluorescent whitening agents; oxidizing agents or reducing agents; stabilizers; photostabilizers such as hindered amines; rheological modifiers such as thickeners or diluents; water retainers; adhesion promoters; acid or base scavengers; inhibitors; defoaming agents; antifoaming agents; and combinations thereof. A composition according to a first or second aspect of the present invention may contain 0.01 to 10 wt% of additives or combinations thereof.

[0073] Alternatively, instead of further comprising the binders and / or near-infrared absorbing compounds and / or solvents and / or additives detailed above, compositions according to the first or second aspects of the present invention may further comprise a hot-melt adhesive having a mixture therein a polyvalent metal oxyanion or oxy acid, or hydrates thereof, and an oxidation-reduction buffer, and an antioxidant, if present. Details of hot-melt adhesives containing polyvalent metal oxyanions or oxy acids, or hydrates thereof, and compositions formed therefrom are fully disclosed in International Publication No. 2022 / 189577, the contents of which are fully incorporated herein by reference.

[0074] Hot melt adhesives are well known in the art. Hot melt adhesives are thermoplastic adhesives that are solid at ambient temperature but, when heat is applied, transition from a solid state, begin to melt, and become flowable. When cooled back to ambient temperature, hot melt adhesives return to a solid state. In relation to hot melt adhesives, the term "melt" means that the hot melt adhesive is flowable. It may be viscous, but it is flowable. To begin melting, the hot melt adhesive is heated or heated above its melting temperature. The melting temperature of a hot melt adhesive is the temperature at which the hot melt adhesive begins to melt and becomes flowable. The melting temperature is the temperature at which the hot melt adhesive transitions from a solid state to a viscous flowable state. The melting temperature is sometimes known in the art as the softening temperature. This melting temperature is the minimum temperature at which the hot melt adhesive is effectively processed. In the context of this invention, there is typically a melting temperature range at which the hot melt adhesive begins to melt and is therefore flowable. This can occur, for example, when a hot-melt adhesive contains two or more thermoplastic polymers, copolymers, or oligomers, as discussed below. A hot-melt adhesive, therefore, melts at and above its melting temperature, but is solid at ambient temperature. A hot-melt adhesive is tacky when melted. Therefore, when melted, a hot-melt adhesive can act as an adhesive or be easily applied to or incorporated into a substrate. A hot-melt adhesive may be tacky when melted and non-tacky when cooled and solid at ambient temperature (typically known in the art as a non-pressure-sensitive hot-melt adhesive), or it may be tacky when melted and remain tacky when cooled and solid at ambient temperature (typically known in the art as a pressure-sensitive hot-melt adhesive).

[0075] As used herein, the term “ambient temperature” means a temperature of 10–35°C, typically 18–28°C. Ambient temperature is encompassed by a broader definition, “ambient conditions,” which refers to the typical range of conditions of the surrounding environment to which a composition according to a first or second aspect of the present invention is exposed, i.e., the range of temperature, pressure, and atmospheric conditions to which a composition according to a first or second aspect of the present invention is exposed during use, storage, etc. This includes solar radiation, including electromagnetic radiation such as X-rays, ultraviolet (UV), and infrared (IR). Typically, ambient conditions include a temperature of 10–35°C and a pressure of 20–100 kPa, and this environment is typically oxygen-containing air.

[0076] Hot-melt adhesives and their components are well known in the art. For example, 'Sustainable Raw Materials in Hot Melt Adhesives: A Review; Vineeth et al.; Open Journal of Polymer Chemistry; Vol. 10, No. 3; August 2020' and 'Basic Study of Evaluation of Thermoplastic Polymers as Hot-Melt Adhesives for Mixed-Substrate Joining; Open Journal of Polymer Chemistry; Col. 6, No. 8; August 2016' discuss hot-melt adhesives.

[0077] In the context of compositions according to the first and second aspects of the present invention, the hot-melt adhesive acts as a vehicle for transferring polyvalent metal oxyanions, or oxyacids, or hydrates thereof, and redox buffers, as well as antioxidants, if present, to a substrate on which a mark or image is to be displayed.

[0078] Hot melt adhesives contain a thermoplastic polymer, copolymer, oligomer, or mixture thereof as a base material. Typically, hot melt adhesives further contain a tackifier or resin. Hot melt adhesives may also typically further contain one or more additive components as described below. It is preferable that hot melt adhesives further contain a tackifier or resin. It is preferable that hot melt adhesives further contain one or more additive components.

[0079] The thermoplastic polymers, copolymers, oligomers, or mixtures thereof for hot melt adhesives may be selected from, but are not limited to, the following: poly(ethylene-vinyl acetate) or ethylene-vinyl acetate copolymers; poly(ethylene acrylate) copolymers; acrylics; polyvinyl butyral; polyolefins such as polybutene, polyethylene, and polypropylene, including low-density (LDPE), medium-density (MDPE), and high-density (HDPE) polyethylenes; polyamides such as ethylenediamine and hexamethylenediamine; nylon; polyesters including poly(lactic acid) (PLA), polyethylene tereftrate (PET), polyhydroxyalkanoate (PHA), and poly(glycolic acid) (PGA); polyurethanes; acrylic and styrene-acrylate copolymers; styrene-isoprene-styrene triblock copolymers; polystyrene (PS); polycaprolactone; polycarbonate; fluoropolymers; elastomers; silicone rubber and polypyrrole, or combinations thereof.

[0080] The thermoplastic polymer, copolymer, or oligomer may be a thermoplastic polymer, copolymer, or oligomer of petroleum-based plastics, or a thermoplastic polymer, copolymer, or oligomer of bioplastics. Preferably, the thermoplastic polymer, copolymer, or oligomer is a thermoplastic polymer, copolymer, or oligomer of bioplastics. The bioplastic thermoplastic polymers, copolymers, or oligomers incorporated herein include, but are not limited to, poly(lactic acid) (PLA), polyhydroxyalkanoates (PHA), and poly(glycolic acid) (PGA), as well as poly(ethylene-vinyl acetate) or ethylene-vinyl acetate (EVA) copolymers formed from ethanol derived from sugarcane and / or other natural raw materials, and polyethylene formed from sugarcane and / or other natural raw materials. With respect to the thermoplastic polymers, copolymers, oligomers, or mixtures thereof, both bioplastic and petroleum-based forms are included with respect to the poly(ethylene-vinyl acetate) or ethylene-vinyl acetate copolymers and polyethylene materials listed herein.

[0081] As used herein, the prefix "petroleum-based plastics" refers to any material derived from petrochemical sources. Such materials are typically recyclable. Therefore, they are typically manufactured from either unused or recycled materials, or a combination thereof.

[0082] As used herein, the prefix “bioplastics” refers to any material derived from natural and sustainable resources. Such materials are typically renewable, biodegradable, and / or compostable, and more specifically, biodegradable and / or compostable. Thus, they are typically manufactured from either unused or recycled materials, or a combination thereof.

[0083] Thermoplastic polymers, copolymers, oligomers, or mixtures thereof are preferably renewable, biodegradable, and / or compostable.

[0084] The thermoplastic polymer, copolymer, oligomer, or mixture thereof is preferably selected from polyethylene terephthalate (PET), polyhydroxyalkanoate (PHA), poly(glycolic acid) (PGA), poly(ethylene-vinyl acetate) or ethylene-vinyl acetate copolymer, low-density polyethylene (LDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), and poly(lactic acid) (PLA). More preferably, the thermoplastic polymer, copolymer, oligomer, or mixture thereof is selected from polyhydroxyalkanoate (PHA), poly(glycolic acid) (PGA), poly(ethylene-vinyl acetate) or ethylene-vinyl acetate (EVA) copolymer, and low-density polyethylene (LDPE). More preferably, the thermoplastic polymer, copolymer, oligomer, or mixture thereof is selected from polyhydroxyalkanoate (PHA), poly(glycolic acid) (PGA), and poly(ethylene-vinyl acetate) or ethylene-vinyl acetate (EVA) copolymer. The thermoplastic polymer, copolymer, or oligomer is most preferably a poly(ethylene-vinyl acetate) or ethylene-vinyl acetate (EVA) copolymer.

[0085] Thermoplastic polymers, copolymers, oligomers, or mixtures thereof may be present in the hot melt adhesive in any suitable amount. These thermoplastic polymers, copolymers, oligomers, or mixtures thereof may be present in amounts of 20–90%, for example, 30–80%, or 40–75% of the hot melt adhesive.

[0086] Thermoplastic polymers, copolymers, oligomers, or mixtures thereof may be present in any suitable amount in the composition according to the first or second aspect of the present invention. Thermoplastic polymers, copolymers, oligomers, or mixtures thereof may be present in an amount of 10 to 90%, for example, 20 to 70%, or even 25 to 60%, of the composition according to the first or second aspect of the present invention.

[0087] The hot melt adhesive may further contain a tackifier or resin. It is preferable that the hot melt adhesive contains a tackifier or resin. Two or more types of tackifiers or resins may be present.

[0088] The tackifier or resin may contain acid, hydroxyl, or ester functional groups. Preferably, the tackifier or resin contains acid or ester functional groups. If the tackifier or resin contains acid functional groups, it preferably has 5 to 250, for example, 5 to 200 acid groups.

[0089] Suitable tackifiers or resins include, but are not limited to, resins containing natural resins such as copal, dammer, mastic, and sandarac; petroleum resins; rosins, rosin acids, rosin esters, and rosin resins—rosins and their derivatives such as gum rosin, wood rosin, or talc rosin; hydrogenated rosins such as Foral AX and Foral AX-E rosin from Eastman Chemical Companies; dimerized rosin resins; modified rosin resins; terpenes and modified terpenes; aliphatic, alicyclic, and aromatic resins such as C5 aliphatic resins, C9 aromatic resins, and C5 / C9 aromatic / aliphatic resins; hydrogenated hydrocarbon resins; terpene-phenol resins; polybutenes and polyisobutenes; and combinations thereof. Examples of commercially available tackifiers or resins include "Piccotac 1020-E hydrocarbon resin," "Piccotac 1095-N hydrocarbon resin," "Piccotac 9095 hydrocarbon resin," and "Piccotac 8095 hydrocarbon resin," all available from Eastman Chemical Companies. The tackifier or resin is preferably selected from rosin and its derivatives, hydrogenated rosin, dimerized rosin resin, and modified rosin resin.

