WO2021026446A1

WO2021026446A1 - Pretreating natural fiber fabrics for dye sublimation ink printing

Info

Publication number: WO2021026446A1
Application number: PCT/US2020/045388
Authority: WO
Inventors: Amir A. AJANEE; Graham A. DRACUP; Carlos J. Hernandez; Travis T. CALHOUN
Original assignee: Prism Inks, Inc.
Priority date: 2019-08-07
Filing date: 2020-08-07
Publication date: 2021-02-11
Also published as: EP4010526A1; EP4010526A4; US20210040684A1; US20240200266A1

Abstract

Provided are pretreatment compositions, pretreated fabrics, and methods of pretreating fabrics for improved printing quality. Pretreated fabrics include natural fiber fabric having a polymer coating. Methods of pretreating fabrics include spraying natural fiber fabric with a pretreatment composition that comprises one or more latex polymers, a coalescing agent composition, a surfactant composition, an ultraviolet stabilizer composition, an antioxidant composition, and a solvent.

Description

PRETREATING NATURAL FIBER FABRICS FOR DYE SUBLIMATION INK

PRINTING

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Application No. 62/884,013, filed August 7, 2019, the entire contents of which are incorporated herein by reference.

FIELD

[0002] This disclosure relates to processes for pretreating fabrics. Specifically, this disclosure relates to pretreatment processes for natural fiber fabrics that may be used for dye sublimation ink printing.

BACKGROUND

[0003] Printed fabrics are useful for several different products including, but not limited to, clothing, bedding, window treatments, signage, upholstery, etc. Printing onto fabrics allows for a variety of patterns and designs to be used on the fabric.

[0004] Presently, dye sublimation inks are often used for printing on synthetic fabrics due to their ability to penetrate the fiber, their color vibrancy, their crock testing results, and their colorfastness to laundering. However, dye sublimation inks are not suitable for printing on natural fiber fabrics because the dyes penetrate and do not adhere to the natural fibers. This lack of adhesion can cause bleeding during laundering, a reduction in color density, a decrease in colorfastness to laundering, and a decrease in crock of the printed fabric.

SUMMARY

[0005] Provided are pretreatment compositions, pretreated natural fiber fabrics, methods for preparing pretreatment compositions, and methods for pretreating natural fiber fabrics that can render fabrics suitable for dye sublimation ink printing by improving the adhesion of the ink to the natural fiber fabric. In particular, pretreatment compositions and methods for pretreating provided herein may be used on natural fiber fabrics such that dye sublimation ink may be used for printing on the natural fiber fabric (after pretreatment). Printed natural fiber fabrics that have been pretreated using the pretreated compositions and/or methods for pretreating provided herein may have improved crock, hand, colorfastness to laundering, adhesion, color density, etc. compared to dye sublimation ink-printed natural fiber fabrics that have not been pretreated with the pretreatment compositions and/or methods for pretreating discussed herein.

[0006] Without pretreating natural fiber fabrics according to the pretreatment compositions and/or methods for pretreating provided herein, dye sublimation inks cannot sufficiently adhere to natural fibers of the natural fiber fabrics, as discussed briefly above. Specifically, natural fiber fabrics are hydrophilic, whereas synthetic fibers are hydrophobic. The hydrophobicity of synthetic fibers aid in absorption of dye sublimation. Thus, the hydrophilicity of natural fiber fabrics inhibit absorption of the dye sublimation inks. However, pretreatment compositions and methods of pretreating provided herein provide a synthetic layer over the natural fibers of the natural fiber fabric to encourage adhesion and absorption of dye sublimation inks to the natural fiber fabric. More specifically, pretreatment compositions can adhere to natural fiber fabric, creating a polymeric, hydrophobic coating overlying the natural fiber fabric. The dye sublimation ink then absorbs into the polymeric hydrophobic coating produced by the pretreatment composition and/or pretreatment method to generate a printed image that will not penetrate through the fabric.

[0007] Pretreatment compositions, pretreated fabric, and methods for pretreating fabric provided herein can allow users to apply dye sublimation ink onto natural fiber fabric to produce a printed fabric having similar properties that are achieved using dye sublimation ink on polyester (i.e., synthetic) fabrics.

[0008] In some embodiments, a pretreatment composition for a natural fiber fabric includes: 15 to 35 wt. % one or more latex polymers; 15 to 35 wt. % one or more humectants; 0.1 to 1 wt. % surfactant composition; 0.1 to 1 wt. % ultraviolet (UV) stabilizer composition; 0.1 to 1 wt. % one or more pH buffers; 0.05 to 0.5 wt. % biocide; and 40 to 60 wt. % solvent. In some embodiments, the one or more latex polymers comprise one or more of a polyester, an acrylic polymer, an aromatic polyamide, a chlorinated polymer, a polyether, a polyurea, a fluorinated polymer, a polyurethane, a styrene, a polyvinyl, a thio/ether polymer, a polyolefin, a polystyrene, a polyacetate, a polyamide, a polyethylene, a polyimide, a polycarbonate, or a polyvinylalcohol. In some embodiments, the one or more latex polymers comprise a polyester. In some embodiments, the polyester has a glass transition temperature from -20 to 100 °C. In some embodiments, a latex dispersion of the polyester has a zeta potential from -60 to -20 mV. In some embodiments, the one or more latex polymers comprise an acrylic polymer. In some embodiments, the acrylic polymer is self-crosslinking. In some embodiments, the coalescing agent composition comprises one or more compounds comprising an aliphatic composition, a cycloaliphatic composition, an ether composition, a glycol composition, an alcohol composition, an ester composition, a carbonate composition, a lactam composition, or a ketone composition. In some embodiments, the coalescing agent composition comprises ethylene glycol butyl ether. In some embodiments, the surfactant composition comprises one or more of an anionic or a nonionic surfactant. In some embodiments, the surfactant composition comprises silicone. In some embodiments, the UV stabilizer composition comprises one or more of a sulfonated benzophenone, a benzotri azole, a salicylate, a cinnamate, a triazole, or a triazine. In some embodiments, the UV stabilizer composition comprises hydroxyphenyl triazine. In some embodiments, the antioxidant composition comprises one or more of a hydroquinone, an alkoxyphenol, a dialkoxyphenol, a phenol, an aniline, an amine, an indane, a chromane, an alkoxyaniline, or a heterocyclic compound. In some embodiments, the antioxidant composition comprises a hindered amine light stabilizer. In some embodiments, the solvent comprises one or more of glycol ether, a diol, an ester, ethanol, or water. In some embodiments, the solvent comprises water.

[0009] In some embodiments, a pretreated natural fiber fabric product includes a natural fiber fabric and a polymer coating on the natural fiber fabric, the polymer coating includes: 20 to 90 wt. % one or more latex polymers; 0.4 to 7 wt. % surfactant composition; and 1 to 8 wt. % ultraviolet (UV) stabilizer composition. In some embodiments, the natural fiber fabric comprises one or more of wool, cotton, silk, linen, leather, hemp, or bamboo. In some embodiments, the pretreated natural fiber fabric product comprises a T-shirt. In some embodiments, the pretreated natural fiber fabric includes an image printed using dye sublimation ink. In some embodiments, the one or more latex polymers comprise one or more of a polyester, an acrylic polymer, an aromatic polyamide, a chlorinated polymer, a polyether, a polyurea, a fluorinated polymer, a polyurethane, a styrene, a polyvinyl, a thio/ether polymer, a polyolefin, a polystyrene, a polyacetate, a polyamide, a polyethylene, a polyimide, a polycarbonate, or a polyvinylalcohol. In some embodiments, the one or more latex polymers comprise a polyester. In some embodiments, the polyester has a glass transition temperature from -20 to 100 °C. In some embodiments, a latex dispersion of the polyester has a zeta potential from -60 to -20 mV.

In some embodiments, the one or more latex polymers comprise acrylic polymer. In some embodiments, the acrylic polymer is self-crosslinking. In some embodiments, the coalescing agent composition comprises one or more compounds comprising an aliphatic composition, a cycloaliphatic composition, an ether composition, a glycol composition, an alcohol composition, an ester composition, a carbonate composition, a lactam composition, or a ketone composition.

In some embodiments, the coalescing agent composition comprises ethylene glycol butyl ether. In some embodiments, the surfactant composition comprises one or more of an anionic or a nonionic surfactant. In some embodiments, the surfactant composition comprises silicone. In some embodiments, the UV stabilizer composition comprises one or more of a sulfonated benzophenone, a benzotri azole, a salicylate, a cinnamate, a triazole, or a triazine. In some embodiments, the UV stabilizer composition comprises hydroxyphenyl triazine. In some embodiments, the antioxidant composition comprises one or more of a hydroquinone, an alkoxyphenol, a dialkoxyphenol, a phenol, an aniline, an amine, an indane, a chromane, an alkoxyaniline, or a heterocyclic compound. In some embodiments, the antioxidant composition comprises a hindered amine light stabilizer.

[0010] In some embodiments, a pretreated natural fiber fabric product includes natural fiber fabric and a polymer coating on the natural fiber fabric, wherein the pretreated natural fiber fabric product is produced by spraying the natural fiber fabric with 8 to 15 grams of a pretreatment composition per square inch of natural fiber fabric. In some embodiments, the pretreatment composition includes 15 to 35 wt. % one or more latex polymers; 15 to 35 wt. % one or more humectants; 0.1 to 1 wt. % surfactant composition; 0.1 to 1 wt. % ultraviolet (UV) stabilizer composition; 0.1 to 1 wt. % one or more pH buffers; 0.05 to 0.5 wt. % biocide; and 40 to 60 wt. % solvent. In some embodiments, the pretreated natural fiber product includes an image printed using dye sublimation ink. In some embodiments, the natural fiber fabric comprises one or more of wool, cotton, silk, linen, leather, hemp, or bamboo. In some embodiments, the pretreated natural fiber fabric product is a T-shirt. In some embodiments, the one or more latex polymers comprise one or more of a polyester, an acrylic polymer, an aromatic polyamide, a chlorinated polymer, a polyether, a polyurea, a fluorinated polymer, a polyurethane, a styrene, a polyvinyl, a thio/ether polymer, a polyolefin, a polystyrene, a polyacetate, a polyamide, a polyethylene, a polyimide, a polycarbonate, or a polyvinylalcohol.

