Cross-linked and dyed textile materials

Abstract

Dyed materials comprising a textile with natural fibers comprising hydroxyl functional groups, a protein, a dye, and a cross-linker. The protein can be covalently linked to at least the natural fibers via the cross-linker. The dye can be bonded to the natural fibers, the cross-linker, the protein, or a combination thereof. The textiles can be dyed using an aqueous dyeing formulation comprising one or more proteins, one or more cross-linkers, and one or more dyes.

Description

CROSS-LINKED AND DYED TEXTILE MATERIALSREFERENCE TO SEQUENCE LISTING SUBMITTED ELECTRONICALLY

[0001] The content of the electronically submitted sequence listing in XML file (Name: 4431_103PC01_Seqlisting_ST26.xml; Size: 2,910 bytes; and Date of Creation: May 31, 2024) filed with the application is herein incorporated by reference in its entirety.FIELD

[0002] This disclosure relates to dyed textile materials. In some embodiments, the dyed textile materials can be used to make various articles, for example fabrics, clothing, fashion accessories, or upholstery.BACKGROUND

[0003] Textile or fabric materials, including natural materials (for example, cotton), synthetic materials (for example, spandex and polyester), and composite textiles including natural and synthetic materials, are used across many industries, including the furniture industry and the clothing industry. Often, these textile or fabric materials are dyed to impart one or more desired colors or patterns on the materials. The demand for dyed textile or fabric materials is high. There is a continuing need for improving in the properties of these dyed materials, as well as a continuing need for improving the manufacturing processes for dyeing the materials.BRIEF SUMMARY

[0004] The present disclosure provides dyed textile materials dyed with a protein formulation. In some embodiments, the dyed textile materials can comprise one or more natural fibers with hydroxyl functional groups dyed with a protein formulation. In some embodiments, the dyed textile materials can comprise composite textile materials comprising a fiber with hydroxyl functional groups and a fiber comprising a synthetic polymer dyed with a protein formulation. The protein formulation can comprise one or more proteins, one or more cross-linkers, and one or more dyes. The one or more cross-linkers can covalently link the protein to the hydroxyl functional groups and the dye can be bound to the hydroxyl functional groups, the one or more cross-linkers, the protein, or a combination thereof. In some embodiments, the bonding between the hydroxyl functional groups, cross-linker(s), protein, and dye can facilitate dyeing of multiple fiber types within composite textile materials using a single dyeing formulation. In some embodiments, the dye can be mixed into a protein formulation before the formulation is applied to the textile material. In some embodiments, a protein formulation can be applied to a textile material and a dye can be applied to the protein formulation on the textile material.

[0005] A first embodiment (1) of the present disclosure is directed to a dyed material comprising: (a) textile comprising natural fibers comprising hydroxyl functional groups; (b) a protein; and (c) a dye; wherein the protein is covalently linked to the natural fibers via one or more cross-linkers; and wherein the dye is bonded to the natural fibers, the one or more cross-linkers, the protein, or a combination thereof.

[0006] In a second embodiment (2), the one or more cross-linkers according to the first embodiment (1) comprise an aziridine cross-linker.

[0007] In a third embodiment (3), the one or more cross-linkers according to the first embodiment (1) are selected from the group consisting of: an aziridine cross-linker, a carbodiimide cross-linker, an isocyanate cross-linker, n-hydroxysuccinimide, a diazirine cross-linker, phenyl azide, and combinations thereof.

[0008] In a fourth embodiment (4), the one or more cross-linkers according to the first embodiment (1) comprise a first cross-linker and a second cross-linker.

[0009] In a fifth embodiment (5), the first cross-linker according to the fourth embodiment (4) is an epoxy cross-linker and the second cross-linker according to the fourth embodiment (4) is an aziridine cross-linker.

[0010] In a sixth embodiment (6), the first cross-linker according to the fourth embodiment (4) is selected the group consisting of: an epoxy cross-linker, an aziridine cross-linker, a carbodiimide cross-linker, an isocyanate cross-linker, n- hydroxysuccinimide, an diazirine cross-linker, and phenyl azide, and the second crosslinker according to the fourth embodiment (4) is a different cross-linker than the first cross-linker and is selected from the group consisting of: an epoxy cross-linker, anaziridine cross-linker, a carbodiimide cross-linker, an isocyanate cross-linker, n- hydroxysuccinimide, an diazirine cross-linker, and phenyl azide.

[0011] In a seventh embodiment (7), the dye according to any one of embodiments (1) - (6) is a reactive dye or an acid dye.

[0012] In an eighth embodiment (8), the dye according to the seventh embodiment (7) is a reactive dye and is covalently bonded to the natural fibers, the one or more crosslinkers, the protein, or a combination thereof.

[0013] In a ninth embodiment (9), the dye according to the seventh embodiment (7) is an acid dye and is non-covalently bonded to the natural fibers, the one or more cross-linkers, the protein, or a combination thereof.

[0014] In a tenth embodiment (10), the textile according to any one of embodiments (1) - (9) is a composite textile comprising the natural fibers and a second fiber comprising a synthetic polymer.

[0015] In an eleventh embodiment (11), the composite textile according to the tenth embodiment (10) is a blended textile comprising the natural fibers blended with the second fiber.

[0016] In a twelfth embodiment (12), the composite textile according to the tenth embodiment (10) comprises a layered textile comprising a first layer comprising the natural fibers and a second layer comprising the second fiber.

[0017] In a thirteenth embodiment (13), the natural fibers according to any one of embodiments (1) - (12) comprise cotton, wool, linen, silk, or a combination thereof.

[0018] In fourteenth embodiment (14) the synthetic polymer according to any one of embodiments (10) - (12) is selected from the group consisting of polyester, nylon, polypropylene, polyethylene, an acrylic polymer, rayon, spandex, lyocell, polylactic acid, polyhydroxyalkanoate, and combinations thereof.

[0019] In a fifteenth embodiment (15), the synthetic polymer according to the fourteenth embodiment (14) is a polyester selected from group consisting of: polybutylene succinate, polybutylene adipate terephthalate, polyethylene furanoate, and combinations thereof.

[0020] In a sixteenth embodiment (16), the one or more cross-linkers according to any one of embodiments (10) - (12) are electrostatically bonded to the synthetic polymer.

[0021] In a seventeenth embodiment (17), the protein according to any one of embodiments (1) - (16) comprises a soy protein.

[0022] In an eighteenth embodiment (18), the soy protein according to the seventeenth embodiment (17) is soy protein isolate.

[0023] In a nineteenth embodiment (19), the dyed material according to any one of embodiments (1) - (18) further comprises an antimicrobial agent.

[0024] In a twentieth embodiment (20), the dyed material according to any one of embodiments (1) - (19) has a wet crocking value of greater than or equal to 2.5.

[0025] In a twenty-first embodiment (21), the dyed material according to any one of embodiments (1) - (20) has a perspiration fastness of greater than or equal to 3.

[0026] A twenty-second embodiment (22) according to the present disclosure is directed to a textile dyeing formulation comprising: water; one or more proteins; one or more cross-linkers, the one or more cross-linkers present at total weight percent ranging from greater than or equal to about 5 wt% to less than or equal to about 90 wt% relative to the one or more proteins in the formulation; and one or more dyes, the one or more dyes present at a total weight percent ranging from greater than or equal to about 5 wt% to less than or equal to about 200 wt% relative to the one or more proteins in the formulation.

[0027] In a twenty-third embodiment (23), the one or more dyes according to the twenty- second embodiment (22) are reactive dyes.

[0028] In a twenty-fourth embodiment (24), the one or more dyes according to the twenty-second embodiment (22) are acid dyes.

[0029] In a twenty-fifth embodiment (25), the one or more cross-linkers according to any one of embodiments (22) - (24) comprise an aziridine cross-linker.

[0030] In a twenty-sixth embodiment (26), the one or more cross-linkers according to any one of embodiments (22) - (24) are selected from the group consisting of: an aziridine cross-linker, a carbodiimide cross-linker, an isocyanate cross-linker, n- hydroxysuccinimide, a diazirine cross-linker, phenyl azide, and combinations thereof.

[0031] In a twenty-seventh embodiment (27), the one or more cross-linkers according to any one of embodiments (22) - (24) comprise a first cross-linker and a second crosslinker.

[0032] In a twenty-eighth embodiment (28), the first cross-linker according to the twentyseventh embodiment (27) is an epoxy cross-linker and the second cross-linker according to the twenty-seventh embodiment (27) is an aziridine cross-linker.

[0033] In a twenty-ninth embodiment (29), the first cross-linker according to the twentyseventh embodiment (27) is selected the group consisting of: an epoxy cross-linker, an aziridine cross-linker, a carbodiimide cross-linker, an isocyanate cross-linker, n- hydroxysuccinimide, a diazirine cross-linker, and phenyl azide, and the second crosslinker according to the twenty-seventh embodiment (27) is a different cross-linker selected the group consisting of an epoxy cross-linker, an aziridine cross-linker, a carbodiimide cross-linker, an isocyanate cross-linker, n-hydroxysuccinimide, a diazirine cross-linker, and phenyl azide.

[0034] In a thirtieth embodiment (30), the dyeing formulation according to any one of embodiments (22) - (29) further comprise one or more bases.

[0035] In a thirty-first embodiment (31), the one or more bases according to the thirtieth embodiment (30) is a nucleophilic base present at a weight percent less than or equal to about 2 wt% relative to the one or more proteins in the formulation.

[0036] In a thirty-second embodiment (32), the one or more bases according to the thirtieth embodiment (30) is a non-nucleophilic base present at a weight percent ranging from greater than or equal to about 1 wt% to less than or equal to about 15 wt% relative to the one or more proteins in the formulation.

[0037] In a thirty-third embodiment (33), the dyeing formulation according to any one of embodiments (22) - (29) further comprises a Lewis acid present at a weight percent ranging from greater than or equal to about 1 wt% to less than or equal to about 15 wt% relative to the one or more proteins in the formulation.

[0038] In a thirty-fourth embodiment (34), the dyeing formulation according to any one of embodiments (22) - (33) further comprises one or more surfactants.

[0039] In a thirty-fifth embodiment (35), the one or more surfactants according to the thirty-fourth embodiment (34) is present at a total weight percent less than or equal to about 50 wt% relative to the one or more proteins in the formulation.

[0040] In a thirty-sixth embodiment (36), the dyeing formulation according to any one of embodiments (22) - (35) further comprises one or more plasticizers.

[0041] In a thirty-seventh embodiment (37), the one or more plasticizers according to the thirty-sixth embodiment (36) are present at a total weight percent less than or equal to about 60 wt% relative to the one or more proteins in the formulation.

[0042] In a thirty-eighth embodiment (38), the one or more plasticizers according to the thirty-sixth embodiment (36) are selected from the group consisting of: glycerol, propylene glycol, sorbitol, a polyol polymer, and combinations thereof.

[0043] In a thirty-ninth embodiment (39), the dyeing formulation according to any one of embodiments (22) - (38) further comprises one or more denaturants present at a total weight percent ranging from greater than or equal to about 1 wt% to less than or equal to about 200 wt% relative to the one or more proteins in the formulation.

[0044] In a fortieth embodiment (40), the dyeing formulation according to any one of embodiments (22) - (39) further comprises one or more binding agents present at a total weight percent less than or equal to about 10 wt% relative to the one or more proteins in the formulation.

[0045] In a forty-first embodiment (41), the one or more binding agents according to the fortieth embodiment (40) are selected from the group consisting of: polyacrylic acid, polyacrylamide, sodium alginate, and combinations thereof.

[0046] In a forty-second embodiment (42), the dyeing formulation according to any one of embodiments (22) - (41) further comprises one or more antimicrobial agents present at a total weight percent less than or equal to about 5 wt% relative to the one or more proteins in the formulation.

[0047] In a forty-third embodiment (43), the one or more proteins according to any one of embodiments (22) - (42) are present at a total weight percent ranging from greater than or equal to about 10 wt% to less than or equal to about 50 wt% relative to the water in the formulation.

[0048] In a forty-fourth embodiment (44), the dyeing formulation according to any one of embodiments (22) - (43) further comprises one or more radial initiators present at a total weight percent less than or equal to about 5 wt% relative to the one or more proteins in the formulation.

[0049] A forty-fifth embodiment (45) according to the present disclosure is directed to a method for dyeing a textile, the method comprising: (a) applying the dyeing formulation according to any one of embodiments (22) - (44) to a textile comprising natural fibers comprising hydroxyl functional groups; and (b) curing the dyeing formulation on the textile.

[0050] A forty-sixth embodiment (46) of the present disclosure is directed to a method for dyeing a textile, the method comprising: (a) applying a protein formulation to a textile, wherein the protein formulation comprises water, one or more proteins, and one or more cross-linkers present at total weight percent ranging from greater than or equal to about 5 wt% to less than or equal to about 90 wt% relative to the one or more proteins in the formulation, and wherein the textile comprises natural fibers comprising hydroxyl functional groups; (b) drying the protein formulation on the textile to form a cross-linked textile; and (c) applying one or more dyes to the cross-linked textile to bond the one or more dyes to the natural fibers, the one or more cross-linkers, the one or more proteins, or a combination thereof.

[0051] In a forty-seventh embodiment (47), drying the protein formulation according to the forty-sixth embodiment (46) comprises drying and curing the protein formulation on the textile.

[0052] A fourth-eighth embodiment (48) of the present disclosure is directed to a composite material, comprising (a) a composite textile comprising (i) a first fiber comprising hydroxyl functional groups, and (ii) a second fiber comprising a synthetic polymer; (b) a protein; and (c) a dye; wherein the protein is covalently linked to at least the first fiber via an epoxy cross-linker; and wherein the dye is bonded to the first fiber, the epoxy cross-linker, the protein, or a combination thereof.

[0053] In a forty-ninth embodiment (49), the dye according to the forty-eighth embodiment (48) is a reactive dye or an acid dye.

[0054] In a fiftieth embodiment (50), the dye according to the forty-ninth embodiment (49) is a reactive dye and is covalently bonded to the first fiber, the epoxy cross-linker, the protein, or a combination thereof.

[0055] In a fifty-first embodiment (51), the dye according to the forty -ninth embodiment (49) is an acid dye and is non-covalently bonded to the first fiber, the epoxy cross-linker, the protein, or a combination thereof.

[0056] In a fifty-second embodiment (52), the first fiber according to any one of embodiments (48) - (51) is a natural fiber.

[0057] In a fifty-third embodiment (53), the natural fiber according to the fifty-second embodiment (52) is cotton, wool, linen, silk, or a combination thereof.

[0058] In a fifty-fourth embodiment (54), the synthetic polymer according to any one of embodiments (48) - (53) is selected from the group consisting of polyester, nylon, polypropylene, polyethylene, an acrylic polymer, rayon, spandex, lyocell, polylactic acid, polyhydroxyalkanoate, and combinations thereof.

[0059] In a fifty-fifth embodiment (55) the synthetic polymer according to the fifty-fourth embodiment (54) is a polyester selected from group consisting of polybutylene succinate, polybutylene adipate terephthalate, polyethylene furanoate, and combinations thereof.

[0060] In a fifty-sixth embodiment (56), the protein according to any one of embodiments (48) - (55) comprises a soy protein.

[0061] In a fifty-seventh embodiment (57), the soy protein according to the fifty-sixth embodiment (56) is soy protein isolate.

[0062] In a fifty-eighth embodiment (58), the epoxy cross-linker according to any one of embodiments (48) - (57) comprises a polyglycidyl ether.

[0063] In a fifty-ninth embodiment (59), the composite material according to any one of embodiments (48) - (58) further comprises an antimicrobial agent.

[0064] In a sixtieth embodiment (60), the composite material according to any one of embodiments (48) - (59) has a wet crocking value of greater than or equal to about 2.5.

[0065] In a sixty-first embodiment (61), the composite material according to any one of embodiments (48) - (60) has a perspiration fastness of greater than or equal to about 3.

[0066] In a sixty-second embodiment (62), the composite textile according to any one of embodiments (48) - (61) is a blended textile comprising the first fiber blended with the second fiber.

[0067] In a sixty-third embodiment (63), the composite textile according to any one of embodiments (48) - (61) comprises a layered textile comprising a first layer comprising the first fiber and a second layer comprising the second fiber.

[0068] In a sixty-fourth embodiment (64), the epoxy cross-linker according to any one of embodiments (48) - (63) is electrostatically bonded to the synthetic polymer.

[0069] A sixty-fifth embodiment (65) of the present disclosure is directed to a textile dyeing formulation comprising water; one or more proteins; one or more epoxy crosslinkers, the one or more epoxy cross-linkers present at a total weight percent ranging from greater than or equal to about 10 wt% to less than or equal to about 90 wt% relative to the one or more proteins in the formulation; and one or more dyes, the one or more dyespresent at a total weight percent ranging from greater than or equal to about 5 wt% to less than or equal to about 200 wt% relative to the one or more proteins in the formulation.

[0070] In a sixty-sixth embodiment (66), the one or more dyes according to the sixty-fifth embodiment (65) are reactive dyes.

[0071] In a sixty-seventh embodiment (67), the one or more dyes according to the sixtyfifth embodiment (65) are acid dyes.

[0072] In a sixty-eighth embodiment (68), the dyeing formulation according to any one of embodiments (65) - (67) further comprises one or more bases.

[0073] In a sixty-ninth embodiment (69), the one or more bases according to the sixtyeighth embodiment (68) is a nucleophilic base present at a weight percent less than or equal to about 2 wt% relative to the one or more proteins in the formulation.

[0074] In a seventieth embodiment (70), the one or more bases according to the sixtyeighth embodiment (68) is a non-nucleophilic base present at a weight percent ranging from greater than or equal to about 1 wt% to less than or equal to about 15 wt% relative to the one or more proteins in the formulation.

[0075] In a seventy -first embodiment (71), the dyeing formulation according to any one of embodiments (65) - (67) further comprises a Lewis acid present at a weight percent ranging from greater than or equal to about 1 wt% to less than or equal to about 15 wt% relative to the one or more proteins in the formulation.

[0076] In a seventy-second embodiment (72), the dyeing formulation according to any one of embodiments (65) - (71) further comprises one or more surfactants.

[0077] In a seventy-third embodiment (73), the one or more surfactants according to the seventy-second embodiment (72) are present at a total weight percent less than or equal to about 50 wt% relative to the one or more proteins in the formulation.

[0078] In a seventy-fourth embodiment (74) the dyeing formulation according to any one of embodiments (65) - (73) further comprises one or more plasticizers.

[0079] In a seventy -fifth embodiment (75), the one or more plasticizers according to the seventy -fourth embodiment (74) are present at a total weight percent less than or equal to about 60 wt% relative to the one or more proteins in the formulation.

[0080] In a seventy-sixth embodiment (76), the one or more plasticizers according to the seventy-fourth embodiment (74) are selected from the group consisting of: glycerol, propylene glycol, sorbitol, a polyol polymer, and combinations thereof.

[0081] In a seventy-seventh embodiment (77), the dyeing formulation according to any one of embodiments (65) - (76) further comprises one or more denaturants present at a total weight percent ranging from greater than or equal to about 1 wt% to less than or equal to about 200 wt% relative to the one or more proteins in the formulation.

[0082] In a seventy-eighth embodiment (78), the dyeing formulation according to any one of embodiments (65) - (77) further comprises one or more binding agents present at a total weight percent less than or equal to about 10 wt% relative to the one or more proteins in the formulation.

[0083] In a seventy -ninth embodiment (79), the one or more binding agents according to the seventy-eighth embodiment (78) are selected from the group consisting of: polyacrylic acid, polyacrylamide, sodium alginate, and combinations thereof.

[0084] In an eightieth embodiment (80), the dyeing formulation according to any one of embodiments (65) - (79) further comprises one or more antimicrobial agents present at a total weight percent less than or equal to about 5 wt% relative to the one or more proteins in the formulation.

[0085] In an eighty-first embodiment (81), the one or more proteins according to any one of embodiments (65) - (80) are present at a total weight percent ranging from greater than or equal to about 10 wt% to less than or equal to about 50 wt% relative to the water in the formulation.

[0086] In an eighty-second embodiment (82), the dyeing formulation according to any one of embodiments (65) - (81) further comprises one or more radial initiators present at a total weight percent less than or equal to about 5 wt% relative to the one or more proteins in the formulation.

[0087] An eighty-third embodiment (83) of the present disclosure is directed to a method for dyeing a textile, the method comprising (a) applying the dyeing formulation according to any one of embodiments (65) - (81) to a composite textile comprising a first fiber comprising hydroxyl functional groups and a second fiber comprising a synthetic polymer; and (b) curing the dyeing formulation on the composite textile.

[0088] An eighty-fourth embodiment (84) of the present disclosure is directed to a method for dyeing a textile, the method comprising (a) applying a protein formulation to a composite textile, wherein the protein formulation comprises water, one or more proteins, and one or more epoxy cross-linkers present at a total weight percent rangingfrom greater than or equal to about 10 wt% to less than or equal to about 90 wt% relative to the one or more proteins in the formulation, and wherein the composite textile comprises a first fiber comprising hydroxyl functional groups and a second fiber comprising a synthetic polymer; (b) drying the protein formulation on the composite textile to form a cross-linked textile; and (c) applying one or more dyes to the crosslinked textile to bond the one or more dyes to the first fiber, the one or more epoxy crosslinkers, the one or more proteins, or a combination thereof.

