TW202500672A - Protein polyurethane alloy membranes - Google Patents

Abstract

Materials with a membrane comprising a protein polyurethane alloy comprising (a) a protein dissolved within a polyurethane prepared from an aqueous polyurethane dispersion and (b) a cross-linker. In some embodiments, the protein polyurethane alloy can have a waterproofness of greater than 3,000 mm of H2O measured according to JIS L 1092 hydrostatic pressure method test. In some embodiments, the protein polyurethane alloy can have a breathability of greater than 3,000 g/m2/24hr measured according to JIS L 1099 B1. The membranes can achieve these waterproofness and/or breathability characteristics at thicknesses less than or equal to about 200 microns.

Description

Protein polyurethane blend membrane

Cross-reference to related applications

The contents of the sequence listing submitted electronically in the XML file submitted with this application (name: 4431_111TW02_SeqListing_ST26.xml; file size: 2,497 bytes; and creation date: June 17, 2024) are incorporated herein by reference in their entirety.

The present disclosure relates to films for use in textile materials. In some embodiments, the films can be applied to textile materials for use in making various articles, such as fabrics, clothing, fashion accessories, or interior decoration.

Textile or woven materials, including natural materials (e.g., cotton), synthetic materials (e.g., spandex and polyester), and composite textiles (including both natural and synthetic materials), are used in a variety of industries, including the furniture and apparel industries. These textile or woven materials may be coated or treated to impart one or more desired characteristics or properties. There remains a continuing need to improve the properties and performance of textile materials, as well as to improve the processes for manufacturing these materials.

The present disclosure provides films having protein polyurethane blends that have high air permeability, high water resistance, or both. The unique combination of one or more proteins and one or more aqueous polyurethane dispersions as described herein can form films (e.g., films having a thickness of less than 50 microns) having desired air permeability and water resistance properties for a variety of textile materials.

The first embodiment (1) of the present disclosure relates to a membrane comprising a protein polyurethane blend, comprising: a protein dissolved in a polyurethane prepared from an aqueous polyurethane dispersion, a crosslinking agent, and having a thickness ranging from about 5 microns to about 200 microns; wherein the protein polyurethane blend has a water resistance of greater than 3,000 mm H ₂ O measured by the hydrostatic pressure test according to JIS L 1092 and an air permeability of greater than 3,000 g/m ² /24hr measured according to JIS L 1099 B1.

In the second embodiment (2), the crosslinking agent according to the first embodiment (1) is selected from the group consisting of epoxy crosslinking agents, aziridine crosslinking agents, isocyanate crosslinking agents, carbodiimide crosslinking agents, melamine crosslinking agents, and combinations thereof.

In the third embodiment (3), the protein polyurethane mixture according to the first embodiment (1) or the second embodiment (2) further comprises a second polyurethane.

In the fourth embodiment (4), the protein is dissolved in the second polyurethane of the third embodiment (3).

In a fifth embodiment (5), the film according to any one of embodiments (1) to (4) has a dry weight greater than or equal to about 5 g/ ^m2 .

In the sixth embodiment (6), the protein polyurethane blend according to any one of embodiments (1) to (5) has an air permeability of more than 5,000 g/m ² /24hr measured according to JIS L 1099 B1.

In the seventh embodiment (7), the protein polyurethane blend according to any one of embodiments (1) to (5) has an air permeability of more than 3,000 g/m ² /24hr measured according to JIS L 1099 A1.

In the eighth embodiment (8), the protein polyurethane blend according to any one of embodiments (1) to (5) has an air permeability measured according to ASTM E 96 B of greater than 250 g/m ² /24hr.

In the ninth embodiment (9), the protein polyurethane blend according to any one of embodiments (1) to (8) has a water repellency of greater than 10,000 mm H ₂ O measured according to JIS L 1092.

In a tenth embodiment (10), the protein-polyurethane blend according to any one of embodiments (1) to (9) comprises greater than or equal to about 5 wt % of the protein.

In an eleventh embodiment (11), the polyurethane according to any one of embodiments (1) to (10) comprises a biocontent greater than or equal to about 15% as measured according to ASTM D6866.

In a twelfth embodiment (12), the protein polyurethane blend according to any one of embodiments (1) to (11) comprises a biocontent greater than or equal to about 35% as measured according to ASTM D6866.

In the thirteenth embodiment (13), the protein polyurethane blend according to any one of embodiments (1) to (12) is dyed with an acidic or reactive dye.

In a fourteenth embodiment (14), the membrane according to any one of embodiments (1) to (13) is non-porous or microporous.

In a fifteenth embodiment (15), the film according to any one of embodiments (1) to (14) is treated with a water repellent finish and comprises a water repellency spray rating of greater than or equal to about 70 as measured according to AATCC 22.

In a sixteenth embodiment (16), a film according to any one of embodiments (1) to (14) is treated with a polyurethane finish and comprises a water repellency spray rating of greater than or equal to about 70 as measured according to AATCC 22.

In the seventeenth embodiment (17), the film according to any one of embodiments (1) to (14) has a dry Martindale abrasion of greater than or equal to about 20,000 cycles as measured according to the Martindale Abrasion Test with a 9 kPa load.

In the eighteenth embodiment (18), the protein according to any one of embodiments (1) to (17) is soy protein isolate.

In the nineteenth embodiment (19), the aqueous polyurethane dispersion according to any one of embodiments (1) to (18), when cured in the absence of a protein and a crosslinking agent, has a water resistance of greater than 10,000 mm H ₂ O as measured by the JIS L 1092 hydrostatic pressure method test.

In the twentieth embodiment (20), the aqueous polyurethane dispersion according to any one of embodiments (1) to (18) comprises an aqueous aliphatic polyether-based polyurethane having a solid content of about 35% and a specific gravity of about 1.02 g/mL; a nonionic aliphatic polycarbonate-polyether polyurethane dispersion having a solid content of about 30% and a specific gravity of about 1.1 g/mL; an aqueous aliphatic nonionic polyurethane dispersion having a solid content of about 32%, a specific gravity of 1.03 g/mL, and a Brookfield viscosity of about 200 mPa.s; an aqueous aliphatic nonionic polyurethane dispersion having a solid content of about 50%, a specific gravity of 1.1 g/mL, a Brookfield viscosity of less than or equal to 1200 mPa.s, a biocontent of about 50% as measured according to ASTM D6866, a specific gravity of 30 An aqueous aliphatic anionic polyester polyurethane dispersion having a tensile strength of about 12 MPa, and an elongation at break of 1000%; an aqueous aliphatic anionic polyester polyurethane dispersion having a solids content of about 50%, a specific gravity of 1.1 g/mL, a Brookfield viscosity of less than or equal to 1200 mPa.s, a biocontent of about 56% as measured according to ASTM D6866, a tensile strength of 12 MPa, and an elongation at break of 800%, or a combination thereof.

The twenty-first embodiment (21) of the present disclosure relates to a precursor formulation comprising: water; protein; aqueous polyurethane dispersion; and one or more crosslinking agents, which are present in a weight percentage ranging from about 0.1 wt % to about 5 wt % relative to the total weight of water, protein, and aqueous polyurethane dispersion in the formulation.

In the twenty-second embodiment (22), the protein of the twenty-first embodiment (21) is dissolved in the polyurethane of the polyurethane dispersion.

In the twenty-third embodiment (23), one or more crosslinking agents according to the twenty-first embodiment (21) or the twenty-second embodiment (22) are selected from the group consisting of epoxy crosslinking agents, aziridine crosslinking agents, isocyanate crosslinking agents, carbodiimide crosslinking agents, melamine crosslinking agents, and combinations thereof.

In the twenty-fourth embodiment (24), the formulation according to any one of embodiments (21) to (23) further comprises an acid dye or a reactive dye.

In the twenty-fifth embodiment (25), the formulation according to any one of embodiments (21) to (24) further comprises a defoaming agent or an antifoaming agent.

In the twenty-sixth embodiment (26), the defoaming agent according to the twenty-fifth embodiment (25) is a defoaming agent based on mineral oil.

In the twenty-seventh embodiment (27), the aqueous polyurethane dispersion according to any one of embodiments (21) to (26), when cured in the absence of a protein and a crosslinking agent, has a water resistance of greater than 3,000 mm H ₂ O as measured by the JIS L 1092 hydrostatic pressure test.

In the twenty-eighth embodiment (28), the aqueous polyurethane dispersion according to any one of embodiments (21) to (26) comprises an aqueous aliphatic polyether-based polyurethane having a solid content of about 35% and a specific gravity of about 1.02 g/mL; a non-ionic aliphatic polycarbonate-polyether polyurethane dispersion having a solid content of about 30% and a specific gravity of about 1.1 g/mL; an aqueous aliphatic non-ionic polyurethane dispersion having a solid content of about 32%, a specific gravity of 1.03 g/mL, and a Brookfield viscosity of about 200 mPa.s; an aqueous aliphatic non-ionic polyurethane dispersion having a solid content of about 50%, a specific gravity of 1.1 g/mL, a Brookfield viscosity of less than or equal to 1200 mPa.s, a biocontent of about 50% as measured according to ASTM D6866, a specific gravity of 30 An aqueous aliphatic anionic polyester polyurethane dispersion having a tensile strength of about 12 MPa, and an elongation at break of 1000%; an aqueous aliphatic anionic polyester polyurethane dispersion having a solids content of about 50%, a specific gravity of 1.1 g/mL, a Brookfield viscosity of less than or equal to 1200 mPa.s, a biocontent of about 56% as measured according to ASTM D6866, a tensile strength of 12 MPa, and an elongation at break of 800%, or a combination thereof.

The twenty-ninth embodiment (29) of the present disclosure relates to an article comprising: a textile; and a film according to any one of embodiments (1) to (20), attached to the textile.

In the thirtieth embodiment (30), the film according to the twenty-ninth embodiment (29) is attached to the textile with an adhesive.

In the thirty-first embodiment (31), the textile according to the twenty-ninth embodiment (29) or the thirtieth embodiment (30) includes a first textile layer and a second textile layer, and the film is disposed between the first textile layer and the second textile layer.

