Ink composition and ink jet printing process

Description

1 / 45 INK COMPOSITION AND INKJET PRINTING PROCESS FIELD OF THE INVENTION

[0001] The present invention relates to an ink composition with improved storage stability and to an inkjet printing process employing such ink composition.

[0002] More particularly, the present invention relates to a water-based ink composition comprising a pigment, a binder, a crosslinking agent and a polyol and to an inkjet printing process that avoids pre- and post-treatment steps. STATE OF THE ART

[0003] Inkjet printing is a non-impact printing method that uses electronic signals to control and direct droplets or a stream of ink to be deposited onto media. This technique has become a popular way to record images on various media. Some of the reasons include low printer noise, variable content recording, high-speed recording capability, and multicolor recording.

[0004] As the popularity of inkjet printing increases, so do the types of uses, generating demand for new ink compositions and printing substrates.

[0005] Such a substrate can be textile. Textile printing can have various applications, including the creation of signs, banners, artwork, clothing, wall coverings, window curtains, upholstery, pillows, blankets, flags, bags, garments, etc.

[0006] Additionally, there is a trend towards replacing dye-based inks with pigment-based inks. Pigment-based inks promise to be compatible with different fibers, both natural fibers, such as cellulose-based fibers, for example, cotton, and synthetic fibers, such as polyester and polyamide. Pigment-based inks also allow printing on fabrics. Petition 870250086035, dated 09 / 23 / 2025, page 8 / 140 2 / 45 of mixed fiber.

[0007] Water-based pigmented inkjet inks prepared with soluble resin binders are used for printing on a wide variety of substrates. The pigment-based dyes used in these inks are much more resistant to fading than dye-based dyes and are thus suitable for applications requiring exposure to direct sunlight.

[0008] However, most fabrics have a porous nature. When printing with pigment inks on different fabrics, the pigments penetrate deeper into the fabric, resulting in loss of gamut and difficulty in obtaining high-density patterns. Additionally, obtaining pigmented images with desirable opacity and good wash durability, for example, can be challenging, partly due to the use of fabrics and also due to fibrillation, for example, fuzzy fibers coming off the fabric surface. Another disadvantage of inkjet printing with pigment ink is that inkjet-printed fabrics are particularly susceptible to color removal by abrasion and thus have low durability or fastness.

[0009] To solve the aforementioned problems, the state of the art has suggested applying various pre- and post-treatments to the textile substrate. Pre-treatment solutions comprising cationic surfactants, water-soluble dispersing agents with crosslinking properties, urethane resins, and crosslinking agents are disclosed, for example, in documents US2016 / 177112, WO2006 / 00384, US2014 / 0186533, US2019 / 367760, WO2020 / 005253, WO2022 / 173425. Post-treatment solutions comprising cationic polymers or copolymers, surfactants, silicone derivatives, oils, waxes, plasticizers, fabric softeners, are disclosed, for example, in documents WO2018 / 163966A1, WO2000 / 056972A1, US2002 / 0130939 and US2003 / 160851.

[0010] Pre- and post-treatments are disadvantageous from a productivity standpoint because they lead to an increase in the number of steps and Petition 870250086035, dated 09 / 23 / 2025, page 9 / 140 3 / 45 cost of producing printed material. Furthermore, since liquid waste treatment is indispensable in the pre- and post-treatment process, environmental pollution must be considered.

[0011] In addition to pigment, water-based ink compositions for inkjet textile printing generally comprise polymeric binders and crosslinking agents.

[0012] The intensity and colorfastness of pigmented inks on textiles are generally controlled by the amount of polymeric binder added to the ink mixture. It is very difficult, however, to achieve good colorfastness of pigmented inks on printed or coated fabric by adding binder without a detrimental alteration of the fabric's softness. When the amount of polymeric binder is high enough to demonstrate good durability (or fastness), the fabric's feel becomes stiff or rough. If the amount of binder is reduced to maintain a consistent fabric feel, good fastness, especially colorfastness, cannot be achieved.

[0013] Increased performance in terms of intensity and colorfastness can also be achieved by increasing the amount of crosslinking agents. The crosslinking agent can be blocked to prevent premature reaction with the binder during transport and storage. However, by increasing the amount, the system becomes unstable, the blocking agent may detach, and the crosslinking agent may begin to react with the binder, thus increasing viscosity and shortening the shelf life of the ink.

[0014] Therefore, the aim is to provide a water-based ink composition that is stable under storage, easy to apply and fix to the fabric, and that will remain on the fabric when exposed to the most common conditions of use and cleaning, i.e., having high intensity and colorfastness.

[0015] It is a further objective of the present invention to provide a printing process employing a water-based ink composition with the advantages Petition 870250086035, dated 09 / 23 / 2025, page 10 / 140 4 / 45 above and which preferably does not require intensive pre- and / or post-treatment steps. SUMMARY OF THE INVENTION

[0016] The Applicant faced the problem of developing a water-based ink composition that would overcome the problems mentioned above and that could be printed on a substrate without the use of pre- and post-treatment steps.

[0017] After extensive experimentation, the Applicant found a solution consisting of a paint composition comprising a pigment, a binder, in particular a polyurethane binder, a blocked crosslinking agent, in particular a blocked isocyanate, and a polyol.

[0018] The Applicant surprisingly found that the use of a specific polyol selected from the group consisting of ethylene glycol, 1,3-budandiol, 1,5-pentandiol, triethylene glycol, trimethylol propane or a mixture thereof allowed the ink composition to be stabilized even under accelerated aging and to obtain better overall printing performance.

[0019] More specifically, the Applicant found that the ink composition according to the invention was stable under accelerated aging at 50 °C for four weeks and had latency, printability and wet rubbing fastness.

[0020] Furthermore, the Applicant found that the ink composition according to the invention can be used in a printing process on substrates without the use of pre- and post-treatment steps.

[0021] Consequently, in one aspect, the present invention relates to a water-based ink composition comprising a pigment, a polyurethane binder, a blocked crosslinking agent and a polyol, wherein said polyol is selected from the group consisting of ethylene glycol, 1,3-budandiol, 1,5-pentandiol, triethylene glycol, trimethylolpropane and mixtures thereof.

[0022] In another aspect, the present invention relates to a process of Petition 870250086035, dated 09 / 23 / 2025, p. 11 / 140 5 / 45 printing comprising • a printing step that applies the ink composition of the present invention to a substrate, • a fixing / drying step that applies heat to chemically react the crosslinking agent and the polyurethane binder of the ink composition.

[0023] In a preferred embodiment of the printing process of the present invention, the substrate is not subjected to a pre-treatment step with a pre-treatment solution before the printing step, nor is it subjected to a post-treatment step with a post-treatment solution after the printing step. DETAILED DESCRIPTION OF THE INVENTION

[0024] Although the present invention can be implemented in many different ways, specific embodiments will be described in more detail in this document, with the understanding that the present disclosure is an exemplification of the principles of the invention and is not intended to limit the invention to the specific embodiments illustrated.

[0025] The water-based paint composition according to the present invention comprises a pigment dispersion, a polyurethane binder, a blocked crosslinking agent, a fluid carrier and a polyol, wherein said polyol is selected from the group consisting of ethylene glycol, 1,3-budandiol, 1,5-pentandiol, triethylene glycol, trimethylol propane and mixtures thereof. Ink composition Pigment

[0026] Pigments refer to a coloring particle that is typically insoluble in water. Suitable pigments that can be used to form the ink composition of the invention may include any organic or inorganic pigment known in the art, including, but not limited to, Petition 870250086035, dated 09 / 23 / 2025, page 12 / 140 6 / 45 black, yellow, orange, brown, red, violet, blue, green, fluorescent, metallic powder and polymer-linked pigments. Pigments may also include, but are not limited to, carbon black, azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, polycyclic pigments, naphthol pigments, anthrapyrimidone pigments, quinacridone pigments, antanthrone pigments, flavantrone pigments, thioindigo pigments, dioxazine pigments, isoindoline and isoindolinone pigments, quinophthalone pigments, azine pigments, nitroso pigments, nitro pigments, triphenylmethane lake pigments, oxazine lake pigments, metal complex pigments, natural pigments and inorganic pigments, among others. The pigment particles must be small enough to allow free flow of ink through the ejection nozzle of an inkjet printing device.