[0090] The tackifier or resin may be present in the hot melt adhesive in any suitable amount. If present, it is preferable that the tackifier or resin be present in an amount of 1 to 90%, for example, 2 to 80%, 5 to 70%, or 10 to 60% of the hot melt adhesive.

[0091] A tackifier or resin may be present in any suitable amount in the composition of the first or second embodiment of the present invention. If present, the tackifier or resin may be present in an amount of 10-90%, 15-80%, 20-70%, preferably 25-60%, of the composition of the first or second embodiment of the present invention.

[0092] Hot melt adhesives may further contain one or more additive components. Preferably, hot melt adhesives contain one or more additive components. Suitable additive components are well known to those skilled in the art. These additive components are typically present to control the rheological properties of the hot melt adhesive and its composition, such as viscosity. Examples of suitable additive components include, but are not limited to: waxes, e.g., fatty amide waxes, Fischer-Tropsch oxidized waxes or waxes based on both the Fischer-Tropsch and Ziegler-Natta processes, water-soluble waxes, polyalkylene waxes, mineral waxes, e.g., paraffin and microcrystalline waxes, polyethylene waxes, polyethylene glycol waxes (Carbowax from DOW Chemical Inc.), oxidized polyethylene waxes, bis-stearamides, e.g., N,N'-ethylenebis-stearamide (Lonza Inc.)Acrawaz obtained from [source], natural and synthetic waxes, such as beeswax, soy wax, carnauba wax, ozokerite and ceresin, as well as silicone waxes; slip agents; lubricants; inhibitors; antioxidants; stabilizers such as Irganox 1010; UV stabilizers and UV absorbers, such as the Tinuvin series including Tinuvin 770, 928 326, 1130, (384-2) and 123, and combinations thereof (BASF); adhesion promoters; plasticizers, such as glyceryl tribenzoate, alkyl benzoates and benzoic acid esters (e.g., Benzoflex obtained from Eastman Chemical Corporation). 9-88) Glycols such as diethylene glycol, C12-15 alkyl benzoates, C2-C22 alkyl benzoates, alkyl citrates, phthalates, phthalates, paraffin oils, and polyisobutylene; light absorbers or energy absorbers; surfactants; wetting agents, e.g., polyhydroxystearic acid, polyglyceryl-4 isostearate, hexyl laurate, esters such as isopropyl myristate, propylene carbonate, isononyl isononanoate, glyceryl behenate / eicosanedioic acid, trihydroxystearin, C2-15 alkyl benzoates, C2-C22 alkyl benzoates, where alkyl is linear or branched, or mixtures thereof. , triethoxycaprylysilane, castor oil; drying accelerators; colorants such as pigments; flame retardants; antistatic agents; fillers; colorants; viscosity modifiers; fluorescent agents; fluorescent whitening agents; oxidizing or reducing agents; stabilizers; light stabilizers such as hindered amines containing Tinuvin 292; rheological modifiers such as thickeners or diluents; matting agents; activated clay; anti-settling agents; anti-sagging agents; dispersants; surface modifiers; slip agents; leveling agents; fillers; water-retaining agents; adhesion promoters; acid or base scavengers; inhibitors; defoaming agents; surfactants; antifoaming agents; biocides; preservatives; antioxidants such as BHT, phosphite and phosphate; antimicrobial agents; antiviral agents; antibacterial agents; antifungal agents; antifungal agents; fungicides; disinfectants; and combinations thereof. Typically, hot-melt adhesives further contain one or more additive components selected from waxes, plasticizers, antioxidants, UV stabilizers, and fillers, or combinations thereof.

[0093] One or more additive components may be present in the hot melt adhesive in any suitable amount. If present, it is preferable that one or more additive components be present in an amount of 0.1 to 35%, for example, 0.1 to 30%, or 0.1 to 25%, or 0.1 to 20% of the hot melt adhesive.

[0094] One or more additive components may be present in any preferred amount in the composition according to the first or second aspect of the present invention. If present, one or more additive components may be present in an amount of 0.1 to 35%, for example, 0.1 to 30%, or further 0.1 to 25%, for example, 0.1 to 20%, of the composition according to the first or second aspect of the present invention.

[0095] Hot melt adhesives can be purchased commercially or formulated from suitable starting materials. Hot melt adhesives and their components are known in the art. Those skilled in the art can easily identify suitable hot melt adhesives, or required components such as thermoplastic polymers, oligomers, copolymers, or mixtures thereof, tackifiers or resins, and one or more additive components, depending on the desired properties of the hot melt adhesive in question. Hot melt adhesives and hot melt adhesive materials known in the art, such as those used in glue guns and hot glue applicators, are suitable for use in the present invention. Such materials are known to those skilled in the art.

[0096] Commercially available thermoplastic polymers, copolymers, oligomers, or mixtures thereof suitable for hot-melt adhesives include, but are not limited to: ExxonMobil under the trademark name "Escorene® Ultra"; Rowak under the trademark name "Rowalit® 300"; and Evatane as "SK Functional Polymers"; Versalis SpA Greenflex HN70 from Distrupol; polypropylene from Borealis under the trademark name "RE 420"; and poly(ethylene-vinyl acetate) or ethylene-vinyl acetate copolymers available from Rowak under the trademark name "Rowalit® H" and from Lyondell Basell under the trademark name "Lupolen 1800S" as low-density polyethylene. Commercial thermoplastic polymers, copolymers, oligomers, or mixtures thereof for bio-based hot-melt adhesives include, but are not limited to, polylactic acid (PLA) known as Ingeo™ Biopolymer 3251D from Nature Works (Minnetonka, MN, USA).

[0097] Suitable commercially available hot melt adhesives for use in compositions according to the first or second aspect of the present invention include those available from Henkel (under the trademark names Technomelt, Technomelt Cool, Technomelt Supra, Technomelt Supra Pro, Technomelt Pur, Technomelt PA, Technomelt DA, Easymelt, and EasyFlow), Caswell Adhesives (Premiermelt or Casmelt products), Loctite, Bostik (Kizen, Kizen Force, Kizen ice, Kizen heat, Supergrip, Close TLH 4280E and TLH 2901E, Protect and Seal TLH 4492E, TLH 2299E, Send TLH 4280E, TLH 4119E, Track TLH 4000E, Show TLH 2211ELO, TLH 2299E, Hang (TLH 2281E and TLH2211ELO, and TEF272), DuPont (ELVAX 40W, 150W, 210W, 220W, 240W, 250, 260, 265, 350, 360, 410, 420, 450, 460, 470, 550, 560, 660, 670, 750, 770, 4260, 4310, 4320 and 4355), Repsol (Primeva EVA's with 15-40 VA%) P1550M, P18150, P18500, P20020, P2430, P2735, P2870, P28025, P28150, P28400, P28045, P28800, P2850M, P2836M, P33015, P33025, P33045, P33400, P40055, and Ebantix EBA's E1715, E1770, E20020, E27150, E33150 EBA (butyl acrylate), used with tackifiers (rosin resin, polyterpene resin, alicyclic aromatic resin), Technology Supplied Ltd ("Proflex 970 Hot Melt Glue Stick"), Tian Tian Adhesive Factory ("Hot melt glue") stick”), Toolstream Ltd(“HotThis includes, but is not limited to, hot melt adhesives such as “Melt Glue Stick” (698462, 652076, 349348, 100024), FPC Corporation (“Hot Melt Glue” (501, 601, 701, 702, 707, 708, 7011, 724) and 3M (Hot Melt Adhesives 3764, 3747, 3748, 3731, 3738, 3796, 3792, 3762, 3779, and 3789).

[0098] The hot melt adhesive may have any suitable melt flow index (MFI). The hot melt adhesive may have a melt flow index of 1 to 1000 g / 10 min, for example, 3 to 900 g / 10 min or 10 to 900 g / 10 min. The melt flow index defines the fluidity of the hot melt adhesive when melted at or above its melting temperature.

[0099] Methods for measuring the melt flow index (MFI) of hot melt adhesives are well known to those skilled in the art, and values ​​can be measured in accordance with ISO standard 1133-1 or ASTM D1238. The term melt flow index may be used interchangeably by those skilled in the art with melt flow rate (MFR) or melt index (MI). The melt flow index is a measure of the flow rate of thermoplastic materials such as hot melt adhesives. The melt flow index is defined as the mass in grams of thermoplastic material that flows through a capillary of a particular diameter and length in 10 minutes under applied pressure. In the context of this invention, the melt flow index is measured as a value that represents the relative velocity of the hot melt adhesive and its behavior when heated to a temperature above ambient temperature, causing the hot melt adhesive to begin melting and become flowable. The melt flow index of a hot melt adhesive may be roughly inversely proportional to the molecular weight of the thermoplastic polymer, copolymer, oligomer, or mixture thereof in the hot melt adhesive. While the melt flow index can be measured at different temperatures, loads, and times, MFI is generally measured at 190°C and / or 230°C with a load of 2.16 kg or 5 kg for 10 minutes. For example, a standard test uses an MFI apparatus, such as an Extruson Plastometer, at 190°C for 10 minutes with a load of 2.16 kg. The applied load introduces shear stress inside the apparatus.

[0100] The thermoplastic polymers, copolymers, oligomers, or mixtures thereof of hot-melt adhesives may have any preferred molecular weight. Molecular weight can typically be determined indirectly using MFI measurement, where generally, a higher MFI corresponds to a lower molecular weight, and vice versa.

[0101] The melting temperature of a hot-melt adhesive can be 50–200°C, or 50–160°C, including 70–150°C. The melting temperature of a hot-melt adhesive is the temperature at which the adhesive begins to melt and becomes flowable. The melting temperature is the temperature at which the hot-melt adhesive transitions from a solid state to a viscous flow state. The melting temperature may also be known in the art as the softening temperature. The melting temperature is the minimum temperature at which the hot-melt adhesive can be effectively processed. As described above, the melting temperature of a hot-melt adhesive may encompass a melting temperature range. In the context of this invention, both ends of any melting temperature range are included in the value stated as the melting temperature of the hot-melt adhesive.

[0102] Preferred methods for measuring the melting point of hot-melt adhesives are well known to those skilled in the art. The melting point can be measured by differential scanning calorimetry (DSC) or by a known “ring-ball” melting point measurement method using a melting point apparatus equipped with a thermometer. This may conform to ISO 4625-1:2020. In the “ring-ball” method, the hot-melt adhesive layer is placed inside a steel ring and cooled. A sphere that can pass through the ring is placed on top of the hot-melt adhesive layer. This entire system is placed in an oil bath and heated. The melting point is determined as the temperature at which the sphere falls through the hot-melt adhesive layer and contacts the bottom of the oil bath. The melting point of hot-melt adhesives is preferably measured by DSC. This may conform to ISO 11357-1:2016.