In the thirty-second embodiment (32), the film according to the twenty-ninth embodiment (29) or the thirtieth embodiment (30) is attached to an outer surface of the textile.

The thirty-third embodiment (33) of the present disclosure relates to an article comprising: a textile; and a coating comprising the formulation according to any one of embodiments (21) to (28), the coating being attached to the textile.

In the thirty-fourth embodiment (34), the coating according to the thirty-third embodiment (33) is directly attached to one surface of the textile.

In the thirty-fifth embodiment (35), the coating according to the thirty-third embodiment (33) or the thirty-fourth embodiment (34) is attached to a front surface of the textile.

In the thirty-sixth embodiment (36), the coating according to any one of embodiments (33) to (35) is attached to a back surface of the textile.

In the thirty-seventh embodiment (37), the article according to any one of embodiments (33) to (36) is dyed with an acid dye, a reactive dye, or a combination thereof.

In the thirty-eighth embodiment (38), the textile according to the thirty-seventh embodiment (37) is dyed with an acid dye, a reactive dye, or a combination thereof.

In the thirty-ninth embodiment (39), the coating according to the thirty-seventh embodiment (37) or the thirty-eighth embodiment (38) is dyed with an acid dye, a reactive dye, or a combination thereof.

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

The terms "comprising" and "including" are open-ended transition phrases. The list of elements following the transition phrase "comprising" or "including" is a non-exclusive list such that there may be elements other than those specifically recited in the list. The phrase "consisting essentially of" limits the composition of a component to the specified materials and materials that do not materially affect the basic and novel properties of the component. The phrase "consisting of" limits the composition of a component to the specified materials and excludes any unspecified materials.

When a numerical range including an upper limit and a lower limit is recorded herein, unless otherwise specified in a specific case, the range is intended to include its end value and all integers and fractions within the range. The disclosure or patent application scope is not intended to be limited to the specific values recorded when defining a range. In addition, when an amount, concentration, or other value or parameter is given as a range, one or more ranges, or as a list with an upper limit and a lower limit, it should be understood to specifically disclose all ranges formed by any pair of any range upper limit (or upper limit value) and any range lower limit (or lower limit value), regardless of whether such pairing is disclosed separately. Finally, when the term "about" is used to describe a numerical value or an end point of a range, the disclosure should be understood to include the specific value or end value mentioned. Regardless of whether a value or an end-point of a range is expressed as "about," the value or the end-point of a range is intended to include two embodiments: one modified by "about" and the other not modified by "about."

As used herein, the term "about" refers to values within ±10% of the stated value. 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). However, if a percentage is listed and the value of the percentage cannot exceed 100% (e.g., 100 wt% or 99 wt%), "about" cannot modify the percentage to include values exceeding 100%. .

As used herein, a first component (e.g., a film, a blend, or a textile) is described as being "attached to" a second component means that the components are attached to each other by direct contact and attachment between the two components or through one or more intermediate adhesive layers. An intermediate adhesive layer can be any layer used to attach a first component to a second component.

As used herein, the phrase "disposed on" means that a first component is in direct contact with a second component. A first component "disposed on" a second component may be deposited, formed, placed, or otherwise applied directly to the second component. In other words, if a first component is disposed on a second component, there are no components between the first component and the second component.

As used herein, the phrase “disposed over” means that other components (eg, films or textiles) may or may not be present between a first component and a second component.

As used herein, "bio-based polyurethane" is a polyurethane in which the building blocks of polyols (such as diols) and diacids (such as succinic acid) are derived from biomaterials (such as corn starch).

As used herein, the term "substantially free of" means that a component is present in a detectable amount of no more than about 0.1 wt%.

As used herein, the term "free of" means that a component is not present in a blend or material (eg, a protein polyurethane blend), even in trace amounts.

As used herein, "collagen" refers to a family of at least 28 different 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. As used herein, the term collagen also refers to collagen prepared using recombinant technology, i.e., recombinant collagen. The term "collagen" includes collagen, collagen fragments, collagenoids, triple helical collagen, alpha chains, monomers, gelatin, trimers, and combinations thereof. The 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; U.S. Patent No. 6,428,978 to Olsen et al. and U.S. Patent No. 8,188,230 to VanHeerde et al., which are incorporated herein by reference in their entirety). Unless otherwise specified, any type of collagen, whether naturally occurring or prepared using recombinant techniques, can be used in any of the embodiments described herein. Nevertheless, in some embodiments, the collagen described herein can be prepared using bovine type I collagen. Collagen is characterized by repeated amino acid triplets - (Gly-XY)n-, such that about one-third of the amino acid residues in collagen are glycine. X is often proline, and Y is often hydroxyproline. Therefore, the structure of collagen can be composed of three intertwined peptide chains of different lengths. Different animals can produce collagen with different amino acid compositions, which can lead to different properties.

In some embodiments, collagen can be chemically modified to improve solubility in water.

Any type of collagen, truncated collagen, unmodified or translationally modified collagen, or collagen with amino acid sequence modifications can be used as part of the protein polyurethane blend.

In some embodiments, the collagen can be plant-based collagen. For example, the collagen can be plant-based collagen produced by CollPlant.

In some embodiments, a recombinant collagen may comprise a collagen fragment having an amino acid sequence of a natural collagen molecule capable of forming tropocollagen (trimeric collagen). The recombinant collagen may also comprise a modified collagen or a truncated collagen having an amino acid sequence that is at least 70%, 80%, 90%, 95%, 96%, 97%, 98%, or 99% identical or similar to the amino acid sequence of natural collagen (or to a fibril-forming region thereof, or to a chain segment substantially comprising [Gly-X-Y]n). In some embodiments, the collagen fragment may be a 50 kDa portion of a natural collagen. The natural collagen sequence includes the amino acid sequences of CollA1, CollA2, and Col3A1 described by accession numbers NP_001029211.1, NP_776945.1, and NP_001070299.1, which are incorporated herein by reference. In some embodiments, the collagen fragment may be a portion of human collagen α-1 (III) (Col3A1; Uniprot # P02461, Entrez Gene ID # 1281). In some embodiments, the collagen fragment may be an amino acid sequence as shown in 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. Exemplary proteins comprising at least 80% sequence identity to SEQ ID NO: 1 are disclosed in PCT/US2022/027016, the disclosure of which is incorporated herein by reference.

Methods for producing recombinant collagen and recombinant collagen fragments are known in the art. For example, U.S. Publication Nos. 2019/0002893, 2019/0040400, 2019/0093116, and 2019/0092838 provide methods for producing collagen and collagen fragments, which can be used to produce the recombinant collagen and recombinant collagen fragments disclosed herein. These four disclosures are incorporated herein by reference in their entirety.

The protein polyurethane blends for membranes described herein may include proteins that are miscible with only one of the multiple phases of polyurethane when blended, or with multiple polyurethanes. For example, in some embodiments, the protein polyurethane blend may include proteins that are miscible with only the hard phase of polyurethane, or with multiple polyurethanes having both a hard phase and a soft phase. In specific embodiments, the protein polyurethane blend may include one or more proteins that are only dissolved in the hard phase of one or more polyurethanes. The protein polyurethane blends described herein may not contain or substantially contain proteins dispersed in the polyurethane in the form of particles. For example, in some embodiments, the protein polyurethane blend may not contain or substantially contain protein particles having an average diameter greater than 1 micron (µm).

Protein polyurethane blends, methods of making them, and exemplary properties of such blends are described in US 2021/0355326, the disclosure of which is incorporated herein by reference.

In some embodiments, the protein polyurethane blend may be free of or substantially free of protein particles having an average diameter greater than 1 micron (µm). In some embodiments, the protein polyurethane blend may be free of or substantially free of soy protein particles having an average diameter greater than 1 micron (µm). In some embodiments, the protein polyurethane blend may be free of or substantially free of collagen particles having an average diameter greater than 1 micron (µm). In some embodiments, the protein polyurethane blend may be free of or substantially free of gelatin particles having an average diameter greater than 1 micron (µm). In some embodiments, the protein polyurethane blend may be free of or substantially free of bovine serum albumin particles having an average diameter greater than 1 micron (µm). In some embodiments, the protein polyurethane blend may be free of or substantially free of pea protein particles having an average diameter greater than 1 micron (µm). In some embodiments, the protein polyurethane blend may be free of or substantially free of egg white albumin particles having an average diameter greater than 1 micron (µm). In some embodiments, the protein polyurethane blend may be free of or substantially free of casein protein particles having an average diameter greater than 1 micron (µm). In some embodiments, the protein polyurethane blend may be free of or substantially free of peanut protein particles having an average diameter greater than 1 micron (µm). In some embodiments, the protein polyurethane blend may be free of or substantially free of linseed protein particles having an average diameter greater than 1 micron (µm). In some embodiments, the protein polyurethane blend may be free of or substantially free of whey protein particles having an average diameter greater than 1 micron (µm). In some embodiments, the protein polyurethane blend may be free of or substantially free of karanja protein particles having an average diameter greater than 1 micron (µm). In some embodiments, the protein polyurethane blend may be free of or substantially free of cellulose enzyme particles having an average diameter greater than 1 micron (µm). In some embodiments, the protein polyurethane blend may be free of or substantially free of recombinant collagen fragment particles having an average diameter greater than 1 micron (µm).

The proteins suitable for use in the blends disclosed herein may be unmodified or chemically modified. In some embodiments, the protein may be modified to promote miscibility of the protein with the hard phase of the polyurethane. In some embodiments, the protein may be chemically modified to enhance solubility in water. In such embodiments, chemical modifications that enhance solubility in water may enhance miscibility of the protein with the hard phase of the polyurethane. In some embodiments, the chemically modified protein may be a partially hydrolyzed protein. In some embodiments, the chemically modified protein may be a protein modified by covalent attachment of a hydrophilic polymer chain, such as a polyethylene glycol (PEG) chain, to the protein.

Polyurethanes suitable for use in the protein polyurethane blends described herein include polyurethanes containing at least two phases, including a "soft phase" and a "hard phase". The soft phase is formed by polyol segments within the polyurethane that separate from the urethane-containing phase due to differences in polarity. The urethane-containing phase is referred to as the hard phase. This phase separation is well known in the art and is the basis of many of the properties of polyurethanes.

