WO2022182358A1

WO2022182358A1 - Multi-fluid kit for inkjet textile printing

Info

Publication number: WO2022182358A1
Application number: PCT/US2021/019901
Authority: WO
Inventors: Dennis Z. Guo; Jie Zheng
Original assignee: Hewlett Packard Development Co LP
Current assignee: Hewlett Packard Development Co LP
Priority date: 2021-02-26
Filing date: 2021-02-26
Publication date: 2022-09-01
Anticipated expiration: 2023-08-26

Abstract

An example of a multi-fluid kit for inkjet textile printing includes a pretreatment fluid, a fixer fluid, and a white inkjet ink. The pretreatment fluid includes a silicon oxide material and a first aqueous vehicle. The fixer fluid includes a cationic polymer and a second aqueous vehicle. The pretreatment fluid, the fixer fluid, and the white inkjet ink are maintained separately in the multi-fluid kit.

Description

MULTI-FLUID KIT FOR INKJET TEXTILE PRINTING

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. 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 is a schematic illustration of an example multi-fluid kit and an example textile printing kit;

[0004] Fig. 2 is a flow diagram illustrating an example printing method; [0005] Fig. 3 is a schematic diagram illustrating different examples of the printing method;

[0006] Figs. 4A through Fig. 4L are black and white reproductions of originally colored photographs of comparative prints (Fig. 4A through Fig. 4D) and example prints (Fig. 4E through Fig. 4L) generated with a first example method disclosed herein, illustrating an improvement in opacity for each of the example prints as compared to the comparative prints; and

[0007] Figs. 5A and 5B are black and white reproductions of originally colored photographs of an example print generated using a second example method disclosed herein.

DETAILED DESCRIPTION

[0008] The textile is a major industry, and printing on textiles, such as cotton, polyester, 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 different textile fabrics introduce different obstacles that can affect the white print. As an example, cotton fabrics are more likely than polyester fabrics to have fibrillation (e.g., hair-like fibers sticking out of the fabric surface).

[0009] Disclosed herein is a multi-fluid kit that is particularly suitable for obtaining white images, which may have desirable opacity, durability (i.e., washfastness), and quality. Examples of the multi-fluid kit include a pretreatment fluid, a fixer fluid, and a white inkjet ink. The pretreatment fluid includes a silicon oxide material, which reacts with a cationic polymer in the fixer fluid to form a gel. This gel forms a film that blocks pores of the textile fabric. As such, the gel film allows the pigment of the white inkjet ink to be fixed at or near the surface of the textile fabric, which improves the opacity of the white image that is formed. Moreover, the gel film may be able to hold the hair-like fibers of the cotton textile fabric, which reduces fibrillation and improves image quality. [0010] The opacity may be measured in terms of L* i.e. , lightness, of a white print generated 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 white inkjet ink, when printed on the colored textile fabric pretreated with the pretreatment fluid and the fixer fluid disclosed herein, may generate prints that have a desirable L* value.

[0011 ] The durability of a print on a textile 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 a change in L* before and after washing. [0012] The fluid(s) and/or white inkjet ink disclosed herein may include different components with different acid numbers. 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. For example, to determine the acid number of a polyurethane-based binder, a known amount of a sample of the 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. [0013] 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 pretreatment fluid, the fixer fluid, or the white inkjet ink. For example, the white pigment may be present in a water-based formulation (e.g., a stock solution or dispersion) before being incorporated into the white 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 white 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 the loading (in the pretreatment fluid, the fixer fluid, or the white inkjet ink) of a 100% active component that does not include other non-active components therein.

[0014] The term “molecular weight” as used herein refers to weight average molecular weight (Mw), the units of which are g/mol or Daltons.

[0015] 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 VISCOLITE™ viscometer (from Hydromotion) or another suitable instrument.

[0016] In some examples, the term “on” may mean that one component or material is positioned directly on another component or material. When one is directly on another, the two are in contact with each other. For example, the fixer fluid may be applied on the textile fabric so that it is directly on and in contact with the textile fabric. [0017] In other examples, the term “on” may mean that one component or material is positioned indirectly on another component or material. By indirectly on, it is meant that an additional component or material may be positioned between the two components or materials. For example, the pretreatment layer may be applied on the fixer fluid which has been applied on the textile fabric, and thus the pretreatment layer may be considered to be in indirect contact with the textile fabric.

[0018] Sets and Kits

[0019] Examples of the multi-fluid kit disclosed herein are shown schematically in Fig. 1. As depicted, one example of the multi-fluid kit 10 for inkjet textile printing includes a pretreatment fluid 12 including a silicon oxide material and a first aqueous vehicle; a fixer fluid 14, which includes a cationic polymer and a second aqueous vehicle; and a white inkjet ink 16, wherein the pretreatment fluid 12, the fixer fluid 14, and the white inkjet ink 16 are maintained separately in the multi-fluid kit 10. Another example of the multi-fluid kit 10 may include two different fixer fluids 14, 14’.

[0020] It is to be understood that any example of the pretreatment fluid 12, the fixer fluid 14, 14’, and the white inkjet ink 16 disclosed herein may be used in the examples of the multi-fluid kit 10.

[0021] In the examples disclosed herein, the multi-fluid kit 10 includes a pretreatment fluid 12 that is formulated for digital application (e.g., by a thermal or piezoelectric inkjet printhead) and a white inkjet ink 16 that is also formulated for digital application. Some examples also include at least one fixer fluid 14, 14’ that is formulated for digital application. In some instances, each of the fluids 12, 14, 14’, 16 is a thermal inkjet fluid, and thus can be digitally applied via a thermal inkjet printer. [0022] In any example of the fluid kit 10, the pretreatment fluid 12, the fixer fluid 14, 14’, and the white 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).

[0023] Examples of the fluid kit 10 may also be part of a kit 20 for textile printing, which is also shown schematically in Fig. 1. In an example, the textile printing kit 20 includes a textile fabric 18, a pretreatment fluid 12 including a silicon oxide material and a first aqueous vehicle; a fixer fluid 14, which includes a cationic polymer and a second aqueous vehicle; and a white inkjet ink 16, wherein the pretreatment fluid 12, the fixer fluid 14, and the white inkjet ink 16 are maintained separately in the kit 20. Another example of the textile printing kit 20 may include two different fixer fluids 14, 14’. It is to be understood that any example of the pretreatment fluid 12, the fixer fluid 14, and the white inkjet ink 16 disclosed herein may be used in the examples of the textile printing kit 20.

[0024] Pretreatment fluid

[0025] The pretreatment fluid 12 includes a silicon oxide material and an aqueous vehicle. This aqueous vehicle may be referred to herein as the “first aqueous vehicle” or the pretreatment aqueous vehicle. [0026] As used herein, the term “silicon oxide material” refers to a silicon based materials that includes at least two oxygen atoms bound to the silicon. The silicon oxide material may be selected from the group consisting of colloidal silica, colloidal layered silicate, magnesium aluminum silicate, and combinations thereof.

[0027] Prior to being incorporated into the pretreatment fluid 12, the silicon oxide material may be colloidal silica dispersed in an aqueous carrier fluid. This dispersion may be added to the aqueous vehicle of the pretreatment fluid 12, and thus components of the dispersion (e.g., colloidal silica, water, etc.) become part of the final pretreatment fluid 12. The colloidal silica may be an elongated shape, which is believed to assist in film forming, bonding, and preventing pigment migration.

Examples of elongated colloidal silica include SNOWTEX™ ST-UP and SNOWTEX™ ST-OUP, which are commercially available from Nissan Chemical Company.

[0028] In another example, prior to being incorporated into the pretreatment fluid 12, the silicon oxide material may be a layered silicate dispersed in a carrier fluid. In one example, this dispersion includes up to 25% layered silicate (the solids content) in the carrier fluid, which may be water. This dispersion may be added to the aqueous vehicle of the pretreatment fluid 12, and thus components of the dispersion (e.g., colloidal layered silicate, water, etc.) become part of the final pretreatment fluid 12. [0029] In an example, the layered silicate is a nano-sized layered silicate. The nano-sized layered silicate is a synthetic and inorganic material. By “nano-sized”, it is meant herein that the size of this material ranges from about 1 nm to about 800 nm. In an example, the size of layered silicate ranges from about 5 nm to about 500 nm, e.g., from about 10 nm to about 200 nm. By “layered”, it is meant herein that the nano sized silicate compounds have structures that are characterized by strong (and often covalent) bonding between atoms in two dimensions and weaker bonding in the third dimension. Such compounds are inorganic layered materials that are composed of stacked nanometer-thick inorganic crystalline sheets, which are weakly bound by electrostatic, van der Waals, or hydrogen-bonding interactions.