[0027] Suitable colored pigments may include, for example: • Yellow pigments such as Yellow Pigment CI 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 16, 17, 24, 55, 61, 65, 73, 74, 81, 83, 93, 94, 95, 97, 99, 100, 108, 109, 110, 117, 120, 123, 124, 128, 129, 133, 138, 139, 147, 150, 151, 153, 154, 155, 156, 167, 168, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 183, 184, 185, 187, 188, 190, 191, 192, 193, 194 and mixtures thereof; • Red pigments such as Red Pigment CI 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 48, 49, 50, 51, 52, 53, 55, 60, 64, 68, 81, 83, 87, 88, 89, 90, 95, 112, 114, 119, 122, 123, 136, 144, 146, 147, 148, 149, 150, 151, 163, 164, 166, 168, 169, 170, 161, 172, 175, 176, 202, 204, 206, 207, 210, 211, 212, 213, 214, 216, 220, 222, 237, 238, 239, 240, 242, 243, 245, 247, 248, 251, 252, 253, 254, 255, 256, 258, 261, 264 and mixtures thereof; • violet pigments such as Violet Pigment CI 1, 2, 3, 5, 13, 19, 23, Petition 870250086035, dated 09 / 23 / 2025, page 13 / 140 7 / 45 25, 27, 29, 31, 32, 37, 39, 42, 44, 50 and mixtures thereof; • blue pigments such as Blue Pigment CI 1, 2, 3, 9, 10, 14, 15, 16, 18, 19, 21, 22, 24, 25, 56, 60, 61, 62, 63, 64, 65, 66 and mixtures thereof; • Orange pigments such as Orange Pigment CI 1, 2, 5, 6, 7, 13, 14, 15, 16, 17, 19, 22, 24, 31, 34, 36, 38, 40, 42, 43, 44, 46, 48, 49, 51, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69 and mixtures thereof; • Green pigments such as Green Pigment CI 1, 2, 4, 7, 8, 10, 34, 36, 45, 47 and mixtures thereof; • Brown pigments such as Brown Pigment CI 1, 2, 3, 5, 22, 23, 25, 26, 32, 38, 41, 42 and mixtures thereof; • Black pigments such as Black Pigment CI 1, 7, 20, 31, 32 and mixtures thereof, and • White pigments such as titanium dioxide.

[0028] Mixtures of pigments of different colors are also included. Commercially available colored pigments may include, for example, Pigment Red 122 and Pigment Violet 19 (available from Lansco Colors, Montvale, NJ or Clariant Colors, Charlotte, NC or Sun Chemical, Cincinnati, Ohio), Pigment Blue 15:1 (available from Fanwood Chemical, Fanwood, NJ), Pigment Blue 15:3, Pigment 15:4, Pigment Yellow 74 and Pigment Yellow 97 (available from Clariant Colors, Charlotte, NC or Sun Chemical, Cincinnati, Ohio), among others.Other suitable pigments may include, but are not limited to, Disperse Blue 14, Disperse Blue 19, Disperse Blue 72, Disperse Blue 334, Disperse Blue 359, Disperse Blue 360, Disperse Orange 25, Disperse Yellow 54, Disperse Yellow 64, Disperse Red 55, Disperse Red 60, Macrolex Red H, Disperse Brown 27, Solvent Blue 67, Solvent Blue 70, Solvent Red 49, Solvent Red 146, Solvent Red 160, Solvent Yellow 162, Solvent Violet 10, and Solvent Black 29, among others. Petition 870250086035, dated 09 / 23 / 2025, page 14 / 140 8 / 45

[0029] Suitable pigments may also include carbon black, which is the generic name for carbon particles derived from the thermal decomposition or incomplete combustion of natural gas and hydrocarbons, such as coal tar-based aromatic oils, mineral oils, coal tar distillate, and acetylene. More than 100 individual grades of carbon black are currently available on the market, each with its own distinctive set of characteristics and properties. Any acid carbon black, neutral carbon black, and alkaline carbon black can be used. This includes channel blacks, gas blacks, lamp blacks, thermal blacks, acetylene blacks, and furnace blacks. More particularly, suitable carbon blacks include channel blacks.

[0030] Examples of commercially available carbon blacks include, but are not limited to, those available from Cabot (Elftex 8, Black Pearls® 490, Black Pearls® 120, Monarch® 120, Monarch® 700, Monarch® 880, Monarch® 1000, Monarch® 1100, Monarch® 1300, Monarch® 1400, Mogul® L, Regal® 99R, Regal® 250R, Regal® 300R, Regal® 330R, Regal® 400R, Regal® 500R, Regal® 660R, Cab-O-Jet® 200, Cab-O-Jet® 300, and Cab-O-Jet® 400), Degussa / Orion Carbon (NIPex® 150IQ, NIPex® 150, Printex® 55, Printex® 80, Printex® 90, Printex® A, Printex® G, Printex® U, Printex® V, Printex® 140U, Printex® 140V, Purex® LS 35, Corax® HP 160, Thermal Black N 990, NIPex® 160 IQ, Nipex® 170IQ, Nipex® 180IQ, NIPex® 90, Special black 4, Special black 4A, Special black 5, Special black 6, Special black 100, Special black 250, Color black FW1, Color black FW2, Color black FW2V, Color black FW18, Color black FW200, Color black S150, Color black S160 and Color black S170), Columbian / Birla Carbon (Raven® 780,Raven® 5000 Ull, Raven® 1255, Raven® 2500 U, Raven® 3600 U, Raven® 3500, Raven® 5000, Raven® 7000, Raven® 1220 e Raven® 1225), Mitsubishi Kagaku KK (MA8, MAll, MA77, MA100, MA220, MA230, MA600, MCF88, n°_10B, n° 20B, n° 30, n° 33, n° 40, n° 44, n° 45, n° 45L, n° 50, n° 55, n° 95, n° 260, n° 900, n° 970, n° 1000, n° 2200B, n° 2300, n° 2350, no 2400B, n° 2650, n° 2700, n° 4000B e, Petition 870250086035, de 23 / 09 / 2025, pág. 15 / 140 9 / 45 CF9), Orient Chemical Industries Ltd. (Bonjet Black CW-1, Bonjet Black CW-2, and Bonjet Black CW-3) and Sun Chemical (Graphitan® 7525).

[0031] In some embodiments, the pigment may be self-dispersing in a selected continuous phase. Self-dispersing pigments are pigments that do not require an additional dispersant to be stable within a polymeric composition. In one embodiment, a self-dispersing pigment is a pigment that has been functionalized with a dispersing agent such as a molecule containing a hydrophilic functional group, for example, by covalent bonding of the molecule to the pigment surface.

[0032] In other embodiments, a pigment is combined with a dispersant such as a water-soluble polymer (e.g., vinyl polymer, urethane polymer). In one embodiment, the pigment is a pigment dispersed in a polymer comprising a polymer adsorbed thereto.

[0033] In one embodiment, the amount (by weight) of pigment in the ink compositions of the present invention is at least 0.5, as well as at least 1, at least 1.5, and at least 2, % by weight. In another embodiment, the amount of dye is at most 15, as well as at most 10, at most 9, at most 8, and at most 7, % by weight. This includes embodiments in which the amount of dye in the compositions is 0.5 to 15% by weight, as well as 1 to 10, 2 to 9, % by weight.

[0034] A pigment used in the ink compositions of the present invention may comprise one or more embodiments described herein. Polyurethane binder

[0035] In one embodiment, the polyurethane binder is a polyurethane polymer that has pendant hydroxyl groups and, optionally, pendant neutralized carboxyl groups attached to the polymer backbone.

[0036] In one embodiment, the polyurethane polymer is a polyurethane polymer that has pendant hydroxyl groups attached to the polymer backbone. Petition 870250086035, dated 09 / 23 / 2025, p. 16 / 140 10 / 45

[0037] The term “pendant group” as used in this document describes a side group of a polymer backbone (main chain). The term “terminal group” describes a group attached to a terminal end of the polymer backbone.

[0038] In one embodiment, the hydroxyl number of the polyurethane polymer is at least 51, such as at least 60, at least 70, and at least 80. In another embodiment, the hydroxyl number of the polyurethane polymer is 1000 or less, such as 750 or less, 500 or less, 250 or less, 200 or less, 150 or less, and 100 or less. This includes embodiments in which the polyurethane polymer has a hydroxyl number from 51 to 1000, such as from 51 to 300, from 80 to 200, and from 80 to 100.

[0039] In one embodiment, the polyurethane polymer has a carboxyl number of zero (0). In other embodiments, the polyurethane polymer has a carboxyl number of at least 1, such as at least 5 and at least 10. In one embodiment, the carboxyl number of the polyurethane polymer is 100 or less, such as 80 or less, 60 or less, and 50 or less. This includes embodiments in which the polyurethane polymer has a carboxyl number from 0 to 100, such as from 1 to 80, from 5 to 60, and from 10 to 50.