In some embodiments, the one or more latex polymers comprise a polyester. In some embodiments, the polyester has a glass transition temperature from 0 to 100 °C. In some embodiments, a latex dispersion of the polyester has a zeta potential from -60 to -20 mV. In some embodiments, the one or more latex polymers comprise acrylic polymer. In some embodiments, the acrylic polymer is self-crosslinking. In some embodiments, the coalescing agent composition comprises one or more compounds comprising an aliphatic composition, a cycloaliphatic composition, an ether composition, a glycol composition, an alcohol composition, an ester composition, a carbonate composition, a lactam composition, or a ketone composition. In some embodiments, the coalescing agent composition comprises ethylene glycol butyl ether. In some embodiments, the surfactant composition comprises one or more of an anionic or a nonionic surfactant. In some embodiments, the surfactant composition comprises silicone. In some embodiments, the UV stabilizer composition comprises one or more of a sulfonated benzophenone, a benzotri azole, a salicylate, a cinnamate, a triazole, or a triazine. In some embodiments, the UV stabilizer composition comprises hydroxyphenyl triazine. In some embodiments, the antioxidant composition comprises one or more of a hydroquinone, an alkoxyphenol, a dialkoxyphenol, a phenol, an aniline, an amine, an indane, a chromane, an alkoxyaniline, or a heterocyclic compound. In some embodiments, the antioxidant composition comprises a hindered amine light stabilizer.

[0011] In some embodiments, a method of pretreating a natural fiber fabric includes spraying a natural fiber fabric with 8 to 15 grams pretreatment composition per square inch of natural fiber fabric to produce sprayed natural fiber fabric; and drying the sprayed natural fiber fabric to form a pretreated natural fiber fabric product. In some embodiments, the pretreatment composition includes 15 to 35 wt. % one or more latex polymers; 15 to 35 wt. % one or more humectants; 0.1 to 1 wt. % surfactant composition; 0.1 to 1 wt. % ultraviolet (UV) stabilizer composition; 0.1 to 1 wt. % one or more pH buffers; 0.05 to 0.5 wt. % biocide; and 40 to 60 wt. % solvent. In some embodiments, the pretreated natural fiber product includes an image printed using dye sublimation ink. In some embodiments, the natural fiber fabric comprises one or more of wool, cotton, silk, linen, leather, hemp, or bamboo. In some embodiments, the pretreated natural fiber fabric product is a T-shirt. In some embodiments, the one or more latex polymers comprise one or more of a polyester, an acrylic polymer, an aromatic polyamide, a chlorinated polymer, a polyether, a polyurea, a fluorinated polymer, a polyurethane, a styrene, a polyvinyl, a thio/ether polymer, a polyolefin, a polystyrene, a polyacetate, a polyamide, a polyethylene, a polyimide, a polycarbonate, or a polyvinylalcohol. In some embodiments, the one or more latex polymers comprise a polyester. In some embodiments, the polyester has a glass transition temperature from 0 to 100 °C. In some embodiments, a latex dispersion of the polyester has a zeta potential from -60 to -20 mV. In some embodiments, the one or more latex polymers comprise acrylic polymer. In some embodiments, the acrylic polymer is self-crosslinking. In some embodiments, the coalescing agent composition comprises one or more compounds comprising an aliphatic composition, a cycloaliphatic composition, an ether composition, a glycol composition, an alcohol composition, an ester composition, a carbonate composition, a lactam composition, or a ketone composition. In some embodiments, the coalescing agent composition comprises ethylene glycol butyl ether. In some embodiments, the surfactant composition comprises one or more of an anionic or a nonionic surfactant. In some embodiments, the surfactant composition comprises silicone. In some embodiments, the UV stabilizer composition comprises one or more of a sulfonated benzophenone, a benzotri azole, a salicylate, a cinnamate, a triazole, or a triazine. In some embodiments, the UV stabilizer composition comprises hydroxyphenyl triazine. In some embodiments, the antioxidant composition comprises one or more of a hydroquinone, an alkoxyphenol, a dialkoxyphenol, a phenol, an aniline, an amine, an indane, a chromane, an alkoxyaniline, or a heterocyclic compound. In some embodiments, the antioxidant composition comprises a hindered amine light stabilizer.

BRIEF DESCRIPTION OF THE DRAWINGS [0012] The invention will now be described, by way of example only, with reference to the accompanying drawings, in which:

[0013] FIGS. 1 A-1D provide the various stages of pretreating fabric, according to some embodiments.

DETAILED DESCRIPTION

[0014] Provided are pretreatment compositions, pretreated natural fiber fabrics, methods for preparing pretreatment compositions, and methods for pretreating that can be applied to natural fiber fabrics to make the fabric suitable for dye sublimation ink printing. By treating natural fiber fabrics with the pretreatment compositions and/or methods of pretreating provided herein, dye sublimation inks may adhere more easily to the natural fiber fabrics. Additionally, pretreating natural fiber fabrics with a pretreatment composition described herein can improve properties such as crock, hand, colorfastness to laundering, adhesion, color density, etc. when printed with dye sublimation ink as compared to non-treated natural fiber fabrics printed with dye sublimation inks.

[0015] Dye sublimation inks are sometimes used to print onto a film. This film can then be transferred to a natural fiber fabric using a heat press to create a printed natural fiber fabric. However, this method does not allow for a user to print onto the fabric. Additionally, this method is limited because only color images having 100% density can be transferred, the thickness of the film leads to poor hand (i.e., a subjective characteristic that includes smoothness, compressibility, and elasticity of the fabric), the tested colorfastness to laundering is poor, and it causes a reduction in the elasticity or elongation of the fabric.

[0016] Accordingly, pretreatment compositions provided herein have been developed to coat natural fiber fabrics and improve the adhesion of colorants (e.g., dye sublimation ink) to the fabric. These pretreatment compositions, in addition to methods for pretreating disclosed herein, improve the adhesion of dye sublimation ink to the natural fiber fabric specifically because natural fiber fabrics are hydrophilic, whereas synthetic fibers are hydrophobic. The hydrophilicity of the natural fiber fabric impairs the ability of dye sublimation inks to adhere and absorb into the natural fibers. Pretreatment compositions and methods of pretreating provided herein can provide a synthetic, or polymeric coating on the surface of the natural fibers of a natural fiber fabric. This synthetic, polymeric coating dries onto the fibers of the fabric and conforms to the surface of the fabric. Further, the coating can in turn provide hydrophobic characteristics to the natural fiber fabric, increasing the affinity of the dye sublimation ink to the fabric. More specifically, the dye sublimation ink can adhere and absorb into the synthetic, polymeric coating of the pretreatment without penetrating the natural fibers of the natural fiber fabric. Thus, pretreating natural fiber fabrics can allow for a more permanent printed image, in contrast to a dye sublimation ink-printed image on a non-pretreated natural fiber that will penetrate the fibers and fail to withstand laundering, for example.

[0017] Accordingly, pretreatment compositions provided herein can provide a coating that adheres to the natural fibers of the natural fiber fabric and also provides an ink-receptive coating for dye. Provided below is a discussion of the various components of pretreatment compositions provided herein. In particular, discussed below are: (1) pretreatment compositions; (2) methods of preparing pretreatment compositions; (3) methods of pretreating fabrics; and (4) pretreated fabrics.

PRETREATMENT COMPOSITIONS

[0018] Pretreatment compositions according to embodiments provided herein may include a polymer, a coalescing agent, a surfactant, an antioxidant/ultraviolet light absorber, a humectant(s), a pH buffer(s), a biocide(s), and/or water. A pretreatment composition comprising each of these components can provide a coating that adheres to the natural fibers of the natural fiber fabric and also provides an ink-receptive coating for dye. As described above, the pretreatment compositions provided herein may be used with natural fiber fabric, synthetic fabric, or a fabric comprising a combination of natural and synthetic fibers. Note that the weight- percents provided with respect to each of these components refer to pretreatment compositions prior to pretreating fabric, unless stated otherwise.

[0019] In some embodiments, pretreatment compositions described herein may include a polymer composition. A polymer provides a component for the dyes to attach to during the printing process. In some embodiments, the polymer composition may include a latex polymer. In some embodiments, the polymer composition may include a non-latex polymer. Suitable latex polymers may include, but are not limited to, a polyester, an acrylic polymer, an aromatic polyamide, a chlorinated polymer, a polyether, a polyurea, a fluorinated polymer, a polyurethane, a styrene, a polyvinyl, a thio/ether polymer, a polyolefin, a polystyrene, a polyacetate, a polyamide, a polyethylene, a polycarbonate, or a polyvinylalcohol and/or any other suitable dispersed or emulsified natural or synthetic polymers. The polymer(s) may be in an aqueous- or a solvent-based environment. In some embodiments, the polymer(s) may be soluble in the pretreatment composition. In some embodiments, the polymer(s) may be dispersed as particulates in the pretreatment composition. In some embodiments, a pretreatment composition provided herein may comprise 10 to 40 wt. %, 15 to 35 wt. %, 20 to 30 wt. %, 25 to 30 wt.% or 26.6 wt.% polymer composition. In some embodiments, a pretreatment composition may comprise less than 40 wt. %, less than 35 wt. %, less than 30 wt. %, less than 25 wt. %, less than 20 wt. %, less than 15 wt. %, less than 10 wt. %, or less than 5 wt. % polymer composition. In some embodiments, a pretreatment composition may include more than 1 wt. %, more than 5 wt. %, more than 10 wt. %, more than 15 wt. %, more than 20 wt. %, more than 25 wt. %, more than 30 wt. %, more than 35 wt. %, or more than 40 wt. % polymer composition.

[0020] In some embodiments, the polymer may be a polyester latex. Polyester latex provides a dye receptor (i.e., coating) that can accept the diffusion of the dye (e.g., sublimating dye). A dye receptor can increase the color density and can improve the colorfastness to laundering of the printed image. Additionally, a polyester latex can adhere to natural fibers. Thus, pretreatment compositions comprising polyester latex can adhere to the natural fibers of a natural fiber fabric, forming a coating over the natural fiber fabric. Once the coating is formed over the natural fiber fabric, it can act as an adhesive between the dye sublimation ink and natural fiber fabric. Polyester latex in pretreatment compositions provided herein may be in dispersed form. Dispersed polyester may be formed from one or more of diols, diacids, and/or anhydrides through a step-growth (condensation) synthesis process.

[0021] In some embodiments, a polyester that may be used for a polyester latex may have a relatively high glass transition temperature. A relatively high glass transition temperature can improve the abrasion resistance and colorfastness to laundering. If the glass transition temperature of the polyester is too low, the abrasion resistance and colorfastness to laundering may be compromised. For instance, the glass transition temperature of a polyester may be from - 30°C to 50°C, from -20°C to 40°C, from -20°C to 100°C, or 0°C to 100°C from 0°C to 30°C. In some embodiments, the glass transition temperature of the polyester may be less than 110°C, less than 100°C, less than 90°C, less than 80°C, less than 70°C, less than 60°C, less than 50°C, less than 40°C, less than 30°C, less than 20°C, less than 10°C, less than 0°C, less than -10°C, or less than -20°C. In some embodiments, the glass transition temperature of the polyester may be greater than -30°C, greater than -20°C, greater than -10°C, greater than 0°C, greater than 10°C, greater than 20°C, greater than 30°C, greater than 40°C, greater than 50°C, greater than 60°C, greater than 70°C, greater than 80°C, greater than 90°C, greater than 100°C, or greater than 110°C.

