WO2021216056A1

WO2021216056A1 - Fluid set

Info

Publication number: WO2021216056A1
Application number: PCT/US2020/029243
Authority: WO
Inventors: Dennis Z. Guo; Jie Zheng; Or Brandstein
Original assignee: Hewlett-Packard Development Company, L.P.
Priority date: 2020-04-22
Filing date: 2020-04-22
Publication date: 2021-10-28

Abstract

A fluid set includes a pre-treatment composition, a fixer composition, and an inkjet ink. The pre-treatment composition has a pH of 6 or greater and includes an alkali swellable emulsion or a hydrophobically modified alkali swellable emulsion. The fixer composition includes a cationic polymer and a fixer vehicle. The inkjet ink includes a white pigment, a polymeric binder, and an ink vehicle.

Description

FLUID SET

BACKGROUND

[0001] Textile printing methods often include rotary and/or flat-screen printing. Traditional analog printing typically involves the creation of a plate or a screen, i.e., an actual physical image from which ink is transferred to the textile. Both rotary and flat screen printing have great volume throughput capacity, but also have limitations on the maximum image size that can be printed. For large images, pattern repeats are used. Conversely, digital inkjet printing enables greater flexibility in the printing process, where images of any desirable size can be printed immediately from an electronic image without pattern repeats. Inkjet printers are gaining acceptance for digital textile printing, e.g., for creating signs, banners, artwork, apparel, wall coverings, window coverings, upholstery, pillows, blankets, flags, tote bags, clothing, etc. Inkjet printing is a non-impact printing method that utilizes electronic signals to control and direct droplets or a stream of ink to be deposited on media.

BRIEF DESCRIPTION OF THE DRAWINGS [0002] Features of examples of the present disclosure will become apparent by reference to the following detailed description and drawings, in which like reference numerals correspond to similar, though perhaps not identical, components. For the sake of brevity, reference numerals or features having a previously described function may or may not be described in connection with other drawings in which they appear.

[0003] Fig. 1 schematically illustrates an example fluid set and an example textile printing kit, each of which includes an example of a pre-treatment composition, an example of a fixer composition, and an example of an inkjet ink; [0004] Fig. 2 is a flow diagram illustrating an example printing method;

[0005] Fig. 3 is a schematic diagram of an example of a printing system;

[0006] Figs. 4A and 4B are reproductions of a black and white photograph and a black and white optical microscope image of a Control print formed with no pre-treatment composition;

[0007] Figs. 5A and 5B are reproductions of a black and white photograph and a black and white optical microscope image of Ex. Print 1 formed with a pre treatment composition that included a hydrophobically modified alkali swellable emulsion;

[0008] Figs. 6A and 6B are reproductions of a black and white photograph and a black and white optical microscope image of Ex. Print 5 formed with another pre-treatment composition that included another hydrophobically modified alkali swellable emulsion;

[0009] Figs. 7A and 7B are reproductions of a black and white photograph and a black and white optical microscope image of Ex. Print 9 formed with another pre-treatment composition that included an alkali swellable emulsion;

[0010] Fig. 8 is a black and white optical microscope image of a side-view of the Control print; and

[0011 ] Fig. 9 is a black and white optical microscope image of a side-view of Ex. Print 9.

DETAILED DESCRIPTION

[0012] The textile market is a major industry, and printing on textiles, such as cotton, etc., has been evolving to include digital printing methods. Some digital printing methods enable direct to garment (or other textile) printing. White ink is one of the most heavily used inks in direct to garment printing. More than two- thirds of the direct to garment printing that is performed utilizes a white ink on a colored textile. Obtaining white images with desirable opacity has proven to be challenging, in part because of fibrillation (e.g., hair-like fibers sticking out of the fabric surface). To control fibrillation and to achieve a suitable opacity of a white image on a colored garment, several techniques have been explored. As one example, a high level (e.g., from about 240 grams per square meter (gsm) to about 320 gsm) of a pre-treatment composition containing calcium salt may be applied onto the garment before the white ink is deposited. As another example, multiple layers of the ink may be deposited in the same spot. Both of these techniques involve applying high levels of fluid, which increases printing cost and drying and/or curing time.

[0013] Disclosed herein is a fluid set that is particularly suitable for obtaining white images with desirable opacity, durability (i.e., washfastness), and quality.

The fluid set includes a pre-treatment composition, a fixer composition, and an inkjet ink. The pre-treatment composition includes an alkali swellable emulsion (ASE) or a hydrophobically modified alkali swellable emulsion (HASE), each of which decreases fibrillation when it is applied on the textile fabric by a squeegee, a roller, or a screen. The pre-treatment fluid applied on the textile fabric forms a viscous layer, and thus subsequently deposited ink is not able to penetrate into the textile rapidly. The fixer composition also helps crash (fix) the white pigment ink.

As such, the combination of the pre-treatment composition, the fixer composition, and the inkjet ink improves the opacity and image quality of white images printed on colored textiles.

[0014] It has been found that relatively small amounts of the pre-treatment composition (e.g., equal to or less than 120 gsm) may be used to achieve the white images, and thus the amount of energy and time involved in drying and/or curing is reduced.

[0015] As mentioned, the fluid set disclosed herein leads to improved opacity and durability.

[0016] The opacity may be measured in terms of L^*, i.e., lightness, of the white print generated with the fluid set disclosed herein on a colored textile fabric.

A greater L^* value indicates a greater opacity of the white ink on the colored textile fabric. L^* is measured in the CIELAB color space, and may be measured using any suitable color measurement instrument (such as those available from HunterLab or X-Rite). The inkjet ink, when printed on the colored textile fabric pretreated with the pre-treatment composition and the fixer composition disclosed herein, may generate prints that have an L^* value that is greater than prints generated on the same colored textile fabric with the same inkjet ink and without the pre-treatment composition. [0017] The durability of a print on a fabric may be assessed by its ability to retain color after being exposed to washing. This is also known as washfastness. Washfastness can be measured in terms of DE. The term “DE”, as used herein, refers to the change in the L^*a^*b^* values of a color (e.g., cyan, magenta, yellow, black, red, green, blue, white) after washing. DE can be calculated by different equations, such as the CIEDE1976 color-difference formula, the CIEDE2000 color- difference formula, and/or the color difference method of the Color Measurement Committee (AE_CMC).

[0018] Throughout this disclosure, a weight percentage that is referred to as “wt% active” refers to the loading of an active component of a dispersion or other formulation that is present in the pre-treatment composition, the fixer composition, or the inkjet ink. For example, a white pigment may be present in a water-based formulation (e.g., a stock solution or dispersion) before being incorporated into the inkjet ink. In this example, the wt% actives of the white pigment accounts for the loading (as a weight percent) of the white pigment that is present in the inkjet ink, and does not account for the weight of the other components (e.g., water, etc.) that are present in the formulation with the white pigment. The term “wt%,” without the term actives, refers to either i) the loading (in the pre-treatment composition, the fixer composition, or the inkjet ink) of a 100% active component that does not include other non-active components therein, or the loading (in the pre-treatment composition, the fixer composition, or the inkjet ink) of a material or component that is used “as is” and thus the wt% accounts for both active and non-active components.

[0019] The viscosity measurements set forth herein represent those measured by a viscometer at a particular temperature and at a particular shear rate (s ¹) or at a particular speed. The temperature and shear rate or temperature and speed are identified with individual values. Viscosity may be measured, for example, by a Brookfield viscometer or another suitable instrument.

[0020] Sets and Kits

[0021] An example of the fluid set disclosed herein is shown schematically in Fig. 1. As depicted, the fluid set 10 comprises a pre-treatment composition 12 having a pH of 6 or greater and including an alkali swellable emulsion or a hydrophobically modified alkali swellable emulsion; a fixer composition 14 including a cationic polymer and a fixer vehicle; and an inkjet ink 16 including a white pigment, a polymeric binder, and an ink vehicle.

[0022] It is to be understood that any example of the pre-treatment composition 12, the fixer composition 14, and the inkjet ink 16 disclosed herein may be used in the examples of the fluid set 10.

[0023] In the examples disclosed herein, the fluid set 10 includes a pre treatment composition 12 that is formulated for analog application (e.g., by a squeegee, a roller, or a screen), and a fixer composition 14 and an inkjet ink 16 that are formulated for thermal or piezoelectric inkjet printing.

[0024] In any example of the fluid set 10, the pre-treatment composition 12, the fixer composition 14, and the inkjet ink 16 may be maintained in separate containers (e.g., respective reservoirs/fluid supplies of respective inkjet cartridges) or separate compartments (e.g., respective reservoirs/fluid supplies) in a single container (e.g., inkjet cartridge).

[0025] The fluid set 10 may also be part of a textile printing kit 20, which is also shown schematically in Fig. 1. In an example, the textile printing kit 20 includes a textile fabric 18 selected from the group consisting of polyester fabrics, polyester blend fabrics, cotton fabrics, cotton blend fabrics, nylon fabrics, nylon blend fabrics, silk fabrics, silk blend fabrics, wool fabrics, wool blend fabrics, and combinations thereof; and the fluid set 10, which includes the pre-treatment composition 12 having a pH of 6 or greater and including an alkali swellable emulsion or a hydrophobically modified alkali swellable emulsion; a fixer composition 14 including a cationic polymer and a fixer vehicle; and an inkjet ink 16 including a white pigment, a polymeric binder, and an ink vehicle.

[0026] It is to be understood that any example of the pre-treatment composition 12, the fixer composition 14, and the inkjet ink 16 disclosed herein may be used in the examples of the textile printing kit 20.

[0027] Pre-Treatment Composition

[0028] The pre-treatment composition 12 has a pH of 6 or greater and includes an alkali swellable emulsion or a hydrophobically modified alkali swellable emulsion. To form the pre-treatment composition 12, the (hydrophobically modified) alkali swellable emulsion is prepared or obtained, and then is diluted with water and neutralized with a base.

