WO2022046100A1

WO2022046100A1 - Coating compositions

Info

Publication number: WO2022046100A1
Application number: PCT/US2020/048721
Authority: WO
Inventors: Xiaoqi Zhou; Zhang-Lin Zhou
Original assignee: Hewlett-Packard Development Company, L.P.
Priority date: 2020-08-31
Filing date: 2020-08-31
Publication date: 2022-03-03

Abstract

The present disclosure describes coating compositions for flame retardant fabric print media. In one example, a coating composition can include water, a water-soluble phosphorus-containing metallic salt, a first crosslinkable film-forming polymer, and a second crosslinkable film-forming polymer. The water-soluble phosphorus-containing metallic salt can include a metal cation that is monovalent, divalent, or trivalent. The second crosslinkable film-forming polymer can be different from the first crosslinkable film-forming polymer.

Description

COATING COMPOSITIONS

BACKGROUND

[0001 ] Inkjet printing has become a popular way of recording images on various media. Some of the reasons include low printer noise, variable content recording, capability of high-speed recording, and multi-color recording. These features can be obtained at a relatively low price to consumers. As the popularity of inkjet printing increases, the types of use also increase providing demand for new print media, for example.

BRIEF DESCRIPTION OF DRAWINGS

[0002] FIG. 1 schematically illustrates an example coating composition in accordance with the present disclosure;

[0003] FIG. 2 schematically illustrates a cross-sectional view of an example fabric print medium in accordance with the present disclosure; and

[0004] FIG. 3 is a flowchart showing an example method of preparing a fabric print medium in accordance with the present disclosure.

DETAILED DESCRIPTION

[0005] The present disclosure describes coating compositions, fabric print media, and methods of preparing fabric print media. In one example, a coating composition includes water and a water-soluble phosphorus-containing metallic salt including a metal cation that is monovalent, divalent, or trivalent. The coating composition also includes a first crosslinkable film-forming polymer and a second crosslinkable filmforming polymer that is different from the first crosslinkable film-forming polymer. In some examples, the water-soluble phosphorus-containing metallic salt can be an inorganic phosphate salt, a phosphonate salt, a phosphinate salt, a hypophosphite salt, a phosphoramidate salt, or a combination thereof. In certain examples, the water- soluble phosphorus-containing metallic salt can be tetrasodium(1- hydroxyethylidene)bisphosphonate; pentasodium aminotrimethylene phosphonate; 2- phosphonobutane-1 ,2,4-tricarboxylic acid sodium salt, or a combination thereof. In other examples, the first crosslinkable film-forming polymer and the second crosslinkable filmforming polymer can independently include polyacrylate, polyurethane, vinyl-urethane, acrylic urethane, polyurethane-acrylic, polyether polyurethane, polyester polyurethane, polycaprolactam polyurethane, polyether polyurethane, alkyl epoxy resin, epoxy novolac resin, polyglycidyl resin, polyoxirane resin, polyamine, styrene maleic anhydride, a derivative thereof, or a combination thereof. In further examples, the coating composition can also include a cross-linking agent that is reactive to crosslink the first crosslinkable film-forming polymer, the second crosslinkable film-forming polymer, or both. In specific examples, the first crosslinkable film-forming polymer can include an epoxy resin, and the cross-linking agent can be reactive to crosslink the epoxy resin, and the second crosslinkable film-forming polymer can include a polyurethane polymer. In some examples, the composition can be free of inorganic solid particles. In still further examples, the coating composition can be transparent.

[0006] The present disclosure also describes fabric print media. In one example, a fabric print medium includes a fabric substrate and a flame retardant coating applied to the fabric substrate. The flame retardant coating includes a water-soluble phosphorus-containing metallic salt including a metal cation that is monovalent, divalent, or trivalent. The coating also includes a first crosslinked polymer network and a second crosslinked polymer network that is a different polymer from the first crosslinked polymer network. In some examples, the flame retardant coating can have a dry coat weight from 0.5 grams per square meter to 5 grams per square meter. In further examples, the water-soluble phosphorus-containing metallic salt can be tetrasodium(1- hydroxyethylidene)bisphosphonate; pentasodium aminotrimethylene phosphonate; 2- phosphonobutane-1 ,2,4-tricarboxylic acid sodium salt, or a combination thereof, and the first crosslinkable film-forming polymer can include an epoxy resin, and the second crosslinkable film-forming polymer can include a polyurethane polymer. In certain examples, the flame retardant coating can be transparent and the coating can be free of inorganic solid particles.

[0007] The present disclosure also describes methods of preparing fabric print media. In one example, a method of preparing a fabric print medium includes applying a flame retardant coating composition to a fabric substrate. The flame retardant coating composition includes water and a water-soluble phosphorus-containing metallic salt including a metal cation that is monovalent, divalent, or trivalent. The flame retardant coating composition also includes a first crosslinkable film-forming polymer and a second crosslinkable film-forming polymer that is different from the first crosslinkable film-forming polymer. The method also includes drying the flame retardant coating composition to form a flame retardant coating. The flame retardant coating includes a first crosslinked polymer network formed from the first crosslinkable film-forming polymer and a second crosslinked polymer network formed from the second crosslinkable film-forming polymer. In some examples, the flame retardant coating composition can be applied at a dry coat weight from 0.5 grams per square meter to 5 grams per square meter. In further examples, drying the flame retardant coating composition can include heating the fabric substrate at a temperature from 95 °C to 120 °C.

[0008] It is noted that when discussing the coating compositions, fabric print media, and methods, these discussions can be considered applicable to one another whether or not they are explicitly discussed in the context of that example. Thus, for example, when discussing cross-linkable polymers related to the coating compositions, such disclosure is also relevant to and directly supported in the context of the fabric print media and methods of preparing fabric print media, and vice versa. It is also understood that terms used herein will take on their ordinary meaning in the relevant technical field unless specified otherwise. In some instances, there are terms defined more specifically throughout the specification or included at the end of the present specification, and thus, these terms have a meaning as described herein. Coating Compositions

[0009] In some examples, the coating compositions described herein can be particularly useful for coating fabric print media. Fabric print media can refer to any type of fabric on which images can be printed. In certain examples, inkjet printing processes can be used to print on fabric print media. Printing on fabric can be challenging for several reasons. Some fabrics are highly absorptive, and it can be difficult to achieve good color saturation with printed ink because the ink, and colorants in the ink, can be absorbed below the surface of the fabric. Other fabrics can be crystalline and nonabsorbent, which can lead to ink bleed. Accordingly, it can be difficult to print images with good image quality on these types of fabric. In some cases, coatings are added to fabric to increase the image quality of images printed on the fabric. However, some coatings can interfere with the soft hand-feel of fabrics. Some coatings that include inorganic filler particles can also display micro-cracking, which can be especially visible when printed fabric is viewed under back-lighting. Some organic coatings can also be flammable, which can reduce the flame retardancy of the fabric.

[0010] The coating compositions described herein can be applied to fabric substrates to provide fabric print media that retains the soft hand-feel of the fabric. In some examples, the coatings can include a soft film-forming polymer that can contribute to soft feel of the media. Additionally, the fabric print media coated with the coating composition can have good flame retardancy. The coating compositions can include a water-soluble phosphorous-containing metallic salt, which can contribute to the flame retardancy of the media. The fabric print media can also provide good image quality for images printed on the media with inkjet ink.