[0030] The nano-sized layered silicate can be a hydrophilic, layered clay. As one example, the nano-sized layered silicate is a synthetic hectorite clay. Synthetic hectorite clay has the formula [Mg_wLixSi₈0₂o(OH)_4.yF_y]^z wherein w = 3 to 6; x = 0 to 3; y = 0 to 4; z = 12-2w-x, wherein the negative lattice charge is balanced by counterions, and wherein the counterions are selected from the group consisting of Na⁺, K⁺, NH₄ ⁺, Li⁺, Mg²⁺, Ca²⁺, Ba²⁺, N(CH₃)⁴⁺, and mixtures thereof.

[0031 ] Some synthetic hectorite clays are commercially available under the tradename LAPONITE® (from available from BYK). LAPONITE® compounds can have a three-layer structure, which extend two-dimensionally to form small plate-like particles. Primary particles of LAPONITE® are extremely minute disk-shaped particles, whereas particles of natural hectorite are rectangular plate-shaped particles. A length of one side of the plate surface of LAPONITE® is from 400 nm to 500 nm and the aspect ratio is from 20 to 40. Such compounds are solid materials which can be readily dispersed in water. When dispersed in water, LAPONITE® is in the form of disc shaped crystals.

[0032] LAPONITE® is an entirely synthetic product. The synthesis process to generate LAPONITE® involves combining salts of sodium, magnesium, and lithium with sodium silicate at carefully controlled rates and temperature in order to produce an amorphous precipitate, which is then partially crystallized by a high temperature treatment.

[0033] Synthetic hectorite clays are commercially available, for example, from BYK, and include LAPONITE®; LUCENITE® SWN, LAPONITE® S, LAPONITE® XL, LAPONITE® RD, LAPONITE® SL25, and LAPONITE® RDS brands of synthetic hectorite.

[0034] Another example of the silicon oxide material may be a magnesium aluminum silicate. An example magnesium aluminum silicate includes VEEGUM™ T, which is commercially available from Vanderbilt Chemicals LLC. Other examples include BENTONE HYDROCLAY™ 1100, BENTONE HYDROCLAY™ 2000, BENTONE™ HC, BENTONE™ AD and BENTONE™ EW NA, which are commercially available from Elementis PLC.

[0035] Combinations of any of the listed silicon oxide materials may be used. Moreover, it is believed that other silicon oxide materials may be used as long as a gel is formed when the pretreatment fluid 12 is combined with the fixer fluid 14 and/or 14’ on the textile fabric 18. [0036] The silicon oxide material may be present in the pretreatment fluid 12 in an amount ranging from about 1 wt% active to about 20 wt% active based on a total weight of the pretreatment fluid 12. The amount used may be determined, in part, by the method that is to be used to deposit the pretreatment fluid 12. In an example, the pretreatment fluid 12 is a piezoelectric inkjet fluid, and the silicon oxide material is present in an amount ranging from about 1 wt% active to about 20 wt% active, e.g., about 5 wt% active to about 20 wt%, 10 wt% active to about 20 wt% active, 8 wt% active to about 18 wt% active, etc. In another example, the pretreatment fluid 12 is a thermal inkjet fluid, and the silicon oxide material is present in an amount ranging from about 1 wt% active to about 20 wt% active, e.g., about 1 wt% active to about 15 wt%,

1 wt% active to about 10 wt% active, 2 wt% active to about 6 wt% active, etc.

[0037] The silicon oxide material may have an average particle size ranging from about 0.5 nm to about 500 nm. In another example, the silicon oxide material may have an average particle size ranging from about 1 nm to about 400 nm. In another example, the silicon oxide material may have an average particle size ranging from about 2 nm to about 200 nm. As used herein, the “average particle size” refers to a volume-weighted mean diameter, or volume-averaged, of a particle size distribution. [0038] The pretreatment fluid 12 may be prepared by adding the desired amount of the silicon oxide material to the aqueous vehicle. In some examples, the aqueous vehicle is water, and thus the pretreatment fluid 12 consists of the silicon oxide material and the water. The water may be deionized or some other form of purified water.

[0039] The pretreatment fluid 12 has a pH ranging from about 6 to about 12. Suitable pH ranges for examples of the pretreatment fluid 12 may include from about 6 to about 8, or from about 9 to about 11. In one example, the pH of the pretreatment fluid 12 is about 10. In some instances, a pH adjuster may be added to the pretreatment fluid 12 to obtain the desired pH. Examples of suitable pH adjusters for the pretreatment fluid 12 include metal hydroxide bases, such as potassium hydroxide (KOH), sodium hydroxide (NaOH), etc. Other examples of suitable pH adjusters for the pretreatment fluid 12 include acids, such as nitric acid or methanesulfonic acid, etc. In an example, the metal hydroxide base or the acid may be added to the pretreatment fluid 12 in an aqueous solution, such as an aqueous solution including 5 wt% of the metal hydroxide base (e.g., a 5 wt% active potassium hydroxide aqueous solution) or including 99% methanesulfonic acid (e.g., a 99 wt% active methanesulfonic acid aqueous solution).

[0040] In an example, the total amount of pH adjuster(s) in the pretreatment fluid 12 ranges from greater than 0 wt% to about 0.5 wt% (based on the total weight of the pretreatment fluid 12). In another example, the total amount of pH adjuster(s) in the pretreatment fluid 12 ranges from about 0.01 wt% to about 0.2 wt%. In another example, the total amount of pH adjuster(s) in the pretreatment fluid 12 is about 0.03 wt% (based on the total weight of the pretreatment fluid 12). The amount of pH adjuster added depends on the desired pH, and the pH adjuster may be added until the desired pH of the pretreatment fluid 12 is achieved.

[0041] In some examples, the first aqueous vehicle (the pretreatment aqueous vehicle) consists of water; and the pretreatment fluid 12 consists of the silicon oxide material and the first aqueous vehicle. In these examples, the pretreatment fluid 12 consists of the water and the silicon oxide material. In other examples, the pretreatment fluid 12 consists of the water, the silicon oxide material, and the pH adjuster. In any of these examples, the pretreatment fluid 12 includes no other components.

[0042] In other examples, the pretreatment fluid 12 may include other additives. In these examples, the first aqueous vehicle includes water and an additive selected from the group consisting of a co-solvent, a non-ionic surfactant, an antimicrobial agent, a pH adjuster, and combinations thereof.

[0043] The co-solvent in the pretreatment fluid 12 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-C12) 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)-l ,3-propane diol (EPHD), dimethyl sulfoxide, sulfolane, and/or alkyldiols such as 1,2-hexanediol.

[0044] 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. [0045] 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.

[0046] The co-solvent(s) may be present in the pretreatment fluid 12 in an amount ranging from about 4 wt% active to about 30 wt% active (based on the total weight of the pretreatment fluid 12). In an example, the total amount of co-solvent(s) present in the pretreatment fluid 12 is about 10 wt% active (based on the total weight of the pretreatment fluid 12).

[0047] The surfactant in the pretreatment fluid 12 may be any non-ionic surfactant. 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.

[0048] 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).

[0049] In any of the examples disclosed herein, the surfactant may be present in the pretreatment fluid 12 in an amount ranging from about 0.01 wt% active to about 5 wt% active (based on the total weight of the pretreatment fluid 12). In an example, the surfactant is present in the pretreatment fluid 12 in an amount ranging from about 0.05 wt% active to about 3 wt% active, based on the total weight of the pretreatment fluid 12. In another example, the surfactant is present in the pretreatment fluid 12 in an amount of about 0.3 wt% active, based on the total weight of the pretreatment fluid 12. [0050] The pretreatment fluid 12 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.

[0051] In an example, the total amount of antimicrobial agent(s) in the pretreatment fluid 12 ranges from about 0.01 wt% active to about 0.05 wt% active (based on the total weight of the pretreatment fluid 12). In another example, the total amount of antimicrobial agent(s) in the pretreatment fluid 12 is about 0.044 wt% active (based on the total weight of the pretreatment fluid 12).

[0052] The viscosity of the pretreatment fluid 12 may vary depending upon the application method that is to be used to apply the pretreatment fluid 12. When the pretreatment fluid 12 is to be applied with a piezoelectric inkjet applicator/printhead, the viscosity of the pretreatment fluid 12 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). When the pretreatment fluid 12 is to be applied with a thermal inkjet applicator/printhead, the pretreatment fluid 12 has a viscosity ranging from about 1 cP to about 4 cP (at 20°C to 25°C and a shear rate of about 3,000 Hz).

[0053] Fixer fluid

[0054] The fixer fluid 14 includes a cationic polymer and a fixer vehicle, which is also referred to herein as a second aqueous vehicle. In some examples, the fixer fluid 14 consists of the cationic polymer and the fixer vehicle. In other examples, the fixer fluid 14 may include additional components.

[0055] The cationic polymer included in the fixer fluid 14 has a weight average molecular weight ranging from about 3,000 to about 3,000,000.

