FIELD

[0001] The present disclosure relates to compositions, systems, and methods. More particularly, the present disclosure relates to thermoreactive compositions that are specifically formulated for application to a cellulosic substrate, and which are capable of being activated following application to a cellulosic substrate by exposure to heat. Also provided are systems that include an applicator device and the thermoreactive compositions, and methods of permanently dying a cellulosic substrate comprising applying the thermoreactive compositions to the cellulosic substrate and applying heat to the cellulosic substrate.

BACKGROUND

[0002] Various means are known for applying a permanent marking on a substrate. Such means may include heat pens or other instruments that scorch a surface of a substrate. However, not all substrates lend themselves to being scorched with a heated instrument, or are inefficiently scorched by such means. Further, typical wood burning is difficult, challenging, and has a steep learning curve, requiring excessive investment in time and cost. Due to these challenges, traditional wood burning is often inaccessible to many.

SUMMARY

[0003] Embodiments of the compositions, systems, devices, methods, and kits provided herein relate to devices for applying a thermoreactive composition to a cellulosic substrate, the compositions contained therein, and methods of permanently dying cellulosic substrates using the compositions and devices.

[0004] Accordingly, some embodiments provided herein relate to compositions. In some embodiments, the compositions include water; copper sulfate; ammonium sulfate; red diketopyrrolopyrrole (DPP); and guar gum. In some embodiments, the copper sulfate is present in an amount ranging from about 10% to about 25% w/v. In some embodiments, the copper sulfate is present in an amount of about 17.5% w/v. In some embodiments, the ammonium sulfate is present in an amount ranging from about 0.1% to about 5% w/v. In some embodiments, the ammonium sulfate is present in an amount of about 1% w/v. In some embodiments, the red DPP is present in an amount ranging from about 0.01% to about 1% w/v. In some embodiments, the red DPP is present in an amount of about 0.1% w/v. In some embodiments, the guar gum is present in an amount ranging from about 0.05% to about 0.5% w/v. In some embodiments, the guar gum is present in an amount of about 0.2% w/v. In some embodiments, the compositions include ferric chloride and glucose syrup. In some embodiments, the ferric chloride is present in an amount ranging from about 0.1% to about 25% w/v. In some embodiments, the glucose syrup is present in an amount ranging from about 0.05% to about 10% w/v. In some embodiments, the compositions further include citric acid. In some embodiments, the citric acid is present in an amount ranging from about 2.5% to about 20% w/v. In some embodiments, the citric acid is present in an amount of about 10% w/v. In some embodiments, the composition includes copper sulfate present in an amount of about 17.5% w/v, ammonium sulfate present in an amount of about 0.1% w/v, red DPP present in an amount of about 0.1% w/v, guar gum present in an amount of about 0.2% w/v, citric acid present in an amount of about 10% w/v, and water in balance. In some embodiments, the compositions include ferric chloride in an amount of about 0.1% to about 25% w/v, glucose syrup in an amount of about 0.05% to about 10% w/v, and water in balance.

[0005] Some embodiments provided herein relate to compositions. In some embodiments, the compositions include a thermoreactive compound; and a thickening agent. In some embodiments, the compositions further include a pigment. In some embodiments, the thermoreactive compound is peroxide, acetyl peroxide, benzoyl peroxide, hydrogen peroxide, hydroperoxide, cyanogen, carbonate, peroxyacetate, peroxybenzoate, citric acid, acetic acid, lactic acid, formic acid, oxalic acid, maleic acid, peroxymaleic acid, ammonium sulfate, ammonium chloride, ammonium nitrate, ammonia, isopropyl alcohol, vitamin C, iodine, sodium bicarbonate, copper sulfate, magnesium sulfate, zinc chloride, ferric acetate, ferrous acetate, ferric chloride, ferrous chloride, or any combination thereof. In some embodiments, the thermoreactive compound is present in an amount ranging from about 0.1% to about 25% w/v. In some embodiments, the pigment is red diketopyrrolopyrrole (DPP), red lake, carbazole dioxazine crude pigment, azo, monoazo, disazo, naphthol AS, salt type (lakes), benzimidazolone, condensation, metal complex, isoindolinone, isoindoline and polycyclic phthalocyanine, quinacridone, perylene, perinone, diketopyrrolo pyrrole, thioindigo, anthraquinone, indanthrone, anthrapyrimidine, flavanthrone, pyranthrone, anthanthrone, dioxazine, triarylcarbonium, quinophthalone pigments, titanium dioxide, carbon black, zinc oxide, antimony oxide, and organic or inorganic UV opacifying pigments such as iron oxide, transparent red or yellow iron oxide, cadmium red, Congo red, alizarin red lake, carmine naccarat, phthalocyanine blue, or any combination thereof. In some embodiments, the pigment is present in an amount ranging from about 0.01% to about 1% w/v. In some embodiments, the thickening agent is guar gum, xantham gum, carrageenan gum, cellulose gum, glycerin, silicone dioxide, silica, glucose, maltose, oligosaccharides, glucose syrup, or combinations thereof. In some embodiments, the thickening agent is present in an amount ranging from about 0.05% to about 10% w/v.