[0011] In some examples, a coating composition can include water, a water- soluble phosphorus-containing metallic salt, and two crosslinkable film-forming polymers. The water-soluble phosphorus-containing metallic salt can include a metal cation that is monovalent, divalent, or trivalent. The two crosslinkable film-forming polymers can be two different polymers.

[0012] FIG. 1 shows an example coating composition 100 in accordance with the present disclosure. The composition includes water 102, a water-soluble phosphorus- containing metallic salt 104, a first crosslinkable film-forming polymer 106, and a second crosslinkable film-forming polymer 108. In this example, the first and second crosslinkable film-forming polymers are in the form of dispersions of polymer particles. The specific water-soluble phosphorus-containing metallic salt shown in this example is tetrasodium (1 -hydroxyethylidene) bisphosphonate.

[0013] As used herein, “water-soluble phosphorus-containing metallic salt” refers to compounds that can be dissolved in water in an amount of 5 wt% or greater. For example, 5 grams or more of the water-soluble phosphorus-containing metallic salt can be dissolved in water at room temperature. In some examples, the water-soluble phosphorus-containing metallic salt can have a solubility in water sufficient to dissolve the particular amount of the water-soluble phosphorus-containing metallic salt that is in the coating composition.

[0014] The water-soluble phosphorus-containing metallic salt can include an anionic part that includes a phosphorus atom. In various examples, the anionic part can be inorganic or organic. The anion can have any negative number charge, such as -1 , - 2, -3, -4, or others. The water-soluble phosphorus-containing metallic salt can also include a metal cation or multiple metal cations. The metal cation or cations can include a monovalent, divalent, or trivalent metal cation, or a combination thereof. Some examples of metal cations can include Li⁺, Na⁺, K⁺, Mg²⁺, Ca²⁺, Mn²⁺, Al³⁺, and others. In certain examples, the salt can also include a monovalent ammonium cation.

[0015] In some examples, the water-soluble phosphorus-containing metallic salt can be an inorganic phosphate salt, a phosphonate salt, a phosphinate salt, a hypophosphite salt, a phosphoramidate salt, or a combination thereof. In certain examples, the water-soluble phosphorus-containing metallic salt can be tetrasodium(1 - hydroxyethylidene)bisphosphonate. In other examples, the water-soluble phosphorus- containing metallic salt can be pentasodium aminotrimethylene phosphonate. In still other examples, the water-soluble phosphorus-containing salt can be 2- phosphonobutane-1 ,2,4-tricarboxylic acid sodium salt. A combination of these can also be used in some examples.

[0016] Additional non-limiting examples of the water-soluble phosphorus- containing metallic salt can include inorganic phosphate salts. Inorganic phosphate salts can include sec-sodium phosphate, disodium hydrogen phosphate, disodium phosphate, sodium hydrogenphosphate, sodium phosphate dibasic, sodium phosphate, sodium orthophosphate, trisodium phosphate, sodium phosphate monobasic monohydrate, monosodium phosphate, sodium dihydrogen phosphate monohydrate, sodium phosphate dibasic heptahydrate, disodium hydrogen phosphate heptahydrate, disodium phosphate, sodium phosphate monobasic, monosodium dihydrogen orthophosphate, monosodium phosphate, sodium dihydrogen phosphate, sodium phosphate dibasic dihydrate, sec-sodium phosphate, disodium hydrogen phosphate dihydrate, disodium phosphate, di-sodium hydrogen phosphate dihydrate, sodium phosphate dibasic dodecahydrate, sec-sodium phosphate, disodium hydrogen phosphate dodecahydrate, disodium phosphate, di-sodium hydrogen phosphate dodecahydrate, sodium phosphate monobasic dihydrate, sodium dihydrogen phosphate dihydrate, sodium phosphate dibasic solution, disodium hydrogen phosphate solution, di-sodium hydrogen phosphate solution, sodium phosphate tribasic dodecahydrate, trisodium phosphate (tert) dodecahydrate, trisodium phosphate dodecahydrate, trisodium phosphate dodecahydrate, di-sodium hydrogen phosphate, sec-sodium phosphate, disodium hydrogen phosphate, disodium phosphate, sodium hydrogenphosphate, sodium phosphate dibasic, di-sodium hydrogen phosphate anhydrous, sec-sodium phosphate, disodium hydrogen phosphate, disodium phosphate, sodium hydrogenphosphate, sodium phosphate dibasic, sec-sodium phosphate, disodium hydrogen phosphate dihydrate, disodium phosphate, sodium monohydrogen phosphate, sodium phosphate dibasic, sodium phosphate dibasic dihydrate, di-sodium hydrogen phosphate dihydrate, di-sodium hydrogen phosphate dodecahydrate, sec-sodium phosphate, disodium hydrogen phosphate dodecahydrate, disodium phosphate, sodium monohydrogen phosphate, sodium phosphate dibasic, sodium phosphate dibasic dodecahydrate, di-sodium hydrogen phosphate dodecahydrate, sodium dihydrogen phosphate dihydrate, sodium dihydrogen phosphate dihydrate, sodium phosphate monobasic dihydrate, mono-sodium orthophosphate, sodium biphosphate, sodium phosphate monobasic, sodium dihydrogen phosphate monohydrate, monosodium phosphate, sodium dihydrogen phosphate monohydrate, sodium phosphate monobasic monohydrate, or combinations thereof. [0017] In further examples, the water-soluble phosphorus-containing metallic salt can be sec-potassium phosphate, dipotassium hydrogen phosphate, dipotassium phosphate, potassium hydrogenphosphate, potassium phosphate dibasic, potassium phosphate, potassium orthophosphate, tripotassium phosphate, potassium phosphate monobasic monohydrate, monopotassium phosphate, potassium dihydrogen phosphate monohydrate, potassium phosphate dibasic heptahydrate, dipotassium hydrogen phosphate heptahydrate, dipotassium phosphate, potassium phosphate monobasic, monopotassium dihydrogen orthophosphate, monopotassium phosphate, potassium dihydrogen phosphate, potassium phosphate dibasic dihydrate, sec-potassium phosphate, dipotassium hydrogen phosphate dihydrate, dipotassium phosphate, dipotassium hydrogen phosphate dihydrate, potassium phosphate dibasic dodecahydrate, sec-potassium phosphate, dipotassium hydrogen phosphate dodecahydrate, dipotassium phosphate, di-potassium hydrogen phosphate dodecahydrate, potassium phosphate monobasic dihydrate, potassium dihydrogen phosphate dihydrate, potassium phosphate dibasic solution, dipotassium hydrogen phosphate solution, di-potassium hydrogen phosphate solution, potassium phosphate tribasic dodecahydrate, tripotassium phosphate (tert) dodecahydrate, tripotassium phosphate dodecahydrate, tri-potassium phosphate dodecahydrate, di-potassium hydrogen phosphate, secpotassium phosphate, dipotassium hydrogen phosphate, dipotassium phosphate, potassium hydrogenphosphate, potassium phosphate dibasic, di-potassium hydrogen phosphate anhydrous, sec-potassium phosphate, dipotassium hydrogen phosphate, dipotassium phosphate, potassium hydrogenphosphate, potassium phosphate dibasic, sec-potassium phosphate, dipotassium hydrogen phosphate dihydrate, dipotassium phosphate, potassium monohydrogen phosphate, potassium phosphate dibasic, potassium phosphate dibasic dihydrate, di-potassium hydrogen phosphate dihydrate, dipotassium hydrogen phosphate dodecahydrate, sec-potassium phosphate, dipotassium hydrogen phosphate dodecahydrate, dipotassium phosphate, potassium monohydrogen phosphate, potassium phosphate dibasic, potassium phosphate dibasic dodecahydrate, di-potassium hydrogen phosphate dodecahydrate, potassium dihydrogen phosphate dihydrate, potassium dihydrogen phosphate dihydrate, potassium phosphate monobasic dihydrate, mono-potassium orthophosphate, potassium biphosphate, potassium phosphate monobasic, potassium dihydrogen phosphate monohydrate, monopotassium phosphate, potassium dihydrogen phosphate monohydrate, potassium phosphate monobasic monohydrate, or combinations thereof.