[0022] Pretreatment compositions comprising polyester latex may also improve abrasion resistance and colorfastness to laundering. In particular, the surface charge density of a polyester latex may impact the abrasion resistance and colorfastness to laundering. In some embodiments, the polyester latex of a pretreatment composition may have a surface charge density from 0.1 to 1 milliequivalent per gram (meq/g), from 0.2 to 0.9 meq/g, or from 0.3 to 0.8 meq/g. In some embodiments, the surface charge density of a polyester latex may be less than 1 meq/g, less than 0.9 meq/g, less than 0.8 meq/g, less than 0.7 meq/g, less than 0.6 meq/g, less than 0.5 meq/g, less than 0.4 meq/g, or less than 0.3 meq/g. In some embodiments, the surface charge density of a polyester latex may be greater than 0.1 meq/g, greater than 0.2 meq/g, greater than 0.3 meq/g, greater than 0.4 meq/g, greater than 0.5 meq/g, greater than 0.6 meq/g, greater than 0.7 meq/g, or greater than 0.8 meq/g.

[0023] Zeta potential is the electrokinetic potential of a colloidal dispersion. The zeta potential of a latex dispersion (e.g., polyester latex, acrylic latex) may be from -100 to -10, from -80 to - 20, from -60 to -20, or from -60 to -30 mV. In some embodiments, the zeta potential of a latex dispersion of a pretreatment composition provided herein may be less than -10, less than -20, less than -30, less than -40, less than -50, less than -60, less than -70, less than -80, or less than - 90 mV. In some embodiments, the seta potential of a latex dispersion of a pretreatment composition provided herein may be more than -100, more than -90, more than -80, more than - 70, more than -60, more than -50, more than -40, more than -30, or more than -20 mV.

[0024] In some embodiments, a pretreatment composition provided herein may comprise 1 to 40 wt. %, 5 to 30 wt. %, 10 to 20 wt. %, 15 to 20 wt.% or 16.6 wt.% polyester. In some embodiments, a pretreatment composition may comprise less than 40 wt. %, less than 35 wt. %, less than 30 wt. %, less than 25 wt. %, less than 20 wt. %, less than 15 wt. %, less than 10 wt. %, or less than 5 wt. % polyester. In some embodiments, a pretreatment composition may include more than 1 wt. %, more than 5 wt. %, more than 10 wt. %, more than 15 wt. %, more than 20 wt. %, more than 25 wt. %, more than 30 wt. %, or more than 35 wt. % polyester. Suitable commercially-available polyesters may include Eastek 1200 (Eastman), Eastek 1400 (Eastman), Vylonol^® MD-100 (Toyobo), Vylonol^® MD-1480 (Toyobo), Vylonol^® MD-1335 (Toyobo), and Vylonol^® MD-1930 (Toyobo).

[0025] In some embodiments, a pretreatment composition according to embodiments provided herein may comprise an acrylic latex. An acrylic latex may be included in addition to, or in lieu of, the polyester latex described above. The acrylic latex may include a self-crosslinking acrylic polymer or a non-self-crosslinking acrylic polymer. A self-crosslinking acrylic polymer may reduce the solubility and improve the adhesion of the pretreatment coating on a pretreated fabric ensuring further improvement in washability. In some embodiments, a pretreatment composition provided herein may comprise 1 to 30 wt. %, 1 to 20 wt. %, 5 to 15 wt. %, 8 to 12 wt.% or 10 wt.% acrylic polymer. In some embodiments, a pretreatment composition may comprise less than 40 wt. %, less than 35 wt. %, less than 30 wt. %, less than 25 wt. %, less than 20 wt. %, less than 15 wt. %, less than 10 wt. %, or less than 5 wt. % acrylic polymer. In some embodiments, a pretreatment composition may include more than 1 wt. %, more than 5 wt. %, more than 10 wt. %, more than 15 wt. %, more than 20 wt. %, more than 25 wt. %, more than 30 wt. %, or more than 35 wt. % acrylic polymer. Acrylic polymers used in pretreatment compositions disclosed herein may be produced by chain polymerization using one or more of alkyl (cyclo)alkyl (meth)acrylate, (meth)acrylic acid, hydroxyalkyl (meth)acrylates, glycidyl group-containing addition polymerizable monomer, n-methylol(meth)acrylamide, and/or monovinyl aromatic compounds. For example, commercially-available acrylic polymers include Acrygen 61192 (OMNOVA Solutions) and Mowinyl 6760.

[0026] Pretreatment compositions including too much acrylic latex may cause poor color density in a printed image. Pretreatment compositions including too little acrylic latex may not reduce the solubility to the necessary extent to improve the washability of the printed image. In some embodiments, a pretreatment composition provided herein may comprise 1 to 40 wt. %, 5 to 30 wt. %, or 8 to 20 wt. % acrylic latex. In some embodiments, a pretreatment composition may comprise less than 40 wt. %, less than 35 wt. %, less than 30 wt. %, less than 25 wt. %, less than 20 wt. %, less than 15 wt. %, less than 10 wt. %, less than 8 wt. %, or less than 5 wt. % acrylic latex. In some embodiments, a pretreatment composition may include more than 1 wt. %, more than 5 wt. %, more than 8 wt. %, more than 10 wt. %, more than 15 wt. %, more than 20 wt. %, more than 25 wt. %, more than 30 wt. %, or more than 35 wt. % acrylic latex.

[0027] Pretreatment compositions described herein may include more than one type of latex. For example, a pretreatment composition may include both polyester latex and acrylic latex. In some embodiments, the total amount of latex in a pretreatment composition may be 2 to 80 wt. %, 10 to 60 wt. %, 10 to 40 wt. %, 15 to 35 wt.%, 20 to 30 wt.%, 25 to 30 wt.%, or 26.6 wt.%. In some embodiments, the total amount of latex in a pretreatment composition may be less than 80 wt.

%, less than 70 wt. %, less than 60 wt. %, less than 50 wt. %, less than 40 wt. %, less than 30 wt. %, less than 25 wt. %, less than 18 wt. %, or less than 10 wt. %. In some embodiments, the total amount of latex in a pretreatment composition may be more than 2 wt. %, more than 10 wt. %, more than 18 wt. %, more than 20 wt.%, more than 25 wt. %, more than 30 wt. %, more than 40 wt. %, more than 50 wt. %, more than 60 wt. %, or more than 70 wt. %.

[0028] In some embodiments, a pretreatment composition may include a coalescing agent composition. A coalescing agent can help a pretreatment composition form a more uniform coating. In some embodiments, a coalescing agent can help reduce the minimum film formation temperature of the latex polymer(s), allowing the pretreatment coating to dry faster at room temperature. Reducing the minimum film formation temperature can create a more uniform saturation level of the dye, as well as improved crock and colorfastness. A lower minimum film formation temperature can also increase the range of temperatures that the pretreatment composition may be applied to a natural fiber fabric without adversely affecting the performance characteristics of the coated natural fiber fabric. Examples of suitable coalescing agents include, but are not limited to, an aliphatic composition, a cycloaliphatic composition, an ether composition, a glycol composition, an alcohol composition, an ester composition, a carbonate composition, a lactam composition, or a ketone composition.

[0029] In some embodiments, the type of coalescing agent composition may be dependent upon the type of latex used. The coalescing agent of a pretreatment composition according to embodiments provided herein may include ethylene glycol butyl ether. Ethylene glycol butyl ether can lower the minimum film formation temperature (MFFT) of the latex(es). Ethylene glycol butyl ether also has a relatively high evaporation rate, which help achieve the final film properties of the polymeric pretreatment composition on the natural fiber fabric in a shorter period of time. Pretreatment compositions comprising too little coalescing agent may not sufficiently lower the MFFT. Pretreatment compositions comprising too much of a coalescing agent composition may alter the ratio of other components in the composition and the properties of the composition. In some embodiments, a pretreatment composition may include from 0.1 to 10 wt. %, from 0.3 to 8 wt. %, or from 0.5 to 5 wt. % coalescing agent. In some embodiments, a pretreatment composition may include less than 10 wt. %, less than 8 wt. %, less than 5 wt. %, less than 3 wt. %, or less than 1 wt. % coalescing agent. In some embodiments, a pretreatment composition may include more than 0.1 wt. %, more than 0.3 wt. %, more than 0.5 wt. %, more than 1 wt. %, more than 3 wt. %, or more than 5 wt. % coalescing agent.

[0030] In some embodiments, a pretreatment composition may include a surfactant composition. Surfactants in pretreatment compositions provided herein can help increase the setting of the pretreatment composition on various fabrics (e.g., synthetic, natural). Specifically, a surfactant can improve the wetting of the pretreatment composition onto the fabric. A surfactant can also improve the hand, or feel, of the fabric by reducing the thickness of the pretreatment coating on the fabric. Suitable surfactants include, but are not limited to, anionic, cationic, nonionic, and/or amphoteric surfactants. Specific examples of suitable surfactants include BYK^®-348 (BYK), Surfynol^® 104 (Evonik Industries), Surfynol^® 504 (Evonik Industries), and Dynol™ 360 (Evonik Industries). Too much surfactant composition in a pretreatment composition may not provide a sufficient polymer coating on the fabric. Too little surfactant and the pretreatment composition may not sufficiently spread to create a thin layer on the fabric and/or may not provide desirable hand of the fabric. In some embodiments, a pretreatment composition may include from 0.01 to 5 wt %, from 0.05 to 4 wt. %, from 0.1 to 3 wt. %, 0.1-2 wt.%, 0.1-1 wt.%, or 0.5 wt.% surfactant composition. In some embodiments, a pretreatment composition may include less than 5 wt. %, less than 4 wt. %, less than 3 wt. %, less than 2 wt. %, less than 1 wt. %, less than 0.5 wt. %, less than 0.1 wt. %, or less than 0.05 wt. % surfactant composition. In some embodiments, a pretreatment composition may include more than 0.01 wt. %, more than 0.05 wt. %, more than 0.1 wt. %, more than 0.5 wt.%, more than 1 wt. %, or more than 3 wt. % surfactant composition.