[0056] In some examples, the cationic polymer of the fixer fluid 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.

[0057] In an example, the cationic polymer of the fixer fluid 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 fluid 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 fluid 14. [0058] In addition to the cationic polymer, the fixer fluid 14 also includes the fixer vehicle. As used herein, the terms “fixer vehicle” and “second aqueous vehicle” may refer to the liquid in which the cationic polymer is mixed to form the fixer fluid 14.

[0059] In an example of the fixer fluid 14, the fixer vehicle includes a surfactant, a co-solvent, an anti-kogation agent, and a balance of water. In another example, the fixer fluid 14 further comprises a pH adjuster. As such, some examples of the fixer vehicle (and thus the fixer fluid 14) include a surfactant, a co-solvent, an anti-kogation agent, and/or a pH adjuster.

[0060] The surfactant in the fixer fluid 14 may be any non-ionic surfactant or cationic surfactant.

[0061 ] 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.

[0062] 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).

[0063] 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, dipalm itoylethyl 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. [0064] In any of the examples disclosed herein, the surfactant may be present in the fixer fluid 14 in an amount ranging from about 0.01 wt% active to about 5 wt% active (based on the total weight of the fixer fluid 14). In an example, the surfactant is present in the fixer fluid 14 in an amount ranging from about 0.05 wt% active to about 3 wt% active, based on the total weight of the fixer fluid 14. In another example, the surfactant is present in fixer fluid 14 in an amount of about 0.3 wt% active, based on the total weight of the fixer fluid 14.

[0065] The co-solvent in the fixer fluid 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-C12) 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)-l ,3-propane diol (EPHD), dimethyl sulfoxide, sulfolane, and/or alkyldiols such as 1,2-hexanediol.

[0066] 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. [0067] 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.

[0068] In one specific example of the fixer fluid 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.

[0069] The co-solvent(s) may be present in the fixer fluid 14 an amount ranging from about 4 wt% to about 30 wt% (based on the total weight of the fixer fluid 14). In an example, the total amount of co-solvent(s) present in the fixer fluid 14 is about 10 wt% (based on the total weight of the fixer fluid 14).

[0070] An anti-kogation agent may also be included in the fixer fluid 14, e.g., when the fixer fluid 14 is to be jetted using a thermal inkjet printhead. 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 fluid 14. The anti-kogation agent(s) may be present in the fixer fluid 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 fluid 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 fluid 14.

[0071 ] 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™ FICE (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.

[0072] The pH of the fixer fluid 14 may be less than 7. As examples, the pH may range from about 1 to less than 7, from about 5.5 to less than 7, from about 5 to less than 6.6, or from about 5.5 to about 6.6, or from about 1 to about 4. In one example, the pH of the fixer fluid 14 is about 3.

[0073] A pH adjuster may also be included in the fixer fluid 14. A pH adjuster may be included in the fixer fluid 14 to achieve a desired pH (e.g., about 4) and/or to counteract any slight pH increase that may occur over time. Examples of a suitable pH adjuster that may be used in the fixer fluid 14 include methane sulfonic acid, nitric acid, and phosphoric acid. Other examples of a suitable pH adjuster that may be used in the fixer fluid 14 include acetic acid, formic acid, glycolic acid, citric acid, sulfuric acid, and hydrochloric acid.

[0074] In an example, the total amount of pH adjuster(s) in the fixer fluid 14 ranges from greater than 0 wt% to about 0.1 wt% (based on the total weight of the fixer fluid 14). In another example, the total amount of pH adjuster(s) in the fixer fluid 14 is about 0.03 wt% (based on the total weight of the fixer fluid 14). It is to understood, however, that the pH adjusted may be added in any suitable amount to achieve the desired pH.

[0075] The balance of the fixer fluid 14 is water. As such, the weight percentage of the water present in the fixer fluid 14 will depend, in part, upon the weight percentages of the other components. The water may be purified water or deionized water.

[0076] The viscosity of the fixer fluid 14 may vary depending upon the application method that is to be used to apply the fixer fluid 14. In one example, when the fixer fluid 14 is to be applied with a thermal inkjet applicator/printhead, the viscosity of the fixer fluid 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 fluid 14 is to be applied with an piezoelectric inkjet applicator/printhead, the viscosity of the fixer fluid 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).

[0077] White Inkjet Ink

[0078] The white inkjet ink 16 includes a white pigment, a polymeric binder, and an ink vehicle (the latter of which may be referred to herein as the third aqueous vehicle). In some examples, the white inkjet ink 16 consists of the white pigment, the polymeric binder, and the ink vehicle. In other examples, the white inkjet ink 16 may include additional components.

[0079] The white pigment may be incorporated into the ink vehicle to form the white inkjet ink 16. The white pigment may be incorporated as a white pigment dispersion. The white pigment dispersion may include a white pigment and a separate pigment dispersant. [0080] 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 vehicle to form the white 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,

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 white inkjet ink 16. [0081] Examples of suitable white pigments include white metal oxide pigments, such as titanium dioxide (T1O2), 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.

[0082] In some examples, the white pigment may include white metal oxide pigment particles coated with silicon dioxide (SiC^). 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 (S1O2) and aluminum oxide (AI2O3). 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 Tl- PURE® R960 (T1O2 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 (T1O2 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 (T1O2 pigment powder with 3.0 wt% silica and 2.5 wt% alumina (based on pigment content)) available from Chemours. [0083] 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.

[0084] 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 white 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 white 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 white inkjet ink 16.

[0085] 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.

[0086] 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. [0087] 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.

[0088] 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 white 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 white inkjet ink 16.

[0089] 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. [0090] The white inkjet ink 16 also includes a polymeric binder, which is one of: 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; or an acrylic latex binder. [0091] In an example, the polymeric binder in the white 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.

[0092] In an example, the white 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 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 C-io in length.

[0093] 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 an 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); C₄ to Cmalkyldiamine (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-di isocyanate (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.

[0094] 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 C-m 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.

[0095] 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.

[0096] The polyester-polyurethane binders disclosed herein may have a weight average molecular weight ranging from about 20,000 to about 300,000. In some examples of the white 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 to about 300,000. 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.

[0097] 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 white 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. [0098] 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 OTRAC® Wave device, from Microtrac, e.g., NAN OTRAC® 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.

[0099] Other examples of the white 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)); or TAKELAC® W-6061T or TAKELAC® WS-6021 (Mitsui (Japan)).

[0100] Still other examples of the white 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)); or TAKELAC® W-6110 (Mitsui (Japan)).

[0101] 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).

[0102] Additional examples of the white inkjet ink 16 include an acrylic latex binder. The acrylic latex binder includes latex particles. As used herein, the term “latex” refers to a stable dispersion of polymer particles in an aqueous medium. As such, the polymer (latex) particles may be dispersed in water or water and a suitable co-solvent. This aqueous latex dispersion may be incorporated into a suitable ink vehicle to form examples of the white inkjet ink 16.

[0103] The acrylic latex binder may be anionic or non-ionic depending upon the monomers used.

[0104] In some examples, the acrylic latex particles can include a polymerization product of monomers including: a copolymerizable surfactant; an aromatic monomer selected from styrene, an aromatic (meth)acrylate monomer, and an aromatic (meth)acrylamide monomer; and multiple aliphatic (meth)acrylate monomers or multiple aliphatic (meth)acrylamide monomers. The term “(meth)” indicates that the acrylamide, the acrylate, etc., may or may not include the methyl group. In one example, the latex particles can include a polymerization product of a copolymerizable surfactant such as HITENOL™ BC-10, BC-30, KH-05, or KH-10. In another example, the latex particles can include a polymerization product of styrene, methyl methacrylate, butyl acrylate, and methacrylic acid.

[0105] In another particular example, the latex particles can include a first heteropolymer phase and a second heteropolymer phase. The first heteropolymer phase is a polymerization product of multiple aliphatic (meth)acrylate monomers or multiple aliphatic (meth)acrylamide monomers. The second heteropolymer phase can be a polymerization product of an aromatic monomer with a cycloaliphatic monomer, wherein the aromatic monomer is an aromatic (meth)acrylate monomer or an aromatic (meth)acrylamide monomer, and wherein the cycloaliphatic monomer is a cycloaliphatic (meth)acrylate monomer or a cycloaliphatic (meth)acrylamide monomer. The second heteropolymer phase can have a higher glass transition temperature than the first heteropolymer phase. The first heteropolymer composition may be considered a soft polymer composition and the second heteropolymers composition may be considered a hard polymer composition.