[0018] In additional examples, the water-soluble phosphorus-containing metallic salt can be sec-lithium phosphate, dilithium hydrogen phosphate, dilithium phosphate, lithium hydrogenphosphate, lithium phosphate dibasic, lithium phosphate, lithium orthophosphate, trilithium phosphate, lithium phosphate monobasic monohydrate, monolithium phosphate, lithium dihydrogen phosphate monohydrate, lithium phosphate dibasic heptahydrate, dilithium hydrogen phosphate heptahydrate, dilithium phosphate, lithium phosphate monobasic, monolithium dihydrogen orthophosphate, monolithium phosphate, lithium dihydrogen phosphate, lithium phosphate dibasic dihydrate, seclithium phosphate, dilithium hydrogen phosphate dihydrate, dilithium phosphate, dilithium hydrogen phosphate dihydrate, lithium phosphate dibasic dodecahydrate, seclithium phosphate, dilithium hydrogen phosphate dodecahydrate, dilithium phosphate, di-lithium hydrogen phosphate dodecahydrate, lithium phosphate monobasic dihydrate, lithium dihydrogen phosphate dihydrate, lithium phosphate dibasic solution, dilithium hydrogen phosphate solution, di-lithium hydrogen phosphate solution, lithium phosphate tribasic dodecahydrate, trilithium phosphate (tert) dodecahydrate, trilithium phosphate dodecahydrate, tri-lithium phosphate dodecahydrate, di-lithium hydrogen phosphate, sec-lithium phosphate, dilithium hydrogen phosphate, dilithium phosphate, lithium hydrogenphosphate, lithium phosphate dibasic, di-lithium hydrogen phosphate anhydrous, sec-lithium phosphate, dilithium hydrogen phosphate, dilithium phosphate, lithium hydrogenphosphate, lithium phosphate dibasic, sec-lithium phosphate, dilithium hydrogen phosphate dihydrate, dilithium phosphate, lithium monohydrogen phosphate, lithium phosphate dibasic, lithium phosphate dibasic dihydrate, di-lithium hydrogen phosphate dihydrate, di-lithium hydrogen phosphate dodecahydrate, sec-lithium phosphate, dilithium hydrogen phosphate dodecahydrate, dilithium phosphate, lithium monohydrogen phosphate, lithium phosphate dibasic, lithium phosphate dibasic dodecahydrate, di-lithium hydrogen phosphate dodecahydrate, lithium dihydrogen phosphate dihydrate, lithium dihydrogen phosphate dihydrate, lithium phosphate monobasic dihydrate, mono-lithium orthophosphate, lithium biphosphate, lithium phosphate monobasic, lithium dihydrogen phosphate monohydrate, monolithium phosphate, lithium dihydrogen phosphate monohydrate, lithium phosphate monobasic monohydrate, or combinations thereof.

[0019] In still further examples, the water-soluble phosphorus-containing metallic salt can be sec-ammonium phosphate, diammonium hydrogen phosphate, diammonium phosphate, ammonium hydrogenphosphate, ammonium phosphate dibasic, ammonium phosphate, ammonium orthophosphate, triammonium phosphate, ammonium phosphate monobasic monohydrate, monoammonium phosphate, ammonium dihydrogen phosphate monohydrate, ammonium phosphate dibasic heptahydrate, diammonium hydrogen phosphate heptahydrate, diammonium phosphate, ammonium phosphate monobasic, monoammonium dihydrogen orthophosphate, monoammonium phosphate, ammonium dihydrogen phosphate, ammonium phosphate dibasic dihydrate, sec-ammonium phosphate, diammonium hydrogen phosphate dihydrate, diammonium phosphate, di-ammonium hydrogen phosphate dihydrate, ammonium phosphate dibasic dodecahydrate, sec-ammonium phosphate, diammonium hydrogen phosphate dodecahydrate, diammonium phosphate, di-ammonium hydrogen phosphate dodecahydrate, ammonium phosphate monobasic dihydrate, ammonium dihydrogen phosphate dihydrate, ammonium phosphate dibasic solution, diammonium hydrogen phosphate solution, di-ammonium hydrogen phosphate solution, ammonium phosphate tribasic dodecahydrate, triammonium phosphate (tert) dodecahydrate, triammonium phosphate dodecahydrate, tri-ammonium phosphate dodecahydrate, di-ammonium hydrogen phosphate, sec-ammonium phosphate, diammonium hydrogen phosphate, diammonium phosphate, ammonium hydrogenphosphate, ammonium phosphate dibasic, di-ammonium hydrogen phosphate anhydrous, sec-ammonium phosphate, diammonium hydrogen phosphate, diammonium phosphate, ammonium hydrogenphosphate, ammonium phosphate dibasic, sec-ammonium phosphate, diammonium hydrogen phosphate dihydrate, diammonium phosphate, ammonium monohydrogen phosphate, ammonium phosphate dibasic, ammonium phosphate dibasic dihydrate, di-ammonium hydrogen phosphate dihydrate, di-ammonium hydrogen phosphate dodecahydrate, sec-ammonium phosphate, diammonium hydrogen phosphate dodecahydrate, diammonium phosphate, ammonium monohydrogen phosphate, ammonium phosphate dibasic, ammonium phosphate dibasic dodecahydrate, di-ammonium hydrogen phosphate dodecahydrate, ammonium dihydrogen phosphate dihydrate, ammonium dihydrogen phosphate dihydrate, ammonium phosphate monobasic dihydrate, mono-ammonium orthophosphate, ammonium biphosphate, ammonium phosphate monobasic, ammonium dihydrogen phosphate monohydrate, monoammonium phosphate, ammonium dihydrogen phosphate monohydrate, ammonium phosphate monobasic monohydrate, or combinations thereof.

[0020] In further examples, the water-soluble phosphorus-containing salt can be a salt of a bisphosphonate. In certain examples, the water-soluble phosphorus- containing salt can be a salt of etidronate. In other examples, the bisphosphonate salt can have the following general structure:

where M is a monovalent cation and where R is an alkyl group with 1 to 10 carbon atoms.

[0021] In other examples, the water-soluble phosphorus-containing metallic salt can be a salt of nitrolotri(methylphosphonic acid). In still other examples, the water- soluble phosphorus-containing metallic salt can have the following general structure:

where M is a monovalent cation and where n is an integer from 1 to 10.