[0006] Some embodiments provided herein relate to systems. In some embodiments, the systems include a thermoreactive composition and an applicator apparatus for dispensing the thermoreactive composition onto a surface of a cellulosic substrate. In some embodiments, the thermoreactive compositions includes a thermoreactive compound; and a thickening agent. In some embodiments, the thermoreactive compositions further include a pigment. In some embodiments, the applicator apparatus is a pen, a marker, a brush, a syringe, or a sprayer. In some embodiments, the applicator apparatus controls the flow rate of thermoreactive composition onto the cellulosic substrate. In some embodiments, the system further includes the cellulosic substrate. In some embodiments, the cellulosic substrate is paper, cardboard, wood, or engineered wood. In some embodiments, the engineered wood is plywood, veneer, particle board, or fiberboard. In some embodiments, the thermoreactive compound is peroxide, acetyl peroxide, benzoyl peroxide, hydrogen peroxide, hydroperoxide, cyanogen, carbonate, peroxyacetate, peroxybenzoate, citric acid, acetic acid, lactic acid, formic acid, oxalic acid, maleic acid, peroxymaleic acid, ammonium sulfate, ammonium chloride, ammonium nitrate, ammonia, isopropyl alcohol, vitamin C, iodine, sodium bicarbonate, copper sulfate, magnesium sulfate, zinc chloride, ferric acetate, ferrous acetate, ferric chloride, ferrous chloride, or any combination thereof. In some embodiments, the thermoreactive compound is present in an amount ranging from about 0.1% to about 25% w/v. In some embodiments, the pigment is red diketopyrrolopyrrole (DPP), red lake, carbazole dioxazine crude pigment, azo, monoazo, disazo, naphthol AS, salt type (lakes), benzimidazolone, condensation, metal complex, isoindolinone, isoindoline and polycyclic phthalocyanine, quinacridone, perylene, perinone, diketopyrrolo pyrrole, thioindigo, anthraquinone, indanthrone, anthrapyrimidine, flavanthrone, pyranthrone, anthanthrone, dioxazine, triarylcarbonium, quinophthalone pigments, titanium dioxide, carbon black, zinc oxide, antimony oxide, and organic or inorganic UV opacifying pigments such as iron oxide, transparent red or yellow iron oxide, cadmium red, Congo red, alizarin red lake, carmine naccarat, phthalocyanine blue, or any combination thereof. In some embodiments, the pigment is present in an amount ranging from about 0.01% to about 1% w/v. In some embodiments, the thickening agent is guar gum, xantham gum, carrageenan gum, cellulose gum, glycerin, silicone dioxide, silica, glucose, maltose, oligosaccharides, glucose syrup, or combinations thereof. In some embodiments, the thickening agent is present in an amount ranging from about 0.05% to about 10% w/v.

[0007] Some embodiments provided herein relate to methods of permanently dying a cellulosic substrate. In some embodiments, the methods include dispensing a thermoreactive composition to a surface of a cellulosic substrate, and applying heat to the dispensed thermoreactive composition, wherein the heat activates the thermoreactive composition to a temperature sufficient to permanently dye the surface of the cellulosic substrate. In some embodiments, the thermoreactive composition includes a thermoreactive compound; and a thickening agent. In some embodiments, the thermoreactive compositions further include a pigment. In some embodiments, applying heat comprises subjecting the cellulosic substrate to heat at a temperature less than about 250°F, such as 175°F, 180°F, 190°F, 200°F, 205°F, 210°F, 215°F, 220°F, 225°F, 230°F, 235°F, 240°F, 245°F, 250°F or less, or at a temperature within a range defined by any two of the aforementioned values. In some embodiments, the surface of the cellulosic substrate is permanently dyed at a location only where the thermoreactive composition is dispensed. In some embodiments, the thermoreactive compound is peroxide, acetyl peroxide, benzoyl peroxide, hydrogen peroxide, hydroperoxide, cyanogen, carbonate, peroxyacetate, peroxybenzoate, citric acid, acetic acid, lactic acid, formic acid, oxalic acid, maleic acid, peroxymaleic acid, ammonium sulfate, ammonium chloride, ammonium nitrate, ammonia, isopropyl alcohol, vitamin C, iodine, sodium bicarbonate, copper sulfate, magnesium sulfate, zinc chloride, ferric acetate, ferrous acetate, ferric chloride, ferrous chloride, or any combination thereof. In some embodiments, the thermoreactive compound is present in an amount ranging from about 10% to about 25% w/v. In some embodiments, the pigment is red diketopyrrolopyrrole (DPP), red lake, carbazole dioxazine crude pigment, azo, monoazo, disazo, naphthol AS, salt type (lakes), benzimidazolone, condensation, metal complex, isoindolinone, isoindoline and polycyclic phthalocyanine, quinacridone, perylene, perinone, diketopyrrolo pyrrole, thioindigo, anthraquinone, indanthrone, anthrapyrimidine, flavanthrone, pyranthrone, anthanthrone, dioxazine, triarylcarbonium, quinophthalone pigments, titanium dioxide, carbon black, zinc oxide, antimony oxide, and organic or inorganic UV opacifying pigments such as iron oxide, transparent red or yellow iron oxide, cadmium red, Congo red, alizarin red lake, carmine naccarat, phthalocyanine blue, or any combination thereof. In some embodiments, the pigment is present in an amount ranging from about 0.01% to about 1% w/v. In some embodiments, the thickening agent is guar gum, xantham gum, carrageenan gum, cellulose gum, glycerin, silicone dioxide, silica, glucose, maltose, oligosaccharides, glucose syrup, or combinations thereof. In some embodiments, the thickening agent is present in an amount ranging from about 0.05% to about 10% w/v.