The soft phase is generally elastic at room temperature and generally has a softening point or glass transition temperature (Tg) below room temperature. Tg can be measured by dynamic analysis (DMA) and quantified by the peak value of tan (δ) or the onset of the decrease in storage modulus. Alternatively, Tg can be measured by differential scanning calorimetry (DSC). In some cases, there may be a degree of crystallinity in the soft phase, which can be regarded as a melting point, generally between 0°C and about 60°C.

The hard phase generally has a Tg or melting point above room temperature, more generally above about 80° C. Softening of the hard phase can be measured by measuring the onset of the drop in storage modulus (sometimes referred to as stiffness) as measured by DMA.

The "soft phase" of the polyurethane or protein polyurethane blend including polyurethane comprises the polyol component of the polyurethane. Its function is to become soft and flexible at a temperature above its Tg to impart toughness, elongation and flexibility to the polyurethane. Typical soft segments may comprise polyether polyols, polyester polyols, polycarbonate polyols, and mixtures thereof. Their general molecular weights range from about 250 Daltons to greater than about 5,000 Daltons. The "hard phase" of the polyurethane or protein polyurethane blend including polyurethane comprises the urethane segments of the polymer, which are imparted by isocyanate(s) used to link polyols and short chain diols (such as butanediol, propylene glycol, and the like). Typical isocyanates that can be used in the polyurethanes of the present invention include, but are not limited to, hexamethylene diisocyanate, isophorone diisocyanate, methylene diisocyanate, phenyl diisocyanate, and the like. These molecules are more polar and harder than the polyols used to make the soft segments. Therefore, the hard segments are harder and have a higher softening point than the soft segments. The function of the hard phase is to provide polyurethane with properties such as strength, temperature resistance and wear resistance.

The protein polyurethane blends and films described herein can be formed by blending one or more proteins with one or more aqueous polyurethane dispersions in a liquid state and drying the blend. In some embodiments, the protein polyurethane blends and films described herein can be formed by blending one or more proteins dissolved or dispersed in an aqueous solution with one or more aqueous polyurethane dispersions in a liquid state and drying the blend. In some embodiments, the polyurethane dispersion can be ionic and can be anionic or cationic. In some embodiments, the polyurethane dispersion can be non-ionic. In some embodiments, the blended protein and polyurethane can form a film and in some embodiments can be attached to a substrate (e.g., a textile) using a suitable attachment process (e.g., direct coating, lamination process, or thermal molding process). In some embodiments, the lamination process can include using an adhesive to attach the film to the substrate. In some embodiments, the blended protein and polyurethane can be coated or otherwise deposited over a substrate to attach the blended protein and polyurethane to the substrate. In some embodiments, attaching the blended protein and polyurethane to the substrate can result in integrating the blended protein and polyurethane into a portion of the substrate.

One or more proteins dissolved in the hard phase of one or more polyurethanes can form a homogeneous mixture when blended. In some embodiments, the protein polyurethane blend can include a plurality of proteins dissolved in one or more polyurethanes, so that the proteins and (multiple) polyurethanes form a homogeneous mixture when blended and dried. Generally speaking, the protein polyurethane blend comprising a homogeneous mixture of protein and polyurethane does not include a large amount of protein that is not dissolved in the polyurethane. Nevertheless, in some embodiments, the protein polyurethane blend can include a portion of the protein dispersed in the polyurethane.

In some embodiments, the protein polyurethane blend may include one or more coloring agents. In some embodiments, the coloring agent may be a dye, such as a fiber-reactive dye, a direct dye, or a natural dye. Exemplary dyes include, but are not limited to, azo acid dyes, metal complex acid dyes, anthraquinone acid dyes, azo/diazo direct dyes, sulfur dyes, and vat dyes. In some embodiments, the coloring agent may be a pigment, such as a lake pigment.

Polyurethanes suitable for blending with one or more proteins according to the embodiments described herein include, but are not limited to, aliphatic polyurethanes, aromatic polyurethanes, bio-based polyurethanes, or polyurethanes modified with acrylic acid. Suitable polyurethanes are commercially available from manufacturers including Lubrizol, Hauthaway, Stahl, and the like. In some embodiments, the polyurethanes used for protein polyurethane blends may be bio-polyurethanes. In some embodiments, the polyurethanes may be polyester polyurethanes. In some embodiments, the polyurethanes may be polyether polyurethanes. In some embodiments, the polyurethanes may be polycarbonate-based polyurethanes. In some embodiments, the polyurethanes may be aliphatic polyester polyurethanes. In some embodiments, the polyurethanes may be aliphatic polyether polyurethanes. In some embodiments, the polyurethane may be an aliphatic polycarbonate polyurethane. In some embodiments, the polyurethane may be an aromatic polyester polyurethane. In some embodiments, the polyurethane may be an aromatic polyether polyurethane. In some embodiments, the polyurethane may be an aromatic polycarbonate polyurethane. In some embodiments, the polyurethane may be an aliphatic anionic polyester polyurethane.

In some embodiments, the polyurethane may have a soft segment selected from the group consisting of: polyether polyols, polyester polyols, polycarbonate polyols, and mixtures thereof. In some embodiments, the polyurethane may have a hard segment comprising a diisocyanate and, optionally, a short-chain diol. Suitable diisocyanates may be selected from the group consisting of: aliphatic diisocyanates, such as hexamethylene diisocyanate, isophorone diisocyanate; aromatic diisocyanates, such as 4,4' diphenylmethylene diisocyanate, toluene diisocyanate, phenyl diisocyanate, and mixtures thereof. Suitable short-chain diols include ethylene glycol, propylene glycol, butanediol, 2,2-methyl-1,3-propanediol, pentanediol, hexanediol, and mixtures thereof. In some embodiments, the crosslinking agent is a polyfunctional alcohol, such as trimethylol propane triol, or a diamine, such as ethylenediamine or 4,4'-diaminodiphenyldiamine.

Exemplary polyurethanes include, but are not limited to, (i) an aqueous aliphatic polyether-based polyurethane dispersion having a solids content of about 35% and a specific gravity of about 1.02 g/mL and a Brookfield viscosity of 160 mPa.s, (ii) a nonionic aliphatic polycarbonate-polyether polyurethane dispersion having a solids content of 30%, a specific gravity of 1.1 g/mL, and a viscosity of <1000 mPa.s, (iii) an aqueous aliphatic nonionic polyurethane dispersion having a solids content of about 32%, a specific gravity of 1.03 g/mL, and a Brookfield viscosity of about 200 mPa.s, (iv) an aqueous aliphatic nonionic polyurethane dispersion having a solids content of about 50%, a specific gravity of 1.1 g/mL, a Brookfield viscosity of less than or equal to 1200 mPa.s, a biocontent of about 50% as measured according to ASTM D6866, a specific gravity of 30 MPa, and an elongation at break of 1000%, (v) an aqueous aliphatic anionic polyester polyurethane dispersion having a solids content of about 50%, a specific gravity of 1.1 g/mL, a Brookfield viscosity less than or equal to 1200 mPa.s, a biocontent of about 56% as measured in accordance with ASTM D6866, a tensile strength of 12 MPa, and an elongation at break of 800%.

In some embodiments, the polyurethane of the membrane can have a biocontent of greater than or equal to about 15% as measured according to ASTM D6866. In some embodiments, the polyurethane of the membrane can have a biocontent in the following ranges: about 15% to about 80%, about 20% to about 80%, about 30% to about 80%, about 40% to about 80%, about 50% to about 80%, or about 60% to about 80%, as measured according to ASTM D6866.

Proteins suitable for blending with one or more polyurethanes according to the embodiments described herein include, but are not limited to, collagen, gelatin, bovine serum albumin (BSA), soy protein, pea protein, egg white albumin, casein, peanut protein, hemp protein, whey protein, karanja protein, barley protein, and fibronectin. Suitable collagen includes, but is not limited to, recombinant collagen (r-collagen), recombinant collagen fragments, and extracted collagen. Suitable soy protein includes, but is not limited to, soy protein isolate (SPI), soybean meal protein, and soy protein derivatives. In some embodiments, soy protein can be partially hydrolyzed soy protein isolate. Suitable pea protein includes, but is not limited to, pea protein isolate, and pea protein derivatives. In some embodiments, the pea protein can be partially hydrolyzed pea protein isolate.

Table 1 below lists some exemplary proteins and the properties of the proteins. Gelatin is gelatin from pig skin, type A (Sigma Aldrich G2500). Collagen is extracted bovine collagen purchased from Wuxi BIOT Biology-technology Company. Bovine serum albumin is Sigma Aldrich 5470 bovine serum albumin. r-Collagen is recombinant collagen from Modern Meadow. Soy protein isolate is soy protein isolate purchased from MP Medicals (IC90545625). Pea protein is pea protein powder purchased from Bobs Red Mills (MTX5232). Ovalbumin protein is albumin from chicken protein (Sigma Aldrich A5253). Casein protein is casein from milk (Sigma Aldrich C7078). Peanut protein is peanut protein powder purchased from Tru-Nut. Whey protein is whey from cow's milk (Sigma Aldrich W1500). Other suitable soy protein isolates include, but are not limited to, soy protein isolates 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 powders purchased from Puris (870 and 870H).

Kalanja protein is a protein found in kalanja seeds harvested from the Pongamia pinnata tree (also known as the Pongamia glabra tree). The protein can be extracted from kalanja seeds using a solvent extraction procedure. In some embodiments, the kalanja protein can be an isolated kalanja protein. In such embodiments, the isolated kalanja protein can be obtained by alkaline extraction and acid precipitation of defatted kalanja seed cakes.

Suitable cellulase proteins are listed in Table 1 below. "Cellulase-RG" protein is a natural Trichoderma cellulase available from Creative Enzymes ^® . "Cellulase-IG" protein is a laboratory grade cellulase available from Carolina Biological Supply Company.

The 50 KDa recombinant collagen fragment (50 KDa r-collagen fragment) in Table 1 is a collagen fragment having the amino acid sequence shown in SEQ ID NO: 1.