[0022] In still further examples, the water-soluble phosphorus-containing metallic salt can have a the following general structure:

where M is a monovalent cation and n is an integer from 1 to 10.

[0023] In another example, the water-soluble phosphorus-containing metallic salt can be a salt of N,N,N',N'-Ethylenediaminetetrakis(methylenephosphonic Acid.

[0024] The amount of the water-soluble phosphorus-containing metallic salt can be from 1 wt% to 50 wt% with respect to the dry weight of the coating composition. In further examples, the amount of water-soluble phosphorus-containing metallic salt can be from 2 wt% to 40 wt% or from 4 wt% to 20 wt% with respect to the dry weight of the coating composition.

[0025] Turning now to details about the polymers in the coating compositions, the polymers can include two crosslinkable film-forming polymers. One or both of the polymers can have characteristics of flexibility and softness that can allow fabric media treated with the coating composition to retain a soft hand-feel. The polymers can form a continuous film and be capable of binding to fibers of the fabric substrate. In some examples, one or both of the polymers can include a polyurethane compound. In other examples, modified polyacrylate compounds can be used, e.g., modified polyacrylates including copolymers of acrylic with methacrylic, acrylic acid, styrene, and anhydrides. In yet other examples, synthetic polymers and copolymers such as polyvinyl alcohol and polyvinyl acetate can be used. In further examples, natural polymers such as starches and chemically modified starches can be used. These film-forming polymers can be formed by polymerization of organic monomers, inorganic monomers, and hybrids of organic and inorganic monomers.

[0026] In some examples, one or both of the polymers in the coating composition can be formed by polymerization and/or copolymerization of hydrophobic addition monomers. Examples of hydrophobic addition monomers include, but are not limited to, C1-C12 alkyl acrylate and methacrylate monomers (e.g., methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, octyl arylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate), aromatic monomers (e.g., styrene, phenyl methacrylate, o-tolyl methacrylate, m-tolyl methacrylate, p-tolyl methacrylate, benzyl methacrylate), hydroxyl containing monomers (e.g., hydroxyethylacrylate, hydroxyethylmethacrylate), carboxylic acid containing monomers (e.g., acrylic acid, methacrylic acid), vinyl ester monomers (e.g., vinyl acetate, vinyl propionate, vinylbenzoate, vinylpivalate, vinyl-2-ethylhexanoate, vinylversatate), vinyl benzene monomers, C1-C12 alkyl acrylamide and methacrylamide monomers (e.g., t-butyl acrylamide, sec-butyl acrylamide, N,N-dimethylacrylamide), and olefin monomers (e.g., polyethylene, polypropylene , and co-polymers).

[0027] In certain examples, one or both of the polymers in the coating composition can be a polyacrylate. Example polyacrylate based polymers can include polymers made by hydrophobic addition monomers including, but are not limited to, CICI 2 alkyl acrylate and methacrylate (e.g., methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tertbutyl acrylate, 2-ethylhexyl acrylate, octyl arylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate), and aromatic monomers (e.g., styrene, phenyl methacrylate, o-tolyl methacrylate, m- tolyl methacrylate, p-tolyl methacrylate, benzyl methacrylate), hydroxyl containing monomers (e.g., hydroxyethylacrylate, hydroxyethylmethacrylate), carboxylic containing monomers (e.g., acrylic acid, methacrylic acid), vinyl ester monomers (e.g., vinyl acetate, vinyl propionate, vinylbenzoate, vinylpivalate, vinyl-2-ethylhexanoate, vinylversatate), vinyl benzene monomer, C1-C12 alkyl acrylamide and methacrylamide (e.g., t-butyl acrylamide, sec-butyl acrylamide, N,N-dimethylacrylamide), crosslinking monomers (e.g., divinyl benzene, ethyleneglycoldimethacrylate, bis(acryloylamido)methylene), or combinations thereof. Polymers made from the polymerization and/or copolymerization of alkyl acrylate, alkyl methacrylate, vinyl esters, and styrene derivatives may also be useful.

[0028] In further examples, one or both of the polymers can be a flexible polymer based on polyurethane chemistry. In certain examples, the polyurethane polymer can have a glass transition temperature (Tg) less than -10 °C. In further examples, the polyurethane polymer can have an acid number less than 60 mg KOH/g. The term “acid value” or “acid number" refers to the mass of potassium hydroxide (KOH) in milligrams that can be used to neutralize one gram of substance (mg KOH/g), such as the various polymers disclosed herein. This value can be determined, in one example, by dissolving or dispersing a known quantity of a material in organic solvent and then titrating with a solution of potassium hydroxide (KOH) of known concentration for measurement.

[0029] In further specific examples, the polyurethane polymer can be in the form of a dispersion having an average particle size from 25 nm to 400 nm or from 25 nm to 300 nm. The polyurethane polymer can also be formed by polymerizing monomers including diols and aliphatic diisocyanates. The aliphatic diisocyanates can include 2,2,4-trimethyl-hexamethylene diisocyanate, 2,4,4-trimethyl-hexamethylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and combinations thereof. The diols can include polyether diols, polyester diols, polycarbonate diols, and combinations thereof.

[0030] In some examples, the polyurethane polymer can include polymerized diamines. Examples of diamines can include 1 ,3-propanediamine, hydrazine, 1 ,2- ethanediamine, 1 ,4-butanediamine, 1 ,5-pentanediamine, 1 ,6-hexanediamine, 1 ,7- heptanediamine, 1 ,8-octanediamine, 1 ,9-nonanediamine, 1 ,10-decanediamine, 2,2,4- trimethyl-1 ,6-hexanediamine, diethylenetriamine, 1 ,4-cyclohexanediamine, 4-methyl- 1 ,3-cyclohexanediamine, 5-amino-1 ,3,3-trimethyl-cyclohexanamine, cyclohexanemethanamine, 4,4'-methylenebis[2-methyl-4,4'-methylenebis- cyclohexanamine, and combinations thereof.

[0031] In further examples, polyurethane polymers for use in the coating composition can be aliphatic or aromatic. In one example, the polyurethane can include an aromatic polyether polyurethane, an aliphatic polyether polyurethane, an aromatic polyester polyurethane, an aliphatic polyester polyurethane, an aromatic polycaprolactam polyurethane, an aliphatic polycaprolactam polyurethane, or a combination thereof. In another example, the polyurethane can include an aromatic polyether polyurethane, an aliphatic polyether polyurethane, an aromatic polyester polyurethane, an aliphatic polyester polyurethane, or a combination thereof. Example commercially-available polyurethanes can include; NEOPAC® R-9000, R-9699, and R- 9030 (available from Zeneca Resins, Ohio), PRINTRITE™ DP376 and SANCURE® AU4010 (available from Lubrizol Advanced Materials, Inc., Ohio), and HYBRIDUR® 570 (available from Air Products and Chemicals Inc., Pennsylvania), SANCURE® 2710, AVALURE® UR445 (which are equivalent copolymers of polypropylene glycol, isophorone diisocyanate, and 2,2-dimethylolpropionic acid, having the International Nomenclature Cosmetic Ingredient name “PPG-17/PPG-34/IPDI/DMPA Copolymer”), SANCURE® 878, SANCURE® 815, SANCURE® 1301 , SANCURE® 2715, SANCURE® 2026, SANCURE® 1818, SANCURE® 853, SANCURE® 830, SANCURE® 825, SANCURE® 776, SANCURE® 850, SANCURE® 12140, SANCURE® 12619, SANCURE® 835, SANCURE® 843, SANCURE® 898, SANCURE® 899, SANCURE® 1511 , SANCURE® 1514, SANCURE® 1517, SANCURE® 1591 , SANCURE® 2255, SANCURE® 2260, SANCURE® 2310, SANCURE® 2725, SANCURE®12471 , (all commercially available from Lubrizol Advanced Materials, Inc., Ohio), or combinations thereof.