BRIEF DESCRIPTION OF THE DRAWINGS

[0008] In addition to the features described above, additional features and variations will be readily apparent from the following descriptions of the drawings and exemplary embodiments. It is to be understood that these drawings depict typical embodiments, and are not intended to be limiting in scope.

[0009] FIG. 1 illustrates an example of an applicator apparatus.

[0010] FIG. 2 illustrates an example of an applicator tip of an applicator apparatus.

[0011] FIGs. 3 A and 3B depict schematic representations of an applicator apparatus depicting one or more composition reservoirs.

DETAILED DESCRIPTION

[0012] Although the invention is described in various exemplary embodiments and implementations as provided herein, it should be understood that the various features, aspects, and functionality described in one or more of the individual embodiments are not limited in their applicability to the particular embodiment with which they are described. Instead, they can be applied alone or in various combinations to one or more of the other embodiments of the invention, whether the embodiments are described or whether the features are presented as being a part of the described embodiment. The breadth and scope of the present invention should not be limited by any exemplary embodiments described or shown herein.

[0013] Embodiments provided herein relate to compositions, devices, systems, methods, and kits used for permanently dying a cellulosic substrate without the need to use traditional wood burning devices, such as heat pens or other heated instruments. Advantages of the compositions, devices, systems, methods, and kits provided herein include decreased cost compared to traditional wood burning devices. In addition, the compositions, devices, systems, methods, and kits provided herein result in ease in application to a cellulosic substrate, and ease in creation of dyed cellulosic substrates. In addition, the embodiments provided herein have lower danger or potential hazards as compared to traditional wood burning devices.

[0014] Some embodiments of the compositions relate to thermoreactive compositions that are applied to a cellulosic substrate, and that are activated upon being exposed to heat. The heat causes the compositions to react and permanently dye the cellulosic substrate only in those locations where the composition has been applied to the cellulosic substrate. Previous compositions have been disclosed that are thermoreactive compositions that generate scorch marks on a cellulosic substrate when applied to heat, including, for example, in PCT Application No. PCT/US2019/056990. However, the compositions provided herein differ from prior compositions, and have been shown to unexpectedly superior to prior compositions. In particular, the compositions provided herein generate improved and consistent dyed marks, are capable of doing so at a lower heat, and exhibit less bleeding through the cellulosic substrate to which the compositions are applied.

[0015] As used herein, the term “activate” has its ordinary meaning as understood in light of the specification, and refers to an increase in a chemical reaction of a compound. In some embodiments, activation is a result of energy applied to the compound in the form of heat, wherein a sufficient amount of heat results in activation, or chemical reaction, of the compound, thereby permanently dying the cellulosic substrate.

[0016] As used herein, the term “permanently dye” has its ordinary meaning as understood in light of the specification, and refers to a mark upon a cellulosic substrate that is irreversible, and is a result of activation of a thermoreactive compound upon application of sufficient energy in the form of heat. In some embodiments, permanently dyed marks resemble and/or appear to be identical to scorch marks. However, permanently dyed marks may differ from scorch marks in that the energy input in the form of heat is significantly lower than the amount of heat required to generate traditional scorch marks. For example, prior art compositions typically require heat in an amount of at least 350°F to generate scorch marks, such as at least 350°F, 375°F, 400°F, 425°F, or 450°F, or greater to generate scorch marks. However, the present compositions and methods are capable of permanently dying the substrate in a manner that resembles scorch marks at a temperature of less than 250°F, such as 175°F, 180°F, 190°F, 200°F, 205°F, 210°F, 215°F, 220°F, 225°F, 230°F, 235°F, 240°F, 245°F, 250°F or less, or at a temperature within a range defined by any two of the aforementioned values. A cellulosic substrate that is permanently dyed, as described herein, refers to permanently dying only in a location where the thermoreactive compounds are placed, such that a mark, design, pattern, decoration, ornament, or other intended branding is impressed upon the cellulosic substrate, wherein the other portions of the cellulosic substrate that does not include the thermoreactive compositions does not undergo any change (such as any permanent dye) or any damage.

Compositions

[0017] Some embodiments provided herein relate to compositions. In some embodiments, the compositions are configured for application to a cellulosic substrate, and upon exposure to heat, undergo a thermal reaction, generating sufficient heat to permanently dye the cellulosic substrate precisely in the location where the compositions are applied. In some embodiments, the compositions include a thermoreactive compound and a pigment and/or a thickening agent.

[0018] As used herein, the term “thermoreactive compound” has its ordinary meaning as understood in light of the specification and refers to a chemical compound that reacts (or activates) upon exposure to sufficient heat. A thermoreactive compound may include, for example, peroxides, acetyl peroxides, benzoyl peroxides, hydrogen peroxide, hydroperoxides, cyanogens, carbonates, peroxyacetates, peroxybenzoates, citric acid, acetic acid, lactic acid, formic acid, oxalic acid, maleic acid, peroxymaleic acid, ammonium sulfate, ammonium chloride, ammonium nitrate, ammonia, isopropyl alcohol, vitamin C, iodine, metal salts, including, for example, sodium bicarbonate, copper sulfate, magnesium sulfate, zinc chloride, ferric acetate, ferrous acetate, ferric chloride, ferrous chloride, or any combination of any of the aforementioned compounds. In some embodiments, the thermoreactive compound, or a combination of such compounds, are selected based on desirable properties, which may include, for example compatibility of the compounds in the compositions provided herein, activation energy, including a lowest possible activation energy sufficient to permanently dye a cellulosic substrate upon exposure to a minimum amount of heat, and avoiding compounds that are capable of generating noxious or toxic byproducts during use.