[0106] The two phases can be physically separated in the latex particles, such as in a core-shell configuration, a two-hemisphere configuration, smaller spheres of one phase distributed in a larger sphere of the other phase, interlocking strands of the two phases, and so on. [0107] The first heteropolymer composition can be present in the latex particles in an amount ranging from about 15 wt% to about 70 wt% of a total weight of the polymer (latex) particle and the second heteropolymer composition can be present in an amount ranging from about 30 wt% to about 85 wt% of the total weight of the polymer particle. In other examples, the first heteropolymer composition can be present in an amount ranging from about 30 wt% to about 40 wt% of a total weight of the polymer particle and the second heteropolymer composition can be present in an amount ranging from about 60 wt% to about 70 wt% of the total weight of the polymer particle. In one specific example, the first heteropolymer composition can be present in an amount of about 35 wt% of a total weight of the polymer particle and the second heteropolymers composition can be present in an amount of about 65 wt% of the total weight of the polymer particle.

[0108] As mentioned herein, the first heteropolymer phase can be polymerized from two or more aliphatic (meth)acrylate ester monomers or two or more aliphatic (meth)acrylamide monomers. The aliphatic (meth)acrylate ester monomers may be linear aliphatic (meth)acrylate ester monomers and/or cycloaliphatic (meth)acrylate ester monomers. Examples of the linear aliphatic (meth)acrylate ester monomers can include ethyl acrylate, ethyl methacrylate, benzyl acrylate, benzyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, hexyl acrylate, hexyl methacrylate, isooctyl acrylate, isooctyl methacrylate, octadecyl acrylate, octadecyl methacrylate, lauryl acrylate, lauryl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxyhexyl acrylate, hydroxyhexyl methacrylate, hydroxyoctadecyl acrylate, hydroxyoctadecyl methacrylate, hydroxylauryl methacrylate, hydroxylauryl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, and combinations thereof. Examples of the cycloaliphatic (meth)acrylate ester monomers can include cyclohexyl acrylate, cyclohexyl methacrylate, methylcyclohexyl acrylate, methylcyclohexyl methacrylate, trimethylcyclohexyl acrylate, trimethylcyclohexyl methacrylate, tert- butylcyclohexyl acrylate, tert- butylcyclohexyl methacrylate, and combinations thereof. [0109] Also as mentioned herein, the second heteropolymer phase can be polymerized from a cycloaliphatic monomer and an aromatic monomer. The cycloaliphatic monomer can be a cycloaliphatic (meth)acrylate monomer or a cycloaliphatic (meth)acrylamide monomer. The aromatic monomer can be an aromatic (meth)acrylate monomer or an aromatic (meth)acrylamide monomer. The cycloaliphatic monomer of the second heteropolymer phase can be cyclohexyl acrylate, cyclohexyl methacrylate, methylcyclohexyl acrylate, methylcyclohexyl methacrylate, trimethylcyclohexyl acrylate, trimethylcyclohexyl methacrylate, tert- butylcyclohexyl acrylate, fe/f-butylcyclohexyl methacrylate, or a combination thereof.

In still further examples, the aromatic monomer of the second heteropolymer phase can be 2-phenoxyethyl methacrylate, 2-phenoxyethyl acrylate, phenyl propyl methacrylate, phenyl propyl acrylate, benzyl methacrylate, benzyl acrylate, phenylethyl methacrylate, phenylethyl acrylate, benzhydryl methacrylate, benzhydryl acrylate, 2- hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, N-benzyl methacrylamide, N-benzyl acrylamide, N,N-diphenyl methacrylamide, N,N-diphenyl acrylamide, naphthyl methacrylate, naphthyl acrylate, phenyl methacrylate, phenyl acrylate, or a combination thereof.

[0110] The latex particles can have a particle size ranging from 20 nm to 500 nm, from 50 nm to 350 nm, or from 150 nm to 270 nm.

[0111] In some examples, the latex particles can be prepared by flowing multiple monomer streams into a reactor. An initiator can also be included in the reactor. The initiator may be selected from a persulfate, such as a metal persulfate or an ammonium persulfate. In some examples, the initiator may be selected from a sodium persulfate, ammonium persulfate or potassium persulfate. The preparation process may be performed in water, resulting in the aqueous latex dispersion.

[0112] Examples of anionic acrylic latex binders include JANTEX™ Binder 924 and JANTEX™ Binder 45 NRF (both of which are available from Jantex). Other examples of anionic acrylic latex binders include TEXICRYL™ 13-216, TEXICRYL™13-217, TEXICRYL™ 13-220, TEXICRYL™ 13-294, TEXICRYL™ 13-295, TEXICRYL™ 13-503, and TEXICRYL™ 13-813 (each of which is available from Scott Bader). Still other examples of anionic acrylic latex binders include TUBIFAST™ AS 4010 FF, TUBIFAST™ AS 4510 FF, and TUBIFAST™ AS 5087 FF (each of which is available from CHT).

[0113] Examples of non-ionic acrylic latex binders include PRINTRITE™ 595, PRINTRITE™ 2015, PRINTRITE™ 2514, PRINTRITE™ 9691, and PRINTRITE™ 96155 (each of which is available from Lubrizol Corporation). Another example of a non-ionic acrylic latex binder includes TEXICRYL™ 13-440 (available from Scott Bader).

[0114] In some examples of the white 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 white inkjet ink 16. In other examples, the polymeric binder can be present, in the white 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 white inkjet ink 16.

[0115] The polymeric binder (prior to being incorporated into the ink vehicle) 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 white inkjet ink 16.

[0116] In addition to the pigment and the polymeric binder, the white inkjet ink 16 includes an ink vehicle.

[0117] As used herein, the terms “ink vehicle” and “third aqueous 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 rheology modifier, a pH adjuster, or combinations thereof. In an example of the white inkjet ink 16, 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 rheology modifier, 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 rheology modifier, a pH adjuster, and water.

[0118] The co-solvent in the white inkjet ink 16 may be any example of the co solvents set forth herein for the pretreatment fluid 12 or fixer fluid 14, 14’, in any amount set forth herein for the pretreatment fluid 12 or fixer fluid 14 (except that the amount(s) are based on the total weight of the white inkjet ink 16 instead of pretreatment fluid 12 or the fixer fluid 14).

[0119] The surfactant in the white inkjet ink 16 may be any anionic and/or non-ionic surfactant.

[0120] 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.

[0121] Any example of the non-ionic surfactants set forth herein for the pretreatment fluid 12 or the fixer fluid 14 may be used in the white inkjet ink 16.

[0122] Furthermore, the anionic and/or non-ionic surfactant may be included in the white inkjet ink 16 in any amount set forth herein for the surfactant in the pretreatment fluid 12 or the fixer fluid 14 (except that the amount(s) are based on the total weight of the white inkjet ink 16 instead of the pretreatment fluid 12 or the fixer fluid 14, 14’). [0123] An anti-kogation agent may also be included in the vehicle of the white inkjet ink 16, for example, when the white inkjet ink 16 is to be applied via a thermal inkjet printhead. As mentioned herein, 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 white inkjet ink 16. Any of the anti-kogation agents set forth herein for the fixer fluid 14, 14’ may be used in the white inkjet ink 16. It is to be understood that any combination of the anti-kogation agents listed may be used. The anti-kogation agent may be present in the white 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 white 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 white inkjet ink 16.

[0124] 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 white inkjet ink 16. An example of a suitable anti-decel agent is ethoxylated glycerin having the following formula:

H₂C— 0(CH₂CH₂0)_aH HC — 0(CH₂CH₂0)_bH H₂C — 0(CH₂CH₂0)_cH 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).

[0125] 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 white inkjet ink 16). In an example, the anti-decel agent is present in the white inkjet ink 16 in an amount of about 1 wt% active, based on the total weight of the white inkjet ink 16.

[0126] The vehicle of the white 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.

[0127] In an example, the total amount of antimicrobial agent(s) in the white inkjet ink 16 ranges from about 0.01 wt% active to about 0.05 wt% active (based on the total weight of the white inkjet ink 16). In another example, the total amount of antimicrobial agent(s) in the white inkjet ink 16 is about 0.044 wt% active (based on the total weight of the white inkjet ink 16).

[0128] The ink vehicle may also include rheology additive(s). The rheology additive may be added to adjust the viscosity of the white inkjet ink 16 and to aid in redispersibility of the white inkjet ink after it has sat idle. Examples of suitable rheology additives include boehmite, anionic cellulose (e.g., carboxymethyl cellulose, cellulose sulfate, nitrocellulose, and combinations thereof), and combinations thereof. [0129] In an example, the total amount of rheology additive(s) in the white inkjet ink 16 ranges from about 0.005 wt% active to about 5 wt% active (based on the total weight of the white inkjet ink 16).

[0130] The ink vehicle of the white inkjet ink 16 may also include a pH adjuster. A pH adjuster may be included in the white 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 7 to about 11 , from greater than 7 to about 10, from about 7.2 to about 10, from about 7.5 to about 10, from about 8 to about 10, from about 7 to about 9, from about 7.2 to about 9, from about 7.5 to about 9, from about 8 to about 9, from about 7 to about 8.5, from about 7.2 to about 8.5, from about 7.5 to about 8.5, from about 8 to about 8.5, from about 7 to about 8, from about 7.2 to about 8, or from about 7.5 to about 8.