[0029] The alkali swellable emulsion includes an acrylic copolymer or a hydrophobically modified acrylic copolymer dispersed in water. It is to be understood that the phrase “(hydrophobically modified) alkali swellable emulsion” refers to either the alkali swellable emulsion or the hydrophobically modified alkali swellable emulsion.

[0030] In an example, the pre-treatment composition 12 includes the alkali swellable emulsion, and the alkali swellable emulsion includes a copolymer of an acrylic acid monomer and an acrylate ester monomer. An example of this acrylic copolymer includes from about 20% to about 80% w/w of monomer A (an ethyl ester of (meth)acrylic acid) and from about 20% to about 80% w/w of monomer B ((meth)acrylic acid). This example has the following structure (monomer A on the left and monomer B on the right):

where R is a short chain alkyl, such as -CH₂CH₃,

and Y₂ are independently selected from H or CH₃. Both m and n are selected so that each monomer is within its respective weight percent range and so that the total weight average molecular weight of the acrylic copolymer ranges from about 5,000 to about 1 ,000,000. Any weight average molecular weight throughout this disclosure is in Daltons or g/mol. [0031] In other examples, the copolymer is hydrophobically modified. In these examples, the hydrophobically modified alkali swellable emulsion includes a copolymer (more specifically a terpolymer) of an acrylic acid monomer, an acrylate ester monomer, and a hydrophobically modified acrylate ester monomer. An example of this acrylic copolymer includes from about 20% to about 80% w/w of monomer A (an ethyl ester of (meth)acrylic acid), from about 20% to about 80% w/w of monomer B ((meth)acrylic acid), and from about 0.2% to about 20% w/w of monomer C (ester of (meth)acrylic acid, modified with a hydrophobic group). This example has the following structure (monomer A on the left, monomer B in the middle, and monomer C on the right):

where R is a short chain alkyl, such as -CH₂CH₃,

Y_2, and Y₃ are independently selected from H or CH₃, R” is a long chain alkyl ranging from Ci₂ to C₂₄, and q ranges from 12 to 30. The values for m, n, and p are selected so that each monomer is within its respective weight percent range and so that the total weight average molecular weight of the acrylic copolymer ranges from about 5,000 to about 1 ,000,000.

[0032] Each of the acrylic copolymer and the hydrophobically modified acrylic copolymer has a high percentage of acid groups, depending upon the value of n in structures I and II. Thus, the emulsion is acidic, and has a low pH, ranging from about 2 to about 4.

[0033] The emulsion may be prepared by dispersing the copolymer in water. The emulsion may also be commercially available. Examples of commercially available alkali swellable emulsions include RHEOVIS® AS 1125 (an acrylic thickener from BASF Corp., 25% solids, pH ~ 2.8, and < 10 cP at 23°C and 250 s ¹). Examples of commercially available hydrophobically modified alkali swellable emulsions include RHEOVIS® AS 1152 (a hydrophobically modified acrylic thickener from BASF Corp., 40% solids, pH 3.2, and ~ 5 cP at 25°C and 0.33 s ¹) and RHEOVIS® AS 1162 (a hydrophobically modified acrylic thickener from BASF Corp., 35% solids, pH 3.5, and ~ 5 cP at 25°C and 0.33 s ¹)

[0034] As mentioned, the pre-treatment composition 12 is prepared by diluting the emulsion with water and neutralizing the diluted emulsion with a base. [0035] The amount of water that is added for dilution will depend upon the solids content of the emulsion and the desired solids in the pre-treatment composition 12. The solids content of the emulsion may vary, depending upon the acrylic copolymer or a hydrophobically modified acrylic copolymer used. As an example, the solids content of the emulsion may range from about 25% active copolymer to about 40% active copolymer. The solids content of the pre-treatment composition 12 ranges from about 0.2 wt% active copolymer to about 5 wt% active copolymer. In some examples, the solids content of the pre-treatment composition 12 ranges from about 0.5 wt% active copolymer to about 4.5 wt% active copolymer, or from about 0.75 wt% active copolymer to about 3 wt% active copolymer. In one example, the solids content of the pre-treatment composition 12 is about 1 wt% active copolymer. The water added may be purified and/or deionized water.

[0036] Neutralization may be performed with any base, such as potassium hydroxide (KOH), sodium hydroxide (NaOH), ammonium hydroxide (NH₄OH), triethanolamine (C₆H₁₅N0₃), etc. As such, examples of the pre-treatment composition 12 further include a base. The amount of base that is added will depend upon the pH of the emulsion, and will be enough to increase the pH to at least 6.

[0037] Upon neutralization of the acid groups with a base (in the presence of water), the rheology of the emulsion, and thus of the pre-treatment composition 12 including the emulsion, is affected. The viscosity of the emulsion (prior to dilution and neutralization) is low, e.g., about 10 mPa.s (or cP) or less (at 23°C and shear rate 250 s ¹) or about 5 cP (at 25°C and shear rate 0.33 s ¹). At the higher, more basic, pH, the copolymer absorbs water and swells. This increases its solubility and thickens the pre-treatment composition 12. However, after dilution and neutralization, the pre-treatment composition 12 has a viscosity of at least 15 cP measured at a shear rate of greater than or equal to 2000 s ¹ and at a temperature ranging from 20°C to 25°C. It is desirable for the pre-treatment composition 12 to be applied, e.g., using a squeegee, a roller, or a screen, and thus the upper limit of the viscosity may depend upon the application technique used. In an example, the viscosity of the pre-treatment composition 12 ranges from about 15 cP to about 60 cP.

[0038] In one example, the pre-treatment composition 12 has a viscosity of at least 15 cP measured at a shear rate of greater than or equal to 2000 s ¹ and at a temperature ranging from 20°C to 25°C; and has a solids content ranging from about 0.5 wt% to about 5 wt%.

[0039] In some examples, the pre-treatment composition 12 consists of the water, the alkali swellable emulsion or the hydrophobically modified alkali swellable emulsion, and the base. In these examples, the pre-treatment composition 12 includes no other components.

[0040] Fixer Composition

[0041] The fixer composition 14 includes a cationic polymer and a fixer vehicle. In some examples, the fixer composition 14 consists of the cationic polymer and the fixer vehicle. In other examples, the fixer composition 14 may include additional components.

[0042] Cationic Polymer

[0043] The cationic polymer included in the fixer composition 14 has a weight average molecular weight ranging from about 3,000 to about 3,000,000. [0044] In some examples, the cationic polymer of the fixer composition 14 is selected from the group consisting of poly(diallyldimethylammonium chloride); poly(methylene-co-guanidine) anion, wherein the anion is selected from the group consisting of hydrochloride, bromide, nitrate, sulfate, and sulfonates; a polyamine; poly(dimethylamine-co-epichlorohydrin); a polyethylenimine; a polyamide epichlorohydrin resin; a polyamine epichlorohydrin resin; and a combination thereof. Some examples of commercially available polyamine epichlorohydrin resins may include CREPETROL™ 73, KYMENE™ 736, KYMENE™ 736NA, POLYCUP™ 7360, and POLYCUP™ 7360A, each of which is available from Solenis LLC.

[0045] In an example, the cationic polymer of the fixer composition 14 is present in an amount ranging from about 1 wt% active to about 15 wt% active based on a total weight of the fixer composition 14. In further examples, the cationic polymer is present in an amount ranging from about 1 wt% active to about 10 wt% active; or from about 4 wt% active to about 8 wt% active; or from about 2 wt% active to about 7 wt% active; or from about 6 wt% active to about 10 wt% active, based on a total weight of the fixer composition 14.

[0046] Fixer Vehicle

[0047] As mentioned above, the fixer composition 14 also includes the fixer vehicle. As used herein, the term “fixer vehicle” may refer to the liquid in which the cationic polymer is mixed to form the fixer composition 14.

[0048] In an example of the fixer composition 14, the fixer vehicle includes a surfactant, a co-solvent, an anti-kogation agent, and a balance of water. In another example, the fixer composition 14 further comprises a pH adjuster. As such, some examples of the fixer vehicle (and thus the fixer composition 14) include a surfactant, a co-solvent, an anti-kogation agent, and/or a pH adjuster.

[0049] The surfactant in the fixer composition 14 may be any non-ionic surfactant or cationic surfactant.

[0050] Examples of the non-ionic surfactant may include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyglycerin fatty acid ester, polyoxyethylene alkylamine, polyoxyethylene fatty acid amide, alkylalkanolamide, polyethylene glycol polypropylene glycol block copolymer, acetylene glycol, and a polyoxyethylene adduct of acetylene glycol. Specific examples of the non-ionic surfactant may include polyoxyethylenenonyl phenylether, polyoxyethyleneoctyl phenylether, and polyoxyethylenedodecyl. Further examples of the non-ionic surfactant may include silicon surfactants such as a polysiloxane oxyethylene adduct; fluorine surfactants such as perfluoroalkylcarboxylate, perfluoroalkyl sulfonate, and oxyethyleneperfluoro alkylether; and biosurfactants such as spiculisporic acid, rhamnolipid, and lysolecithin.