[0019] The thermoreactive compounds may be present in the compositions in an amount ranging from about 0.5% w/v to about 75% w/v, such as 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, or 75% w/v, or in an amount within a range defined by any two of the aforementioned values. In some embodiments, the amount of thermoreactive compounds present in the compositions is selected based on the type of thermoreactive compound(s) selected for use in the compositions, the degree (darkness) of permanently dying intended with the compositions, or the type of other components present in the compositions.

[0020] In some embodiments, the thermoreactive compounds are present in an amount to permanently dye a surface of a cellulosic substrate to a sufficient degree. For example, a surface of a cellulosic substrate may be permanently dyed sufficient to create a visual indication of a dye mark. The dye mark may be a dark or a light dye mark, where a dark dye mark is a dye mark that has a high degree of contrast in color compared to the color of the surface of the cellulosic substrate, and wherein a light dye mark is a dye mark that has a low degree of contrast in color compared to the color of the surface of the cellulosic substrate.

[0021] In some embodiments, the thermoreactive compound or combination of thermoreactive compounds generates heat sufficient to permanently dye a surface of a cellulosic substrate when exposed to heat at a temperature of less than 250°F, such as 175°F, 180°F, 190°F, 200°F, 205°F, 210°F, 215°F, 220°F, 225°F, 230°F, 235°F, 240°F, 245°F, 250°F or less, or at a temperature within a range defined by any two of the aforementioned values.

[0022] As used herein, the term “pigment” has its ordinary meaning as understood in light of the specification, and refers to a compound that is capable of providing a composition to which the pigment is added with a visual characteristic. For example, a pigment renders a composition visually perceptible, whereas the composition without the pigment would otherwise not be visually perceptible, or would be less visually perceptible. Example pigments include, but are not limited to, carbazole dioxazine crude pigment, azo, monoazo, disazo, naphthol AS, salt type (lakes), red lake, benzimidazolone, condensation, metal complex, isoindolinone, isoindoline and polycyclic phthalocyanine, quinacridone, perylene, perinone, diketopyrrolo pyrrole, thioindigo, anthraquinone, indanthrone, anthrapyrimidine, flavanthrone, pyranthrone, anthanthrone, dioxazine, triarylcarbonium, quinophthalone pigments, red diketopyrrolopyrrole (DPP), titanium dioxide, carbon black, zinc oxide, antimony oxide, and organic or inorganic UV opacifying pigments such as iron oxide, transparent red or yellow iron oxide, cadmium red, Congo red, alizarin red lake, carmine naccarat, phthalocyanine blue, and mixtures thereof. In some embodiments, the pigment is a pigment that does not interfere with the thermoreactive components of the composition. For example, in some embodiments, the pigment does not interfere with the ability of a thermoreactive compound to permanently dye a cellulosic substrate surface, does not interfere with the temperature at which a cellulosic substrate is permanently dyed, does not interfere with the viscosity of the composition, or does not interfere in any other material aspects with the composition. Thus, the pigment may be referred to as an inert substance that is provided in the composition for the purpose of visualizing the composition during application of the composition onto a cellulosic substrate.

[0023] In some embodiments, the pigment is present in the compositions in an amount ranging from about 0.01% w/v to about 10% w/v, such as 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 6, 7, 8, 9, or 10% w/v, or in an amount within a range defined by any two of the aforementioned values. In some embodiments, the amount of pigment is selected based on the type of pigment that is used, the visual intensity of the pigment selected, or the degree of visualization desired in a particular composition.

[0024] As used herein, the term “thickening agent” has its ordinary meaning as understood in light of the specification and refers to a compound that modulates the viscosity of the compositions. A thickening agent may include one or more compounds, which may act in concert to modulate the viscosity of the compositions. In some embodiments, the viscosity of the compositions provided herein is selected and specially tuned in order to: function within the dispensing apparatus that is used, more precisely apply the compositions to the cellulosic substrate, prevent excessive bleeding of the compositions on the cellulosic substrate, or otherwise increase the usability of the compositions. In some applications, a composition having lower viscosity is desirable, for example when dispensing the compositions through an apparatus that requires low viscosity compositions. In some embodiments, a composition having higher viscosity is desirable, for example, when precisely applying the compositions to a cellulosic substrate in a manner to avoid excessive bleeding on the cellulosic substrate. In some embodiments, certain substrates may be more prone to bleeding than other types of substrates, and increased viscosity may prevent bleeding of the compositions in such substrates.

[0025] Examples of thickening agents, include, for example, guar gum, xantham gum, carrageenan gum, cellulose gum, glycerin, silicone dioxide, silica, glucose, maltose, oligosaccharides, glucose syrup, or combinations thereof. In some embodiments, the thickening agent is a thickening agent that does not interfere with the thermoreactive components of the composition. For example, in some embodiments, the thickening agent does not interfere with the ability of a thermoreactive compound to permanently dye a cellulosic substrate surface, does not interfere with the temperature at which a cellulosic substrate is permanently dyed, does not interfere with the viscosity of the composition, or does not interfere in any other material aspects with the composition. Thus, the thickening agent may be referred to as an inert substance that is provided in the composition for the purpose of modulating the viscosity of the composition.