[0089] In an eighty-fifth embodiment (85), drying the protein formulation according to the eighty-fourth embodiment (84) comprises drying and curing the protein formulation on the composite textile.BRIEF DESCRIPTION OF THE FIGURES

[0090] The accompanying figures, which are incorporated herein, form part of the specification and illustrate embodiments of the present disclosure. Together with the description, the figures further serve to explain the principles of and to enable a person skilled in the relevant art(s) to make and use the disclosed embodiments. These figures are intended to be illustrative, not limiting. Although the disclosure is generally described in the context of these embodiments, it should be understood that it is not intended to limit the scope of the disclosure to these particular embodiments. In the drawings, like reference numbers indicate identical or functionally similar elements.

[0091] FIG. 1 A schematically illustrates a dyed textile material comprising a blended textile according to some embodiments.

[0092] FIG. IB schematically illustrates a dyed multi-layer textile material according to some embodiments.DETAILED DESCRIPTION

[0093] The indefinite articles “a,” “an,” and “the” include plural referents unless clearly contradicted or the context clearly dictates otherwise.

[0094] The terms “comprising” and “including” are open-ended transitional phrases. A list of elements following the transitional phrase “comprising” or “including” is a nonexclusive list, such that elements in addition to those specifically recited in the list canalso be present. The phrase “consisting essentially of’ limits the composition of a component to the specified materials and those that do not materially affect the basic and novel characteristic(s) of the component. The phrase “consisting of’ limits the composition of a component to the specified materials and excludes any material not specified.

[0095] Where a range of numerical values comprising upper and lower values is recited herein, unless otherwise stated in specific circumstances, the range is intended to include the endpoints thereof, and all integers and fractions within the range. It is not intended that the disclosure or claims be limited to the specific values recited when defining a range. Further, when an amount, concentration, or other value or parameter is given as a range, one or more ranges, or as list of upper values and lower values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or value and any lower range limit or value, regardless of whether such pairs are separately disclosed. Finally, when the term “about” is used in describing a value or an end-point of a range, the disclosure should be understood to include the specific value or end-point referred to. Whether or not a numerical value or end-point of a range recites “about,” the numerical value or end-point of a range is intended to include two embodiments: one modified by “about,” and one not modified by “about.”

[0096] As used herein, the term “about” refers to a value that is within ± 10% of the value stated. For example, “about 3 MPa” includes any number between 2.7 MPa and 3.3 MPa as well as the endpoints (i.e. 2.7 and 3.3). That said, if a percentage is listed and the value of that percentage cannot go above 100%, for example 100 wt% or 99 wt%, “about” does not modify the percentage to include values over 100%.

[0097] As used herein, the term “substantially free of’ means that a component is present in a detectable amount not exceeding about 0.1 wt%.

[0098] As used herein, the term “free of’ means that a component is not present in a formulation or material (e.g., a dyeing formulation), even in trace amounts.

[0099] As used herein “collagen” refers to the family of at least 28 distinct naturally occurring collagen types including, but not limited to collagen types I, II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII, XIX, and XX. The term collagen as used herein also refers to collagen prepared using recombinant techniques. The term collagen includes collagen, collagen fragments, collagen-like proteins, triplehelical collagen, alpha chains, monomers, gelatin, trimers and combinations thereof. Recombinant expression of collagen and collagen-like proteins is known in the art (see, e.g., Bell, EP 1232182B1, Bovine collagen and method for producing recombinant gelatin; Olsen, et al., U.S. Patent No. 6,428,978 and VanHeerde, et al., U.S. Patent No. 8,188,230, incorporated by reference herein in their entireties) Unless otherwise specified, collagen of any type, whether naturally occurring or prepared using recombinant techniques, can be used in any of the embodiments described herein. That said, in some embodiments, the collagen described herein can be prepared using bovine Type I collagen. Collagens are characterized by a repeating triplet of amino acids, -(Gly-X-Y)n-, so that approximately one-third of the amino acid residues in collagen are glycine. X is often proline and Y is often hydroxyproline. Thus, the structure of collagen may consist of three intertwined peptide chains of differing lengths. Different animals may produce different amino acid compositions of the collagen, which may result in different properties (and differences in the resulting leather).

[0100] In some embodiments, the collagen can be chemically modified to promote solubility in water.

[0101] Any type of collagen, truncated collagen, unmodified or post-translationally modified, or amino acid sequence-modified collagen can be used for protein formulations, dyeing formulations, or dyed textiles described herein.

[0102] In some embodiments, the collagen can be plant-based collagen. For example, the collagen can be a plant-based collagen made by CollPlant.

[0103] In some embodiments, a recombinant collagen can comprise a collagen fragment of the amino acid sequence of a native collagen molecule capable of forming tropocollagen (trimeric collagen). A recombinant collagen can also comprise a modified collagen or truncated collagen having an amino acid sequence at least 70, 80, 90, 95, 96, 97, 98, or 99% identical or similar to a native collagen amino acid sequence (or to a fibril forming region thereof or to a segment substantially comprising [Gly-X-Y]n). In some embodiments, the collagen fragment can be a 50 kDa portion of a native collagen. Native collagen sequences include the amino acid sequences of CollAl, CollA2, and Col3 Al, described by Accession Nos. NP_001029211.1, NP_776945.1 and NP_001070299.1, which are incorporated by reference. In some embodiments, the collagen fragment can be a portion of human collagen alpha-l(III) (Col3Al; Uniprot # P02461, Entrez Gene ID #1281). In some embodiments, the collagen fragment can be the amino acid sequence listed as SEQ ID NO: 1. In some embodiments, the collagen fragment can be the amino acid sequence listed as SEQ ID NO: 1. In some embodiments, the collagen fragment comprises an amino sequence having at least 80% sequence identity to SEQ ID NO: 1. Example proteins comprising at least 80% sequence identify to SEQ ID NO: 1 are disclosed in PCT / US2022 / 027016, the disclosure of which is incorporated herein by reference.

[0104] Methods of producing recombinant collagen and recombinant collagen fragments are known in the art. For example, U.S. Pub. Nos. 2019 / 0002893, 2019 / 0040400, 2019 / 0093116, and 2019 / 0092838 provide methods for producing collagen and collagen fragments that can be used to produce the recombinant collagen and recombinant collagen fragments disclosed herein. The contents of these four publications are incorporated by reference in their entirety.

[0105] As used herein, a “fiber” refers to a construct having a length that is substantially larger than its effective diameter. A “fiber” may be a filament, a thread, a yam, a cable, a cord, a fiber tow, a tape, a ribbon, a monofilament, a braid, a string, or any other form of material that can be spooled. In some embodiments, a fiber can have a length that is at least ten times larger than its effective diameter. In some embodiments, a fiber can have a length that is at least 50 times larger than its effective diameter. In some embodiments, a fiber can have a length that is at least 100 times larger than its effective diameter. In some embodiments, a fiber can have a length that is at least 200 times larger than its effective diameter. In some embodiments, a fiber can have a length that is at least 300 times larger than its effective diameter. In some embodiments, a fiber can have a length that is at least 500 times larger than its effective diameter. In materials comprising one or more fibers, the fiber(s) can be in the form of, but are not limited to, woven fiber(s), non-woven fiber(s), or knitted fiber(s).

[0106] An “effective diameter” is used herein to describe the diameter of a fiber, but this term should not be interpreted as requiring a fiber to have a circular diameter or shape. Instead, a fiber can have a non-circular shape, and in such embodiments, the term “effective diameter” is intended to refer to the maximum cross-sectional dimension of the shape. For example, the “effective diameter” of a fiber having an elliptical cross-sectional shape would be the length of the major axis of the elliptical shape. For a fiber having aneffective diameter that varies along the length of the fiber, the effective diameter is the largest effective diameter.

[0107] Textile materials comprising hydroxyl functional groups (for example, natural textile materials such as cotton, wool, linen, and silk) are typically dyed with reactive dyes in a salty alkaline solution. In contrast, synthetic polymer fibers (for example, polyester fibers) are typically dyed with disperse dyes because the synthetic polymers lack the necessary functional groups along the backbone of the polymer that enable dye fixation through covalent bonding. Use of disperse dyes for dyeing synthetic polymer fibers requires high-temperature and / or high-pressure processes to force diffusion of the dye into synthetic polymer fibers because disperse dyes interact weakly with hydrophobic substrates. The use of disperse dyes for dyeing materials comprising hydroxyl functional groups or materials comprising a synthetic polymer can be ineffective because the disperse dyes do not covalently bond to the functional groups, but rather interact with the fibers through physical entanglement and Van der Waals interactions. The lack of chemical interactions leads to poor dye fixation.

[0108] Dyed textile materials described herein comprise one or more fibers dyed using a protein formulation comprising one or more cross-linkers. In some embodiments, dyed textile materials described herein comprise a natural fiber with hydroxyl functional groups dyed using a protein formulation comprising one or more cross-linkers. In some embodiments, the dyed textile materials comprise dyed composite textile materials comprising a fiber with hydroxyl functional groups and a fiber comprising a synthetic polymer that are both dyed using a protein formulation comprising one or more crosslinkers. In some embodiments, the protein formulation can comprise one or more proteins and one or more cross-linkers, and a post-dyeing process can be used to dye the textiles after application of the protein formulation. In some embodiments, the protein formulation can be a dyeing formulation comprising one or more proteins, one or more cross-linkers, and one or more dyes. In such embodiments, the textiles can be dyed with the dyeing formulation.

[0109] In embodiments comprising a composite textile, application of the protein formulations or dyeing formulations described herein allows different fiber types within the composite textile to be dyed uniformly with a single dyeing step and with a single dye type. In other words, the protein formulation or the dyeing formulation is “fiber agnostic,”meaning the formulation can be used to dye both fiber types simultaneously. The protein formulations and dyeing formulations described herein can strongly adhere dye molecules (for example reactive dye molecules or acid dye molecules) to both synthetic polymer fibers and fibers comprising hydroxyl functional groups (for example, natural fibers). By providing strong adherence of dye molecules to both synthetic polymer fibers and fibers comprising hydroxyl functional groups, the formulations can circumvent traditional two- step dyeing process for composite textiles (for example, a first reactive dyeing step for natural fibers and a second disperse dyeing step for synthetic polymer fibers).

[0110] Surprisingly, protein formulations and dyeing formulations described herein can strongly adhere dye molecules to a synthetic polymer even though the one or more crosslinkers will not covalently bond to an unmodified synthetic polymer surface. Without wishing to be bound by a particular theory, it is believed that the one or more crosslinkers may form an electrostatic bond with the surface of an unmodified synthetic polymer. Again, without wishing to be bound by theory, it is believed covalent links between a protein and the hydroxyl functional groups in combination with bonds between the dye, the first fiber, the one or more cross-linkers, the protein, or a combination thereof, creates a synergy within the composite material that fixes the one or more cross- likers and dye molecules on unmodified synthetic polymer surfaces more strongly than would occur in the absence of the covalent links between the protein and the hydroxyl functional groups. It is believed that without such an interaction, dye molecules would flake off the surface of the synthetic polymer and / or the materials would have poor color properties and poor dye migration properties.[OHl] The protein formulations and dyeing formulations described herein overcome deficiencies in traditional dyeing processes for composite textiles. The formulations allow the application of a dye on multiple fibers types using a single dyeing step. What is more, materials prepared from these formulations are less susceptible to color and / or dye migration and have superior color levelness and color uniformity compared to textile materials dyed using a single traditional dyeing process for natural fibers, synthetic polymer fibers, and combinations thereof. The formulations can achieve these improvements while simultaneously reducing water usage and manufacturing costs, and avoiding the need for formulation additives, such as anti-migrants, used to reduce the propensity of a disperse dye to migrate between fibers during processing and use.

[0112] Dyed materials described herein can comprise (a) a textile comprising natural fibers comprising hydroxyl functional groups, (b) a protein, and (c) a dye. The protein can be covalently linked to at least the natural fibers via one or more cross-linkers and the dye can be covalently or non-covalently bonded to the natural fibers, the one or more crosslinkers, the protein, or a combination thereof.

[0113] Composite materials described herein can comprise (a) a composite textile comprising a first fiber comprising hydroxyl functional groups and a second fiber comprising a synthetic polymer, (b) a protein, and (c) a dye. The protein can be covalently linked to at least the first fiber via one or more cross-linkers and the dye can be covalently or non-covalently bonded to the first fiber, one or more cross-linkers, the protein, or a combination thereof.

[0114] To be clear, each molecule of reactive dye will only covalently bond based on the number of reactive sites on the reactive dye. That notwithstanding, different molecules of reactive dye can bind to different reactive groups dispersed throughout the textiles, for example, a plurality of reactive dye molecules can bind to hydroxyl functional groups, while a different plurality of reactive dye molecules can also bond to the protein.

[0115] In some embodiments, the dye can be applied to the textile by mixing the dye with a protein formulation to create a dyeing formulation that is applied to the textile as described herein. In some embodiments, the dye can be applied on a protein formulation that has been previously applied to a textile as described herein. This process is referred to as “post-dyeing.”

[0116] In some embodiments, the textile can comprise one or more natural fibers comprising hydroxyl functional groups. In some embodiments, the textile can be a composite textile comprising one or more fibers comprising hydroxyl functional groups and one or more fibers comprising a synthetic polymer. In some embodiments, the one or more fibers comprising hydroxyl functional groups in the composite textile can be natural fibers.

[0117] FIGS. 1A and IB schematically illustrate dyed composite materials 100 according to some embodiments. Material 100 comprises a composite textile comprising one or more first fibers 110 and one or more second fibers 120. First fiber(s) 110 can comprise hydroxyl functional groups. Second fiber(s) 120 can comprise a synthetic polymer. Material 100 further comprises a formulation 130 comprising one or more cross-linkers,one or more proteins, and one or more dyes. The dye of the formulation 130 can be covalently or non-covalently linked to the first fibers 110 via the one or more crosslinkers. In some embodiments, the one or more cross-linkers can be electrostatically bonded to the synthetic polymer of the second fiber(s) 120. Formulation 130 can be infused, impregnated, coated, deposited, or otherwise applied to the composite textile.

[0118] In some embodiments, as shown for example in FIG. 1 A, the composite textile can comprise one or more blended textiles 140 comprising one or more first fibers 110 blended with one or more second fibers 120. In such embodiments, the first fiber(s) 110 and second fiber(s) 120 can be interwoven, intermixed, intertwined, or otherwise blended together to form blended textile. In some embodiments, as shown for example in FIG. IB, the composite textile can comprise a layered textile comprising a first layer 150 comprising the one or more first fibers 110 and a second layer 160 comprising the one or more second fibers 120. In some embodiments, the first layer 150 and second layer 160 can be combined before dyeing and dyed simultaneously using a protein formulation or a dyeing formulation as described herein. In some embodiments, a protein formulation as described herein can be applied to the first layer 150 and second layer 160 separately, the first layer 150 and second layer 160 can be combined, and a dye can be applied to the combined first layer 150 and second layer 160 using a post-dyeing process as described herein.

[0119] In some embodiments, the composite textile 140 can comprise a first weight percentage of first fiber(s) 110 ranging from greater than or equal to about 10 wt% to less than or equal to about 90 wt% and a second weight percentage of second fiber(s) 120 ranging from greater than or equal to about 10 wt% to less than or equal to about 90 wt%. In some embodiments, the sum of the first weight percentage and the second weight percentage can be at least about 95 wt%, at least about 96 wt%, at least about 97 wt%, at least about 98 wt%, or at least about 99 wt%. For example, in some embodiments, the sum of the amount of first fiber(s) 110 and second fiber(s) 120 can range from about 95 wt% to 100 wt%, from about 96 wt% to 100 wt%, from about 97 wt% to 100 wt%, from about 98 wt% to 100 wt%, or from about 99 wt% to 100 wt%.

[0120] The first weight percentage can range from greater than or equal to about 10 wt% to less than or equal to about 90 wt%, including subranges. For example, the first weight percentage can range from greater than or equal to about 10 wt% to less than or equal toabout 90 wt%, from greater than or equal to about 20 wt% to less than or equal to about 90 wt%, from greater than or equal to about 30 wt% to less than or equal to about 90 wt%, from greater than or equal to about 40 wt% to less than or equal to about 90 wt%, from greater than or equal to about 50 wt% to less than or equal to about 90 wt%, from greater than or equal to about 60 wt% to less than or equal to about 90 wt%, from greater than or equal to about 70 wt% to less than or equal to about 90 wt%, from greater than or equal to about 80 wt% to less than or equal to about 90 wt%, from greater than or equal to about 10 wt% to less than or equal to about 80 wt%, from greater than or equal to about 10 wt% to less than or equal to about 70 wt%, from greater than or equal to about 10 wt% to less than or equal to about 60 wt%, from greater than or equal to about 10 wt% to less than or equal to about 50 wt%, from greater than or equal to about 10 wt% to less than or equal to about 40 wt%, from greater than or equal to about 10 wt% to less than or equal to about 30 wt%, or from greater than or equal to about 10 wt% to less than or equal to about 20 wt%.

[0121] The second weight percentage can range from greater than or equal to about 10 wt% to less than or equal to about 90 wt%, including subranges. For example, the second weight percentage can range from greater than or equal to about 10 wt% to less than or equal to about 90 wt%, from greater than or equal to about 20 wt% to less than or equal to about 90 wt%, from greater than or equal to about 30 wt% to less than or equal to about 90 wt%, from greater than or equal to about 40 wt% to less than or equal to about 90 wt%, from greater than or equal to about 50 wt% to less than or equal to about 90 wt%, from greater than or equal to about 60 wt% to less than or equal to about 90 wt%, from greater than or equal to about 70 wt% to less than or equal to about 90 wt%, from greater than or equal to about 80 wt% to less than or equal to about 90 wt%, from greater than or equal to about 10 wt% to less than or equal to about 80 wt%, from greater than or equal to about 10 wt% to less than or equal to about 70 wt%, from greater than or equal to about 10 wt% to less than or equal to about 60 wt%, from greater than or equal to about 10 wt% to less than or equal to about 50 wt%, from greater than or equal to about 10 wt% to less than or equal to about 40 wt%, from greater than or equal to about 10 wt% to less than or equal to about 30 wt%, or from greater than or equal to about 10 wt% to less than or equal to about 20 wt%.

[0122] Fibers comprising hydroxyl functional groups suitable for incorporation into the dyed material described herein include, but are not limited to, natural fibers. Suitable natural fibers include, but are not limited to, cotton, wool, linen, silk, and combinations thereof.

[0123] Synthetic polymer fibers suitable for incorporation into the dyed composite material described herein include, but are not limited to, polyester, nylon, polypropylene, polyethylene, an acrylic polymer, rayon, spandex, lyocell, polylactic acid, polyhydroxyalkanoate, and combinations thereof. In some embodiments, the polyester can be polybutylene succinate, polybutylene adipate terephthalate, polyethylene furanoate, or a combination thereof.

[0124] Composite materials described herein can comprise one or more fibers comprising hydroxyl functional groups selected from the group above and one or more fibers comprising a synthetic polymer selected from the group above. For example, in some embodiments, the composite material can comprise one or more cotton fibers and one or more polyester fibers.

[0125] Dyes suitable for incorporation into the material described herein include, but are not limited to fiber reactive dyes and acid dyes. Exemplary fiber reactive dyes include reactive dyes with one or more chromophores that contain at least one pendant group capable of forming at least one covalent bond with at least a natural fiber, such as a cellulosic fiber (i.e. cotton). Exemplary fiber reactive dyes, include but are not limited to, sulphatoethyl sulphone (Remazol), triazine, vinyl sulphone, and acrylamido dyes. Exemplary acid dyes include, but are not limited to, azo structure acid dyes, metal complex structure acid dyes, aniline structure dyes, and anthraquinone structure acid dyes. Without wishing to be bound by a particular theory, acid dyes are believed to be bound to the natural fiber, the one or more cross-linkers, the protein, or a combination thereof via hydrogen bonding, Van der Waals forces, ionic bonds, or a combination thereof.

[0126] In some embodiments, the dyed material can comprise only a single dye type. In some embodiments, the dyed material can comprise only a single dye type and be substantially free of, or free of, all other dye types. In some embodiments, the dyed material can comprise one or more fiber reactive dyes and be substantially free of, or free of, all other dye types, including acid dyes, natural dyes, direct dyes, and dispersed dyes.In some embodiments, the dyed material can comprise one or more acid dyes and be substantially free of, or free of, all other dye types, including reactive dyes, natural dyes, direct dyes, and dispersed dyes.

[0127] In some embodiments, the dyed material can comprise a plurality of different dyes of the same type. For example, in some embodiments, the dyed material can comprise a plurality of different color reactive dyes or a plurality of different color acid dyes.

[0128] Proteins suitable for incorporation into the presently described dyed material, dyeing formulations, and protein formulations include, but are not limited to, collagen, gelatin, bovine serum albumin (BSA), soy proteins, pea protein, egg white albumin, casein, peanut protein, edestin protein, whey protein, karanja protein, and cellulase. Suitable collagens include, but are not limited to, recombinant collagen (r-Collagen), a recombinant collagen fragment, and extracted collagens. Suitable soy proteins include, but are not limited to, soy protein isolate (SPI), soymeal protein, and soy protein derivatives. In some embodiments, the soy protein isolate can be partially hydrolyzed soy protein isolate. Suitable pea proteins include, but are not limited to, pea protein isolate, and pea protein derivatives. In some embodiments, the pea protein isolate can be partially hydrolyzed pea protein isolate.