[0032] One or both of the polymers in the coating composition can have a low glass transition temperature and high surface energy. For example, the glass transition temperature can be from -40 °C to 20 °C and the surface energy in the form of a film can be from 35-50 dyne/cm. Relatively low glass transition temperature can provide a flexible polymer chain and provide that the polymer will not adversely impact the softness of fabric materials. Relatively high surface energy can provide acceptable adhesive bonding strength. That being stated, the film-forming polymers can be cationic, anionic, or neutral in charge when presented in aqueous or other solution in preparation for application to the fabric substrate as part of a coating composition.

[0033] The polymers in the coating composition can also be crosslinkable. In some examples, one or both of the polymers can be in the form of a dispersion or emulsion such as latex. This composition can include reactive polymer particles. Reactive polymer particles can be capable of crosslinking via self-crosslinking or crosslinking in the presence of a crosslinking agent. In certain examples, the reactive particles can crosslink upon exposure to heat or evaporation of water from the coating composition. Under such conditions, the reactive polymers or polymeric particles can also coalesce so that the reactive polymer particles flow together to form a film due in part to chemical bonding generated in the crosslinking reaction. The crosslinking of the reactive polymer particles can form a continuous, substantially non-porous protective film that can be both heat flowed and cross-linked. When this is the case, when there is a rise in temperature during printing or curing processes, the crosslinkable functional group can be activated under the heat and initialize the crosslinking reaction. As a result, upon printing, the collapse of the particle and the crosslinking of the crosslinkable functional groups can cause the particles coalesce and embed printed ink pigment particles so that they physically interlock with the printed or otherwise deposited ink.

[0034] In further examples, one or both of the polymers in the coating composition can include particles of a polymer having an epoxy functionality on a backbone of the polymer, particles of a polymer having an epoxy functionality on a side chain of the polymer, particles of a polymer having fatty acid groups, particles of a polymer having alkoxy-silane groups, particles of a polymer having acetoacetoxy groups, particles of a polymer having hydroxyl groups, particles of a polymer having amine groups, and particles of a polymer having carboxyl groups.

[0035] In some examples, one or both of the polymers can have a polyurethane backbone that can be further crosslinked using a crosslinking agent. In one example, the cross-linking agent can be a blocked polyisocyanate. In another example, the blocked polyisocyanate can be blocked using polyalkylene oxide units. In some examples, the blocking units on the blocked polyisocyanate can be removed by heating the blocked polyisocyanate to a temperature at or above the deblocking temperature of the blocked polyisocyanate in order to yield free isocyanate groups. An example blocked polyisocyanate can include BAYHYDUR® VP LS 2306 (available from Bayer AG, Germany). In another example, the crosslinking can occur at trimethyloxysilane groups along the polyurethane chain. Hydrolysis can cause the trimethyloxysilane groups to crosslink and form a silesquioxane structure. In another example, the crosslinking can occur at acrylic functional groups along the polyurethane chain. Nucleophilic addition to an acrylate group by an acetoacetoxy functional group can allow for crosslinking on polyurethanes including acrylic functional groups. In other examples the polyurethane polymer can be a self-crosslinked polyurethane. Self- crosslinked polyurethanes can be formed, in one example, by reacting an isocyanate with a polyol.

[0036] In another example, one or both of the polymers in the coating composition can include an epoxy. The epoxy can be an alkyl epoxy resin, an alkyl aromatic epoxy resin, an aromatic epoxy resin, epoxy novolac resins, epoxy resin derivatives, or combinations thereof. In some examples, the epoxy can include an epoxy functional resin having one, two, three, or more pendant epoxy moieties. Example epoxy functional resins can include ANCAREZ® AR555 (commercially available from Air Products and Chemicals Inc., Pennsylvania), ANCAREZ® AR550, EPI-REZ™ 3510W60, EPI-REZ™ 3515W6, EPI-REZ™ 3522W60 (all commercially available from Hexion, Texas) and combinations thereof. In some examples, the epoxy resin can be an aqueous dispersion of an epoxy resin. Example commercially available aqueous dispersions of epoxy resins can include ARALDITE® PZ3901 , ARALDITE® PZ3921 , ARALDITE® PZ3961-1 , ARALDITE® PZ323 (commercially available from Huntsman International LLC, Texas), WATERPOXY® 1422 (commercially available from BASF, Germany), ANCAREZ® AR555 1422 (commercially available from Air Products and Chemicals, Inc., Pennsylvania), and combinations thereof. In yet another example, the epoxy resin can include a polyglycidyl or polyoxirane resin.

[0037] In one example, the epoxy resin can be self-crosslinked. Self-crosslinked epoxy resins can include polyglycidyl resins, polyoxirane resins, and combinations thereof. Polyglycidyl and polyoxirane resins can be self-crosslinked by a catalytic homopolymerization reaction of the oxirane functional group or by reacting with coreactants such as polyfunctional amines, acids, acid anhydrides, phenols, alcohols, and/or thiols.

[0038] In other examples, the epoxy resin can be crosslinked by an epoxy resin hardener. Epoxy resin hardeners can be included in solid form, in a water emulsion, and/or in a solvent emulsion. The epoxy resins hardener, in one example, can include liquid aliphatic amine hardeners, cycloaliphatic amine hardeners, amine adducts, amine adducts with alcohols, amine adducts with phenols, amine adducts with alcohols and phenols, amine adducts with emulsifiers, ammine adducts with alcohols and emulsifiers, polyamines, polyfunctional polyamines, acids, acid anhydrides, phenols, alcohols, thiols, and combinations thereof. Example commercially available epoxy resin hardeners can include ANQUAWHITE™ 100 (commercially available from Air Products and Chemicals Inc., Pennsylvania), ARADLIR® 3985 (commercially available from Huntsman International LLC, Texas), EPIKURE™ 8290-Y-60 (commercially available from Hexion, Texas), and combinations thereof.

[0039] In one example, one or both of the polymers in the coating composition can include an epoxy resin and the epoxy resin can include a water based epoxy resin and a water based polyamine. In another example, the polymer or polymers can include a vinyl urethane hybrid polymer, a water based epoxy resin, and a water based polyamine epoxy resin hardener. In yet another example, the polymer or polymers can include an acrylic-urethane hybrid polymer, a water based epoxy resin, and a water based polyamine epoxy resin hardener.

