BACKGROUND

[0001 ] Inkjet printing has become a popular way of recording images on various media. Some of the reasons include low printer noise, variable content recording, capability of high speed recording, and multi-color recording. As the popularity of inkjet printing increases, the types of use also increase providing demand for new ink compositions. In one example, textile printing can have various applications including the creation of signs, banners, artwork, apparel, wall coverings, window coverings, upholstery, pillows, blankets, flags, tote bags, clothing, etc.

BRIEF DESCRIPTION OF DRAWINGS

[0002] FIG. 1 is a schematic diagram of an example fluid set In accordance with examples of the present disclosure.

[0003] FIG. 2 is a flowchart of an example method of textile printing in accordance with examples of the present disclosure.

[0004] FIG. 3 is a schematic diagram of an example textile printing system in accordance with examples of the present disclosure.

[0005] FIG. 4 is a schematic diagram of another example textile printing system In accordance with examples of the present disclosure.

DETAILED DESCRIPTION

[0006] The present technology relates to fluid sets, methods, and systems for textile printing. In particular, the present disclosure describes a fluid set for printing with white ink on textile fabrics. The fiuid set includes a pretreat composition, a fixer composition, and a white ink composition. The pretreat composition includes water and an emulsion of a silicone polymer, where the silicone polymer includes a polysiloxane backbone having aminoalkyl side chains bonded to silicon atoms of the polysiloxane backbone. Additionally, the polysiloxane backbone terminates at trimethylsilyl terminal groups. The fixer composition includes a liquid vehicle and a cationic polymer. The white ink composition includes a liquid vehicle, a white pigment dispersion, and a polymeric binder. The aminoalkyl side chains in the silicone polymer of the pretreat composition can include from 1 to 6 carbon atoms. The silicone polymer can also include a plurality of methyl groups bonded to the silicon atoms of the polysiloxane backbone. In certain examples, the aminoalkyl side chains can include N-(2- aminoethyl)-3-aminopropyl groups, N-(2-aminoethyl)-3-aminoisobutyl groups, or both. The silicone polymer emulsion can have an average particle size from 1 nm to 450 nm. In some examples, the silicone polymer can be included in the pretreat composition in an amount from 1 wt% to 15 wt%. The amount of nitrogen in the silicone polymer can be from 0.4 wt% to 1 .5 wt%. In further examples, the pretreat composition can also include a surfactant, a glycol ether, or a combination thereof. In some examples, the cationic polymer in the fixer composition can be curable by forming crosslinking at a curing temperature from 80 °C to 200 °C. The white pigment dispersion in the white ink composition can include titanium dioxide, zinc oxide, zinc sulfide, antimony oxide, zirconium dioxide, alumina hydrate, or a combination thereof.

[0007] The present disclosure also describes methods of textile printing. A method of textile printing includes applying a pretreat composition onto a fabric substrate. The pretreat composition includes water and an emulsion of a silicone polymer, where the silicone polymer includes a polysiloxane backbone having aminoalkyl side chains bonded to silicon atoms of the polysiloxane backbone. The polysiloxane backbone terminates at trimethylsilyl terminal groups. The method also includes heat pressing the fabric substrate with the pretreat composition applied thereon. A fixer composition is ejected onto the fabric substrate. The fixer composition includes a liquid vehicle and a cationic polymer. A white ink composition is also ejected onto the fabric substrate. The white ink composition includes a liquid vehicle, a white pigment dispersion, and a polymeric binder. The method also includes curing the fixer composition and the white ink composition by heating the fabric substrate. In some examples, the curing is performed at a temperature from 80 °C to 200 °C. The pretreat composition can be applied by spraying or by ejecting from jetting architecture. [0008] The present disclosure also describes textile printing systems. A textile printing system includes a fabric substrate, a pretreat composition to be applied to the fabric substrate, a fixer composition to be applied to the fabric substrate, and a white ink composition to be applied to the fabric substrate. The pretreat composition includes water and an emulsion of a silicone polymer, where the silicone polymer includes a polysiloxane backbone having aminoalkyl side chains bonded to silicon atoms of the polysiloxane backbone. The polysiloxane backbone terminates at trimethylsilyl terminal groups. The fixer composition includes a liquid vehicle and a cationic polymer. The white ink composition includes a liquid vehicle, a white pigment dispersion, and a polymeric binder. In certain examples, the aminoalkyl side chains include N-(2- aminoethyl)-3-aminopropyl groups, N-(2-aminoethyi)-3-aminoisobutyl groups, or both. The silicone polymer can also include a plurality of methyl groups bonded to the silicon atoms of the polysiloxane backbone. The emulsion of the silicone polymer can have an average particle size from 1 nm to 450 nm.

[0009] As a note, with respect to the compositions, fluid sets, methods, and systems for textile printing described herein, more specific descriptions can be considered applicable to other examples whether or not they are explicitly discussed in the context of that example. Thus, for example, in discussing a pigment related to the ink composition, such disclosure is also relevant to and directly supported in context of the fluid sets and the methods of textile printing, and vice versa.

Fluid Sets for Printing

[0010] As mentioned above, the fluid sets described herein can include a pretreat composition, a fixer composition, and a white ink composition. The fluid sets can be used to print white images and patterns, in particular, on fabric substrates. Washfastness, or the ability of printed ink to retain its color after washing the fabric, is one consideration involved in textile printing. To achieve good washfastness with pigmented ink, the printed ink is often cured at a high temperature after printing to increase the durability of the printed image. However, the high temperatures used during curing, such as 150 °C or higher, can tend to increase migration of colored dye from the fabric substrate into the printed ink when printing on dyed polyester fabrics. Therefore, when a white ink is printed on a dyed polyester fabric substrate and subsequently cured at a high temperature, the colored dye from the fabric can affect the color of the white ink. The result can be an off-white color that has an obvious shade of the underlying dye color.

[0011] Some analog methods of printing on colored polyester, such as screen printing, include applying a dye blocker to dyed fabric before printing pigmented ink on the fabric. A dye blocker prevents dye migration from colored polyester into the printed image during the curing typically at 150°C or higher. However, dye blockers used in analog printing are often unsuitable for digital printing because the dye blockers can be pastes or have a very high viscosity, which can make the dye blockers unusable in digital printing processes. Another way to mitigate this dye migration issue is to cure the printed images at a lower temperature, e.g., <130°C, at which dye migration Is reduced. However, printed images cured at lower temperature can have poor durability such as washfastness.