[0131] The type and amount of pH adjuster that is added 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 while inkjet ink 16 in an aqueous solution. In another example, the metal hydroxide base may be added to the white inkjet ink 16 in an aqueous solution including 5 wt% of the metal hydroxide base (e.g., a 5 wt% potassium hydroxide aqueous solution). Any of the acidic pH adjusters mentioned herein may also be used.

[0132] In an example, the total amount of pH adjuster(s) in the white inkjet ink 16 ranges from greater than 0 wt% to about 0.1 wt% (based on the total weight of the white inkjet ink 16). In another example, the total amount of pH adjuster(s) in the white inkjet ink 16 is about 0.03 wt% (based on the total weight of the white inkjet ink 16). [0133] The balance of the white inkjet ink 16 is water. In an example, purified water or deionized water may be used. The water included in the white 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 white 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.

[0134] One specific example of the white 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 white 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 white inkjet ink 16; an additive selected from the group consisting of a non-ionic surfactant, an antimicrobial agent, an anti-decel agent, a rheology modifier, and combinations thereof; and the liquid vehicle, which includes water and an organic solvent (e.g., the co-solvent disclosed herein).

[0135] Examples of the white inkjet ink 16 disclosed herein may be used in a thermal inkjet printer or in a piezoelectric printer. The viscosity of the white 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 white 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 white 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).

[0136] Textile Fabrics

[0137] In the examples disclosed herein, the textile fabric 18 may be 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. In a further example, the textile fabric 18 is selected from the group consisting of cotton fabrics and cotton blend fabrics.

[0138] 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.

[0139] 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.

[0140] 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.

[0141 ] 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.

[0142] 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.

[0143] The textile fabric 18 may be any color, and in an example is a color other than white (e.g., black, grey, etc.).

[0144] Printing Method and System

[0145] Fig. 2 depicts an example of the printing method 100, and Fig. 3 depicts examples of various printing modes (e.g., routes A, B, C, and D). As shown in Fig. 2, an example of the printing method 100 comprises: forming a gel on a textile fabric 18 by: inkjet printing a pretreatment fluid 12 on an area of the textile fabric 18, the pretreatment fluid 12 including a silicon oxide material and a first aqueous vehicle; and inkjet printing a fixer fluid 14, 14’ on the area of the textile fabric 18, the fixer fluid 14, 14’ including a cationic polymer and a second aqueous vehicle (as shown at reference numeral 102); inkjet printing a white inkjet ink 16 on the gel on the textile fabric 18 (reference numeral 104); and thermally curing the textile fabric 18 having the gel and the white inkjet ink 16 thereon, thereby generating a print (reference numeral 106). As described in more detail in Fig. 3, some examples of the method 100 involve inkjet printing a second fixer fluid 14’ that is different in composition than the fixer fluid 14. [0146] It is to be understood that any example of the pretreatment fluid 12, the fixer fluid 14, 14’, and the white 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.

[0147] As shown in reference numerals 102 and 104 in Fig. 2, the method 100 includes inkjet printing the pretreatment fluid 12 on the textile fabric 18 and the fixer fluid 14 on the textile fabric 18 at ambient temperature. In other words, the textile fabric 18 is maintained at a temperature ranging from about 18°C to about 25°C during printing. The gel film 24 is formed when the pretreatment fluid 12 and the fixer fluid 14 come in contact with each other on the textile fabric 18.

[0148] The pretreatment fluid 12 is applied to the textile fabric 18, either directly or indirectly. When directly applied, the pretreatment fluid 12 is the first of the fluids that is applied to the textile fabric 18. When indirectly applied, the fixer fluid 14 is applied prior to the pretreatment fluid 12. The application of the pretreatment fluid 12 may be accomplished via piezoelectric inkjet printing, or via thermal inkjet printing.

[0149] The fixer fluid 14 is applied to the textile fabric 18, either directly or indirectly. When directly applied, the fixer fluid 14 is the first of the fluids that is applied to the textile fabric 18. When indirectly applied, the pretreatment fluid 12 is applied prior to the fixer fluid 14. The application of the fixer fluid 14 may be accomplished via piezoelectric inkjet printing, or via thermal inkjet printing.

[0150] When used, the second fixer fluid 14’ is indirectly applied to the textile fabric 18. The application of the second fixer fluid 14’ may be accomplished via piezoelectric inkjet printing, or via thermal inkjet printing.

[0151] The white inkjet ink 16 is applied to the textile fabric 18 after the application of each of the pretreatment fluid 12 and the fixer fluid 14, and in some instances, after the application of the second fixer fluid 14’. The application of the white inkjet ink 16 may be accomplished via piezoelectric inkjet printing, or via thermal inkjet printing.

[0152] Because inkjet printing is used, the pretreatment fluid 12, the fixer fluid 14, 14’, and the white inkjet ink 16 may be selectively applied to the textile fabric 18. In some examples, the pretreatment fluid 12, the fixer fluid 14, 14’, and the white inkjet ink 16 may be applied on all or substantially all of the textile fabric 18. In these examples, the applied fluids 12, 14, 14’, 16 are continuous across all or substantially all of the textile fabric 18. In other examples, the pretreatment fluid 12, the fixer fluid 14, 14’, and the white inkjet ink 16 may be applied on areas of the textile fabric 18 where it is desirable to form the print 28. In these examples, area(s) of the textile fabric 18 where it is not desirable to form the print 28 may remain exposed (i.e. , not have any of the fluids 12, 14, 14’, 16, applied thereon). [0153] As will be discuss in more detail in Fig. 3, the various fluids may be applied in multiple passes, and thus the following amounts encompass the total amount of the individual fluid 12, 14, 14’, 16 that is applied to form the print 28. In an example, the pretreatment fluid 12 is applied in an amount ranging from about 30 gsm (grams per square meter, when wet) to about 200 gsm. In another example, the pretreatment fluid 12 is applied in an amount ranging from about 85 gsm to about 100 gsm. The amount of fixer fluid 14 that is applied depends upon the amount of white inkjet ink 16 that is to be applied. In some examples, the fixer fluid 14 is applied in an amount ranging from about 10 gsm to about 100 gsm. In other examples, the fixer fluid 14 is applied in an amount ranging from about 15 gsm to about 60 gsm. The white inkjet ink 16 is applied in an amount ranging from about 40 gsm to about 400 gsm. In another example, the white inkjet ink 16 is applied in an amount ranging from about 45 gsm to about 200 gsm.

[0154] Referring now to Fig. 3, several examples printing modes of the method 100 are depicted. Each printing mode is identified as an individual route, including route A, route B, route C, and route D. As depicted in Fig. 2, the method 100 involves the formation of a gel on the textile fabric 18. The various routes A, B, C, D depict a variety of ways to generate the gel, and the final print 28A, 28B, 28C, 28D.

[0155] In some examples, forming the gel involves one of: i) inkjet printing the pretreatment fluid 12 directly on the area of the textile fabric 18, and inkjet printing the fixer fluid 14 on the pretreatment fluid 12 (route A); or ii) inkjet printing the fixer fluid 14 directly on the area of the textile fabric 18; and inkjet printing the pretreatment fluid 12 on the fixer fluid 14 (route B).

[0156] Referring specifically to route A, an applicator 22A is used to inkjet print the pretreatment fluid 12 on a desired area of the textile fabric 18. The applicator 22A (and any of the applicators 22B, 22C, 22D disclosed herein) may be a thermal inkjet applicator or a piezoelectric inkjet applicator. The inkjet applicator may be a cartridge or pen including, e.g., a reservoir, a droplet generator (e.g., resistor, piezoelectric actuator), and a plurality of nozzles.

[0157] As shown in route A, a layer 12A of the pretreatment fluid 12 is deposited on the desired area of the textile fabric 18. Then, the fixer fluid 14 is deposited on the layer 12A to form the gel 24. The pretreatment fluid 12 and the fixer fluid 14 are applied sequentially, one immediately after the other as the applicators 22A, 22B pass over the textile fabric 18. As such, the fixer fluid 14 is printed onto the pretreatment fluid 12 while the pretreatment fluid 12 is wet. Wet-on-wet printing is desirable in the examples disclosed herein so that the fluids 12, 14 intermingle to form the gel 24, and because the printing workflow is simplified without the additional drying. In an example of wet-on-wet printing, the fixer fluid 14 is printed onto the pretreatment fluid 12 within a period of time ranging from about 0.01 second to about 30 seconds after the pretreatment fluid 12 is printed. Wet-on-wet printing may be accomplished in a single pass.