[0051 ] More specific examples of non-ionic surfactant include a silicone-free alkoxylated alcohol surfactant such as, for example, TEGO® Wet 510 (Evonik Degussa) and/or a self-emulsifiable wetting agent based on acetylenic diol chemistry, such as, for example, SURFYNOL® SE-F (Evonik Degussa). Other suitable commercially available non-ionic surfactants include SURFYNOL® 465 (ethoxylatedacetylenic diol), SURFYNOL® 440 (an ethoxylated low-foam wetting agent) SURFYNOL® CT-211 (now CARBOWET® GA-211 , non-ionic, alkylphenylethoxylate and solvent free), and SURFYNOL® 104 (non-ionic wetting agent based on acetylenic diol chemistry), (all of which are from Evonik Degussa); ZONYL® FSO (a.k.a. CAPSTONE®, which is a water-soluble, ethoxylated non ionic fluorosurfactant from DuPont); TERGITOL® TMN-3 and TERGITOL® TMN-6 (both of which are branched secondary alcohol ethoxylate, non-ionic surfactants), and TERGITOL® 15-S-3, TERGITOL® 15-S-5, and TERGITOL® 15-S-7 (each of which is a secondary alcohol ethoxylate, non-ionic surfactant) (all of the TERGITOL® surfactants are available from The Dow Chemical Company); and BYK® 345, BYK® 346, BYK® 347, BYK® 348, BYK® 349 (each of which is a silicone surfactant) (all of which are available from BYK Additives and Instruments). [0052] Examples of the cationic surfactant include quaternary ammonium salts, such as benzalkonium chloride, benzethonium chloride, methylbenzethonium chloride, cetalkonium chloride, cetylpyridinium chloride, cetrimonium, cetrimide, dofanium chloride, tetraethylammonium bromide, didecyldimethylammonium chloride, domiphen bromide, alkylbenzyldimethylammonium chlorides, distearyldimethylammonium chloride, diethyl ester dimethyl ammonium chloride, dipalmitoylethyl hydroxyethylmonium methosulfate, and ACCOSOFT® 808 (methyl (1) tallow amidoethyl (2) tallow imidazolinium methyl sulfate available from Stepan Company). Other examples of the cationic surfactant include amine oxides, such as lauryldimethylamine oxide, myristamine oxide, cocamine oxide, stearamine oxide, and cetamine oxide.

[0053] In any of the examples disclosed herein, the surfactant may be present in an amount ranging from about 0.01 wt% active to about 5 wt% active (based on the total weight of the fixer composition 14). In an example, the surfactant is present in the fixer composition 14 in an amount ranging from about 0.05 wt% active to about 3 wt% active, based on the total weight of the fixer composition 14. In another example, the surfactant is present in fixer composition 14 in an amount of about 0.3 wt% active, based on the total weight of the fixer composition 14. [0054] The co-solvent in the fixer composition 14 may be a water soluble or water miscible co-solvent. Examples of co-solvents include alcohols, amides, esters, ketones, lactones, and ethers. In additional detail, the co-solvent may include aliphatic alcohols, aromatic alcohols, diols, glycol ethers, polyglycol ethers, caprolactams, formamides, acetamides, and long chain alcohols. Examples of such compounds include primary aliphatic alcohols, secondary aliphatic alcohols, 1 ,2-alcohols, 1 ,3-alcohols, 1 ,5-alcohols, ethylene glycol alkyl ethers, propylene glycol alkyl ethers (e.g., DOWANOL™ TPM (from Dow Chemical), higher homologs (C₆-Ci₂) of polyethylene glycol alkyl ethers, N-alkyl caprolactams, unsubstituted caprolactams, both substituted and unsubstituted formamides, both substituted and unsubstituted acetamides, and the like. Specific examples of alcohols may include ethanol, isopropyl alcohol, butyl alcohol, and benzyl alcohol. Other specific examples include 2-ethyl-2-(hydroxymethyl)-1 , 3-propane diol (EPHD), dimethyl sulfoxide, sulfolane, and/or alkyldiols such as 1 ,2-hexanediol.

[0055] The co-solvent may also be a polyhydric alcohol or a polyhydric alcohol derivative. Examples of polyhydric alcohols may include ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1 ,5- pentanediol, 1 ,2-hexanediol, 1 ,2,6-hexanetriol, glycerin, trimethylolpropane, and xylitol. Examples of polyhydric alcohol derivatives may include an ethylene oxide adduct of diglycerin.

[0056] The co-solvent may also be a nitrogen-containing solvent. Examples of nitrogen-containing solvents may include 2-pyrrolidone, 1-(2-hydroxyethyl)-2- pyrrolidone, N-methyl-2-pyrrolidone, cyclohexylpyrrolidone, and triethanolamine. [0057] In one specific example of the fixer composition 14, the co-solvent includes 2-pyrrolidone, 1-(2-hydroxyethyl)-2-pyrrolidone, glycerol, 2-methyl-1 ,3- propanediol, 1 ,2-butane diol, diethylene glycol, triethylene glycol, tetraethylene glycol, or a combination thereof.

[0058] The co-solvent(s) may be present in an amount ranging from about 4 wt% to about 30 wt% (based on the total weight of the fixer composition 14). In an example, the total amount of co-solvent(s) present in the fixer composition 14 is about 10 wt% (based on the total weight of the fixer composition 14).

[0059] An anti-kogation agent may also be included in a fixer composition that is to be thermal inkjet printed. Kogation refers to the deposit of dried printing liquid on a heating element of a thermal inkjet printhead. Anti-kogation agent(s) is/are included to assist in preventing the buildup of kogation. In some examples, the anti-kogation agent may improve the jettability of the fixer composition 14. The anti-kogation agent(s) may be present in the fixer composition 14 in a total amount ranging from about 0.1 wt% active to about 1.5 wt% active, based on the total weight of the fixer composition 14. In an example, the anti-kogation agent(s) is/are present in an amount of about 0.5 wt% active, based on the total weight of the fixer composition 14.

[0060] Examples of suitable anti-kogation agents include oleth-3-phosphate (commercially available as CRODAFOS™ 03A or CRODAFOS™ N-3A), oleth-5- phosphate (commercially available as CRODAFOS™ 05A), or dextran 500k.

Other suitable examples of the anti-kogation agents include CRODAFOS™ HCE (phosphate-ester from Croda Int.), CRODAFOS™ CES (phosphate-based emulsifying and conditioning wax from Croda Int.), CRODAFOS® N10 (oleth-10- phosphate from Croda Int.), or DISPERSOGEN® LFH (polymeric dispersing agent with aromatic anchoring groups, acid form, anionic, from Clariant), etc. It is to be understood that any combination of the anti-kogation agents listed may be used. [0061] A pH adjuster may also be included in the fixer composition 14. A pH adjuster may be included in the fixer composition 14 to achieve a desired pH (e.g., about 4) and/or to counteract any slight pH increase that may occur over time. An example of a suitable pH adjuster that may be used in the fixer composition 14 includes methane sulfonic acid, nitric acid, and phosphoric acid. In an example, the total amount of pH adjuster(s) in the fixer composition 14 ranges from greater than 0 wt% to about 0.1 wt% (based on the total weight of the fixer composition 14). In another example, the total amount of pH adjuster(s) in the fixer composition 14 is about 0.03 wt% (based on the total weight of the fixer composition 14).

[0062] Suitable pH ranges for examples of the fixer composition 14 can be less than pH 7, from pH 2 to less than pH 7, from pH 5.5 to less than pH 7, from pH 5 to pH 6.6, or from pH 5.5 to pH 6.6. In one example, the pH of the fixer composition 14 is pH 4.

[0063] The balance of the fixer composition 14 is water. As such, the weight percentage of the water present in the fixer composition 14 will depend, in part, upon the weight percentages of the other components. The water may be purified water or deionized water.

[0064] The viscosity of the fixer composition 14 may vary depending upon the application method that is to be used to apply the fixer composition 14. As an example, when the fixer composition 14 is to be applied with an analog applicator, the viscosity of the fixer composition 14 may range from about 20 centipoise (cP) to about 300 cP (at 20°C to 25°C and a shear rate of about 3,000 Hz). As other examples, when the fixer composition 14 is to be applied with an thermal inkjet applicator/printhead, the viscosity of the fixer composition 14 may range from about 1 cP to about 9 cP (at 20°C to 25°C and a shear rate of about 3,000 Hz), and when the fixer composition 14 is to be applied with an piezoelectric inkjet applicator/printhead, the viscosity of the fixer composition 14 may range from about 1 cP to about 20 cP (at 20°C to 25°C and a shear rate of about 3,000 Hz).

[0065] Inkjet Ink

[0066] The inkjet ink 16 includes a white pigment, a polymeric binder, and an ink vehicle. In some examples, the inkjet ink 16 consists of the white pigment, the polymeric binder; and the ink vehicle. In other examples, the inkjet ink 16 may include additional components.

[0067] White Pigment Dispersion

[0068] The white pigment may be incorporated into the inkjet ink 16 as a white pigment dispersion. The white pigment dispersion may include a white pigment and a separate pigment dispersant.

[0069] For the white pigment dispersions disclosed herein, it is to be understood that the white pigment and separate pigment dispersant (prior to being incorporated into the ink formulation), may be dispersed in water alone or in combination with an additional water soluble or water miscible co-solvent, such as 2-pyrrolidone, 1-(2-hydroxyethyl)-2-pyrrolidone, glycerol, 2-methyl-1 , 3-propanediol, 2, 2-dimethyl-1 , 3-propanediol, 1 ,2-butane diol, diethylene glycol, 1 ,3-propanediol, 1 ,4-butanediol, 1 ,5-pentanediol, triethylene glycol, tetraethylene glycol, hexylene glycol, or a combination thereof. It is to be understood however, that the liquid components of the white pigment dispersion become part of the ink vehicle in the inkjet ink 16. [0070] White Pigments

[0071] Examples of suitable white pigments include white metal oxide pigments, such as titanium dioxide (Ti0₂), zinc oxide (ZnO), zirconium dioxide (Zr0₂), or the like. In one example, the white pigment is titanium dioxide. In an example, the titanium dioxide is in its rutile form.

[0072] In some examples, the white pigment may include white metal oxide pigment particles coated with silicon dioxide (Si0₂). In one example, the white metal oxide pigment content to silicon dioxide content can be from 100:3.5 to 5:1 by weight. In other examples, the white pigment may include white metal oxide pigment particles coated with silicon dioxide (Si0₂) and aluminum oxide (Al₂0₃). In one example, the white metal oxide pigment content to total silicon dioxide and aluminum oxide content can be from 50:3 to 4:1 by weight. One example of the white pigment includes TI-PURE® R960 (Ti0₂ pigment powder with 5.5 wt% silica and 3.3 wt% alumina (based on pigment content)) available from Chemours. Another example of the white pigment includes TI-PURE® R931 (Ti0₂ pigment powder with 10.2 wt% silica and 6.4 wt% alumina (based on pigment content)) available from Chemours. Still another example of the white pigment includes TI- PURE® R706 (Ti0₂ pigment powder with 3.0 wt% silica and 2.5 wt% alumina (based on pigment content)) available from Chemours.