[0040] In still further examples, one or both of the polymers can include a styrene maleic anhydride (SMA). In one example, the SMA can include NOVACOTE 2000® (Georgia-Pacific Chemicals LLC, Georgia). In another example, the styrene maleic anhydride can be combined with an amine terminated polyethylene oxide (PEG), amine terminated polypropylene oxide (PPG), copolymer thereof, or a combination thereof. In one example, combining a styrene maleic anhydride with an amine terminated PEG and/or PPG can strengthen the polymeric network by crosslinking the acid carboxylate functionalities of the SMA to the amine moieties on the amine terminated PEG and/or PPG. The amine terminated PEG and/or PPG, in one example, can include amine moieties at one or both ends of the PEG and/or PPG chain, and/or as branched side chains on the PEG and/or PPG. In one example, utilizing an amine terminated PEG and/or PPG in combination with a SMA can retain the glossy features of the SMA while eliminating the brittle nature of SMA. Example commercially available amine terminated PEG and/or PPG compounds can include JEFFAMINE® XTJ-500, JEFFAMINE® XTJ- 502, and JEFFAMINE® XTJ D-2000 (all available from Huntsman International LLC, Texas). In some examples, a weight ratio of SMA to the amine terminated PEG and/or PPG can range from about 100: 1 to about 2.5:1. In another, a weight ratio of the SMA to the amine terminated PEG and/or PPG can range from about 90:1 to about 10:1. In yet another example, a weight ratio of the SMA to the amine terminated PEO and/or PPO can range from about 75:1 to about 25:1.

[0041] In various examples, the first and second polymers can be included in the coating composition in a combined amount from 50 wt% to 99 wt% with respect to the dry weight of the coating composition. In further examples, the first and second polymers can be included in the coating composition in a combined amount from 70 wt% to 98 wt% or from 80 wt% to 96 wt% with respect to the dry weight of the coating composition. In some examples, the first and second polymers can be included in equal amounts. In other examples, the ratio of the weight of the first polymer to the weight of the second polymer can be from 1 :4 to 4:1 .

[0042] As mentioned above, the coating compositions can include water, the water-soluble phosphorus-containing metallic salt, and the two different polymers. In certain examples, from 90 wt% to 99.9 wt% of the dry weight of the coating composition can consist of the water-soluble phosphorus-containing metallic salt and the two polymers. Accordingly, the coating composition can be mostly made up of the water- soluble phosphorus-containing metallic salt and the polymers. In some examples, the coating composition can include additional additives such as surfactants, organic cosolvents, and others. In certain examples, these additional ingredients can be included in a total amount from 0.01 wt% to 5 wt% with respect to the total weight of the coating composition. In further examples, the coating compositions can be devoid of certain ingredients. For example, in some cases the coating composition can be devoid of inorganic solid particles such as fillers, pigments, and so on. Although coatings for fabric print media often include fillers, the coating compositions described herein can be devoid of fillers in some examples. This can help maintain softness of the fabric media. Additionally, in some examples, the coating compositions can be transparent.

Fabric Print Media

[0043] The coating compositions described above can be applied to a fabric substrate to form a coated fabric print medium. The fabric print media can be used in a variety of applications, such as the creation of apparel, artwork, signs, banners, wall coverings, window coverings, upholstery, pillows, flags, tote bags, and so on. The coating formed from the coating compositions described herein can provide good image quality for images printed on the fabric media, while also retaining the softness of the media and achieving good flame retardance.

[0044] FIG. 2 shows a schematic cross-sectional view of an example fabric print medium 200 in accordance with the present disclosure. The fabric print medium includes a fabric substrate 210 and a flame retardant coating 220 applied to the fabric substrate. The flame retardant coating is formed by applying a coating composition as described above. In this example, the flame retardant coating includes a water-soluble phosphorus-containing metallic salt including a metal cation that is monovalent, divalent, or trivalent. The coating also includes a first crosslinked polymer network 206 and a second crosslinked polymer network 208 that is a different polymer from the first crosslinked polymer network. The first and second crosslinked polymer networks can be formed from the first and second crosslinkable film-forming polymers in the coating composition. Because the water-soluble phosphorus-containing metallic salt was dissolved in the coating composition, molecules of the water-soluble phosphorus- containing metallic salt can be well distributed throughout the coating.

[0045] In some examples, the flame-retardant coating on the fabric print media can have a dry coat weight from 0.5 grams/m² (gsm) to 5 gsm. In other examples, the flame-retardant can have a dry coat weight from 1 gsm to 4 gsm or from 2 gsm to 4 gsm.

[0046] As mentioned above, the first and second crosslinkable film-forming polymers can crosslink when the coating composition is applied to the fabric substrate. This can form two crosslinked polymer networks. In some examples, the first crosslinked polymeric network can be crosslinked to itself. In another example, the first crosslinked polymeric network can be crosslinked to itself and to the second crosslinked polymeric network. In one example, the second crosslinked polymeric network can be crosslinked to itself. When the first crosslinked polymeric network and the second crosslinked polymeric network are not crosslinked to one another they can be entangled or appear layered onto one another.

[0047] The coating compositions described herein can be applied to fabric substrates using any method appropriate for the coating application properties, e.g., thickness, viscosity, etc. Non-limiting examples of methods include dipping coating, padding, slot die, blade coating, and Meyer rod coating. When the coating composition is dried by removal of water and/or other volatile solvent content, the coating composition can form a coating layer. Drying can be carried out by air drying, heated airflow drying, baking, infrared heated drying, etc. Other processing methods and equipment can also be used. For one example, the print media substrate can be passed between a pair of rollers, as part of a calendering process, after drying. The calendering device can be any kind of calendaring apparatus, including but not limited to off-line super-calender, on-line calender, soft-nip calender, hard-nip calender, or the like.

[0048] The coating compositions described herein can be suitable for use with many types of fabric substrates, including cotton fibers, treated and untreated cotton substrates, polyester substrates, nylons, blended substrates thereof, etc. It is notable that the term “fabric substrate” or “fabric print media substrate” does not include print media substrate materials such as any paper (even though paper can include multiple types of natural and synthetic fibers or mixtures of both types of fibers). Example natural fiber fabrics that can be used include treated or untreated natural fabric textile substrates, e.g., wool, cotton, silk, linen, jute, flax, hemp, rayon fibers, thermoplastic aliphatic polymeric fibers derived from renewable resources such as cornstarch, tapioca products, or sugarcanes, etc. Example synthetic fibers that can be used include polymeric fibers such as nylon fibers (also referred to as polyamide fibers), polyvinyl chloride (PVC) fibers, PVC-free fibers made of polyester, polyamide, polyimide, polyacrylic, polypropylene, polyethylene, polyurethane, polystyrene, polyaramid, e.g., KEVLAR® (E. I. du Pont de Nemours Company, USA), polytetrafluoroethylene, fiberglass, polytrimethylene, polycarbonate, polyethylene terephthalate, polyester terephthalate, polybutylene terephthalate, or a combination thereof. In some examples, the fiber can be a modified fiber from the above-listed polymers. The term “modified fiber” refers to one or both of the polymeric fiber and the fabric as a whole having undergone a chemical or physical process such as, but not limited to, copolymerization with monomers of other polymers, a chemical grafting reaction to contact a chemical functional group with one or both of the polymeric fiber and a surface of the fabric, a plasma treatment, a solvent treatment, acid etching, or a biological treatment, an enzyme treatment, or antimicrobial treatment to prevent biological degradation.