[0103] DSC (Deep-Sensitive Discharge) is a well-known technique to those skilled in the art, a thermal analysis technique in which the difference in the amount of thermal energy required to change the temperature of a hot-melt adhesive sample and a reference material is measured as a function of temperature. The goal is to maintain the same temperature for both the hot-melt adhesive sample and the reference material, and as a result, DSC can determine the endothermic transition, i.e., the melting temperature, at which the hot-melt adhesive begins to melt and become flowable. The fundamental principle of DSC is that when a hot-melt adhesive sample undergoes a physical transition, more energy is required for the sample to flow compared to the reference material in order to maintain both at the same temperature. By measuring the difference in thermal fluidity between the sample and the reference material, DSC can determine the amount of heat absorbed during the endothermic transition.

[0104] Therefore, hot melt adhesives and compositions according to the first or second embodiment of the present invention, when formed from hot melt adhesives, are tacky when melted. The "tackiness" of hot melt adhesives and their compositions can be measured in accordance with ASTM 3121 ("rolling ball tack method").

[0105] When the thermoplastic polymer, copolymer, oligomer, or mixture thereof of a hot melt adhesive is poly(ethylene-vinyl acetate) or ethylene-vinyl acetate copolymer, the ratio of vinyl acetate to ethylene in the copolymer can vary. For example, poly(ethylene-vinyl acetate) or ethylene-vinyl acetate copolymer may contain 1 to 60% vinyl acetate, e.g., 10 to 40%, or even 15 to 33% vinyl acetate. Poly(ethylene-vinyl acetate) or ethylene-vinyl acetate copolymer may contain 25% or more vinyl acetate. Poly(ethylene-vinyl acetate) or ethylene-vinyl acetate copolymer may contain 24% or less vinyl acetate.

[0106] Changes to the ratio of vinyl acetate to ethylene monomer in the poly(ethylene-vinyl acetate) or ethylene-vinyl acetate copolymer structure affect properties such as the bonding between the composition and the substrate, and therefore may affect properties such as the type of substrate to which the composition can be coated or incorporated. For example, if the poly(ethylene-vinyl acetate) or ethylene-vinyl acetate copolymer contains a high content of vinyl acetate (25% or more), the composition is preferably coated on or incorporated into a substrate having a lower surface energy, such as a polymer film, which requires a composition that is "more tacky." On the other hand, if the poly(ethylene-vinyl acetate) or ethylene-vinyl acetate copolymer contains a lower content of vinyl acetate (24% or less), the composition is preferably coated on or incorporated into a substrate having a higher surface energy, such as a porous or semi-porous substrate, such as a paper-based substrate including paper, cardboard, and corrugated cardboard, which requires a composition that is "less tacky."

[0107] It is preferable that the hot-melt adhesive makes up 20-80%, for example 30-70%, of the composition according to the first or second aspect of the present invention.

[0108] If a composition according to the first or second aspect of the present invention includes a hot-melt adhesive, a polyvalent metal oxyanion or oxy acid, or hydrates thereof, and an oxidation-reduction buffer, and if present, an antioxidant, are mixed into the hot-melt adhesive and homogeneously distributed, dispersed, suspended, and incorporated throughout the hot-melt adhesive to form the composition according to the first or second aspect of the present invention. The polyvalent metal oxyanion or oxy acid, or hydrates thereof, the oxidation-reduction buffer, and if present, the antioxidant, may be introduced into the hot-melt adhesive in the form of solid particulate matter.

[0109] When formulating a composition according to a first or second embodiment of the present invention using a hot melt adhesive, i.e., when incorporating a polyvalent metal oxyanion, or oxy acid, or hydrate thereof, and an oxidation-reduction buffer, or antioxidant, if present, into the hot melt adhesive, or when applying the composition to a substrate as described in detail below, the hot melt adhesive needs to be able to melt and flow. This is achieved by heating the hot melt adhesive, and therefore the composition, to a temperature above, preferably above, the melting temperature of the hot melt adhesive. As described above, this can encompass the melting temperature range. In order for color to be formed on the composition through the application of radiation after these formulation or application steps, the decomposition temperature of the polyvalent metal oxyanion, or oxy acid, or hydrate thereof should not be reached. Therefore, in order for marks or images to be formed on the composition through application or radiation after these formulation or application steps, it is necessary to appropriately select the hot melt adhesive during heating in either the formulation or application step. Such selections depend on the relationship between the melting temperature of the hot-melt adhesive and the decomposition temperature of the polyvalent metal oxyanions, oxyacids, or their hydrates.

[0110] Polyvalent metal oxyanions, oxyacids, or their hydrates may have decomposition temperatures of 80–700°C, or 80–500°C, 100–500°C, 150–400°C, or even 200–300°C. The decomposition temperature is the temperature at which the polyvalent metal oxyanions, oxyacids, or their hydrates form color. The decomposition temperature of polyvalent metal oxyanions, oxyacids, or their hydrates is the temperature at which the compound chemically decomposes. In some literature, this is also known as the melting temperature.

[0111] The decomposition temperature of ammonium octamolybdate (AOM) is 275°C.

[0112] The decomposition temperatures of polyvalent metal oxyanions, oxyacids, or their hydrates can be measured using differential scanning calorimetry (DSC) or thermogravimetric analysis (TGA). It is preferable to measure the decomposition temperature using DSC. This is a well-known technique to those skilled in the art.

[0113] DSC (Deep Sediment Spectroscopy) is a well-known technique to those skilled in the art, a thermal analysis technique in which the difference in the amount of thermal energy required to change the temperature of a sample of polyvalent metal oxyanions and a comparative reference material is measured as a function of temperature. The goal is to maintain the same temperature for both the sample of polyvalent metal oxyanions, or oxyacids, or hydrates thereof, and the reference material, and as a result, DSC can determine the endothermic transition, or decomposition temperature, that occurs when polyvalent metal oxyanions decompose. The fundamental principle of DSC is that when a sample of polyvalent metal oxyanions, or oxyacids, or hydrates thereof undergoes a physical transformation, it is necessary to supply more thermal energy to the sample compared to the reference material in order to maintain both at the same temperature. By measuring the difference in thermal fluidity between the sample and the reference material, DSC can determine the amount of heat absorbed during the endothermic transition.

[0114] The melting temperature of hot-melt adhesives is lower than the temperature at which polyvalent metal oxyanions, oxyacids, or their hydrates form color; in other words, the melting temperature of hot-melt adhesives is lower than the decomposition temperature of polyvalent metal oxyanions, oxyacids, or their hydrates.

[0115] Conversely, the decomposition temperatures of polyvalent metal oxyanions, oxyacids, or their hydrates are higher than the melting temperature of the hot-melt adhesive. Therefore, the hot-melt adhesive, or the composition, can be heated to a temperature above, preferably higher than, the melting temperature of the hot-melt adhesive, resulting in the hot-melt adhesive beginning to melt and becoming suitable for application to the substrate. However, this temperature is lower than the decomposition temperature of polyvalent metal oxyanions, oxyacids, or their hydrates. Therefore, the formation of marks or images can then be controlled and achieved, if necessary, by applying radiation to the composition.

[0116] When the polyvalent metal oxyanion, or oxyacid, or their hydrate is ammonium molybdate (AOM), the decomposition temperature is higher than the melting temperature of the hot melt adhesive and is 50–200°C or 50–160°C, including 70–150°C, as detailed herein.

[0117] The decomposition temperature ranges of polyvalent metal oxyanions, oxyacids, or their hydrates overlap with the melting temperature ranges of the hot melt adhesives detailed herein, but the hot melt adhesives are selected to maintain the aforementioned relationship.

[0118] The melting temperature of the hot melt adhesive is lower than that of the redox buffer and, if present, the antioxidant. Conversely, the melting temperatures of the redox buffer and, if present, the antioxidant are higher than those of the hot melt adhesive. Therefore, the hot melt adhesive, or the composition, can be heated to a temperature above, preferably higher than, the melting temperature of the hot melt adhesive, resulting in the hot melt adhesive beginning to melt and becoming suitable for application to a substrate. However, this temperature is lower than the melting temperature of the redox buffer and, if present, the antioxidant. Therefore, the formation of marks or images can still be controlled and achieved, if necessary, through the application of radiation to the composition.

[0119] The melting temperatures of redox buffers and antioxidants can be measured by differential scanning calorimetry (DSC) or thermogravimetric analysis (TGA) using a melting point apparatus equipped with a thermometer.

[0120] If an antioxidant is present in the composition according to the first aspect of the present invention, the melting temperature of the hot-melt adhesive may be 50 to 150°C, preferably 50 to 100°C, for example, 50 to 95°C. The formation of a mark or image can then be controlled and achieved, if necessary, by applying radiation to the composition.

[0121] If a composition according to a first or second aspect of the present invention includes a hot-melt adhesive, the present invention also includes compositions in which the hot-melt adhesive is molten during manufacturing, processing, and application, and similarly, compositions in which the hot-melt adhesive is in a solid state (cooled to ambient temperature) during storage or after application of the composition to a substrate.

[0122] If a composition according to the first or second aspect of the present invention includes a hot-melt adhesive, the composition may further contain, mixed therein, a near-infrared absorbing compound. The near-infrared absorbing compound is homogeneously distributed, dispersed, suspended, and incorporated throughout the hot-melt adhesive of the composition. Two or more near-infrared absorbing compounds may be present. The near-infrared absorbing compounds are as described above. The near-infrared absorbing compound may be present in an amount of 0.1 to 5 wt% of the composition according to the first or second aspect of the present invention. The infrared absorbing compound may be introduced into the composition in the form of solid particulate matter. If present, the infrared absorbing compound may be present in the form of solid particulate matter.

[0123] When a hot-melt adhesive is used, the composition according to the first or second aspect of the present invention does not contain a solvent or water. Neither the hot-melt adhesive nor the composition according to the first or second aspect of the present invention contains water or a solvent.