[0012] The fluid sets described herein can be used to print white ink on fabric substrates with good durability and good opacity. When printing on colored fabric with 100% cotton, the white images can be cured at 80°C to 200°C. When printing on colored polyester fabric, the white images can be cured at 80°C to 130°C. The white ink can retain its whiteness because dye migration from the polyester fabric is reduced when cured at a lower temperature. The printed images with the said fluid set cured at a lower temperature also have excellent durability such as washfastness. If a white Image is cured at a temperature over 130°C, dye migration can become visible and the image quality may not be satisfactory.

[0013] The fluid sets can include a pretreat composition including water and an emulsion of a silicone polymer. The silicone polymer can include a polysiloxane backbone having aminoalkyl side chains bonded to silicon atoms of the polysiloxane backbone. The polysiloxane backbone can terminate at trimethylsilyl terminal groups. This pretreat composition can be applied to a fabric substrate before printing the white ink. This pretreat composition reduces white ink penetration into fabrics and increases white opacity. In some cases, the pretreat composition can be applied and then the fabric substrate can be heated to dry and cure the pretreat composition. The fluid sets can also include a fixer composition and a white ink composition. In various examples, the fixer composition can be applied before or after the white ink composition. In some examples, the fixer composition can include a liquid vehicle and a cationic polymer. The white ink composition can include a liquid vehicle, a white pigment dispersion, and a polymeric binder. The fixer composition and the white ink composition printed on the pretreated fabric substrate can provide a durable white image with good washfastness and good opacity after it is cured.

[0014] FIG. 1 shows a schematic representation of an example fluid set 100. This fluid set includes a pretreat composition 110, a fixer composition 120, and a white ink composition 130. In this example, the pretreat composition includes water and an emulsion of a silicone polymer. As explained above, the silicone polymer has a polysiloxane backbone with aminoalkyl side chains bonded to silicon atoms of the polysiloxane backbone. The polysiloxane backbone terminates at trimethylsilyl terminal groups. The fixer composition includes a liquid vehicle and a cationic polymer. The white ink composition includes a liquid vehicle, a white pigment dispersion, and a polymeric binder.

[0015] In some examples, the pretreat composition can be applied before the fixer composition and the white ink. The silicone polymer emulsion in the pretreat composition can increase the hydrophobicity of the fabric surface when cured, which helps enhance opacity by reducing penetration of the white ink into the fabric. The cured silicone can also form a film that flattens fibers of the fabric, which can increase image quality of white ink printed on the fabric. The silicone polymer can include a polysiloxane backbone, which is a polymer chain made up of alternating silicon and oxygen atoms. Additionally, the polymer can include a plurality of methyl groups attached to silicon atoms of the polysiloxane backbone, where some of the methyl groups are replaced by aminoalkyl side chains. In particular, some silicon atoms in the polysiloxane backbone can be bonded to one methyl group and one aminoalkyl side chain. In certain examples, the aminoalkyl side chains can indude from 1 to 6 carbon atoms. Examples of the aminoalkyl side chains can include N-(2-aminoethyl)-3-aminopropyl, N-(2-aminoethyl)-3- aminoisobutyl groups, or both.

[0016] The silicone polymer can also include trimethylsilyl terminal groups. This means that at the ends of the polysiloxane backbone, the last groups at the ends can include a silicone atom bonded to three methyl groups. The silicon atom is also bonded to the remainder of the polysiloxane backbone through an oxygen atom. The trimethylsilyl terminal groups can be non-reactive in the conditions encountered when applying and curing the pretreat composition. Trimethylsilyl groups from multiple molecules of the silicone polymer will not react with each other. This is different from other types of silicone polymer that include reactive terminal groups, such as alkoxy groups or hydroxyl groups. These reactive groups may react with reactive terminal groups of other molecules to join two molecules together and form a longer polymer chain, for example. Since the silicone polymers described herein do not include reactive terminal groups, the terminal groups do not react with terminal groups of other molecules to join molecules together.

[0017] Some examples of the silicone polymer can have a chemical structure according to scheme (I) shown below: [0018] In scheme (I), n is the number of dimethyl siloxane monomer units in the silicone polymer, and m is the number of methyl N-(2-aminoethyl)-3-aminopropyl siloxane monomer units. In some examples, n and m can independently be integers such that the molecular weight (Mw) of the polymer is from about 1 ,000 Mw to about 300,000 Mw. The number of amino groups can be sufficient such that the polymer includes about 0.1 meq/gram or more of the amino groups. In certain examples, the amount of nitrogen by weight in the silicone polymer can be from 0.4 wt% to 1 .5 wt% with respect to the dry weight of the silicone polymer. It is noted that the polymer structure can include any arrangement of dimethyl siloxane monomer units and methyl N-(2-aminoethyl)-3-aminopropyl siloxane monomer units. For example, the monomers can be polymerized in blocks, or in an alternating pattern, or in a random pattern. As shown in scheme (I), the polymer has trimethylsilyl terminal groups at the ends of the polymer. In this structure, the “polysiloxane backbone” refers to the alternating silicon and oxygen atoms forming a backbone of the polymer molecule. The methyl groups and N-(2-aminoethyl)-3-aminopropyl groups that are attached to this backbone can be referred to as side chains. [0019] In further examples, the silicone polymer can have a chemical structure according to scheme (II) shown below:

[0020] In scheme (II), n is the number of dimethyl siloxane monomer units in the silicone polymer, and m is the number of methyl N-(2-aminoethyl)-3-aminoisobutyl siloxane monomer units. As in the previous example, n and m can independently be integers such that the molecular weight (Mw) of the polymer is from about 1 ,000 Mw to about 300,000 Mw. The number of amino groups can be sufficient such that the poiymer includes about 0.1 meq/gram or more of the amino groups. In certain examples, the amount of nitrogen by weight in the silicone polymer can be from 0.4 wt% to 1 .5 wt%.

As explained above, the monomers can be arranged in any arrangement, including a block copolymer arrangement, or an alternating arrangement, or a random arrangement.