[0031] Pretreatment compositions according to embodiments described herein may also include an ultraviolet (UV) stabilizer composition. A UV stabilizer composition in the pretreatment composition may help increase the weatherfastness of the printed inks on the pretreated fabric. Suitable UV stabilizer compositions include, but are not limited to, sulfonated benzophenones, benzotriazoles, salicylates, cinnamates, triazoles, and triazines. Specific examples of commercially-available UV stabilizers that may be suitable for pretreatment compositions provided herein may include Tinuvin^® 400 (BASF), Tinuvin® 477DW, or Chiguard^® 5400 (Chitec). Both Tinuvin^® 400 (BASF) and Chiguard^® 5400 (Chitec) are hydroxyphenyl triazines. Pretreatment compositions including too little UV stabilizer composition may not provide enough protection against weather damage. Pretreatment compositions including too much UV stabilizer composition may compromise the beneficial effects of other components in the pretreatment composition. In some embodiments, a pretreatment composition may include from 0.01-1 wt.%, 0.1 to 1 wt. %, 0.25 wt.%, 0.1-0.5 wt.%, 0.3 to 8 wt. %, 0.5 to 5 wt. % UV stabilizer composition. In some embodiments, a pretreatment composition may include less than 10 wt. %, less than 8 wt. %, less than 5 wt. %, less than 3 wt. %, less than 1 wt. %, less than 0.5 wt.%, less than 0.3 wt.%, or less than 0.25 wt.% UV stabilizer composition. In some embodiments, a pretreatment composition may include more than 0.01 wt.%, more than 0.05, more than 0.1 wt. %, more than 0.2 wt%, more than 0.25 wt.% more than 0.3 wt. %, more than 0.5 wt. %, more than 1 wt. %, more than 3 wt. %, more than 5 wt. %, or more than 8 wt. % UV stabilizer composition.

[0032] Pretreatment compositions provided herein may also include an antioxidant composition. Like UV absorbers, described above, antioxidants may help increase the weatherfastness of the printed inks on the pretreated fabric. Suitable antioxidants include, but are not limited to, hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromanes, alkoxyanilines, and heterocyclic compounds. Specific examples of antioxidants that may be suitable for pretreatment compositions provided herein may include Chiguard^® 101 WB (Chitec) or Tinuvin^® 123 DW (BASF). In some embodiments, a pretreatment composition may include from 0.01-1 wt.%, 0.1 to 1 wt. %, 0.25 wt.%, 0.1-0.5 wt.%, 0.3 to 8 wt. %, 0.5 to 5 wt. % antioxidant. In some embodiments, a pretreatment composition may include less than 10 wt. %, less than 8 wt. %, less than 5 wt. %, less than 3 wt. %, less than 1 wt. %, less than 0.5 wt.%, less than 0.3 wt.%, or less than 0.25 wt.% antioxidant. In some embodiments, a pretreatment composition may include more than 0.01 wt.%, more than 0.05, more than 0.1 wt. %, more than 0.2 wt%, more than 0.25 wt.% more than 0.3 wt. %, more than 0.5 wt. %, more than 1 wt. %, more than 3 wt. %, more than 5 wt. %, or more than 8 wt. % antioxidant.

[0033] Pretreatment compositions provided herein may also include at least one humectant. Humectants can help ensure that the pretreatment composition does not prematurely dry.

Suitable types of humectants that can be used are alcohols, glycols, polyols, glycol ethers, ketones, esters, carbonates, lactams and/or lactones. More specifically, suitable humectants include, but are not limited to, glycerine and dipropylene glycol. In some embodiments, a pretreatment composition may include 10-40 wt.%, 15-35 wt.%, 20-30 wt.%, or 25 wt.% humectant(s). In some embodiments, a pretreatment composition may include less than 50 wt%, less than 45 wt.%, less than 40 wt.%, less than 35 wt.%, less than 30 wt.%, less than 27 wt.%, less than 25 wt.%, less than 20 wt.%, or less than 15 wt.% humectant(s). In some embodiments, a pretreatment composition may include more than 5 wt. %, more than 10 wt. %, more than 15 wt. %, more than 20 wt. %, more than 23 wt. %, more than 25 wt. %, more than 30 wt. %, or more than 35 wt. % humectant.

[0034] Pretreatment compositions provided herein may also include at least one pH buffer. Suitable classes of compounds are the following: amines, organic and inorganic buffers.

Specific examples of amines include but are not limited to alkylamines, ammonia (in equilibrium with ammonium hydroxide), ethanolamine derivatives, pyridine derivatives, and/or amino acids. Specific examples of organic and inorganic buffers include, but are not limited to, Trizma ((tris)hydroxymethylaminomethane), MOPS (4-morpholinopro-panesulfonic acid), MES (4-morpholinoethanesulfonic acid), sodium acetate, sodium bicarbonate, sodium dihydrogen phosphate, phosphonates and organic phosphates. In some embodiments, the pH of the pretreatment composition is between about 6 and 10. Suitable pH buffers include, but are not limited to, triethanolamine. In some embodiments, a pretreatment composition may include from 0.1 to 2 wt. %, from 0.1 to 1 wt. %, from 0.3 to 0.7 wt. %, or 0.5 wt.% pH buffer(s). In some embodiments, a pretreatment composition may include less than 5 wt. %, less than 3 wt.

%, less than 2 wt. %, less than 1 wt. %, less than 0.75 wt.%, less than 0.5 wt.%, or less than .25 wt. % pH buffer(s). In some embodiments, a pretreatment composition may include more than 0.1 wt. %, more than 0.3 wt. %, more than 0.4 wt.%, more than 0.5 wt. %, more than 0.75 wt. %, more than 1 wt. %, more than 2 wt. %, or more than 3 wt. % pH buffer(s).

[0035] Pretreatment compositions provided herein may also include at least one biocide. Biocides can help prevent the formation of bacteria and/or fungus (e.g., mold) in the pretreatment composition. Suitable types of biocides include, but are not limited to, 1,2- Benzisothiazolin-3-one (BIT), methylchloroisothizolinone (CMIT), methylisothiazolinone (MIT), 2-Bromo-2-nitro-propane-l,3 diol (Bronopol), Formaldehyde releasing biocides (FA-R), and/or dodecylguanidine hydrochloride (DGH). Suitable biocides include, but are not limited to, Proxel GXL. In some embodiments, a pretreatment composition may include from 0.01 to 1 wt. %, from 0.05 to 0.5 wt. %, from 0.1 to 0.2 wt. %, or 0.15 wt.% biocide(s). In some embodiments, a pretreatment composition may include less than 2 wt. %, less than 1 wt. %, less than 0.75 wt. %, less than 0.5 wt. %, less than 0.25 wt.%, less than 0.2 wt.%, or less than .15 wt. % biocide(s). In some embodiments, a pretreatment composition may include more than 0.01 wt. %, more than 0.05 wt. %, more than 0.075 wt.%, more than 0.1 wt. %, more than 0.15 wt. %, more than 0.2 wt. %, or more than 0.5 wt. % biocide(s). [0036] In some embodiments, pretreatment compositions described herein include a solvent. Suitable solvents may include glycol ether, diols, esters, ethanol and/or water. For example, a pretreatment composition may include from 10 to 80 wt. % solvent, from 20 to 70 wt. % solvent, from 30-60 wt.%, from 40-50 wt.%, from 45-50 wt.%, 47 wt. % solvent. In some embodiments, a pretreatment composition may include less than 80 wt. %, less than 75 wt. %, less than 70 wt. %, less than 60 wt. %, less than 50 wt. %, less than 45 wt.%, less than 40 wt. %, or less than 30 wt. % solvent. In some embodiments, a pretreatment composition may include more than 20 wt. %, more than 30 wt. %, more than 40 wt. %, more than 45 wt.%, more than 50 wt. %, more than 60 wt. %, more than 70 wt. %, or more than 75 wt. % solvent.

[0037] In some embodiments, after pretreatment and drying of the pretreatment composition, the pretreatment coating may comprise 20 to 90 wt. % latex polymer, 2 to 8 wt. % coalescing agent composition, 0.4 to 7 wt. % surfactant composition, 1 to 8 wt. % ultraviolet (UV) stabilizer composition, 1 to 8 wt. % antioxidant composition, 20 to 90 wt. % humectant(s), 0 01-1 wt.% pH buffer(s), and/or 001-1 wt.% biocide(s).

PREPARING PRETREATMENT COMPOSITIONS

[0038] Provided below are methods of preparing pretreatment compositions.

[0039] Each of the components are measured/weighed in a suitable container (e.g., neoprene beaker) using a microbalance. The solvent and humectant(s) can be added first, and then the latex with the lowest pH. The components can be mixed together using a suitable mixing device, such as a magnetic stirrer or a mechanical stirrer. Once the solvent and latex are mixed, the pH of the mixture is adjusted using a basic solution until the pH of the mixture reaches a value close to the pH of the next latex to be added. The next latex is added to the solution while the mixture is being stirred.

[0040] The coalescing agent composition can be diluted and added to the solution slowly. The rest of the components may be added to the solution and mixed in any order.

METHODS OF PRETREATING NATURAL FIBER FABRIC

[0041] Provided below are methods of pretreating fabrics according to some embodiments provided herein. In some embodiments, methods may be used to pretreat natural fiber fabrics. Methods may also be used to treat synthetic fabrics. In some embodiments, methods may be used to treat fabrics that have both natural and synthetic fibers.

[0042] Figures 1 A-1C provide various phases of a method of pretreating fabric. [0043] Figure 1A includes fabric 102 and pretreatment composition 104. Fabric 102 may comprise a natural fiber fabrics including, but not limited to, wool, hemp, jute, cotton, silk, linen, leather, hemp, or bamboo. In some embodiments, fabric 102 may comprise a synthetic fiber fabric including, but not limited to, nylon, Kevlar, spandex, polyester, polyvinyl chloride, or rayon. In some embodiments, fabric 102 may comprise a combination of natural fiber fabric and synthetic fiber fabric. In some embodiments, methods may use pretreatment compositions discussed above to treat fabrics.

[0044] Pretreatment composition 104 is shown in droplet form in Figure 1A. Specifically, pretreatment composition 104 has been applied to fabric 102, but has not yet formed a dry coating. Pretreatment composition 104 may be applied to fabric 102 using various methods including, but not limited to, ink-jetting, spraying, dip-coating, and/or roll-to-roll processes. For example, fabric 102 (such as a T-shirt) may be pretreated by using a spraying process.

[0045] If too much pretreatment composition is applied to the fabric, it may take away from the benefits of the natural fiber fabric (e.g., sustainability, durability, biodegradability, etc.). If too little pretreatment composition is applied to the fabric, the pretreated product won’t lend itself to a high-quality printed image (particularly with dye sublimation ink) The size of the fabric area to be printed on is measure and the amount of pretreatment composition is calculated based on the desired amount of pretreatment composition per square inch of fabric.

[0046] In some embodiments, 0.001 to 1 grams of pretreatment composition per square inch (g/in²) of fabric surface area applied. In some embodiments, 0.01 to 0.8 or 0.05 to 0.5 g/in² pretreatment composition is applied. In some embodiments, less than 1 g/in², less than 0.8 g/in², less than 0.5 g/in², less than 0.3 g/in², less than 0.2 g/in², less than 0.1 g/in², less than 0.05 g/in², or less than 0.01 g/in² pretreatment composition is applied. In some embodiments, more than 0.001 g/in², more than 0.01 g/in², more than 0.05 g/in², more than 0.1 g/in², more than 0.2 g/in², more than 0.3 g/in², more than 0.5 g/in², or more than 0.8 g/in² pretreatment composition is applied.