[0040] Polyurethanes can be produced by methods known and used in the art. In general, the polyurethane polymer can be produced by the reaction of an isocyanate compound with a polyol, an ionic polyol, or a combination thereof, in the presence of a catalyst.

[0041] Examples of isocyanate compounds are well known in the art and include, for example, but are not limited to, 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate, methylene diphenyl diisocyanate (MDI) and toluene diisocyanate (TDI), among others.

[0042] Examples of suitable polyols include diols, triols, tetraols, pentaols, and oligomers that have pendant or terminal hydroxyl groups. Examples of diols include, but are not limited to, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, Petition 870250086035, dated 09 / 23 / 2025, page 17 / 140 11 / 45 diethylene glycol, triethylene glycol, and dipropylene glycol. Examples of triols include, but are not limited to, glycerol and trimethylolpropane. Examples of tetraols include, but are not limited to, tetramethylolmethane (pentaerythritol) and diglycerol. Examples of pentaols include, but are not limited to, xylitol. Examples of oligomers that have pendant or terminal hydroxyl groups include, but are not limited to, polyether polyols such as polypropylene glycol, polyester polyols, polycarbonate polyols, and polyolefin polyols such as polybutadiene polyol.

[0043] In one embodiment, the ionic polyol is a diol, triol, tetraol, or pentaol with one or more carboxyl groups, or an oligomer that has both hydroxyl and carboxyl groups. In another embodiment, the ionic polyol is a dihydroxycarboxylic acid such as 2,2-di(hydroxymethyl)acetic acid, dimethylolpropionic acid (DMPA), 2,2-bis(hydroxymethyl)butyric acid, or 2,2-di(hydroxymethyl)pentanoic acid. “Ionic polymer” means a polymer that contains an ionic functional group.

[0044] In one embodiment, the pendant group is a polymer side group without a linear chain structure that extends from and is attached to the main chain, for example, branched, hyperbranched, star, and dendritic polymer groups. “Branched polymer” means that the polymer has secondary polymer chains that branch off from a main chain. “Hyperbranched polymer” means a polymer that is tall and densely branched with an irregular branching structure, and the term includes polymers that have a regular branching structure which are referred to as “dendrimeric polymers.” “Dendrimer” or “dendritic polymer” means a polymer that looks like a tree-like structure with densely branched structures that typically consists of a core from which branches extend and with a large number of terminal groups.A "star" polymer refers to a branched polymer in which a single branch has multiple linear chains or arms that radiate outward.

[0045] Branched polyurethanes can be produced, for example, by the reaction of a diisocyanate with excessive amounts of triols, pentaols and Petition 870250086035, dated 09 / 23 / 2025, p. 18 / 140 12 / 45 other multifunctional polyols (e.g., having a hydroxyl functionality greater than 2), and their mixtures with diols and / or ionic polyols. Methods for producing branched polyurethanes are known in the art, as described, for example, in U.S. Patents Nos. 4,801,553, 4,895,894, 5,863,980, U.S. 2010 / 0222448, U.S. Patents Nos. 4,861,826, 5,334,690, 6,583,215, 6,642,303, 6,784,243 and US 2011 / 0306724.

[0046] Hyper-branched, star-shaped and dendritic polyurethanes with pendant carboxyl and hydroxyl groups can be prepared, for example, by gradual growth polymerization of triisocyanates with multifunctional polyols and ionic polyols. Methods for producing hyper-branched polyurethanes are known in the art, as described, for example, in US Patents Nos. 6,927,271, 7,863,375, 8,044,140 and US 2012 / 0183692.

[0047] Examples of commercially available polyurethane polymers include, but are not limited to, Impranil® (available from Covestro Deutschland AG), such as Impranil DLT-C, Neboplast® (available from Safic-Alcan Necarbo BV), such as Neboplast PEU 3500, and Daotan® (available from Allnex Netherland BV), such as Daotan TW6425 / 40WA.

[0048] In one embodiment, the water-dispersible polyurethane polymer may include one or more pendant carboxyl groups and will undergo an optional crosslinking reaction by means of the reaction of the pendant carboxyl groups with a crosslinking agent. To prevent the occurrence of a premature crosslinking reaction by mixing the components of an inkjet paint composition that includes a polyurethane polymer having pendant carboxyl group(s) and a crosslinking agent (and thus stabilize the paint composition during a storage period and before use), the carboxyl groups of the polyurethane polymer are neutralized.

[0049] To neutralize the carboxyl groups, the polyurethane polymer can be reacted with a neutralizing agent (e.g., a base) to form Petition 870250086035, dated 09 / 23 / 2025, page 19 / 140 13 / 45 a carboxylate salt. A neutralizing agent may be used alone or in combination of two or more types. The neutralizing agent as used in this document is capable of being detached from the carboxyl group and, in one embodiment, removed from the ink composition at the desired time to allow the crosslinking reaction to proceed. Examples of suitable neutralizing agents include, but are not limited to, ammonia and tertiary amines.

[0050] In one embodiment, the neutralizing agent is ammonia so that neutralized carboxyl groups are in the form of an ammonium carboxylate salt. An ammonia neutralizing agent can be disengaged from the carboxyl group and removed from the paint composition, for example, by evaporation upon exposure of the composition to atmospheric conditions with or without the application of heat, to allow the crosslinking reaction to proceed.

[0051] In one embodiment, the neutralizing agent is a tertiary amine such that the neutralized carboxyl groups are in the form of a tertiary amine carboxylate salt. Any tertiary amine can be used as a neutralizing agent provided that the tertiary amine can be disengaged from the carboxyl group and removed from the ink composition, to allow the crosslinking reaction to proceed, for example, by evaporation of the composition upon exposure to atmospheric conditions with or without the application of heat.Non-limiting examples of tertiary amines include triethylamine (TEA), 2dimethylaminoethanol (DMEA), triethanolamine (TEA-OH), trimethylamine, dimethylethylamine (DMEA), diethylmethylamine (DEMA), dimethyl-isopropylamine (DMIPA), dimethyl-n-pyrropylamine (DMPA), N N,N-diisopropylethylamine, N,N-di-isopropylethylamine, N,N-diethylethanolamine, Ntribuethylamine, N-butyl-N-ethyl-N-methylamine, N-isopentyldimethylamine, N,Ndiethylmethylamine, N-amyldimethylamine, N-methylmorpholine, N,N-methyl-helamine, N,N-dimethylisobutylamine, N,N-dimethyl-2-(2-aminoethoxyethanol), Nmethyldiethanolamine, N,N-dimethylbenzylamine, tri-n-butylamine, among others.

[0052] In another embodiment, the water-dispersible polyurethane polymer Petition 870250086035, of 23 / 09 / 2025, p. 20 / 140 14 / 45 includes one or more pendant carboxyl groups that can be neutralized by reaction with an alkali metal hydroxide, such that the neutralized carboxyl groups are in the form of an alkali metal carboxylate salt (e.g., sodium, lithium, potassium). Examples of alkali metal hydroxides include, but are not limited to, lithium hydroxide, potassium hydroxide, and sodium hydroxide.

[0053] In one embodiment, the polyurethane polymer has a glass transition temperature (Tg) of at least -50 °C, and preferably at least 0 °C. In one embodiment, the Tg of the polyurethane polymer is at most 120 °C, and preferably at most 50 °C. In one embodiment, the Tg of the polyurethane polymer is -50 °C to 120 °C, and preferably 0 °C to 50 °C.

[0054] In one embodiment, the polyurethane polymer has a number average molecular weight (Mn) of at least 1,000 and preferably at least 2,000. In one embodiment, the Mn of the polyurethane polymer is at most 1,000,000 and preferably at most 100,000. In one embodiment, the Mn of the polyurethane polymer is 1,000 to 1,000,000 and preferably 2,000 to 100,000.

[0055] In one embodiment, the amount (by weight) of the water-dispersible polyurethane polymer having pendant hydroxyl groups and optional pendant neutralized carboxyl group(s) in the paint composition of the invention is at least 1, at least 2, at least 5, at least 10, and at least 15% by weight. In one embodiment, the amount of the polyurethane polymer is at most 40%, as well as at most 35%, at most 30%, at most 25%, and at most 20% by weight. This includes embodiments in which the amount of the polyurethane polymer in the paint composition of the invention is 1 to 40% by weight, as well as 2 to 35%, 5 to 30%, 10 to 25%, and 15 to 20% by weight.