[0021] The silicone polymer can be prepared as an emulsion in water in some examples. In certain examples, the emulsion can have an average particle size from 1 nm to 450 nm, or from 2 nm to 400 nm, or from 2 nm to 50 nm, or from 100 nm to 450 nm, or from 200 nm to 450 nm, or from 300 nm to 450 nm. Non-limiting examples of silicone emulsions that can be used can include MOMENTIVE™ SF1708 available from Momentive Performance Materials (USA), BEAUSIL™ AMO 808 and BEAUSIL™ AMO 804 available from CHT (Germany), WACKER® BELSIL® ADM 1650 available from Wacker (Germany), and GELEST® AMS-233 and AMS-242 available from Gelest, Inc. (USA).

[0022] In some cases, the emulsion can include an emulsifying agent such as a surfactant. In other examples, the emulsion can be free of surfactants. If a surfactant is included, non-limiting surfactants that can be used include TERGITOL™ 15-S-7 available from Dow Chemical Company (USA), MERPOL® SH and STEPANTEX® TD- 560 from Stepan Company (USA), MARLIPAL™ O 13/108 and NOVEL® TDA-6 ethoxylate from Sasol (South Africa), METOLAT® 364 from Munzing Chemie GmbH (Germany), RHODASURF™ BC 840 from Solvay (Belgium), ETHYLAN™ TD-100 from Nouryon (Netherlands), and GENAPOL® X-080 and X-100 from Clariant (Switzerland). Certain glycol ether solvents can also be used as emulsifying agents. Non-limiting examples of such glycol ethers include ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, propylene glycol butyl ether, and ethylene glycol monohexyl ether. Accordingly, the pretreat composition can include a surfactant, or a glycol ether, or both.

[0023] The pretreat composition can be dried and cured after applying to a fabric substrate to form a dry layer of the silicone polymer. In some examples, heat can be used to dry and cure the silicone polymer. For example, the fabric substrate can be heat pressed after the pretreat composition is appiied. In certain examples, the silicone polymer can be dried and/or cured by heat pressing the fabric substrate at a temperature from 80 °C to 180 °C. In a specific example, the fabric substrate can be heat pressed at a temperature from 100 °C to 120 °C for a time of 30 seconds to 2 minutes or from 1 minute to 2 minutes. In another specific example, the fabric substrate can be heat pressed at a temperature from 120 °C to 150 °C for a time from 30 seconds to 90 seconds or from 30 seconds to 60 seconds.

[0024] The silicone emulsion can be diluted in water or an aqueous vehicle. In certain examples, the amount of the silicone polymer in the pretreat composition can be from 1 wt% to 15 wt% by dry weight of the silicone polymer out of the total weight of the pretreat composition. In further examples, the amount of silicone polymer can be from 2 wt% to 10 wt% or from 3 wt% to 8 wt%.

[0025] The pretreat composition can be applied by analog application methods or by digital application methods, in various examples. When applied using an analog method, the silicone emulsion can be applied as-is or diluted to an appropriate concentration in water. Analog methods of application can include spraying, padding, roll-on and other coating methods. When applied using a digital method such as inkjet printing, the pretreat composition can include an aqueous vehicle that is formulated to be jettable. In either case, the pretreat composition can include additives in addition to the silicone polymer and water.

[0026] The aqueous liquid vehicle used in the pretreat composition can include water and various additives. In some examples, the aqueous vehicle can include a water content of from 50 wt% to 99 wt% or from 60 wt% to 85 wt%, as well as organic co-solvent, e.g., from 1 wt% to 25 wt%, from 2 wt% to 20 wt%, or from 4 wt% to 15 wt%. Other liquid vehicle components can also be included, such as antibacterial agents, etc. In further detail regarding the liquid vehicle, co-solvent(s) can be present and can include any co-solvent or combination of co-solvents that are compatible with the silicone emulsion and other ingredients in the pretreat composition. Examples of suitable classes of co-solvents include polar solvents, such as alcohols, amides, esters, ketones, lactones, and ethers. In additional detail, solvents that can be used can include aliphatic alcohols, aromatic alcohols, diols, glycol ethers, polyglycol ethers, caprolactams, formamides, acetamides, and iong chain alcohols. Exampies 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, higher homologs (C ₆ -C ₁₂ ) of polyethylene glycol alkyl ethers, N-alkyl caprolactams, unsubstituted caprolactams, both substituted and unsubstituted formamides, both substituted and unsubstituted acetamides, and the like. More specific examples of organic solvents can include 2-pyrrolidone, 2-ethyl-2-(hydroxymethyl)-1 , 3- propane diol (EPHD), glycerol, dimethyl sulfoxide, sulfolane, glycol ethers, alkyldiols such as 1 ,2-hexanediol, and/or ethoxylated glycerols such as LEG-1 , etc. [0027] The pH of the pretreat composition is from 3 to 6, 3.5 to 5.5 or 4 to 5. The pH of the pretreat composition can be adjusted with an acid to a desirable target.

Examples of acids for pH adjustment include formic acid, acetic acid, glycolic acid, citric acid, hydrochloric acid, sulfuric acid and phosphoric acid.

[0028] Consistent with the formulations of the present disclosure, various other additives may be included to provide desired properties of the pretreat composition for specific applications. Examples of these additives are those added to inhibit the growth of harmful microorganisms. These additives may be biocides, fungicides, and other microbial agents, which are routinely used in these types of formulations. Examples of suitable microbial agents include, but are not limited to, ACTICIDE®, e.g., ACTICIDE® B20 (Thor Specialties Inc.), NUOSEPT™ (Nudex, Inc.), UCARCIDE™ (Union carbide

Corp.), VANCIDE® (R.T. Vanderbilt Co.), PROXEL™ (ICI America), and combinations thereof. Sequestering agents, such as EDTA (ethylene diamine tetra acetic acid) or trisodium salt of methylglycinediacetic acid, may be included to eliminate the deleterious effects of heavy metal impurities, and buffer solutions may be used to control the pH. Viscosity modifiers and buffers may also be present, as well as other additives to modify properties of the pretreat composition as desired.

[0029] In a particular example, the pretreat composition can include the silicone polymer emulsion in an amount from 1 wt% to 15 wt%, organic co-solvent in an amount from 1 wt% to 20 wt%, surfactant in an amount from 0.1 wt% to 5 wt%, and water. [0030] Turning now to the fixer composition, in some examples the fixer composition can be applied by digital methods such as inkjet printing. Accordingly, the fixer composition can aiso include a liquid vehicle formulated to be jettable. In some examples, the fixer composition can include any of the same liquid vehicle ingredients described above with respect to the liquid vehicle of the pretreat composition. In particular examples, the fixer liquid vehicle can include water, organic co-solvent, and other additives.