[0049] Thus, the fabric substrate can include natural fiber and synthetic fiber, e.g., cotton/polyester blend. The amounts of the fiber types can vary. For example, the amount of the natural fiber can vary from about 5 wt% to about 95 wt% and the amount of the synthetic fiber can range from about 5 wt% to 95 wt%. In yet another example, the amount of the natural fiber can vary from about 10 wt% to 80 wt% and the synthetic fiber can be present from about 20 wt% to about 90 wt%. In other examples, the amount of the natural fiber can be about 10 wt% to 90 wt% and the amount of the synthetic fiber can also be about 10 wt% to about 90 wt%. Likewise, the ratio of natural fiber to synthetic fiber in the fabric substrate can vary. For example, the ratio of natural fiber to synthetic fiber can be 1 :1 , 1 :2, 1 :3, 1 :4, 1 :5, 1 :6, 1 :7, 1 :8, 1 :9, 1 :10, 1 :11 , 1 :12, 1 :13, 1 :14, 1 :15, 1 :16, 1 :17, 1 :18, 1 :19, 1 :20, or vice versa. The fabric substrate can be in one of many different forms, including, for example, a textile, a cloth, a fabric material, fabric clothing, or other fabric product suitable for applying ink, and the fabric substrate can have any of a number of fabric structures, including structures that can have warp and weft, and/or can be woven, non-woven, knitted, tufted, crocheted, knotted, and pressured, for example. The terms “warp” as used herein, refers to lengthwise or longitudinal yams on a loom, while “weft” refers to crosswise or transverse yams on a loom.

[0050] The basis weight of the fabric substrate can be from 20 gsm to 500 gsm, from 40 gsm to 400 gsm, from 50 gsm to 250 gsm, from 50 gsm to 400 gsm, or from 75 gsm to 150 gsm, for example. Some substrates can be toward the thinner end of the spectrum, and other substrates may be thicker, and thus, the weight basis ranges given are provided by example, and are not intended to be limiting.

[0051] Regardless of the substrate used, such substrates can contain or be coated with additives including, but not limited to, colorant (e.g., pigments, dyes, and tints), antistatic agents, brightening agents, nucleating agents, antioxidants, UV stabilizers, and/or fillers and lubricants, for example. Methods of Preparing Fabric Print Media

[0052] The present disclosure also describes methods of preparing fabric print media. FIG. 3 is a flowchart illustration one example method 300 of preparing a fabric print medium. The method includes: applying a flame retardant coating composition to a fabric substrate, wherein the flame retardant coating composition includes water, a water-soluble phosphorus-containing metallic salt including a metal cation that is monovalent, divalent, or trivalent, a first crosslinkable film-forming polymer, and a second crosslinkable film-forming polymer that is different from the first crosslinkable film-forming polymer 310; and drying the flame retardant coating composition to form a flame retardant coating, wherein the flame retardant coating includes a first crosslinked polymer network formed from the first crosslinkable film-forming polymer and a second crosslinked polymer network formed from the second crosslinkable film-forming polymer 320.

[0053] The coating composition can be applied to the fabric substrate by any suitable coating method, as described above. Additionally, the coating composition can include any of the types of water-soluble phosphorus-containing salts and film-forming polymers described above.

[0054] In certain examples, drying the flame retardant coating composition can include heating the fabric substrate. In one example, the fabric substrate can be heated to a temperature from 95 °C to 120 °C. With some types of polymers, the heating can contribute to film-forming and crosslinking of the polymers in the coating. As mentioned above, drying can be carried out by air drying, heated airflow drying, baking, infrared heated drying, or other drying methods. Accordingly, in some examples, a drying method that involves heating the fabric substrate to 95 °C to 120 °C can be used.

[0055] It is noted that, as used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the content clearly dictates otherwise.

[0056] As used herein, the term “about” is used to provide flexibility to a numerical range endpoint by providing that a given value may be “a little above” or “a little below” the endpoint. The degree of flexibility of this term can be dictated by the particular variable based on experience and the associated description herein. [0057] As used herein, the term "fabric" is used to describe any textile structure. A fabric can include textiles in the filament form, cloth materials, and finished articles. Fabrics can be woven, non-woven, knitted, tufted, etc., and can be natural or synthetic. As used herein, fabrics exclude paper.

[0058] “Warp-knit fabric” refers to loops in a fabric structure that is formed in a longitudinal fabric direction.

[0059] “Weft knit fabric” refers to loops of one row of fabric formed in a horizontal fabric direction.

[0060] As used herein, a plurality of items, structural elements, compositional elements, and/or materials may be presented in a common list for convenience. However, these lists should be construed as though the members of the list are individually identified as separate and unique members. Thus, no individual member of such list should be construed as a de facto equivalent of any other member of the same list solely based on their presentation in a common group without indications to the contrary.

[0061] Concentrations, dimensions, amounts, and other numerical data may be presented herein in a range format. It is to be understood that such range format is used merely for convenience and brevity and should be interpreted flexibly to include the numerical values explicitly recited as the limits of the range, and also to include all the individual numerical values or sub-ranges encompassed within that range as if the numerical values and sub-ranges are explicitly recited. For example, a weight ratio range of about 1 wt% to about 20 wt% should be interpreted to include the explicitly recited limits of about 1 wt% and about 20 wt%, and also to include individual weights such as 2 wt%, 11 wt%, 14 wt%, and sub-ranges such as 10 wt% to 20 wt%, 5 wt% to 15 wt%, etc.

EXAMPLES

[0062] The following examples illustrate the technology of the present disclosure. However, it is to be understood that the following is merely illustrative of the methods and systems herein. Numerous modifications and alternative methods and systems may be devised without departing from the present disclosure. Thus, while the technology has been described above with particularity, the following provides further detail in connection with what are presently deemed to be the acceptable examples. Example 1 - Coating Compositions

[0063] Five coating compositions were formulated. Compositions C1 , C2 and C3 were examples of the coating compositions described herein. Compositions C4 and C5 were comparative examples. The coating compositions were made by mixing ingredients in the amounts shown in Table 1 . The amounts of the ingredients are in parts by weight. In addition to the ingredients listed in Table 1 , the compositions included water in a sufficient amount to adjust the solids content to 5 wt%.

Table 1

ARALDITE® PZ 3901 is a crosslinkable polymer (epoxy resin) from Huntsman International LLC, Texas.

ARADUR® 3985 is an epoxy hardener from Huntsman International LLC, Texas. SANCURE® 2026 and SANCURE® AU4010 are polyurethane dispersions from

Lubrizol Advanced Materials, Inc., Ohio.

EXOLITE® OP 935 is a water-insoluble organic phosphinate from Palmer Holland, Ohio.

TEGO® Wet 510 is a surfactant from Evonik, Germany.

Example 2 - Coated Fabric Print Media

[0064] Coating compositions C1-C5 were applied to fabric substrates to make coated fabric print media. The fabric substrates were a 100% polyester fabric with a plain weave. The basis weight of the fabric substrate was 105 gsm. The coating compositions were coated on the fabric substrate at a dry pick up weight of 2 gsm. The coating compositions were deposited using a lab Methis padder with a speed of 5 meters per minute, at a roller pressure of 50 psi. The applied compositions were then dried using a box oven dryer with peak temperature at 120 °C for 15 minutes.

Example 3 - Image Quality and Durability

[0065] The coated fabric substrates were printed with a pigmented ink composition using an HP® L 360 printer available from HP, Inc. (USA). The coated and subsequently printed fabric substrates were evaluated for resistance to scratch, dry rub, wrinkle, fold, and flame resistance using a testing protocol referred to the NFPA 701 FR Test. The printed images were also evaluated for dark line, gamut, optical density (OD), and L*min. The test results are shown in Tables 2 and 3.