[0047] Figure IB shows heat press or calender 106 being applied to pretreatment composition 104 on fabric 102. In some embodiments, the heat press or calender can apply uniform pressure during the pretreatment application for improved color and washability. In some embodiments, pretreatment composition 104 may air dry without the application of a heat press. Heat press 106 may apply heat from 40 to 250 °C, from 50 to 150 °C, or from 60 to 100 °C. In some embodiments, heat press 106 may apply heat that is less than 250 °C, less than 200 °C, less than 150 °C, less than 120 °C, less than 100 °C, less than 90 °C, less than 80 °C, less than 70 °C, less than 60 °C, or less than 50 °C. In some embodiments, heat press may apply heat that is more than 40 °C, more than 50 °C, more than 60 °C, more than 70 °C, more than 80 °C, more than 90 °C, more than 100 °C, more than 120 °C, more than 150 °C, or more than 200 °C.

[0048] In some embodiments, heat press 106 may be applied to the pretreated fabric for 1 to 120 seconds, for 5 to 90 seconds, or for 10 to 60 seconds. In some embodiments, heat press 106 may be applied for less than 120 seconds, less than 90 seconds, less than 60 seconds, less than 50 seconds, less than 40 seconds, less than 30 seconds, less than 20 seconds, or less than 10 seconds. In some embodiments, heat press 106 may be applied for more than 1 second, more than 10 seconds, more than 20 seconds, more than 30 seconds, more than 40 seconds, more than 50 seconds, more than 60 seconds, or more than 90 seconds.

[0049] In some embodiments, instead of heat press 106, the pretreated fabric may be placed in an oven to dry. In some embodiments, an oven may heat the pretreated fabric from 40 to 250 °C, from 50 to 150 °C, or from 60 to 100 °C. In some embodiments, an oven may heat the pretreated fabric less than 250 °C, less than 200 °C, less than 150 °C, less than 120 °C, less than 100 °C, less than 90 °C, less than 80 °C, less than 70 °C, less than 60 °C, or less than 50 °C. In some embodiments, an oven may heat the pretreated fabric more than 40 °C, more than 50 °C, more than 60 °C, more than 70 °C, more than 80 °C, more than 90 °C, more than 100 °C, more than 120 °C, more than 150 °C, or more than 200 °C.

[0050] In some embodiments, an oven may heat the pretreated fabric from 1 to 60, from 5 to 50, or from 10 to 40 minutes. In some embodiments, the pretreated fabric may be heated in an oven for less than 60 minutes, less than 50 minutes, less than 40 minutes, less than 30 minutes, less than 20 minutes, less than 10 minutes, or less than 5 minutes. In some embodiments, the pretreated fabric may be heated in an oven for more than 1 minute, more than 5 minutes, more than 10 minutes, more than 20 minutes, more than 30 minutes, more than 40 minutes, or more than 50 minutes.

[0051] Figure 1C shows a dry pretreatment coating 108 on fabric 102. In some embodiments, after pretreatment and drying of the pretreatment composition, the pretreatment coating may comprise 20 to 90 wt. % latex polymer, 2 to 8 wt. % coalescing agent composition, 0.4 to 7 wt. % surfactant composition, 1 to 8 wt. % ultraviolet (UV) stabilizer composition, 1 to 8 wt. % antioxidant composition, 20 to 90 wt. % humectant(s), 0.01-1 wt.% pH buffer(s), and/or 0.01-1 wt.% biocide(s). Once dry, colorants including dye sublimation ink may be printed onto pretreated fabric 110.

[0052] Figure ID shows a pretreated fabric product 114 that includes a printed image. Product 114 includes fabric 102 and colorant from the printed image absorbed into the pretreatment coating (i.e., item 112). In some embodiments, the printed image may be applied using dye sublimation ink. In some embodiments, the printed image may be printed onto the pretreated natural fiber fabric product. In some embodiments, the printed image may be printed onto a film and then transferred onto the pretreated natural fiber fabric product. For example, an image may be printed onto a standard transfer sheet using a drop-on-demand printer, which can then be transferred onto the dried pretreated natural fiber fabric using a heat press, for example. In some embodiments, an image can be transferred using heat press at about 300-500°F, about 350- 450°F, about 350-400°F, about 375-395°F, about 380-390°F, or about 385°F for about 10-200 seconds, about 30-150 seconds, about 35-125 seconds, about 75-125 seconds, about 80-100 seconds, about 85-95 seconds, or about 90 seconds.

PRETREATED FABRICS

[0053] The pretreatment compositions described above may be used to prepare various articles or products for printing. For example, a pretreatment composition may be applied to an article of clothing (e.g., T-shirt, sweater, dress), bedding, window treatment (e.g., curtains), and other types of fabrics that a consumer may wish to print onto.

[0054] As described above, a coating provided by a pretreatment composition can adhere to the fabric and allow the colorant (e.g., dye sublimation ink) to absorb and stay onto the pretreated fabric. Various properties may be used to characterize the pretreated fabric such as colorfastness to laundering, hand, crock, weatherfastness, and color uniformity. These properties, in addition to other properties that may be used to characterize the pretreatment composition, are described in more detail below.

TESTING METHODS

[0055] Various chemical and physical properties may be used to characterize the sufficiency of a pretreated natural fiber fabric. In some embodiments, the pretreated natural fiber fabric may be printed with an ink or dye (e.g., dye sublimation ink) prior to characterization. Discussed below are properties used for characterizing fabrics and the testing methods used for each. [0056] Pretreatment Application: The pretreatment application of the various examples can be applied using Method 1, Method 2, and/or Method 3, described below.

[0057] Method 1: 0.11 g/in² of pretreatment was added to each cotton substrate. The pretreatment can be applied using either a handheld sprayer or an automatic pretreatment machine. A piece of parchment paper can placed on top of the treated fabric followed by a piece of polyester fabric. The substrate can then be pressed using a heat press at 385°F for 15 seconds.

[0058] Method 2: The cotton substrate can be dip coated at 75% wet pickup (+/- 5%) and then dried using an oven at 100°C at 5 meters/min.

[0059] Method 3: The amount of pretreatment added to each cotton substrate can be 0.1 g/in². The pretreatment can be applied using a handheld sprayer onto a cotton t-shirt. The cotton t- shirt can be setup with a section of aluminum of the same size as the printed image inside the shirt and a plastic cut out of the print image outside to ensure that no pretreatment is applied outside the area where the print image will be transferred. Once the pretreatment was applied, the shirt can be slipped onto the bottom half of the heat press and the same aluminum substrate can be placed inside. This can ensure that the area covered with pretreatment will be the only area pressed. The shirt can be pressed for 325 F for 10 seconds. This can reduce the level of oxidation that the cotton undergoes and thus can reduce the yellowing of the fabric. In some embodiments, the pretreatment application of the pretreatment composition can be applied in an amount of 0.01-5 g/in², 0.5 - 1.5 g/in², or 0.1 g/in² and pressed at 200-400°F, 250-400°F, 300- 350°F, or 325°F for 1-60 seconds, 1-30 seconds, 1-20 seconds, or 10 seconds.

[0060] Colorfastness to Laundering: A printed fabric’s colorfastness determines its ability to retain its depth and shade throughout the life of the product, and in particular, throughout laundering of the product. Ideally, a printed image on a fabric can withstand the lifetime of the product without significantly compromising the quality (e.g., depth, shade) of the printed image. The colorfastness of a printed natural fiber fabric may be tested using Method 1, Method 2, and/or Method 3, described below.

[0061] Method 1: Colorfastness to laundering may be tested by placing a printed fabric sample measuring 4.5 inches by 5.5 inches in a consumer washing machine and washed for 15 minutes with room temperature water and 0.5 g of Tide^® detergent per 0.5 L of water. A standard wash cycle was used (cotton/medium) with a standard spin cycle. (The sample was washed with 9-14 other printed fabric samples). The printed fabric sample was rinsed with 0.5 L water per sample for six minutes. The sample(s) was then spin-dried for five minutes and placed in an oven at 60°C until dry.

[0062] The washed and dried samples were analyzed using a Gretag spectrophotometer for optical density, L, a*, and b* values. The ink used was drawn down using a 2 Krod at speed 10 on a K Control Coater (RKPrint) onto Wing Wing Hybrid transfer paper. The image was transferred at 392°F for 40 seconds.

[0063] Method 2: Colorfastness to laundering may be tested by placing a printed fabric sample measuring 9 inches by 5 inches was placed in a consumer washing machine and washed for 15 minutes with room temperature water and 0.5 g of Woolite^® Delicate detergent per 0.5 L of water. A standard wash cycle was used (cotton/medium) with a standard spin cycle. (The sample was washed with 4-7 other printed fabric samples). The printed fabric sample was rinsed with 0.5 L water per sample for six minutes. The sample(s) was then spin-dried for five minutes and hung to air dry.

[0064] The washed and dried samples were analyzed using a Gretag spectrophotometer for optical density, L, a*, and b* values. The image was printed using a standard DOD inkjet printer (Mutoh 90 lx) using standard dye sublimation inks onto Wing Wing Hybrid transfer paper. The image was transferred at 385°F for 35 seconds.

[0065] Method 3: Colorfastness to laundering may be tested by placing a printed fabric sample measuring 9 inches by 5 inches was placed in a consumer washing machine and washed for 15 minutes with room temperature water and 0.5 g of Woolite^® Delicate detergent per 0.5 L of water. A standard wash cycle was used (cotton/medium) with a standard spin cycle. (The sample was washed with 4-7 other printed fabric samples). The printed fabric sample was rinsed with 0.5 L water per sample for six minutes. The sample(s) was then spin-dried for five minutes and hung to air dry.

[0066] The washed and dried samples were analyzed using a Gretag spectrophotometer for optical density, L, a*, and b* values. The image was printed using a standard DOD inkjet printer (Mutoh 90 lx) using standard dye sublimation inks onto Jacquard pretreated cotton. The image was heat pressed at 385°F for 35 seconds.

[0067] Particle Size and Polydispersity Index: The particle size and polydispersity of a pretreatment compostion was measured using ASTM E2490 (referring to the American Society for Testing and Materials standards) Standard Guide for Measurement of Particle Size Distribution of Nanomaterials in Suspension by Photon Correlation Spectroscopy (PCS). [0068] Zeta Potential: Zeta potential is the electrokinetic potential of a colloidal dispersion. The zeta potential of a latex dispersion (e.g., polyester latex, acrylic latex) and/or pretreatment composition may be measured using ASTM E2865 Standard Guide for Measurement of Electrophoretic Mobility and Zeta Potential of Nanosized Biological Materials.