[0026] In some embodiments, the thickening agent is present in the compositions in an amount ranging from about 0.01% w/v to about 10% w/v, such as 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 6, 7, 8, 9, or 10% w/v, or in an amount within a range defined by any two of the aforementioned values. In some embodiments, the amount of thickening is selected based on the type of thickening agent that is used, the compatibility of the thickening agent in the compositions and with the thermoreactive compounds, or the degree of viscosity desired in a particular composition.

[0027] In some embodiments, the compositions provided herein have a viscosity ranging from about 1 mPa»s to about 5000 mPa»s, such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 50, 100, 150, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, or 5000 mPa»s. The degree of viscosity is selected depending on the applicator apparatus that is used to dispense the compositions, the degree of bleeding to be avoided, or the type of substrate being used, wherein different substrates tolerate a liquid composition in terms of the degree of bleeding that occurs when the liquid composition is applied to the substrate.

[0028] In some embodiments, the compositions provided herein include additional components for further improvement of application to a substrate, improved thermal reactivity, improved dye marking, improved visualization, improved viscosity, or the improvement of other characteristics of the compositions. Such additional components may include, for example, water, salts, sugars, lipids, alcohols, or other components.

[0029] As noted previously, prior compositions, such as those described and set forth in PCT/US2019/056990 included components that differ from those set forth herein. The resulting compositions in the prior art are ineffective at generating consistent permanently dye marks on a surface of a cellulosic substrate. Further, excess heat of at least 350°F is required to cause thermal reactivity of prior compositions. In contrast, the present compositions require heat of less than 250°F, such as 175°F, 180°F, 190°F, 200°F, 205°F, 210°F, 215°F, 220°F, 225°F, 230°F, 235°F, 240°F, 245°F, 250°F or less, or at a temperature within a range defined by any two of the aforementioned values. The requirement for less heat results in an improved composition that generates more consistent permanently dye marks without compromising the substrate or the surface of the substrate, while concomitantly generating distinct visual dye marks. In addition, the compositions provided herein have improved dispensing characteristics, due to the components described herein that are present in the compositions, resulting in less bleeding, improved application to a surface of a cellulosic substrate, resulting in improved utility. Finally, in prior art applications, wood burning results in inconsistent darkening of the wood depending on the type of wood. However, the compositions provided herein result in consistent darkening (permanently dying) different types of cellulosic substrates, including different types of materials within a single substrate (such as wood rings present in sapwood or heartwood), thereby providing consistent results in permanent dying.

Applicator Apparatus

[0030] Some embodiments provided herein relate to applicator apparatuses that are configured to apply the thermoreactive compositions described herein to a surface of a cellulosic substrate. In some embodiments, the applicator apparatus is a pen, a marker, a brush, a syringe, or a sprayer. In some embodiments, the pen is a ballpoint pen, a felt tip pen, a brush pen, a paint pen, a fountain pen, a rollerball pen, a gel pen, a stylus pen, a novelty pen, a pen especially configured to apply or dispense the thermoreactive compositions, or other pen. In some embodiments, the marker is a felt tip marker, a bullet tip marker, a brush tip marker, a chisel tip marker, a calligraphy marker, a brush marker, a marker especially configured to apply or dispense the thermoreactive compositions, or other marker. In some embodiments, the brush is a round brush, a pointed round brush, a flat brush, a bright brush, a filbert brush, an angular flat brush, a fan brush, a detail round brush, a brush especially configured to apply or dispense the thermoreactive compositions, or other brush. In some embodiments, the tip of the pen, marker, brush, or syringe, is a fine tip, medium tip, or broad tip. In some embodiments, the applicator apparatus includes more than one tip, for example a first tip on a first end and a second tip on a second end. In some embodiments, the first tip and the second tip are different types of tips.

[0031] Figure 1 illustrates an example applicator apparatus. As shown in Figure 1, the applicator apparatus 100 is an elongate member that includes a thermoreactive composition reservoir 105 that is configured to hold a volume of thermoreactive composition. The volume of thermoreactive composition in the reservoir ranges from an amount of about 0.1 mL to about 10 mL, such as 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, or 10 mL, or a volume within a range defined by any two of the aforementioned values. As shown in Figure 1, the applicator apparatus 100 may include one or more tips, including a first tip 110 and a second tip 120. In the embodiment of Figure 1, the first tip 110 is a bullet tip, and the second tip 120 is a brush tip. Figure 1 also depicts a first cap 111 that cover the first tip 110, and a second cap 121 that is coupled to the second tip 120. In particular, the second cap 121 acts as a handle to the brush tip, which can be immersed into the thermoreactive composition reservoir 105, thereby saturating the brush tip, which can be removed from the thermoreactive reservoir 105 by pulling on the second cap 121. Figure 1 also depicts a spring and valve system 115 couple to the first tip 110.

[0032] As shown in Figure 2, the spring and valve system 215 is implemented to allow flow of the thermoreactive composition from the reservoir into the tip 210, thereby saturating the first tip 210. The system includes a valve 213 and a spring 212. Upon depressing the tip 210, the valve 213 opens and pushes against the spring 212, thereby allowing the thermoreactive composition to flow into the tip 210.

[0033] In some embodiments, the applicator apparatuses include a reservoir that is configured to hold the thermoreactive compositions described herein. In some embodiments, the thermoreactive compositions flow from the reservoir, through a tip of the applicator apparatus, to the substrate. In some embodiments, the tip of the applicator apparatus is coupled to a valve and/or spring, such that upon placement of the tip of the applicator apparatus to the surface of the substrate, sufficient pressure is generated, causing the valve and/or spring to release thermoreactive composition from the reservoir, which flows through the tip to the surface of the substrate.