[0073] The white pigment may have high light scattering capabilities, and the average particle size of the white pigment may be selected to enhance light scattering and lower transmittance, thus increasing opacity. The average particle size of the white pigment may range anywhere from about 10 nm to about 2000 nm. In some examples, the average particle size ranges from about 120 nm to about 2000 nm, from about 150 nm to about 1000 nm, from about 150 nm to about 750 nm, or from about 200 nm to about 500 nm. Smaller particles may be desirable depending upon the jetting architecture that is used. The term “average particle size”, as used herein, may refer to a volume-weighted mean diameter of a particle distribution.

[0074] The amount of the white pigment in the dispersion may range from about 20 wt% to about 60 wt%, based on the total weight of the dispersion. The white pigment dispersion may then be incorporated into the ink vehicle so that the white pigment is present in an active amount that is suitable for the inkjet printing architecture that is to be used. In an example, the white pigment dispersion is incorporated into the ink vehicle so that the white pigment is present in an amount ranging from about 3 wt% active to about 20 wt% active, based on a total weight of the inkjet ink 16. In other examples, the white pigment dispersion is incorporated into the ink vehicle so that the white pigment is present in an amount ranging from about 5 wt% active to about 20 wt% active, or from about 5 wt% active to about 15 wt% active, based on a total weight of the inkjet ink 16. In still another example, the white pigment dispersion is incorporated into the ink vehicle so that the white pigment is present in an amount of about 10 wt% active or about 9.75 wt% active, based on a total weight of the inkjet ink 16.

[0075] Pigment Dispersants

[0076] The white pigment may be dispersed with the pigment dispersant. In an example, the pigment dispersant is selected from the group consisting of a water-soluble acrylic acid polymer, a branched co-polymer of a comb-type structure with polyether pendant chains and acidic anchor groups attached to a backbone, and a combination thereof.

[0077] Some examples of the water-soluble acrylic acid polymer include CARBOSPERSE® K7028 (polyacrylic acid having a weight average molecular weight (Mw) of about 2,300), CARBOSPERSE® K752 (polyacrylic acid having a weight average molecular weight (Mw) of about 2,000), CARBOSPERSE® K7058 (polyacrylic acid having a weight average molecular weight (Mw) of about 7,300), and CARBOSPERSE® K732 (polyacrylic acid having a weight average molecular weight (Mw) of about 6,000), all available from Lubrizol Corporation.

[0078] Some examples of the branched co-polymer of the comb-type structure with polyether pendant chains and acidic anchor groups attached to the backbone include DISPERBYK®-190 (an acid number of about 10 mg KOH/g) and DISPERBYK®-199, both available from BYK Additives and Instruments, as well as DISPERSOGEN® PCE available from Clariant.

[0079] The amount of the pigment dispersant in the dispersion may range from about 0.1 wt% to about 2 wt%, based on the total weight of the dispersion.

The white pigment dispersion may then be incorporated into the ink vehicle so that the pigment dispersant is present in an amount ranging from about 0.01 wt% active to about 0.5 wt% active, based on a total weight of the inkjet ink 16. In one of these examples, the dispersant is present in an amount of about 0.04 wt% active, based on a total weight of the inkjet ink 16.

[0080] In some examples, the pigment dispersant includes both the water- soluble acrylic acid polymer and the branched co-polymer of the comb-type structure with polyether pendant chains and acidic anchor groups attached to the backbone. In some of these examples, the pigment dispersant includes CARBOSPERSE® K7028 and DISPERBYK®-190. In some of these examples, the pigment dispersant includes both the water-soluble acrylic acid polymer and the branched co-polymer of the comb-type structure with polyether pendant chains and acidic anchor groups attached to the backbone, where the water-soluble acrylic acid polymer is present in an amount ranging from about 0.02 wt% active to about 0.4 wt% active, and the branched co-polymer of the comb-type structure with polyether pendant chains and acidic anchor groups attached to the backbone is present in an amount ranging from about 0.03 wt% active to about 0.6 wt% active.

In one of these examples, the water-soluble acrylic acid polymer is present in an amount of about 0.09 wt% active, and the branched co-polymer of the comb-type structure with polyether pendant chains and acidic anchor groups attached to the backbone is present in an amount of about 0.14 wt% active.

[0081] Polymeric Binder

[0082] The inkjet ink 16 also includes a polymeric binder, which may be anionic and/or non-ionic. In an example, the polymeric binder in the inkjet ink 16 is a polyurethane-based binder selected from the group consisting of a polyester- polyurethane binder, a polyether-polyurethane binder, a polycarbonate- polyurethane binder, and combinations thereof.

[0083] In an example, the inkjet ink 16 includes the polyester-polyurethane binder. In an example, the polyester-polyurethane binder is an anionic sulfonated polyester-polyurethane binder. The sulfonated polyester-polyurethane binder can include diaminesulfonate groups. In an example, the polymeric binder is the polyester-polyurethane binder. The polyester-polyurethane binder is a sulfonated polyester-polyurethane binder, and is one of: i) an aliphatic compound including multiple saturated C₄ to Cm carbon chains and/or an alicyclic carbon moiety, that is devoid of an aromatic moiety, or ii) an aromatic compound including an aromatic moiety and multiple saturated carbon chain portions ranging from C₄ to Cm in length.

[0084] As mentioned, the sulfonated polyester-polyurethane binder can be anionic. In further detail, the sulfonated polyester-polyurethane binder can also be aliphatic, including saturated carbon chains as part of the polymer backbone or as a side-chain thereof, e.g., C₂ to Cm, C₃ to C₉, or C₃ to C₆ alkyl. The sulfonated polyester-polyurethane binder can also contain alicyclic carbon moiety. These polyester-polyurethane binders can be described as “aliphatic” because these carbon chains are saturated and because they are devoid of aromatic moieties. An example of a commercially available anionic aliphatic polyester-polyurethane binder that can be used is IMPRANIL® DLN-SD (Mw 133,000; Acid Number 5.2; Tg -47°C; Melting Point 175-200°C) from Covestro. Example components used to prepare the IMPRANIL® DLN-SD or other anionic aliphatic polyester-polyurethane binders suitable for the examples disclosed herein can include pentyl glycols (e.g., neopentyl glycol); C₄ to Cm alkyldiol (e.g., hexane-1 ,6-diol); C₄ to Cm alkyl dicarboxylic acids (e.g., adipic acid); C₄to Cmalkyldiarnine (e.g., (2, 4, 4)- trimethylhexane-1 ,6-diamine (TMD), isophorone diamine (IPD)); C₄ to Cm alkyl diisocyanates (e.g., hexamethylene diisocyanate (HDI), (2, 4, 4)-trimethylhexane- 1 , 6-diisocyanate (TMDI)); alicyclic diisocyanates (e.g. isophorone diisocyanate (IPDI), 1 ,3-bis(isocyanatomethyl)cyclohexane (H6XDI)); diamine sulfonic acids (e.g., 2-[(2-aminoethyl)amino]ethanesulfonic acid); etc.

[0085] Alternatively, the sulfonated polyester-polyurethane binder can be aromatic (or include an aromatic moiety) and can include aliphatic chains. An example of an anionic aromatic polyester-polyurethane binder that can be used is DISPERCOLL® U42. Example components used to prepare the DISPERCOLL® U42 or other similar aromatic polyester-polyurethane binders can include aromatic dicarboxylic acids, e.g., phthalic acid; C₄ to Cm alkyl dialcohols (e.g., hexane-1 , 6- diol); C₄ to Cm alkyl diisocyanates (e.g., hexamethylene diisocyanate (HDI)); diamine sulfonic acids (e.g., 2-[(2-aminoethyl)amino]ethanesulfonic acid); etc.

[0086] Other types of anionic polyester-polyurethanes can also be used, including IMPRANIL® DL 1380, which can be somewhat more difficult to jet from thermal inkjet printheads compared to IMPRANIL® DLN-SD and DISPERCOLL® U42, but still can be acceptably jetted in some examples, and can also provide acceptable washfastness results on a variety of fabric types.

[0087] The polyester-polyurethane binders disclosed herein may have a weight average molecular weight (Mw, g/mol or Daltons) ranging from about 20,000 to about 300,000. In some examples of the inkjet ink 16, the polymeric binder is the polyester-polyurethane binder, and the polyester-polyurethane binder has a weight average molecular weight ranging from about 20,000 Mw to about 300,000 Mw. As examples, the weight average molecular weight can range from about 50,000 to about 1 ,000,000, from about 100,000 to about 400,000, or from about 150,000 to about 300,000.

[0088] The polyester-polyurethane binders disclosed herein may have an acid number that ranges from about 1 mg KOH/ g to about 50 mg KOH/g. In some examples of the inkjet ink 16, the polymeric binder is the polyester-polyurethane binder, and the polyester-polyurethane binder has an acid number that ranges from about 1 mg KOH/ g to about 50 mg KOH/g. As other examples, the acid number of the polyester-polyurethane binder can range from about 1 mg KOH/g to about 200 mg KOH/g, from about 2 mg KOH/g to about 100 mg KOH/g, or from about 3 mg KOH/g to about 50 mg KOH/g.