The "Dissolution Methods" listed in Table 1 are exemplary aqueous solvents in which proteins can be dissolved in solutions that are miscible with the hard phase of the polyurethane as described herein. Proteins that are at least partially soluble in aqueous solutions are suitable for use in forming protein-polyurethane blends with polyurethane dispersions. Table 1 : Exemplary Proteins Protein name Protein Source Dissolution method Molecular weight Isoelectric point Amino acid composition: Lysine (g/100g) Thermal stability of proteins up to 200 °C Gelatin pig water ~100 KDa ~4.8 2.6 yes Collagen ox water ~120 KDa - 2.2 - BSA (Bovine Serum Albumin) ox water ~ 66 KDa ~4.7 11.98 - r-Collagen yeast water ~100 KDa - 3.6 - Soy Protein Isolate Soybean Water + NaOH ~ 30 to 60 KDa ~4.0 to 5.0 5.6 yes Pea protein pea Water + NaOH ~ 60 to 80 KDa ~4.5 7.6 yes Ovalbumin Eggs water ~ 40 KDa ~4.8 5.7 yes Casein Milk Water + NaOH ~ 24 KDa ~4.6 7.4 - Peanut protein peanut Water + NaOH ~ 60 KDa ~4.5 2.5 yes whey Milk water ~18 KDa ~4.5 to 5.2 9.7 no Karanja protein isolation Karanja seeds water - - 14.6 - 50 KDa r-collagen fragment yeast water ~50 KDa ~9.3 3.9 - Cellulase-RG Trichoderma reesei water ~20 to 90 KDa ~4.6 to 6.9 - - Cellulase-IG Trichoderma reesei water - - - -

In some embodiments, the protein can have one or more of the following properties: (i) a molecular weight within the ranges described herein, (ii) an isoelectric point within the ranges described below, (iii) an amino acid composition measured as grams of lysine per 100 grams of protein within the ranges described below, and (iv) thermal stability of the protein up to 200°C. Protein Molecular Weight

In some embodiments, the protein can have a molecular weight in the range of about 1 KDa (kilodaltons) to about 700 KDa, inclusive. For example, the protein can have a molecular weight in the range of about 1 KDa to about 700 KDa, about 10 KDa to about 700 KDa, about 20 KDa to about 700 KDa, about 50 KDa to about 700 KDa, about 100 KDa to about 700 KDa, about 200 KDa to about 700 KDa, about 300 KDa to about 700 KDa, about 400 KDa to about 700 KDa, about 500 KDa to about 700 KDa, about 600 KDa to about 700 KDa, about 1 KDa to about 600 KDa, about 1 KDa to about 500 KDa, about 1 KDa to about 400 KDa, about 1 KDa to about 300 KDa, about 1 KDa to about 200 KDa, about 1 KDa to about 100 KDa, about 1 KDa to about 50 KDa, about 1 KDa to about 20 KDa, or about 1 KDa to about 100 KDa. KDa to about 10 KDa. Protein isoelectric point

In some embodiments, the protein can have an isoelectric point in the range of about 4 to about 10 (including subranges). For example, the protein can have an isoelectric point in the range of about 4 to about 10, about 4.5 to about 9.5, about 5 to about 9, about 5.5 to about 8.5, about 6 to about 8, about 6.5 to about 7.5, about 6.5 to about 7. In some embodiments, the protein can have an isoelectric point in the range of about 4 to about 5. Protein Amino Acid Composition

In some embodiments, the protein can have an amino acid composition in the range of about 0.5 wt % to about 100 wt %, inclusive, measured as grams of lysine per 100 grams of protein (referred to as the "lysine weight percent"). For example, the protein can have a lysine weight percentage in the following ranges: about 0.5 wt % to about 100 wt %, about 1 wt % to about 100 wt %, about 5 wt % to about 100 wt %, about 10 wt % to about 100 wt %, about 20 wt % to about 100 wt %, about 30 wt % to about 100 wt %, about 40 wt % to about 100 wt %, about 50 wt % to about 100 wt %, about 60 wt % to about 100 wt %, about 70 wt % to about 100 wt %, about 80 wt % to about 100 wt %, or about 90 wt % to about 100 wt %. In some embodiments, the protein can be polylysine.

In some embodiments, the protein can have a lysine weight percentage in the range of about 0.5 wt % to about 20 wt %, including sub-ranges. For example, the protein can have a lysine weight percentage in the following ranges: about 0.5 wt % to about 20 wt %, about 1 wt % to about 19 wt %, about 2 wt % to about 18 wt %, about 3 wt % to about 17 wt %, about 4 wt % to about 16 wt %, about 5 wt % to about 15 wt %, about 6 wt % to about 14 wt %, about 7 wt % to about 13 wt %, about 8 wt % to about 12 wt %, about 9 wt % to about 11 wt %, or about 9 wt % to about 10 wt %. In some embodiments, the protein can have a lysine weight percentage in the range of about 1 wt % to about 20 wt %. In some embodiments, the protein may have a weight percent of lysine in the range of about 5 wt % to about 20 wt %. In some embodiments, the protein may have a weight percent of lysine in the range of about 1 wt % to about 12 wt %. In some embodiments, the protein may have a weight percent of lysine in the range of about 5 wt % to about 12 wt %. In some embodiments, the protein may have a weight percent of lysine in the range of about 1 wt % to about 15 wt %. In some embodiments, the protein may have a weight percent of lysine in the range of about 5 wt % to about 15 wt %.

In some embodiments, the protein may be thermostable. In some embodiments, the protein may be non-thermally stable. As described herein, protein thermostability is determined by differential scanning calorimetry (DSC), wherein a pre-dried protein powder (wherein the moisture is less than 3%) is scanned from 0°C to 200°C. In the DSC curve of the protein, an endothermic peak greater than 10 mW/mg is determined to be a "denaturation peak", and the temperature corresponding to the endothermic "denaturation peak" is defined as the "denaturation temperature" of the protein. A "thermally stable" protein means that the protein has a denaturation temperature of 200°C or higher. For the purposes of this disclosure, a protein with a denaturation temperature below 200°C is considered to be "non-thermally stable". For example, the whey from bovine milk listed in Table 1 was found to have a denaturation temperature of 158°C by DSC and therefore the whey is considered to be non-thermostable. Protein Solubilization

In some embodiments, one or more proteins may be dissolved in an aqueous solution to form an aqueous protein mixture prior to blending with one or more polyurethanes. In some embodiments, dissolving the protein in an aqueous solution prior to blending the protein with the one or more polyurethanes may promote miscibility of the protein with the hard phase of the one or more polyurethanes. For example, dissolving the protein in an aqueous solution prior to blending the protein with the one or more polyurethanes may promote miscibility of the protein with the hard phase of the polyurethane(s). Not all proteins are naturally miscible with any phase of the polyurethanes.

Suitable aqueous solutions include, but are not limited to, water, alkaline aqueous solutions, acidic aqueous solutions, aqueous solutions including organic solvents, urea solutions, and mixtures thereof. In some embodiments, the alkaline aqueous solution may be an alkaline solution, such as sodium hydroxide, ammonia, or ammonium hydroxide solution. In some embodiments, examples of acidic aqueous solutions may be acetic acid or hydrochloric acid (HCl) solutions. Suitable organic solvents include, but are not limited to, ethanol, isopropanol, acetone, ethyl acetate, isopropyl acetate, glycerol, and the like. In some embodiments, the protein concentration in the aqueous protein mixture may be in the range of about 10 g/L to about 300 g/L, including subranges. For example, the protein concentration in the aqueous protein mixture can be about 10 g/L, about 20 g/L, about 30 g/L, about 40 g/L, about 50 g/L, about 60 g/L, about 70 g/L, about 80 g/L, about 90 g/L, about 100 g/L, about 150 g/L, about 200 g/L, about 250 g/L, or about 300 g/L, or in a range having any two of these values as endpoints (inclusive). In some embodiments, the protein concentration in the aqueous protein mixture can be in the range of about 10 g/L to about 300 g/L, about 20 g/L to about 250 g/L, about 30 g/L to about 200 g/L, about 40 g/L to about 150 g/L, about 50 g/L to about 100 g/L, about 60 g/L to about 90 g/L, or about 70 g/L to about 80 g/L.

In some embodiments, the protein may be pretreated and/or purified to improve solubility in water. Suitable pretreatments include, but are not limited to, acid treatment, alkaline treatment, enzymatic hydrolysis, and salt treatment. Exemplary acid treatments are acid hydrolysis with a suitable acid (such as acetic acid or HCl). Exemplary alkaline treatments are alkaline hydrolysis with a suitable base (such as ammonium hydroxide, NaOH, KOH, or a mixture thereof). Exemplary enzymes for hydrolysis include, but are not limited to, papain, pineapple enzyme, trypsin, alkaline proteases, and the like. Suitable purification treatments include, but are not limited to, removal of phytate with calcium salts, diafiltration, superfiltration, centrifugation, and the like.

In some embodiments, the addition of lysine or other hydrophilic amino acids to the protein prior to blending with one or more polyurethanes can promote the miscibility of the protein with the hard phase of the one or more polyurethanes.

In some embodiments, the protein may be partially hydrolyzed. Partial hydrolysis of the protein may enhance the solubility of the protein in water and/or promote the miscibility of the protein with the hard phase of the polyurethane. Partial hydrolysis of the protein may be accomplished using enzymes or strong to moderate bases.

In some embodiments, the protein can be chemically modified by covalent attachment of PEG to the protein. PEG modification of the protein can enhance the solubility of the protein in water and/or promote the miscibility of the protein with the rigid phase of polyurethane. PEG modification of the protein can be accomplished using a method of covalently attaching a hydrophilic polyethylene glycol (PEG) chain to the protein.

Membranes and membrane precursor formulations according to some embodiments described herein may include (a) a protein polyurethane blend comprising a protein dissolved in a polyurethane prepared from an aqueous polyurethane dispersion, and (b) one or more crosslinking agents.

Crosslinkers suitable for incorporation into the film and precursor formulations include, but are not limited to, epoxy crosslinkers, aziridine crosslinkers, carbodiimide crosslinkers, isocyanate crosslinkers, melamine crosslinkers, and combinations thereof.