[0129] Table 1 below lists several exemplary proteins and properties of the proteins. The gelatin is gelatin from porcine skin, Type A (Sigma Aldrich G2500). The collagen is extracted bovine collagen purchased from Wuxi BIOT Biology-technology Company. The bovine serum albumin Sigma Aldrich 5470 bovine serum albumin. The r-Collagen is recombinant collagen from Modem Meadow. The soy protein isolate is soy protein isolate purchased from MP Medicals (IC90545625). The pea protein is pea protein powder purchased from Bobs Red Mills (MTX5232). The egg white albumin protein is albumin from chicken egg white (Sigma Aldrich A5253). The casein protein is casein from bovine milk (Sigma Aldrich C7078). The peanut protein is peanut protein powder purchased from Tru-Nut. The whey protein is whey from bovine milk (Sigma Aldrich W1500). Other suitable soy protein isolates include, but are not limited to, soy protein isolate purchased from AMD (Clarisoy 100, 110, 150, 170, 180), or DuPont (SUPRO® XT 55, SUPRO® XT 221D, and SOBIND® Balance). Other suitable pea protein powders include, but are not limited to, pea protein powder purchased from Puris (870 and 870H).

[0130] Karanja protein is a protein found in Karanja seeds harvested from Pongamia pinnata trees (also known as Pongamia glabra trees). See Rahman, M., and Netravali, “Green Resin from Forestry Waste Residue ‘Karanja (Pongamia pinnata) Seed Cake’ for Biobased Composite Structures,” ACS Sustainable Chem. Eng., 2: 2318-2328 (2014); see also Mandal et al.. “Nutritional Evaluation of Proteins from three Non-traditional Seeds with or without Amino Acids Supplementation in Albino Rats,” Proc. Indian natn. Sci. Acad., B50, No. 1, 48-56 (1984). The protein can be extracted from Karanja seeds using a solvent extraction process. Id. In some embodiments, the karanja protein can be karanja protein isolate. In such embodiments, karanja protein isolate can be obtained by alkaline extraction and acid precipitation of defatted karanja seed cake. See Rahman, M., and Netravali, “Green Resin from Forestry Waste Residue ‘Karanja (Pongamia pinnata) Seed Cake’ for Biobased Composite Structures,” ACS Sustainable Chem. Eng., 2: 2318-2328 (2014).

[0131] Suitable cellulase proteins are listed below in Table 1. The “Cellulase-RG” protein is Native Trichoderma sp. Cellulase available from CREATIVE ENZYMES®. The “Cellulase-IG” protein is laboratory grade cellulase available from Carolina Biological Supply Company.

[0132] The 50 KDa recombinant collagen fragment (50 KDa r-Collagen fragment) in Table 1 is a collagen fragment having the amino acid sequence listed as SEQ ID NO: 1.

[0133] The “dissolution method” listed in Table 1 is an exemplary aqueous solvent in which the protein can be dissolved.Table 1: Example Proteins

[0134] Cross-linkers suitable for incorporation into the dyed material, dyeing formulations, and protein formulations include, but are not limited to, epoxy crosslinkers, aziridine cross-linkers, carbodiimide cross-linkers, isocyanate cross-linkers, n- hydroxysuccinimide, diazirine cross-linkers, phenyl azide, and combinations thereof.

[0135] In some embodiments, the dyed material can comprise a single cross-linker. In some embodiments, the dyed material can comprise a plurality of cross-linkers. In some embodiments, the dyed material can comprise a plurality of epoxy cross-linkers. In some embodiments, the dyed material can comprise a plurality of aziridine cross-linkers. In some embodiments, the dyed material can comprise a plurality of carbodiimide crosslinkers. In some embodiments, the dyed material can comprise a plurality of isocyanate cross-linkers. In some embodiments, the dyed material can comprise a plurality of diazirine cross-linkers.

[0136] In some embodiments, the one or more cross-linkers can comprise an aziridine cross-linker. In some embodiments, the one or more cross-linkers can comprise an epoxycross-linker. In some embodiments, the one or more cross-linkers comprise (a) a first cross-linker selected from the group consisting of an epoxy cross-linker, an aziridine cross-linker, a carbodiimide cross-linker, an isocyanate cross-linker, n- hydroxysuccinimide, a diazirine cross-linker, and phenyl azide, and (b) a second crosslinker that is different than the first cross-linker and is selected from the group consisting of an epoxy cross-linker, an aziridine cross-linker, a carbodiimide cross-linker, an isocyanate cross-linker, n-hydroxysuccinimide, a diazirine cross-linker, and phenyl azide. In some embodiments, the first cross-linker can be an epoxy cross-linker and the second cross-linker can be an aziridine cross-linker. In some embodiments, the one or more cross-linkers can comprise at least three cross-linkers, with each cross-linker being a different cross-linker selected from the group consisting of an epoxy cross-linker, an aziridine cross-linker, a carbodiimide cross-linker, an isocyanate cross-linker, n- hydroxysuccinimide, a diazirine cross-linker, and phenyl azide.

[0137] In some embodiments, the dyed material can comprise a single aziridine crosslinker. In some embodiments, the dyed material can comprise a single epoxy cross-linker. In some embodiments, the dyed material can comprise a single carbodiimide cross-linker. In some embodiments, the dyed material can comprise a single isocyanate cross-linker. In some embodiments, the dyed material can comprise a single diazirine cross-linker.

[0138] In some embodiments, the dyed material can comprise only a single cross-linker type. In some embodiments, the dyed material can comprise only a single cross-linker type and be substantially free of, or free of, all other cross-linker types.

[0139] In some embodiments, the dyed material can comprise one or more aziridine cross-linkers and be substantially free of, or free of, all other cross-linker types, including epoxy cross-linkers, carbodiimide cross-linkers, isocyanate cross-linkers, n- hydroxysuccinimide, diazirine cross-linkers, and phenyl azide. In some embodiments, the dyed material can comprise one or more epoxy cross-linkers and be substantially free of, or free of, all other cross-linker types, including aziridine cross-linkers, carbodiimide cross-linkers, isocyanate cross-linkers, n-hydroxysuccinimide, diazirine cross-linkers, and phenyl azide. In some embodiments, the dyed material can comprise one or more carbodiimide cross-linkers and be substantially free of, or free of, all other cross-linker types, including epoxy cross-linkers, aziridine cross-linkers, isocyanate cross-linkers, n- hydroxysuccinimide, diazirine cross-linkers, and phenyl azide. In some embodiments, thedyed material can comprise one or more isocyanate cross-linkers and be substantially free of, or free of, all other cross-linker types, including epoxy cross-linkers, aziridine crosslinkers, carbodiimide cross-linkers, n-hydroxysuccinimide, diazirine cross-linkers, and phenyl azide. In some embodiments, the dyed material can comprise n- hydroxysuccinimide and be substantially free of, or free of, all other cross-linker types, including epoxy cross-linkers, aziridine cross-linkers, carbodiimide cross-linkers, isocyanate cross-linkers, diazirine cross-linkers, and phenyl azide. In some embodiments, the dyed material can comprise one or more diazirine cross-linkers and be substantially free of, or free of, all other cross-linker types, including epoxy cross-linkers, aziridine cross-linkers, carbodiimide cross-linkers, isocyanate cross-linkers, n-hydroxysuccinimide, and phenyl azide. In some embodiments, the dyed material can comprise phenyl azide and be substantially free of, or free of, all other cross-linker types, including epoxy crosslinkers, aziridine cross-linkers, carbodiimide cross-linkers, isocyanate cross-linkers, n- hydroxysuccinimide, and diazirine cross-linkers.

[0140] Epoxy cross-linkers suitable for incorporation into the dyed material, dyeing formulations, and protein formulations include, but are not limited to, a diglycidyl ether or a polyglycidyl ether, and combinations thereof. Exemplary diglycidyl ethers include, but are not limited to, glycerol diglycidyl ether, polyglycerol diglycidyl ether, trimethylolpropane diglycidyl ether, polyoxypropylene glycol diglycidyl ether, resorcinol diglycidyl ether, isosorbide diglycidyl ether, polypropylene glycol) diglycidyl ether, and ethylene glycol diglycidyl ether. Exemplary polyglycidyl ethers include, but are not limited to, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, glycerol triglycidyl ether, sorbitol polyglycidyl ether, alkoxylated glycerol polyglycidyl ether, trimethylolpropane triglycidyl ether, and pentaerythritol tetraglycidyl ether.

[0141] Aziridine cross-linkers suitable for incorporation into the dyed material, dyeing formulations, and protein formulations include, but are not limited to aziridine functionalized branched polyester cross-linkers and polyfunctional aziridines. WH- PZ5150, available from An Fong Development Co., Ltd is an exemplary aziridine functionalized branched polyester cross-linker. PZ-28 Poly functional Aziridine (a propylene imine based tri-functional polyaziridine) and PZ-33 Polyfunctional Aziridine (an ethylene imine based tri-functional polyaziridine), both available from Poly Aziridine LLC, are exemplary polyfunctional aziridines.

[0142] Carbodiimide cross-linkers suitable for incorporation into the dyed material, dyeing formulations, and protein formulations include, but are not limited to l-Ethyl-3- (3 -dimethylaminopropyl) carbodiimide (available from Sigma-Aldrich), and PERMUTEX® XR-5577 (available from Stahl).

[0143] Isocyanate cross-linkers suitable for incorporation into the dyed material, dyeing formulations, and protein formulations include, but are not limited to PERMUTEX® XR- 5588 (available from Stahl), XR-13-820 (available from Stahl), and AM-1506XL (available from Quaker Color, a division of McAdoo & Allen, Inc.).

[0144] Diazirine cross-linkers suitable for incorporation into the dyed material, dyeing formulations, and protein formulations include, but are not limited to succinimidyl 4,4'- azipentanoate, succinimidyl 2-((4,4'-azipentanamido)ethyl)-l,3'-dithiopropionate, and succinimidyl 6-(4,4'-azipentanamido)hexanoate (all available from Thermo-Fisher Scientific).

[0145] In some embodiments, the dyed material can comprise one or more antimicrobial agents. The antimicrobial agent can comprise one or more of a sodium organic salt, a copper organic salt, a zinc organic salt, a silver organic salt, or a combination thereof. Suitable examples of an antimicrobial agent are example Ultra-Fresh DW-56 (an aqueous antimicrobial dispersion) and AGION® (a metal-based antimicrobial agent available from Sciessent).

[0146] Textile dyeing formulations described herein can comprise water, one or more proteins, one or more cross-linkers, and one or more dyes. Suitable proteins, crosslinkers, and dyes are described above. As described below, cross-linker(s), dye(s), and any other component of the textile dyeing formulations can be present in the formulation at a wt% relative to the one or more proteins in the formulation. This means the wt% of the component is measured relative to the amount of the protein(s) in the formulation. For example, for a formulation comprising 10 grams of protein and 10 grams of dye, the dye is present at 100 wt%. As another example, for a formulation comprising 10 grams of protein, five grams of a first dye, and five grams of a second dye, the dyes are present at 100 wt% (with each individual dye being present at 50 wt%).

[0147] In some embodiments, the textile dyeing formulation can comprise a single crosslinker. In some embodiments, the textile dyeing formulation can comprise a plurality of cross-linkers. In some embodiments, the textile dyeing formulation can comprise aplurality of epoxy cross-linkers. In some embodiments, the textile dyeing formulation can comprise a plurality of aziridine cross-linkers. In some embodiments, the textile dyeing formulation can comprise a plurality of carbodiimide cross-linkers. In some embodiments, the textile dyeing formulation comprise a plurality of isocyanate crosslinkers. In some embodiments, the textile dyeing formulation can comprise a plurality of diazirine cross-linkers.

[0148] In some embodiments, the textile dyeing formulation can comprise an aziridine cross-linker. In some embodiments, the textile dyeing formulation can comprise an epoxy cross-linker. In some embodiments, the textile dyeing formulation can comprise (a) a first cross-linker selected from the group consisting of an epoxy cross-linker, an aziridine cross-linker, a carbodiimide cross-linker, an isocyanate cross-linker, n- hydroxysuccinimide, a diazirine cross-linker, and phenyl azide, and (b) a second crosslinker that is different than the first cross-linker and is selected from the group consisting of an epoxy cross-linker, an aziridine cross-linker, a carbodiimide cross-linker, an isocyanate cross-linker, n-hydroxysuccinimide, a diazirine cross-linker, and phenyl azide. In some embodiments, the first cross-linker can be an epoxy cross-linker and the second cross-linker can be an aziridine cross-linker. In some embodiments, the textile dyeing formulation can comprise at least three cross-linkers, with each cross-linker being a different cross-linker selected from the group consisting of an epoxy cross-linker, an aziridine cross-linker, a carbodiimide cross-linker, an isocyanate cross-linker, n- hydroxysuccinimide, a diazirine cross-linker, and phenyl azide.

[0149] In some embodiments, the textile dyeing formulation can comprise a single aziridine cross-linker. In some embodiments, the textile dyeing formulation can comprise a single epoxy cross-linker. In some embodiments, the textile dyeing formulation can comprise a single carbodiimide cross-linker. In some embodiments, the textile dyeing formulation can comprise a single isocyanate cross-linker. In some embodiments, the textile dyeing formulation can comprise a single diazirine cross-linker.

[0150] In some embodiments, the textile dyeing formulation can comprise only a single cross-linker type. In some embodiments, the textile dyeing formulation can comprise only a single cross-linker type and be substantially free of, or free of, all other cross-linker types.

[0151] In some embodiments, the textile dyeing formulation can comprise one or more aziridine cross-linkers and be substantially free of, or free of, all other cross-linker types, including epoxy cross-linkers, carbodiimide cross-linkers, isocyanate cross-linkers, n- hydroxysuccinimide, diazirine cross-linkers, and phenyl azide. In some embodiments, the textile dyeing formulation can comprise one or more epoxy cross-linkers and be substantially free of, or free of, all other cross-linker types, including aziridine crosslinkers, carbodiimide cross-linkers, isocyanate cross-linkers, n-hydroxysuccinimide, diazirine cross-linkers, and phenyl azide. In some embodiments, the textile dyeing formulation can comprise one or more carbodiimide cross-linkers and be substantially free of, or free of, all other cross-linker types, including epoxy cross-linkers, aziridine cross-linkers, isocyanate cross-linkers, n-hydroxysuccinimide, diazirine cross-linkers, and phenyl azide. In some embodiments, the textile dyeing formulation can comprise one or more isocyanate cross-linkers and be substantially free of, or free of, all other cross-linker types, including epoxy cross-linkers, aziridine cross-linkers, carbodiimide cross-linkers, n-hydroxysuccinimide, diazirine cross-linkers, and phenyl azide. In some embodiments, the textile dyeing formulation can comprise n-hydroxysuccinimide and be substantially free of, or free of, all other cross-linker types, including epoxy cross-linkers, aziridine cross-linkers, carbodiimide cross-linkers, isocyanate cross-linkers, diazirine cross-linkers, and phenyl azide. In some embodiments, the textile dyeing formulation can comprise one or more diazirine cross-linkers and be substantially free of, or free of, all other crosslinker types, including epoxy cross-linkers, aziridine cross-linkers, carbodiimide crosslinkers, isocyanate cross-linkers, n-hydroxysuccinimide, and phenyl azide. In some embodiments, the textile dyeing formulation can comprise phenyl azide and be substantially free of, or free of, all other cross-linker types, including epoxy cross-linkers, aziridine cross-linkers, carbodiimide cross-linkers, isocyanate cross-linkers, n- hydroxysuccinimide, and diazirine cross-linkers.

[0152] In some embodiments, the one or more cross-linkers can be present in the dyeing formulation at a total weight percent ranging from greater than or equal to about 5 wt% to less than or equal to about 90 wt% relative to the one or more proteins in the formulation, including subranges. For example, relative to the one or more proteins in the formulation, the one or more cross-linkers can be present in the dyeing formulation at a total weight percent ranging from greater than or equal to about 5 wt% to less than or equal to about90 wt%, from greater than or equal to about 10 wt% to less than or equal to about 90 wt%, from greater than or equal to about 15 wt% to less than or equal to about 90 wt%, from greater than or equal to about 20 wt% to less than or equal to about 90 wt%, from greater than or equal to about 25 wt% to less than or equal to about 90 wt%, from greater than or equal to about 30 wt% to less than or equal to about 90 wt%, from greater than or equal to about 35 wt% to less than or equal to about 90 wt%, from greater than or equal to about 40 wt% to less than or equal to about 90 wt%, from greater than or equal to about 45 wt% to less than or equal to about 90 wt%, from greater than or equal to about 50 wt% to less than or equal to about 90 wt%, from greater than or equal to about 55 wt% to less than or equal to about 90 wt%, from greater than or equal to about 60 wt% to less than or equal to about 90 wt%, from greater than or equal to about 65 wt% to less than or equal to about 90 wt%, from greater than or equal to about 70 wt% to less than or equal to about 90 wt%, from greater than or equal to about 75 wt% to less than or equal to about 90 wt%, from greater than or equal to about 80 wt% to less than or equal to about 90 wt%, from greater than or equal to about 5 wt% to less than or equal to about 85 wt%, from greater than or equal to about 5 wt% to less than or equal to about 80 wt%, from greater than or equal to about 5 wt% to less than or equal to about 75 wt%, from greater than or equal to about 5 wt% to less than or equal to about 70 wt%, from greater than or equal to about 5 wt% to less than or equal to about 65 wt%, from greater than or equal to about 5 wt% to less than or equal to about 60 wt%, from greater than or equal to about 5 wt% to less than or equal to about 55 wt%, from greater than or equal to about 5 wt% to less than or equal to about 50 wt%, from greater than or equal to about 5 wt% to less than or equal to about 45 wt%, from greater than or equal to about 5 wt% to less than or equal to about 40 wt%, from greater than or equal to about 5 wt% to less than or equal to about 35 wt%, from greater than or equal to about 5 wt% to less than or equal to about 30 wt%, from greater than or equal to about 5 wt% to less than or equal to about 25 wt%, from greater than or equal to about 5 wt% to less than or equal to about 20 wt%, or from greater than or equal to about 5 wt% to less than or equal to about 15 wt%.

[0153] In some embodiments, the one or more dyes can be present in the dyeing formulation at a total weight percent ranging from greater than or equal to about 5 wt% to less than or equal to about 200 wt% relative to the one or more proteins in the formulation, including subranges. For example, relative to the one or more proteins in theformulation, the one or more dyes can be present in the dyeing formulation at a total weight percent ranging from greater than or equal to about 5 wt% to less than or equal to about 200 wt%, from greater than or equal to about 10 wt% to less than or equal to about 200 wt%, from greater than or equal to about 20 wt% to less than or equal to about 200 wt%, from greater than or equal to about 30 wt% to less than or equal to about 200 wt%, from greater than or equal to about 40 wt% to less than or equal to about 200 wt%, from greater than or equal to about 50 wt% to less than or equal to about 200 wt%, from greater than or equal to about 60 wt% to less than or equal to about 200 wt%, from greater than or equal to about 70 wt% to less than or equal to about 200 wt%, from greater than or equal to about 80 wt% to less than or equal to about 200 wt%, from greater than or equal to about 90 wt% to less than or equal to about 200 wt%, from greater than or equal to about 100 wt% to less than or equal to about 200 wt%, from greater than or equal to about 110 wt% to less than or equal to about 200 wt%, from greater than or equal to about 120 wt% to less than or equal to about 200 wt%, from greater than or equal to about 130 wt% to less than or equal to about 200 wt%, from greater than or equal to about 140 wt% to less than or equal to about 200 wt%, from greater than or equal to about 150 wt% to less than or equal to about 200 wt%, from greater than or equal to about 5 wt% to less than or equal to about 190 wt%, from greater than or equal to about 5 wt% to less than or equal to about 180 wt%, from greater than or equal to about 5 wt% to less than or equal to about 170 wt%, from greater than or equal to about 5 wt% to less than or equal to about 160 wt%, from greater than or equal to about 5 wt% to less than or equal to about 150 wt%, from greater than or equal to about 5 wt% to less than or equal to about 140 wt%, from greater than or equal to about 5 wt% to less than or equal to about 130 wt%, from greater than or equal to about 5 wt% to less than or equal to about 120 wt%, from greater than or equal to about 5 wt% to less than or equal to about 110 wt%, from greater than or equal to about 5 wt% to less than or equal to about 100 wt%, from greater than or equal to about 5 wt% to less than or equal to about 90 wt%, from greater than or equal to about 5 wt% to less than or equal to about 80 wt%, from greater than or equal to about 5 wt% to less than or equal to about 70 wt%, from greater than or equal to about 5 wt% to less than or equal to about 60 wt%, or from greater than or equal to about 5 wt% to less than or equal to about 50 wt%.

[0154] In some embodiments, the one or more dyes present in the dyeing formulation at any of the total weight percent ranges described above can be reactive dyes. In some embodiments, the dyeing formulation can comprise two or more reactive dyes present at any of the total weight percent ranges described above. In some embodiments, the one or more dyes present in the dyeing formulation at any of the total weight percent ranges described above can be acid dyes. In some embodiments, the dyeing formulation can comprise two or more acid dyes present at any of the total weight percent ranges described above.

[0155] In some embodiments, the dyeing formulation can comprise only a single dye type. In some embodiments, the dyeing formulation can comprise only a single dye type and be substantially free of, or free of, all other dye types. In some embodiments, the dyeing formulation can comprise one or more fiber reactive dyes and be substantially free of, or free of, all other dye types, including acid dyes, natural dyes, direct dyes, and dispersed dyes. In some embodiments, the dyeing formulation can comprise one or more acid dyes and be substantially free of, or free of, all other dye types, including reactive dyes, natural dyes, direct dyes, and dispersed dyes.