[0056] A polyurethane polymer used in the paint composition of the invention may comprise one or more embodiments described herein. Relinking agent blocked Petition 870250086035, dated 09 / 23 / 2025, p. 21 / 140 15 / 45

[0057] As used in this document, the terms “crosslinking agent” and “crosslinker” are used interchangeably.

[0058] In one embodiment, the ink composition of the invention includes a crosslinking agent capable of reacting with a hydroxyl group of the polyurethane polymer.

[0059] Suitable crosslinking agents capable of reacting with a hydroxyl group of the polyurethane polymer include, but are not limited to, water-dispersible blocked isocyanate compounds.

[0060] Examples of blocked isocyanates are known in the art and include, but are not limited to, lactam-blocked isocyanate, such as ε-caprolactam, δ-valerolactam or γ-butyrolactam-blocked isocyanate, pyridine-blocked isocyanate, such as 2-hydroxypyridine-blocked isocyanate, oxime-blocked isocyanate, such as formaldehyde-blocked isocyanate, acetaldoxime, acetone oxime, cyclohexanone oxime, methyl isobutyl ketoxime or methyl ethyl ketoxime, azole-blocked isocyanate, such as pyrazole-blocked isocyanate, carbazole, triazole, imidazole, thiazole, oxazole and 3,5-dimethylpyrazole, malonate-blocked isocyanate, such as dimethyl or diethyl malonate-blocked isocyanate, phenol-blocked isocyanate, such as cresol-blocked isocyanate, ethylphenol, butylphenol or nonylphenol-blocked isocyanate, alcohol-blocked isocyanate, such as propanol or butanol-blocked isocyanate, mercaptan-blocked isocyanate,such as butyl mercaptan- or dodecyl mercaptan-blocked isocyanate, urethdione-blocked isocyanate, acetanilide-blocked isocyanate, sebacate-blocked isocyanate, such as bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, polymer-blocked isocyanate, and mixtures thereof. Pyrazole-blocked isocyanates, in particular 3,5-dimethylpyrazole-blocked isocyanate, are preferably used in the paint composition of the present invention.

[0061] The crosslinking reaction can proceed when the blocking agent Petition 870250086035, dated 09 / 23 / 2025, page 22 / 140 16 / 45 of the isocyanate compound (crosslinker) is removed, for example, at an elevated temperature. The temperature at which the reaction to dissociate the blocking agent, or specifically the unlocking reaction, becomes prominent (hereinafter referred to as the unlocking temperature) can be adjusted based on the type of blocking agent, the type of isocyanate compound to be blocked, and other factors. Although the specific level of this unlocking temperature is not limited in any way, the unlocking temperature is generally between 65° and 135°C.

[0062] Examples of commercially available blocked isocyanate compounds include, but are not limited to, Imprafix® (available from Covestro Deutschland AG), such as Imprafix 2794 and Imprafix 2794 / 1, and Tanaltinta® (available from Tanatex Chemicals BV), such as Tanaltinta PCI.

[0063] The amount (by weight) of the crosslinking agent in the ink composition is at least 1.0, at least 2.0, and at least 5.0, % by weight. In one embodiment, the amount (by weight) of the crosslinking agent is at most 20, as well as at most 15 and at most 10, % by weight. This includes embodiments in which the amount of the crosslinking agent in the ink composition of the invention is 1 to 20% by weight, as well as 2 to 15, and 5 to 10, % by weight.

[0064] In one embodiment, the crosslinking reaction between a crosslinking agent and hydroxyl group(s) of the polyurethane polymer can be facilitated by heat. For example, in some embodiments, the paint composition of the invention can be applied to a substrate and then dried, whereupon the crosslinking agent and hydroxyl group(s) undergo a crosslinking reaction. In one embodiment, the crosslinking reaction can be facilitated by applying heat to the paint after application or during the drying process. Fluid carrier

[0065] The aqueous paint compositions of the present invention comprise a fluid carrier which, in one embodiment, comprises water and optionally one or more organic cosolvents, which may be Petition 870250086035, dated 09 / 23 / 2025, page 23 / 140 17 / 45 water-soluble organic cosolvents, water-miscible organic cosolvents, or a combination thereof. Organic cosolvents may be added alone or in combination.

[0066] In one embodiment, organic cosolvents are wetting agents, which can reduce the evaporation rate of the water component and prevent an ink composition from drying or fouling in the printhead nozzles to minimize nozzle clogging.

[0067] In a further embodiment, organic cosolvents can improve the solubility of the components in the ink composition of the invention and facilitate the penetration of a printed ink composition into a substrate.

[0068] Suitable water-soluble and water-miscible organic solvents include, but are not limited to, alcohols (e.g., methanol, ethanol, propanol, isopropyl alcohol, and butanol), ketones and ketone alcohols (e.g., acetone alcohol and diacetone, among others), ethers (e.g., tetrahydrofuran, dioxane, and alkyl ethers, among others), nitrogen-containing solvents (e.g., 2-pyrrolidone and N-methyl-2-pyrrolidone, among others), sulfur-containing solvents (e.g., 2,2'-thiodiethanol, dimethyl sulfoxide, tetramethylene sulfone, and sulfolane, among others), and sugars and derivatives thereof (e.g., glucose, glyceryl oxyethylene adducts, and diglyceryl oxyethylene adducts, among others).

[0069] In one embodiment, the amount (by weight) of the organic cosolvent in the ink composition of the present invention is at least 1, as well as at least 2, and at least 5, % by weight. In another embodiment, the amount (by weight) of the organic cosolvent is at most 15, as well as at most 14, at most 14, and at most 10, % by weight. This includes embodiments in which the amount of the organic cosolvent in the composition is 1 to 15% by weight, as well as 5 to 10% by weight.

[0070] An organic cosolvent used in the ink composition of the invention may comprise one or more embodiments described herein. Petition 870250086035, dated 09 / 23 / 2025, p. 24 / 140 18 / 45

[0071] In one embodiment, the amount (by weight) of water in the ink composition of the present invention is at least 5, at least 8, at least 10, at least 15, at least 20, and at least 25, % by weight. In another embodiment, the amount (by weight) of water is at most 95, at most 85, at most 80, at most 75, at most 70, at most 65, and at most 60, % by weight. This includes embodiments in which the amount of water in the composition is 5 to 95% by weight, such as 10 to 80, and 20 to 70, % by weight. The range of water in the composition is typically 15 to 75% by weight, and more typically 25 to 60% by weight. Polyol

[0072] The ink composition according to the present invention comprises a polyol selected from the group consisting of ethylene glycol, 1,3-budandiol, 1,5-pentandiol, triethylene glycol, trimethylol propane and mixtures thereof.

[0073] Preferably, the ink composition according to the present invention does not comprise any polyol other than ethylene glycol, 1,3-budandiol, 1,5-pentandiol, triethylene glycol and trimethylol propane.

[0074] A polyol used in the paint composition of the invention may comprise one or more embodiments described in this document.

[0075] In one embodiment, the amount (by weight) of polyol in the paint composition of the present invention is at least 1%, at least 2%, at least 3%, and at least 5% by weight. In another embodiment, the amount (by weight) of polyol is at most 30%, at most 25%, at most 20%, and at most 15% by weight. This includes embodiments in which the amount of polyol in the paint composition of the present invention is 1% to 30% by weight, as well as 2% to 25% and 3% to 20% by weight. The range of polyol in the composition is typically 5% to 15% by weight. Most preferably, the amount (by weight) of polyol in the paint composition of the present invention is 6%, 8%, 10%, 12%, 14% by weight, or any value between them. Additives Petition 870250086035, dated 09 / 23 / 2025, p. 25 / 140 19 / 45

[0076] In one embodiment, the ink composition of the invention may optionally include one or more additives that are compatible with the other components of the composition. Additives may be included in the composition to impart any number of desired properties, including, but not limited to, stability, stain resistance, viscosity, surface tension, coating penetration, optical density, color depth, adhesion, marker resistance, and fouling resistance, among others. The additives suitable for such uses and the amounts of such additives used are known and conventionally used in the art.

[0077] Examples of additives include, but are not limited to, defoamers, preservatives, surfactants, pH modifiers, viscosity modifiers, wetting agents, penetration agents and additional polymers, among others.

[0078] In one embodiment, defoamers may be included in the paint composition of the present invention to inhibit foam formation. Examples of suitable defoamers include, but are not limited to, silicone-based or non-silicone-based defoamers. Commercially available defoamers include, but are not limited to, Dow Corning® 71 and Dow Corning® 74 (from Dow Corning), TegoAirex® 901W, 902W, 904W from Evonik Industries, Tergitol® L-61, L-62, L-64 and L-101 (from Dow Chemical). A typical amount (by weight) of defoamer included in the composition is 0.1 to 3% by weight.