Epoxy crosslinking agents suitable for incorporation into the film and propellant formulations include, but are not limited to, diglycidyl ethers, or polyglycidyl ethers, and combinations thereof. Exemplary diglycidyl ethers include, but are not limited to, glycerol diglycidyl ether, polyglycerol diglycidyl ether, trihydroxymethylpropane diglycidyl ether, polyoxypropylene glycol diglycidyl ether, resorcinol diglycidyl ether, isosorbide diglycidyl ether, poly(propylene 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, trihydroxymethylpropane triglycidyl ether, and pentaerythritol tetraglycidyl ether.

Aziridine crosslinkers suitable for incorporation into the membrane and precursor formulations include, but are not limited to, aziridine functionalized branched polyester crosslinkers and polyfunctional aziridines, and combinations thereof. WH-PZ5150 available from An Fong Development Co., Ltd is an exemplary aziridine functionalized branched polyester crosslinker. PZ-28 polyfunctional aziridine (trifunctional polyaziridine based on propylene imine) and PZ-33 polyfunctional aziridine (trifunctional polyaziridine based on ethylene imine) (both available from PolyAziridine LLC) are exemplary polyfunctional aziridines.

Carbodiimide crosslinking agents suitable for incorporation into the membrane and precursor formulations include, but are not limited to, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (available from Sigma-Aldrich), and ^Permutex® XR-5577 (available from Stahl).

Isocyanate crosslinkers suitable for incorporation into film and precursor formulations include, but are not limited to, ^Permutex® XR-5588 (available from Stahl), XR-13-820 (available from Stahl), AM-1506XL (available from Quaker Color, a division of McAdoo & Allen, Inc.), ^Imprafix® AH (a water-based, co-solvent-free, blocked aliphatic isocyanate available from Covestro LLC), and ^Imprafix® 2794/1 (a water-based, aliphatic blocked polyisocyanate available from Covestro LLC).

Permutex ^® XR-9181 (melamine crosslinker, available from Stahl) is an exemplary melamine crosslinker suitable for incorporation into film and precursor formulations.

In some embodiments, one or more crosslinking agents may include epoxy crosslinking agents. In some embodiments, one or more crosslinking agents may include aziridine crosslinking agents. In some embodiments, one or more crosslinking agents may include isocyanate crosslinking agents. In some embodiments, one or more crosslinking agents may include carbodiimide crosslinking agents. In some embodiments, one or more crosslinking agents may include melamine crosslinking agents. In some embodiments, one or more crosslinking agents may include two or more crosslinking agents.

In some embodiments, the one or more crosslinking agents may include at least three crosslinking agents, wherein each crosslinking agent is a different crosslinking agent selected from the group consisting of an epoxy crosslinking agent, an aziridine crosslinking agent, a carbodiimide crosslinking agent, an isocyanate crosslinking agent, and a melamine crosslinking agent.

In some embodiments, the one or more crosslinking agents include (a) a first crosslinking agent selected from the group consisting of epoxy crosslinking agents, aziridine crosslinking agents, isocyanate crosslinking agents, carbodiimide crosslinking agents, and melamine crosslinking agents, and (b) a second crosslinking agent that is different from the first crosslinking agent and is selected from the group consisting of epoxy crosslinking agents, aziridine crosslinking agents, isocyanate crosslinking agents, carbodiimide crosslinking agents, and melamine crosslinking agents. In some embodiments, the one or more crosslinking agents may include at least three crosslinking agents, wherein each crosslinking agent is a different crosslinking agent selected from the group consisting of an epoxy crosslinking agent, an aziridine crosslinking agent, an isocyanate crosslinking agent, a carbodiimide crosslinking agent, and a melamine crosslinking agent.

In some embodiments, the protein polyurethane blend of the membrane can have a thickness in the range of about 5 microns to about 200 microns (including sub-ranges) (e.g., thickness 126 shown in Figures 1A and 1B). For example, the protein polyurethane blend of the membrane can have a thickness in the following ranges: about 5 microns to about 200 microns, about 10 microns to about 200 microns, about 15 microns to about 200 microns, about 20 microns to about 200 microns, about 25 microns to about 200 microns, about 30 microns to about 200 microns, about 35 microns to about 200 microns, about 40 microns to about 200 microns, about 45 microns to about 200 microns, about 50 microns to about 200 microns, about 75 microns to about 200 microns, about 100 microns to about 200 microns, about 125 microns to about 200 microns, about 150 microns to about 200 microns, about 160 microns to about 200 microns, about 180 microns to about 200 microns, about 190 microns to about 200 microns, about 210 microns to about 200 microns, about 230 microns to about 200 microns, about 240 microns to about 200 microns, about 250 microns to about 200 microns, about 260 microns to about 200 microns, about 270 microns to about 200 microns, about 280 microns to about 200 microns, about 260 microns to about 200 microns, about 280 microns to about 200 microns, about 2 In some embodiments, the present invention relates to a nanostructured carbon foam having a thickness of 400 nm to about 800 nm, about 5 nm to about 200 nm, about 5 nm to about 175 nm, about 5 nm to about 150 nm, about 5 nm to about 125 nm, about 5 nm to about 100 nm, about 5 nm to about 75 nm, about 5 nm to about 50 nm, about 5 nm to about 45 nm, about 5 nm to about 40 nm, about 5 nm to about 35 nm, about 5 nm to about 30 nm, about 5 nm to about 25 nm, about 5 nm to about 20 nm, about 5 nm to about 15 nm, about 5 nm to about 10 nm, about 10 nm to about 40 nm, about 10 nm to about 30 nm, or about 20 nm to about 40 nm.

In some embodiments, the protein polyurethane blend of the membrane may have a dry weight greater than or equal to about 5 g/m ^2. In some embodiments, the protein polyurethane blend of the membrane may comprise a dry weight in the range of about 5 g/m ² to about 200 g/m ^2, including sub-ranges. For example, the protein polyurethane blend of the membrane can have a dry weight in the following ranges: 5 g/m ² to about 200 g/m ² , about 10 g/m ² to about 200 g/m ² , about 15 g/m ² to about 200 g/m ² , about 20 g/m ² to about 200 g/m ² , about 25 g/m ² to about 200 g/m ² , about 30 g/m ² to about 200 g/m ² , about 35 g/m ² to about 200 g/m ² , about 40 g/m ² to about 200 g/m ² , about 45 g/m ² to about 200 g/m ² , about 50 g/m ² to about 200 g/m ² , about 75 g/m ² to about 200 g/m ² , about 100 g/m ² to about 200 g/m ² , about 125 g/m ² to about 200 g/m ² , about 150 g/m ² to about 200 g/m ² , about 5 g/m ² to about 175 g/m ² , about 5 g/m ² to about 150 g/m ² , about 5 g/m ² to about 125 g/m ² , about 5 g/m ² to about 100 g/m ² , about 5 g/m ² to about 75 g/m ² , about 5 g/m ² to about 50 g/m ² , about 5 g/m ² to about 45 g/m ² , about 5 g/m ² to about 40 g/m ² , about 5 g/m ² to about 35 g/m ² , about 5 g/m ² to about 30 g/m 2 ² , about 5 g/ ^m2 to about 25 g/ ^m2 , about 5 g/ ^m2 to about 20 g/ ^m2 , about 5 g/ ^m2 to about 15 g/ ^m2 , about 5 g/ ^m2 to about 10 g/ ^m2 , about 10 g/ ^m2 to about 40 g/ ^m2 , about 10 g/ ^m2 to about 30 g/ ^m2 , or about 20 g/ ^m2 to about 40 g/ ^m2 .

In some embodiments, the membrane may comprise a plurality of polyurethanes. In some embodiments, one or more proteins may be soluble in only one of the plurality of polyurethanes. For example, in some embodiments, the membrane may comprise a first polyurethane and a second polyurethane, and one or more proteins may be soluble in only the first polyurethane. In some embodiments, one or more proteins may be soluble in a plurality of polyurethanes. For example, in some embodiments, the membrane may comprise a first polyurethane and a second polyurethane, and one or more proteins may be soluble in both the first polyurethane and the second polyurethane.

In some embodiments, the protein polyurethane blend of the membrane may have a water resistance of greater than 10,000 mm H ₂ O as measured by the JIS L 1092 hydrostatic pressure test. In some embodiments, the protein polyurethane blend of the membrane may have a water resistance of greater than 15,000 mm H ₂ O as measured by the JIS L 1092 hydrostatic pressure test. In some embodiments, the protein polyurethane blend of the membrane may have a water resistance of greater than 20,000 mm H ₂ O as measured by the JIS L 1092 hydrostatic pressure test. In some embodiments, the protein polyurethane blend of the membrane may have a water resistance greater than 10,000 mm _H2O and less than or equal to 30,000 mm _H2O as measured by the JIS L 1092 hydrostatic pressure test. In some embodiments, the protein polyurethane blend of the membrane may have a water resistance greater than 10,000 mm _H2O and less than or equal to 20,000 mm _H2O as measured by the JIS L 1092 hydrostatic pressure test. In some embodiments, the protein polyurethane blend of the membrane can have a water resistance greater than 10,000 mm H ₂ O and less than or equal to 15,000 mm H ₂ O as measured according to the JIS L 1092 hydrostatic pressure test.

In some embodiments, the protein polyurethane blend of the membrane may have a water resistance of greater than 3,000 mm H ₂ O as measured by the JIS L 1092 hydrostatic pressure test. In some embodiments, the protein polyurethane blend of the membrane may have a water resistance of greater than 4,000 mm H ₂ O as measured by the JIS L 1092 hydrostatic pressure test. In some embodiments, the protein polyurethane blend of the membrane may have a water resistance of greater than 5,000 mm H ₂ O as measured by the JIS L 1092 hydrostatic pressure test.