[0156] In some embodiments, the dyeing formulation can comprise a plurality of different dyes of the same type. For example, in some embodiments, the dyeing formulation can comprise a plurality of different color reactive dyes or a plurality of different color acid dyes.

[0157] In some embodiments, the one or more proteins can be present in the dyeing formulation at a total weight percent ranging from greater than or equal to about 10 wt% to less than or equal to about 50 wt% relative to the water in the formulation, including subranges. For example, relative to the water in the formulation, the one or more proteins can be present in the dyeing formulation at a total weight percent ranging from greater than or equal to about 10 wt% to less than or equal to about 50 wt%, from greater than or equal to about 15 wt% to less than or equal to about 50 wt%, from greater than or equal to about 20 wt% to less than or equal to about 50 wt%, from greater than or equal to about 25 wt% to less than or equal to about 50 wt%, from greater than or equal to about 30 wt% to less than or equal to about 50 wt%, from greater than or equal to about 35 wt% to less than or equal to about 50 wt%, from greater than or equal to about 40 wt% to less than or equal to about 50 wt%, from greater than or equal to about 10 wt% to less than or equal toabout 45 wt%, from greater than or equal to about 10 wt% to less than or equal to about 40 wt%, from greater than or equal to about 10 wt% to less than or equal to about 35 wt%, from greater than or equal to about 10 wt% to less than or equal to about 30 wt%, from greater than or equal to about 10 wt% to less than or equal to about 25 wt%, or from greater than or equal to about 10 wt% to less than or equal to about 20 wt%.

[0158] In some embodiments, the dyeing formulation can comprise one or more bases or one or more acids. Suitable bases include, but are not limited to, nucleophilic bases, non- nucleophilic bases, and combination thereof. Suitable acids include, but are not limited to, Lewis acids. Sodium hydroxide is both a strong base and an exemplary nucleophilic base. Sodium bicarbonate is an exemplary non-nucleophilic base. Boric acid is an exemplary Lewis acid.

[0159] In some embodiments, the dyeing formulation can comprise a nucleophilic base present at a weight percent less than or equal to about 2 wt% relative to the one or more proteins in the formulation. In some embodiments, relative to the one or more proteins in the formulation, the dyeing formulation can comprise a nucleophilic base present at a weight percent less than or equal to about 1 wt%, from greater than or equal to about 0.1 wt% to less than or equal to about 2 wt%, from greater than or equal to about 0.5 wt% to less than or equal to about 2 wt%, or from greater than or equal to about 0.1 wt% to less than or equal to about 1 wt%.

[0160] In some embodiments, the dyeing formulation can comprise a non-nucleophilic base present at a weight percent ranging from greater than or equal to about 1 wt% to less than or equal to about 15 wt% relative to the one or more proteins in the formulation, including subranges. For example, relative to the one or more proteins in the formulation, the non-nucleophilic base can be present at a weight percent ranging from greater than or equal to about 1 wt% to less than or equal to about 15 wt%, from greater than or equal to about 5 wt% to less than or equal to about 15 wt%, from greater than or equal to about 10 wt% to less than or equal to about 15 wt%, from greater than or equal to about 1 wt% to less than or equal to about 10 wt%, or from greater than or equal to about 1 wt% to less than or equal to about 5 wt%.

[0161] In some embodiments, the dyeing formulation can comprise a Lewis acid present at a weight percent ranging from greater than or equal to about 1 wt% to less than or equal to about 15 wt% relative to the one or more proteins in the formulation, includingsubranges. For example, relative to the one or more proteins in the formulation, the Lewis acid can be present at a weight percent ranging from greater than or equal to about 1 wt% to less than or equal to about 15 wt%, from greater than or equal to about 5 wt% to less than or equal to about 15 wt%, from greater than or equal to about 10 wt% to less than or equal to about 15 wt%, from greater than or equal to about 1 wt% to less than or equal to about 10 wt%, or from greater than or equal to about 1 wt% to less than or equal to about 5 wt%.

[0162] In some embodiments, the dyeing formulation can comprise one or more surfactants. Suitable surfactants include, but are not limited to, sodium lauryl sulfate and nonionic surfactants, such as UNIFROTH® 0520 (a nonionic surfactant available from Unichem Specialty Chemicals, LLC).

[0163] In some embodiments, the dyeing formulation can comprise one or more surfactants present at a total weight percent less than or equal to about 5 wt% relative to the one or more proteins in the formulation. In some embodiments, relative to the one or more proteins in the formulation, the dyeing formulation can comprise one or more surfactants present at a total weight percent less than or equal to about 4 wt%, less than or equal to about 2 wt%, less than or equal to about 1 wt%, from greater than or equal to about 0.1 wt% to less than or equal to about 5 wt%, from greater than or equal to about 0.5 wt% to less than or equal to about 5 wt%, from greater than or equal to about 1 wt% to less than or equal to about 5 wt%, from greater than or equal to about 0.1 wt% to less than or equal to about 2 wt%, or from greater than or equal to about 0.1 wt% to less than or equal to about 1 wt%. In some embodiments, the dyeing formulation can comprise sodium lauryl sulfate present at a weight percent of about 1 wt%.

[0164] In some embodiments, the dyeing formulation can comprise one or more surfactants present at a total weight percent less than or equal to about 50 wt% relative to the one or more proteins in the formulation. In some embodiments, relative to the one or more proteins in the formulation, the dyeing formulation can comprise one or more surfactants present at a total weight percent from greater than or equal to about 0.1 wt% to less than or equal to about 50 wt%, from greater than or equal to about 1 wt% to less than or equal to about 50 wt%, from greater than or equal to about 10 wt% to less than or equal to about 50 wt%, from greater than or equal to about 15 wt% to less than or equal to about 50 wt%, or from greater than or equal to about 20 wt% to less than or equal toabout 50 wt%. In some embodiments, the dyeing formulation can comprise sodium lauryl sulfate present at a weight percent of about 10 wt%.

[0165] In some embodiments, the dyeing formulation can comprise one or more plasticizers. In some embodiments, the dyeing formulation can comprise one or more plasticizers present at a total weight percent less than or equal to about 60 wt% relative to the one or more proteins in the formulation. In some embodiments, relative to the one or more proteins in the formulation, the dyeing formulation can comprise one or more plasticizers present at a total weight percent less than or equal to about 50 wt%, less than or equal to about 40 wt%, less than or equal to about 30 wt%, less than or equal to about 20 wt%, less than or equal to about 10 wt%, from greater than or equal to about 1 wt% to less than or equal to about 60 wt%, from greater than or equal to about 1 wt% to less than or equal to about 50 wt%, from greater than or equal to about 1 wt% to less than or equal to about 40 wt%, from greater than or equal to about 1 wt% to less than or equal to about 30 wt%, from greater than or equal to about 1 wt% to less than or equal to about 20 wt%, or from greater than or equal to about 1 wt% to less than or equal to about 10 wt%.

[0166] In some embodiments, the one or more plasticizers can comprise glycerol, propylene glycol, sorbitol, polyol polymers, or a combination thereof. Suitable polyol polymers comprise polyethylene glycol (PEG) and polypropylene glycol (PPG).

[0167] In some embodiments, the dyeing formulation can comprise one or more denaturants. Suitable denaturants include, but are not limited to, urea, guanidine hydrochloride, and a combination thereof.

[0168] In some embodiments, the dyeing formulation can comprise one or more denaturants present at a total weight percent ranging from greater than or equal to about 1 wt% to less than or equal to about 200 wt% relative to the one or more proteins in the formulation. In some embodiments, relative to the one or more proteins in the formulation, the dyeing formulation can comprise one or more denaturants present at a total weight percent from greater than or equal to about 5 wt% to less than or equal to about 200 wt%, from greater than or equal to about 10 wt% to less than or equal to about 200 wt%, from greater than or equal to about 25 wt% to less than or equal to about 200 wt%, from greater than or equal to about 50 wt% to less than or equal to about 200 wt%, from greater than or equal to about 75 wt% to less than or equal to about 200 wt%, from greater than or equal to about 100 wt% to less than or equal to about 200 wt%, fromgreater than or equal to about 150 wt% to less than or equal to about 200 wt%, from greater than or equal to about 1 wt% to less than or equal to about 150 wt%, from greater than or equal to about 1 wt% to less than or equal to about 100 wt%, from greater than or equal to about 1 wt% to less than or equal to about 75 wt%, from greater than or equal to about 1 wt% to less than or equal to about 50 wt%, from greater than or equal to about 1 wt% to less than or equal to about 25 wt%, or from greater than or equal to about 1 wt% to less than or equal to about 10 wt%.

[0169] In some embodiments, the dyeing formulation can comprise one or more binding agents. In some embodiments, the one or more binding agents can selected from the group consisting of polyacrylic acid, polyacrylamide, sodium alginate, and combinations thereof.

[0170] In some embodiments, the dyeing formulation can comprise one or more binding agents present at a total weight percent less than or equal to about 10 wt% relative to the one or more proteins in the formulation. In some embodiments, relative to the one or more proteins in the formulation, the dyeing formulation can comprise one or more binding agents present at a total weight percent less than or equal to about 8 wt%, less than or equal to about 6 wt%, less than or equal to about 5 wt%, less than or equal to about 4 wt%, less than or equal to about 2 wt%, from greater than or equal to about 1 wt% to less than or equal to about 10 wt%, from greater than or equal to about 1 wt% to less than or equal to about 8 wt%, from greater than or equal to about 1 wt% to less than or equal to about 6 wt%, from greater than or equal to about 1 wt% to less than or equal to about 5 wt%, from greater than or equal to about 1 wt% to less than or equal to about 4 wt%, or from greater than or equal to about 1 wt% to less than or equal to about 2 wt%.

[0171] In some embodiments, the dyeing formulation can comprise one or more antimicrobial agents. The antimicrobial agent can comprise one or more of a sodium organic salt, a copper organic salt, a zinc organic salt, a silver organic salt, or a combination thereof. Exemplary antimicrobial agents include Ultra-Fresh DW-56 and AGION®.

[0172] In some embodiments, the dyeing formulation can comprise one or more antimicrobial agents present at a total weight percent less than or equal to about 5 wt% relative to the one or more proteins in the formulation. In some embodiments, relative to the one or more proteins in the formulation, the dyeing formulation can comprise one ormore antimicrobial agents present at a total weight percent less than or equal to about 4 wt%, less than or equal to about 2 wt%, from greater than or equal to about 0.1 wt% to less than or equal to about 5 wt%, from greater than or equal to about 0.1 wt% to less than or equal to about 4 wt%, or from greater than or equal to about 0.1 wt% to less than or equal to about 2 wt%.

[0173] In some embodiments, the dyeing formulation can comprise one or more radical initiators. In some embodiments, the one or more radical initiators can be a peroxide radical initiator. Suitable radical initiators include, but are not limited to, LUPEROX® A98 (an anhydrous benzoyl peroxide powder), LUPEROX® DCP (dicumyl peroxide), LUPEROX® LP (dilauroyl peroxide), LUPEROX® DI (tert-Butyl peroxide), LUPEROX® 101 (2,5-Bis(tert-butylperoxy)-2,5-dimethylhexane), LUPEROX® TBH (tert-Butyl hydroperoxide solution), PERKADOX® 14 (Di(tert-butylperoxyisopropyl) benzene), and PERKADOX® PM (Di(4-methylbenzoyl) peroxide).

[0174] In some embodiments, the dyeing formulation can comprise one or more radical initiators present at a total weight percent less than or equal to about 5 wt% relative to the one or more proteins in the formulation. In some embodiments, relative to the one or more proteins in the formulation, the dyeing formulation can comprise one or more radical initiators present at a total weight percent less than or equal to about 4 wt%, less than or equal to about 2 wt%, from greater than or equal to about 0.1 wt% to less than or equal to about 5 wt%, from greater than or equal to about 0.1 wt% to less than or equal to about 4 wt%, or from greater than or equal to about 0.1 wt% to less than or equal to about 2 wt%.

[0175] In some embodiments, the dyeing formulation can comprise one or more wetting agents. Suitable wetting agents can be anionic, cationic, amphoteric, or nonionic. Exemplary wetting agents include, but are not limited to, Uniwet 0371 (65-75%, a sulfonated diester blend available from UniChem Specialty Chemicals, LLC).

[0176] In some embodiments, the dyeing formulation can comprise one or more wetting agents present at a total weight percent less than or equal to about 5 wt% relative to the one or more proteins in the formulation. In some embodiments, relative to the one or more proteins in the formulation, the dyeing formulation can comprise one or more wetting agents present at a total weight percent less than or equal to about 4 wt%, less than or equal to about 2 wt%, from greater than or equal to about 0.1 wt% to less than orequal to about 5 wt%, from greater than or equal to about 0.1 wt% to less than or equal to about 4 wt%, or from greater than or equal to about 0.1 wt% to less than or equal to about 2 wt%.

[0177] Protein formulations used to dye a textile as described herein can comprise water, one or more proteins, and one or more cross-linkers. Suitable proteins and cross-linkers are described above. As described below, cross-linker(s) and any other component of the protein formulations can be present in the formulation at a wt% relative to the one or more proteins in the formulation.

[0178] In some embodiments, the protein formulation can comprise a single cross-linker. In some embodiments, the protein formulation can comprise a plurality of cross-linkers as described above for the textile dyeing formulation. Relative to the one or more proteins in the formulation, the one or more cross-linkers can be present in the protein formulation at a total weight percent within any of the same ranges described above for the textile dyeing formulation.

[0179] Relative to the water in the protein formulation, the one or more proteins can be present in the formulation at a total weight percent within any of the same ranges described above for the textile dyeing formulation.

[0180] In some embodiments, the protein formulation can comprise one or more bases. Suitable bases for the protein formulation comprise the same bases described above for the textile dyeing formulation. Relative to the one or more proteins in the formulation, the one or more bases can be present in the protein formulation at a weight percent within any of the same ranges described above for the textile dyeing formulation.

[0181] In some embodiments, the protein formulation can comprise one or more surfactants. Suitable surfactants for the protein formulation comprise the same surfactants described above for the textile dyeing formulation. Relative to the one or more proteins in the formulation, the one or more surfactants can be present in the protein formulation at a total weight percent within any of the same ranges described above for the textile dyeing formulation.

[0182] In some embodiments, the protein formulation can comprise one or more plasticizers. Suitable plasticizers for the protein formulation comprise the same plasticizers described above for the textile dyeing formulation. Relative to the one or more proteins in the formulation, the one or more plasticizers can be present in the proteinformulation at a total weight percent within any of the same ranges described above for the textile dyeing formulation.

[0183] In some embodiments, the protein formulation can comprise one or more denaturants. Suitable denaturants for the protein formulation comprise the same denaturants described above for the textile dyeing formulation. Relative to the one or more proteins in the formulation, the one or more denaturants can be present in the protein formulation at a total weight percent within any of the same ranges described above for the textile dyeing formulation.

[0184] In some embodiments, the protein formulation can comprise one or more binding agents. Suitable binding agents for the protein formulation comprise the same binding agents described above for the textile dyeing formulation. Relative to the one or more proteins in the formulation, the one or more binding agents can be present in the protein formulation at a total weight percent within any of the same ranges described above for the textile dyeing formulation.

[0185] In some embodiments, the protein formulation can comprise one or more antimicrobial agents. Suitable antimicrobial agents for the protein formulation comprise the same antimicrobial agents described above for the textile dyeing formulation. Relative to the one or more proteins in the formulation, the one or more antimicrobial agents can be present in the protein formulation at a total weight percent within any of the same ranges described above for the textile dyeing formulation.

[0186] In some embodiments, the protein formulation can comprise one or more radical initiators. Suitable radical initiators for the protein formulation comprise the same radical initiators described above for the textile dyeing formulation. Relative to the one or more proteins in the formulation, the one or more radical initiators can be present in the protein formulation at a total weight percent within any of the same ranges described above for the textile dyeing formulation.

[0187] In some embodiments, the protein formulation can comprise one or more wetting agents. Suitable wetting agents for the protein formulation comprise the same wetting agents described above for the textile dyeing formulation. Relative to the one or more proteins in the formulation, the one or more wetting agents can be present in the protein formulation at a total weight percent within any of the same ranges described above for the textile dyeing formulation.

[0188] In some embodiments, the dyeing formulations and protein formulations described herein can be substantially free of polyurethane. In some embodiments, the protein and dye combination cross-linked to the dyed textiles described herein can be substantially free of polyurethane. In some embodiments, the dyeing formulations and protein formulations can be free of polyurethane. In some embodiments, the protein and dye combination cross-linked to the dyed textiles described herein can be free of polyurethane.

[0189] To make an aqueous textile dyeing formulation or protein formulation described herein, one or more proteins can be dispersed or dissolved in an aqueous solution and blended with one or more cross-linkers, one or more dyes, or both.

[0190] Suitable aqueous solutions include, but are not limited to, water, an aqueous alkali solution, or urea solution, and mixtures thereof.

[0191] During or after blending the one or more proteins with the one or more crosslinkers, the one or more dyes, or both, additional additives can be blended into the textile dyeing formulation or protein formulation. These additional additives include, but at not limited to, the surfactants, plasticizers, denaturants, binding agents, antimicrobial agents, and radial initiators described herein.

[0192] In some embodiments, the blending temperature for an aqueous textile dyeing formulation or protein formulation can range from about 18 °C to about 90 °C, including subranges. For example, the blending temperature can range from greater than or equal to about 18 °C to less than or equal to about 80 °C, from greater than or equal to about 18 °C to less than or equal to about 70 °C, from greater than or equal to about 18 °C to less than or equal to about 60 °C, from greater than or equal to about 18 °C to less than or equal to about 50 °C, from greater than or equal to about 18 °C to less than or equal to about 40 °C, or greater than or equal to from about 18 °C to less than or equal to about 30 °C.

[0193] The textile dyeing formulation or protein formulation can be applied to a textile using any suitable application technique, including but not limiting to spray coating, dip coating, or pouring. In some embodiments, a foamed textile dyeing formulation or protein formulation can be applied to a textile using any suitable application technique, including but not limiting to spray coating, dip coating, or pouring.

[0194] After applying the formulation to a textile, solvent (for example, water) can be removed from the formulation in a drying step, a curing step, or both. Suitable solventremoval methods include, but are not limited to tunnel drying or curing, vacuum drying or curing, oven drying or curing with hot air, humidity chamber drying or curing, flotation drying or curing with hot air, and ovens with a combination of medium range IR (infrared) for preheating and then hot air for subsequent drying or curing.

[0195] Suitable drying temperatures can range from about 18 °C to about 140 °C, including subranges. For example, in some embodiments, drying can be performed at a temperature ranging from greater than or equal to about 18 °C to less than or equal to about 130 °C, from greater than or equal to about 18 °C to less than or equal to about 120 °C, from greater than or equal to about 18 °C to less than or equal to about 110 °C, from greater than or equal to about 18 °C to less than or equal to about 100 °C, from greater than or equal to about 18 °C to less than or equal to about 90 °C, from greater than or equal to about 18 °C to less than or equal to about 80 °C, from greater than or equal to about 18 °C to less than or equal to about 70 °C, from greater than or equal to about 18 °C to less than or equal to about 60 °C, or from greater than or equal to about 18 °C to less than or equal to about 50 °C.

[0196] Suitable curing temperatures can range from greater than or equal to about 100 °C to about less than or equal to 250 °C, including subranges. For example, in some embodiments, curing can be performed at a temperature ranging from greater than or equal to about 100 °C to less than or equal to about 250 °C, from greater than or equal to about 120 °C to less than or equal to about 250 °C, from greater than or equal to about 140 °C to less than or equal to about 250 °C, from greater than or equal to about 160 °C to less than or equal to about 250 °C, from greater than or equal to about 180 °C to less than or equal to about 250 °C, from greater than or equal to about 200 °C to less than or equal to about 250 °C, from greater than or equal to about 160 °C to less than or equal to about 240 °C, from greater than or equal to about 160 °C to less than or equal to about 220 °C, from greater than or equal to about 180 °C to less than or equal to about 220 °C, or from greater than or equal to about 200 °C to less than or equal to about 220 °C.

[0197] In some embodiments, a textile dyeing formulation as described herein can be applied to a textile and the textile dyeing formulation can be dried and cured on the textile to form the dyed material described herein. In some embodiments, the textile dyeing formulation can be dried on the textile before curing.

[0198] In some embodiments, a protein formulation as described herein can be applied to a textile and dried on the textile. Without wishing to be bound by a particular theory, it is believed that drying the protein formulation may partially cure the formulation on the textile to form at least a partially cross-linked textile. Then, after drying, one or more dyes can be applied to the dried protein formulation to bond the one or more dyes to the dried material, thereby forming a dyed textile. In some embodiments, after application of the one or more dyes, the dyed textile can be cured to form the dyed material described herein.

[0199] In some embodiments, drying the protein formulation on the textile before application of the one or more dyes can comprise drying and curing the protein formulation on the textile to form a cross-linked textile. Then, in such embodiments, after drying and curing, the one or more dyes can be applied to the protein formulation to bond the one or more dyes to fibers comprising hydroxyl functional groups, the one or more cross-linkers, the one or more proteins, or a combination thereof, and thereby form a dyed textile material.