[0158] Once the gel 24 is formed, the white inkjet ink 16 is deposited on the gel 24. The deposited white inkjet ink 16 forms an ink layer 16A on the gel 24. The combination of the gel 24 and the ink layer 16A forms a stack 30. The gel 24 forms a film that blocks pores of the textile fabric 18, and thus the pigment of the ink layer 16A is located at or near the surface of the textile fabric 18, which ultimately contributes to improved opacity of the white image 28A that is formed.

[0159] The processes involved in forming the stack 30 may be repeated as many times as desired to create multiple stacks 30 on the textile fabric 18. Multiple stacks 30 may contribute to increased opacity. To form a second stack on the first stack 30, the pretreatment fluid 12 is inkjet printed onto the stack 30, the fixer fluid 14 is inkjet printed onto the additional layer of pretreatment fluid 12 to form a second layer of gel, and the white inkjet ink 16 is inkjet printed onto the second layer of gel. It is to be understood that any desired number of stacks 30 may be generated, and in one example, the process is repeated six times to generate six stacks 30 on the textile fabric 18.

[0160] Once a desired number of stacks 30 is formed, the example shown in route A then involves thermally curing the textile fabric 18 having the stack(s) 30 thereon. This generates the white print 28A (shown in Fig. 3, route A). The thermal curing may be accomplished by applying heat to the textile fabric 18. Heating may be performed using any suitable heating mechanism 26, such as a heat press, oven, etc. The heat generated is sufficient to initiate crosslinking or other interactions that bind the pigment onto the textile fabric 18. In an example, the thermal curing the textile fabric 18 (having the stack(s) 30 thereon) involves heating at a temperature ranging from about 80°C to about 200°C for a time ranging from about 5 seconds to about 10 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 textile fabric 18 to a temperature of 150°C for about 3 minutes.

[0161] Pressure may also be applied during thermal curing. The pressure applied to the textile fabric 18 (with the stack(s) 30 thereon) ranges from about 0.1 atm to about 8 atm.

[0162] In the example printing mode of route B, forming the gel involves inkjet printing the fixer fluid 14 on the area (of the textile fabric 18); and then inkjet printing the pretreatment fluid 12 on the area (where the fixer fluid 14 has been applied).

[0163] Referring specifically to route B, an applicator 22B is used to inkjet print the fixer fluid 14 on a desired area of the textile fabric 18. As shown in route B, a layer 14A of the fixer fluid 14 is deposited on the desired area of the textile fabric 18. Then, the pretreatment fluid 12 is deposited on the layer 14A to form the gel 24. The fixer fluid 14 and the pretreatment fluid 12 are applied sequentially, one immediately after the other as the applicators 22B, 22A pass over the textile fabric 18. As such, the pretreatment fluid 12 is printed onto the fixer fluid 14 while the fixer fluid 14 is wet. Wet-on-wet printing is desirable in the examples disclosed herein so that the fluids 14, 12 intermingle to form the gel 24, and because the printing workflow is simplified without the additional drying. In an example of wet-on-wet printing, the pretreatment fluid 12 is printed onto the fixer fluid 14 within a period of time ranging from about 0.01 second to about 30 seconds after the fixer fluid 14 is printed. Wet-on-wet printing may be accomplished in a single pass.

[0164] Once the gel 24 is formed, the white inkjet ink 16 is deposited on the gel 24. The deposited white inkjet ink 16 forms an ink layer 16A on the gel 24. The combination of the gel 24 and the ink layer 16A forms a stack 30. The gel 24 forms a film that blocks pores of the textile fabric 18, and thus the pigment of the ink layer 16A is located at or near the surface of the textile fabric 18, which ultimately contributes to improved opacity of the white image 28B that is formed. [0165] The processes involved in forming the stack 30 may be repeated as many times as desired to create multiple stacks 30 on the textile fabric 18. Multiple stacks 30 may contribute to increased opacity. To form a second stack on the first stack 30, the fixer fluid 14 is inkjet printed onto the stack 30, the pretreatment fluid 12 is inkjet printed onto the additional layer of fixer fluid 14 to form a second layer of gel, and the white inkjet ink 16 is inkjet printed onto the second layer of gel. It is to be understood that any desired number of stacks 30 may be generated, and in one example, the process is repeated six times to generate six stacks 30 on the textile fabric 18.

[0166] Once a desired number of stacks 30 is formed, the example shown in route B then involves thermally curing the textile fabric 18 having the stack(s) 30 thereon. This generates the white print 28B (shown in Fig. 3, route B). The thermal curing may be accomplished by applying heat or heat and pressure to the textile fabric 18 using the heating mechanism 26 as described in route A.

[0167] Route C illustrates two different example printing modes.

[0168] In a first example printing mode of route C, forming the gel 24 involves inkjet printing a first layer 14A of the fixer fluid 14 on the area before the pretreatment fluid 12 is inkjet printed on the area; and inkjet printing a second layer 14B of the fixer fluid 14 on the area after the pretreatment fluid 12 is inkjet printed on the area.

[0169] Referring specifically to the first example in route C, an applicator 22B is used to inkjet print the fixer fluid 14 on a desired area of the textile fabric 18. In this example of route C, the fixer fluid 14 is deposited on the desired area of the textile fabric 18 to form a layer 14A. Then, the pretreatment fluid 12 is deposited on the layer 14A to form the gel 24. Then, a second layer 14B of the fixer fluid 14 is formed when the fixer fluid 14 is deposited on the gel 24 in the desired area of the textile fabric 18.

In these examples, the fixer fluid 14 is used to generate both the first layer 14A and the second layer 14B. As such, the same applicator 22B is used to form both of the layers 14A, 14B.

[0170] While the second fixer fluid layer 14B is shown as being separate from the gel 24, it is to be understood that some of the fixer fluid components may react with any unreacted silicon oxide material in the gel 24 to form additional gel 24.

Additionally or alternatively, the fixer fluid components may form a separate layer on the gel 24. This may be desirable for having the cationic polymer of the fixer fluid 14 in close contact with the pigment of the white inkjet ink 16 for fixing the pigment at the surface of the textile fabric 18.

[0171] In a second example printing mode of route C, forming the gel involves inkjet printing the fixer fluid 14 on the area; and then inkjet printing the pretreatment fluid 12 on the area; and the method further includes inkjet printing a second fixer fluid 14’ that is different from the fixer fluid 14 on the area. In these examples, the fixer fluid 14’ is a different composition than the fixer fluid 14, and forms a second layer 14B’ on the gel 24. Any formulation set forth herein for the fixer fluid 14 may be used for the second fixer fluid 14’, as long as the fluids do not deleteriously affect gel 24 formation or alter the already formed gel 24, or can contribute to further gel 24 formation. In these examples, the fixer fluid 14’ is deposited from a different applicator 22D than the fixer fluid 14.

[0172] While the second fixer fluid layer 14B’ is shown as being separate from the gel 24, it is to be understood that some of the second fixer fluid components may react with any unreacted silicon oxide material in the gel 24 to form additional gel 24. Additionally or alternatively, the second fixer fluid components may form a separate layer on the gel 24. This may be desirable for having the cationic polymer of the second fixer fluid 14’ in close contact with the pigment of the white inkjet ink 16 for fixing the pigment at the surface of the textile fabric 18.

[0173] In either example in route C, the additional layer 14B, 14B’ of either of the fixer fluids 14, 14’ may contribute to increased opacity in the final print 28C as it may contribute to an increased amount of immobilized white pigment.

[0174] In either of the examples of shown in route C, once the gel 24 is formed and the second fixer fluid 14, 14’ is applied, the white inkjet ink 16 is deposited on the gel 24. The deposited white inkjet ink 16 forms an ink layer 16A on the gel 24. The combination of the gel 24 and the ink layer 16A forms a stack 30’. As described herein, this stack 30’ may also include a separate layer 14B, 14B’ depending upon the interaction of the second fixer fluid 14, 14’ at the surface of the gel 24. The gel 24 forms a film that blocks pores of the textile fabric 18, and thus the pigment of the ink layer 16A is located at or near the surface of the textile fabric 18, which ultimately contributes to improved opacity of the white image 28B that is formed.

[0175] The processes involved in forming the stack 30’ may be repeated as many times as desired to create multiple stacks 30’ on the textile fabric 18. Multiple stacks 30’ may contribute to increased opacity. To form a second stack on the first stack 30’, the fixer fluid 14 is inkjet printed onto the stack 30’, and then the following fluids are printed sequentially onto the newly formed fixer fluid layer: the pretreatment fluid 12, the fixer fluid 14 or 14’, and the white inkjet ink 16. It is to be understood that any desired number of stacks 30’ may be generated, and in one example, the process is repeated six times to generate six stacks 30’ on the textile fabric 18.