[0089] As used herein, the term “acid number” refers to the mass of potassium hydroxide (KOH) in milligrams that is used to neutralize one (1) gram of a particular substance. The test for determining the acid number of a particular substance may vary, depending on the substance. To determine the acid number of the polyester-polyurethane binder, a known amount of a sample of the polyester- polyurethane binder may be dispersed in water and the aqueous dispersion may be titrated with a polyelectrolyte titrant of a known concentration. In this example, a current detector for colloidal charge measurement may be used. An example of a current detector is the Miitek PCD-05 Smart Particle Charge Detector (available from BTG). The current detector measures colloidal substances in an aqueous sample by detecting the streaming potential as the sample is titrated with the polyelectrolyte titrant to the point of zero charge. An example of a suitable polyelectrolyte titrant is poly(diallyldimethylammonium chloride) (i.e.,

PolyDADMAC). It is to be understood that any suitable test for a particular component may be used. [0090] The average particle size of the polyester-polyurethane binders disclosed herein may range from about 20 nm to about 500 nm. As examples, the sulfonated polyester-polyurethane binder can have an average particle size ranging from about 20 nm to about 500 nm, from about 50 nm to about 350 nm, or from about 100 nm to about 350 nm. The particle size of any solids herein, including the average particle size of the dispersed polymer binder, can be determined using a NAN OT RAC® Wave device, from Microtrac, e.g., NANOTRAC® Wave II or NANOTRAC® 150, etc., which measures particles size using dynamic light scattering. Average particle size can be determined using particle size distribution data generated by the NANOTRAC® Wave device. As mentioned, the term “average particle size” may refer to a volume-weighted mean diameter of a particle distribution.

[0091] Other examples of the inkjet ink 16 include an anionic polyether- polyurethane binder. Examples of anionic polyether-polyurethanes that may be used include IMPRANIL® LP DSB 1069, IMPRANIL® DLE, IMPRANIL® DAH, or IMPRANIL® DL 1116 (Covestro (Germany)); or HYDRAN® WLS-201 or HYDRAN® WLS-201 K (DIC Corp. (Japan)); orTAKELAC® W-6061T or TAKE LAC® WS-6021 (Mitsui (Japan)).

[0092] Still other examples of the inkjet ink 16 include an anionic polycarbonate-polyurethane binder. Examples of anionic polycarbonate- polyurethanes that may be used as the polymeric binder include IMPRANIL® DLC- F or IMPRANIL® DL 2077 (Covestro (Germany)); or HYDRAN® WLS-213 (DIC Corp. (Japan)); orTAKELAC® W-6110 (Mitsui (Japan)).

[0093] Examples of non-ionic polyurethane binders include RUCO-PUR® SPH (a hydrophilic, non-ionic polyurethane available from Rudolf Group) and RUCO-COAT® EC 4811 (an aqueous polyurethane/polyether dispersion available from Rudolf Group). Another example of a non-ionic polyurethane binder includes IMPRANIL® DLI (polyether-polyurethane available from Covestro).

[0094] In some examples of the inkjet ink 16, the polymeric binder is present in an amount ranging from about 1 wt% active to about 20 wt% active, based on a total weight of the inkjet ink 16. In other examples, the polymeric binder can be present, in the inkjet ink 16, in an amount ranging from about 2 wt% active to about 15 wt% active, or from about from about 3 wt% active to about 11 wt% active, or from about 4 wt% active to about 10 wt% active, or from about 5 wt% active to about 9 wt% active, each of which is based on the total weight of the inkjet ink 16. [0095] The polymeric binder (prior to being incorporated into the inkjet ink 16) may be dispersed in water alone or in combination with an additional water soluble or water miscible co-solvent, such as 2-pyrrolidone, 1-(2-hydroxyethyl)-2- pyrrolidone, glycerol, 2-methyl-1 , 3-propanediol, 1 ,2-butane diol, diethylene glycol, triethylene glycol, tetraethylene glycol, or a combination thereof. It is to be understood however, that the liquid components of the binder dispersion become part of the vehicle in the inkjet ink 16.

[0096] Ink Vehicle

[0097] In addition to the pigment and the polymeric binder, the inkjet ink 16 includes an ink vehicle.

[0098] As used herein, the term “ink vehicle” may refer to the liquid with which the pigment (dispersion) and polymeric binder (dispersion) are mixed to form a thermal or a piezoelectric inkjet ink(s) composition. A wide variety of vehicles may be used with the ink composition(s) of the present disclosure. The ink vehicle may include water and any of: a co-solvent, a surfactant, an anti-kogation agent, an anti-decel agent, an antimicrobial agent, a pH adjuster, or combinations thereof. In an example of the ink inkjet ink, the vehicle includes water and a co-solvent. In another example, the vehicle consists of water and the co-solvent, the anti-kogation agent, the anti-decel agent, the surfactant, the antimicrobial agent, a pH adjuster, or a combination thereof. In still another example, the ink vehicle consists of the anti-kogation agent, the anti-decel agent, the surfactant, the antimicrobial agent, a pH adjuster, and water.

[0099] The co-solvent in the inkjet ink 16 may be any example of the co solvents set forth herein for the fixer composition 14, in any amount set forth herein for the fixer composition 14 (except that the amount(s) are based on the total weight of the inkjet ink 16 instead of the fixer composition 14).

[0100] The surfactant in the inkjet ink 16 may be any anionic and/or non ionic surfactant.

[0101 ] Examples of the anionic surfactant may include alkylbenzene sulfonate, alkylphenyl sulfonate, alkylnaphthalene sulfonate, higher fatty acid salt, sulfate ester salt of higher fatty acid ester, sulfonate of higher fatty acid ester, sulfate ester salt and sulfonate of higher alcohol ether, higher alkyl sulfosuccinate, polyoxyethylene alkylether carboxylate, polyoxyethylene alkylether sulfate, alkyl phosphate, and polyoxyethylene alkyl ether phosphate. Specific examples of the anionic surfactant may include dodecylbenzenesulfonate, isopropylnaphthalenesulfonate, monobutylphenylphenol monosulfonate, monobutylbiphenyl sulfonate, monobutylbiphenylsul fonate, and dibutylphenylphenol disulfonate.

[0102] Any example of the non-ionic surfactants set forth herein for the fixer composition 14 may be used in the inkjet ink 16.

[0103] Furthermore, the anionic and/or non-ionic surfactant may be included in the inkjet ink in any amount set forth herein for the surfactant in the fixer composition 14 (except that the amount(s) are based on the total weight of the inkjet ink 16 instead of the fixer composition 14).

[0104] An anti-kogation agent may also be included in the vehicle of the inkjet ink 16, for example, when the inkjet ink 16 is to be applied via a thermal inkjet printhead. Anti-kogation agent(s) is/are included to assist in preventing the buildup of kogation. In some examples, the anti-kogation agent may improve the jettability of the inkjet ink 16. Examples of suitable anti-kogation agents include oleth-3- phosphate (commercially available as CRODAFOS™ 03A or CRODAFOS™ N-3A) or dextran 500k. Other suitable examples of the anti-kogation agents include CRODAFOS™ HCE (phosphate-ester from Croda Int.), CRODAFOS® 010A (oleth-10-phosphate from Croda Int.), or DISPERSOGEN® LFH (polymeric dispersing agent with aromatic anchoring groups, acid form, anionic, from Clariant), etc. It is to be understood that any combination of the anti-kogation agents listed may be used.

[0105] The anti-kogation agent may be present in the inkjet ink 16 in an amount ranging from about 0.1 wt% active to about 1.5 wt% active, based on the total weight of the inkjet ink 16. In an example, the anti-kogation agent is present in an amount of about 0.5 wt% active, based on the total weight of the inkjet ink 16. [0106] The ink vehicle may also include anti-decel agent(s). The anti-decel agent may function as a humectant. Decel refers to a decrease in drop velocity over time with continuous firing. In the examples disclosed herein, the anti-decel agent(s) is/are included to assist in preventing decel. In some examples, the anti- decel agent may improve the jettability of the inkjet ink 16. An example of a suitable anti-decel agent is ethoxylated glycerin having the following formula:

in which the total of a+b+c ranges from about 5 to about 60, or in other examples, from about 20 to about 30. An example of the ethoxylated glycerin is LIPONIC® EG-1 (LEG-1 , glycereth-26, a+b+c=26, available from Lipo Chemicals).

[0107] The anti-decel agent(s) may be present in an amount ranging from about 0.2 wt% active to about 5 wt% active (based on the total weight of the inkjet ink 16). In an example, the anti-decel agent is present in the inkjet ink 16 in an amount of about 1 wt% active, based on the total weight of the inkjet ink 16.

[0108] The vehicle of the inkjet ink 16 may also include antimicrobial agent(s). Antimicrobial agents are also known as biocides and/or fungicides. Examples of suitable antimicrobial agents include the NUOSEPT® (Ashland Inc.), UCARCIDE™ or KORDEK™ or ROCIMA™ (Dow Chemical Co.), PROXEL® (Arch Chemicals) series, ACTICIDE® B20 and ACTICIDE® M20 and ACTICIDE® MBL (blends of 2-methyl-4-isothiazolin-3-one (MIT), 1 ,2-benzisothiazolin-3-one (BIT) and Bronopol) (Thor Chemicals), AXIDE™ (Planet Chemical), NIPACIDE™ (Clariant), blends of 5-chloro-2-methyl-4-isothiazolin-3-one (CIT or CMIT) and MIT under the tradename KATHON™ (Dow Chemical Co.), and combinations thereof.

[0109] In an example, the total amount of antimicrobial agent(s) in the inkjet ink 16 ranges from about 0.01 wt% active to about 0.05 wt% active (based on the total weight of the inkjet ink 16). In another example, the total amount of antimicrobial agent(s) in the inkjet ink 16is about 0.044 wt% active (based on the total weight of the inkjet ink 16).

[0110] The ink vehicle of the inkjet ink 16 may also include a pH adjuster. A pH adjuster may be included in the inkjet ink 16 to achieve a desired pH of greater than 7. Suitable pH ranges for examples of the ink composition can be from greater than pH 7 to pH 11 , from greater than pH 7 to pH 10, from pH 7.2 to pH 10, from pH 7.5 to pH 10, from pH 8 to pH 10, 7 to pH 9, from pH 7.2 to pH 9, from pH 7.5 to pH 9, from pH 8 to pH 9, from 7 to pH 8.5, from pH 7.2 to pH 8.5, from pH 7.5 to pH 8.5, from pH 8 to pH 8.5, from 7 to pH 8, from pH 7.2 to pH 8, or from pH 7.5 to pH 8.