[0200] The dyed materials described herein can be used in a variety of applications. For example, the materials can be used in footwear, garments, gloves, furniture, vehicle upholstery, and other good and products, such as overcoats, coats, jackets, shirts, trousers, pants, shorts, swimwear, undergarments, uniforms, emblems or letters, costumes, ties, skirts, dresses, blouses, leggings, gloves, mittens, shoes, shoe components such as sole, quarter, tongue, cuff, welt, and counter, dress shoes, athletic shoes, running shoes, casual shoes, athletic, running or casual shoe components such as toe cap, toe box, outsole, midsole, upper, laces, eyelets, collar, lining, Achilles notch, heel, and counter, fashion or women’s shoes and their shoe components such as upper, outer sole, toe spring, toe box, decoration, vamp, lining, sock, insole, platform, counter, and heel or high heel, boots, sandals, buttons, sandals, hats, masks, headgear, headbands, head wraps, and belts; jewelry such as bracelets, watch bands, and necklaces; gloves, umbrellas, walking sticks, wallets, mobile phone or wearable computer coverings, purses, backpacks, suitcases, handbags, folios, folders, boxes, and other personal objects; athletic, sports, hunting or recreational gear such as harnesses, bridles, reins, bits, leashes, mitts, tennis rackets, golf clubs, polo, hockey, or lacrosse gear, chessboards and game boards, medicine balls, kick balls, baseballs, and other kinds of balls, and toys; book bindings, book covers, pictureframes or artwork; furniture and home, office or other interior or exterior furnishings including chairs, sofas, doors, seats, ottomans, room dividers, coasters, mouse pads, desk blotters, or other pads, tables, beds, floor, wall or ceiling coverings, flooring, automobile, boat, aircraft and other vehicular products including seats, headrests, upholstery, paneling, steering wheel joystick or control coverings and other wraps or coverings.

[0201] In some embodiments, the dyed textile materials described herein can have a wet crocking value of greater than or equal to 2.5, greater than or equal to 3, greater than or equal to 3.5, or greater than or equal to 4. Unless specified otherwise, the wet crocking value for a dyed textile material described herein is measured according to ISO 105-X12 (Textiles - Tests for Color Fastness - Part X12: Color Fastness to Rubbing). In some embodiments, the dyed textile materials described herein can have a perspiration fastness of greater than or equal to 3, greater than or equal to 3.5, or greater than or equal to 4. Unless specified otherwise, the perspiration fastness value for a dyed textile material described herein is measured according to ISO 105-X12 (Textiles - Tests for Color Fastness - Part X12: Color Fastness to Rubbing). The dyed textile materials can achieve these properties while also providing a high degree of color levelness and color uniformity.

[0202] The embodiments discussed herein will be further clarified in the following examples. It should be understood that these examples are not limiting to the embodiments described above.General Procedures:

[0203] In the following examples, ISO 105-X12 was used to measure wet crocking, which evaluates color migration of dyed and washed fabrics under wet-abrasion conditions. A James Heal crockmaster was used to measure wet crocking values. ISO 105: E04 was used to measure perspiration fastness, which evaluates the color migration of dyed fabrics in the presence of human perspiration. To evaluate color saturation, K / S values were measured using a Hunter Lab ULTRASCAN® PRO.

[0204] In the following examples, unless specified otherwise, textile substrates are cured according to the following process: 1) the textile substrate was dried at 80 °C for 5 minutes; and 2) the textile substrate was cured at 210 °C for 5 minutes.

[0205] Further, unless specified otherwise, textile substrates were washed according to the following process: 1) excess dye was washed off the textile substrate by washingwith an aqueous laundry detergent solution at 95 °C for 20 minutes; and 2) the textile was dried at 80 °C for 15 minutes. The concentration of detergent in the solution was 4 g detergent per liter of water.

[0206] Unless specified otherwise, dyeing formulations applied to a textile substrate by dipping, were applied according to the following process: 1) the textile substrate was dipped into the dyeing formulation at room temperature; 2) the textile was removed from the dyeing formulation and squeezed between two rollers with a four-pound weight applied; 3) the textile was dried at 80 °C. The pressure applied with the four-point weight was selected to achieve a final dry weight pick-up of greater than or equal to 3% and less than or equal to 10%. It should be appreciated that the weight applied to achieve a final dry between 3% and 10% may vary depending on at least the equipment used to squeeze the textile and the viscosity of the dyeing formulation.

[0207] Unless specified otherwise, dyeing formulations applied to a textile substrate by foam application, were applied according to the following process: 1) the dyeing formulation was poured into a foam applicator; 2) the dyeing formulation was foamed to a density of 100 g / L in the foam applicator; and 3) the foamed formulation was applied to the textile substrate. The parameter inputs for the foam applicator were selected to apply the dyeing formulation at a wet pick-up of about 30%, which is measured before any drying or washing steps are performed on the dyed textile.

[0208] Unless specified otherwise, the following materials were used in the examples. The soy protein isolate (SPI) used for each example was SUPRO® XT 221D-IP; made by DuPont; available from Solae LLC. The cotton-polyester blend textile substrate used for each example was a 9-inch by 12-inch piece of cotton-polyester blend with 120 grams per square meter (gsm) cotton and 120 gsm polyester. The reactive red 1126 dye was NOVACRON® Deep Red EC-D from Huntsman International LLC. The reactive blue 1143 dye was Reactive Blue LX from B. A. Special Chem & Color S.r.l. The reactive yellow 1154 dye was Reactive Yellow ED-R from B.A. Special Chem & Color S.r.l.EXAMPLE 1 : Control - Protein without Cross-linker

[0209] 220 g of water and 1100 pl of sodium hydroxide (10 N) were added to a flask to prepare a caustic solution. After the caustic solution was prepared, 33 g of SPI, 2.56 g of reactive red 1126 dye, 2.48 g of reactive blue 1143 dye, and 11.47 g of reactive yellow1154 dye were added to the flask and mixed thoroughly to create a dyeing formulation. The formulation was then diluted 2: 1 (v:v) with water. After dilution, the dyeing formulation was applied to two cotton-polyester blend textile substrates by dipping according to the general procedure described above.

[0210] The textile substrates were then cured according to the general procedure described above. After curing, the textile substrates were washed according to the general procedure described above. The resulting dyed textile substrates had an average wet crocking value of 2 and an average perspiration fastness value of 4.5.EXAMPLE 2: Control - Epoxy Cross-linker without Protein

[0211] 220 g of water and 1100 pl of sodium hydroxide (10N) were added to a flask to prepare a caustic solution. After the caustic solution was prepared, 2.56 g of reactive red 1126 dye, 2.48 g of reactive blue 1143 dye, and 11.47 g of reactive yellow 1154 dye were added to the flask and mixed thoroughly to create a dyeing formulation. Then, 6.6 g of DENACOL® 614B (sorbitol polyglycidyl ether cross-linker, >99%, available from Nagase ChemteX Corporation) was added to the flask and mixed. The formulation was then diluted 2: 1 (v:v) with water. After dilution, the dyeing formulation was applied to two cotton-polyester blend textile substrates by dipping according to the general procedure described above.

[0212] The textile substrates were then cured according to the general procedure described above. After curing, the textile substrates were washed according to the general procedure described above. The resulting dyed textile substrates had an average wet crocking value of 3 and an average perspiration fastness value of 4.5.EXAMPLE 3: Control - Aziridine Cross-linker without Protein

[0213] 220 g of water and 1100 pl of sodium hydroxide (10N) were added to a flask and mixed to prepare a caustic solution. After the caustic solution is prepared, 2.56 g of reactive red 1126 dye, 2.48 g of reactive blue 1143 dye, and 11.47 g of reactive yellow 1154 dye were added to the flask and mixed thoroughly to create a dyeing formulation. Then, 3.3 g of WH-PZ5150 (an aziridine functionalized branched polyester cross-linker, available from An Fong Development Co., Ltd.) was added to the flask and mixed. Theformulation was then diluted 2: 1 (v:v) with water. After dilution, the dyeing formulation was applied two to cotton-polyester blend textile substrates by dipping according to the general procedure described above.

[0214] The textile substrates were then cured according to the general procedure described above. After curing, the textile substrates were washed according to the general procedure described above. The resulting dyed textile substrates had an average wet crocking value of 4 and an average perspiration fastness value of 4.EXAMPLE 4: Control - Dye Only

[0215] 100 g of water and 2.5 g of reactive blue 1143 dye were added to a flask and thoroughly mixed until the dye was fully dispersed. After mixing, the dye mixture was applied to two cotton-polyester blend textile substrates by dipping according to the general procedure described above.

[0216] The textile substrates were then cured according to the general procedure described above. After curing, the textile substrates were washed according to the general procedure described above. The resulting dyed textile substrates had an average wet crocking value of 2.5, an average perspiration fastness value of 2, and an average K / S value of 1.25 at -630 nm.EXAMPLE 5 : Control - Dye & Salts

[0217] 100 g of water, two g of sodium bicarbonate, and six g of sodium sulfate decahydrate were added to a flask and mixed to prepare a salt solution. After the salt solution was prepared, 2.5 g of reactive blue 1143 dye was added to the flask and the mixture was thoroughly mixed until the dye was fully dispersed. After mixing, the dye mixture was applied to two cotton-polyester blend textile substrates by dipping according to the general procedure described above.

[0218] The textile substrates were then cured according to the general procedure described above. After curing, the textile substrates were washed according to the general procedure described above. The resulting dyed textile substrates had an average wet crocking value of 3, an average perspiration fastness value of 2.5, and an average K / S value of 5.56 at -630 nm.EXAMPLE 6: Protein, Aziridine Cross-linker, and Dye

[0219] 200 g of water and 0.3 g of sodium hydroxide were added to a flask and mixed to prepare a caustic solution. After the caustic solution was prepared, 27.1 g of SPI, 2.11 g of reactive red 1126 dye, 2.04 g of reactive blue 1143 dye, and 9.45 g of reactive yellow 1154 dye were added to the flask and mixed thoroughly. Then, 2.7 g of WH-PZ5150 was added to the flask mixed to create a dyeing formulation.

[0220] The dyeing formulation was then diluted 2: 1 (v:v) with water. After dilution, the dyeing solution was applied to two cotton-polyester blend textile substrates by dipping according to the general procedure described above, expect an eight-pound weight was used in place of the four-pound weight. The textile substrates were then cured according to the general procedure described above. After curing, the textile substrates were washed according to the general procedure described above.

[0221] Visually, the resulting dyed textile substrates exhibited superior color levelness and color uniformity compared to Examples 1-5. The resulting dyed textile substrates had an average wet crocking value of 2.5 and an average K / S value of 9.48 at -425 nm.EXAMPLE 7 : Protein, Urea, Aziridine Cross-linker, and Dye

[0222] 80 g of water and 20 g of urea were added to a flask and mixed to prepare a solution. After the solution was prepared, 18 g of SPI, 1.51 g of reactive red 1126 dye, 1.5 g of reactive blue 1143 dye, and 6.95 g of reactive yellow 1154 dye were added to the flask and mixed thoroughly. Then, 1.8 g of WH-PZ5150 was added to the flask and mixed to create a dyeing formulation.

[0223] The dyeing formulation was then diluted 2: 1 (v:v) with water. After dilution, the dyeing formulation was applied to two cotton-polyester blend textile substrates by dipping according to the general procedure described above. The textile substrates were then cured according to the general procedure described above. After curing, the textile substrates were washed according to the general procedure described above.

[0224] Visually, the resulting dyed textile substrates exhibited superior color levelness and color uniformity compared to Examples 1-5. The resulting dyed textile substrates had a wet crocking value between 3 and 4.5.EXAMPLE 8: Protein, Epoxy Cross-linker, Aziridine Cross-linker, Dye, and Surfactant

[0225] 20 g of water and 0.3 g of sodium hydroxide were added to a flask and mixed to prepare a caustic solution. After the caustic solution was prepared, 30 g of SPI and 13.7 g of reactive blue 1143 dye were added to the flask and mixed thoroughly. Then, six g of DENACOL® 614B (sorbitol polyglycidyl ether cross-linker, >99%, available from Nagase ChemteX Corporation), three g of WH-PZ5150, and six grams of UNIFROTH® 0520 (a nonionic surfactant available from Unichem Specialty Chemicals, LLC) were added to the flask and mixed to create a dyeing formulation.

[0226] The dyeing formulation was then diluted 2: 1 (v:v) with water. After dilution, the dyeing formulation was applied to two cotton-polyester blend textile substrates by dipping according to the general procedure described above, expect a ten-pound weight was used in place of the four-pound weight. The textile substrates were then cured according to the general procedure described above. After curing, the textile substrates were washed according to the general procedure described above.

[0227] Visually, the resulting dyed textile substrates exhibited superior color levelness and color uniformity compared to Examples 1-5. The resulting dyed textile substrates had an average wet crocking value of 3.5, an average perspiration fastness value of 4, and an average K / S value of 8.53 at -630 nm.EXAMPLE 9: Protein, Epoxy Cross-linker, and Dye

[0228] 100 g of water and 0.15 g of sodium hydroxide were added to a flask and mixed to prepare a caustic solution. After the caustic solution was prepared, 15 g of SPI and 6.85 g of reactive blue 1143 were added to the flask and mixed thoroughly. Then, three g of DENACOL® 614B was added to the flask and mixed to create a dyeing formulation.

[0229] The dyeing formulation was then diluted 2: 1 (v:v) with water. After dilution, the dyeing formulation was applied to two cotton-polyester blend textile substrates by dipping according to the general procedure described above. The textile substrates were then cured according to the general procedure described above. After curing, the textile substrates were washed according to the general procedure described above.

[0230] Visually, the resulting dyed textile substrates exhibited superior color levelness and color uniformity compared to Examples 1-5. The resulting dyed textile substrates hada wet crocking value between 3 and 3.5 and an average perspiration fastness value of greater than 4.EXAMPLE 10: Protein, Epoxy Cross-linker, Dye, and Surfactant

[0231] 250 g of water and 0.5 g of sodium hydroxide were added to a flask and mixed to prepare a caustic solution. After the caustic solution was prepared, 37.6 g of SPI, 2.62 g of reactive red 1126 dye, 2.54 g of reactive blue 1143 dye, and 11.75 g of reactive yellow 1154 dye were added to the flask and mixed thoroughly. Then, 6.35 g of DENACOL® 614B, 13.5 g of UNIFROTH® 0520 surfactant (a nonionic surfactant available from Unichem Specialty Chemicals, LLC), 10.2 g of Uniwet 0371 (65-75%, a sulfonated diester blend available from UniChem Specialty Chemicals, LLC), and 15 g of glycerol were added to the flask and mixed to create a dyeing formulation.

[0232] The dyeing formulation was then applied to two cotton-polyester blend textile substrates by foam application according to the general procedure described above. After application of the dyeing formulation, the textile substrates were cured according to the general procedure described above. After curing, the textile substrates were washed according to the general procedure described above.

[0233] Visually, the resulting dyed textile substrates exhibited superior color levelness and color uniformity compared to Examples 1-5. The resulting dyed textile substrates had an average wet crocking value of 2.5 and an average perspiration fastness value of 3.EXAMPLE 11 : Protein, Epoxy Cross-linker, Dye, and Sodium Bicarbonate

[0234] 110 g of water and two g of sodium bicarbonate were added to a flask and mixed to prepare a caustic solution. After the caustic solution was prepared, 19.45 g of SPI, 1.27 g of reactive red 1126 dye, 1.23 g of reactive blue 1143 dye, and 5.70 g of reactive yellow 1154 dye were added to the flask and mixed thoroughly. Then, 6.6 g of DENACOL® 614B was added to the flask and mixed to create a dyeing formulation.

[0235] The dyeing formulation was then diluted 2: 1 (v:v) with water. After dilution, the dyeing formulation was applied to two cotton-polyester blend textile substrates by dipping according to the general procedure described above. The textile substrates werethen cured according to the general procedure described above. After curing, the textile substrates were washed according to the general procedure described above.

[0236] Visually, the resulting dyed textile substrates exhibited superior color levelness and color uniformity compared to Examples 1-5. The resulting dyed textile substrates had a wet crocking value between 2.5 and 3.EXAMPLE 12: Protein, Epoxy Cross-linker, Dye, and Urea

[0237] 90 g of water and ten g of urea were added to a flask and mixed to prepare a solution. After the solution was prepared, 18 g of SPI, 1.51 g of reactive red 1126 dye, 1.5 g of reactive blue 1143 dye, and 6.95 g of reactive yellow 1154 dye were added to the flask and mixed thoroughly. Then, 3.6 g of DENACOL® 614B was added to the flask and mixed to create a dyeing formulation.

[0238] The dyeing formulation was then diluted 2: 1 (v:v) with water. After dilution, the dyeing formulation was applied to two cotton-polyester blend textile substrates by dipping according to the general procedure described above. The textile substrates were then cured according to the general procedure described above. After curing, the textile substrates were washed according to the general procedure described above.

[0239] Visually, the resulting dyed textile substrates exhibited superior color levelness and color uniformity compared to Examples 1-5. The resulting dyed textile substrates had a wet crocking value between 3 and 4.EXAMPLE 13: Protein, Epoxy Cross-linker, Dye, Urea, and Radical Initiator

[0240] 100 g of water and 11 g of urea were added to a flask and mixed to prepare a solution. After the solution was prepared, 15 g of SPI and 6.85 g of reactive blue 1143 dye were added to the flask and mixed thoroughly. Then, three g of DENACOL® 614B and 0.75 g of LUPEROX® A98 (an anhydrous benzoyl peroxide powder, available from Sigma- Aldrich) were added to the flask and mixed to create a dyeing formulation.

[0241] The dyeing formulation was then diluted 2: 1 (v:v) with water. After dilution, the dyeing formulation was applied to two cotton-polyester blend textile substrates by dipping according to the general procedure described above. The textile substrates werethen cured according to the general procedure described above. After curing, the textile substrates were washed according to the general procedure described above.

[0242] Visually, the resulting dyed textile substrates exhibited superior color levelness and color uniformity compared to Examples 1-5. The resulting dyed textile substrates had an average wet crocking value of 3 and an average perspiration fastness value of greater than 4.EXAMPLE 14: Protein, Epoxy Cross-linker, Dye, and Polyacrylamide

[0243] 100 g of water and 500 pl of sodium hydroxide (10N) were added to a flask and mixed to create a caustic solution. After the caustic solution was prepared, 16.5 g SPI and 8.25 g of reactive blue 1143 dye were added to the flask and mixed thoroughly. Then, 3.3 g of DENACOL® 614B and 0.625 g of polyacrylamide (solid, available from Sigma Aldrich) were added to the flask and mixed to create a dyeing formulation.

[0244] The dyeing formulation was then diluted 2: 1 (v:v) with water. After dilution, the dyeing formulation was applied to two cotton-polyester blend textile substrates by dipping according to the general procedure described above. The textile substrates were then cured according to the general procedure described above. After curing, the textile substrates were washed according to the general procedure described above.

[0245] Visually, the resulting dyed textile substrates exhibited superior color levelness and color uniformity compared to Examples 1-5. The resulting dyed textile substrates had an average wet crocking value of 2.5.EXAMPLE 15 : Protein, Epoxy Cross-linker, Dye, and Radical Initiator

[0246] 100 of water and 0.15 g of sodium hydroxide were added to a flask and mixed to prepare a caustic solution. After the caustic solution was prepared, 15 g of SPI and 6.85 g of reactive blue 1143 dye were added to the flask and mixed thoroughly. Then, three g of DENACOL® 614B and 0.75 g of LUPEROX® A98 were added to the flask and mixed to create a dyeing formulation.

[0247] The dyeing formulation was then diluted 2: 1 (v:v) with water. After dilution, the dyeing formulation was applied to two cotton-polyester blend textile substrates by dipping according to the general procedure described above. The textile substrates werethen cured according to the general procedure described above. After curing, the textile substrates were washed according to the general procedure described above.

[0248] Visually, the resulting dyed textile substrates exhibited superior color levelness and color uniformity compared to Examples 1-5. The resulting dyed textiles substrate had an average wet crocking value of 2.5 and an average perspiration fastness value of greater than 4.EXAMPLE 16: Protein, Epoxy Cross-linker, Dye, Sodium Bicarbonate, and Radical Initiator

[0249] 100 g of water and two g of sodium bicarbonate were added to a flask and mixed to prepare a caustic solution. After the caustic solution was prepared, 15 g of SPI and 6.85 g of reactive blue 1143 dye were added to the flask and mixed thoroughly. Then, three g of DENACOL® 614B and 0.75 g of LUPEROX® A98 were added to the flask and mixed to create a dyeing formulation.

[0250] The dyeing formulation was the diluted 2: 1 (v:v) ratio with water. After dilution, the dyeing formulation was applied to two cotton-polyester blend textile substrates by dipping according to the general procedure described above. The textile substrates were then cured according to the general procedure described above. After curing, the textile substrates were washed according to the general procedure described above.

[0251] Visually, the resulting dyed textile substrates exhibited superior color levelness and color uniformity compared to Examples 1-5. The resulting dyed textile substrates had an average wet crocking value of 2.5 and an average perspiration fastness value of greater than 4.EXAMPLE 17: Protein, Epoxy Cross-linker, Dye, and Urea (20 wt. %)

[0252] 80 g of water and 20 g of urea were added to a flask and mixed to prepare a solution. After the solution was prepared, 18 g of SPI, 1.51 g of reactive red 1126 dye, 1.54 g of reactive blue 1143 dye, and 6.95 g of reactive yellow 1154 dye were added to the flask and mixed thoroughly. Then, 3.6 g of DENACOL® 614B was added to the flask and mixed to create a dyeing formulation.

[0253] The dyeing formulation was then diluted 2: 1 (v:v) with water. After dilution, the dyeing formulation was applied to two cotton-polyester blend textile substrates bydipping according to the general procedure described above. The textile substrates were then cured according to the general procedure described above. After curing, the textile substrates were washed according to the general procedure described above.