[0034] Figures 3A and 3B depict exemplary schematic representations of applicator apparatuses. In Figure 3A, an applicator apparatus 300 is shown having a first tip 310 and a second tip 320, and including a single composition reservoir 305. Both the first tip 310 and the second tip 320 access the composition reservoir 305. In some embodiments, such as that depicted in Figure 3B, more than one composition reservoirs are present. As shown in Figure 3B, the applicator apparatus 301 includes a first tip 311 and a second tip 321, which each separately access different composition reservoirs. The first tip 311 access a first composition reservoir 306, and the second tip 321 accesses a second composition reservoir 307. In some embodiments, the first composition reservoir 306 and the second composition reservoir 307 hold the same thermoreactive composition. In some embodiments, the first composition reservoir 306 and the second composition reservoir 307 hold different thermoreactive compositions. For example, the reservoirs may include differences in thermoreactive compound, pigment, and/or thickening agent, and/or concentrations thereof. In some embodiments, the composition in the separate reservoirs is determined based on the type of applicator tip, based on variability in application to a cellulosic substrate, and/or based on variability in dying characteristics. In some embodiments, the volume of the first composition reservoir 306 is the same as the volume of the second composition reservoir 307. In some embodiments, the volume of the first composition reservoir 306 is different from the volume of the second composition reservoir 307. The number of reservoirs with an applicator apparatus, the volume of each reservoir, and the type of composition within each reservoir may be specifically configured to provide desired properties of a particular applicator apparatus, and may therefore include any number of variations.

[0035] In some embodiments, the applicator apparatuses do not include a reservoir. In such embodiments, a tip of the applicator apparatus is immersed or contacted with the thermoreactive composition, which may be contained within a separate container, thereby coating and/or soaking the tip with the thermoreactive composition. The coated and/or soaked tip may then contact a surface of a cellulosic substrate, thereby dispensing the thermoreactive compositions to a surface of a substrate using the applicator apparatus.

[0036] In some embodiments, the applicator apparatus is a sprayer, configured to spray thermoreactive composition to a surface of a cellulosic substrate. In some embodiments, the sprayer is a spray gun, a spray bottle, a sprayer especially configured to spray the thermoreactive compositions, or other sprayer. In some embodiments, the sprayer includes a tip or a nozzle sufficient to finely control the spray of the thermoreactive compositions.

Systems

[0037] Some embodiments provided herein relate to systems for permanently dying a surface of a cellulosic substrate. In some embodiments, the systems include any of the compositions described herein and any of the applicator apparatuses described herein. In some embodiments, the applicator apparatuses include the thermoreactive compositions, such that the thermoreactive compositions are integrated into the applicator apparatuses. In some embodiments, the systems include the applicator apparatuses separate from the thermoreactive compositions, wherein a user implements the thermoreactive compositions into the applicator apparatuses, and/or contacts the applicator apparatus with thermoreactive compositions. In some embodiments, the systems include a container having reserve thermoreactive compositions, such that upon depletion of the thermoreactive compositions that are contained and/or implemented within the applicator apparatuses, a user can refill the applicator apparatus with the reserve thermoreactive compositions.

[0038] In some embodiments, the systems further include one or more cellulosic substrates for application of the thermoreactive compositions thereon. In some embodiments, the cellulosic substrate is any substrate capable of being permanently dyed by a thermal reaction due to the thermoreactive compositions. A cellulosic substrate is a substrate that is typically used in wood burning type applications, and is composed of a material that includes cellulose, or is manufactured to be similar to such materials. Such cellulosic substrates include, for example, paper, cardboard, wood, engineered wood, or wood products. In some embodiments, the paper is any type of paper, including, for example, art paper, canvas paper, transfer paper, printer paper, cardstock, construction paper, tissue paper, or origami paper. In some embodiments, the cardboard is any type of cardboard, including, for example, corrugated fiberboard, paperboard, carton paper, or mat board. In some embodiments, the wood is any type of wood, including, for example, balsa wood, pine, basswood, birch, oak, poplar, pallet wood, beech, cherry, maple, pacific albus, alder, hickory, apple, ash, bamboo, blackthorn, cedar, cypress, douglas fir, ebony, elder, elm, eucalyptus, hawthorn, hazel, heartwood, hemlock, holly, hornbeam, horse chestnut, larch, lime, pear, plane, redwood, rowan, sapwood, spruce, sweet chestnut, sycamore, walnut, willow, yew, palm, aspen, sourwood, light craft woods, mahogany, or teak. In some embodiments, the engineered wood is any type of engineered wood, including, for example, plywood, veneer, particle board, or fiberboard. With reference to substrates throughout this application, substrates include those intended or desirable for use in wood burning applications, and does not include metal or plastic substrates.

[0039] In some embodiments, the systems further include a heat source. In some embodiments, the heat source is capable of causing the thermoreactive compositions to undergo a thermal reaction, thereby permanently dying the surface of the substrate only where the thermoreactive compositions are applied. In some embodiments, the heat source is a heat gun, an oven, a blow dryer, or an open flame source (such as a match, candle, lighter, or blow torch). In some embodiments, the heat source is capable of reaching a temperature of less than 250°F, such as 175°F, 180°F, 190°F, 200°F, 205°F, 210°F, 215°F, 220°F, 225°F, 230°F, 235°F, 240°F, 245°F, 250°F or less, or at a temperature within a range defined by any two of the aforementioned values. [0040] In some embodiments, the systems further include instructions for permanently dying a surface of a substrate. In some embodiments, the instructions include the methods or portions of the methods described herein elsewhere.