[0111] The type and amount of pH adjuster that is added to the ink composition may depend upon the initial pH of the ink composition and the desired final pH of the ink composition. If the initial pH is too high, an acid may be added to lower the pH, and if the initial pH is too low, a base may be added increase the pH. Examples of suitable pH adjusters include metal hydroxide bases, such as potassium hydroxide (KOH), sodium hydroxide (NaOH), etc. In an example, the metal hydroxide base may be added to the inkjet ink 16 in an aqueous solution. In another example, the metal hydroxide base may be added to the inkjet ink 16 in an aqueous solution including 5 wt% of the metal hydroxide base (e.g., a 5 wt% potassium hydroxide aqueous solution).

[0112] In an example, the total amount of pH adjuster(s) in the inkjet ink 16 ranges from greater than 0 wt% to about 0.1 wt% (based on the total weight of the inkjet ink 16). In another example, the total amount of pH adjuster(s) in the inkjet ink 16 is about 0.03 wt% (based on the total weight of the inkjet ink 16).

[0113] The balance of the inkjet ink 16 is water. In an example, purified water or deionized water may be used. The water included in the inkjet ink 16 may be: i) part of the pigment dispersion, and/or binder dispersion, ii) part of the ink vehicle, iii) added to a mixture of the pigment dispersion, and/or binder dispersion and the ink vehicle, or iv) a combination thereof. In examples where the inkjet ink 16 is a thermal inkjet ink, the ink vehicle includes at least 70% by weight of water.

In examples where the ink composition is a piezoelectric inkjet ink, the liquid vehicle is a solvent based vehicle including at least 50% by weight of the co solvent.

[0114] One specific example of the inkjet ink 16 includes the pigment in an amount ranging from about 1 wt% active to about 10 wt% active based on the total weight of the inkjet ink 16; the polymeric binder in an amount ranging from about 2 wt% active to about 10 wt% active of the total weight of the inkjet ink 16; an additive selected from the group consisting of a non-ionic surfactant, an antimicrobial agent, an anti-decel agent, and combinations thereof; and the liquid vehicle, which includes water and an organic solvent (e.g., the co-solvent disclosed herein).

[0115] Examples of the inkjet ink 16 disclosed herein may be used in a thermal inkjet printer or in a piezoelectric printer. The viscosity of the inkjet ink 16 may be adjusted for the type of printhead by adjusting the co-solvent level, adjusting the polymeric binder level, and/or adding a viscosity modifier. When used in a thermal inkjet printer, the viscosity of the inkjet ink 16 may be modified to range from about 1 cP to about 9 cP (at 20°C to 25°C measured at a shear rate of about 3,000 Hz). When used in a piezoelectric printer, the viscosity of the inkjet ink 16 may be modified to range from about 1 cP to about 20 cP (at 20°C to 25°C measured at a shear rate of about 3,000 Hz), depending on the type of the printhead that is being used (e.g., low viscosity printheads, medium viscosity printheads, or high viscosity printheads).

[0116] Textile Fabrics

[0117] In the examples disclosed herein, the textile fabric 18 may be selected from the group consisting of cotton fabrics, cotton blend fabrics, polyester fabrics, polyester blend fabrics, nylon fabrics, nylon blend fabrics, silk fabrics, silk blend fabrics, wool fabrics, wool blend fabrics, and combinations thereof. In a further example, the textile fabric 18 is selected from the group consisting of cotton fabrics and cotton blend fabrics.

[0118] It is to be understood that organic textile fabrics and/or inorganic textile fabrics may be used for the textile fabric 18. Some types of fabrics that can be used include various fabrics of natural and/or synthetic fibers. It is to be understood that the polyester fabrics may be a polyester coated surface. The polyester blend fabrics may be blends of polyester and other materials (e.g., cotton, linen, etc.). In another example, the textile fabric 18 may be selected from nylons (polyamides) or other synthetic fabrics.

[0119] Example natural fiber fabrics that can be used include treated or untreated natural fabric textile substrates, e.g., wool, cotton, silk, linen, jute, flax, hemp, rayon fibers, thermoplastic aliphatic polymeric fibers derived from renewable resources (e.g. cornstarch, tapioca products, sugarcanes), etc. Example synthetic fibers used in the textile fabric/substrate 18 can include polymeric fibers such as nylon fibers, polyvinyl chloride (PVC) fibers, PVC-free fibers made of polyester, polyamide, polyimide, polyacrylic, polypropylene, polyethylene, polyurethane, polystyrene, polyaramid (e.g., KEVLAR®) polytetrafluoroethylene (TEFLON® )

(both trademarks of E.l. du Pont de Nemours and Company, Delaware), fiberglass, polytrimethylene, polycarbonate, polyethylene terephthalate, polyester terephthalate, polybutylene terephthalate, or a combination thereof. In an example, natural and synthetic fibers may be combined at ratios of 1 :1 , 1 :2, 1 :3, 1 :4, 1 :5, 1 :6, 1 :7, 1 :8, 1 :9, 1 :10, 1 :11 , 1 :12, 1 :13, 1 :14, 1 :15, 1 :16, 1 :17, 1 :18, 1 :19, 1 :20, or vice versa. In some examples, the fiber can be a modified fiber from the above-listed polymers. The term “modified fiber” refers to one or both of the polymeric fiber and the fabric as a whole having undergone a chemical or physical process such as, but not limited to, copolymerization with monomers of other polymers, a chemical grafting reaction to contact a chemical functional group with one or both the polymeric fiber and a surface of the fabric, a plasma treatment, a solvent treatment, acid etching, or a biological treatment, an enzyme treatment, or antimicrobial treatment to prevent biological degradation.

[0120] In addition, the textile fabric 18 can contain additives, such as a colorant (e.g., pigments, dyes, and tints), an antistatic agent, a brightening agent, a nucleating agent, an antioxidant, a UV stabilizer, a filler, and/or a lubricant, for example.

[0121] It is to be understood that the terms “textile fabric” or “fabric substrate” do not include materials commonly known as any kind of paper (even though paper can include multiple types of natural and synthetic fibers or mixtures of both types of fibers). Fabric substrates can include textiles in filament form, textiles in the form of fabric material, or textiles in the form of fabric that has been crafted into finished articles (e.g., clothing, blankets, tablecloths, napkins, towels, bedding material, curtains, carpet, handbags, shoes, banners, signs, flags, etc.). In some examples, the fabric substrate can have a woven, knitted, non-woven, or tufted fabric structure. In one example, the fabric substrate can be a woven fabric where warp yarns and weft yarns can be mutually positioned at an angle of about 90°. This woven fabric can include fabric with a plain weave structure, fabric with twill weave structure where the twill weave produces diagonal lines on a face of the fabric, or a satin weave. In another example, the fabric substrate can be a knitted fabric with a loop structure. The loop structure can be a warp-knit fabric, a weft-knit fabric, or a combination thereof. A warp-knit fabric refers to every loop in a fabric structure that can be formed from a separate yarn mainly introduced in a longitudinal fabric direction. A weft-knit fabric refers to loops of one row of fabric that can be formed from the same yarn. In a further example, the fabric substrate can be a non-woven fabric. For example, the non-woven fabric can be a flexible fabric that can include a plurality of fibers or filaments that are one or both bonded together and interlocked together by a chemical treatment process (e.g., a solvent treatment), a mechanical treatment process (e.g., embossing), a thermal treatment process, or a combination of multiple processes.

[0122] In one example, the textile fabric 18 can have a basis weight ranging from 10 gsm to 500 gsm. In another example, the textile fabric 18 can have a basis weight ranging from 50 gsm to 400 gsm. In other examples, the textile fabric 18 can have a basis weight ranging from 100 gsm to 300 gsm, from 75 gsm to 250 gsm, from 125 gsm to 300 gsm, or from 150 gsm to 350 gsm.

[0123] The textile fabric 18 may be any color, and in an example is a color other than white (e.g., black, grey, etc.).

[0124] Printing Method and System

[0125] Fig. 2 depicts an example of the printing method 100. As shown in Fig. 2, an example of the printing method 100 comprises: generating a print by: applying a pre-treatment composition 12 on a textile fabric 18 to form a pre treatment composition layer, the pre-treatment composition having a pH of 6 or greater and including an alkali swellable emulsion or a hydrophobically modified alkali swellable emulsion; inkjet printing a fixer composition 14 on the pre-treatment composition layer to form a fixer layer, the fixer composition including a cationic polymer and a fixer vehicle; and inkjet printing an inkjet ink 16 on the fixer layer to form an ink layer, the inkjet ink 16 including a white pigment, a polymeric binder, and an ink vehicle (as shown at reference numeral 102); and thermally curing the print (as shown at reference numeral 104).

[0126] It is to be understood that any example of the pre-treatment composition 12, the fixer composition 14, and the inkjet ink 16 may be used in the examples of the method 100. Further, it is to be understood that any example of the textile fabric 18 may be used in the examples of the method 100.

[0127] As shown in reference numeral 102 in Fig. 2, the method 100 includes generating the print.

[0128] When generating the print, the pre-treatment composition 12 is applied directly to the textile fabric 18. Due in part to the high viscosity of the pre treatment composition 12, the application of the pre-treatment composition 12 may be accomplished via an analog method. As examples, the pre-treatment composition 12 may be applied using an auto analog pretreater, a drawdown coater, a slot die coater, a roller coater, a fountain curtain coater, a blade coater, a rod coater, an air knife coater, a sprayer, or a gravure application. In these examples, the pre-treatment composition may be coated on all or substantially all of the textile fabric 18. As such, the pre-treatment composition layer that is formed may be a continuous layer that covers all or substantially all of the textile fabric 18. [0129] In an example, the pre-treatment composition 12 is applied in an amount ranging from about 50 gsm (grams per square meter, when wet) to about 120 gsm. In another example, the pre-treatment composition 12 is applied in an amount ranging from about 85 gsm to about 100 gsm.