In some embodiments, the protein polyurethane blend of the membrane may have a water resistance greater than 3,000 mm H ₂ O and less than or equal to 30,000 mm H ₂ O as measured by the JIS L 1092 hydrostatic pressure test. In some embodiments, the protein polyurethane blend of the membrane may have a water resistance greater than 3,000 mm H ₂ O and less than or equal to 20,000 mm H ₂ O as measured by the JIS L 1092 hydrostatic pressure test. In some embodiments, the protein polyurethane blend of the membrane may have a water resistance greater than 3,000 mm H ₂ O and less than or equal to 15,000 mm H ₂ O as measured by the JIS L 1092 hydrostatic pressure test. In some embodiments, the protein polyurethane blend of the membrane can have a water resistance greater than 3,000 mm _H2O and less than or equal to 10,000 mm _H2O as measured according to the JIS L 1092 hydrostatic pressure test.

In some embodiments, the protein polyurethane blend of the membrane may have a water resistance greater than 4,000 mm H ₂ O and less than or equal to 30,000 mm H ₂ O as measured by the JIS L 1092 hydrostatic pressure test. In some embodiments, the protein polyurethane blend of the membrane may have a water resistance greater than 4,000 mm H ₂ O and less than or equal to 20,000 mm H ₂ O as measured by the JIS L 1092 hydrostatic pressure test. In some embodiments, the protein polyurethane blend of the membrane may have a water resistance greater than 4,000 mm H ₂ O and less than or equal to 15,000 mm H ₂ O as measured by the JIS L 1092 hydrostatic pressure test. In some embodiments, the protein polyurethane blend of the membrane can have a water resistance greater than 4,000 mm _H2O and less than or equal to 10,000 mm _H2O as measured according to the JIS L 1092 hydrostatic pressure test.

In some embodiments, the protein polyurethane blend of the membrane may have a water resistance greater than 5,000 mm H ₂ O and less than or equal to 30,000 mm H ₂ O as measured by the JIS L 1092 hydrostatic pressure test. In some embodiments, the protein polyurethane blend of the membrane may have a water resistance greater than 5,000 mm H ₂ O and less than or equal to 20,000 mm H ₂ O as measured by the JIS L 1092 hydrostatic pressure test. In some embodiments, the protein polyurethane blend of the membrane may have a water resistance greater than 5,000 mm H ₂ O and less than or equal to 15,000 mm H ₂ O as measured by the JIS L 1092 hydrostatic pressure test. In some embodiments, the protein polyurethane blend of the membrane can have a water resistance greater than 5,000 mm H ₂ O and less than or equal to 10,000 mm H ₂ O as measured according to the JIS L 1092 hydrostatic pressure test.

In some embodiments, the protein polyurethane blend may have a water resistance of greater than 10,000 mm H ₂ O as measured by the JIS L 1092 hydrostatic pressure test. In some embodiments, an article comprising a film comprising a protein polyurethane blend may have a water resistance of greater than 15,000 mm H ₂ O as measured by the JIS L 1092 hydrostatic pressure test. In some embodiments, an article comprising a film comprising a protein polyurethane blend may have a water resistance of greater than 20,000 mm H ₂ O as measured by the JIS L 1092 hydrostatic pressure test. In some embodiments, an article comprising: a film comprising a protein polyurethane blend may have a water resistance greater than 10,000 mm _H2O and less than or equal to 30,000 mm _H2O as measured by the JIS L 1092 hydrostatic pressure test. In some embodiments, an article comprising: a film comprising a protein polyurethane blend may have a water resistance greater than 10,000 mm _H2O and less than or equal to 20,000 mm _H2O as measured by the JIS L 1092 hydrostatic pressure test. In some embodiments, an article comprising a film comprising a protein polyurethane blend may have a water resistance greater than 10,000 mm H ₂ O and less than or equal to 15,000 mm H ₂ O as measured according to the JIS L 1092 hydrostatic pressure test.

In some embodiments, the protein polyurethane blend of the membrane may have an air permeability greater than 5,000 g/m ² /24hr measured according to JIS L 1099 B1. In some embodiments, the protein polyurethane blend of the membrane may have an air permeability greater than 10,000 g/m ² /24hr measured according to JIS L 1099 B1. In some embodiments, the protein polyurethane blend of the membrane may have an air permeability greater than 20,000 g/m ² /24hr measured according to JIS L 1099 B1. In some embodiments, the protein polyurethane blend of the membrane may have an air permeability greater than 30,000 g/m ² /24hr measured according to JIS L 1099 B1. In some embodiments, the protein polyurethane blend of the membrane may have an air permeability greater than 40,000 g/ ^m2 /24hr as measured according to JIS L 1099 B1. In some embodiments, the protein polyurethane blend of the membrane may have an air permeability greater than 50,000 g/ ^m2 /24hr as measured according to JIS L 1099 B1.

In some embodiments, the protein polyurethane blend of the membrane may have an air permeability greater than 5,000 g/m ² /24hr and less than or equal to 100,000 g/m ² /24hr as measured according to JIS L 1099 B1. In some embodiments, the protein polyurethane blend of the membrane may have an air permeability greater than 5,000 g/m ² /24hr and less than or equal to 90,000 g/m ² /24hr as measured according to JIS L 1099 B1. In some embodiments, the protein polyurethane blend of the membrane may have an air permeability greater than 5,000 g/m ² /24hr and less than or equal to 80,000 g/m ² /24hr as measured according to JIS L 1099 B1. In some embodiments, the protein polyurethane blend of the membrane may have an air permeability greater than 5,000 g/m ² /24hr and less than or equal to 60,000 g/m ² /24hr as measured according to JIS L 1099 B1. In some embodiments, the protein polyurethane blend of the membrane may have an air permeability greater than 5,000 g/m ² /24hr and less than or equal to 50,000 g/m ² /24hr as measured according to JIS L 1099 B1. In some embodiments, the protein polyurethane blend of the membrane may have an air permeability greater than 10,000 g/m ² /24hr and less than or equal to 50,000 g/m ² /24hr as measured according to JIS L 1099 B1. In some embodiments, the protein polyurethane blend of the membrane can have an air permeability greater than 15,000 g/m ² /24 hr and less than or equal to 50,000 g/m ² /24 hr as measured according to JIS L 1099 B1.

In some embodiments, the protein polyurethane blend of the membrane may have an air permeability greater than 3,000 g/ ^m2 /24hr measured according to JIS L 1099 B1. In some embodiments, the protein polyurethane blend of the membrane may have an air permeability greater than 4,000 g/ ^m2 /24hr measured according to JIS L 1099 B1.

In some embodiments, the protein polyurethane blend of the membrane may have an air permeability greater than 3,000 g/m ² /24hr and less than or equal to 100,000 g/m ² /24hr as measured according to JIS L 1099 B1. In some embodiments, the protein polyurethane blend of the membrane may have an air permeability greater than 3,000 g/m ² /24hr and less than or equal to 90,000 g/m ² /24hr as measured according to JIS L 1099 B1. In some embodiments, the protein polyurethane blend of the membrane may have an air permeability greater than 3,000 g/m ² /24hr and less than or equal to 80,000 g/m ² /24hr as measured according to JIS L 1099 B1. In some embodiments, the protein polyurethane blend of the membrane may have an air permeability greater than 3,000 g/ ^m2 /24hr and less than or equal to 60,000 g/ ^m2 /24hr as measured according to JIS L 1099 B1. In some embodiments, the protein polyurethane blend of the membrane may have an air permeability greater than 3,000 g/ ^m2 /24hr and less than or equal to 50,000 g/ ^m2 /24hr as measured according to JIS L 1099 B1.

In some embodiments, the protein polyurethane blend of the membrane may have an air permeability greater than 4,000 g/m ² /24hr and less than or equal to 100,000 g/m ² /24hr as measured according to JIS L 1099 B1. In some embodiments, the protein polyurethane blend of the membrane may have an air permeability greater than 4,000 g/m ² /24hr and less than or equal to 90,000 g/m ² /24hr as measured according to JIS L 1099 B1. In some embodiments, the protein polyurethane blend of the membrane may have an air permeability greater than 4,000 g/m ² /24hr and less than or equal to 80,000 g/m ² /24hr as measured according to JIS L 1099 B1. In some embodiments, the protein polyurethane blend of the membrane may have an air permeability greater than 4,000 g/ ^m2 /24hr and less than or equal to 60,000 g/ ^m2 /24hr as measured according to JIS L 1099 B1. In some embodiments, the protein polyurethane blend of the membrane may have an air permeability greater than 4,000 g/ ^m2 /24hr and less than or equal to 50,000 g/ ^m2 /24hr as measured according to JIS L 1099 B1.

In some embodiments, an article comprising a film comprising a protein polyurethane blend may have an air permeability greater than 3,000 g/m ² /24hr measured according to JIS L 1099 B1. In some embodiments, an article comprising a film comprising a protein polyurethane blend may have an air permeability greater than 4,000 g/m ² /24hr measured according to JIS L 1099 B1. In some embodiments, an article comprising a film comprising a protein polyurethane blend may have an air permeability greater than 5,000 g/m ² /24hr measured according to JIS L 1099 B1. In some embodiments, an article comprising a film comprising a protein polyurethane blend may have an air permeability greater than 10,000 g/ ^m2 /24hr measured according to JIS L 1099 B1. In some embodiments, an article comprising a film comprising a protein polyurethane blend may have an air permeability greater than 15,000 g/ ^m2 /24hr measured according to JIS L 1099 B1.

In some embodiments, an article comprising a film comprising a protein polyurethane blend may have an air permeability greater than 3,000 g/m ² /24hr and less than or equal to 115,000 g/m ² /24hr measured according to JIS L 1099 B1. In some embodiments, an article comprising a film comprising a protein polyurethane blend may have an air permeability greater than 4,000 g/m ² /24hr and less than or equal to 115,000 g/m ² /24hr measured according to JIS L 1099 B1. In some embodiments, an article including a film containing a protein polyurethane blend may have an air permeability of greater than 5,000 g/m ² /24hr and less than or equal to 115,000 g/m ² /24hr measured according to JIS L 1099 B1. In some embodiments, an article including a film containing a protein polyurethane blend may have an air permeability of greater than 10,000 g/m ² /24hr and less than or equal to 115,000 g/m ² /24hr measured according to JIS L 1099 B1. In some embodiments, an article including a film containing a protein polyurethane blend may have an air permeability of greater than 15,000 g/m ² /24 hr and less than or equal to 115,000 g/m ² /24 hr as measured according to JIS L 1099 B1.