[0031] The fixer composition can also include a cationic polymer. In some examples, the cationic polymer can be capable of crosslinking a polymeric binder present in the white ink composition or the functional group on the fabric surface. Therefore, the fixer composition can crosslink the polymeric binder in the white ink composition after curing. This can increase the durability of the white image printed on the fabric. The cationic polymer can also crash the negatively charged white pigment dispersion to increase opacity. In some examples, the fixer composition can be applied onto the fabric substrate before jetting the white ink composition. In other examples, the fixer composition can be applied after or concurrently with the white ink composition. [0032] The cationic polymer included in the fixer composition can have a weight average molecular weight ranging from 3,000 Mw to 3,000,000 Mw. Any weight average molecular weight (Mw) throughout this disclosure may be expressed as Mw, and is in Daltons. In some examples, the cationic polymer included in the fixer composition can have a weight average molecular weight from 3,000 Mw to 200,000, or from 3,000 Mw to 100,000 Mw, or from 3,000 Mw to 50,000 Mw, for example. This molecular weight may provide for the cationic polymer to be printed by thermal inkjet printheads with good print reliability in many instances. When using other technology to eject the fixer composition, higher molecular weights may be useable, such as from 200,000 Mw to 3,000,000 Mw, e.g., applied by piezoelectric printheads and/or analog methods. [0033] Examples of the cationic polymer include poly(diallyldlmethylammonium chloride); or poly(methylene-co-guanidine) anion with the anion selected from the hydrochloride, bromide, nitrate, sulfate, or sulfonate; a polyamine; poly(dimethylamine- co-epichlorohydrin); a polyethylenimine; a polyamide epichlorohydrin resin: a polyamine epichlorohydrin resin; or a combination thereof. Some examples of commercially available polyamine epichlorohydrin resins may include CREPETROL™ 73, KYMENE™ 736, KYMENE™ 736NA, POLYCUP™ 7360, and POLYCUP™ 7360A, available from Solenis LLC.

[0034] The amount of the cationic polymer in the fixer composition can be from 1 wt% to 15 wt% based on the dry weight of the cationic polymer out of the total weight of the fixer composition, in some examples. In further examples, the amount can be from 2 wt% to 10 wt% or from 2 wt% to 5 wt%. The amounts of ingredients included in the liquid vehicle of the fixer composition can be any of the amounts described above for the liquid vehicle of the pretreat composition.

[0035] In certain examples, the fixer composition can include a cationic polymer in an amount from 1 wt% to 15 wt%, organic co-solvent in an amount from 1 wt% to 20 wt%, surfactant in an amount from 0.1 wt% to 5 wt%, and water.

[0036] The white ink composition can include a liquid vehicle, a white pigment dispersion, a polymeric binder, a surfactant, a biocide and other additives such as a rheology modifier. The white pigment can include pigments such as titanium dioxide, zinc oxide, zinc sulfide, antimony oxide, zirconium dioxide, alumina hydrate, or combinations thereof. In a certain example, the white pigment can be rutile titanium dioxide. In certain examples, the white pigment can be present in the white ink composition in an amount from 1 wt% to 20 wt%, or from 2 wt% to 15 wt%, or from 5 wt% to 15 wt%. The particle size of the white pigment can be suitable for jetting. In some examples, the white pigment can have an average particle size from 100 nm to 800 nm, or from 150 nm to 500 nm, or from 200 nm to 400 nm.

[0037] The white pigment can be dispersed by a dispersant, such as a polymer dispersant or any other dispersant technology suitable for suspending the pigment in the liquid vehicle. Example polymer dispersants can include anionic polymers, non-ionic polymers or a combination of both. Examples of anionic dispersants include CARBOSPERSE™ K7028 from Lubrizol (USA), TAMOL™ 731 A from Dow Chemicals (USA) and COADIS™ 123 Kfrom Coatex (France). Examples of non-ionic and low ionic dispersants include DISPERBYK® 190, 2012, and 2015 from BYK (Germany).

[0038] The white inkjet ink can also Include a polymeric binder. In some examples, the polymeric binder 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.

[0039] In an example, the white inkjet ink includes the polyester-polyurethane binder. In an example, the polyester-polyurethane binder is a sulfonated polyester- polyurethane binder. The sulfonated polyester-polyurethane binder can include diaminesulfonate groups. In an example, the polyurethane-based binder is the polyester-polyurethane binder, the polyester-polyurethane binder is a sulfonated polyester-polyurethane binder, and is one of: i) an aliphatic compound including multiple saturated C4 to C10 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 C10 in length.

[0040] In one example, 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 C10, C3 to 09, or C3 to C6 alkyl. The sulfonated polyester-polyurethane binder can also contain alicyclic carbon moiety. These polyester-polyurethane binders can be described as “aliphatic” because these carbon chains are saturated and because they are devoid of aromatic moieties. An example of a commercially available anionic aliphatic polyester-polyurethane binder that can be used is IMPRANIL® DLN-SD (CAS# 375390-41 -3; 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; 04 to C10 alkyldiol, e.g., hexane-1 ,6-diol; 04 to C10 alkyl dicarboxylic acids, e.g., adipic acid; C4-C10 alkyldiamine, e.g., (2, 4, 4)-trimethylhexane-1 ,6-diamine

(TMD), isophorone diamine (IPD); C4 to C10 alkyl diisocyanates, e.g., hexamethylene diisocyanate (HDI), (2, 4, 4)-trimethylhexane-1 ,6-diisocyanate (TMDI); alicyclic diisocyanates, e.g. isophorone diisocyanate (IPDI), 1 ,3- bis(isocyanatomethyl)cyclohexane (H6XDI); diamine sulfonic acids, e.g., 2-[(2- aminoethyl)amino]ethanesulfonic acid; etc. [0041] Alternatively, the sulfonated polyester-polyurethane binder can be aromatic (or include a commercially available aromatic moiety) and can include aliphatic chains. An example of an aromatic polyester-polyurethane binder that can be used is DISPERCOLL® U42 (CAS# 157352-07-3). 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 C10 alkyl dialcohols, e.g., hexane-1 ,6-diol; C4 to C10 alkyl diisocyanates, e.g., hexamethylene diisocyanate (HDI); diamine sulfonic acids, e.g., 2-[(2-aminoethyl)amino]ethanesulfonic acid; etc.