[0066] The testing protocols for the data collected below as shown in Table 2 was as follows:

Scratch testing was carried out using a coin to scratch the ink printed on the coated fabric substrates. Scratch testing was carried out on the printed fabrics using all available colors (cyan, magenta, yellow, and any others available). The samples were subjected to a scratch testing by a coin-like test header which was 45 degrees facing the surface of the tested samples. Scratching under a normal force of 800 g was used. The test was done in a BYK Abrasion Tester (from BYK-Gardner, USA) with a linear, back-and-forth action, attempting to scratch off the image side of the samples (5 cycles). The image durability was evaluated visually. Scores ranging from 1 to 4 were used, as indicated at the bottom of Table 1 . “MD” refers to machine direction, in which the fabric weaving direction is parallel to the movement of the test header. “CMD” refers to cross machine direction, in which the fabric weaving direction is perpendicular to the movement of the test header.

Dark Line testing was carried out for visual inspection under lighting. The sample is prepared by folding printed fabric three turnings and placing a 5 pound weight on top of the folded fabric for 10 minutes.

Wrinkle Resistance was evaluated manually by multiple operators (n=5) by crinkling and holding the textile in hands for 1 minute and then placing the fabric samples flatly on a surface and evaluating the degree of wrinkle. Scores ranging from 1 to 4 were used, with 4 indicating the best performance (insignificant wrinkling), 1 indicating the worst performance, and a score of 3 was considered passing.

Dry Rub resistance was tested by using an abrasion scrub tester. For this test, the fabrics were printed with available colors, e.g., cyan, magenta, yellow, and/or others). A weight of 250 g was loaded on a test header. The test tip made of acrylic resin with crock cloth was used. The device was set to move the tip at 25 cm/min for a total of 8 inches, cycled 5 times. The test probe was evaluated in dry (dry rub) mode. The ink transferred to the test cloth was evaluated visually. Scores ranging from 1 to 4 were used, with 4 indicating the best performance, 1 indicating the worst performance, and a score of 3 was considered passing.

Gamut was measured using a Macbeth® TD904 (Macbeth Process Measurement) machine.

Optical Density (OD) was measured in this example using a X Rite 938 Spectro Densitometer.

L*min was measured in this example using a X Rite 938 Spectro Densitometer. Table 2

[0067] Flame retardance or resistance is evaluated based on NFPA 701 standard (Standard Methods of Fire Tests for Flame Propagation of Textiles and Films). This methodology measures ignition resistance of a fabric after it is exposed to a flame for 12 seconds, and then the flame, char length, and flaming residue are recorded, with “passing” criteria based on a total weight loss less than 40 w% after burning, and a burning time of residual drops at less than 2 seconds. “Residual drops” refer to the melted burning drops from the fabric substrate that occur during the burning test when the samples are handled vertically.

The flame retardance test results are shown in Table 3.

Table 3

[0068] The test results show that example coating compositions C1 , C2, and C3 provided good image quality and durability while also passing the flame retardance tests. Comparative example 4 showed passable image quality and durability but failed the flame retardance test. Comparative example 5 marginally passed the flame retardance test but failed several image durability tests. Therefore, the combination of a water-soluble phosphorus-containing salt with the polymers in the example coating composition provided the best overall results.

Claims

CLAIMS What Is Claimed Is:

1. A coating composition, comprising: water; a water-soluble phosphorus-containing metallic salt including a metal cation that is monovalent, divalent, or trivalent; a first crosslinkable film-forming polymer; and a second crosslinkable film-forming polymer that is different from the first crosslinkable film-forming polymer.

2. The coating composition of claim 1 , wherein the water-soluble phosphorus- containing metallic salt is an inorganic phosphate salt, a phosphonate salt, a phosphinate salt, a hypophosphite salt, a phosphoramidate salt, or a combination thereof.

3. The coating composition of claim 1 , wherein the water-soluble phosphorus- containing metallic salt is tetrasodium(1 -hydroxyethylidene)bisphosphonate; pentasodium aminotrimethylene phosphonate; 2-phosphonobutane-1 ,2,4-tricarboxylic acid sodium salt, or a combination thereof.

4. The coating composition of claim 1 , wherein the first crosslinkable film-forming polymer and the second crosslinkable film-forming polymer independently comprise polyacrylate, polyurethane, vinyl-urethane, acrylic urethane, polyurethane-acrylic, polyether polyurethane, polyester polyurethane, polycaprolactam polyurethane, polyether polyurethane, alkyl epoxy resin, epoxy novolac resin, polyglycidyl resin, polyoxirane resin, polyamine, styrene maleic anhydride, a derivative thereof, or a combination thereof.

29

5. The coating composition of claim 1 , further comprising a cross-linking agent that is reactive to crosslink the first crosslinkable film-forming polymer, the second crosslinkable film-forming polymer, or both.

6. The coating composition of claim 5, wherein the first crosslinkable film-forming polymer comprises an epoxy resin, and wherein the cross-linking agent is reactive to crosslink the epoxy resin, and wherein the second crosslinkable film-forming polymer comprises a polyurethane polymer.

7. The coating composition of claim 1 , wherein the composition is free of inorganic solid particles.

8. The coating composition of claim 1 , wherein the composition is transparent.

9. A fabric print medium, comprising: a fabric substrate; a flame retardant coating applied to the fabric substrate, wherein the flame retardant coating comprises: a water-soluble phosphorus-containing metallic salt including a metal cation that is monovalent, divalent, or tri valent, a first crosslinked polymer network, and a second crosslinked polymer network that is a different polymer from the first crosslinked polymer network.

10. The fabric print medium of claim 9, wherein the flame retardant coating has a dry coat weight from 0.5 grams per square meter to 5 grams per square meter.

11 . The fabric print medium of claim 9, wherein the water-soluble phosphorus- containing metallic salt is tetrasodium(1-hydroxyethylidene)bisphosphonate; pentasodium aminotrimethylene phosphonate; 2-phosphonobutane-1 ,2,4-tricarboxylic acid sodium salt, or a combination thereof, and wherein the first crosslinkable film-

30 forming polymer comprises an epoxy resin, and wherein the second crosslinkable filmforming polymer comprises a polyurethane polymer.

12. The fabric print medium of claim 9, wherein the flame retardant coating is transparent and wherein the coating is free of inorganic solid particles.

13. A method of preparing a fabric print medium, comprising: applying a flame retardant coating composition to a fabric substrate, wherein the flame retardant coating composition comprises: water, a water-soluble phosphorus-containing metallic salt including a metal cation that is monovalent, divalent, or tri valent, a first crosslinkable film-forming polymer, and a second crosslinkable film-forming polymer that is different from the first crosslinkable film-forming polymer; and drying the flame retardant coating composition to form a flame retardant coating, wherein the flame retardant coating comprises a first crosslinked polymer network formed from the first crosslinkable film-forming polymer and a second crosslinked polymer network formed from the second crosslinkable film-forming polymer.

14. The method of claim 13, wherein the flame retardant coating composition is applied at a dry coat weight from 0.5 grams per square meter to 5 grams per square meter.

15. The method of claim 13, wherein drying the flame retardant coating composition comprises heating the fabric substrate at a temperature from 95 °C to 120 on