[0069] Fabric Hand: The hand of a fabric measures the “feel” of the fabric against skin. The hand of a fabric can change with the printing of an image on the fabric. However, it is generally not desirable for the printed image to significantly impact the hand of the fabric, particularly for wearable products. The hand of a fabric was measured using standard AATCC EP 5 (referring to the American Association of Fabric Chemists and Colorists standards) Guidelines to the Subjective Evaluation of Fabric Hand. This standard uses a scale of 1-5 to characterize the hand of the fabric, where 1 is worst and 5 is best.

[0070] Crock Testing: Crock refers to the transfer of ink/dye from the fabric to another. For example, if the ink/dye of a printed image does not sufficiently adhere to the fabric, it may transfer to another substrate that it contacts. Ideally, the ink/dye of a printed image sufficiently adheres to the fabric to minimize any tendency for the ink/dye to crock. Crock may be tested using standard AATCC 8 Colorfastness to Crock: Crockmeter Method and a scale of 1 to 5, 5 being the best, and 1 being the worst. AATCC 8 includes testing methods for wet crock and dry crock as well.

[0071] Weatherfastness: Weatherfastness may refer to the ability of a printed image on a fabric to withstand extended periods of weathering. For example, weatherfastness may refer to a printed image’s ability to resist fading when exposed to ultraviolet light. A high quality printed image will have a higher tolerance to weather and will be able to resist fading due to ultraviolet light exposure. Weatherfastness may be tested using ASTM G154 Standard Practice for Operating Fluorescent Light Apparatus for UV Exposure of Nonmetallic Materials.

[0072] Color Measurement: The color uniformity of a printed image may be tested. In many cases, a higher quality printed image will have a higher uniformity. The color may be tested using ASTM D2244-16 Standard Practice for Calculation of Color Tolerances and Color Differences from Instrumentally Measured Color Coordinates.

EXAMPLES

[0073] Provided below are several examples that highlight different characteristics of specific components of a pretreatment composition and/or the pretreatment compositions provided herein. Testing Different Latexes for Pretreatment Composition

[0074] Table 1 and 2 shows pretreatment compositions with different types of latexes. Specifically, pretreatment compositions were prepared and tested using seven different latex polymers: Acrygen 61192 (50%) (Omnova Solutions), Eastek 1200 (30%) (Eastman), Vylonel MD-1100 (30%) (Toyobo), Eastek 1400 (30%) (Eastman), Vylonel MD-1480 (25%) (Toyobo), Vylonel MD-1335 (30%) (Toyobo), and Vylonel MD-1930 (31%) (Toyobo).

[0075] Table 1, below, shows the properties of each latex polymer used in this trial.

Table 1. Properties of each of latex polymer tested.

[0076] Table 2, below, provides the type and amount of latex in each of the seven different samples, in addition to a control.

Table 2. Amount of latex for each sample. [0077] Each latex composition was applied to a 100% cotton natural fiber fabric by spraying using a consumer spray bottle with spray trigger such that 0.11 g/in² composition was applied ( i.e Method of Pretreatment 1). An image was printed on the treated natural fiber fabric by printing the image using dye sublimation ink onto a standard transfer sheet with a drop-on- demand printer and transferring the image onto the dried natural fiber fabric using a heat press at 370 °F for 60 seconds. Table 3, below, provides the charge density, particle size, polydispersity index, zeta potential, fabric hand, crock wet, and crock dry of each sample, tested using the methods provided above.

Table 3. Test results for each of the seven samples (in addition to the control) treated with a different latex and printed with dye sublimation ink.

[0078] The particle size can indicate a composition’s ability to create a smoother and more uniform film. In particular, a composition having a smaller particle size indicates better film forming properties than a larger particle size. As shown in Table 3, the particle size may vary from about 15 to about 100 nm. In some embodiments, the particle size may be from about 20 to about 80 nm or from about 25 to about 60 nm. In some embodiments, depending on the latex used, the particle size may be less than 100 nm, less than 90 nm, less than 80 nm, less than 70 nm, less than 60 nm, less than 50 nm, less than 40 nm, less than 30 nm, less than 25 nm, or less than 20 nm. In some embodiments, depending on the latex, the particle size may be more than 15 nm, more than 20 nm, more than 25 nm, more than 30 nm, more than 40 nm, more than 50 nm, more than 60 nm, more than 70 nm, more than 80 nm, or more than 90 nm.

[0079] The polydispersity index may also vary depending on the type of latex used. In some embodiments, depending on the latex, the polydispersity index used may be from about 0.1 to about 0.3. In some embodiments, the polydispersity index may be from about 0.15 to 0.25. Depending on the latex used, the polydispersity index may be less than 0.3, less than 0.25, less than 0.2, or less than 0.15. In some embodiments, the polydispersity index may be more than 0.1, more than 0.15, more than 0.2, or more than 0.25.

[0080] As shown in Table 3, pretreating and printing a natural fiber fabric can compromise the fabric hand to an extent. Specifically, the control (an untreated sample) was tested at having the “best” hand, with a value of 5. The samples pretreated with a latex composition each exhibited a hand value from 1 to 3.5. In some samples, the hand was less than 3.5, less than 3, less than 2.5, less than 2, or less than 1.5. In some samples, the hand value was more than 1, more than 1.5, more than 2, more than 2.5, or more than 3.

[0081] Pretreating and printing a natural fiber fabric can also compromise the crock wet and the crock dry results. In particular, the control sample tested a crock wet value of 3.5. However, the crock wet values of the samples pretreated with the various latex compositions tested a crock wet value of 2 to 3.5. For some types of latex, the crock wet value was less than 3.5, less than 3, or less than 2.5. For some types of latex, the crock wet value was more than 2, more than 2.5, or more than 3. Additionally, the crock dry value for the control sample was 5. However, the crock dry measurements for the pretreated samples were from 3 to 5. Some samples had a crock dry value of less than 5, less than 4.5, less than 4, or less than 3.5. Some samples had a crock dry value of more than 3, more than 3.5, more than 4, or more than 4.5.

[0082] Table 4, provided below, shows the testing results of color density and colorfastness for each sample (i.e., the same samples provided in Table 2). Color was tested using ASTM D2244 -16, and colorfastness was tested using Method 1 .

Table 4. Color and colorfastness results for each sample.

[0083] As described above, the color measurement of a printed image is the measurement of the color density, or amount of dye transfer. A smaller number (L value) indicates a darker shade and more dye transfer, whereas a larger L value indicates a lighter shade and less dye transfer.

As shown in Table 4, the color measurements for each color tested — black, yellow, magenta, and cyan, were all lower in the pretreated samples than they were for the non-pretreated control sample. The control sample tested a 59.7 color measurement value for black dye, compared to the color measurement values from about 35 to about 55 for the pretreated samples, depending on the latex. The color measurement of some pretreated samples for black dye was less than 55, less than 50, less than 45, or less than 40. The color measurement of some pretreated samples for black dye was more than 35, more than 40, more than 45, or more than 50. The control sample tested a color measurement of 87.8 for yellow dye. However, the pretreated samples tested a color measurement value for yellow dye of about 80 to about 90.

[0084] The color measurement of the control sample tested a value of 71.3 for magenta dye. The pretreated samples tested color measurement values of about 50 to about 70 for magenta dye. Depending on the latex, the pretreated samples tested a color measurement value of less than 70, less than 65, less than 60, or less than 55 for magenta dye. Depending on the latex, the pretreated samples tested a color measurement value of more than 50, more than 55, more than 60, or more than 65 for magenta dye. For cyan dye, the color measurement of the control sample was 74.9. The pretreated samples tested a color measurement of about 60 to 70 for cyan dye. For some pretreated samples, the color measurement of cyan dye was less than 70 or less than 65. For some pretreated samples, the color measurement of cyan dye was more than 60 or more than 65.

[0085] The colorfastness test results show that the pretreated samples exhibited a smaller color change and thus, better colorfastness results. The results are reported as delta E (DE) values, which is the color difference between the original L a* b* values measured before laundering and after the five washes. The non-pretreated control sample exhibited a change in color for black dye of 20.9. The pretreated samples tested a black dye DE value of about 10 to about 30. Each of the pretreated samples tested a black dye DE of less than 30, less than 25, less than 20, or less than 15. Each of the pretreated samples tested a black dye DE of greater than 10, greater than 15, greater than 20, or greater than 25.

[0086] The non-pretreated control sample tested a yellow dye DE of 20.7. Pretreated samples tested a yellow dye DE of 15 to 25. Each of the pretreated samples tested a yellow dye DE of less than 25 or less than 20, and more than 15 or more than 20.

[0087] The non-pretreated control sample tested a magenta dye DE of 32.3. In contrast, most of the pretreated samples tested a magenta dye DE of less than 32.3. In particular, the pretreated samples tested a magenta dye DE of 10 to 35. Each of the pretreated samples tested a magenta dye DE of less than 35, less than 30, less than 25, less than 20, or less than 15. Each of the pretreated samples tested a magenta dye DE of more than 10, more than 15, more than 20, more than 25, or more than 30.

[0088] For the cyan dye, the non-pretreated control sample tested a DE value of 16.4. The pretreated samples tested from about 5 to about 30. Each of the pretreated samples tested a cyan dye DE of less than 30, less than 25, less than 20, less than 15, or less than 10. Each of the pretreated samples tested a cyan dye DE of more than 5, more than 10, more than 15, more than 20, or more than 25.

Testing the Effects of Various Light Stabilizers on Weatherfastness

[0089] Provided below is a description of testing that was performed to test different light stabilizers. In particular, the light stabilizers Tinuvin 123 DW HAL (BASF), Tinuvin 400 DW UVA (BASF), Tinuvin 477 DW UVA (BASF), Tinuvin 479 DW UVA (BASF), Tinuvin 5333 DW UVA/HAL (BASF), Chiguard 5400 UVA (Chitec), and Chiguard 101 WB HAL (Chitec) were tested. Table 5 provides the amounts used in each of nine different samples (including the control sample).

Table 5. Samples of different light stabilizers.

[0090] Each composition was applied to a 100% cotton natural fiber fabric by spraying using a consumer spray bottle with spray trigger such that 0.11 g/in² composition was applied (i.e., Method of Pretreatment 1). An image was printed on the treated natural fiber fabric by printing the image using dye sublimation ink onto a standard transfer sheet with a drop-on-demand printer and transferring the image onto the dried natural fiber fabric using a heat press at 370 °F for 60 seconds. Table 6, below, provides the weatherfastness results for each sample, tested using ASTM G154 (described above) And QLAB’s QUV Accelerated Weathering Tester.

Table 6. Weatherfastness results for natural fiber fabric samples pretreated with different types and amounts of light stabilizers, according to Table 5. Note that “S” stands for “Sample.”

[0091] As shown, the color change for cyan dye (as indicated by DE) varied from 7.5 to almost 40. At 25 hours, the color change for cyan dye measured from 7.5 to about 16. At 69 hours, the color change was from about 13 to about 24; at 162 hours, from about 18 to about 27; at 185 hours, from about 19 to about 28; at 210 hours, from about 21 to about 30; at 234 hours, from about 23 to about 30; at 262 hours, from about 24 to about 32; at 291 hours, from about 24 to about 33; at 312 hours, from about 25 to about 34; and at 387 hours, the color change was from about 27 to about 37, depending on the light stabilizer.