[0042] Other types of 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.

[0043] The polyester-polyurethane binders disclosed herein may have a weight average molecular weight (Mw, g/mol or Daltons) ranging from about 20,000 to about 1 ,000,000. In some examples of the white inkjet ink, the polyurethane-based binder is the polyester-polyurethane binder, and the polyester-polyurethane binder has a weight average molecular weight ranging from about 20,000 Mw to about 300,000 Mw. As examples, the weight average molecular weight can range from about 50,000 to about 500,000, from about 100,000 to about 400,000, or from about 150,000 to about

300,000.

[0044] The polyester-polyurethane binders disclosed herein may have an acid number that ranges from about 1 mg KOH/ g to about 50 mg KOH/g. In some examples of the inkjet ink, the polyurethane-based 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. For this binder, the term “acid number” refers to the mass of potassium hydroxide (KOH) in milligrams that is used to neutralize one gram of the polyester- polyurethane binder. [0045] To determine this acid number, a known amount of a sampie of the polyester-poiyurethane 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 measurements may be used. An example of a current detector is the Mutek 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), e.g., PolyDADMAC.

[0046] The average particle size of the polyester-poiyurethane binders disclosed herein may range from about 20 nm to about 500 nm. As examples, the sulfonated polyester-poiyurethane 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 NANOTRAC® Wave device, from Microtrac, e.g., NANOTRAC® Wave II or NANOTRAC® 150, etc., which measures particle size using dynamic light scattering. Average particle size can be determined using particle size distribution data, e.g., volume weighted mean diameter, generated by the NANOTRAC® Wave device.

[0047] Other examples of the white inkjet Ink include a polyether-polyurethane binder. Examples of 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 (DIG Corp. (Japan)); or TAKELAC® W-6061T or TAKELAC® WS-6021 (Mitsui (Japan)).

[0048] Still other examples of the white inkjet ink include a polycarbonatepolyurethane binder. Examples of polycarbonate-polyurethanes that may be used as the polyurethane-based binder include IMPRANIL® DLC-F or IMPRANIL® DL 2077 (Covestro (Germany)); or HYDRAN® WLS-213 (DIC Corp. (Japan)); or TAKELAC® W- 6110 (Mitsui (Japan)).

[0049] A non-ionic polyurethane binder can also be included as the binder in the white ink. Examples of non-ionic polyurethane binders include RUCO-PUR® SPH (a hydrophilic, non-ionic polyurethane available from Rudolf Group, Germany), RUCO- COAT® EC 4811 (an aqueous polyurethane/polyether dispersion available from Rudolf Group, Germany), and IMPRANIL® DLI (polyether-polyurethane available from Covestro, Germany). [0050] An acrylic latex can also be used as the polymeric binder of the white ink.

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.

[0051] The acrylic latex binder may be anionic or non-ionic depending upon the monomers used.

[0052] 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 available from Dai-lchi Kogyo Seiyaku Co. (Japan). In another example, the latex particles can include a polymerization product of styrene, methyl methacrylate, butyl acrylate, and methacrylic acid.

[0053] 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.

[0054] 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.

[0055] 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 heteropolymer composition can be present in an amount of about 65 wt% of the total weight of the polymer particle.

[0056] 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- butyicyclohexyl acrylate, terf-butylcyclohexyl methacrylate, and combinations thereof. [0057] 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, fert-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.

[0058] 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.

[0059] 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. [0060] Examples of anionic acrylic latex binders include JANTEX™ Binder 924 and JANTEX™ Binder 45 NRF (both of which are available from Jantex, USA). 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 (available from Scott Bader, United Kingdom). Still other examples of anionic acrylic latex binders include TUBIFAST™ AS 4010 FF, TUBIFAST™ AS 4510 FF, and TUBIFAST™ AS 5087 FF (available from CHT, Germany).

[0061 ] Examples of non-ionic acrylic latex binders include PRINTRITE™ 595, PRINTRITE™ 2015, PRINTRITE™ 2514, PRINTRITE™ 9691 , and PRINTRITE™ 96155 (available from Lubrizol Corporation, USA). Another example of a non-ionic acrylic latex binder includes TEXICRYL™ 13-440 (available from Scott Bader, United Kingdom).

[0062] In some examples, the polymeric binder of the white ink composition can be reactive with the cationic polymer in the fixer composition. When the white ink composition and the fixer composition are printed together, the cationic polymer of the fixer composition can crosslink with the polymeric binder of the white ink composition. In certain examples, this cross-linking can occur with a polyester polyurethane binder in the white ink composition. The substrate can be heated after applying the white ink composition and the fixer composition to dry and cure these compositions. The heating can help form cross-linking in some examples. The substrate can be heated to a temperature from 80 °C to 200 °C for colored fabric with 100% cotton after applying the white ink composition and fixer composition, in some examples. In further examples, the substrate can be heated to a temperature from 90° to 150 °C or from 100 °C to 120 °C. For colored polyester substrates, the drying and curing temperature can be from 80° to 120 °C to minimize dye migration. [0063] The pH of the white ink composition can be adjusted to be suitable for jetting and for maintaining the dispersion of white pigment. In some examples, suitable pH ranges for the white ink composition can be from pH 7 to pH 11 , from pH 7 to pH 10, from pH 7.2 to pH 10, from pH 7.5 to pH 10, from pH 8 to pH 10, from pH 7 to pH 9, from pH 7.2 to pH 9, from pH 7.5 to pH 9, from pH 8 to pH 9, from pH 7 to pH 8.5, from pH 7.2 to pH 8.5, from pH 7.5 to pH 8.5, from pH 8 to pH 8.5, from pH 7 to pH 8, from pH 7.2 to pH 8, or from pH 7.5 to pH 8. Methods of Textile Printing

[0064] The present disclosure also describes methods of textile printing using the fluid sets described above. In some examples, the pretreat composition described above can be applied to a fabric substrate and then the fixer composition and white ink composition described above can be applied after the pretreat composition. In certain examples, the methods can include heating the fabric substrate after applying the pretreat composition and/or after applying the fixer and white ink compositions. White images and patterns printed using these methods can have good washfastness and good opacity.