[0079] In one embodiment, preservatives, such as biocides and fungicides, may be included in the paint composition of the present invention to inhibit the growth of microorganisms. Examples of suitable preservatives include, but are not limited to, sodium benzoate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, sodium sorbate, sodium dehydroacetate, benzisothiazolinone, 1,2-dibenzothiazolin-3-one, 1-(3-chloralyl)-3,5,7-triaza-1-azonia-adamantane chloride (CTAC), methylisothiazolinone, and chloromethylisothiazolinone, among others. Commercially available biocides Petition 870250086035, dated 09 / 23 / 2025, page 26 / 140 20 / 45 includes UCARCIDE® 250 (available from Union Carbide Company), Proxel® CRL, Proxel® BDN, Proxel® GXL, Proxel® XL-2, Proxel® TN (available from Arch Chemicals, Smyrna, Ga.), Dowicil® (Dow Chemical, Midland, Mich.), Nuosept® (Huls America, Inc., Piscataway, NJ), Omidines® (Olin Corp., Cheshire, Conn.), Nopcocides® (Henkel Corp., Ambler, Pa.), Troysan® (CO (Troy Chemical Corp., Newark, NJ) and XBINX® (PMC Specialties Group, Inc., Cincinnati, Ohio). Preservatives may be used alone or in combination. A typical amount (by weight) of preservative included in the composition is 0.1 to 1.5% by weight.

[0080] In one embodiment, surfactants may be included to reduce the surface tension of the paint composition of the present invention. The surfactant may be an anionic surfactant, a nonionic surfactant, or a cationic surfactant. Suitable surfactants may include, but are not limited to, those listed below and in U.S. Patents Nos. 5,116,409, 5,861,447, and 6,849,111. The exemplary surfactants are commercially available under various trade names, such as the PLURONIC® series (BASF Corporation, Parsippany, NJ), TETRONIC® series (BASF Corporation, Parsippany, NJ), ARQUAD® series (Akzo Chemical Inc., Chicago, Ill.), TRITON® series (Union Carbide Corp., Danbury, Conn.), SURFONIC® series (Texaco Chemical Company, Houston, Tex.), ETHOQUAD® series (Akzo Chemical Inc., Chicago, Ill.), ARMEEN® series (Akzo Chemical Inc., Chicago, Ill.), ICONOL® series (BASF Corporation, Parsippany, NJ), SURFYNOL® series (Air Products and Chemicals, Inc., Allentown, Pa.).) and the ETHOMEEN® series (Akzo Chemical Inc., Chicago, Ill.), among others. Surfactants can be used alone or in combination. A typical amount (by weight) of surfactant included in the composition is 0.1 to 10% by weight.

[0081] In one embodiment, pH modifiers may be included to adjust or buffer the ink composition of the present invention to a desired pH. Suitable pH modifiers include, but are not limited to, alkaline hydroxides, carbonates, and alkaline bicarbonates. Petition 870250086035, dated 09 / 23 / 2025, page 27 / 140 21 / 45 triethylamine, dimethylethanolamine, triethanolamine, mineral acids, hydrochloric acid, and sulfuric acid, among others. pH modifiers can be used alone or in combination. A typical amount (by weight) of pH modifier in the composition is 0.1 to 2% by weight. In one embodiment, the paint composition of the present invention has a pH of 7 to 10 at 25 °C. More preferably, the pH is between 7 and 9. Most preferably, the pH is equal to 7.0, 7.2, 7.4, 7.6, 7.8, 8.0, 8.2, 8.4, 8.6, 8.8, or 9.0, or any value between them.

[0082] In one embodiment, the ink composition of the present invention may include one or more viscosity modifiers. Examples of suitable viscosity modifiers include, but are not limited to, resin compounds, alginic acid compounds, polyvinyl alcohol, hydroxypropyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose, polyacrylic acid salts, polyvinylpyrrolidone, gum arabic and starch, hydrophobic ethoxylated urethanes (HEURs), hydrophobically modified alkaline swelling emulsions (HASEs), alkaline swelling emulsions (ASEs), among others. Viscosity modifiers may be used alone or in combination. A typical amount (by weight) of viscosity modifier in the composition is 0.5 to 10% by weight. In one embodiment, the paint composition of the present invention has a viscosity of 1 mPa.s to 15 mPa.s as determined with a Brookfield viscometer at 25 °C. More preferably, said viscosity is comprised between 2 mPa.sIf 14 mPa.s. More preferably, said viscosity is 2 mPa.s, 4 mPa.s, 6 mPa.s, 8 mPa.s, 10 mPa.s, 12 mPa.s, 14 mPa.s or any value between them.

[0083] In some embodiments, the ink composition of the present invention may optionally include one or more conductive agents. In some embodiments, the conductive agent may be a salt (for example, an organic salt or an inorganic salt). For example, the salt may be a quaternary phosphonium salt (for example, a tetra-alkylphosphonium or tetra-arylphosphonium salt), Petition 870250086035, dated 09 / 23 / 2025, page 28 / 140 22 / 45 a quaternary ammonium salt (for example, a tetraalkylammonium or tetraarylammonium salt), an imidazolium salt or an alkaline salt (for example, a Li, Na, K or Cs salt).

[0084] In general, the ink composition of the present invention may have any suitable conductivity. In some embodiments, the ink composition may have a conductivity ranging from at least about 0 pS / cm (e.g., at least about 10 pS / cm, at least about 50 pS / cm, at least about 100 pS / cm, at least about 200 pS / cm, at least about 300 pS / cm, at least about 400 pS / cm, at least about 500 pS / cm, or at least about 1000 pS / cm) to at most about 8000 pS / cm (e.g., at most about 7000 pS / cm, at most about 6000 pS / cm, at most about 5000 pS / cm, at most about 4000 pS / cm, at most about 3000 pS / cm, at most about 2000 pS / cm, or at most around... 1000 pS / cm).For example, when an ink composition is designed for use in a continuous inkjet printing process, the ink composition may have adequate conductivity (e.g., 100-8000 pS / cm) to allow the ink composition to be printed in that process. As another example, when an ink composition is designed for use in a thermal inkjet printing process, the ink composition may have zero conductivity, as conductivity is not required in that printing process.

[0085] In one embodiment, in addition to an organic cosolvent of the fluid carrier component that can function as a wetting agent, one or more wetting agents may be included in the ink composition of the present invention to reduce the evaporation rate of the water component and prevent an ink composition from drying in the printhead nozzles, which can occur during latency periods, to minimize nozzle clogging. The wetting agents may be selected from materials that have high hygroscopicity and water solubility. Examples of suitable wetting agents include, but are not limited to, lactams (by Petition 870250086035, dated 09 / 23 / 2025, p. 29 / 140 23 / 45 For example, 2-pyrrolidone, urea compounds such as urea, 1,3-dimethylimidazolidinone), saccharides (e.g., sorbitol), 1,4-cyclohexanedimethanol, 1-methyl-2-piperidone, N-ethylacetamide, 3-amino-1,2-propanediol, ethylene carbonate; butyrolacetone and Liponic EG-1, among others. There are no particular limitations on the amount of humectant used. A typical amount (by weight) of humectant in the composition is 0.5 to 30% by weight.

[0086] In one embodiment, penetrating agents may be included to reduce bleeding of an ink composition of the present invention when applied to a printing substrate such as paper, among others. Examples of suitable penetrating agents include, but are not limited to, alkyl alcohols having 1 to 4 carbon atoms (e.g., ethanol), formamide, acetamide, dimethyl sulfoxide, sorbitol, and sulfolan, among others. Penetrating agents may be used alone or in combination. A typical amount (by weight) of penetrating agents in the composition is 1 to 20% by weight.