[0254] Visually, the resulting dyed textile substrates exhibited superior color levelness and color uniformity compared to Examples 1-5. The resulting dyed textile substrates had an average wet crocking value of 4.EXAMPLE 18: Protein, Epoxy Cross-linker, Dye, and Urea (30 wt. %)

[0255] 70 g of water and 30 g of urea were added to a flask and mixed to prepare a solution. After the solution was prepared, 18 g of SPI, 1.51 g of reactive red 1126 dye, 1.54 g of reactive blue 1143 dye, and 6.95 g of reactive yellow 1154 dye were added to the flask and mixed thoroughly. Then, 3.6 g of DENACOL® 614B was added to the flask and mixed to create a dyeing formulation.

[0256] The dyeing formulation was then diluted 2: 1 (v:v) with water. After dilution, the dyeing formulation was applied to two cotton-polyester blend textile substrates by dipping according to the general procedure described above. The textile substrates were then cured according to the general procedure described above. After curing, the textile substrates were washed according to the general procedure described above.

[0257] Visually, the resulting dyed textile substrates exhibited superior color levelness and color uniformity compared to Examples 1-5. The resulting dyed textile substrates had an average wet crocking value of 4.EXAMPLE 19: Protein, Epoxy Cross-linker, Dye, and Guanidine Hydrochloride (27.7 wt. %)

[0258] 95 g of water and five g of guanidine hydrochloride were added to a flask and mixed to prepare a solution. After the solution was prepared, 18 g of SPI, 1.51 g of reactive red 1126 dye, 1.54 g of reactive blue 1143 dye, and 6.95 g of reactive yellow 1154 dye were added to the flask and mixed thoroughly. Then, 3.6 g of DENACOL® 614B and 3 g of UNIFROTH® 0520 were added to the flask and mixed to create a dyeing formulation.

[0259] The dyeing formulation was then diluted 2: 1 (v:v) with water. After dilution, the dyeing formulation was applied to two cotton-polyester blend textile substrates bydipping according to the general procedure described above. The textile substrates were then cured according to the general procedure described above. After curing, the textile substrates were washed according to the general procedure described above.

[0260] Visually, the resulting dyed textile substrates exhibited superior color levelness and color uniformity compared to Examples 1-5. The resulting dyed textile substrates had a wet crocking value between 2.5 and 4 and an average perspiration fastness value of 4.5.EXAMPLE 20: Protein, Epoxy Cross-linker, Dye, and Guanidine Hydrochloride (5.6 wt. %)

[0261] 99 g of water and one g of guanidine hydrochloride were added to a flask and mixed to prepare a solution. After the solution was prepared, 18 g of SPI, 1.51 g of reactive red 1126 dye, 1.54 g of reactive blue 1143 dye, and 6.95 g of reactive yellow 1154 dye were added to the flask and mixed thoroughly. Then, 3.6 g of DENACOL® 614B and 3 g of UNIFROTH® 0520 were added to the flask and mixed to create a dyeing formulation.

[0262] The dyeing formulation was then diluted 2: 1 (v:v) with water. After dilution, the dyeing formulation was applied to two cotton-polyester blend textile substrates by dipping according to the general procedure described above. The textile substrates were then cured according to the general procedure described above. After curing, the textile substrates were washed according to the general procedure described above.

[0263] Visually, the resulting dyed textile substrates exhibited superior color levelness and color uniformity compared to Examples 1-5. The resulting dyed textile substrates had a wet crocking value between 3 and 4 and an average perspiration fastness value of 4.5.EXAMPLE 21

[0264] 220 g of water and 1100 pl of sodium hydroxide (10N) are added to a flask and mixed to prepare a solution. After the solution is prepared, 33 g of SPI and 16.5 g of reactive blue 1143 dye are added to the flask and mixed thoroughly. Then, 3.3 g of WH- PZ5150 is added to the flask and mixed. After mixing, 7.5 g of UNIFROTH® 0520 is added to the flask and mixed to create a dyeing formulation. Then, the dyeing formulation is applied to a cotton-polyester blend textile substrate by foam application according to the general procedure described above. After application of the dyeing formulation, thetextile substrate is cured according to the general procedure described above. After curing, the textile substrate is washed according to the general procedure described above.EXAMPLE 22

[0265] 220 g of water and four g of sodium bicarbonate are added to a flask and mixed to prepare a solution. After the solution is prepared, 33 g of SPI and 16.5 g of reactive blue 1143 dye are added to the flask and mixed thoroughly. Then, 3.3 g of WH-PZ5150 is added to the flask and mixed to create a dyeing formulation. Then, the dyeing formulation diluted 2: 1 (v:v) with water. After dilution, the dyeing formulation is applied to a cotton- polyester blend textile substrate by dipping according to the general procedure described above. After application of the dyeing formulation, the textile substrate is cured according to the general procedure described above. After curing, the textile substrate is washed according to the general procedure described above.EXAMPLE 23

[0266] 220 g of water and four grams of sodium bicarbonate are added to a flask and mixed to prepare a solution. After the solution is prepared, 33 g of SPI and 16.5 g of reactive blue 1143 are added to the flask and mixed thoroughly. Then, 3.3 g of WH- PZ5150 is added to the flask and mixed. After mixing, 7.5 g of UNIFROTH® 0520 is added to the flask and mixed to create a dyeing formulation. Then, the dyeing formulation is applied to a cotton-polyester blend textile substrate by foam application according to the general procedure described above. After application of the dyeing formulation, the textile substrate is cured according to the general procedure described above. After curing, the textile substrate is washed according to the general procedure described above.EXAMPLE 24

[0267] 220 g of water and 3.3 g of sodium lauryl sulfate are added to a flask and mixed to prepare a solution. After the solution is prepared, 33 g of SPI and 16.5 g of reactive blue 1143 dye are added to the flask mixed thoroughly. Then, 3.3 g of WH-PZ5150 is added to the flask and mixed to create a dyeing formulation. Then, the dyeing formulation is diluted 2: 1 (v:v) ratio with water. After dilution, the dyeing formulation is applied to acotton-polyester blend textile substrate by dipping according to the general procedure described above. After application of the dyeing formulation, the textile substrate is cured according to the general procedure described above. After curing, the textile substrate is washed according to the general procedure described above.EXAMPLE 25

[0268] 220 g of water and 3.3 g of sodium lauryl sulfate are added to a flask and mixed to prepare a solution. After the solution is prepared, 33 g of SPI and 16.5 g of reactive blue 1143 dye are added to the flask and mixed thoroughly. Then, 3.3 g of WH-PZ5150 is added to the flask and mixed. After mixing, 7.5 g of UNIFROTH® 0520 is added to the flask and mixed to create a dyeing formulation. Then, the dyeing formulation is applied to a cotton-polyester blend textile substrate by foam application according to the general procedure described above. After application of the dyeing formulation, the textile substrate is cured according to the general procedure described above. After curing, the textile substrate is washed according to the general procedure described above.EXAMPLE 26

[0269] 90 g of water and ten g of urea are added to a flask and mixed to prepare a solution. After the solution is prepared, 18 g of SPI and ten g of reactive blue 1143 dye are added to the flask and mixed thoroughly. Then, 1.8 g of WH-PZ5150 is added to the flask and mixed. After mixing, 4.4 g of UNIFROTH® 0520 is added to the flask and mixed to create a dyeing formulation. Then, the dyeing formulation is applied to a cotton- polyester blend textile substrate by foam application according to the general procedure described above. After application of the dyeing formulation, the textile substrate is cured according to the general procedure described above. After curing, the textile substrate is washed according to the general procedure described above.EXAMPLE 27

[0270] 100 g of water and 11 g of urea are added to a flask and mixed to prepare a solution. After the solution is prepared, 15 g of SPI and 6.85 g of reactive blue 1143 dye are added to the flask and mixed thoroughly. Then, 1.5 g of WH-PZ5150 and 0.75 g ofLUPEROX® A98 (an anhydrous benzoyl peroxide powder, available from Sigma- Aldrich) are added to the flask and mixed to create a dyeing formulation. Then, the dyeing formulation is then diluted 2: 1 (v:v) with water. After dilution, the dyeing formulation is applied to a cotton-polyester blend textile substrate by dipping according to the general procedure described above. After application of the dyeing formulation, the textile substrate is cured according to the general procedure described above. After curing, the textile substrate is washed according to the general procedure described above.EXAMPLE 28

[0271] 100 g of water and 11 g of urea are added to a flask and mixed to prepare a solution. After the solution is prepared, 15 g of SPI and 6.85 g of reactive blue 1143 dye are added to the flask and mixed thoroughly. Then, 1.5 g of WH-PZ5150 and 0.75 g of LUPEROX® A98 are added and to the flask and mixed. After mixing, 6.6 g of UNIFROTH® 0520 is added to the flask and mixed to create a dyeing formulation. Then, the dyeing formulation is applied to a cotton-polyester blend textile substrate by foam application according to the general procedure described above. After application of the dyeing formulation, the textile substrate is cured according to the general procedure described above. After curing, the textile substrate is washed according to the general procedure described above.EXAMPLE 29

[0272] 220 grams of water and 1100 pl of sodium hydroxide (10N) are added to a flask and mixed to prepare a solution. After the solution is prepared, 33 g of SPI and 16.5 g of reactive blue 1143 dye are added to the flask mixed thoroughly. Then, 3.3 g of WH- PZ5150 and 4.95 g of polyacrylamide are added to the flask and mixed to create a dyeing formulation. Then, the dyeing formulation is diluted 2:1 (v:v) with water. After dilution, the dyeing formulation is applied to a cotton-polyester blend textile substrate by dipping according to the general procedure described above. After application of the dyeing formulation, the textile substrate is cured according to the general procedure described above. After curing, the textile substrate is washed according to the general procedure described above.EXAMPLE 30

[0273] 220 g of water and 1100 pl of sodium hydroxide (ION) are added to a flask and mixed to prepare a solution. After the solution is prepared, 33 g of SPI and 16.5 g of reactive blue 1143 dye are added to the flask and mixed thoroughly. Then, 3.3 g of WH- PZ5150 and 4.95 g of polyacrylamide are added to the flask and mixed. After mixing, 7.5 g of UNIFROTH® 0520 is added to the flask and mixed to create a dyeing formulation. Then, the dyeing formulation is applied to a cotton-polyester blend textile substrate by foam application according to the general procedure described above. After application of the dyeing formulation, the textile substrate is cured according to the general procedure described above. After curing, the textile substrate is washed according to the general procedure described above.EXAMPLE 31

[0274] 220 g of water and 1100 pl of sodium hydroxide (10N) are added to a flask and mixed to prepare a solution. After the solution is prepared, 33 g of SPI and 16.5 g of reactive blue 1143 dye are added to the flask mixed thoroughly. Then, 3.3 g of WH- PZ5150 and 4.95 g of polyacrylic acid are added to the flask and mixed to create a dyeing formulation. Then, the dyeing formulation is diluted 2:1 (v:v) with water. After dilution, the dyeing formulation is applied to a cotton-polyester blend textile substrate by dipping according to the general procedure described above. After application of the dyeing formulation, the textile substrate is cured according to the general procedure described above. After curing, the textile substrate is washed according to the general procedure described above.EXAMPLE 32

[0275] 220 g of water and 1100 pl of sodium hydroxide (10N) are added to a flask and mixed to prepare a solution. After the solution is prepared, 33 g of SPI and 16.5 g of reactive blue 1143 dye are added to the flask and mixed thoroughly. Then, 3.3 g of WH- PZ5150 and 4.95 g of polyacrylic acid are added to the flask and mixed. After mixing, 7.5 g of UNIFROTH® 0520 is added to the flask and mixed to create a dyeing formulation. Then, the dyeing formulation is applied to a cotton-polyester blend textile substrate byfoam application according to the general procedure described above. After application of the dyeing formulation, the textile substrate is cured according to the general procedure described above. After curing, the textile substrate is washed according to the general procedure described above.EXAMPLE 33

[0276] 220 g of water and four g of sodium bicarbonate are added to a flask and mixed to prepare a solution. After the solution is prepared, 33 g of SPI and 16.5 g of reactive blue 1143 dye are added to the flask and mixed thoroughly. Then, 3.3 g of WH-PZ5150 and 4.95 g of polyacrylamide are added to the flask and mixed to create a dyeing formulation. Then, the dyeing formulation is diluted 2: 1 (v:v) with water. After dilution, the dyeing formulation is applied to a cotton-polyester blend textile substrate by dipping according to the general procedure described above. After application of the dyeing formulation, the textile substrate is cured according to the general procedure described above. After curing, the textile substrate is washed according to the general procedure described above.EXAMPLE 34

[0277] 220 g of water and four g of sodium bicarbonate are added to a flask and mixed to prepare a solution. After the solution is prepared, 33 g of SPI and 16.5 g of reactive blue 1143 dye are added to the flask and mixed thoroughly. Then, 3.3 g of WH-PZ5150 and 4.95 g of polyacrylamide are added to the flask and mixed. After mixing, 7.5 g of UNIFROTH® 0520 is added to the flask and mixed to create a dyeing formulation. Then, the dyeing formulation is applied to a cotton-polyester blend textile substrate by foam application according to the general procedure described above. After application of the dyeing formulation, the textile substrate is cured according to the general procedure described above. After curing, the textile substrate is washed according to the general procedure described above.EXAMPLE 35

[0278] 220 g of water and four g of sodium bicarbonate are added to a flask and mixed to prepare a solution. After the solution is prepared, 33 g of SPI and 16.5 g of reactive blue1143 dye are added to the flask and mixed thoroughly. Then, 3.3 g of WH-PZ5150 and 4.95 g of polyacrylic acid are added to the flask and mixed to create a dyeing formulation. The dyeing formulation is then diluted 2:1 (v:v) with water. After dilution, the dyeing formulation is applied to a cotton-polyester blend textile substrate by dipping according to the general procedure described above. After application of the dyeing formulation, the textile substrate is cured according to the general procedure described above. After curing, the textile substrate is washed according to the general procedure described above.EXAMPLE 36

[0279] 220 g of water and 4 g of sodium bicarbonate are added to a flask and mixed to prepare a solution. After the solution is prepared, 33 g of SPI and 16.5 g of reactive blue 1143 dye are added to the flask and mixed thoroughly. Then, 3.3 g of WH-PZ5150 and 4.95 g of polyacrylic acid are added to the flask and mixed. After mixing, 7.5 g of UNIFROTH® 0520 is added to the flask and mixed to create a dyeing formulation. Then, the dyeing formulation is applied to a cotton-polyester blend textile substrate by foam application according to the general procedure described above. After application of the dyeing formulation, the textile substrate is cured according to the general procedure described above. After curing, the textile substrate is washed according to the general procedure described above.EXAMPLE 37

[0280] 90 g of water and ten g of urea are added to a flask and mixed to create a solution.After the solution is prepared, 18 g of SPI and ten g of reactive blue 1143 dye are added to the flask and mixed thoroughly. Then, 1.8 g of WH-PZ5150 and 2.7 g of polyacrylic acid are added to the flask and mixed to create a dyeing formulation. The dyeing formulation is then acidified with dilute hydrochloric acid and applied to a cotton- polyester blend textile substrate by dipping according to the general procedure described above. After application of the dyeing formulation, the textile substrate is cured according to the general procedure described above. After curing, the textile substrate is washed according to the general procedure described above.EXAMPLE 38

[0281] 90 g of water and ten g of urea are added to a flask and mixed to prepare a solution. After the solution is prepared, 18 g of SPI and ten g of reactive blue 1143 dye are added to the flask and mixed thoroughly. Then, 1.8 g of WH-PZ5150 and 2.7 g of polyacrylic acid are added to the flask and mixed. After mixing, 4.4 g of UNIFROTH® 0520 is added to the flask and mixed to create a dyeing formulation. The dyeing formulation is then acidified with dilute hydrochloric acid and applied to a cotton- polyester blend textile substrate by foam application according to the general procedure described above. After application of the dyeing formulation, the textile substrate is cured according to the general procedure described above. After curing, the textile substrate is washed according to the general procedure described above.EXAMPLE 39

[0282] 100 g of water and 11 g of urea are added to a flask and mixed to prepare a solution After the solution is prepared, 15 g of SPI and 6.85 g of reactive blue 1143 dye are added to the flask and mixed thoroughly. Then, 1.5 g of WH-PZ5150, 0.75 g of LUPEROX® A98, and 2.7 g of polyacrylic acid are added to the flask and mixed to create a dyeing formulation. The dyeing formulation is then acidified with dilute hydrochloric acid and applied to a cotton-polyester blend textile substrate by dipping according to the general procedure described above. After application of the dyeing formulation, the textile substrate is cured according to the general procedure described above. After curing, the textile substrate is washed according to the general procedure described above.EXAMPLE 40

[0283] 100 g of water and 11 g of urea are added to a flask and mixed to prepare a solution. After the solution is prepared, 15 g of SPI and 6.85 g of reactive blue 1143 dye are added to the flask and mixed thoroughly. Then, 1.5 g of WH-PZ5150, 0.75 g of LUPEROX® A98, and 2.7 g of polyacrylic acid are added to the flask and mixed. After mixing, 6.6 g of UNIFROTH® 0520 is added to the flask and mixed to create a dyeing formulation. The dyeing formulation is then acidified with dilute hydrochloric acid andapplied to a cotton-polyester blend textile substrate by foam application according to the general procedure described above. After application of the dyeing formulation, the textile substrate is cured according to the general procedure described above. After curing, the textile substrate is washed according to the general procedure described above.EXAMPLE 41

[0284] 220 g of water and 1100 pl of sodium hydroxide (ION) are added to a flask and mixed to prepare a solution. After the solution is prepared, 33 g of SPI and 16.5 g of reactive blue 1143 dye are added to the flask and mixed thoroughly. Then, 6.6 g of DENACOL® 614B and 3.3 g of WH-PZ5150 are added to the flask and mixed. Then, 7.5 g of UNIFROTH® 0520 is added to the flask and mixed to create a dyeing formulation. Then, the dyeing formulation is applied to a cotton-polyester blend textile substrate by foam application according to the general procedure described above. After application of the dyeing formulation, the textile substrate is cured according to the general procedure described above. After curing, the textile substrate is washed according to the general procedure described above.EXAMPLE 42

[0285] 220 g of water and four g of sodium bicarbonate are added to a flask and mixed to prepare a solution. After the solution is prepared, 33 g of SPI and 16.5 g of reactive blue 1143 dye are added to the flask and mixed thoroughly. Then, 6.6 g of DENACOL® 614B and 3.3 g of WH-PZ5150 are added to the flask and mixed to create a dyeing formulation. The dyeing formulation is then diluted 2: 1 (v:v) with water. After dilution, the dyeing formulation is applied to a cotton-polyester blend textile substrate by dipping according to the general procedure described above. After application of the dyeing formulation, the textile substrate is cured according to the general procedure described above. After curing, the textile substrate is washed according to the general procedure described above.EXAMPLE 43

[0286] 220 g of water and four g of sodium bicarbonate are added to a flask and mixed to create a solution. After the solution is prepared, 33 g of SPI and 16.5 g of reactive blue1143 dye are added to the flask and mixed thoroughly. Then, 6.6 g of DENACOL® 614B and 3.3 g of WH-PZ5150 are added to the flask and mixed. After mixing, 7.5 g of UNIFROTH® 0520 is added to the flask and mixed to create a dyeing formulation. Then, the dyeing formulation is applied to a cotton-polyester blend textile substrate by foam application according to the general procedure described above. After application of the dyeing formulation, the textile substrate is cured according to the general procedure described above. After curing, the textile substrate is washed according to the general procedure described above.EXAMPLE 44

[0287] 220 g of water and four g of sodium bicarbonate are added to a flask and mixed to prepare a solution. After the solution is prepared, 33 g of SPI and 16.5 g of reactive blue 1143 are added to the flask and mixed thoroughly. Then, 6.6 g of DENACOL® 614B is added to the flask and mixed. After mixing, 7.5 g of UNIFROTH® 0520 is added to the flask and mixed to create a dyeing formulation. Then, the dyeing formulation is applied to a cotton-polyester blend textile substrate by foam application according to the general procedure described above. After application of the dyeing formulation, the textile substrate is cured according to the general procedure described above. After curing, the textile substrate is washed according to the general procedure described above.EXAMPLE 45

[0288] 220 g of water and 3.3 g of sodium lauryl sulfate are added to a flask and mixed to prepare a solution. After the solution is prepared, 33 g of SPI and 16.5 g of reactive blue 1143 dye are added to the flask and mixed thoroughly. Then, 6.6 g of DENACOL® 614B is added to the flask and mixed to create a dyeing formulation. Then, the dyeing formulation is diluted 2: 1 (v:v) with water. After dilution, the dyeing formulation is applied to a cotton-polyester blend textile substrate by dipping according to the general procedure described above. After application of the dyeing formulation, the textile substrate is cured according to the general procedure described above. After curing, the textile substrate is washed according to the general procedure described above.EXAMPLE 46

[0289] 220 g of water and 3.3 g of sodium lauryl sulfate are added to a flask and mixed to prepare a solution. After the solution is prepared, 33 g of SPI and 16.5 of reactive blue 1143 dye are added to the flask and mixed thoroughly. Then, 6.6 g of DENACOL® 614B is added to the flask and mixed. After mixing, 7.5 g of UNIFROTH® 0520 is added to the flask and mixed to create a dyeing formulation. Then, the dyeing formulation is applied to a cotton-polyester blend textile substrate by foam application according to the general procedure described above. After application of the dyeing formulation, the textile substrate is cured according to the general procedure described above. After curing, the textile substrate is washed according to the general procedure described above.EXAMPLE 47 : Protein, Epoxy Cross-linker, Dye, Urea, and Surfactant

[0290] 90 g of water and ten g of urea were added to a flask and mixed to prepare a solution. After the solution was prepared, 18 g of SPI and ten g of reactive blue 1143 dye were added to the flask and mixed thoroughly. Then, 3.6 g of DENACOL® 614B was added to the flask and mixed. After mixing, 4.4 g of UNIFROTH® 0520 was added to the flask and mixed to create a dyeing formulation. Then, the dyeing formulation was applied to a cotton-polyester blend textile substrate by foam application according to the general procedure described above. After application of the dyeing formulation, the textile substrate was cured according to the general procedure described above. After curing, the textile substrate was washed according to the general procedure described above.