[0124] When a hot-melt adhesive is used to form a composition according to the first or second aspect of the present invention, the hot-melt adhesive is heated above its melting temperature, and as a result, the hot-melt adhesive begins to melt (the melting temperature of the hot-melt adhesive is lower than the decomposition temperature of the polyvalent metal oxyanion, or oxy acid, or their hydrates), and the polyvalent metal oxyanion, or oxy acid, or their hydrates, and the redox buffer, or antioxidant, if used similarly, come into contact with the molten hot-melt adhesive, are introduced and mixed. Near-infrared absorbing compounds are also introduced by this method when used. Alternatively, the hot melt adhesive, a polyvalent metal oxyanion or oxyacid, or hydrate thereof, and an oxidation-reduction buffer, or antioxidant, when used similarly, are brought into contact and heated above the melting temperature of the hot melt adhesive (the melting temperature of the hot melt adhesive is lower than the decomposition temperature of the polyvalent metal oxyanion or oxyacid, or hydrate thereof), and then mixed into the molten hot melt adhesive. Near-infrared absorbing compounds are also introduced using this method.

[0125] Polyvalent metal oxyanions or oxyacids, or hydrates thereof, redox buffers, and antioxidants if present, as well as infrared-absorbing compounds, are introduced into the composition, preferably in the form of solid particulate matter.

[0126] When a hot-melt adhesive is used, in the method for forming a composition according to the first or second aspect of the present invention, the hot-melt adhesive is heated above its melting temperature, and as a result, the hot-melt adhesive begins to melt and becomes flowable. The melting temperature of the hot-melt adhesive is as described above with respect to the composition according to the first or second aspect of the present invention. The hot-melt adhesive is preferably heated to 50-200°C, or 50-160°C, for example, 70-150°C.

[0127] If a composition according to the first or second aspect of the present invention includes a hot-melt adhesive, as described above, the decomposition temperature of the polyvalent metal oxyanion, oxy acid, or hydrate thereof is not reached during the formation of the composition according to the first or second aspect of the present invention. The decomposition temperatures of the polyvalent metal oxyanion, oxy acid, or hydrate thereof are as described above.

[0128] If a composition according to a first or second aspect of the present invention includes a hot-melt adhesive, heating of the hot-melt adhesive in the formation of the composition according to a first or second aspect of the present invention can be achieved by any means. Suitable heating devices include hot-melt guns and applicators, extrusion and molding equipment, injection, blow molding, calendering, rotational molding, thermoforming, and hot-melt coating equipment. The production of a composition according to a first or second aspect of the present invention can be achieved using standard thermoplastic machinery, such as equipment used for molding including extrusion, blending, mixing, pulverization, and injection and blow molding, and other typical equipment of various sizes and specifications can be used for calendering, rotational molding, thermoforming, and hot-melt coating. This may include processing of liquid or solid masterbatches, as well as processing used in solid forms such as sticks, blocks, lumps, rods, spheres, beads, pellets, granules, and powders. Once a composition according to a first or second aspect of the present invention is formed, if the hot-melt adhesive melts, the composition can be applied directly to or incorporated into a substrate. A composition according to a first or second aspect of the present invention is then cooled to ambient temperature, and solidifies on the substrate as the hot-melt adhesive cools and transitions back to a solid state. Alternatively, once a composition according to a first or second aspect of the present invention is formed, the composition may solidify as it is allowed to cool to ambient temperature, and the hot-melt adhesive transitions back to a solid state. A composition according to a first or second aspect of the present invention then becomes solid as a whole. A composition according to a first or second aspect of the present invention may then be stored or transported in a solid state and, if necessary, reheated to the melting temperature of the hot-melt adhesive (selected to be below the decomposition temperature of a polyvalent metal oxyanion, or oxy acid, or their hydrates), causing the hot-melt adhesive to begin melting, and the composition according to a first or second aspect of the present invention may be applied to or incorporated into a substrate.

[0129] When a hot melt adhesive is used in a composition according to the first aspect of the present invention, the melting temperature of the hot melt adhesive used is preferably less than 100°C, for example, less than 100°C and greater than 50°C. In the production of the above-described composition, the temperature at which the hot melt is heated is less than 100°C, for example, less than 100°C and greater than 50°C.

[0130] When a hot-melt adhesive is used, the composition is preferably a composition according to a second aspect of the present invention, comprising a polyvalent metal oxyanion, oxy acid, or hydrate thereof as defined herein, and a redox buffer.

[0131] A composition according to a first or second aspect of the present invention preferably further comprises the binder and / or near-infrared absorbing compound and / or solvent and / or additive described in detail above. A composition according to a first or second aspect of the present invention preferably does not contain a hot-melt adhesive.

[0132] A composition according to a first or second aspect of the present invention is a radiation-reactive composition, such as a laser-reactive composition, that is, it is possible to form a mark or image when radiation is applied to the composition, preferably using a non-contact source, such as a laser source. A composition according to a first or second aspect of the present invention is suitable as an ink composition. A composition according to a first or second aspect of the present invention is suitable for forming a mark or image on a substrate.

[0133] A composition according to a first or second aspect of the present invention may be applied to or incorporated into any suitable substrate.

[0134] Accordingly, according to third and fourth aspects of the present invention, a substrate is provided which includes a composition according to the first or second aspect of the present invention, either coated thereon or incorporated therein.

[0135] Examples of suitable substrates for a third or fourth aspect of the present invention to which a composition according to a first or second aspect of the present invention may be applied or incorporated include, but are not limited to, those formed from the following substrate materials: polymers and recycled polymer materials, e.g., polyhydroxyalkanoates (PHA), poly(glycolic acid) (PGA), polyethylene terephthalate (PET), poly(ethylene vinyl acetate) or ethylene-vinyl acetate copolymer, polyethylene (PE), low-density polyethylene (LDPE), high-density polyethylene (HDPE), polystyrene (PS), polypropylene (PP), oriented poly Polyamides such as polypropylene (OPP), biaxially oriented polypropylene (BOPP), unoriented polypropylene (CPP), nylon (PA), polyvinyl chloride (PVC), or combinations thereof; cellulose; glass; plastics; metal foils such as metals and tinplate; textiles; paper-based substrates including paper, cards, cardboard boxes, corrugated cardboard, corrugated paper, corrugated cards, corrugated cardboard boxes, corrugated cardboard, thick paper, corrugated corrugated cardboard, folding boxes and equivalent recycled analogues, or combinations thereof; ceramics; food and pharmaceutical preparations; or combinations thereof, e.g., polymer-backed paper or polymer-impregnated paper. Suitable substrates include multilayer substrates formed from the materials and substrates listed above. Polymers and recycled polymer materials may also be in the form of polymer film substrates. Polymers and recycled polymer materials may be metallized. Metallization means that the material is coated with a thin layer of metal, such as aluminum. In these cases, polymers and recycled polymer materials may be metallized polymer films. Such films can be used, for example, as barrier layers in multilayer substrate structures.

[0136] A substrate according to a third or fourth aspect of the present invention may include one or more layers of a composition according to a first or second aspect of the present invention, either coated thereon or incorporated therein.

[0137] If the composition according to the first or second aspect of the present invention includes a hot-melt adhesive, the substrate according to the third or fourth aspect of the present invention includes a substrate on which the composition is applied or incorporated, and the composition is molten immediately after application, i.e., before it cools to ambient temperature. The composition according to the first or second aspect of the present invention also includes a substrate on which the composition is applied or incorporated, and the composition is solid at ambient temperature. The composition may be tacky or non-tacky at ambient temperature.

[0138] A composition according to a first or second aspect of the present invention, and a substrate according to a third or fourth aspect of the present invention to which a composition according to a first or second aspect is applied or incorporated, may be suitable for final use as packaging in everyday consumer goods; such as disposable packaging including containers for food and hot or cold beverages; packaging for hygiene products and personal care products such as shampoo bottles; cosmetic packaging; metal decorative products; blister pack packaging; laminate pouches; and packaging for medical and diagnostic devices and related equipment.

[0139] A composition according to a first or second aspect of the present invention, and a substrate according to a third or fourth aspect of the present invention to which a composition according to a first or second aspect is applied or incorporated, may find specific uses in the packaging industry. The substrate according to a third or fourth aspect of the present invention may be an article such as a packaging product, including, but not limited to, paper boxes and container boxes including cardboard and corrugated boxes, paper tubes including cardboard tubes, plastic bottles, paper bottles for plastic packaging, plastic lids, glass bottles, aluminum cans and lids, steel cans and lids, wrap-around labels, stretchable sleeves, shrinkable sleeves, and self-adhesive labels. The substrate according to a third or fourth aspect of the present invention is preferably a packaging product. Packaging products include lids and containers, for example, containers for food and / or beverages, or containers for pharmaceuticals or non-consumable personal care products and household goods. Preferred examples of containers include boxes, pouches, bottles such as beverage bottles, blister packaging typically used in the pharmaceutical and tobacco or e-cigarette industries, and clamshell packaging typically used in the food industry. Such substrates are typically formed from plastic, cardboard, or paper, preferably plastic. Substrates include the substrates described herein combined with additional components, such as a plastic bottle combined with a plastic lid. Plastic substrates also include the plastic substrates described herein combined with additional non-plastic components, such as a metal, aluminum foil, or paper sealing layer (lidding) in blister packaging. Plastic substrates also include plastic substrates combined with closures, pumps, caps, spouts, handles, lids, or covers. Substrates according to third or fourth aspects of the present invention may be used for storing, transporting, and distributing goods such as pharmaceuticals, food and beverages, and non-consumable personal care products and household goods.

[0140] In relation to a third or fourth aspect of the present invention, the substrate may be a multilayer substrate structure. Such a multilayer substrate structure may comprise multiple layers of different substrate materials bonded together. A composition according to a first or second aspect of the present invention may be applied thereto. Alternatively, or in addition, such a multilayer substrate structure may comprise a composition according to a first or second aspect of the present invention, which is present between at least two substrate material layers. Such a structure is a substrate having a composition according to a first or second aspect of the present invention incorporated therein. This may be known in the art as a “laminated structure”. A multilayer substrate structure may be thought to comprise multiple separate layers. The substrate material layers may be formed from the same substrate materials as detailed above with respect to the substrate.

[0141] By “a substrate containing a composition incorporated therein” or similar terms as used herein, this refers to a multilayer substrate structure described herein, which preferably includes a composition according to a first or second aspect of the present invention, present between at least two substrate material layers.

[0142] A multilayer substrate structure may include two or more substrate material layers. These two or more substrate material layers may be the same or different. This may relate to the type of material, color, thickness, and / or transparency. If one or all of the substrate material layers are polymer films, one or more of the two or more layers may be metallized, for example, to act as a barrier layer. If one or all of the two or more substrate material layers are polymer films, one or more of the substrate material layers may be "heat-sealable" plastic materials. Such materials are typically formed through processing, for example, by melting the plastic material itself.