[0130] In some examples, the method 100 further comprises applying heat and pressure to the pre-treatment composition layer on the textile fabric prior to inkjet printing the fixer composition 14. The application of heat and pressure may be accomplished using a heat press, an iron, or another suitable mechanism. In an example of the method 100, the application of heat and pressure involves heating the textile fabric 18 (with the pre-treatment composition 12 applied thereon) to a temperature for a period of time and at a pressure. The heat applied to pre treatment composition layer 12 on the textile fabric 18 ranges from about 80°C to about 200°C. The pressure applied to the pre-treatment composition layer 12 on the textile fabric 18 ranges from about 0.1 atm to about 8 atm. The heat and the pressure are applied to pre-treatment composition layer 12 on the textile fabric 18 for a period of time ranging from about 10 seconds to about 30 minutes. In one example, the temperature ranges from about 100°C to about 150°C, the pressure ranges from about 0.5 atm to about 5 atm, and the time ranges for about 1 minute to about 30 minutes. [0131] During the application of heat and pressure, the copolymer in the pre treatment composition 12 may coalesce to form a pre-treatment film (see 12’ in Fig. 3). Copolymer coalescence forms the film 12’ on the surfaces of the textile fabric fibers and/or in the pores between the textile fabric fibers. The copolymer film 12’ can slow down ink penetration into the textile fabric 18, which allows the pigment of the inkjet ink 16 to be fixed, through its interaction with the fixer composition 14, at or near the surface of the textile fabric 18. This, in turn, improves the opacity and the image quality of the white image that is formed. Moreover, the film can hold the hair-like fibers of the textile fabric 18, which reduces fibrillation and improves image quality.

[0132] In other examples, the pre-treatment composition 12 may not be exposed to heat and pressure before the application of the fixer composition 14 and the inkjet ink 16. This method involves wet-on-wet-on-wet printing.

[0133] As shown in reference numeral 102 in Fig. 2, generating the print also includes applying the fixer composition 14 on the pre-treatment composition (either in the form of the dried film 12’ form or in a wet form) to form a fixer layer.

[0134] The application of the fixer composition 14 may be accomplished via a digital inkjet printing method. As examples, the fixer composition 14 may be applied using thermal inkjet printing or piezoelectric inkjet printing. Any suitable inkjet applicator, such as a thermal inkjet printhead, a piezoelectric printhead, a continuous inkjet printhead, etc. may be used. In these examples, the fixer composition 14 may be printed at desirable areas. As such, the layer that is formed by the application of the fixer composition 14 may be non-continuous. In other words, the fixer composition layer may contain gaps where no fixer composition 14 is printed.

[0135] In an example, the fixer composition 14 depends upon the amount of inkjet ink 16 that is to be applied. In some examples, the fixer composition 14 is applied in an amount ranging from about 10 gsm to about 100 gsm. In other examples, the fixer composition 14 is applied in an amount ranging from about 50 gsm to about 75 gsm.

[0136] As shown in reference numeral 102 in Fig. 2, generating the print also includes inkjet printing the inkjet ink 16 on the fixer layer. It is to be understood that the inkjet ink 16 is printed at desirable areas to form an image. [0137] In an example, the inkjet ink 16 is applied in an amount ranging from about 200 gsm to about 400 gsm. In another example, the inkjet ink 16 is applied in an amount ranging from about 200 gsm to about 350 gsm.

[0138] In some examples, multiple inkjet inks (including white inkjet ink 16) may be inkjet printed onto the textile fabric 18. In these examples, each of the other inkjet inks may include a pigment, an example of the polymeric binder, and the ink vehicle. Each of the inkjet inks may include a different colored pigment so that a different color (e.g., cyan, magenta, yellow, black, violet, green, brown, orange, purple, etc.) is generated by each of the inkjet inks.

[0139] In other examples, a single white inkjet ink 16 may be inkjet printed onto the textile fabric 18.

[0140] In examples of the method 100, both the fixer composition 14 and the inkjet ink 16 are applied using inkjet printing. As an example, the fixer composition 14 and the inkjet ink 16 are applied sequentially one immediately after the other as the applicators (e.g., cartridges, pens, printheads, etc.) pass over the textile fabric 18. In these examples, the inkjet ink 16 is printed onto the fixer layer while the fixer layer is wet. Wet-on-wet printing may be desirable because less fixer composition 14 may be applied during this process (as compared to when the fixer composition 14 is dried prior to inkjet ink 16 application), and because the printing workflow may be simplified without the additional drying. In an example of wet-on-wet printing, the inkjet ink 16 is printed onto the fixer layer within a period of time ranging from about 0.01 second to about 30 seconds after the fixer composition 16 is printed. In further examples, the inkjet ink 16 is printed onto the fixer layer within a period of time ranging from about 0.1 second to about 20 seconds; or from about 0.2 second to about 10 seconds; or from about 0.2 second to about 5 seconds after the fixer composition 14 is applied to form the fixer layer. Wet-on-wet printing may be accomplished in a single pass.

[0141] In another example of the method 100, drying takes place after the application of the fixer composition 14 and before the application of the inkjet ink 16. As such, the fixer composition 14 may be dried on the textile fabric 18 before the inkjet ink 16 is applied. It is to be understood that in this example, drying of the fixer composition 14 may be accomplished in any suitable manner, e.g., air dried (e.g., at a temperature ranging from about 20°C to about 80°C for 30 seconds to 5 minutes), exposure to electromagnetic radiation (e.g. infra-red (IR) radiation for 5 seconds), and/or the like. When drying is performed, the fixer composition 14 and the inkjet ink 16 may be applied in separate passes to allow time for the drying to take place.

[0142] The inkjet printing of the fixer composition 14 and the inkjet ink 16 may be accomplished at high printing speeds. In an example, the inkjet printing of the fixer composition 14 and the inkjet ink 16 may be accomplished at a printing speed of at least 25 feet per minute (fpm). In another example, the fixer composition 14 and the inkjet ink 16 may be inkjet printed a printing speed ranging from 100 fpm to 1000 fpm.

[0143] As shown in reference numeral 104 in Fig. 2, the method 100 includes thermally curing the print. The thermal curing of the print may be accomplished by applying heat to the print. In an example of the method 100, the thermal curing involves heating the print to a temperature ranging from about 80°C to about 200°C, for a period of time ranging from about 10 seconds to about 15 minutes. In another example, the temperature ranges from about 100°C to about 180°C. In still another example, thermal curing is achieved by heating the print to a temperature of 150°C for about 3 minutes.

[0144] Referring now to Fig. 3, a schematic diagram of a printing system 30 is depicted. The printing system 30 includes three zones A, B, C, including a pre treatment zone A, a printing zone B, and a curing zone C.

[0145] In one example, a textile fabric/substrate 18 may be transported through the printing system 30 to the pre-treatment zone A. In the pre-treatment zone A, an example of the pre-treatment composition 12 is applied to the textile fabric 18. The pre-treatment composition 12 is applied using an analog applicator 24 (e.g., an auto analog pretreater, a drawdown coater, a slot die coater, a roller coater, a fountain curtain coater, a blade coater, a rod coater, an air knife coater, a sprayer, or a gravure application).

[0146] The application of the pre-treatment composition 12 forms a pre treatment composition layer 12 on the textile fabric 18. The textile fabric 18 having the pre-treatment composition layer 12 thereon may be exposed to one of two paths. [0147] Along the first path, the textile fabric 18 having the wet pre-treatment composition layer 12 thereon is transported to the printing zone B, where the fixer composition 14 and inkjet ink 16 are printed (as described below). This path involves wet-on-wet-on-wet printing.

[0148] Along the second path, the textile fabric 18 (having the wet pre treatment composition layer 12 thereon) remains in the pre-treatment zone A, where it is exposed to heating and pressure. The application of heat and pressure may be accomplished, for example, using a heat press 26 or other suitable heated mechanism that can be pushed into contact with pre-treatment composition layer 12. This process forms the pre-treatment film 12’.

[0149] The textile fabric 18 is transported through the printing zone B where an example of the fixer composition 14 is first applied onto the wet pre-treatment composition layer 12 or onto the dried pre-treatment film 12’. The fixer composition 14 is applied by an inkjet printhead 22A. In the printing zone B, the inkjet ink 16 is also applied to the fixer layer 14’ to from an ink layer 16’.

[0150] The fixer layer 14’ and the ink layer 16’ may be heated in the printing zone B (for example, the air temperature in the printing zone B may range from about 10°C to about 90°C) such that water may be at least partially evaporated from the layer 14’, 16’. The fixer layer 14’ may or may not be dried before the inkjet ink 16 is applied.

[0151] The textile fabric 18 (having the wet pre-treatment composition layer 12 or the pre-treatment film 12’, the fixer layer 14’, and the ink layer 16’ thereon) may then be transported to the curing zone C where the compositions/layers are heated to cure the print. The heat is sufficient to initiate film formation and crosslinking or other interactions that bind the pigment onto the textile fabric 18.

The heat to initiate fixation (thermal curing) may range from about 80°C to 200°C as described above. This process forms the printed article 34 including the image 32 formed on the textile fabric 18.

[0152] To further illustrate the present disclosure, an example is given herein. It is to be understood that this example is provided for illustrative purposes and is not to be construed as limiting the scope of the present disclosure. EXAMPLE

[0153] A commercially available hydrophobically modified alkali swellable emulsion (RHEOVIS® 1162 from BASF Corp.,) was used to prepare 5 different pre treatment compositions. RHEOVIS® 1162 was diluted to 1 wt% with deionized water. Different amounts of a 10 wt% KOH solution was added to obtain different pre-treatment compositions with different viscosities. Each of the RHEOVIS® 1162 pre-treatment compositions are shown in Table 1 .

TABLE 1 - Pre-treatment Compositions w/ RHEOVIS® 1162

[0154] A commercially available hydrophobically modified alkali swellable emulsion (RHEOVIS® 1152 from BASF Corp.) was used to prepare 7 different pre treatment compositions. RHEOVIS® 1152 was diluted to 1 wt% with deionized water. Different amounts of a 10 wt% KOH solution was added to obtain different pre-treatment compositions with different viscosities. Each of the RHEOVIS® 1152 pre-treatment compositions are shown in Table 2.