In some embodiments, an article comprising a film containing a protein polyurethane blend may have a water resistance of greater than 10,000 mm H ₂ O as measured by the JIS L 1092 hydrostatic pressure test and an air permeability of greater than 3,000 g/m ² /24 hr as measured by JIS L 1099 B1. In some embodiments, an article comprising a film containing a protein polyurethane blend may have a water resistance of greater than 10,000 mm H ₂ O as measured by the JIS L 1092 hydrostatic pressure test and an air permeability of greater than 5,000 g/m ² /24 hr as measured by JIS L 1099 B1. In some embodiments, an article including a film containing a protein polyurethane blend can have a water resistance greater than 10,000 mm H ₂ O as measured by the JIS L 1092 hydrostatic pressure test and an air permeability greater than 10,000 g/m ² /24 hr as measured by JIS L 1099 B1.

In some embodiments, an article including a film containing a protein polyurethane blend can have a water resistance greater than 10,000 mm _H2O and less than or equal to 30,000 mm _H2O measured according to JIS L 1092 hydrostatic pressure test and an air permeability greater than 3,000 g/ ^m2 /24hr and less than or equal to 115,000 g/ ^m2 /24h measured according to JIS L 1099 B1. In some embodiments, an article including a film containing a protein polyurethane blend can have a water resistance greater than 10,000 mm _H2O and less than or equal to 30,000 mm _H2O measured according to JIS L 1092 hydrostatic pressure test and an air permeability greater than 10,000 g/ ^m2 /24hr and less than or equal to 115,000 g/ ^m2 /24h measured according to JIS L 1099 B1.

In some embodiments, the protein polyurethane blend of the membrane may have an air permeability greater than 3,000 g/ ^m2 /24hr as measured according to JIS L 1099 A1. In some embodiments, the protein polyurethane blend of the membrane may have an air permeability greater than 4,000 g/ ^m2 /24hr as measured according to JIS L 1099 A1. In some embodiments, the protein polyurethane blend of the membrane may have an air permeability greater than 5,000 g/ ^m2 /24hr as measured according to JIS L 1099 A1. In some embodiments, the protein polyurethane blend of the membrane may have an air permeability greater than 3,000 g/m ² /24hr and less than or equal to 10,000 g/m ² /24hr as measured according to JIS L 1099 A1. In some embodiments, the protein polyurethane blend of the membrane may have an air permeability greater than 4,000 g/m ² /24hr to less than or equal to 10,000 g/m ² /24hr as measured according to JIS L 1099 A1. In some embodiments, the protein polyurethane blend of the membrane may have an air permeability greater than 5,000 g/m ² /24hr to less than or equal to 10,000 g/m ² /24hr as measured according to JIS L 1099 A1.

In some embodiments, the protein polyurethane blend of the membrane may have an air permeability greater than 250 g/m ² /24hr measured according to ASTM E 96 B. In some embodiments, the protein polyurethane blend of the membrane may have an air permeability greater than 500 g/m ² /24hr measured according to ASTM E 96 B. In some embodiments, the protein polyurethane blend of the membrane may have an air permeability greater than 700 g/m ² /24hr measured according to ASTM E 96 B. In some embodiments, the protein polyurethane blend of the membrane may have an air permeability greater than 1,000 g/m ² /24hr measured according to ASTM E 96 B. In some embodiments, the protein polyurethane blend of the membrane may have an air permeability of greater than 250 g/m ² /24hr to less than or equal to 1,200 g/m ² /24hr as measured according to ASTM E 96 B. In some embodiments, the protein polyurethane blend of the membrane may have an air permeability of greater than 250 g/m ² /24hr to less than or equal to 1,000 g/m ² /24hr as measured according to ASTM E 96 B. In some embodiments, the protein polyurethane blend of the membrane may have an air permeability of greater than 700 g/m ² /24hr to less than or equal to 1,000 g/m ² /24hr as measured according to ASTM E 96 B.

In some embodiments, the protein polyurethane blend of the membrane may have two or more of the following: (i) a water resistance value measured according to the JIS L 1092 hydrostatic pressure test as disclosed herein, (ii) a breathability value measured according to the JIS L 1099 B1 as disclosed herein, (iii) a breathability value measured according to the JIS L 1099 A1 as disclosed herein, and (iv) a breathability value measured according to the ASTM E 96 B as disclosed herein. In some embodiments, the protein polyurethane blend of the membrane may have three or more of (i) to (iv). In some embodiments, the protein polyurethane blend of the membrane may have all four of (i) to (iv).

For example, in some embodiments, the protein polyurethane blend of the membrane can have a water resistance greater than 10,000 mm _H2O as measured according to the JIS L 1092 hydrostatic pressure test and an air permeability greater than 5,000 g/ ^m2 /24hr as measured according to JIS L 1099 B1.

As another example, in some embodiments, the protein polyurethane blend of the membrane can have a water resistance greater than 10,000 mm _H2O and less than or equal to 30,000 mm _H2O as measured according to the JIS L 1092 hydrostatic pressure test and an air permeability greater than 5,000 g/ ^m2 /24hr and less than or equal to 100,000 g/ ^m2 /24hr as measured according to JIS L 1099 B1.

As another example, in some embodiments, the protein polyurethane blend of the membrane can have a water resistance greater than 3,000 mm H2O as measured by the JIS L 1092 hydrostatic pressure test and an air permeability greater than 3,000 g/m2/24h as measured by JIS L 1099 B1.

As another example, in some embodiments, the protein polyurethane blend of the membrane can have a water resistance greater than 3,000 mm _H2O and less than or equal to 30,000 mm _H2O as measured according to the JIS L 1092 hydrostatic pressure test and an air permeability greater than 3,000 g/ ^m2 /24hr and less than or equal to 100,000 g/ ^m2 /24hr as measured according to JIS L 1099 B1.

As another example, in some embodiments, the protein polyurethane blend of the membrane can have a water resistance greater than 4,000 mm H ₂ O as measured by the JIS L 1092 hydrostatic pressure test and an air permeability greater than 4,000 g/m ² /24 hr as measured by JIS L 1099 B1.

As another example, in some embodiments, the protein polyurethane blend of the membrane can have a water resistance greater than 4,000 mm _H2O and less than or equal to 30,000 mm _H2O as measured according to the JIS L 1092 hydrostatic pressure test and an air permeability greater than 4,000 g/ ^m2 /24hr and less than or equal to 100,000 g/ ^m2 /24hr as measured according to JIS L 1099 B1.

As another example, in some embodiments, the protein polyurethane blend of the membrane can have a water resistance greater than 10,000 mm _H2O and less than or equal to 15,000 mm _H2O as measured by the JIS L 1092 hydrostatic pressure test and an air permeability greater than 20,000 g/ ^m2 /24hr and less than or equal to 40,000 g/ ^m2 /24hr as measured by JIS L 1099 B1.

In some embodiments, the protein polyurethane blend of the membrane can have a biocontent greater than or equal to about 15% as measured according to ASTM D6866. In some embodiments, the protein polyurethane blend of the membrane can have a biocontent in the following ranges: about 15% to about 80%, about 20% to about 80%, about 30% to about 80%, about 40% to about 80%, about 50% to about 80%, or about 60% to about 80% as measured according to ASTM D6866.

In some embodiments, the protein polyurethane blend of the membrane can have a biocontent greater than or equal to about 35% as measured according to ASTM D6866. In some embodiments, the protein polyurethane blend of the membrane can have a biocontent in the range of about 35% to about 80% as measured according to ASTM D6866.

In some embodiments, the protein polyurethane blend of the membrane can have a Martindale Dry Abrasion of greater than or equal to about 20,000 cycles as measured according to the Martindale Abrasion Test with a 9 kPa load.

In some embodiments, when cured in the absence of protein and crosslinking agent, the aqueous polyurethane dispersion used for film and precursor formulations can have a water resistance greater than 10,000 mm H ₂ O as measured by the JIS L 1092 hydrostatic pressure test. In some embodiments, when cured in the absence of protein and crosslinking agent, the aqueous polyurethane dispersion can comprise a water resistance greater than 10,000 mm H ₂ O and less than or equal to 20,000 mm H ₂ O as measured by the JIS L 1092 hydrostatic pressure test. In some embodiments, the aqueous polyurethane dispersion can comprise a water resistance greater than 10,000 mm _H2O and less than or equal to 15,000 mm _H2O as measured according to the JIS L 1092 hydrostatic pressure test when cured in the absence of a protein and a crosslinking agent.

In some embodiments, the aqueous polyurethane dispersion for membrane and precursor formulations may include an aqueous aliphatic polyether-based polyurethane having a solid content of about 35% and a specific gravity of about 1.02 g/mL. In some embodiments, the aqueous polyurethane dispersion for membrane and precursor formulations may include a nonionic aliphatic polycarbonate-polyether polyurethane having a solid content of about 30% and a specific gravity of about 1.1 g/mL. In some embodiments, the aqueous polyurethane dispersion used in the membrane and precursor formulations may include an aqueous aliphatic anionic polyester polyurethane dispersion having a solids content of about 50%, a specific gravity of 1.1 g/mL, a Brookfield viscosity of less than or equal to 1200 mPa.s, a biocontent of about 50% as measured according to ASTM D6866, a tensile strength of 30 MPa, and an elongation at break of 1000%. In some embodiments, the aqueous polyurethane dispersion used in the membrane and precursor formulations may include an aqueous aliphatic anionic polyester polyurethane dispersion having a solids content of about 50%, a specific gravity of 1.1 g/mL, a Brookfield viscosity of less than or equal to 1200 mPa.s, a biocontent of about 56% as measured according to ASTM D6866, a tensile strength of 12 MPa, and an elongation at break of 800%.