Methods of Use

[0041] Some embodiments provided herein relate to methods of permanently dying a substrate. In some embodiments, the methods include dispensing any of the thermoreactive compositions as described herein onto a surface of a substrate, and applying heat to the surface of a substrate at a temperature sufficient to cause a thermal reaction of the thermoreactive composition, thereby permanently dying the surface of the substrate only where the thermoreactive composition is applied. In some embodiments, the temperature sufficient to cause a thermal reaction is a temperature of less than 250°F, such as 175°F, 180°F, 190°F, 200°F, 205°F, 210°F, 215°F, 220°F, 225°F, 230°F, 235°F, 240°F, 245°F, 250°F or less, or at a temperature within a range defined by any two of the aforementioned values.

[0042] In some embodiments, applying heat to the surface includes using a heat source to direct heat to the surface of the substrate. A heat source may include any heat source capable of heating the substrate, the surface of the substrate, or the thermoreactive composition applied to the substrate to a temperature of less than 250°F, such as 175°F, 180°F, 190°F, 200°F, 205°F, 210°F, 215°F, 220°F, 225°F, 230°F, 235°F, 240°F, 245°F, 250°F or less, or at a temperature within a range defined by any two of the aforementioned values.

EXAMPLES

[0043] Embodiments of the present invention are further defined in the following Examples. It should be understood that these Examples are given by way of illustration only. From the above discussion and these Examples, one skilled in the art can ascertain the essential characteristics of this invention, and without departing from the spirit and scope thereof, can make various changes and modifications of the embodiments of the invention to adapt it to various usages and conditions. Thus, various modifications of the embodiments of the invention, in addition to those shown and described herein, will be apparent to those skilled in the art from the foregoing description. Such modifications are also intended to fall within the scope of the appended claims. The disclosure of each reference set forth herein is incorporated herein by reference in its entirety, and for the disclosure referenced herein. Example 1 Thermoreactive Composition

[0044] The following example provides exemplary thermoreactive compositions.

[0045] Thermoreactive compositions were prepared having desirable characteristics that include sufficient viscosity for implementation in an applicator device and application to a substrate in a precise and defined manner, visibility such that the composition can be visually recognized upon application to a substrate, sensitive reactivity to heat, low bleeding on substrates, and high stability. In addition to these characteristics, the components of the composition must be compatible in a formulation, and enable the composition to properly function.

[0046] Accordingly, a thermoreactive composition was prepared as set forth in

Table 1.

Table 1: Thermoreactive Composition

[0047] The formulations described in Example 1 exhibit surprising and unexpected characteristics. In particular, it was unexpectedly discovered that the composition as set forth in Table 1 is capable of undergoing a thermal reaction at a lower temperature than is required for prior art compositions. Specifically, the composition set forth in Table 1 was capable of undergoing a thermal reaction at a temperature of 250°F. As a result, a lower heat is required to permanently dye the surface of the substrate, resulting in better control in dying the surface of the substrate, with a simultaneous decrease in damage to the surface of the substrate that occurs as a result of excess heat.

[0048] In addition, the composition of Table 1 is capable of being applied to a surface of a substrate in more controlled manner as compared to prior art compositions, due to improved viscosity, decreased bleeding, and improved surface dynamics of the compositions on the substrates, thereby resulting in a more controlled application of the compositions on the surface of the substrate, and more consistent dye marks.

[0049] A second thermoreactive composition was prepared as set forth in Table 2.

Table 2: Thermoreactive Composition

[0050] The formulation described in Table 2 was optionally formulated with additional components, such as a pigment, or with different viscosity agents. In particular, ferric chloride was selected due to its hygroscopic characteristics, thereby selected to prevent wicking and/or bleeding of the formulation when applied to a substrate. However, it was entirely unexpected and surprisingly discovered that the formulation described in Table 2 resulted in superior formulations having lower activation temperatures compared to other formulations. In particular, permanent dying was observed at temperatures of less than 250°F, specifically at a temperature of about 220°F or less. As a result, a significantly lower heat is required to permanently dye the surface of the substrate, resulting in better control in dying the surface of the substrate, with a simultaneous decrease in damage to the surface of the substrate that occurs as a result of excess heat. In contrast, traditional formulations used to scorch or permanently dye a substrate require a temperature of at least 400°F, for example temperatures of about 430°F. In addition, the formulation had improved characteristics in decreasing or minimizing bleeding. Furthermore, it was unexpectedly discovered that the compositions of Table 2 resulted in consistent permanent dying across variations in the substrates (such as across wood rings present within the substrates). These results were unexpected and could not have been predicted by those of skill in the art.

Example 2

Preparing an Applicator Device

[0051] The following example demonstrates preparation of a system that includes the thermoreactive compositions described herein implemented into an applicator apparatus.