[0087] In one embodiment, the ink composition of the present invention may include additional polymers (besides the polyurethane polymer) to enhance water fastness, friction, and light fastness of an ink image applied and dried on a printing substrate. Examples of such polymers include, but are not limited to, polyvinyl alcohols, polyesters, polyester-melamines, styrene / acrylic acid copolymers, styrene / maleic acid copolymers, styrene / maleic acid / alkyl acrylate copolymers, styrene / methacrylic acid copolymers, styrene / methacrylic acid / alkyl acrylate copolymers, styrene / maleic half-ester copolymers, vinyl naphthalene / acrylic acid copolymers, vinyl naphthalene / maleic acid copolymers, and salts thereof, among others. Such additional polymers may be used alone or in combination. A typical amount (by weight) of such additional polymers that may be included in the composition is 0.1 to 20% by weight. Petition 870250086035, dated 09 / 23 / 2025, page 30 / 140 24 / 45

[0088] Other additives that may be included in the ink composition of the present invention include, but are not limited to, antioxidants, ultraviolet absorbers, chelating agents, electrical conductivity adjusters, oxygen absorbers, anticoagulation agents, anti-waxing agents, and fragrances, among others. The quantities of such additives for use in aqueous ink compositions are known and conventionally used in the art. Printing process and product

[0089] In general, the ink composition of the present invention can be used in any suitable printing process, including a continuous inkjet (CIJ) printing process and an on-demand droplet printing process (e.g., thermal inkjet (TIJ) printing process or a piezo printing process). In some embodiments, the ink composition can be used in a printing process that includes ejecting the ink composition (continuously or on demand) from a print head in an inkjet printer onto a substrate to form an image.

[0090] Examples of suitable substrates include, but are not limited to, plain papers, bound papers, coated papers, transparent materials, and textile materials. The ink composition of the present invention is especially applicable to textile substrates.

[0091] In some embodiments, in a continuous inkjet printing process, a continuous stream of conductive ink droplets can be ejected from one or more nozzles of an inkjet printer's printhead. The droplets are electrostatically deflected to direct multiple vertical pixels as the substrate moves relative to the nozzles. CIJ inks generally have adequate conductivity and allow the droplets to be deflected. The process of continuously jetting ink droplets and directing unnecessary droplets to the chute allows CIJ systems to utilize fast-evaporating solvents (e.g., those Petition 870250086035, dated 09 / 23 / 2025, page 31 / 140 25 / 45 with a relative evaporation rate (RER) greater than 1, as determined by ASTM method D3359 and relative to n-butyl acetate) without concern for stripping (i.e., the ability to remain in a fluid condition at the printhead nozzle opening when exposed to air) and nozzle clogging, since the nozzles are never idle during operation.

[0092] In some embodiments, in a continuous inkjet printing process, a continuous stream of ink ejected from a print head is diverted by at least one electrode to which a high static or sinusoidal voltage is applied. Most of the ink stream is not printed and is directed to an ink recovery chute. During printing, segments of the ink stream are sampled asynchronously, diverted differently depending on their length (length provides a means of varying the distribution of embodied electrical charge per unit length), and directed to the substrate. These segments, which can be transformed into spherical droplets under the effect of surface tension, are separated from the jet before being diverted so that their trajectory is different from the ink stream.

[0093] In some embodiments, in a drop-on-demand printing process, inks can be jetted by thermal inkjet cartridges or piezoelectric drop-on-demand printheads. To print inks, an ink is loaded into a reservoir, where it is pumped or gravity-fed into a jet chamber of a cartridge or printhead. In the case of the thermal inkjet cartridge, a liquid ink is ejected from a printhead by being rapidly heated, causing a rapid phase change from liquid to gas, thus causing a rapid volume expansion and subsequently causing a drop to be ejected from an orifice. In the case of a piezoelectric-based device, a liquid ink is ejected from a printhead by the activation of a piezoelectric transformer (PZT), which causes a pressure wave. Petition 870250086035, dated 09 / 23 / 2025, page 32 / 140 26 / 45 is applied to the ink and a drop of ink can be ejected from a nozzle. Both devices refer to on-demand drops, as a drop of ink is ejected only when a heater or PZT material is activated. Each cartridge or print head contains an arrangement of several nozzles across its width. The activation of each nozzle in such an arrangement is performed methodically by the printer, so that an image is formed drop by drop onto a substrate, which is positioned a short distance from the nozzle arrangement. Printers are designed so that a nozzle arrangement and a substrate move relative to each other to form an image.

[0094] According to one embodiment, the present invention relates to a printing process comprising • a printing step that applies the ink composition of the present invention to a substrate, • a fixing / drying step that applies heat to chemically react the crosslinking agent and the polyurethane binder of the ink composition.

[0095] According to a preferred embodiment of the printing process of the present invention, the substrate is not subjected to a pre-treatment step with a pre-treatment solution before the printing step.

[0096] According to a preferred embodiment of the printing process of the present invention, the substrate is not subjected to a post-treatment step with a post-treatment solution after the printing step.

[0097] In one embodiment, the substrate is a textile material, such as, for example, wool, cotton, silk, polypropylene, polyethylene, polyamides such as aliphatic polyamides (i.e., nylon 6, nylon 6,6) and aromatic polyamides (i.e., Kevlar®, Nomex®), viscose, cellulose or polyester.

[0098] The following examples illustrate numerous forms of the present Petition 870250086035, dated 09 / 23 / 2025, p. 33 / 140 27 / 45 inventions that are currently known. However, it should be understood that the following is only exemplary or illustrative of the application of the principles of the present invention. Various modifications and compositions, methods and alternative systems may be envisioned by those skilled in the art without departing from the spirit and scope of the present invention. The appended claims are intended to encompass such modifications and arrangements. Thus, although the present invention has been described above in particular, the following examples provide further details in connection with what are currently considered acceptable embodiments. EXPERIMENTAL PART

[0099] Exemplary aqueous inkjet ink compositions were prepared comprising a pigment dispersion, a surfactant, a biocide, a wetting agent and different combinations of a binder, a crosslinking agent and a polyol as described in the following tables 1 to 6.