[0143] If the multilayer substrate structure includes a composition according to the first or second aspect of the present invention, which is present between at least two substrate material layers, then preferably at least one of the substrate material layers is transparent or translucent, preferably transparent. Thus, marks or images formed in the composition according to the first or second aspect of the present invention can be seen through them.

[0144] The first or second composition according to the present invention may exist in a multilayer substrate structure as a single layer or multiple layers, i.e., once or multiple times. It may exist at the same location in the multilayer substrate structure or between different substrate material layers. The multilayer substrate structure may comprise two or more layers of the composition according to the first or second aspect of the present invention.

[0145] Typically, in the context of the present invention, the multilayer substrate structure corresponds to laminated film packaging. Typically, the multilayer substrate structure is a plastic pouch, a plastic box, or a plastic bottle, and is preferably a plastic pouch. The substrate material layer is preferably in the form of a polymer film.

[0146] A multilayer substrate structure may further include one or more additional layers. Such additional layers may be selected from, but are not limited to, an insulating layer; a protective layer; an adhesion-promoting layer; an adhesive layer; a barrier layer containing a metal foil or coated plastic material; a quench layer; and a light-stabilizing layer; or a combination thereof. The location of one or more additional layers in the multilayer substrate structure may vary depending on the type of one or more additional layers used and their function within the multilayer substrate structure. It is preferable that the multilayer substrate structure includes an adhesive layer and / or a barrier layer.

[0147] The multilayer substrate structure preferably includes a composition according to the first or second aspect of the present invention and an adhesive located between the two substrate material layers.

[0148] The multilayer substrate structure preferably comprises, in the following order: substrate material; composition according to a first or second aspect of the present invention; adhesive; and substrate material layer.

[0149] If a composition according to a first or second aspect of the present invention includes a hot-melt adhesive, the composition may be tacky at ambient temperature, and two substrate material layers may be bonded to each other by the composition in a multilayer substrate structure. An additional adhesive layer may not be necessary.

[0150] However, with respect to the multilayer substrate structures described herein, the compositions of the first or second embodiments of the present invention preferably do not contain a hot-melt adhesive. With respect to the multilayer substrate structures described herein, the compositions of the first or second embodiments of the present invention preferably further contain the binder and / or near-infrared absorbing compound and / or solvent and / or additive as detailed above.

[0151] With respect to multilayer substrate structures, the substrate material layers may typically have a thickness of 8 to 100 μm individually. Any layer of the composition according to the first or second aspect of the present invention in the multilayer substrate structure may have the coat weight described herein with respect to application to the substrate. The multilayer substrate structure may typically have an overall thickness of 500 μm or less, for example, 200 μm or less. Any one or more additional layers in the multilayer substrate structure may have a thickness of 100 μm or less.

[0152] If the multilayer substrate structure includes a composition according to the first or second aspect of the present invention, which is present between at least two substrate material layers, the composition according to the first or second aspect of the present invention between the two substrate material layers is preferably not exposed to an oxidizing atmosphere and is contained between the substrate material layers.

[0153] In the context of the present invention, a substrate according to a third or fourth aspect of the present invention includes a substrate that does not display a mark or image, i.e., a substrate that has been coated with a composition according to a first or second aspect of the present invention but before a mark or image is formed by the application of radiation, and similarly includes a substrate that displays a mark or image, i.e., a substrate that has been coated with a composition according to a first or second aspect of the present invention and has been subjected to radiation.

[0154] With respect to a multilayer substrate structure, any mark or image formed is formed using a composition according to a first or second aspect of the present invention, and therefore, if the multilayer substrate structure includes a composition according to a first or second aspect of the present invention present between at least two substrate material layers, the mark or image is formed "inside" the multilayer substrate structure or "incorporated" within the multilayer substrate structure. The multilayer substrate structure displays the mark or image.

[0155] A fifth aspect of the present invention provides a method for forming a substrate according to a third or fourth aspect of the present invention, the method comprising applying or incorporating a composition according to a first or second aspect of the present invention onto the substrate, respectively.

[0156] A composition according to a first or second aspect of the present invention may be applied to or incorporated into a substrate by any preferred method. Methods for applying a composition to a substrate or to a substrate material layer in a multilayer substrate structure are well known to those skilled in the art. Preferred application methods include, but are not limited to, flexographic printing, gravure printing, screen printing, pad printing, offset printing, and Meyer bar coating. When a hot melt adhesive is used in a composition according to a first or second aspect of the present invention, preferred application methods include, but are not limited to, hot melt guns and applicators, extrusion, injection molding, and molding equipment and coating equipment.

[0157] A composition according to a first or second aspect of the present invention can be applied to at least a portion of a substrate material layer in a substrate or multilayer substrate structure.

[0158] If a composition according to a first or second aspect of the present invention includes a hot-melt adhesive, and relating to a method for forming a substrate according to a third or fourth aspect, the composition, when melted, can be applied to a substrate or a substrate material layer in a multilayer substrate structure and allowed to cool to ambient temperature to solidify. By applying a composition according to a first or second aspect of the present invention to a substrate or a substrate material layer in a multilayer substrate structure and then allowing it to cool to ambient temperature to solidify, the hot-melt adhesive of the composition transitions to a solid state. If the hot-melt adhesive used is non-stick at ambient temperature, this cooling results in the composition according to a first or second aspect of the present invention solidifying, making it difficult to remove during subsequent handling, storage, or use of the substrate. Typically, in this case, the time required for the composition according to a first or second aspect of the present invention to cool and solidify depends on the volume of the applied composition, i.e., the coat weight, but typically the time required is 0.1 to 100 seconds, for example, 1 to 10 seconds, at ambient temperature.

[0159] A composition according to a first or second aspect of the present invention may be applied to a substrate or a substrate material layer in a multilayer substrate structure at any suitable coat weight, depending on both the substrate to which the composition is applied and the application method. Typically, a composition according to a first or second aspect of the present invention may be applied at a coat weight of 0.1 to 50 gsm (grams per square meter), for example, 0.1 to 25 gsm, or 0.1 to 15 gsm. If the composition according to a first or second aspect of the present invention contains a hot melt adhesive, the composition may be applied at a coat weight of 0.1 to 1000 gsm, for example, 0.1 to 500 gsm, or 0.1 to 250 gsm, more preferably 0.1 to 150 gsm.

[0160] The coat weight can be measured by any preferred method. Preferred measurement methods are well known to those skilled in the art. Preferably, the coat weight is measured by weighing the same area of ​​a substrate with and without the coated composition and comparing the difference between the two weights. All coat weights are the weight per individual layer of the composition according to the first or second embodiment of the present invention applied to the substrate.

[0161] A composition according to a first or second aspect of the present invention can be applied to a substrate or a substrate material layer in a multilayer substrate structure as a single layer or as multiple layers.

[0162] A composition according to a first or second aspect of the present invention can be applied to at least a portion or the entire surface of a substrate, or to a substrate material layer in a multilayer substrate structure.

[0163] If a composition according to a first or second aspect of the present invention contains a hot-melt adhesive, the composition must be heated to a temperature above the melting temperature of the hot-melt adhesive (but below the melting and decomposition temperature of polyvalent metal oxyanions, or oxyacids, or their hydrates, and below the melting temperature of redox buffers and antioxidants, if present) so that application of the composition to a substrate or to a substrate material layer of a multilayer substrate structure occurs when the hot-melt adhesive is melted. This may be immediately after the composition is formed or after storage of the composition, while the hot-melt adhesive is melting, and the composition is heated to a temperature above the melting temperature of the hot-melt adhesive (but below the decomposition temperature of polyvalent metal oxyanions, or oxyacids, or their hydrates, and below the melting temperature of redox buffers and antioxidants, if present) so that the hot-melt adhesive begins to melt for application to a substrate or to a substrate material layer of a multilayer substrate structure. Suitable methods for heating the composition are well known to those skilled in the art and typically include industrial thermoplastic processing and coating equipment, such as those used in extrusion, molding, injection, blow molding, calendering, rotational molding, thermoforming, hot melt coating, glue guns, and hot glue applicators. Since the composition is not heated to the decomposition temperature of polyvalent metal oxyanions, or oxyacids, or their hydrates, or the melting temperature of redox buffers and antioxidants, if present, the formation of marks or images may be facilitated by subsequent application of radiation.

[0164] By applying a composition according to a first or second aspect of the present invention to a substrate or a substrate material layer of a multilayer substrate structure, the substrate becomes capable of displaying a mark or image. Accordingly, a substrate according to a third or fourth aspect of the present invention includes a substrate before the application of radiation, in which the composition is applied or incorporated therein, i.e., a substrate before the mark or image is displayed therein, and similarly, a substrate after the application of radiation, in which the composition is applied or incorporated therein, resulting in the display of a mark or image therein.

[0165] Accordingly, a sixth aspect of the present invention provides a method for forming a mark or image on a substrate according to a third or fourth aspect of the present invention, on which a composition according to a first or second aspect of the present invention is applied or incorporated therein, the method comprising exposing the composition to radiation to form a mark or image.

[0166] Marks or images are formed by polyvalent metal oxyanions, or oxyacids, or hydrates thereof. Polyvalent metal oxyanions, or oxyacids, or hydrates thereof form color when radiation is applied. As used herein, “color” means the colors, hues, shades, and colors of the visible light color spectrum, namely red, orange, yellow, blue, green, and blue-violet, in addition to black, brown, turquoise, purple, pink, cyan, magenta, white, and all mixtures thereof. All primary, secondary, tertiary, quaternary, and quintic colors are included; that is, the resulting color may be a primary, secondary, tertiary, quaternary, or quintic color. In the context of this invention, the term “color” may also be used to represent different shades of each color in the visible light color spectrum, in addition to black, brown, turquoise, purple, pink, cyan, white, and magenta. In the context of the present invention, if a composition according to a first or second aspect of the present invention has an original color (before any radiation is applied thereto), the color formed when radiation is applied to the composition according to a first or second aspect of the present invention, and therefore the mark or image, is different from or has a stronger optical density than the color that the composition according to a first or second aspect of the present invention may have when it is compounded, stored, or applied to a substrate before the application of radiation.

[0167] Polyvalent metal oxyanions are color-forming compounds, and therefore, mark or image-forming compounds, and are particularly suitable for forming marks or images that display variable information.