[0176] Once a desired number of stacks 30’ is formed, each of the examples shown in route C then involve thermally curing the textile fabric 18 having the stack(s) 30’ thereon. This generates the white print 28C (shown in Fig. 3, route C). The thermal curing may be accomplished by applying heat or heat and pressure to the textile fabric 18 using the heating mechanism 26 as described in reference to route A. [0177] In the examples of route C, wet-on-wet-on-wet-on-wet printing is used. This type of printing is desirable in the examples disclosed herein so that the fluids 12, 14 (and potentially 14’) intermingle to form the gel 24, and because the printing workflow is simplified without the additional drying. The respective fluids (14, 12, 14, 16 or 14, 12, 14’, 16) are deposited within a period of time ranging from about 0.01 second to about 30 seconds after the preceding fluid is printed. Wet-on-wet-on-wet-on-wet printing may be accomplished in a single pass.

[0178] In one example printing mode of route D, forming the gel involves inkjet printing a first layer of the fixer fluid 14 area before the pretreatment fluid is inkjet printed on the area; and inkjet printing a second layer of the fixer fluid on the area after the pretreatment fluid is inkjet printed on the area, and the further includes squeegeeing the textile fabric after the first layer of the fixer fluid and the pretreatment fluid are inkjet printed on the area and before the second layer of the fixer is inkjet printed.

[0179] Route D illustrates two different example printing modes. These printing modes are similar to the first and second examples described in reference to route C. However, the first example of route C further includes squeegeeing the textile fabric 18 after the first layer 14A of the fixer fluid 14 and the pretreatment fluid 12 are inkjet printed on the area and before the second layer 14B of the fixer fluid 14 is inkjet printed. Similarly, the second example of route C further includes squeegeeing the textile fabric 18 after the fixer fluid 14 and the pretreatment fluid 12 are inkjet printed on the area and before the second fixer fluid 14’ is inkjet printed.

[0180] Referring to the first and second examples in route D, an applicator 22B is used to inkjet print the fixer fluid 14 on a desired area of the textile fabric 18. As shown in route D, a layer 14A of the fixer fluid 14 is formed on the desired area of the textile fabric 18. Then, the pretreatment fluid 12 is deposited on the layer 14A to form the gel 24. The fixer fluid 14 and the pretreatment fluid 12 are applied sequentially, one immediately after the other as the applicators 22B, 22A pass over the textile fabric 18. As such, the pretreatment fluid 12 is printed onto the fixer fluid 14 while the fixer fluid 14 is wet.

[0181] In the first and second examples of route D, the resulting gel 24 is then squeegeed. As used herein, the term “squeegeeing” means that the surface of the textile fabric 18 having the gel 24 thereon is wiped (e.g., with a squeegee or roller) or is exposed to pressure that can flatten fibers at the surface of the textile fabric 18. The process of squeegeeing may involve moving a squeegee (shown in Fig. 3) or roller across the textile fabric 18, or by pressing the textile fabric 18 with a press (that is not heated). Squeegeeing may push the gel 24 into the textile fabric 18, which can flatten the fibers and/or better fill pores of the textile fabric 18, and may assist in mitigating fibrillation effects in printing.

[0182] While a single layer of the gel 24 may be formed and squeegeed, it is to be understood that multiple layers of gel 24 may be formed prior to squeegeeing. To form a second layer of gel on the gel 24, the fixer fluid 14 is inkjet printed onto the gel 24, and then the pretreatment fluid 12 is applied. The fluids 12, 14 have to be in contact with one another to form the gel 24, and thus when forming multiple layers of gel 24, the process should not involve forming multiple layers of fixer fluid 14 followed by multiple layers of pretreatment fluid 12. Rather, the fixer fluid 14 and pretreatment fluid 12 are applied sequentially to form the gel. It is to be understood that any desired number of gel 24 layers may be generated, and in one example, the process is repeated from three to six times to generate from three to six layers of gel 24 on the textile fabric 18. The formation of a subsequent layer of gel 24 may be repeated multiple times before all of the gel 24 layers are squeegeed at the same time.

[0183] In route D, a second layer 14B or 14B’ of the fixer fluid 14 or of a second fixer fluid 14’ is formed on the desired area of the textile fabric 18, i.e., where the gel 24 has been formed and squeegeed. In the first example of route D, the fixer fluid 14 is inkjet printed to form the second layer 14B, and thus is the same fluid used to form the first layer 14A. In this example, the fixer fluid 14 is deposited by the applicator 22B to form the second layer 14B. In the second example of route D, a second fixer fluid 14’ is inkjet printed to form the second layer 14B’, and thus is a different fluid from that used to form the first layer 14A. In these examples, the second fixer fluid 14’ is deposited by a different applicator (e.g., applicator 22D).

[0184] The potential interactions and/or reactions taking place between the deposited fixer fluid 14 or the deposited second fixer fluid 14’ and the underlying layer(s) of gel 24 may be any of those described in reference to each of the examples of route C. As described, the additional layer of fixer fluid 14, 14’ may contribute to increased opacity in the final print 28D.

[0185] In either of the examples of shown in route D, once the gel 24 is formed and squeegeed and the second fixer fluid 14, 14’ is applied, the white inkjet ink 16 is deposited on the gel 24. The deposited white inkjet ink 16 forms an ink layer 16A on the gel 24. The combination of the fixer layer 14B, 14B’ (which may be present at the outermost surface of the gel 24) and the ink layer 16A forms a stack 30”.

[0186] The processes involved in forming the stack 30” may be repeated as many times as desired to create multiple stacks 30” on the squeegeed gel 24 on the textile fabric 18. Multiple stacks 30” may contribute to increased opacity. To form a second stack on the first stack 30”, the second fixer fluid 14, 14’ is inkjet printed on the ink layer 16A, and the white inkjet ink 16 is inkjet printed onto the additional layer of the second fixer fluid 14, 14’. It is to be understood that any desired number of stacks 30” may be generated, and in one example, the process is repeated six times to generate six stacks 30” on the gel 24 on the textile fabric 18. [0187] Once a desired number of stacks 30” is formed, the first and second examples shown in route D then involve thermally curing the textile fabric 18 having the gel 24 and the stack(s) 30” thereon. This generates the white print 28D (shown in Fig. 3, route D). The thermal curing may be accomplished by applying heat or heat and pressure to the textile fabric 18 using the heating mechanism 26 as described in reference to route A.

[0188] 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

[0189] Commercially available silicon oxide materials were used to prepare example pretreatment fluids as described herein of various compositions.

LAPONITE® SL-25 (layered synthetic silicate) was diluted to 2 wt% with deionized water to form the first example pretreatment fluid (PT 1 ). SNOWTEX®-UP (colloidal silica) was diluted to 4 wt% with deionized water to form the second example pretreatment fluid (PT2). SNOWTEX®-UP was also diluted to 6 wt% with deionized water to form the third example pretreatment fluid (PT3). VEEGUM® T (magnesium aluminum silicate) was diluted to 1 wt% with deionized water to form the fourth example pretreatment fluid (PT4). The formulations, as well as the pH and the viscosity, of each of the example pretreatment fluids is shown in Table 1. The viscosity was measured at 25°C and 3000 Hz using a Hydramotion VISCOLITE™ viscometer.

Table 1: Pretreatment Fluid Formulations

[0190] A fixer fluid and a white inkjet ink were also used in the example. The formulations are listed below in Tables 2 and 3.

Table 2: Fixer Fluid

Table 3: White Inkjet Ink

[0191] PT1 and the fixer fluid were mixed together in a vial, and the formation of a gel was observed.

[0192] Gildan black midweight 780 cotton T-shirts (referred to herein as GBC) were used as the textile fabric. The fluids in the vial were at ambient temperature when the gel was formed. Additionally, the pH of the fixer fluid was adjusted from 3 to 10.7 with KOH. This solution remained clear during pH adjustment, thus indicating that gel formation is not the result of pH increase, but rather is due to the interaction of the fixer fluid with the pretreatment fluid.

[0193] Several example and comparative example prints were generated on the textile fabric. All of the prints (comparative and example) were generated with the fixer fluid and the white inkjet ink. The example prints were also generated with one of the example pretreatment fluids, which was sandwiched between the fixer fluid. Comparative print 1 included alternating layers of the fixer fluid and white inkjet ink without any pretreatment fluid, and comparative print 2 included a repeated sequence of two layers of fixer fluid and a layer of the white inkjet ink. Table 4 sets forth the fluids that were used to generate the various prints, the order in which the fluids were printed, and the amount of fluid that was dispensed. Each of the fluids was inkjet printed using an 11 ng thermal inkjet printhead and wet-on-wet printing. The printing sequence set forth in Table 4 was repeated 6 times for each example and comparative example.

Table 4: Print Condition and Components

[0194] After all of the fluids were applied, the textile fabrics were thermally cured to generate the respective example and comparative example prints. The thermal curing was performing using a heat press set at 150°C for about 3 minutes.