[0100] More specifically, the compositions comprised the following commercially available ingredients. Diamond D80K Black Pigment Dispersion comprising 15% PB7, Lubrizol Advanced Materials UK Limited, United Kingdom; Sabosol DOS70 Surfactant, sodium diiso-octyl sulfosuccinate, Sabo SpA, Italy; Acticide MBS Biocide, Mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one, Thor Specialties Srl, Italy Daotan TW6425 / 40WA Binder, aqueous polyurethane dispersion based on Impranil DLT-C polyester, Allnex GmbH Binder, aqueous aliphatic dispersion of anionic polyurethane based on polyester-polycarbonate, Covestro Deutschland AG Neboplast PEU 3500 Binder, aliphatic aqueous polyurethane dispersion, Safic-Alcan Necarbo BV, Netherlands Petition 870250086035, dated 09 / 23 / 2025, p. 34 / 140 28 / 45 Imprafix 2794 Crosslinking agents, aliphatic blocked polyisocyanate, water-based, Covestro Deutschland AG; Tanaltinta PCI Crosslinking agents, aliphatic blocked isocyanate, water-based, Tanatex Chemicals BV Petition 870250086035, dated 09 / 23 / 2025, page 35 / 140 29 / 45 TABLE 1 Composition 1 2 3 4 5 6 7 8 9 10 11 Diamond D80K Pigment Dispersion 40 40 40 40 40 40 40 40 40 40 40 Surfactant Sabosol DOS70 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Biocide Acticide MBS 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Humectant Urea 15 15 15 15 15 15 15 15 15 15 15 Water qs 100 qs 100 qs 100 qs 100 qs 100 qs 100 qs 100 qs 100 qs 100 qs 100 qs 100 Daotan Binder TW6425 / 40WA 18 18 18 18 18 18 18 18 18 18 18 Crosslinking Agent Imprafix 2794 8 8 8 8 8 8 8 8 8 8 8 Polyol Ethylene glycol 14 - - - - - - - - - - 1,2-Propylene glycol - 14 - - - - - - - - - 1,3-Propylene glycol - - 14 - - - - - - - - 1,3-Butandiol - - - 14 - - - - - - - Petition 870250086035, dated 09 / 23 / 2025, page 36 / 140 30 / 45 Composition 1 2 3 4 5 6 7 8 9 10 11 Glycerol - - - - 14 - - - - - - 1,5-Pentandiol - - - - - 14 - - - - - PEG 1500 - - - - - - 5 - - - - Diethylene glycol - - - - - - - 14 - - - Triethylene glycol - - - - - - - - 14 - - Ethoxylated glycerin - - - - - - - - - 10 - Trimethylolpropane - - - - - - - - - - 7 Petition 870250086035, dated 09 / 23 / 2025, page 37 / 140 31 / 45 TABLE 2 Composition 12 13 14 15 16 17 18 19 20 21 22 Diamond D80K Pigment Dispersion 40 40 40 40 40 40 40 40 40 40 40 Surfactant Sabosol DOS70 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Biocide Acticide MBS 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Humectant Urea 15 15 15 15 15 15 15 15 15 15 15 Water qs 100 qs 100 qs 100 qs 100 qs 100 qs 100 qs 100 qs 100 qs 100 qs 100 qs 100 Daotan Binder TW6425 / 40WA 18 18 18 18 18 18 18 18 18 18 18 Crosslinking Agent Tanaltinta PCI 8 8 8 8 8 8 8 8 8 8 8 Polyol Ethylene glycol 14 - - - - - - - - - - 1,2-Propylene glycol - 14 - - - - - - - - - 1,3-Propylene glycol - - 14 - - - - - - - - 1,3-Butandiol - - - 14 - - - - - - - Petition 870250086035, dated 09 / 23 / 2025, p. 38 / 140 32 / 45 Composition 12 13 14 15 16 17 18 19 20 21 22 Glycerol - - - - 14 - - - - - - 1,5-Pentandiol - - - - - 14 - - - - - PEG 1500 - - - - - - 5 - - - - Diethylene glycol - - - - - - - 14 - - - Triethylene glycol - - - - - - - - 14 - - Ethoxylated glycerin - - - - - - - - - 10 - Trimethylolpropane - - - - - - - - - - 7 Petition 870250086035, dated 09 / 23 / 2025, page 39 / 140 33 / 45 TABLE 3 Composition 23 24 25 26 27 28 29 30 31 32 33 Diamond D80K Pigment Dispersion 40 40 40 40 40 40 40 40 40 40 40 Surfactant Sabosol DOS70 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Biocide Acticide MBS 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Humectant Urea 15 15 15 15 15 15 15 15 15 15 15 Water qs 100 qs 100 qs 100 qs 100 qs 100 qs 100 qs 100 qs 100 qs 100 qs 100 qs 100 Impranil Binder DLC-T 18 18 18 18 18 18 18 18 18 18 18 Crosslinking agent Imprafix 2794 8 8 8 8 8 8 8 8 8 8 8 Polyol Ethylene glycol 14 - - - - - - - - - - 1,2-Propylene glycol - 14 - - - - - - - - - 1,3-Propylene glycol - - 14 - - - - - - - - Petition 870250086035, dated 09 / 23 / 2025, pp. 40 / 140 34 / 45 Composition 23 24 25 26 27 28 29 30 31 32 33 1,3-Butandiol - - - 14 - - - - - - - Glycerol - - - - 14 - - - - - - 1,5-Pentandiol - - - - - 14 - - - - - PEG 1500 - - - - - - 5 - - - - Diethylene glycol - - - - - - - 14 - - - Triethylene glycol - - - - - - - - 14 - - Ethoxylated glycerin - - - - - - - - - 10 - Trimethylolpropane - - - - - - - - - - 7 TABLE 4 Composition 34 35 36 37 38 39 40 41 42 43 44 Diamond D80K Pigment Dispersion 40 40 40 40 40 40 40 40 40 40 40 Sabosol DOS70 Surfactant 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Biocide Acticide MBS 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Petition 870250086035, dated 09 / 23 / 2025, page 41 / 140 35 / 45 Composition 34 35 36 37 38 39 40 41 42 43 44 Humectant Urea 15 15 15 15 15 15 15 15 15 15 15 Water qs 100 qs 100 qs 100 qs 100 qs 100 qs 100 qs 100 qs 100 qs 100 qs 100 Binder Impranil DLT-C 18 18 18 18 18 18 18 18 18 18 18 Crosslinking agent Tanalik PCI 8 8 8 8 8 8 8 8 8 8 8 Polyol Ethylene glycol 14 - - - - - - - - - - 1,2-Propylene glycol - 14 - - - - - - - - - 1,3-Propylene glycol - - 14 - - - - - - - - 1,3-Butandiol - - - 14 - - - - - - - Glycerol - - - - 14 - - - - - - 1,5-Pentandiol - - - - - 14 - - - - - PEG 1500 - - - - - - 5 - - - - Diethylene glycol - - - - - - - 14 - - - Petition 870250086035, dated 09 / 23 / 2025, page 42 / 140 36 / 45 Composition 34 35 36 37 38 39 40 41 42 43 44 Triethylene glycol - - - - - - - - 14 - - Ethoxylated glycerin - - - - - - - - - 10 - Trimethylolpropane - - - - - - - - - - 7 TABLE 5 Composition 45 46 47 48 49 50 51 52 53 54 55 Diamond D80K Pigment Dispersion 40 40 40 40 40 40 40 40 40 40 40 Surfactant Sabosol DOS70 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Biocide Acticide MBS 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Humectant Urea 15 15 15 15 15 15 15 15 15 15 15 Water qs 100 qs 100 qs 100 qs 100 qs 100 qs 100 qs 100 qs 100 qs 100 qs 100 qs 100 Binder Neboplast PEU 3500 18 18 18 18 18 18 18 18 18 18 18 Petition 870250086035, dated 09 / 23 / 2025, p. 43 / 140 37 / 45 Composition 45 46 47 48 49 50 51 52 53 54 55 Crosslinking agent Imprafix 2794 8 8 8 8 8 8 8 8 8 8 8 Polyol Ethylene glycol 14 - - - - - - - - - - 1,2-Propylene glycol - 14 - - - - - - - - - 1,3-Propylene glycol - - 14 - - - - - - - - 1,3-Butandiol - - - 14 - - - - - - - Glycerol - - - - 14 - - - - - - 1,5-Pentandiol - - - - - 14 - - - - - PEG 1500 - - - - - - 5 - - - - Diethylene glycol - - - - - - - 14 - - - Triethylene glycol - - - - - - - - 14 - - Ethoxylated glycerin - - - - - - - - - 10 - Trimethylol propane - - - - - - - - - - 7 Petition 870250086035, dated 09 / 23 / 2025, page 44 / 140 38 / 45 TABLE 6 Composition 56 57 58 59 60 61 62 63 64 65 66 Diamond D80K Pigment Dispersion 40 40 40 40 40 40 40 40 40 40 40 Surfactant Sabosol DOS70 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Biocide Acticide MBS 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Humectant Urea 15 15 15 15 15 15 15 15 15 15 15 Water qs 100 qs 100 qs 100 qs 100 qs 100 qs 100 qs 100 qs 100 qs 100 qs 100 qs 100 Binder Neboplast PEU 3500 18 18 18 18 18 18 18 18 18 18 18 Crosslinking agent Tanaltinta PCI 8 8 8 8 8 8 8 8 8 8 8 Polyol Ethylene glycol 14 - - - - - - - - - - 1,2-Propylene glycol - 14 - - - - - - - - - 1,3-Propylene - - 14 - - - - - - - - Petition 870250086035, dated 09 / 23 / 2025, p. 45 / 140 39 / 45 Composition 56 57 58 59 60 61 62 63 64 65 66 Glycol 1,3-Butandiol - - - 14 - - - - - - - Glycerol - - - - 14 - - - - - - 1,5-Pentandiol - - - - - 14 - - - - - PEG 1500 - - - - - - 5 - - - - Diethylene glycol - - - - - - - 14 - - - Triethylene glycol - - - - - - - - 14 - - Ethoxylated glycerin - - - - - - - - - 10 - Trimethylolpropane - - - - - - - - - - 7 Petition 870250086035, dated 09 / 23 / 2025, p. 46 / 140 40 / 45

[0101] The performance of all paint compositions 1 to 66 was evaluated according to the following methods.

[0102] Stability to aging was evaluated by measuring the viscosity of the paint compositions at 25 °C before and after aging at 50 °C for 4 weeks with the Brookfield DV2-T viscometer at a shear rate of approximately 264 s-1 according to the following score based on the percentage increase in viscosity: Very weak = more than 60% Weak = 30% to 60% Acceptable = 15% to 30% Good = 10% to 15% Very good = less than 10%

[0103] Printability was evaluated by printing 50 meters of 100% cotton poplin fabric weighing 103 g / m2 (160 cm wide) using an MS JP7 printer with Kyocera KJ4B printheads filled with ink compositions in grayscale mode, 4 passes at 30 kHz. Printability was evaluated according to the following score based on the percentage of nozzles lost or misplaced: Weak = more than 2% Acceptable = 0.5% to 2% Good = less than 0.5%

[0104] Wet rub fastness was tested on 100% cotton poplin fabric weighing 103 g / m2 according to the standard method UNI EN ISO 105 X12:2016 under the following conditions: Type of friction Sedimentation conditions Test conditions Instrument Wet at least 4 ha 20 °C and 65% RH 20 °C and 65% RH Crockmeter Joint size Friction pressure 16 mm 9 N Petition 870250086035, dated 09 / 23 / 2025, p. 47 / 140 41 / 45 Soaking percentage 95%-100% Friction cycles 10

[0105] The results were evaluated by comparison with the gray scale prescribed by the UNI EN 20105-A03:1996 standard according to the following scoring: Weak = less than 2.5 Acceptable = 2.5 to 3.5 Good = 3.5 to 4 Very good = 4 to 5

[0106] Latency was evaluated using the same MS JP7 printer with Kyocera KJ4B printheads according to the following score based on the percentage of nozzles lost or misplaced after leaving the print carriage for 45 minutes outside the encapsulation station. Weak = more than 2% Acceptable = 0.5% to 2% Good = less than 0.5%

[0107] The printing process did not include any pre- or post-treatment of the textile substrate, but only included the step of printing the ink composition onto the textile substrate and fixing / drying the ink on the textile substrate at 160 °C for 3 minutes.