[0065] FIG. 2 is a flowchart illustrating an example method of textile printing 200. The method can include applying 210 a pretreat composition onto a fabric substrate. The pretreat composition includes the ingredients described above, including water and an emulsion of a silicone polymer. The silicone polymer includes a polysiloxane backbone having aminoalkyl side chains bonded to silicon atoms of the polysiloxane backbone, and the polysiloxane backbone terminates at trimethylsilyl terminal groups. The method can further include heat pressing 220 the fabric substrate with the pretreat composition applied thereon. The method can further include ejecting 230 a fixer composition onto the fabric substrate. The fixer composition includes a liquid vehicle and a cationic polymer. The method also includes ejecting 240 a white ink composition onto the fabric substrate. The white ink composition includes a liquid vehicle, a white pigment dispersion, and a polymeric binder. Finally, the method includes curing 250 the fixer composition and the white ink composition by heating the fabric substrate.

[0066] The pretreat composition can be applied by a digital method or an analog method, as mentioned above. In certain examples, the pretreat composition can be applied by spraying. Other analog coating methods can also be used, such as padding, gravure coating, roll coating, wire rod coating, and so on. In other examples, a digital method, such as inkjet printing, can be used to apply the pretreat composition. The pretreat composition can be printed using similar or identical inkjet print heads used to print the white ink composition and the fixer composition. The pretreat composition can also be printed using a piezo print head or a valve jet print head. [0067] As mentioned above, in some exampies heating the fabric substrate can be accomplished by heat pressing. Other heating methods can also be used, including the use of a drying oven, infrared heaters, hot air, heated rollers, or others. In some examples, the fabric substrate can be heated after applying the pretreat composition to dry and/or cure the pretreat composition. For example, the fabric can be heat pressed after applying the pretreat composition and before applying the fixer composition and the white ink composition. In certain examples, the heat pressing can be performed at a temperature from 80 °C to 180 °C, or from 100 °C to 150 °C, or from 100 °C to 120 °C. The heating can be performed for a time period from 10 seconds to 180 seconds, or from 30 seconds to 120 seconds, or from 60 seconds to 90 seconds. In further examples, the fabric can be heated a second time after the fixer composition and white ink composition are applied. This heating can be accomplished by heat pressing or by another heating method. In certain examples, the fabric can be heated to a temperature from 80 °C to 200 °C after the fixer and white ink composition are applied. In other examples, the fabric can be heated to a temperature from 100 °C to 180 °C, or from 100 °C to 150 °C, or from 90°C to 120 °C, or from 90 °C to 110 °C. Depending on the method used to heat the fabric substrate, the heating can be performed for a time period from 30 seconds to 12 minutes, or from 30 seconds to 3 minutes, or from 30 seconds to 1 minute, or from 1 minute to 2 minutes, or from 8 minutes to 12 minutes, or from 10 minutes to 12 minutes. In certain examples, heat pressing can be performed for a time from 30 seconds to 3 minutes. In other examples, heat can be applied with an oven for a time from 3 minutes to 12 minutes or from 10 minutes to 12 minutes.

[0068] The fixer composition and white ink composition can be applied after heating the fabric to dry and cure the pretreat composition. In some examples, the fixer composition can be applied before the white ink composition. In other examples, the fixer composition and white ink composition can be applied concurrently. These compositions can be applied by inkjet printing. The relative amounts of fixer composition and white ink composition can vary, and can depend on the concentration of ingredients in the compositions. In some examples, the weight ratio of fixer composition to white ink composition that is applied can be from 1:10 to 10:1 , or from 1:8 to 1:1 , or from 1:6 to 1:2. [0069] The fabric substrate can be any desired type of fabric, in certain examples, the fabric can be a dyed polyester fabric. The fluid sets described herein can be particularly useful for preventing dye migration from dyed polyester fabrics into the white ink when cured at a low temperature. The polyester fabric can be dyed any color, including black, red, navy, green or any other color. However, the fluid sets described herein can also be used successfully on many other types of fabric besides polyester and cotton fabrics. Examples of fabric substrates include various fabrics of natural and/or synthetic fibers. 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 fabric substrates can include polymeric fibers such as, nylon fibers, spandex fabrics, 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.

I. du Pont de Nemours Company, Delaware), fiberglass, polytrimethylene, polycarbonate, polyethylene terephthalate, polyester terephthalate, polybutylene terephthalate, or a combination thereof. 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 of 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.

[0070] The fabric substrate can be in one of many different forms, including, for example, a textile, a cloth, a fabric material, fabric clothing, or other fabric product suitable to apply ink, and the fabric substrate can have any of a number of fabric structures. The term “fabric structure” is intended to include structures that can have warp and weft, and/or can be woven, non-woven, knitted, tufted, crocheted, knotted, and pressured, for example. The terms “warp" and “weft” have their ordinary meaning in the textile arts, as used herein, e.g., warp refers to lengthwise or longitudinal yams on a loom, while weft refers to crosswise or transverse yams on a loom.

[0071 ] It is notable that the term “fabric substrate” or “fabric media substrate” does not include materials commonly referred to 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 but is not limited to, fabric with a plain weave structure, fabric with a 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 yam. 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. [0072] As previously mentioned, the fabric substrate can be a combination of fiber types, e.g. a combination of natural fiber with another natural fiber, natural fiber with a synthetic fiber, a synthetic fiber with another synthetic fiber, or mixtures of multiple types of natural fibers and/or synthetic fibers in any of the above combinations. In some examples, the fabric substrate can include natural fiber and synthetic fiber, e.g., cotton/polyester blend. The amount of individual fiber types can vary. For example, the amount of the natural fiber can vary from 5 wt% to 94.5 wt% and the amount of the synthetic fiber can range from 5 wt% to 94.5 wt%. In yet another example, the amount of the natural fiber can vary from 10 wt% to 80 wt% and the synthetic fiber can be present from 20 wt% to 90 wt%. In other examples, the amount of the natural fiber can be 10 wt% to 90 wt% and the amount of the synthetic fiber can also be 10 wt% to 90 wt%. Likewise, the ratio of natural fiber to synthetic fiber in the fabric substrate can vary. For example, the ratio of natural fiber to synthetic fiber can be 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.