[0168] Before the application of radiation, the composition according to the first or second aspect of the present invention may have any color. Alternatively, the composition according to the first or second aspect of the present invention may be colorless before the application of radiation.

[0169] A composition according to a first or second aspect of the present invention may be transparent or opaque before the application of radiation.

[0170] In the context of the present invention, polyvalent metal oxyanions, oxyacids, or hydrates thereof preferably do not form a color until controlled, specific radiation is applied to the composition. In some cases, typically when a composition according to the first or second aspect of the present invention includes a hot-melt adhesive, the polyvalent metal oxyanions, oxyacids, or hydrates thereof may display a certain color before radiation is applied to the composition. This may be a result of the temperature reached when processing, manufacturing, or applying the composition according to the first or second aspect of the present invention to a substrate. However, even in this case, the application of radiation may cause the polyvalent metal oxyanions, oxyacids, or hydrates thereof to display a color of much sharper optical density than the formed “background” color, resulting in the formation of an effective and contrasting mark or image, thus allowing the formation of a desired mark or image through the application of radiation to the composition. It is preferable that, before radiation is applied to the composition according to the first or second aspect of the present invention, the polyvalent metal oxyanions, oxyacids, or hydrates thereof do not display a color in the portion of the composition not to be irradiated. It is preferable that polyvalent metal oxyanions, oxyacids, or hydrates thereof display color only in the portion of the composition according to the first or second aspect of the present invention to which radiation is applied, i.e., in the portion of the composition exposed to radiation.

[0171] The term “mark or image” includes, but is not limited to, words or text, logos, graphics, figures, photographs, symbols, codes, linear barcodes, two-dimensional data matrices, QR (fast read) codes, Digimarc codes and text, microtext, and text containing alphanumeric fonts and symbolic fonts and characters. In the context of the present invention, the formation of a mark or image is facilitated by the skillful manipulation of polyvalent metal oxyanions, or oxyacids, or hydrates thereof ("color-forming compounds"). The formed marks or images are human and / or machine-readable and can be used for coding and marking, tagging, tracking and tracing, and for subsequent customization or personalization purposes. Codes may consist of, for example, alphanumeric text or symbolic fonts and represent expiration dates and / or batch codes or lot codes. Codes may also be graphical and can be scanned or verified using equipment such as barcode scanners, verification devices, or using a smartphone camera or app. The formed marks or images are typically used to display variable information about a substrate.

[0172] In the context of the present invention, a mark or image is a contrasting mark or image. By “contrasting mark or image,” it means that the formed mark or image is easily identifiable from the “background” of the composition according to the first or second aspect of the present invention, i.e., the portion of the composition not exposed to radiation, or the color of the substrate visible through the composition after it has been applied to the substrate.

[0173] In the context of the present invention, the formed mark or image is sharp and clear. Preferably, the mark or image has improved optical density.

[0174] The optical density of a mark or image can be evaluated, for example, by measuring the absolute optical density black (ODB), optical density magenta (ODM), optical density cyan (ODC), or optical density yellow (ODY). The ODB value is suitable for evaluating a mark or image in terms of black, or its shade or hue. The ODM value is suitable for evaluating a mark or image in terms of red, or its shade or hue. The ODC value is suitable for evaluating a mark or image in terms of blue, or its shade or hue. The ODY value is suitable for evaluating a mark or image in terms of yellow, or its shade or hue. In the context of ODB, ODM, ODC, and ODY values, the higher the value, the more vivid the resulting color. Absolute ODB, ODM, ODC, and ODY values ​​are quantitative representations of optical density on a black, magenta, cyan, or yellow color scale, from lowest to highest, and can be obtained using standard instruments such as a densitometer and an X-Rite eXact, SpectroEye, or TechKon SpectroDens spectrophotometer. Sharp and clear images preferably have absolute ODB, ODC, ODM, or ODY values ​​of 0.4 or higher, for example, 0.7 or higher, or even 1.0 or higher.

[0175] In the context of the present invention, when a polyvalent metal oxyanion, or oxyacid, or hydrate thereof is an ammonium salt of a polyvalent metal oxyanion, such as an ammonium salt of a molybdenum oxyanion, e.g., ammonium octamolybdate (AOM), the resulting color and / or image will typically include a grayscale, black, or its shades or hues, depending on the density of the black formed by radiation, when a polyvalent metal oxyanion, or oxyacid, or hydrate thereof is used as a color-forming compound. In such cases, except for those that are visually identifiable, the effective formation of the color or image can be demonstrated by the measured absolute optical density (ODB) black value, as described above. This measures the density of the black in the mark or image. In the context of ODB values, the higher the value, the darker the black formed. With respect to the present invention, an ODB value of 0.4 or higher, for example 0.7 or higher, or even 1.0 or higher is preferred. This quantifies the optical density on a black scale from low to high, and ODB measurements can be obtained using standard instruments such as a densitometer and an X-Rite eXact, SpectroEye, or TechKon SpectroDens spectrophotometer. Such values ​​demonstrate that, upon exposure to radiation, a “highly optically dense” mark or image is effectively formed by a composition according to the first or second aspect of the present invention.

[0176] The determination of improper coloration of a composition according to a first or second aspect of the present invention, in which a mark or image is formed or is to be formed, can be evaluated by measuring the ΔE value. This determination is particularly relevant to compositions according to a first aspect of the present invention, which contain the antioxidants discussed herein. The ΔE value represents a measurable difference in L*a*b* colors and determines whether coloration has occurred in the composition according to a first or second aspect of the present invention, other than the desired formation of a mark or image. A sample of the composition according to a first or second aspect of the present invention, with or without an image formed on the "background," is compared to a white background. ΔE can be measured using the following standard formula for an X-rite eXact spectrophotometer (L=L*, a=a*, and b=b*).

[0177]

number

[0178] ΔE measurements can be performed against a white background. ΔE allows for visual quantification between two colors. Low ΔE demonstrates no visual difference, i.e., no improper color formation or undesirable coloration. ΔE measurements may be less than 5. Such ΔE measurements provide a good indicator that there is no visual difference between the two colors.

[0179] Radiation can be applied to a composition according to a first or second aspect of the present invention at localized locations on the composition to selectively form a mark or image. A mark or image that is readable by humans and / or machines is formed.

[0180] As used herein, terms such as “radiation” refer to energy in wave or particle form, and more specifically to electromagnetic radiation such as ultraviolet (UV), visible light, near-infrared (NIR), and infrared (IR), and particle radiation such as alpha (α) rays, beta (β) rays, neutrons, and plasma. The wavelength ranges of different regions of the electromagnetic spectrum are known to those skilled in the art. For completeness, the term “near-infrared” means radiation in the near-infrared region of the electromagnetic spectrum having wavelengths of 780 nm to 2500 nm, preferably 780 nm to 1600 nm. Typically, near-infrared radiation is applied at wavelengths of 780 nm to 1600 nm when using commercially available fiber lasers. The term "mid-infrared" refers to radiation in the mid-infrared region of the electromagnetic spectrum with wavelengths of 2500 nm to 50000 nm, preferably 9000 to 12000 nm, or 9300 nm, 9600 nm, 10200 nm, or 10600 nm, or more preferably 10600 nm. Typically, mid-infrared radiation is applied using a commercially available CO2 laser at wavelengths of 9000 to 12000 nm, for example, 9300 nm, 9600 nm, 10200 nm, or 10600 nm, preferably 10600 nm.

[0181] The radiation can be selected from ultraviolet (UV) rays with wavelengths of 10–400 nm, visible light with wavelengths of 400–700 nm, near-infrared (NIR) rays with wavelengths of 700–1600 nm, and infrared (IR) rays with wavelengths of 700 nm–1 mm.

[0182] The radiation is preferably selected from ultraviolet (UV) rays having wavelengths of 10 to 400 nm, infrared (IR) rays having wavelengths of 9000 to 12000 nm, infrared (IR) rays having wavelengths of 700 nm to 1 mm, and near-infrared (NIR) rays having wavelengths of 700 to 1600 nm, for example, 950 to 1100 nm. More preferably, the radiation is selected from ultraviolet (UV) rays having wavelengths of 10 to 400 nm and infrared (IR) rays having wavelengths of 9000 to 12000 nm, for example, 9300, 9600, 10200, or 10600 nm. More preferably, the radiation is selected from ultraviolet (UV) rays having wavelengths of 10 to 400 nm and infrared (IR) rays having wavelengths of 10600 nm.

[0183] It is preferable to apply infrared light having wavelengths of 9000 to 12000 nm, for example, 9300, 9600, 10300, or 10600 nm, using a CO2 laser.

[0184] If the composition according to the first or second aspect of the present invention includes a hot-melt adhesive, the composition is typically applied to or incorporated into a substrate, cooled to ambient temperature and solidified, and then radiation is applied to the composition.

[0185] Radiation may be applied to a composition according to a first or second aspect of the present invention by any suitable means. Preferably, radiation is applied to a composition according to a first or second aspect of the present invention using non-contact means or a radiation source. “Non-contact” means that, when irradiating with radiation, the means or radiation source does not come into contact with the composition according to a first or second aspect of the present invention or the substrate according to a third or fourth aspect of the present invention. Suitable means include laser excitation methods, which involve applying radiation to a composition according to a first or second aspect of the present invention using a laser source. Preferably, radiation is applied to a composition according to a first or second aspect of the present invention using a laser source. As used herein, terms such as “laser source” mean any suitable commercially available or non-commercially available laser source. Suitable examples include, but are not limited to, fiber lasers, fiber-coupled laser diode arrays, CO2 lasers, laser diode arrays, or direct diode lasers for providing radiation including near-infrared or mid-infrared radiation. Those skilled in the art will understand that radiation may be applied to a composition according to a first or second embodiment of the present invention at localized locations to selectively facilitate the formation of color, and therefore, marks or images, at these localized locations in the composition. These localized locations may overlap with each other. Those skilled in the art will also understand that radiation may be applied to a composition according to a first or second embodiment of the present invention for a suitable amount of time required to facilitate the formation of an image. Typically, the time required to irradiate with sufficient radiation depends on the means and method of application used for the application of radiation. For example, in one embodiment, radiation may be applied to the composition for a period of less than 120 seconds or less than 60 seconds, for example, less than 20 seconds, or even less than 10 seconds or less than 5 seconds.