[0108] The results are summarized in the following Tables 7 to 12. TABLE 7 Composition Stability to aging Printability Latency Fastness to wet rubbing 1 Acceptable Good Acceptable Good 2 Poor Acceptable Acceptable Good 3 Poor Acceptable Acceptable Good 4 Very good Good Good Good 5 Very Good Good Good Petition 870250086035, dated 09 / 23 / 2025, pp. 48 / 140 42 / 45 Insufficient 6 Very good Good Good Good 7 Poor Poor Acceptable - 8 Poor - - - 9 Acceptable Acceptable Acceptable Good 10 Very insufficient - - Good 11 Good Acceptable Good Good TABLE 8 Composition Stability to aging Printability Latency Fastness to wet rubbing 12 Acceptable Good Acceptable Acceptable 13 Poor Acceptable Acceptable Acceptable 14 Poor Acceptable Acceptable Acceptable 15 Very good Good Good Acceptable 16 Very insufficient Good Good Acceptable 17 Very good Good Good Acceptable 18 Poor Poor Acceptable - 19 Poor - - - 20 Acceptable Acceptable Acceptable Acceptable 21 Very insufficient - - Acceptable 22 Good Acceptable Good Acceptable TABLE 9 Composition, Stability to aging, Printability, Latency, Fastness to wet friction Petition 870250086035, dated 09 / 23 / 2025, page 49 / 140 43 / 45 23 Acceptable Good Acceptable Excellent 24 Poor Acceptable Acceptable Excellent 25 Poor Acceptable Acceptable Excellent 26 Very good Good Good Excellent 27 Very insufficient Good Good Excellent 28 Very good Good Good Excellent 29 Poor Poor Acceptable - 30 Poor - - - 31 Acceptable Acceptable Acceptable Excellent 32 Very insufficient - - Excellent 33 Good Acceptable Good Excellent TABLE 10 Composition Stability to aging Printability Latency Fastness to wet rubbing 34 Acceptable Good Acceptable Good 35 Poor Acceptable Acceptable Good 36 Poor Acceptable Acceptable Good 37 Very good Good Good Good 38 Very insufficient Good Good Good 39 Very good Good Good Good 40 Poor Poor Acceptable - 41 Poor - - - 42 Acceptable Acceptable Acceptable Good 43 Very insufficient - - Good Petition 870250086035, dated 09 / 23 / 2025, page 50 / 140 44 / 45 44 Good Acceptable Good Good TABLE 11 Composition Stability to aging Printability Latency Fastness to wet rubbing 45 Acceptable Good Acceptable Good 46 Poor Acceptable Acceptable Good 47 Poor Acceptable Acceptable Good 48 Very good Good Good Good 49 Very insufficient Good Good Good 50 Very good Good Good Good 51 Poor Poor Acceptable - 52 Poor - - - 53 Acceptable Acceptable Acceptable Good 54 Very insufficient - - Good 55 Good Acceptable Good Good TABLE 12 Composition Stability to aging Printability Latency Fastness to wet rubbing 56 Acceptable Good Acceptable Acceptable 57 Poor Acceptable Acceptable Acceptable 58 Poor Acceptable Acceptable Acceptable 59 Very good Good Good Acceptable 60 Very insufficient Good Good Acceptable 61 Very good Good Good Acceptable Petition 870250086035, dated 09 / 23 / 2025, page 51 / 140 45 / 45 62 Weak Weak Acceptable - 63 Weak - - - 64 Acceptable Acceptable Acceptable Acceptable 65 Very insufficient - - Acceptable 66 Good Acceptable Good Acceptable

[0109] The results summarized in tables 7 to 12 confirmed that only the compositions comprising the selected polyols, namely, ethylene glycol (compositions 1, 12, 23, 34, 45 and 56), 1,3-butandiol (compositions 4, 15, 26, 37, 48 and 59), 1,5-pentandiol (compositions 6, 17, 28, 39, 50 and 61), triethylene glycol (compositions 9, 20, 31, 42, 53 and 64) and trimethylol propane (compositions 11, 22, 33, 44, 55 and 66) obtained at least an acceptable rating in all performances evaluated.

[0110] The best results were obtained with 1,3-butandiol (compositions 4, 15, 26, 37, 48, and 59) and 1,5-pentandiol (compositions 6, 17, 28, 39, 50, and 61).

[0111] It is understood that, given the above description of embodiments of the invention, various modifications may be made by one skilled in the art. Such modifications are intended to be covered by the claims below. Petition 870250086035, dated 09 / 23 / 2025, p. 52 / 140

Claims

1 / 3 CLAIMS 1. Water-based paint composition comprising a pigment, a polyurethane binder, a blocked crosslinking agent and a polyol, characterized in that said polyol is selected from the group consisting of ethylene glycol, 1,3-budandiol, 1,5-pentandiol, triethylene glycol, trimethylol propane and mixtures thereof.

2. Water-based paint composition according to claim 1, characterized in that said polyurethane binder is a polyurethane polymer comprising pendant hydroxyl groups attached to the polymer backbone.

3. Water-based paint composition according to claim 2, characterized in that said polyurethane polymer further comprises pendant neutralized carboxyl groups attached to the polymer backbone.

4. Water-based paint composition according to claim 1, characterized in that said paint composition comprises an amount of said polyurethane binder in the range of 1% to 40% by weight.

5. Water-based paint composition according to claim 1, characterized in that said blocked crosslinking agent is capable of reacting with a hydroxyl group of the polyurethane binder.

6. Aqueous ink composition according to claim 1, characterized in that said blocked crosslinking agent is a water-dispersible blocked isocyanate compound.

7. Water-based ink composition according to claim 1, characterized in that said blocked crosslinking agent is selected from the group consisting of lactam-blocked isocyanate, pyridine-blocked isocyanate, oxime-blocked isocyanate, azole-blocked isocyanate, malonate-blocked isocyanate, phenol-blocked isocyanate, alcohol-blocked isocyanate, mercaptan-blocked isocyanate, urethdione-blocked isocyanate, acetanilide-blocked isocyanate, sebacate-blocked isocyanate, polymer-blocked isocyanate and mixtures thereof.

8. Water-based ink composition according to claim 1, said ink composition being characterized by comprising an amount of said blocked crosslinking agent in the range of 1% to 20% by weight.

9. Water-based ink composition according to claim 1, characterized in that said polyol is selected from the group consisting of 1,3-budandiol and 1,5-pentandiol.

10. Water-based paint composition according to claim 1, said paint composition being characterized by comprising an amount of said polyol in the range of 1% to 30% by weight.

11. Water-based ink composition according to claim 1, said ink composition being characterized by comprising an amount of said pigment in the range of 0.5 to 15% by weight.

12. Water-based paint composition according to claim 1, said paint composition being characterized in that it does not comprise any polyol other than ethylene glycol, 1,3-budandiol, 1,5-pentandiol, triethylene glycol and trimethylol propane.

13. Printing process characterized by comprising: • a printing step that applies the water-based ink composition as defined in claims 1 to 12 onto a substrate, • a fixing / drying step by applying heat to chemically react the crosslinking agent and the polyurethane binder of the water-based ink composition.

14. Printing process according to claim 13, characterized in that the substrate is not subjected to a pre-treatment step with a pre-treatment solution before the printing step. Petition 870250086035, dated 09 / 23 / 2025, p. 58 / 140 3 / 3 15. Printing process according to claim 13, characterized in that the substrate is not subjected to a post-treatment step with a post-treatment solution after the printing step.

16. Printing process, according to any one of claims 13 to 15, characterized in that said substrate is a textile substrate.

17. Printing process according to claim 16, characterized in that said textile substrate is selected from the group consisting of wool, cotton, silk, polypropylene, polyethylene, aliphatic and aromatic polyamides, viscose, cellulose and polyester. Petition 870250086035, dated 09 / 23 / 2025, p. 59 / 140