[0073] In one example, the fabric substrate can have a basis weight ranging from 10 gsm to 500 gsm. In another example, the fabric substrate can have a basis weight ranging from 50 gsm to 400 gsm. In other examples, the fabric substrate 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.

[0074] In addition, the fabric substrate can contain additives including, but not limited to, colorant (e.g., pigments, dyes, and tints), antistatic agents, brightening agents, nucleating agents, antioxidants, UV stabilizers, and/or fillers and lubricants, for example. Alternatively, the fabric substrate may be pre-treated in a solution containing the substances listed above before applying other treatments or coating layers.

[0075] Regardless of the substrate, whether natural, synthetic, blends thereof, treated, untreated, etc., the fabric substrates printed with the fluid sets of the present disclosure can provide good opacity and/or washfastness properties. The term “washfastness” can be defined as the opacity that is retained or delta E (ΔE) after five (5) standard washing machine cycles using warm water and a standard clothing detergent, e.g., TIDE® available from Proctor and Gamble, Cincinnati, OH, USA. By measuring L*a*b* both before and after washing, ΔL* and ΔE value can be determined, which is a quantitative way of expressing the difference between the L*and/or L*a*b* prior to and after undergoing the washing cycles. Thus, the lower the ΔOD and ΔE values, the better. In further detail, ΔE is a single number that represents the '‘distance” between two colors, which in accordance with the present disclosure, is the white color of the ink prior to washing and the modified color after washing. [0076] Colors, for example, can be expressed as CIELAB values. It is noted that color differences may not be symmetrical going in both directions (pre-washing to post washing vs. post-washing to pre-washing). Using the CIE 1976 definition, the color difference can be measured and the ΔE value calculated based on subtracting the pre- washing color values of L* a* and b* from the post-washing color values of L*, a* and b*. Those values can then be squared, and then a square root of the sum can be determined to arrive at the ΔE value. The 1976 standard can be referred to herein as “ΔE _CIE .” The CIE definition was modified in 1994 to address some perceptual non- uniformities, retaining the L*a*b* color space, but modifying to define the L*a*b* color space with differences in lightness (L*), chroma (C*), and hue (h*) calculated from L*a*b* coordinates. Then in 2000, the CIEDE standard was established to further resolve the perceptual non-uniformities by adding five corrections, namely i) hue rotation (R _T ) to deal with the blue region at hue angles of about 275°), ii) compensation for neutral colors or the primed values in the L*C*h differences, iii) compensation for lightness (S _L ), iv) compensation for chroma (S _C ), and v) compensation for hue (SH). The 2000 modification can be referred to herein as “ΔE ₂₀₀₀ .” In accordance with examples of the present disclosure, ΔE value can be determined using the CIE definition established in 1976, 1994, and 2000 to demonstrate washfastness. However, in the examples of the present disclosure, ΔE _CIE is used.

Textile Printing Systems

[0077] The present disclosure also describes textile printing systems that can print on fabric substrates using the fluid sets described above. The system can include the fabric substrate and the pretreat composition, fixer composition, and white ink composition as described above. FIG. 3 shows an example textile printing system 300 that includes a fabric substrate 340, a pretreat composition 110 to be applied to the fabric substrate, a fixer composition 120 to be applied to the fabric substrate, and a white ink composition 130 to be applied to the fabric substrate. The pretreat composition includes water and an emulsion of a silicone polymer. The silicone polymer includes a polysiloxane backbone with aminoalkyl side chains bonded to silicon atoms of the polysiloxane backbone, and the polysiloxane backbone terminates at trimethylsilyl terminal groups. The fixer composition includes a liquid vehicle and a cationic polymer. The white ink composition includes a liquid vehicle, a white pigment dispersion, and a polymeric binder.

[0078] FIG. 4 shows another example of a textile printing system 400. This figure shows the textile printing system divided into multiple zones, where various operations of a textile printing method can be carried out. This system includes a pretreat composition applicator 112 applying a pretreat composition 110 to a fabric substrate 340. In this example, the pretreat composition applicator is a sprayer, but in other examples the pretreat applicator can include an inkjet printhead or another type of coating mechanism. The system also includes a heat press 450 that can be used to heat the fabric substrate. The heat press is shown heating and applying pressure to the fabric substrate after a coating of the pretreat composition has been applied. After the heat pressing, a layer of fixer composition 120 is applied by a fixer composition applicator 122. In this case, the fixer composition applicator is an inkjet printhead. A layer of white ink composition 130 is then applied by a white ink composition applicator 132. The white ink composition applicator is also an inkjet printhead in this example. The heat press is then used again to apply heat and pressure to the fabric substrate. The final result in this system is the fabric substrate having a dried and cured white image 134 on the surface of the fabric substrate. [0079] In further examples, textile printing systems can include different arrangements of components to perform the various operations of textile printing described herein. Accordingly, textile printing systems may not include all the same zones or components in the same order as in the example shown in FIG. 4.

[0080] It is noted that, as used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the content clearly dictates otherwise.

[0081] As used herein, the term “about” is used to provide flexibility to a numerical range endpoint by providing that a given value may be “a little above” or “a little below” the endpoint. The degree of flexibility of this term can be dictated by the particular variable based on experience and the associated description herein. [0082] As used herein, a plurality of items, structural elements, compositional elements, and/or materials may be presented in a common list for convenience. However, these lists should be construed as though individual members of the list are individually identified as a separate and unique member. Thus, no individual member of such list should be construed as a de facto equivalent of any other member of the same list solely based on their presentation in a common group without indications to the contrary.

[0083] Concentrations, dimensions, amounts, and other numerical data may be presented herein in a range format. It is to be understood that such range format is used merely for convenience and brevity and should be interpreted flexibly to include the numerical values explicitly recited as the limits of the range, and also include individual numerical values or sub-ranges encompassed within that range as if the numerical values and sub-range is explicitly recited. For example, a weight ratio range of 1 wt% to 20 wt% should be interpreted to include explicitly recited limits of 1 wt% and 20 wt%, as well as individual weights such as 2 wt%, 11 wt%, 14 wt%, and sub-ranges such as 10 wt% to 20 wt%, 5 wt% to 15 wt%, etc.