[0186] When applied using a laser source, the applied radiation dose depends on the duration of application of the radiation, the power (wattage) of the means used to apply the radiation, and therefore the fluence (amount of energy irradiated per unit area) delivered by the laser source, e.g., J / cm². 2This can be controlled by changing the fluence (the amount of energy irradiated per unit area). For example, when a laser source is used to apply radiation, the fluence (the amount of energy irradiated per unit area) can affect the optical density of the resulting image. In the context of this invention, the fluence depends on the power (wattage) of the means used to apply the radiation and the time the radiation is applied to particularly localized locations on the substrate, which can be controlled by the scanning speed of the laser or the moving speed of the stage. By changing these two variables, the fluence can be altered. When the fluence is low (e.g., lower power and / or shorter irradiation time), the resulting image has lower optical density (low ODB), and when the fluence is high (e.g., higher power and / or longer irradiation time), the resulting image has higher optical density (high ODB) and greater contrast with the "background" or unimaged parts of the composition. In the context of this invention, the fluence value is 0.01 to 50 J / cm². 2 For example, 0.1~25 J / cm 2 Furthermore, 0.5~10 J / cm 2 It could be within the range of.

[0187] It is preferable that radiation be applied to a composition according to a first or second aspect of the present invention to localized locations on the composition in order to form a desired mark or image. Essentially, when radiation is applied, color is formed in the area of ​​the composition according to the first or second aspect of the present invention on the substrate to which the radiation is applied. Polyvalent metal oxyanions, or oxyacids, or hydrates thereof, form color through a reaction (chemical decomposition). A human and / or machine-readable mark or image is thus produced.

[0188] All references to specific chemical compounds in this specification should be interpreted as encompassing the compound itself, and, where appropriate, its derivatives, hydrates, solvates, complexes, isomers, and tautomers.

[0189] All features included herein may be combined with any of the above-described embodiments, and may be in any combination.

[0190] To better understand the present invention and to demonstrate how embodiments of the present invention can be actually carried out, the following experimental data are referenced as an example. [Examples]

[0191] [Example 1] A composition according to a first aspect of the present invention, comprising a polyvalent metal oxyanion or oxy acid, or hydrates thereof, a redox buffer, and an antioxidant, was prepared based on Table 1.

[0192] [Table 1]

[0193] [Example 2] A composition according to a second aspect of the present invention, comprising a polyvalent metal oxyanion or oxyacid, or hydrates thereof, and a redox buffer, was prepared based on Table 2.

[0194] [Table 2]

[0195] Comparative Example 1 Comparative compositions containing only polyvalent metal oxyanions, oxyacids, or hydrates thereof, and antioxidants, but without redox buffers, were prepared according to Table 3.

[0196] [Table 3]

[0197] Comparative Example 2 Comparative compositions containing only polyvalent metal oxyanions, oxyacids, or hydrates thereof, but without redox buffers, were prepared according to Table 4.

[0198] [Table 4]

[0199] Rating 1 The compositions of Examples 1 and 2, and Comparative Examples 1 and 2, were respectively coated onto a 50 μm white PET film at a coating weight of 4 gsm using an RK K controlled coating machine.

[0200] Radiation was applied to each composition using a 10.6 μm CO2 laser to form black marks.

[0201] Absolute ODB and ΔE measurements were obtained using an X-rite eXact spectrometer (averaging of 10 measurements was taken). ΔE measurements were obtained 1 hour and 24 hours after coating the PET film with the composition and applying radiation. Absolute ODB measurements were obtained 1 hour after coating the PET film with the composition and applying radiation. Samples were kept under ambient conditions. The results are shown in Table 5 below.

[0202] [Table 5]

[0203] Comparing Example 2 with Comparative Example 2, it can be seen that the presence of the redox buffer in Example 2 allows for a 43% increase in the optical density of the formed marks compared to Comparative Example 2.

[0204] Comparing Example 1 with Comparative Example 2, it can be seen that the presence of the redox buffer and antioxidant in Example 1 allows for a 50% increase in the optical density of the formed marks compared to Comparative Example 2.

[0205] Comparing Example 1 with Comparative Example 1, it can be seen that the presence of the redox buffer in Example 1 prevents the development of undesirable discoloration of the composition over time. The marks in Example 1 remain clear and distinct.

[0206] Rating 2 The compositions of Examples 1 and 2, and Comparative Examples 1 and 2, were respectively coated onto a 50 μm white PET film at a coating weight of 4 gsm using an RK K controlled coating machine.

[0207] Each composition on a PET film was coated with Novote SF716A + CA336 adhesive (adhesive layer) at a coat weight of 2 gsm using an RK K controlled coating machine.

[0208] Next, a 20 μm transparent OPP film was laminated onto the adhesive layer using a Cheminstruments LL-100 laboratory laminator to form a multilayer substrate structure.

[0209] Radiation was applied to the composition of each multilayer substrate structure using a 10.6 μm CO2 laser to form black marks.

[0210] Absolute ODB and ΔE measurements were obtained using an X-rite eXact spectrometer (averaging of 10 measurements was taken). ΔE measurements were obtained 1 hour after coating the PET film with the composition, forming a multilayer substrate structure, and applying radiation. Absolute ODB measurements were obtained 1 hour after coating the PET film with the composition, forming a multilayer substrate structure, and applying radiation. Samples were kept under ambient conditions. The results are shown in Table 6 below.

[0211] [Table 6]

[0212] Comparing Example 1 with Comparative Example 1, it can be seen that the presence of the redox buffer in Example 1 prevents the development of undesirable coloration in the composition. The mark in Example 1 is clearer and more distinct than the mark in Comparative Example 1.

[0213] Comparing Example 2 with Comparative Example 2, it can be seen that the presence of the redox buffer in Example 2 allows for a 52% increase in the optical density of the formed marks compared to Comparative Example 2.

[0214] [Example 3] A composition according to a second aspect of the present invention, comprising a polyvalent metal oxyanion or oxyacid, or hydrates thereof, and a redox buffer, was prepared based on Table 7.

[0215] [Table 7]

[0216] Comparative Example 3 Comparative compositions containing polyvalent metal oxyanions, oxyacids, or hydrates thereof, but without redox buffers, were prepared according to Table 8.

[0217] [Table 8]

[0218] Rating 3 The compositions of Example 3 and Comparative Example 3 were applied to a 50 μm transparent PET film at a coating weight of 6 gsm using an RK K controlled coating machine.

[0219] Radiation was applied to each composition using a 10.6 μm CO2 laser to form black marks.

[0220] Absolute ODB measurements were obtained using an X-rite eXact spectrometer (averaging of 10 measurements). Absolute ODB measurements were obtained 1 hour after coating the PET film with the composition and applying radiation. Samples were kept under ambient conditions. The results are shown in Table 9 below.

[0221] [Table 9]

[0222] When comparing Example 3 with Comparative Example 3, it can be seen that the presence of the redox buffer in Example 3 allows for a 20% increase in the optical density of the formed marks compared to Comparative Example 3.

[0223] Embodiment 1. (a) Polyvalent metal oxyanions, or oxyacids, or hydrates thereof; (b) Redox buffers; and (c) Antioxidants; A composition comprising, The redox buffer is a polyvalent metal salt. The aforementioned composition. 2. (a) polyvalent metal oxyanions, or oxyacids, or hydrates thereof; and (b) Redox buffers; A composition comprising, The redox buffer is a polyvalent metal salt selected from manganese or iron gluconate, polyvalent metal acetate, polyvalent metal carbonate, metal sulfate, and polyvalent metal oxide. The aforementioned composition. 3. The composition according to Embodiment 1 or 2, wherein the polyvalent metal oxyanion, or oxyacid, or hydrate thereof is an ammonium salt of a polyvalent metal oxyanion, preferably an ammonium salt of a molybdenum oxyanion, more preferably ammonium octamolybdate (AOM). 4. The composition according to Embodiment 1, or Embodiment 3 if dependent on Embodiment 1, wherein the redox buffer is selected from polyvalent metal salts of organic acids or inorganic acids, or polyvalent metal oxides, preferably selected from polyvalent metal salts of organic acids or inorganic acids, and more preferably from polyvalent metal salts of organic acids. 5. The composition according to Embodiment 1, or Embodiment 3 or 4 if dependent on Embodiment 1, wherein the redox buffer is selected from polyvalent metal carboxylates, polyvalent metal oxalates, polyvalent metal carbonates, and polyvalent metal sulfates, more preferably selected from polyvalent metal carboxylates, polyvalent metal oxalates, and polyvalent metal carbonates, and more preferably selected from polyvalent metal carboxylates. 6. The composition according to Embodiment 1, or Embodiments 3, 4, or 5, which are dependent on Embodiment 1, wherein the redox buffer is selected from manganese or iron organic or inorganic salts, or manganese oxide or iron oxide, preferably manganese or iron organic or inorganic salts, more preferably manganese or iron organic salts. 7. The composition according to Embodiment 6, wherein the redox buffer is selected from manganese or iron carboxylates, manganese or iron oxalates, manganese or iron carbonates, and manganese or iron sulfates, preferably selected from manganese or iron carboxylates, manganese or iron oxalates, and manganese or iron carbonates, and more preferably selected from manganese or iron carboxylates. 8. The composition according to Embodiment 6 or 7, wherein the redox buffer is selected from an organic or inorganic salt of manganese or manganese oxide, preferably from an organic or inorganic salt of manganese, and more preferably from an organic salt of manganese. 9. The composition according to any one of Embodiments 6 to 8, wherein the redox buffer is selected from manganese carboxylate, manganese oxalate, manganese carbonate, and manganese sulfate, preferably selected from manganese carboxylate, manganese oxalate, and manganese carbonate, and more preferably from manganese carboxylate. 10. The composition according to Embodiment 1, or any of Embodiments 3 to 5 if dependent on Embodiment 1, wherein the redox buffer is a metal carboxylate, preferably a metal gluconate salt. 11. The composition according to Embodiment 2, or Embodiment 3 if dependent on Embodiment 2, wherein the redox buffer is selected from manganese or iron gluconate, polyvalent metal acetate, polyvalent metal carbonate, and polyvalent metal sulfate, preferably selected from manganese or iron gluconate, polyvalent metal acetate, and polyvalent metal carbonate. 12. The composition according to Embodiment 2, or, if dependent on Embodiment 2, Embodiment 3 or 11, wherein the redox buffer is selected from manganese or iron gluconate, manganese or iron acetate, manganese or iron carbonate, manganese or iron sulfate, and manganese oxide or iron oxide, preferably selected from manganese or iron gluconate, manganese or iron acetate, manganese or iron carbonate, and more preferably selected from manganese or iron gluconate, manganese or iron acetate, and manganese or iron carbonate. 13. The composition according to any one of Embodiment 2, or Embodiment 3, 11, or 12, wherein the redox buffer is selected from manganese gluconate, manganese acetate, manganese carbonate, manganese sulfate, and manganese oxide, preferably selected from manganese gluconate, manganese acetate, manganese carbonate, and manganese sulfate, and more preferably selected from manganese gluconate, manganese acetate, and manganese carbonate. 14. The composition according to any one of Embodiments 1 to 13, wherein the redox buffer is manganese or iron gluconate, preferably manganese gluconate, and more preferably manganese(II) gluconate. 15. The composition according to Embodiment 1, or any of Embodiments 3 to 10 or 14 if dependent on Embodiment 1, wherein the antioxidant is selected from organic acids, organic alcohols, and esters of organic acids. 16. The composition according to Embodiment 15, Embodiment 1, or any of Embodiments 3 to 10 or 14 if dependent on Embodiment 1, wherein the antioxidant is an organic acid, preferably selected from tartaric acid, glycolic acid, and mandelic acid, and more preferably selected from tartaric acid and glycolic acid. 17. A composition according to Embodiment 1, or any of Embodiments 3 to 16 that are dependent thereon, wherein the ratio of the redox buffer to the antioxidant is 5:1 to 1:1. 18. A substrate comprising the composition described in any of Embodiments 1 to 17, either coated thereon or incorporated therein. 19. The substrate according to Embodiment 18, wherein the composition described in any of Embodiments 1 to 17 is incorporated therein in the multilayer substrate structure. 20. A composition or substrate according to any of Embodiments 1 to 19, wherein the composition displays a mark or image. twenty one. A method for forming a substrate according to Embodiment 18 or 19, comprising applying a composition according to any one of Embodiments 1 to 17 to a substrate material of a substrate or a multilayer substrate structure. twenty two. A method for displaying a mark or image on a substrate according to Embodiment 18 or 19, the method comprising, preferably using a laser source, exposing a composition to radiation to form a mark or image, preferably by applying radiation to localized locations on the composition to selectively produce the mark or image. twenty three. The use of a redox buffer in forming a mark or image with improved optical density on a substrate coated thereon, wherein the composition according to Embodiment 2, or any of Embodiments 11, 12, or 14 relating thereto, comprises a redox buffer and a polyvalent metal oxyanion or oxy acid, or hydrates thereof, wherein the redox buffer is a polyvalent metal salt selected from manganese or iron gluconate, polyvalent metal acetate, polyvalent metal carbonate, polyvalent metal sulfate, and polyvalent metal oxide. twenty four. The use of an oxidation-reduction buffer, wherein the use is for controlling reaction stability and for achieving the formation of a mark or image, preferably with improved optical density, on a substrate coated thereon, of the composition described in Embodiment 1 or any of Embodiments 3 to 16 that is dependent thereon.