[0052] Thermoreactive compositions were prepared as set forth in Example 1. The thermoreactive compositions were implemented into an applicator apparatus as shown in Figure 1. The applicator apparatus included a reservoir, into which the thermoreactive compositions was dispensed. The applicator apparatus includes a tip located at each end of the applicator apparatus. One tip was a bullet tip marker and one tip was a brush tip. The bullet tip was implemented into a valve and spring system as shown in Figure 2, such that upon depressing the bullet tip, the spring is depressed, opening the valve into the reservoir, causing thermoreactive composition to flow from the reservoir into the bullet tip, thereby saturating the bullet tip with thermoreactive composition, which was then contacted onto the surface of the substrate, and thermoreactive composition applied thereto. The brush tip was implemented into the applicator apparatus on the opposing end of the applicator apparatus from the bullet tip. The brush tip was configured in such a way as to be immersed into the reservoir containing the thermoreactive compositions, thereby saturating the brush tip with thermoreactive composition, which was then contacted onto the surface of the substrate, and thermoreactive composition applied thereto.

[0053] Those of skill in the art will recognize and appreciate that other implementations of the applicator apparatus may be achieved, and that the example described herein is provided for illustration.

Example 3

Applying Thermoreactive Compositions to a Substrate

[0054] The following example demonstrates application of the thermoreactive compositions described herein to a substrate.

[0055] The applicator apparatus as described in Example 2 was used to apply any of the thermoreactive compositions of Example 1 to the surface of a pine wood substrate. The bullet tip of the applicator apparatus was pressed onto a surface of a substrate to open the valve in the applicator apparatus, thereby allowing thermoreactive composition to flow into and saturate the bullet tip. The user then applied thermoreactive composition to the surface of the substrate in a controlled and specific design. In addition to applying thermoreactive composition through the bullet tip, the user saturated the brush tip with thermoreactive composition, and contacted the brush tip to the surface of the substrate in a controlled manner to generate a specific design. Example 4 Permanently Dying a Substrate

[0056] The following example demonstrate a method of permanently dying a substrate using the thermoreactive compositions described herein.

[0057] Following application of any of the thermoreactive compositions to the substrate, as performed in Example 3, the substrate was exposed to a heat source using a heat gun. The heat gun reached a temperature of less than 250°F, upon which the thermoreactive compositions underwent a thermal reaction, causing the surface of the substrate to permanently dye only in the area where the thermoreactive composition was applied. Varying degrees of dye marks were achieved by exposing the surface of the substrate or portions thereof to lesser or greater temperatures, depending on the degree of dye desired in any particular region.

[0058] With respect to the use of substantially any plural or singular terms herein, those having skill in the art can translate from the plural to the singular or from the singular to the plural as is appropriate to the context or application. The various singular/plural permutations may be expressly set forth herein for sake of clarity.

[0059] The embodiments illustratively described herein suitably may be practiced in the absence of any element(s) not specifically disclosed herein. Thus, for example, in each instance herein any of the terms “comprising,” “consisting essentially of,” and “consisting of’ may be replaced with either of the other two terms. The terms and expressions which have been employed are used as terms of description and not of limitation, and use of such terms and expressions do not exclude any equivalents of the features shown and described or portions thereof, and various modifications are possible within the scope of the technology claimed. The term “a” or “an” can refer to one of or a plurality of the elements it modifies (e.g., “a reagent” can mean one or more reagents) unless it is contextually clear either one of the elements or more than one of the elements is described.

[0060] The term “about” as used herein refers to a value within 10% of the underlying parameter (i.e., plus or minus 10%), and use of the term “about” at the beginning of a string of values modifies each of the values (i.e., “about 1, 2 and 3” refers to about 1, about 2 and about 3). For example, a weight of “about 100 grams” can include weights between 90 grams and 110 grams. Further, when a listing of values is described herein (e.g., about 50%, 60%, 70%, 80%, 85% or 86%) the listing includes all intermediate and fractional values thereof (e.g., 54%, 85.4%). Thus, it should be understood that although the present technology has been specifically disclosed by representative embodiments and optional features, modification and variation of the concepts herein disclosed may be resorted to by those skilled in the art, and such modifications and variations are considered within the scope of the embodiments.

[0061] In addition, where features or aspects of the disclosure are described in terms of Markush groups, those skilled in the art will recognize that the disclosure is also thereby described in terms of any individual member or subgroup of members of the Markush group.

[0062] As will be understood by one skilled in the art, for any and all purposes, such as in terms of providing a written description, all ranges disclosed herein also encompass any and all possible sub-ranges and combinations of sub-ranges thereof. Any listed range can be easily recognized as sufficiently describing and enabling the same range being broken down into at least equal halves, thirds, quarters, fifths, tenths, etc. As a nonlimiting example, each range discussed herein can be readily broken down into a lower third, middle third and upper third, etc. As will also be understood by one skilled in the art all language such as “up to,” “at least,” “greater than,” “less than,” and the like include the number recited and refer to ranges which can be subsequently broken down into sub-ranges as discussed above. Finally, as will be understood by one skilled in the art, a range includes each individual member. Thus, for example, a group having 1-3 articles refers to groups having 1, 2, or 3 articles. Similarly, a group having 1-5 articles refers to groups having 1, 2, 3, 4, or 5 articles, and so forth.

[0063] The entirety of each patent, patent application, publication and document referenced herein hereby is incorporated by reference. Citation of the above patents, patent applications, publications, and documents is not an admission that any of the foregoing is pertinent prior art, nor does it constitute any admission as to the contents or date of these publications or documents. Their citation is not an indication of a search for relevant disclosures. All statements regarding the date(s) or contents of the documents are based on available information and is not an admission as to their accuracy or correctness.

[0064] The previous description of the disclosed implementations is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these implementations will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other implementations without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the implementations shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.