[0195] The example prints and the comparative 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 before the prints were exposed to any washing. The results are shown in Table 5. Table 5: Lightness

[0196] A greater L* value indicates a greater opacity of the white ink on the colored textile fabric. All of the example prints 1-4 had improved opacity compared to the comparative prints 1 and 2.

[0197] The example and comparative prints were also tested for washfastness and change in opacity after being washed 5 times. For the washfastness test, the L*a*b* values of a color (e.g., white) before and after the 5 washes were measured. For the change in opacity test, the L* values of the color (e.g., white) before and after the 5 washes were measured. The L* values before the 5 washes correspond with the values set forth in Table 5. L* is lightness (as noted above), 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 comparative example print was washed 5 times in a Whirlpool Washer (Model WTW5000DW) with warm water (at about 40°C) and detergent. Each example print and the comparative example print was allowed to air dry between each wash. Then, the L*a*b* values after the 5 washes of each example and comparative print were measured. AL* was calculated by subtracting the L* taken after the 5 washed from the L* taken before the 5 washed. 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*i ,a*i,b*i and L*2,a*₂,b*₂, the CIEDE1976 color difference between them is as follows:

[0198] The results are shown in Table 6.

Table 6: Change in Opacity and Washfastness

[0199] While the example prints and the comparative example prints exhibited minimal change in opacity and good washfastness, the example prints exhibits a smaller change. This indicated an improvement in both opacity and washfastness for the example prints 1-4 (generated with an example of the pretreatment fluid) when compared to comparative prints 1 and 2 (not generated with any pretreatment fluid). [0200] Photographs of all of the example and comparative prints were taken before washing and after the 5 washes. These photographs are reproduced herein in black and white in Fig. 4A through Fig. 4L. As such, Fig. 4A through Fig. 4L show the change in opacity of each print before and after the washfastness test. Comparative print 1 before washing is shown in Fig. 4A and after washing is shown Fig. 4B. Comparative print 2 before washing is shown in Fig. 4C and after washing is shown in Fig. 4D. Example print 1 before washing is shown in Fig. 4E and after washing is shown in Fig. 4F. Example print 2 before washing is shown in Fig. 4G and after washing is shown in Fig. 4H. Example print 3 before washing is shown in Fig.4l and after washing is shown in Fig. 4J. Some of the darkness in Fig. 4J is due to a showdown in the image. Example print 4 before washing is shown in Fig. 4K and after washing is shown in Fig. 4L. The images corresponded with the quantitative L* values, illustrating an improvement in opacity for each of the example prints as compared to the comparative prints. The example prints were more opaque and less prone to fading after the washfastness test.

[0201 ] Another example of a print method was tested using the first example pretreatment fluid (PT 1 ), the fixer fluid, and the white inkjet ink. In this example print method, the fixer fluid and the first example pretreatment fluid were first inkjet printed on the textile fabric, and then were squeegeed into the textile fabric The fixer fluid (total of 36.7 gsm) and the pretreatment (total of 195.6 gsm) were inkjet printed (using an 11 ng thermal inkjet printhead and wet-on-wet printing) over 4 passes. Then, a squeegee was pressed over the textile fabric, and over the gel formed by the mixed fixer and pretreatment fluids. The gel formed on the textile fabric by the combined pretreatment fluid and fixer fluid was not dried or cured during or immediately after the squeegee process.

[0202] Then, the print method continued with the fixer fluid (total of 55 gsm) and the white inkjet ink (total of 300 gsm) being printed (using an 11 ng thermal inkjet printhead and wet-on-wet printing) over 6 passes, onto the squeegeed gel.

[0203] This example was thermally cured to generate example print 5. Thermal curing was performing using a heat press set at 150°C for about 3 minutes.

[0204] Example print 5 was tested for washfastness and change in opacity after being washed 5 times, as described above. The initial L* value for example print 5 was 94.9. The results showed good opacity and good washfastness, and can be seen in Table 7.

Table 7: Change in Opacity and Washfastness

[0205] Photographs of example print 5 were taken before washing and after the 5 washes. These photographs are reproduced herein in black and white in Fig. 5A and Fig. 5B. The images illustrate sufficient opacity before wash and very little change in opacity, thus indicating good washfastness. These images also appear smoother than example print 1 (Fig. 4E and Fig. 4F), indicating that the squeegee process helps to flatten the fibers of the textile fabric. These results illustrate that the pretreatment fluid and fixer fluid may be printed utilizing different printing method and still achieve an improvement in opacity and washfastness.

[0206] 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^) within the stated range were explicitly recited. For example, a range from about 1 wt% active to about 20 wt% active, should be interpreted to include not only the explicitly recited limits of from about 1 wt% active to about 20 wt% active, but also to include individual values, such as about 2.15 wt% active, about 6.5 wt% active, 12.0 wt% active, 15.77 wt% active, 18 wt% active, 19.33 wt% active, etc., and sub-ranges, such as from about 5 wt% active to about 15 wt% active, from about 3 wt% active to about 17 wt% active, from about 10 wt% active to about 20 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.

[0207] 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.

[0208] In describing and claiming the examples disclosed herein, the singular forms “a”, “an”, and “the” include plural referents unless the context clearly dictates otherwise.

[0209] 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 multi-fluid kit for inkjet textile printing, comprising: a pretreatment fluid including: a silicon oxide material; and a first aqueous vehicle; a fixer fluid including: a cationic polymer; and a second aqueous vehicle; and a white inkjet ink; wherein the pretreatment fluid, the fixer fluid, and the white inkjet ink are maintained separately in the multi-fluid kit.

2. The multi-fluid kit as defined in claim 1, wherein the silicon oxide material is selected from the group consisting of colloidal silica, colloidal layered silicate, magnesium aluminum silicate, and combinations thereof.

3. The multi-fluid kit as defined in claim 1 wherein the silicon oxide material is present in an amount ranging from about 1 wt% active to about 20 wt% active based on a total weight of the pretreatment fluid.

4. The multi-fluid kit as defined in claim 1 wherein: the first aqueous vehicle consists of water; and the pretreatment fluid consists of the silicon oxide material and the first aqueous vehicle.

5. The multi-fluid kit as defined in claim 1 wherein the silicon oxide material has an average particle size ranging from about 0.5 nm to about 500 nm.

6. The multi-fluid kit as defined in claim 1 wherein the pretreatment fluid has a viscosity ranging from about 1 cP to about 20 cP at about 25°C.

7. The multi-fluid kit as defined in claim 1 wherein the first aqueous vehicle includes water and an additive selected from the group consisting of a co-solvent, a non-ionic surfactant, an antimicrobial agent, a pH adjuster, and combinations thereof.

8. A printing method, comprising: forming a gel on a textile fabric by: inkjet printing a pretreatment fluid on an area of the textile fabric, the pretreatment fluid including: a silicon oxide material; and a first aqueous vehicle; and inkjet printing a fixer fluid on the area of the textile fabric, the fixer fluid including: a cationic polymer; and a second aqueous vehicle; inkjet printing a white inkjet ink on the gel on the textile fabric; and thermally curing the textile fabric having the gel and the white inkjet ink thereon, thereby generating a print.

9. The printing method as defined in claim 8 wherein forming the gel involves: inkjet printing a first layer of the fixer fluid on the area before the pretreatment fluid is inkjet printed on the area; and inkjet printing a second layer of the fixer fluid on the area after the pretreatment fluid is inkjet printed on the area.

10. The printing method as defined in claim 9, further comprising squeegeeing the textile fabric after the first layer of the fixer fluid and the pretreatment fluid are inkjet printed on the area and before the second layer of the fixer fluid is inkjet printed.

11. The printing method as defined in claim 8 wherein: forming the gel involves: inkjet printing the fixer fluid on the area; and then inkjet printing the pretreatment fluid on the area; and the method further comprises inkjet printing a second fixer fluid that is different from the fixer fluid on the area.

12. The printing method as defined in claim 11 , further comprising squeegeeing the textile fabric after the fixer fluid and the pretreatment fluid are inkjet printed on the area and before the second fixer fluid is inkjet printed.

13. The printing method as defined in claim 8 wherein forming the gel involves one of: i) inkjet printing the pretreatment fluid directly on the area of the textile fabric; and inkjet printing the fixer fluid on the pretreatment fluid; or ii) inkjet printing the fixer fluid directly on the area of the textile fabric; and inkjet printing the pretreatment fluid on the fixer fluid.

14. The printing method as defined in claim 8 wherein thermally curing the textile fabric having the gel and the white inkjet ink thereon involves heating at a temperature ranging from about 80°C to about 200°C for a time ranging from about 5 seconds to about 10 minutes.

15. A kit for textile printing, 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 pretreatment fluid including: a silicon oxide material; and a first aqueous vehicle; a fixer fluid including: a cationic polymer; and a second aqueous vehicle; and a white inkjet ink; wherein the pretreatment fluid, the fixer fluid, and the white inkjet ink are maintained separately in the multi-fluid kit.