Claims

1. (a) polyvalent metal oxyanions, or oxyacids, or hydrates thereof; and (b) Redox buffering agents; A composition comprising, The aforementioned oxidation-reduction buffer is a polyvalent metal salt selected from manganese or iron gluconate, polyvalent metal acetate, polyvalent metal carbonate, metal sulfate, and polyvalent metal oxide. The aforementioned composition.

2. The composition according to claim 1, wherein the redox buffer is selected from manganese or iron gluconate, polyvalent metal acetate, polyvalent metal carbonate, and polyvalent metal sulfate, and preferably selected from manganese or iron gluconate, polyvalent metal acetate, and polyvalent metal carbonate.

3. The composition according to claim 1 or 2, wherein the oxidation-reduction buffer is selected from manganese or iron gluconate, manganese or iron acetate, manganese or iron carbonate, manganese or iron sulfate, and manganese oxide or iron oxide, preferably selected from manganese or iron gluconate, manganese or iron acetate, manganese or iron carbonate, and manganese or iron sulfate, more preferably selected from manganese or iron gluconate, manganese or iron acetate, and manganese or iron carbonate.

4. The composition according to any one of claims 1 to 3, wherein the redox buffer is selected from manganese gluconate, manganese acetate, manganese carbonate, manganese sulfate, and manganese oxide, preferably selected from manganese gluconate, manganese acetate, manganese carbonate, and manganese sulfate, and more preferably selected from manganese gluconate, manganese acetate, and manganese carbonate.

5. (a) Polyvalent metal oxyanions, or oxyacids, or hydrates thereof; (b) Redox buffers; and (c) Antioxidants; A composition comprising, The aforementioned oxidation-reduction buffer is a polyvalent metal salt. The aforementioned composition.

6. The composition according to claim 5, wherein the oxidation-reduction buffer is selected from polyvalent metal salts of organic acids or inorganic acids, or polyvalent metal oxides, preferably from polyvalent metal salts of organic acids or inorganic acids, and more preferably from polyvalent metal salts of organic acids.

7. The composition according to claim 5 or 6, wherein the redox buffer is selected from polyvalent metal carboxylates, polyvalent metal oxalates, polyvalent metal carbonates, and polyvalent metal sulfates, more preferably selected from polyvalent metal carboxylates, polyvalent metal oxalates, and polyvalent metal carbonates, and more preferably selected from polyvalent metal carboxylates.

8. The composition according to any one of claims 5 to 7, wherein the oxidation-reduction buffer is selected from manganese or iron organic salts or inorganic salts, or manganese oxide or iron oxide, preferably manganese or iron organic salts or inorganic salts, more preferably manganese or iron organic salts.

9. The composition according to claim 8, wherein the oxidation-reduction buffer is selected from manganese or iron carboxylates, manganese or iron oxalates, manganese or iron carbonates, and manganese or iron sulfates, preferably selected from manganese or iron carboxylates, manganese or iron oxalates, and manganese or iron carbonates, and more preferably selected from manganese or iron carboxylates.

10. The composition according to claim 8 or 9, wherein the redox buffer is selected from an organic salt or inorganic salt of manganese or manganese oxide, preferably from an organic salt or inorganic salt of manganese, and more preferably from an organic salt of manganese.

11. The composition according to any one of claims 8 to 10, wherein the redox buffer is selected from manganese carboxylate, manganese oxalate, manganese carbonate, and manganese sulfate, preferably selected from manganese carboxylate, manganese oxalate, and manganese carbonate, and more preferably from manganese carboxylate.

12. The composition according to any one of claims 5 to 7, wherein the redox buffer is a polyvalent metal carboxylate, preferably a metal gluconate salt.

13. The composition according to any one of claims 5 to 12, wherein the antioxidant is selected from organic acids, organic alcohols, and esters of organic acids.

14. The composition according to any one of claims 5 to 13, wherein the antioxidant is an organic acid, preferably selected from tartaric acid, glycolic acid, and mandelic acid, and more preferably selected from tartaric acid and glycolic acid.

15. The composition according to any one of claims 5 to 14, wherein the ratio of the redox buffer to the antioxidant is 5:1 to 1:

1.

16. The composition according to any one of claims 5 to 15, wherein the antioxidant is present in an amount of 0.1 wt% or more, preferably 0.25 wt% or more, more preferably 0.5 wt% or more, more preferably 0.75 wt% or more, more preferably 1 wt% or more, and more preferably 2 wt% or more of the composition.

17. The composition according to any one of claims 5 to 16, wherein the antioxidant is present in an amount of 0.1 to 17.5 wt%, preferably 0.25 to 17.5 wt%, more preferably 0.5 to 17.5 wt%, more preferably 0.75 to 5 wt%, and more preferably 1 to 5 wt% of the composition.

18. The composition according to any one of claims 1 to 17, wherein the oxyanion or oxyacid of the polyvalent metal, or a hydrate thereof, is present in an amount of 1 to 70 wt%, preferably 5 to 40 wt%, more preferably 10 to 40 wt% of the composition.

19. The composition according to any one of claims 1 to 18, wherein the oxyanion or oxyacid of the polyvalent metal, or a hydrate thereof, is present in an amount of 1 wt% or more, preferably 5 wt% or more, and more preferably 10 wt% or more of the composition.

20. The composition according to any one of claims 1 to 19, wherein the oxidation-reduction buffer is present in an amount of 0.1 wt% or more, preferably 0.25 wt% or more, more preferably 0.5 wt% or more, more preferably 0.75 wt% or more, more preferably 1 wt% or more, and more preferably 2 wt% or more of the composition.

21. The composition according to any one of claims 1 to 20, wherein the oxidation-reduction buffer is present in an amount of 0.1 to 35 wt%, preferably 0.25 to 35 wt%, more preferably 0.5 to 35 wt%, more preferably 0.75 to 35 wt%, more preferably 1 to 10 wt%, and more preferably 2 to 10 wt% of the composition.

22. The composition according to any one of claims 1 to 21, wherein the polyvalent metal oxyanion, or oxyacid, or hydrate thereof is an ammonium salt of a polyvalent metal oxyanion, preferably an ammonium salt of a molybdenum oxyanion, more preferably ammonium octamolybdate (AOM).

23. The composition according to any one of claims 1 to 22, wherein the redox buffer is a manganese or iron gluconate, preferably a manganese gluconate, and more preferably manganese(II) gluconate.

24. A substrate comprising the composition according to any one of claims 1 to 23, either coated thereon or incorporated therein.

25. The substrate according to claim 24, wherein the composition according to any one of claims 1 to 23 is incorporated therein in a multilayer substrate structure.

26. The composition or substrate according to any one of claims 1 to 25, wherein the composition displays a mark or image.

27. The substrate according to claim 24 or 25, wherein the composition applied to or incorporated therein displays a mark or image.

28. A method for forming a substrate according to claim 24 or 25, comprising applying the composition according to any one of claims 1 to 23 to a substrate material of a substrate or a multilayer substrate structure.

29. A method for displaying a mark or image on a substrate according to claim 24 or 25, the method comprising, preferably using a laser source, exposing the composition to radiation to form a mark or image, preferably the radiation being applied to localized locations on the composition to selectively produce the mark or image.

30. The use of an oxidation-reduction buffer in which a composition according to any one of claims 1 to 4, or claims 18 to 23, if dependent thereon, is applied to or incorporated therein on a substrate, in which a mark or image with improved optical density is formed.

31. The use of an oxidation-reduction buffer, wherein the use controls reaction stability and achieves the formation of a mark or image, preferably with improved optical density, on a substrate coated thereon or incorporated therein, of any one of the compositions according to claims 5 to 17, or dependent thereon, claims 18 to 23.

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