[0092] The color change for magenta dye varied from 2 to about 40. At 25 hours, the color change was from 2 to about 6; at 69 hours, from 4 to about 10; at 162 hours, from 8 to about 17; at 185 hours, from about 8 to about 19; at 210 hours, from about 8 to about 20; at 234 hours, from about 10 to about 22; at 262 hours, from about 11 to about 25, at 291 hours, from about 15 to about 29; at 312 hours, from about 12 to about 31; and at 387 hours, the color change was from about 14 to about 40, depending on the light stabilizer.

[0093] The color change for yellow dye varied from about 6 to about 60, depending on the light stabilizer. At 25 hours, the color change was from about 6 to about 11; at 69 hours, from about 8 to about 13; at 162 hours, from about 10 to about 21; at 185 hours, from about 10 to about 24; at 210 hours, from about 11 to about 28; at 234 hours, from about 13 to about 36; at 262 hours, from about 14 to about 42; at 291 hours, from about 15 to about 49; at 312 hours, from about 16 to about 52; and at 387 hours, the color change was from about 21 to about 60, depending on the light stabilizer.

[0094] The color change for black dye varied from about 9 to about 34, depending on the light stabilizer. At 25 hours, the color change was from about 9 to about 13; at 69 hours, from about 14 to about 17; at 162 hours, from about 18 to about 21; at 185 hours, from about 16 to about 22; at 210 hours, from about 16 to about 23; at 234 hours, from about 15 to about 24; at 262 hours, from about 16 to about 25; at 291 hours, from about 14 to about 26; at 312 hours, from about 15 to about 26; and at 387 hours, the color change was from about 13 to about 32, depending on the light stabilizer.

Market Comparison

[0095] Provided below is a description of testing that was performed to test a pretreatment composition disclosed herein and commercially available products that are related to the pretreatment compositions provided herein. In particular, the commercially available products used in this analysis were Forever Sublilight, Hanrun, and Shockline TopCut (and a control sample). Table 7 provides the amounts used of the pretreatment sample.

Table 7. Pretreatment Composition Used in Market Analysis.

[0096] The pretreatment method used for each of the compositions tested in the market analysis was Pretreatment Method 2. Table 8, provided below, shows the testing results of fabric hand, color density, and colorfastness for each sample. Color was tested using ASTM D2244 -16, and colorfastness was tested using Method 2 for samples with images transferred and Method 3 for direct print samples.

Table 8. Color and colorfastness results for each sample.

[0097] As described above, the color measurement of a printed image is the measurement of the color density, or amount of dye transfer. A smaller number (L value) indicates a darker shade and more dye transfer, whereas a larger L value indicates a lighter shade and less dye transfer.

As shown in Table 8, the color measurements for each color tested — black, yellow, magenta, and cyan, were all lower in the pretreated samples than they were for the non-pretreated control sample. In some embodiments, the color measurement of a pretreated sample with a pretreatment composition disclosed herein for black dye was less than 45, less than 40, less than 38, or less than 35. In some embodiments, the color measurement of a pretreated sample with a pretreatment composition disclosed herein for black dye was more than 25, more than 30, more than 32, or more than 35. In some embodiments, the color measurement of a pretreated sample with a pretreatment composition disclosed herein for yellow dye was less than 95, less than 90, less than 85, or less than 83. In some embodiments, the color measurement of a pretreated sample with a pretreatment composition disclosed herein for yellow dye was more than 70, more than 75, more than 80, or more than 82. In some embodiments, the color measurement of a pretreated sample with a pretreatment composition disclosed herein for magenta dye was less than 65, less than 60, less than 55, or less than 52. In some embodiments, the color measurement of a pretreated sample with a pretreatment composition disclosed herein for magenta dye was more than 35, more than 40, more than 45, or more than 50. In some embodiments, the color measurement of a pretreated sample with a pretreatment composition disclosed herein for cyan dye was less than 60, less than 55, less than 50, or less than 46. In some embodiments, the color measurement of a pretreated sample with a pretreatment composition disclosed herein for cyan dye was more than 30, more than 35, more than 40, or more than 44.

[0098] The colorfastness test results show that the pretreated sample exhibited a smaller color change and thus, better colorfastness results. The results are reported as delta E (DE) values, which is the color difference between the original L a* b* values measured before laundering and after the five washes. In some embodiments, a pretreated sample with the pretreatment composition disclosed herein tested a black dye DE of less than 25, less than 20, or less than 15. In some embodiments, a pretreated sample with the pretreatment composition disclosed herein tested a black dye DE of greater than 1, greater than 5, or greater than 10. In some embodiments, a pretreated sample with the pretreatment composition disclosed herein tested a yellow dye DE of less than 45, less than 40, less than 35, or less than 30. In some embodiments, a pretreated sample with the pretreatment composition disclosed herein tested a yellow dye DE of greater than 15, greater than 20, or greater than 25. In some embodiments, a pretreated sample with the pretreatment composition disclosed herein tested a magenta dye DE of less than 30, less than 25, or less than 20. In some embodiments, a pretreated sample with the pretreatment composition disclosed herein tested a magenta dye DE of greater than 5, greater than 10, or greater than 15. In some embodiments, a pretreated sample with the pretreatment composition disclosed herein tested a cyan dye DE of less than 25, less than 20, or less than 15. In some embodiments, a pretreated sample with the pretreatment composition disclosed herein tested a cyan dye DE of greater than 1, greater than 5, or greater than 10.

[0099] The preceding description sets forth exemplary methods, parameters and the like. It should be recognized, however, that such description is not intended as a limitation on the scope of the present disclosure but is instead provided as a description of exemplary embodiments. The illustrative embodiments described above are not meant to be exhaustive or to limit the disclosure to the precise forms disclosed. Many modifications and variations are possible in view of the above teachings. The embodiments were chosen and described to best explain the principles of the disclosed techniques and their practical applications. Others skilled in the art are thereby enabled to best utilize the techniques, and various embodiments with various modifications as are suited to the particular use contemplated.

[0100] Although the disclosure and examples have been thoroughly described with reference to the accompanying figures, it is to be noted that various changes and modifications will become apparent to those skilled in the art. Such changes and modifications are to be understood as being included within the scope of the disclosure and examples as defined by the claims. In the preceding description of the disclosure and embodiments, reference is made to the accompanying drawings, in which are shown, by way of illustration, specific embodiments that can be practiced. It is to be understood that other embodiments and examples can be practiced, and changes can be made without departing from the scope of the present disclosure.

[0101] Although the preceding description uses terms first, second, etc. to describe various elements, these elements should not be limited by the terms. These terms are only used to distinguish one element from another.

[0102] Also, it is also to be understood that the singular forms “a,” “an,” and “the” used in the preceding description are intended to include the plural forms as well unless the context indicates otherwise. It is also to be understood that the term “and/or” as used herein refers to and encompasses any and all possible combinations of one or more of the associated listed items. It is further to be understood that the terms “includes, “including,” “comprises,” and/or “comprising,” when used herein, specify the presence of stated features, integers, steps, operations, elements, components, and/or units but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, units, and/or groups thereof.

[0103] The term “if’ may be construed to mean “when” or “upon” or “in response to determining” or “in response to detecting,” depending on the context.

[0104] Although the disclosure and examples have been fully described with reference to the accompanying figures, it is to be noted that various changes and modifications will become apparent to those skilled in the art. Such changes and modifications are to be understood as being included within the scope of the disclosure and examples as defined by the claims.

Claims

1. A pretreatment composition for a natural fiber fabric comprising:

15 to 35 wt. % one or more latex polymers;

15 to 35 wt. % one or more humectants;

0.1 to 1 wt. % surfactant composition;

0.1 to 1 wt. % ultraviolet (UV) stabilizer composition;

0.1 to 1 wt. % one or more pH buffers;

0.05 to 0.5 wt. % biocide; and 40 to 60 wt. % solvent.

2. The pretreatment composition of claim 1, wherein the one or more latex polymers comprise one or more of a polyester, an acrylic polymer, an aromatic polyamide, a chlorinated polymer, a polyether, a polyurea, a fluorinated polymer, a polyurethane, a styrene, a polyvinyl, a thio/ether polymer, a polyolefin, a polystyrene, a polyacetate, a polyamide, a polyethylene, a polyimide, a polycarbonate, or a polyvinylalcohol.

3. The pretreatment composition of claim 1 or 2, wherein the one or more latex polymers comprise a polyester.

4. The pretreatment composition of claim 3, wherein the polyester has a glass transition temperature from -20 to 100 °C.

5. The pretreatment composition of claim 3 or 4, wherein a latex dispersion of the polyester has a zeta potential from -60 to -20 mV.

6. The pretreatment composition of any of claims 2-5, wherein the one or more latex polymers comprise an acrylic polymer.

7. The pretreatment composition of claim 6, wherein the acrylic polymer is self crosslinking.

8. The pretreatment composition of any of claims 1-7, further comprising a coalescing agent, wherein the coalescing agent composition comprises one or more compounds comprising an aliphatic composition, a cycloaliphatic composition, an ether composition, a glycol composition, an alcohol composition, an ester composition, a carbonate composition, a lactam composition, or a ketone composition.

9. The pretreatment composition of claim 8, wherein the coalescing agent composition comprises ethylene glycol butyl ether.

10. The pretreatment composition of any of claims 1-9, wherein the surfactant composition comprises one or more of an anionic or a nonionic surfactant.

11. The pretreatment composition of any of claims 1-10, wherein the surfactant composition comprises silicone.

12. The pretreatment composition of any of claims 1-11, wherein the UV stabilizer composition comprises one or more of a sulfonated benzophenone, a benzotri azole, a salicylate, a cinnamate, a triazole, or a triazine.

13. The pretreatment composition of any of claims 1-12, wherein the UV stabilizer composition comprises hydroxyphenyl triazine.

14. The pretreatment composition of any of claims 1-13, further comprising an antioxidant composition, wherein the antioxidant composition comprises one or more of a hydroquinone, an alkoxyphenol, a dialkoxyphenol, a phenol, an aniline, an amine, an indane, a chromane, an alkoxyaniline, or a heterocyclic compound.

15. The pretreatment composition of claim 14, wherein the antioxidant composition comprises a hindered amine light stabilizer.

16. The pretreatment composition of any of claims 1-15, wherein the solvent comprises one or more of glycol ether, a diol, an ester, ethanol, or water.

17. The pretreatment composition of any of claims 1-16, wherein the solvent comprises water.

18. A pretreated natural fiber fabric product comprising: natural fiber fabric; and a polymer coating on the natural fiber fabric, the polymer coating comprising:

20 to 90 wt. % one or more latex polymers;

0.4 to 7 wt. % surfactant composition; and 1 to 8 wt. % ultraviolet (UV) stabilizer composition.