EXAMPLES [0084] The following examples illustrate the technology of the present disclosure.

However, it is to be understood that the following are examples or illustrative of the application of the principles of the presented formulations and methods. Numerous modifications and alternative methods may be devised without departing from the present disclosure. The appended claims are intended to cover such modifications and arrangements. Thus, while the technology has been described above with particularity, the following provides further detail in connection with what are presently deemed to be the acceptable examples.

Example 1 - Fluid Set Compositions [0085] Example fluid sets were prepared, including a pretreat composition, a fixer composition, and a white ink composition. A single fixer formulation and a single white ink formulation were prepared. The ingredients of the fixer composition are shown in Table 1 below. Similarly, the ingredients of the white ink composition are shown in Table 2 below.

Table 1 - Fixer Composition

[0086] In the above formulations, CRODAFOS® N10A is a surfactant available from Croda International PLC, United Kingdom. SURFYNOL® 440 is a surfactant available from Evonik, Germany. POLYCUP™ 7360A is a cationic polymer available from Solenis, USA. ACTICIDE® B20 is a biocide available from Thor Specialties, USA. LEG-1 is an organic co-solvent.

[0087] A series of 12 different pretreat compositions were prepared. Pretreat compositions 1 through 11 included silicone polymers as described in the present disclosure. Pretreat composition 12 was a comparative example, which included a different type of silicone polymer that did not have trimethylsilyl terminal groups as described herein. The silicone emulsions were made by emulsifying a silicone oil in water with a glycol ether or a surfactant and in the presence of acetic acid. The acetic acid assisted in emulsifying the silicone by protonating amino groups. The ingredients in the pretreat compositions are shown in Table 3 below. Table 3 also shows the surface tension, viscosity, pH, average particle size, and visual appearance of the pretreat compositions.

Table 3 - Pretreat Compositions

[0088] In Table 3, the following silicone polymers were used: MOMENTIVE™ SF1708 available from Momentive Performance Materials (USA), BEAUSIL™ AMO 808 and BEAUSIL™ AMO 804 available from CHT (Germany), WACKER® BELSIL® ADM 1650 available from Wacker (Germany), and GELEST® AMS-233 and AMS-242 available from Gelest, Inc. (USA). The above silicone polymers include aminoalkyl side chains and trimethylsilyl terminal groups as described in this disclosure. The comparative silicone polymer was BEAUSIL™ AMO 8721 available from CHT (Germany). This silicone did not include trimethylsilyl terminal groups. Instead, this silicone included reactive groups such as hydroxyl groups or methoxy groups at the terminal ends. The following surfactants were used: TERGITOL™ 15-S-7 available from Dow Chemical Company (USA) and MERPOL® SH from Stepan Company (USA).

Example 2 - Washfastness with Example Fluid Sets

[0089] A series of printed samples were made by printing the pretreat compositions of Table 3 onto black cotton fabric. The sample numbers in Table 3 for samples 1-12 match the number of the pretreat composition used. The pretreat compositions were applied by spraying in an amount from about 110 grams per square meter to about 140 grams per square meter. The fabric was then heat pressed at 150 °C for 1 minute to cure the pretreat composition. The fixer composition and white ink composition of Table 1 and Table 2 were then printed over the pretreat compositions using an inkjet printer. After printing the fixer and the white ink, the fabric was heat pressed at 150 °C for 3 minutes. An additional comparative example (sample 13) was prepared by printing the fixer and white ink compositions on the black fabric without applying any pretreat composition.

[0090] The L*a*b* color values of the printed fabric samples were measured. The fabric was then washed 5 times, and the L*a*b* color values were measured again. The printed fabric substrates were washed in a standard washing machine typically used to wash clothing, namely the WHIRLPOOL® WTW5000DW, with detergent. The washing machine settings were set as follows: Soil level “medium,” temperature “warm,” e.g., about 30 ° to 40 °C, and wash setting “normal” with a single rinse cycle. The full washing machine cycle was repeated for 5 full washes, air drying the printed fabric substrates between wash cycles. After the five full washing cycles, the L*a*b* values were again measured for comparison. The delta E (ΔE) values were calculated using the 1976 standard denoted as ΔE _CIE .

[0091] Table 4 shows the washfastness data for the printed fabric samples. Table 4 - White printing and Washfastness Data

[0092] The experimental resuits show that printing the fixer composition and the white ink composition without a pretreat composition results in low opacity. This is indicated by the low L* measurement of 80.25 for sample 13. The other samples included a pretreat composition and had better L* values. It is also noted that the samples that included a surfactant (samples 10 and 11 ) had slightly lower L* values than the samples that included a glycol ether instead of a surfactant. However, the L* values of the samples including surfactants were adequate. All of the samples showed good washfastness after 5 washes. [0093] The comparative silicone polymer used in sample 12 was able to produce similarly good results as the working example silicone polymers in samples 1-9.

However, silicone polymers with reactive groups such as hydroxyl groups and methoxy groups, as in sample 12, can produce poor results if the particle size of the silicone emulsion is larger than around 50 nm. In contrast, the example silicone polymers used in samples 1 -9 had particle sizes up to over 400 nm while producing good results. Thus, the type of silicone polymer described herein, having trimethylsilyl terminal groups, appears to provide more flexibility in terms of the particle size of the silicone polymer.

Example 3 - Testing on Black Polyester [0094] A few of the pretreat compositions were also tested on black polyester fabric. These tests included pretreat compositions 6, 7, and 12 (comparative). A sample of black polyester was also printed without applying any pretreat composition as another comparative example. These printed polyester fabric samples are numbered 14-17 in Table 5. To prepare the printed polyester fabric samples, the pretreat composition was sprayed onto the fabric and the fabric was heat pressed at 150 °C for 30 seconds. The fixer composition and white ink composition were then printed. The fabric was then heated in an oven at 100 °C for 10 minutes. The same washfastness tests were then performed as explained above. The results are shown in Table 5 below.

Table 5 - Example Printed Black Polyester Fabric Substrates [0095] These results show again that the pretreat compositions increase the initial L* value compared to sample 17, which had fixer and white ink printed without any pretreat composition.

[0096] While the present technology has been described with reference to certain examples, various modifications, changes, omissions, and substitutions can be made without departing from the spirit of the disclosure. It is intended, therefore, that the disclosure be limited by the scope of the following claims.