[0291] Visually, the resulting dyed textile substrate exhibited superior color levelness and color uniformity compared to Examples 1-5. The resulting dyed textile substrate had a wet crocking value between 3 and 4 and an average perspiration fastness value of 4.5.EXAMPLE 48

[0292] 100 g of water and 11 g of urea are added to a flask and mixed to prepare a solution. After the solution is prepared, 15 g of SPI and 6.85 g of reactive blue 1143 dye are added to the flask and mixed thoroughly. Then, three g of DENACOL® 614B and 0.75 g of LUPEROX® A98 are added to the flask and mixed. After mixing, 6.6 g of UNIFROTH® 0520 is added to the flask and mixed to create a dyeing formulation. Then,the dyeing formulation is applied to a cotton-polyester blend textile substrate by foam application according to the general procedure described above. After application of the dyeing formulation, the textile substrate is cured according to the general procedure described above. After curing, the textile substrate is washed according to the general procedure described above.EXAMPLE 49

[0293] 220 g of water and 1100 pl of sodium hydroxide (ION) are added to a flask and mixed to prepare a solution. After the solution is prepared, 33 g of SPI and 16.5 g of reactive blue 1143 dye are added to the flask mixed thoroughly. Then, 6.6 g of DENACOL® 614B and 4.95 g of polyacrylamide are added to the flask and mixed. After mixing, 7.5 g of UNIFROTH® 0520 is added to the flask and mixed to create a dyeing formulation. Then, the dyeing formulation is applied to a cotton-polyester blend textile substrate by foam application according to the general procedure described above. After application of the dyeing formulation, the textile substrate is cured according to the general procedure described above. After curing, the textile substrate is washed according to the general procedure described above.EXAMPLE 50

[0294] 220 g of water and 1100 pl of sodium hydroxide (10N) are added to a flask and mixed to prepare a solution. After the solution is prepared, 33 g of SPI and 16.5 g of reactive blue 1143 dye are added to the flask and mixed thoroughly. Then, 6.6 g of DENACOL® 614B and 4.95 g of polyacrylic acid are added to the flask and mixed to create a dyeing formulation. Then, the dyeing formulation is diluted 2: 1 (v:v) with water. After dilution, the dying solution is applied a cotton-polyester blend textile substrate by dipping according to the general procedure described above. After application of the dyeing formulation, the textile substrate is cured according to the general procedure described above. After curing, the textile substrate is washed according to the general procedure described above.EXAMPLE 51

[0295] 220 g of water and 1100 pl of sodium hydroxide (ION) are added to a flask and mixed to prepare a solution. After the solution is prepared, 33 g of SPI and 16.5 g of reactive blue 1143 dye are added to the flask and mixed thoroughly. Then, 6.6 g of DENACOL® 614B and 4.95 g of polyacrylic acid are added to the flask and mixed. After mixing, 7.5 g of UNIFROTH® 0520 is added to the flask and mixed to create a dyeing formulation. Then, the dyeing formulation is applied to a cotton-polyester blend textile substrate by foam application according to the general procedure described above. After application of the dyeing formulation, the textile substrate is cured according to the general procedure described above. After curing, the textile substrate is washed according to the general procedure described above.EXAMPLE 52

[0296] 220 g of water and four g of sodium bicarbonate are added to a flask and mixed to prepare a solution. After the solution is prepared, 33 g of SPI and 16.5 g of reactive blue 1143 dye are added to the flask and mixed thoroughly. Then, 6.6 g of DENACOL® 614B and 4.95 g of polyacrylamide are added to the flask and mixed to create a dyeing formulation. Then, the dyeing formulation is diluted 2:1 (v:v) with water. After dilution, the dyeing formulation is applied to a cotton-polyester blend textile substrate by dipping according to the general procedure described above. After application of the dyeing formulation, the textile substrate is cured according to the general procedure described above. After curing, the textile substrate is washed according to the general procedure described above.EXAMPLE 53

[0297] 220 g of water and four g of sodium bicarbonate are added to a flask and mixed to prepare a solution. After the solution is prepared, 33 g of SPI and 16.5 g of reactive blue 1143 dye are added to the flask and mixed thoroughly. Then, 6.6 g of DENACOL® 614B and 4.95 g of polyacrylamide are added to the flask and mixed. After mixing, 7.5 g of UNIFROTH® 0520 is added to the flask and mixed to create a dyeing formulation. Then, the dyeing formulation is applied to a cotton-polyester blend textile substrate by foamapplication according to the general procedure described above. After application of the dyeing formulation, the textile substrate is cured according to the general procedure described above. After curing, the textile substrate is washed according to the general procedure described above.EXAMPLE 54

[0298] 220 g of water and four g of sodium bicarbonate are added to a flask and mixed to prepare a solution. After the solution is prepared, 33 g of SPI and 16.5 g of reactive blue 1143 dye are added to the flask and mixed thoroughly. Then, 6.6 g of DENACOL® 614B and 4.95 g of polyacrylic acid are added to the flask and mixed to create a dyeing formulation. Then, the dyeing formulation is diluted 2:1 (v:v) with water. After dilution, the dyeing formulation is applied a cotton-polyester blend textile substrate by dipping according to the general procedure described above. After application of the dyeing formulation, the textile substrate is cured according to the general procedure described above. After curing, the textile substrate is washed according to the general procedure described above.EXAMPLE 55

[0299] 220 g of water and four g of sodium bicarbonate are added to a flask and mixed to prepare a solution. After the solution is prepared, 33 g of SPI and 16.5 g of reactive blue 1143 dye are added to the flask and mixed thoroughly. Then, 6.6 g of DENACOL® 614B and 4.95 g of polyacrylic acid are added to the flask and mixed. After mixing, 7.5 g of UNIFROTH® 0520 is added to the flask and mixed to create a dyeing formulation. Then, the dyeing formulation is applied to a cotton-polyester blend textile substrate by foam application according to the general procedure described above. After application of the dyeing formulation, the textile substrate is cured according to the general procedure described above. After curing, the textile substrate is washed according to the general procedure described above.EXAMPLE 56

[0300] 90 g of water and ten g of urea are added to a flask and mixed to prepare a solution. After the solution is prepared, 18 g of SPI and ten g of reactive blue 1143 dye are added to the flask and mixed thoroughly. Then, 3.6 g of DENACOL® 614B and 2.7 g of polyacrylic acid are to the flask and mixed to create a dyeing formulation. After mixing, the dyeing formulation is acidified with dilute hydrochloric acid and applied to a cotton-polyester blend textile substrate by dipping according to the general procedure described above. After application of the dyeing formulation, the textile substrate is cured according to the general procedure described above. After curing, the textile substrate is washed according to the general procedure described above.EXAMPLE 57

[0301] 90 g of water and ten g of urea are added to a flask and mixed to prepare a solution. After the solution is prepared, 18 g of SPI and ten g of reactive blue 1143 dye are added to the flask and mixed thoroughly. Then, 3.6 g of DENACOL® 614B and 2.7 g of polyacrylic acid are added to the flask and mixed. After mixing, 4.4 g of UNIFROTH® 0520 is added to the flask and mixed to create a dyeing formulation. Then, the dyeing formulation is acidified with dilute hydrochloric acid and applied to a cotton-polyester blend textile substrate by foam application according to the general procedure described above. After application of the dyeing formulation, the textile substrate is cured according to the general procedure described above. After curing, the textile substrate is washed according to the general procedure described above.EXAMPLE 58

[0302] 100 g of water and 11 g of urea are added to a flask and mixed to prepare a solution. After the solution is prepared, 15 g of SPI and 6.85 g of reactive blue 1143 dye are added to the flask and mixed thoroughly. Then, three g of DENACOL® 614B, 0.75 g of LUPEROX® A98, and 2.7 g of polyacrylic acid are added to the flask and mixed to create a dyeing formulation. After mixing, the dyeing formulation is acidified with dilute hydrochloric acid and applied to a cotton-polyester blend textile substrate by dipping according to the general procedure described above. After application of the dyeingformulation, the textile substrate is cured according to the general procedure described above. After curing, the textile substrate is washed according to the general procedure described above.EXAMPLE 59

[0303] 100 g of water and 11 g of urea are added to a flask and mixed to prepare a solution. After the solution is prepared, 15 g of SPI and 6.85 g of reactive blue 1143 dye are added to the flask and mixed thoroughly. Then, three g of DENACOL® 614B, 0.75 g of LUPEROX® A98, and 2.7 g of polyacrylic acid are added to the flask and mixed. After mixing, 6.6 g of LTNIFROTEI® 0520 is added to the flask and mixed to create a dyeing formulation. Then, the dyeing formulation is acidified with dilute hydrochloric acid and applied to a cotton-polyester blend textile substrate by foam application according to the general procedure described above. After application of the dyeing formulation, the textile substrate is cured according to the general procedure described above. After curing, the textile substrate is washed according to the general procedure described above.EXAMPLE 60: Protein, Epoxy Cross-linker, and Dye

[0304] 100 g of water and 0.15 g of sodium hydroxide were added to a flask and mixed to prepare a solution. After the solution was prepared, 10 g of SPI, 0.077 g of reactive red 1126 dye, 0.075 g of reactive blue 1143 dye, and 0.348 grams of reactive yellow 1154 dye were added to the flask and mixed thoroughly. Then, one g of DENACOL® 614B was added to the flask and mixed to create a dyeing formulation.

[0305] The dyeing formulation was then diluted 2: 1 (v:v) with water. After dilution, the dyeing formulation was applied to a cotton-polyester blend textile substrate by dipping according to the general procedure described above. The textile substrate was then cured according to the general procedure described above. After curing, the textile substrate was washed according to the general procedure described above.

[0306] Visually, the resulting dyed textile substrate exhibited superior color levelness and color uniformity compared to Examples 1-5. The resulting dyed textile substrate had a wet crocking value between 3 and 4 and an average perspiration fastness value of 4.EXAMPLE 61 : Protein, Epoxy Cross-linker, and Dye

[0307] 100 g of water and 0.15 g of sodium hydroxide were added to a flask and mixed to prepare a solution. After the solution was prepared, 10 g of SPI, 0.077 g of reactive red 1126 dye, 0.075 g of reactive blue 1143 dye, and 0.348 grams of reactive yellow 1154 dye were added to the flask and mixed thoroughly. Then, five g of DENACOL® 614B was added to the flask and mixed to create a dyeing formulation.

[0308] The dyeing formulation was then diluted 2: 1 (v:v) with water. After dilution, the dyeing formulation was applied to a cotton-polyester blend textile substrate by dipping according to the general procedure described above. The textile substrate was then cured according to the general procedure described above. After curing, the textile substrate was washed according to the general procedure described above.

[0309] Visually, the resulting dyed textile substrate exhibited superior color levelness and color uniformity compared to Examples 1-5. The resulting dyed textile substrate had a wet crocking value between 3 and 4 and an average perspiration fastness value of 4.EXAMPLE 62: Protein, Epoxy Cross-linker, and Dye

[0310] 100 g of water and 0.15 g of sodium hydroxide were added to a flask and mixed to prepare a solution. After the solution was prepared, 10 g of SPI, 0.077 g of reactive red 1126 dye, 0.075 g of reactive blue 1143 dye, and 0.348 grams of reactive yellow 1154 dye were added to the flask and mixed thoroughly. Then, nine g of DENACOL® 614B was added to the flask and mixed to create a dyeing formulation.

[0311] The dyeing formulation was then diluted 2: 1 (v:v) with water. After dilution, the dyeing formulation was applied to a cotton-polyester blend textile substrate by dipping according to the general procedure described above. The textile substrate was then cured according to the general procedure described above. After curing, the textile substrate was washed according to the general procedure described above.

[0312] Visually, the resulting dyed textile substrate exhibited superior color levelness and color uniformity compared to Examples 1-5. The resulting dyed textile substrate had a wet crocking value between 3 and 4 and an average perspiration fastness value of 4.EXAMPLE 63

[0313] 100 g of water and 0.15 g of sodium hydroxide are added to a flask and mixed to prepare a solution. After the caustic solution is prepared, 50 g of SPI, 0.388 g of reactive red 1126 dye, 0.375 grams of reactive blue 1143 dye, and 1.738 grams of reactive yellow 1154 dye are added to the flask and mixed thoroughly. Then, five g of DENACOL® 614B is added to the flask and mixed to create a dyeing formulation.

[0314] The dyeing formulation is then diluted 2: 1 (v:v) with water. After dilution, the dyeing formulation is applied to a cotton-polyester blend textile substrate by dipping according to the general procedure described above. The textile substrate is then cured according to the general procedure described above. After curing, the textile substrate is washed according to the general procedure described above.EXAMPLE 64

[0315] 100 g of water and 0.15 g of sodium hydroxide are added to a flask and mixed to prepare a solution. After the solution is prepared, 50 g of SPI, 0.388 g of reactive red 1126 dye, 0.375 grams of reactive blue 1143 dye, and 1.738 grams of reactive yellow 1154 dye are added to the flask and mixed thoroughly. Then, 25 g of DENACOL® 614B is added to the flask and mixed to create a dyeing formulation.

[0316] The dyeing formulation is then diluted 2: 1 (v:v) with water. After dilution, the dyeing formulation is applied to a cotton-polyester blend textile substrate by dipping according to the general procedure described above. The textile substrate is then cured according to the general procedure described above. After curing, the textile substrate is washed according to the general procedure described above.EXAMPLE 65

[0317] 100 g of water and 0.15 g of sodium hydroxide are added to a flask and mixed to prepare a solution. After the solution is prepared, 50 g of SPI, 0.388 g of reactive red 1126 dye, 0.375 grams of reactive blue 1143 dye, and 1.738 grams of reactive yellow 1154 dye are added to the flask and mixed thoroughly. Then, 45 g of DENACOL® 614B is added to the flask and mixed to create a dyeing formulation.

[0318] The dyeing formulation is then diluted 2: 1 (v:v) with water. After dilution, the dyeing formulation is applied to a cotton-polyester blend textile substrate by dipping according to the general procedure described above. The textile substrate is then cured according to the general procedure described above. After curing, the textile substrate is washed according to the general procedure described above.EXAMPLE 66: Protein, Epoxy Cross-linker, and Dye

[0319] 100 g of water and 0.15 g of sodium hydroxide were added to a flask and mixed to prepare a solution. After the solution was prepared, 10 g of SPI, 0.775 g of reactive red 1126 dye, 0.75 g of reactive blue 1143 dye, and 3.475 g of reactive yellow 1154 dye were added to the flask and mixed thoroughly. Then, one g of DENACOL® 614B was added to the flask and mixed to create a dyeing formulation.

[0320] The dyeing formulation was then diluted 2: 1 (v:v) with water. After dilution, the dyeing formulation was applied to a cotton-polyester blend textile substrate by dipping according to the general procedure described above. The textile substrate was then cured according to the general procedure described above. After curing, the textile substrate was washed according to the general procedure described above.

[0321] Visually, the resulting dyed textile substrate exhibited superior color levelness and color uniformity compared to Examples 1-5. The resulting dyed textile substrate had a wet crocking value between 3 and 4 and an average perspiration fastness value of 4.EXAMPLE 67 : Protein, Epoxy Cross-linker, and Dye

[0322] 100 g of water and 0.15 g of sodium hydroxide was added to a flask and mixed to prepare a solution. After the solution was prepared, 10 g of SPI, 0.775 g of reactive red 1126 dye, 0.75 g of reactive blue 1143 dye, and 3.475 g of reactive yellow 1154 dye were added to the flask and mixed thoroughly. Then, five g of DENACOL® 614B was added to the flask and mixed to create a dyeing formulation.

[0323] The dyeing formulation was then diluted 2: 1 (v:v) with water. After dilution, the dyeing formulation was applied to a cotton-polyester blend textile substrate by dipping according to the general procedure described above. The textile substrate was then curedaccording to the general procedure described above. After curing, the textile substrate was washed according to the general procedure described above.

[0324] Visually, the resulting dyed textile substrate exhibited superior color levelness and color uniformity compared to Examples 1-5. The resulting dyed textile substrate had a wet crocking value between 3 and 4 and an average perspiration fastness value of 4.EXAMPLE 68: Protein, Epoxy Cross-linker, and Dye

[0325] 100 g of water and 0.15 g of sodium hydroxide were added to a flask and mixed to prepare a solution. After the solution was prepared, 10 g of SPI, 0.775 g of reactive red 1126 dye, 0.75 g of reactive blue 1143 dye, and 3.475 g of reactive yellow 1154 dye were added to the flask and mixed thoroughly. Then, nine g of DENACOL® 614B was added to the flask and mixed to create a dyeing formulation.

[0326] The dyeing formulation was then diluted 2: 1 (v:v) with water. After dilution, the dyeing formulation was applied to a cotton-polyester blend textile substrate by dipping according to the general procedure described above. The textile substrate was then cured according to the general procedure described above. After curing, the textile substrate was washed according to the general procedure described above.

[0327] Visually, the resulting dyed textile substrate exhibited superior color levelness and color uniformity compared to Examples 1-5. The resulting dyed textile substrate had a wet crocking value between 3 and 4 and an average perspiration fastness value of 4.EXAMPLE 69

[0328] 100 g of water and 0.15 g of sodium hydroxide are added to a flask and mixed to prepare a solution. After the solution is prepared, 50 g of SPI, 3.88 g of reactive red 1126 dye, 3.75 g of reactive blue 1143 dye, and 17.38 g of reactive yellow 1154 dye are added to the flask and mixed thoroughly. Then, five g of DENACOL® 614B is added to the flask and mixed to create a dyeing formulation.

[0329] The dyeing formulation is then diluted 2: 1 (v:v) with water. After dilution, the dyeing formulation is applied to a cotton-polyester blend textile substrate by dipping according to the general procedure described above. The textile substrate is then curedaccording to the general procedure described above. After curing, the textile substrate is washed according to the general procedure described above.EXAMPLE 70

[0330] 100 g of water and 0.15 g of sodium hydroxide are added to a flask and mixed to prepare a solution. After the solution is prepared, 50 g of SPI, 3.88 g of reactive red 1126 dye, 3.75 g of reactive blue 1143 dye, and 17.38 g of reactive yellow 1154 dye are added to the flask and mixed thoroughly. Then, 25 g of DENACOL® 614B is added to the flask and mixed to create a dyeing formulation.

[0331] The dyeing formulation is then diluted 2: 1 (v:v) with water. After dilution, the dyeing formulation is applied to a cotton-polyester blend textile substrate by dipping according to the general procedure described above. The textile substrate is then cured according to the general procedure described above. After curing, the textile substrate is washed according to the general procedure described above.EXAMPLE 71

[0332] 100 g of water and 0.15 g of sodium hydroxide are added to a flask and mixed to prepare a solution. After the solution is prepared, 50 g of SPI, 3.88 g of reactive red 1126 dye, 3.75 g of reactive blue 1143 dye, and 17.38 g of reactive yellow 1154 dye are added to the flask and mixed thoroughly. Then, 45 g of DENACOL® 614B is added to the flask and mixed to create a dyeing formulation.

[0333] The dyeing formulation is then diluted 2: 1 (v:v) with water. After dilution, the dyeing formulation is applied to a cotton-polyester blend textile substrate by dipping according to the general procedure described above. The textile substrate is then cured according to the general procedure described above. After curing, the textile substrate is washed according to the general procedure described above.EXAMPLE 72

[0334] 100 g of water and 0.15 g of sodium hydroxide are added to a flask and mixed to prepare a solution. After the solution is prepared, 10 g of SPI, 3.1 g of reactive red 1126 dye, three g of reactive blue 1143 dye, and 13.9 g of reactive yellow 1154 dye are addedto the flask and mixed thoroughly. Then, one g of DENACOL® 614B is added to the flask and mixed to create a dyeing formulation.

[0335] The dyeing formulation is then diluted 2: 1 (v:v) with water. After dilution, the dyeing formulation is applied to a cotton-polyester blend textile substrate by dipping according to the general procedure described above. The textile substrate is then cured according to the general procedure described above. After curing, the textile substrate is washed according to the general procedure described above.EXAMPLE 73

[0336] 100 g of water and 0.15 g of sodium hydroxide are added to a flask and mixed to prepare a solution. After the solution is prepared, 10 g of SPI, 3.1 g of reactive red 1126 dye, three g of reactive blue 1143 dye, and 13.9 g of reactive yellow 1154 dye are added to the flask and mixed thoroughly. Then, five g of DENACOL® 614B is added to the flask and mixed to create a dyeing formulation.