19. The pretreated natural fiber fabric product of claim 18, wherein the natural fiber fabric comprises one or more of wool, cotton, silk, linen, leather, hemp, or bamboo.

20. The pretreated natural fiber fabric product of claim 18 or 19, wherein the pretreated natural fiber fabric product comprises a T-shirt.

21. The pretreated natural fiber fabric product of any of claims 18-20, comprising an image printed using dye sublimation ink.

22. The pretreated natural fiber fabric product of any of claims 18-21, wherein the one or more latex polymers comprise one or more of a polyester, an acrylic polymer, an aromatic polyamide, a chlorinated polymer, a polyether, a polyurea, a fluorinated polymer, a polyurethane, a styrene, a polyvinyl, a thio/ether polymer, a polyolefin, a polystyrene, a polyacetate, a polyamide, a polyethylene, a polyimide, a polycarbonate, or a polyvinylalcohol.

23. The pretreated natural fiber fabric product of claim 22, wherein the one or more latex polymers comprise a polyester.

24. The pretreated natural fiber fabric product of claim 23, wherein the polyester has a glass transition temperature from -20 to 100 °C.

25. The pretreated natural fiber fabric product of any of claims 23 or 24, wherein a latex dispersion of the polyester has a zeta potential from -60 to -20 mV.

26. The pretreated natural fiber fabric product of any of claims 18-25, wherein the one or more latex polymers comprise acrylic polymer.

27. The pretreated natural fiber fabric product of claim 26, wherein the acrylic polymer is self-crosslinking.

28. The pretreated natural fiber fabric product of any of claims 18-27, the coating comprising a coalescing agent composition, wherein the coalescing agent composition comprises one or more compounds comprising an aliphatic composition, a cycloaliphatic composition, an ether composition, a glycol composition, an alcohol composition, an ester composition, a carbonate composition, a lactam composition, or a ketone composition.

29. The pretreated natural fiber fabric product of claim 28, wherein the coalescing agent composition comprises ethylene glycol butyl ether.

30. The pretreated natural fiber fabric product of any of claims 18-29, wherein the surfactant composition comprises one or more of an anionic or a nonionic surfactant.

31. The pretreated natural fiber fabric product of any of claims 18-30, wherein the surfactant composition comprises silicone.

32. The pretreated natural fiber fabric product of any of claims 18-31, wherein the UV stabilizer composition comprises one or more of a sulfonated benzophenone, a benzotri azole, a salicylate, a cinnamate, a triazole, or a triazine.

33. The pretreated natural fiber fabric product of any of claims 18-32, wherein the UV stabilizer composition comprises hydroxyphenyl triazine.

34. The pretreated natural fiber fabric product of any of claims 18-33, the coating comprising an antioxidant composition, wherein the antioxidant composition comprises one or more of a hydroquinone, an alkoxyphenol, a dialkoxyphenol, a phenol, an aniline, an amine, an indane, a chromane, an alkoxyaniline, or a heterocyclic compound.

35. The pretreated natural fiber fabric product of claim 34, wherein the antioxidant composition comprises a hindered amine light stabilizer.

36. A pretreated natural fiber fabric product comprising: natural fiber fabric; and a polymer coating on the natural fiber fabric, wherein the pretreated natural fiber fabric product is produced by spraying the natural fiber fabric with 8 to 15 grams of a pretreatment composition per square inch of natural fiber fabric.

37. The pretreated natural fiber fabric product of claim 36, wherein the pretreatment composition comprises:

15 to 35 wt. % one or more latex polymers;

15 to 35 wt. % one or more humectants;

0.1 to 1 wt. % surfactant composition;

0.1 to 1 wt. % ultraviolet (UV) stabilizer composition;

0.1 to 1 wt. % one or more pH buffers;

0.05 to 0.5 wt. % biocide; and 40 to 60 wt. % solvent.

38. The pretreated natural fiber fabric product of claim 36 or 37, comprising an image printed using dye sublimation ink.

39. The pretreated natural fiber fabric product of any of claims 36-38, wherein the natural fiber fabric comprises one or more of wool, cotton, silk, linen, leather, hemp, or bamboo.

40. The pretreated natural fiber fabric product of any of claims 35-39, wherein the pretreated natural fiber fabric product is a T-shirt.

41. The pretreated natural fiber fabric product of any of claims 36-40, wherein the one or more latex polymers comprise one or more of a polyester, an acrylic polymer, an aromatic polyamide, a chlorinated polymer, a polyether, a polyurea, a fluorinated polymer, a polyurethane, a styrene, a polyvinyl, a thio/ether polymer, a polyolefin, a polystyrene, a polyacetate, a polyamide, a polyethylene, a polyimide, a polycarbonate, or a polyvinylalcohol.

42. The pretreated natural fiber fabric product of claim 41, wherein the one or more latex polymers comprise a polyester.

43. The pretreated natural fiber fabric product of claim 42, wherein the polyester has a glass transition temperature from 0 to 100 °C.

44. The pretreated natural fiber fabric product of any of claims 42 or 43, wherein a latex dispersion of the polyester has a zeta potential from -60 to -20 mV.

45. The pretreated natural fiber fabric product of any of claims 37-44, wherein the one or more latex polymers comprise acrylic polymer.

46. The pretreated natural fiber fabric product of claim 45, wherein the acrylic polymer is self-crosslinking.

47. The pretreated natural fiber fabric product of any of claims 37-46, the pretreatment composition comprising a coalescing agent composition, wherein the coalescing agent composition comprises one or more compounds comprising an aliphatic composition, a cycloaliphatic composition, an ether composition, a glycol composition, an alcohol composition, an ester composition, a carbonate composition, a lactam composition, or a ketone composition.

48. The pretreated natural fiber fabric product of claim 47, wherein the coalescing agent composition comprises ethylene glycol butyl ether.

49. The pretreated natural fiber fabric product of any of claims 37-48, wherein the surfactant composition comprises one or more of an anionic or a nonionic surfactant.

50. The pretreated natural fiber fabric product of any of claims 37-49, wherein the surfactant composition comprises silicone.

51. The pretreated natural fiber fabric product of any of claims 37-50, wherein the UV stabilizer composition comprises one or more of a sulfonated benzophenone, a benzotri azole, a salicylate, a cinnamate, a triazole, or a triazine.

52. The pretreated natural fiber fabric product of any of claims 37-51, wherein the UV stabilizer composition comprises hydroxyphenyl triazine.

53. The pretreated natural fiber fabric product of any of claims 37-52, the pretreatment composition comprising an antioxidant composition, wherein the antioxidant composition comprises one or more of a hydroquinone, an alkoxyphenol, a dialkoxyphenol, a phenol, an aniline, an amine, an indane, a chromane, an alkoxyaniline, or a heterocyclic compound.

54. The pretreated natural fiber fabric product of claim 53, wherein the antioxidant composition comprises a hindered amine light stabilizer.

55. A method of pretreating a natural fiber fabric comprising: spraying a natural fiber fabric with 8 to 15 grams pretreatment composition per square inch of natural fiber fabric to produce sprayed natural fiber fabric; and drying the sprayed natural fiber fabric to form a pretreated natural fiber fabric product.

56. The method of pretreating a natural fiber fabric of claim 55, wherein the pretreatment composition comprises:

15 to 35 wt. % one or more latex polymers;

15 to 35 wt. % one or more humectants;

0.1 to 1 wt. % surfactant composition;

0.1 to 1 wt. % ultraviolet (UV) stabilizer composition;

0.1 to 1 wt. % one or more pH buffers;

0.05 to 0.5 wt. % biocide; and 40 to 60 wt. % solvent.

57. The method of claim 55 or 56, comprising printing an image on the pretreated natural fiber fabric product.

58. The method of pretreating a natural fiber fabric of any of claims 55-57, wherein the natural fiber fabric comprises one or more of wool, cotton, silk, linen, leather, hemp, or bamboo.

59. The method of pretreating a natural fiber fabric of any of claims 55-58, wherein the pretreated natural fiber fabric product comprises a T-shirt.

60. The method of pretreating a natural fiber fabric of any of claims 54-59, wherein the one or more latex polymers comprise one or more of a polyester, an acrylic polymer, an aromatic polyamide, a chlorinated polymer, a polyether, a polyurea, a fluorinated polymer, a polyurethane, a styrene, a polyvinyl, a thio/ether polymer, a polyolefin, a polystyrene, a polyacetate, a polyamide, a polyethylene, a polyimide, a polycarbonate, or a polyvinylalcohol.

61. The method of pretreating a natural fiber fabric of any of claims 56-60, wherein the one or more latex polymers comprise a polyester.

62. The method of pretreating a natural fiber fabric of claim 61, wherein the polyester has a glass transition temperature from 0 to 100 °C.

63. The method of pretreating a natural fiber fabric of any of claims 61 or 62, wherein a latex dispersion of the polyester has a zeta potential from -60 to -20 mV.

64. The method of pretreating a natural fiber fabric of any of claims 56-63, wherein the one or more latex polymers comprise acrylic polymer.

65. The method of pretreating a natural fiber fabric of claim 56-64, wherein the acrylic polymer is self-crosslinking.

66. The method of pretreating a natural fiber fabric of any of claims 56-65, the pretreatment composition including a coalescing agent composition, wherein the coalescing agent composition comprises one or more compounds comprising an aliphatic composition, a cycloaliphatic composition, an ether composition, a glycol composition, an alcohol composition, an ester composition, a carbonate composition, a lactam composition, or a ketone composition.

67. The method of pretreating a natural fiber fabric of claim 66, wherein the coalescing agent composition comprises ethylene glycol butyl ether.

68. The method of pretreating a natural fiber fabric of any of claims 56-67, wherein the surfactant composition comprises one or more of an anionic or a nonionic surfactant.

69. The method of pretreating a natural fiber fabric of any of claims 56-68, wherein the surfactant composition comprises silicone.

70. The method of pretreating a natural fiber fabric of any of claims 56-69, wherein the UV stabilizer composition comprises one or more of a sulfonated benzophenone, a benzotri azole, a salicylate, a cinnamate, a triazole, or a triazine.

71. The method of pretreating a natural fiber fabric of any of claims 56-70, wherein the UV stabilizer composition comprises hydroxyphenyl triazine.

72. The method of pretreating a natural fiber fabric of any of claims 56-71, the pretreatment composition comprising an antioxidant composition, wherein the antioxidant composition comprises one or more of a hydroquinone, an alkoxyphenol, a dialkoxyphenol, a phenol, an aniline, an amine, an indane, a chromane, an alkoxyaniline, or a heterocyclic compound.

73. The method of pretreating a natural fiber fabric of claim 72, wherein the antioxidant composition comprises a hindered amine light stabilizer.