TABLE 2 - Pre-treatment Compositions w/ RHEOVIS® 1152

[0155] A commercially available alkali swellable emulsion (RHEOVIS® 1125 from BASF Corp.) was used to prepare 7 different pre-treatment compositions. RHEOVIS® 1125 was diluted to 1 wt% with deionized water. Different amounts of a 10 wt% KOH solution was added to obtain different pre-treatment compositions with different viscosities. Each of the RHEOVIS® 1125 pre-treatment compositions are shown in Table 3.

TABLE 3 - Pre-treatment Compositions w/ RHEOVIS® 1125

[0156] As more base was added, the thicker and more optically clear the pre-treatment compositions became.

[0157] Pre-treatment fluids 1162-2, 1162-4, 1152-3, 1152-4, 1152-5, 1152-6, 1125-3, 1125-4, 1125-5, and 1125-6 were selected for additional testing.

[0158] Gildan black midweight 780 cotton T-shirts (having a basis weight of 180 gsm) were used as the textile fabric.

[0159] Each of the pre-treatment fluids was applied on the fabric to form a thin layer with a loading ranging from about 80 gsm (wet) to about 120 gsm (wet). Some of the pre-treated fabrics were exposed to 150°C and pressure of 3 atm when pressed in a clam shell hot press for 30 seconds. The pre-treatment conditions for each sample are shown in Table 6.

[0160] A control sample was also prepared. The control sample did not have any pre-treatment fluid applied thereto and was not exposed to any other form of pre-treatment processing.

[0161] Each of the pre-treated samples was used to generate an example print. The control sample was used to generate a control print. A fixer composition (Table 4) and a white inkjet ink (Table 5) were used to generate the prints. For each print (example and control), fixer composition (total of 55 gsm) and the inkjet ink (total of 300 gsm) were inkjet printed (using an 11 ng thermal inkjet printhead and wet on wet printing) over 6 passes. The example and control prints were cured at 150°C for 3 minutes in a clam shell hot press or in an oven. The thermal curing conditions for each sample are also shown in Table 6. TABLE 4 - Fixer Composition

TABLE 5 - White Inkjet Ink

TABLE 6 - Pre-treatment and Curing Conditions

[0162] The example prints and the control print were tested for opacity, in terms of L^*, i.e., lightness, of the white print. The measurements were taken with an X-Rite color measurement instrument. The results are shown in Table 7. TABLE 7 - Opacity

[0163] A greater L^* value indicates a greater opacity of the white ink on the colored textile fabric. As depicted, all of the example prints had improved opacity compared to the control print, regardless of whether the pre-treatment composition was dried before fixer and ink printing (Ex. Prints 3 and 4) or whether wet-on-wet- on-wet printing was performed (Ex. Prints 1 , 2, and 5-12).

[0164] A photograph and an optical microscope image were taken the Control Print, Ex. Print 1 , Ex. Print 5, and Ex. Print 9 to compare print quality.

These images are shown, respectively, for the Control Print in Figs. 4A and 4B, for Ex. Print 1 in Figs. 5A and 5B, for Ex. Print 5 in Figs. 6A and 6B, and for Ex. Print 9 in Figs. 7A and 7B. As depicted, the print quality was improved for each of the example prints, as compared to the Control print.

[0165] Optical microscope images were also taken of a side view of the Control Print (Fig. 8) and of Ex. Print 9 (Fig. 9). As depicted, the print quality was improved significantly, as compared to the Control print. In particular, Ex. Print 9 was smoother and has a less hairy surface.

[0166] Ex. Print 1 , Ex. Print 2, Ex. Print 3, Ex. Print 5, and the Control Print were also tested for washfastness. For this test, the L^*a^*b^* values of a color (e.g., white) before and after the 5 washes were measured. L^* is lightness, a^* is the color channel for color opponents green-red, and b^* is the color channel for color opponents blue-yellow. After the initial L^*a^*b^* measurements were taken, each example print and the control print were washed 5 times in a Whirlpool Washer (Model WTW5000DW) with warm water (at about 40°C) and detergent. Each example print and the control print was allowed to air dry between each wash. Then, the L^* a^*b^* values after the 5 washes of each example and comp print were measured. DE76 was calculated using the CIEDE1976 color-difference formula, which is based on the CIELAB color space. Given a pair of color values in CIELAB space L^*·, .a^.b^ and L^* ₂,a^* ₂,b^* ₂, the CIEDE1976 color difference between them is as follows:

The results are shown in Table 8.

TABLE 8 - Washfastness

[0167] All of the example prints and the control print exhibited good washfastness.

[0168] It is to be understood that the ranges provided herein include the stated range and any value or sub-range within the stated range, as if the value(s) or sub-range(s) within the stated range were explicitly recited. For example, a range from about 1 wt% active to about 10 wt% active, should be interpreted to include not only the explicitly recited limits of from about 1 wt% active to about 10 wt% active, but also to include individual values, such as about 1.15 wt% active, about 2.5 wt% active, 4.0 wt% active, 6.77 wt% active, 8.85 wt% active, 9.33 wt% active, etc., and sub-ranges, such as from about 2 wt% active to about 5.65 wt% active, from about 3 wt% active to about 7 wt% active, from about 4.35 wt% active to about 8.95 wt% active, etc. Furthermore, when “about” is utilized to describe a value, this is meant to encompass minor variations (up to +/- 10%) from the stated value.

[0169] Reference throughout the specification to “one example”, “another example”, “an example”, and so forth, means that a particular element (e.g., feature, structure, and/or characteristic) described in connection with the example is included in at least one example described herein, and may or may not be present in other examples. In addition, it is to be understood that the described elements for any example may be combined in any suitable manner in the various examples unless the context clearly dictates otherwise.

[0170] In describing and claiming the examples disclosed herein, the singular forms “a”, “an”, and “the” include plural referents unless the context clearly dictates otherwise.

[0171] While several examples have been described in detail, it is to be understood that the disclosed examples may be modified. Therefore, the foregoing description is to be considered non-limiting.

Claims

What is claimed is:

1. A fluid set, comprising: a pre-treatment composition having a pH of 6 or greater and including an alkali swellable emulsion or a hydrophobically modified alkali swellable emulsion; a fixer composition, including: a cationic polymer; and a fixer vehicle; and an inkjet ink, including: a white pigment; a polymeric binder; and an ink vehicle.

2. The fluid set as defined in claim 1 wherein the pre-treatment composition has a viscosity of at least 15 cP measured at a shear rate of greater than or equal to 2000 s ¹ and at a temperature ranging from 20°C to 25°C.

3. The fluid set as defined in claim 1 wherein the pre-treatment composition includes the alkali swellable emulsion, and wherein the alkali swellable emulsion includes a copolymer of an acrylic acid monomer and an acrylate ester monomer.

4. The fluid set as defined in claim 1 wherein the pre-treatment composition has a solids content ranging from about 0.2 wt% to about 5 wt%.

5. The fluid set as defined in claim 1 wherein the pre-treatment composition further includes a base.

6. The fluid set as defined in claim 1 wherein the pre-treatment composition consists of the water, the alkali swellable emulsion or the hydrophobically modified alkali swellable emulsion, and a base.

7. The fluid set as defined in claim 1 wherein the polymeric binder in the inkjet ink is a polyurethane-based binder selected from the group consisting of a polyester-polyurethane binder, a polyether-polyurethane binder, a polycarbonate- polyurethane binder, and combinations thereof.

8. The fluid set as defined in claim 1 wherein the cationic polymer of the fixer composition is selected from the group consisting of poly(diallyldimethylammonium chloride); poly(methylene-co-guanidine) anion, wherein the anion is selected from the group consisting of hydrochloride, bromide, nitrate, sulfate, and sulfonates; a polyamine; poly(dimethylamine-co- epichlorohydrin); a polyethylenimine; a polyamide epichlorohydrin resin; a polyamine epichlorohydrin resin; and a combination thereof.

9. A textile printing kit, comprising: a textile fabric selected from the group consisting of polyester fabrics, polyester blend fabrics, cotton fabrics, cotton blend fabrics, nylon fabrics, nylon blend fabrics, silk fabrics, silk blend fabrics, wool fabrics, wool blend fabrics, and combinations thereof; a pre-treatment composition having a pH of 6 or greater and including an alkali swellable emulsion or a hydrophobically modified alkali swellable emulsion; a fixer composition, including: a cationic polymer; and a fixer vehicle; and an inkjet ink, including: a white pigment; a polymeric binder; and an ink vehicle.

10. The textile printing kit as defined in claim 9 wherein the pre-treatment composition: has a viscosity of at least 15 cP measured at a shear rate of greater than or equal to 2000 s ¹ and at a temperature ranging from 20°C to 25°C; and has a solids content ranging from about 0.2 wt% to about 5 wt%.

11. A printing method, comprising: generating a print by: applying a pre-treatment composition on a textile fabric to form a pre treatment composition layer, the pre-treatment composition having a pH of 6 or greater and including an alkali swellable emulsion or a hydrophobically modified alkali swellable emulsion; inkjet printing a fixer composition on the pre-treatment composition layer to form a fixer layer, the fixer composition, including: a cationic polymer; and a fixer vehicle; and inkjet printing an inkjet ink on the fixer layer to form an ink layer, the inkjet ink including: a white pigment; a polymeric binder; and an ink vehicle; and thermally curing the print.

12. The printing method as defined in claim 11 , further comprising applying heat and pressure to the pre-treatment composition layer on the textile fabric prior to inkjet printing the fixer composition.

13. The printing method as defined in claim 12 wherein the heat applied to the pre-treatment composition layer on the textile fabric ranges from about 80°C to about 200°C.

14. The printing method as defined in claim 12 wherein the pressure applied to the pre-treatment composition layer on the textile fabric ranges from about 0.1 atm to about 8 atm.

15. The printing method as defined in claim 12 wherein the heat and the pressure are applied to pre-treatment composition layer on the textile fabric for a period of time ranging from about 10 seconds to about 30 minutes.