[0337] The dyeing formulation is then diluted 2: 1 (v:v) with water. After dilution, the dyeing formulation is applied to a cotton-polyester blend textile substrate by dipping according to the general procedure described above. The textile substrate is then cured according to the general procedure described above. After curing, the textile substrate is washed according to the general procedure described above.EXAMPLE 74

[0338] 100 g of water and 0.15 g of sodium hydroxide are added to a flask and mixed to prepare a solution. After the solution is prepared, 10 g of SPI, 3.1 g of reactive red 1126 dye, three g of reactive blue 1143 dye, and 13.9 g of reactive yellow 1154 dye are added to the flask and mixed thoroughly. Then, nine g of DENACOL® 614B is added to the flask and mixed to create a dyeing formulation.

[0339] The dyeing formulation is then diluted 2: 1 (v:v) with water. After dilution, the dyeing formulation is applied to a cotton-polyester blend textile substrate by dipping according to the general procedure described above. The textile substrate is then cured according to the general procedure described above. After curing, the textile substrate is washed according to the general procedure described above.EXAMPLE 75

[0340] 100 g of water and 0.15 g of sodium hydroxide are added to a flask and mixed to prepare a solution. After the solution is prepared, 50 g of SPI, 15.5 g of reactive red 1126 dye, 15 g of reactive blue 1143 dye, and 69.5 g of reactive yellow 1154 dye are added to the flask and mixed thoroughly. Then, five g of DENACOL® 614B is added to the flask and mixed to create a dyeing formulation.

[0341] The dyeing formulation is then diluted 2: 1 (v:v) with water. After dilution, the dyeing formulation is applied to a cotton-polyester blend textile substrate by dipping according to the general procedure described above. The textile substrate is then cured according to the general procedure described above. After curing, the textile substrate is washed according to the general procedure described above.EXAMPLE 76

[0342] 100 g of water and 0.15 g of sodium hydroxide are added to a flask and mixed to prepare a solution. After the solution is prepared, 50 g of SPI, 15.5 g of reactive red 1126 dye, 15 g of reactive blue 1143 dye, and 69.5 g of reactive yellow 1154 dye are added to the flask and mixed thoroughly. Then, 25 g of DENACOL® 614B is added to the flask and mixed to create a dyeing formulation.

[0343] The dyeing formulation is then diluted 2: 1 (v:v) with water. After dilution, the dyeing formulation is applied to a cotton-polyester blend textile substrate by dipping according to the general procedure described above. The textile substrate is then cured according to the general procedure described above. After curing, the textile substrate is washed according to the general procedure described above.EXAMPLE 77

[0344] 100 g of water and 0.15 g of sodium hydroxide are added to a flask and mixed to prepare a solution. After the solution is prepared, 50 g of SPI, 15.5 g of reactive red 1126 dye, 15 g of reactive blue 1143 dye, and 69.5 g of reactive yellow 1154 dye are added to the flask and mixed thoroughly. Then, 45 g of DENACOL® 614B is added to the flask and mixed to create a dyeing formulation.

[0345] The dyeing formulation is then diluted 2: 1 (v:v) with water. After dilution, the dyeing formulation is applied to a cotton-polyester blend textile substrate by dipping according to the general procedure described above. The textile substrate is then cured according to the general procedure described above. After curing, the textile substrate is washed according to the general procedure described above.

[0346] For each prophetic example provided above, the resulting dyed textile substrate visually exhibits superior color levelness and color uniformity compared to Examples 1- 5. The resulting dyed textile substrate has a wet crocking value greater than or equal to 2.5 and a perspiration fastness value of greater than or equal to 3.

[0347] While various embodiments have been described herein, they have been presented by way of example, and not limitation. It should be apparent that adaptations and modifications are intended to be within the meaning and range of equivalents of the disclosed embodiments, based on the teaching and guidance presented herein. It therefore will be apparent to one skilled in the art that various changes in form and detail can be made to the embodiments disclosed herein without departing from the spirit and scope of the present disclosure. The elements of the embodiments presented herein are not necessarily mutually exclusive, but can be interchanged to meet various situations as would be appreciated by one of skill in the art.

[0348] Embodiments of the present disclosure are described in detail herein with reference to embodiments thereof as illustrated in the accompanying drawings, in which like reference numerals are used to indicate identical or functionally similar elements. References to “one embodiment,” “an embodiment,” “some embodiments,” “in certain embodiments,” etc., indicate that the embodiment described can include a particular feature, structure, or characteristic, but every embodiment can not necessarily include the particular feature, structure, or characteristic. Moreover, such phrases are not necessarily referring to the same embodiment. Further, when a particular feature, structure, or characteristic is described in connection with an embodiment, it is submitted that it is within the knowledge of one skilled in the art to affect such feature, structure, or characteristic in connection with other embodiments whether or not explicitly described.

[0349] The examples are illustrative, but not limiting, of the present disclosure. Other suitable modifications and adaptations of the variety of conditions and parameters-n - normally encountered in the field, and which would be apparent to those skilled in the art, are within the spirit and scope of the disclosure.

[0350] It is to be understood that the phraseology or terminology used herein is for the purpose of description and not of limitation. The breadth and scope of the present disclosure should not be limited by any of the above-described exemplary embodiments, but should be defined in accordance with the following claims and their equivalents.SEQUENCESSEQ ID NO: 1 : Collagen FragmentDVKSGVAVGGLAGYPGPAGPPGPPGPPGTSGHPGSPGSPGYQGPPGEPGQAGPSGPPGPPGAIGPSGPAGKDGESGRPGRPGERGLPGPPGIKGPAGIPGFPGMKGHRGFDGRNGEKGETGAPGLKGENGLPGENGAPGPMGPRGAPGERGRPGLPGAAGARGNDGARGSDGQPGPPGPPGTAGFPGSPGAKGEVGPAGSPGSNGAPGQRGEPGPQGHAGAQGPPGPPGINGSPGGKGEMGPAGIPGAPGLMGARGPPGPAGANGAPGLRGGAGEPGKNGAKGEPGPRGERGEAGIPGVPGAKGEDGKDGSPGEPGANGLPGAAGERGAPGFRGPAGPNGIPGEKGPAGERGAPGPAGPRGAAGEPGRDGVPGGPGMRGMPGSPGGPGSDGKPGPPGSQGESGRPGPPGPSGPRGQPGVMGFPGPKGNDGAPGKNGERGGPGGPGPQGPPGKNGETGPQGPPGPTGPGGDKGDTGPPGPQGLQGLPGTGGPPGENGKPGEPGPKGDAGAPGAPGGKGDAGAPGERGPPAIAGIGGEKAGGFAPYYG

Claims

WHAT IS CLAIMED IS:

1. A dyed material, comprising: a. a textile comprising natural fibers comprising hydroxyl functional groups; b. a protein; and c. a dye; wherein the protein is covalently linked to the natural fibers via one or more crosslinkers; and wherein the dye is bonded to the natural fibers, the one or more cross-linkers, the protein, or a combination thereof.

2. The dyed material of claim 1, wherein the one or more cross-linkers comprise an aziridine cross-linker.

3. The dyed material of claim 1, wherein the one or more cross-linkers are selected from the group consisting of: an aziridine cross-linker, a carbodiimide cross-linker, an isocyanate cross-linker, n-hydroxysuccinimide, a diazirine cross-linker, phenyl azide, and combinations thereof.

4. The dyed material of claim 1, wherein the one or more cross-linkers comprise a first cross-linker and a second cross-linker.

5. The dyed material of claim 4, wherein the first cross-linker is an epoxy cross-linker and the second cross-linker is an aziridine cross-linker.

6. The dyed material of claim 4, wherein the first cross-linker is selected the group consisting of: an epoxy cross-linker, an aziridine cross-linker, a carbodiimide crosslinker, an isocyanate cross-linker, n-hydroxysuccinimide, an diazirine cross-linker, and phenyl azide, and wherein the second cross-linker is a different cross-linker than the first crosslinker and is selected from the group consisting of: an epoxy cross-linker, an aziridine cross-linker, a carbodiimide cross-linker, an isocyanate cross-linker, n- hydroxysuccinimide, an diazirine cross-linker, and phenyl azide.

7. The dyed material of any one of claims 1-6, wherein the dye is a reactive dye or an acid dye.

8. The dyed material of claim 7, wherein the dye is a reactive dye and is covalently bonded to the natural fibers, the one or more cross-linkers, the protein, or a combination thereof.

9. The dyed material of claim 7, wherein the dye is an acid dye and is non-covalently bonded to the natural fibers, the one or more cross-linkers, the protein, or a combination thereof.

10. The dyed material of any of any one of claims 1-9, wherein the textile is a composite textile comprising the natural fibers and a second fiber comprising a synthetic polymer.

11. The dyed material of claim 10, wherein the composite textile is a blended textile comprising the natural fibers blended with the second fiber.

12. The dyed material of claim 10, wherein the composite textile comprises a layered textile comprising a first layer comprising the natural fibers and a second layer comprising the second fiber.

13. The dyed material of any one of claims 1-12, wherein the natural fibers comprise cotton, wool, linen, silk, or a combination thereof.

14. The dyed material of any one of claims 10-12, wherein the synthetic polymer is selected from the group consisting of polyester, nylon, polypropylene, polyethylene, an acrylic polymer, rayon, spandex, lyocell, polylactic acid, polyhydroxyalkanoate, and combinations thereof.

15. The dyed material of claim 14, wherein the synthetic polymer is a polyester selected from group consisting of: polybutylene succinate, polybutylene adipate terephthalate, polyethylene furanoate, and combinations thereof.

16. The dyed material of any one of claims 10-12, wherein the one or more cross-linkers are electrostatically bonded to the synthetic polymer.

17. The dyed material of any one of claims 1-16, wherein the protein comprises a soy protein.

18. The dyed material of claim 17, wherein the soy protein is soy protein isolate.

19. The dyed material of any one of claims 1-18, further comprising an antimicrobial agent.

20. The dyed material of any one of claims 1-19, wherein the material has a wet crocking value of greater than or equal to 2.5.

21. The dyed material of any one of claims 1-20, wherein the material has a perspiration fastness of greater than or equal to 3.

22. A textile dyeing formulation, comprising: water; one or more proteins; one or more cross-linkers, the one or more cross-linkers present at total weight percent ranging from greater than or equal to about 5 wt% to less than or equal to about 90 wt% relative to the one or more proteins in the formulation; and one or more dyes, the one or more dyes present at a total weight percent ranging from greater than or equal to about 5 wt% to less than or equal to about 200 wt% relative to the one or more proteins in the formulation.

23. The dyeing formulation of claim 22, wherein the one or more dyes are reactive dyes.

24. The dyeing formulation of claim 22, wherein the one or more dyes are acid dyes.

25. The dyeing formulation of any one of claims 22-24, wherein the one or more crosslinkers comprise an aziridine cross-linker.

26. The dyeing formulation of any one of claims 22-24, wherein the one or more crosslinkers are selected from the group consisting of: an aziridine cross-linker, a carbodiimide cross-linker, an isocyanate cross-linker, n-hydroxysuccinimide, a diazirine cross-linker, phenyl azide, and combinations thereof.

27. The dyeing formulation of any one of claims 22-24, wherein the one or more crosslinkers comprise a first cross-linker and a second cross-linker.

28. The dyeing formulation of claim 27, wherein the first cross-linker is an epoxy cross-linker and the second cross-linker is an aziridine cross-linker.

29. The dyeing formulation of claim 27, wherein the first cross-linker is selected the group consisting of: an epoxy cross-linker, an aziridine cross-linker, a carbodiimide crosslinker, an isocyanate cross-linker, n-hydroxysuccinimide, a diazirine cross-linker, and phenyl azide, and wherein the second cross-linker is a different cross-linker selected the group consisting of: an epoxy cross-linker, an aziridine cross-linker, a carbodiimide crosslinker, an isocyanate cross-linker, n-hydroxysuccinimide, a diazirine cross-linker, and phenyl azide.

30. The dyeing formulation of any one of claims 22-29, further comprising one or more bases.

31. The dyeing formulation of claim 30, wherein the one or more bases is a nucleophilic base present at a weight percent less than or equal to about 2 wt% relative to the one or more proteins in the formulation.

32. The dyeing formulation of claim 30, wherein the one or more bases is a non-nucleophilic base present at a weight percent ranging from greater than or equal to about 1 wt% to less than or equal to about 15 wt% relative to the one or more proteins in the formulation.

33. The dyeing formulation of any one of claims 22-29, further comprising a Lewis acid present at a weight percent ranging from greater than or equal to about 1 wt% to less than or equal to about 15 wt% relative to the one or more proteins in the formulation.

34. The dyeing formulation of any one of claims 22-33, further comprising one or more surfactants.

35. The dyeing formulation of claim 34, wherein the one or more surfactants is present at a total weight percent less than or equal to about 50 wt% relative to the one or more proteins in the formulation.

36. The dyeing formulation of any one of claims 22-35, further comprising one or more plasticizers.

37. The dyeing formulation of claim 36, wherein the one or more plasticizers are present at a total weight percent less than or equal to about 60 wt% relative to the one or more proteins in the formulation.

38. The dyeing formulation of claim 36, wherein the one or more plasticizers are selected from the group consisting of: glycerol, propylene glycol, sorbitol, a polyol polymer, and combinations thereof.

39. The dyeing formulation of any one of claims 22-38, further comprising one or more denaturants present at a total weight percent ranging from greater than or equal to about 1 wt% to less than or equal to about 200 wt% relative to the one or more proteins in the formulation.

40. The dyeing formulation of any one of claims 22-39, further comprising one or more binding agents present at a total weight percent less than or equal to about 10 wt% relative to the one or more proteins in the formulation.

41. The dyeing formulation of claim 40, wherein the one or more binding agents are selected from the group consisting of: polyacrylic acid, polyacrylamide, sodium alginate, and combinations thereof.

42. The dyeing formulation of any one of claims 22-41, further comprising one or more antimicrobial agents present at a total weight percent less than or equal to about 5 wt% relative to the one or more proteins in the formulation.

43. The dyeing formulation of any one of claims 22-42, wherein the one or more proteins are present at a total weight percent ranging from greater than or equal to about 10 wt% to less than or equal to about 50 wt% relative to the water in the formulation.

44. The dyeing formulation of any one of claims 22-43, further comprising one or more radial initiators present at a total weight percent less than or equal to about 5 wt% relative to the one or more proteins in the formulation.

45. A method for dyeing a textile, the method comprising: a. applying the dyeing formulation according to any one of claims 22-44 to a textile comprising natural fibers comprising hydroxyl functional groups; andb. curing the dyeing formulation on the textile.

46. A method for dyeing a textile, the method comprising: a. applying a protein formulation to a textile, wherein the protein formulation comprises water, one or more proteins, and one or more cross-linkers present at total weight percent ranging from greater than or equal to about 5 wt% to less than or equal to 90 about wt% relative to the one or more proteins in the formulation, and wherein the textile comprises natural fibers comprising hydroxyl functional groups; b. drying the protein formulation on the textile to form a cross-linked textile; and c. applying one or more dyes to the cross-linked textile to bond the one or more dyes to the natural fibers, the one or more cross-linkers, the one or more proteins, or a combination thereof.

47. The method of claim 46, wherein drying the protein formulation comprises drying and curing the protein formulation on the textile.

48. A composite material, comprising: a. a composite textile comprising: i. a first fiber comprising hydroxyl functional groups, and ii. a second fiber comprising a synthetic polymer; b. a protein; and c. a dye; wherein the protein is covalently linked to at least the first fiber via an epoxy cross-linker; and wherein the dye is bonded to the first fiber, the epoxy cross-linker, the protein, or a combination thereof.

49. The composite material of claim 48, wherein the dye is a reactive dye or an acid dye.

50. The composite material of claim 49, wherein the dye is a reactive dye and is covalently bonded to the first fiber, the epoxy cross-linker, the protein, or a combination thereof.

51. The composite material of claim 49, wherein the dye is an acid dye and is non-covalently bonded to the first fiber, the epoxy cross-linker, the protein, or a combination thereof.

52. The composite material of any one of claims 48-51, wherein the first fiber is a natural fiber.

53. The composite material of claim 52, wherein the natural fiber is cotton, wool, linen, silk, or a combination thereof.

54. The composite material of any one of claims 48-53, wherein the synthetic polymer is selected from the group consisting of: polyester, nylon, polypropylene, polyethylene, an acrylic polymer, rayon, spandex, lyocell, polylactic acid, polyhydroxyalkanoate, and combinations thereof.

55. The composite material of claim 54, wherein the synthetic polymer is a polyester selected from group consisting of: polybutylene succinate, polybutylene adipate terephthalate, polyethylene furanoate, and combinations thereof.

56. The composite material of any one of claims 48-55, wherein the protein comprises a soy protein.

57. The composite material of claim 56, wherein the soy protein is soy protein isolate.

58. The composite material of any one of claims 48-57, wherein the epoxy cross-linker comprises a polyglycidyl ether.

59. The composite material of any one of claims 48-58, further comprising an antimicrobial agent.

60. The composite material of any one of claims 48-59, wherein the material has a wet crocking value of greater than or equal to about 2.5.

61. The composite material of any one of claims 48-60, wherein the material has a perspiration fastness of greater than or equal to about 3.

62. The composite material of any one of claims 48-61, wherein the composite textile is a blended textile comprising the first fiber blended with the second fiber.

63. The composite material of any one of claims 48-61, wherein the composite textile comprises a layered textile comprising a first layer comprising the first fiber and a second layer comprising the second fiber.

64. The composite material of any one of claims 48-63, wherein the epoxy cross-linker is electrostatically bonded to the synthetic polymer.

65. A textile dyeing formulation, comprising: water; one or more proteins; one or more epoxy cross-linkers, the one or more epoxy cross-linkers present at a total weight percent ranging from greater than or equal to about 10 wt% to less than or equal to about 90 wt% relative to the one or more proteins in the formulation; and one or more dyes, the one or more dyes present at a total weight percent ranging from greater than or equal to about 5 wt% to less than or equal to about 200 wt% relative to the one or more proteins in the formulation.

66. The dyeing formulation of claim 65, wherein the one or more dyes are reactive dyes.

67. The dyeing formulation of claim 65, wherein the one or more dyes are acid dyes.

68. The dyeing formulation of any one of claims 65-67, further comprising one or more bases.

69. The dyeing formulation of claim 68, wherein the one or more bases is a nucleophilic base present at a weight percent less than or equal to about 2 wt% relative to the one or more proteins in the formulation.

70. The dyeing formulation of claim 68, wherein the one or more bases is a non-nucleophilic base present at a weight percent ranging from greater than or equal to about 1 wt% to less than or equal to about 15 wt% relative to the one or more proteins in the formulation.

71. The dyeing formulation of any one of claims 65-67, further comprising a Lewis acid present at a weight percent ranging from greater than or equal to about 1 wt% to less than or equal to about 15 wt% relative to the one or more proteins in the formulation.

72. The dyeing formulation of any one of claims 65-71, further comprising one or more surfactants.

73. The dyeing formulation of claim 72, wherein the one or more surfactants are present at a total weight percent less than or equal to about 50 wt% relative to the one or more proteins in the formulation.

74. The dyeing formulation of any one of claims 65-73, further comprising one or more plasticizers.

75. The dyeing formulation of claim 74, wherein the one or more plasticizers are present at a total weight percent less than or equal to about 60 wt% relative to the one or more proteins in the formulation.

76. The dyeing formulation of claim 74, wherein the one or more plasticizers are selected from the group consisting of: glycerol, propylene glycol, sorbitol, a polyol polymer, and combinations thereof.

77. The dyeing formulation of any one of claims 65-76, further comprising one or more denaturants present at a total weight percent ranging from greater than or equal to about 1 wt% to less than or equal to about 200 wt% relative to the one or more proteins in the formulation.

78. The dyeing formulation of any one of claims 65-77, further comprising one or more binding agents present at a total weight percent less than or equal to about 10 wt% relative to the one or more proteins in the formulation.

79. The dyeing formulation of claim 78, wherein the one or more binding agents are selected from the group consisting of: polyacrylic acid, polyacrylamide, sodium alginate, and combinations thereof.

80. The dyeing formulation of any one of claims 65-79, further comprising one or more antimicrobial agents present at a total weight percent less than or equal to about 5 wt% relative to the one or more proteins in the formulation.

81. The dyeing formulation of any one of claims 65-80, wherein the one or more proteins are present at a total weight percent ranging from greater than or equal to about 10 wt% to less than or equal to about 50 wt% relative to the water in the formulation.

82. The dyeing formulation of any one of claims 65-81, further comprising one or more radial initiators present at a total weight percent less than or equal to about 5 wt% relative to the one or more proteins in the formulation.

83. A method for dyeing a textile, the method comprising: a. applying the dyeing formulation according to any one of claims 65-81 to a composite textile comprising a first fiber comprising hydroxyl functional groups and a second fiber comprising a synthetic polymer; and b. curing the dyeing formulation on the composite textile.

84. A method for dyeing a textile, the method comprising: a. applying a protein formulation to a composite textile, wherein the protein formulation comprises water, one or more proteins, and one or more epoxy crosslinkers present at a total weight percent ranging from greater than or equal to about 10 wt% to less than or equal to about 90 wt% relative to the one or more proteins in the formulation, and wherein the composite textile comprises a first fiber comprising hydroxyl functional groups and a second fiber comprising a synthetic polymer; b. drying the protein formulation on the composite textile to form a cross-linked textile; and c. applying one or more dyes to the cross-linked textile to bond the one or more dyes to the first fiber, the one or more epoxy cross-linkers, the one or more proteins, or a combination thereof.

85. The method of claim 84, wherein drying the protein formulation comprises drying and curing the protein formulation on the composite textile.

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