In some embodiments, the aqueous polyurethane dispersion used in the membrane and precursor formulations may include two or more of the following: (i) an aqueous aliphatic polyether-based polyurethane having a solids content of about 35% and a specific gravity of about 1.02 g/mL; (ii) a nonionic aliphatic polycarbonate-polyether polyurethane dispersion having a solids content of about 30% and a specific gravity of about 1.1 g/mL; (iii) an aqueous aliphatic nonionic polyurethane dispersion having a solids content of about 32%, a specific gravity of 1.03 g/mL, and a Brookfield viscosity of about 200 mPa.s; (iv) an aqueous aliphatic nonionic polyurethane dispersion having a solids content of about 50%, a specific gravity of 1.1 g/mL, a Brookfield viscosity of less than or equal to 1200 mPa.s, a biocontent of about 50% as measured according to ASTM D6866, a specific gravity of 30 MPa, and an elongation at break of 1000%; and (vi) an aqueous aliphatic anionic polyester polyurethane dispersion having a solids content of about 50%, a specific gravity of 1.1 g/mL, a Brookfield viscosity less than or equal to 1200 mPa.s, a biocontent of about 56% as measured in accordance with ASTM D6866, a tensile strength of 12 MPa, and an elongation at break of 800%.

In some embodiments, the protein polyurethane blend of the membrane can have greater than or equal to 5 wt % protein. In some embodiments, the amount of protein in the protein polyurethane blend of the membrane can be in the range of about 5 wt % to about 50 wt % protein, including subranges. For example, in some embodiments, the amount of protein in the protein polyurethane blend can be in the range of about 10 wt % to about 50 wt %, about 15 wt % to about 50 wt %, about 20 wt % to about 50 wt %, about 25 wt % to about 50 wt %, about 30 wt % to about 50 wt %, about 35 wt % to about 50 wt %, about 40 wt % to about 50 wt %, about 45 wt % to about 50 wt %, about 5 wt % to about 45 wt %, about 5 wt % to about 40 wt %, about 5 wt % to about 35 wt %, about 5 wt % to about 30 wt %, about 5 wt % to about 25 wt %, about 5 wt % to about 20, or about 5 wt % to about 15 wt %.

In some embodiments, the amount of protein in the protein polyurethane blend of the membrane can be in the range of about 50 wt % to about 95 wt %, including subranges. For example, in some embodiments, the amount of polyurethane in the protein polyurethane blend can be in the range of about 55 wt % to about 95 wt %, about 60 wt % to about 95 wt %, about 65 wt % to about 95 wt %, about 70 wt % to about 95 wt %, about 75 wt % to about 95 wt %, about 80 wt % to about 95 wt %, about 85 wt % to about 95 wt %, about 50 wt % to about 90 wt %, about 50 wt % to about 85 wt %, about 50 wt % to about 80 wt %, about 50 wt % to about 75 wt %, about 50 wt % to about 70 wt %, about 50 wt % to about 65 wt %, about 50 wt % to about 60 wt %, or about 50 wt % to about 55 wt %.

In some embodiments, the weight percentage values and ranges listed above can be based on the total weight of the protein polyurethane blend. In some embodiments, the weight percentage values and ranges listed above can be based on the total weight of only the protein and polyurethane in the protein polyurethane blend. Unless otherwise specified, the weight percentage values or ranges of polyurethane and protein are based on the total weight of only the protein and polyurethane in the protein polyurethane blend.

In some embodiments, the sum of the amount of protein plus the amount of polyurethane in the protein polyurethane blend of the membrane may be about 80 wt% or more. For example, in some embodiments, the sum of the amount of protein plus the amount of polyurethane in the protein polyurethane blend may be in the range of about 80 wt% to 100 wt%, about 82 wt% to 100 wt%, about 84 wt% to 100 wt%, about 86 wt% to 100 wt%, about 88 wt% to 100 wt%, about 90 wt% to 100 wt%, about 92 wt% to 100 wt%, about 94 wt% to 100 wt%, about 96 wt% to 100 wt%, or about 98 wt% to 100 wt%.

In some embodiments, the protein polyurethane blend of the membrane can be dyed with a colored dye. In some embodiments, the protein polyurethane blend of the membrane can be dyed with an acid dye. In some embodiments, the protein polyurethane blend of the membrane can be dyed with a reactive dye. Exemplary fiber reactive dyes include, but are not limited to, sulphatoethylsulphone (Remazol), tris(thiazole), vinyl sulphone, and acrylamide dyes. Exemplary acid dyes include, but are not limited to, azo structured acid dyes, metal complex structured acid dyes, aniline structured dyes, and anthraquinone structured acid dyes.

In some embodiments, the protein polyurethane blend of the membrane can be nonporous. In some embodiments, the protein polyurethane blend of the membrane can be microporous.

The film precursor formulation according to some embodiments described herein comprises water, protein, aqueous polyurethane dispersion, and one or more crosslinking agents. The one or more crosslinking agents may be present in a weight percentage in the range of about 0.1 wt % to about 5 wt % relative to the total weight of the water, protein, and aqueous polyurethane dispersion in the formulation. In some embodiments, the protein may be dissolved in the polyurethane of the polyurethane dispersion of the formulation.

In some embodiments, the membrane prodrug formulation may include one or more crosslinking agents in the following weight percentage ranges relative to the total weight of water, protein, and aqueous polyurethane dispersion in the formulation: about 0.2 wt% to about 5 wt%, about 0.5 wt% to about 5 wt%, about 0.75 wt% to about 5 wt%, about 1 wt% to about 5 wt%, about 1.5 wt% to about 5 wt%, about 2 wt% to about 5 wt%, about 3 wt% to about 5 wt%, about 0.1 wt% to about 4 wt%, about 0.1 wt% to about 3 wt%, about 0.1 wt% to about 2 wt%, or about 0.1 wt% to about 1 wt%.

In some embodiments, the membrane pre-drive formulation may include a defoamer. In some embodiments, the defoamer may include a mineral oil-based defoamer. In some embodiments, the membrane pre-drive formulation may include an antifoamer.

In some embodiments, the membrane prodrug formulation may include greater than or equal to 5 wt % protein. In some embodiments, the amount of protein in the membrane prodrug formulation may be in the range of about 5 wt % to about 50 wt % protein, including subranges. For example, in some embodiments, the amount of protein in the membrane propellant formulation can be in the range of about 10 wt % to about 50 wt %, about 15 wt % to about 50 wt %, about 20 wt % to about 50 wt %, about 25 wt % to about 50 wt %, about 30 wt % to about 50 wt %, about 35 wt % to about 50 wt %, about 40 wt % to about 50 wt %, about 45 wt % to about 50 wt %, about 5 wt % to about 45 wt %, about 5 wt % to about 40 wt %, about 5 wt % to about 35 wt %, about 5 wt % to about 30 wt %, about 5 wt % to about 25 wt %, about 5 wt % to about 20, or about 5 wt % to about 15 wt %.

In some embodiments, the amount of polyurethane in the membrane prodrive formulation may be in the range of about 50 wt % to about 95 wt %, including subranges. For example, in some embodiments, the amount of polyurethane in the membrane pre-drive formulation can be in the range of about 55 wt% to about 95 wt%, about 60 wt% to about 95 wt%, about 65 wt% to about 95 wt%, about 70 wt% to about 95 wt%, about 75 wt% to about 95 wt%, about 80 wt% to about 95 wt%, about 85 wt% to about 95 wt%, about 50 wt% to about 90 wt%, about 50 wt% to about 85 wt%, about 50 wt% to about 80 wt%, about 50 wt% to about 75 wt%, about 50 wt% to about 70 wt%, about 50 wt% to about 65 wt%, about 50 wt% to about 60 wt%, or about 50 wt% to about 55 wt%.

Unless otherwise stated, the weight percentage values or ranges of polyurethane and protein in the membrane pre-driver formulation are based on the total weight of only protein and polyurethane solids in the formulation.

In some embodiments, the membrane prodrug formulation may include one or more colored dyes. In some embodiments, the membrane prodrug formulation may include one or more acid dyes. In some embodiments, the membrane prodrug formulation may include one or more reactive dyes. Exemplary fiber reactive dyes include, but are not limited to, sulphatoethylsulphone (Remazol), tris(thionine), vinyl sulphone, and acrylamide 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.

In some embodiments, the protein polyurethane blend film can be applied to a textile. In some embodiments, the protein polyurethane blend film can be attached to a textile.

1A and 1B show a material 100 according to some embodiments. The material 100 includes a textile 110 and a protein polyurethane blend film 120. The protein polyurethane blend film 120 includes a bottom surface 122, a top surface 124, and a thickness 126 measured between the bottom surface 122 and the top surface 124. The bottom surface 122 and the top surface 124 can be the exterior surfaces of the textile 110. In some embodiments, the material 100 can include a plurality of protein polyurethane blend films 120.

The protein polyurethane blend film 120 may be coated or otherwise deposited on the textile 110. In some embodiments, the protein polyurethane blend film 120 may be disposed on the textile 110. In some embodiments, the protein polyurethane blend film 120 may be disposed on the top surface 114 of the textile 110, as shown in FIG. 1A. In some embodiments, the protein polyurethane blend film 120 may be disposed on the bottom surface 112 of the textile 110, as shown in FIG. 1B. In some embodiments, the protein polyurethane blend film 120 may be disposed on the top surface 114 of the textile 110. In some embodiments, the protein polyurethane blend film 120 may be disposed on the bottom surface 112 of the textile 110.

In some embodiments, top surface 114 of textile 110 may be a front surface of textile 110. In such embodiments, when an article of clothing containing article 100 is worn by a user, top surface 114 of textile 110 may be an exterior-facing surface of textile 110. In some embodiments, bottom surface 112 of textile may be a rear surface of textile 100. In such embodiments, when an article of clothing containing article 100 is worn by a user, bottom surface 112 may be an interior, skin-facing surface of textile 110.

The textile 110 may include one or more textile layers. The one or more textile layers may be, for example, a woven layer, a nonwoven layer, a knitted layer, a mesh fabric layer, or a leather layer. In some embodiments, the textile 110 may include a first textile layer and a second textile layer, and the film 120 may be disposed between the first textile layer and the second textile layer.

One or more textile layers may be made of recycled or virgin fibers, filaments, or yarns. In some embodiments, the textile 110 may be or may include a polyester knitted fabric layer, a polyester-cotton blended fabric layer, a polyester-cotton-spandex blended knitted fabric layer, or a suede leather layer.

In some embodiments, the textile 110 may be made from one or more natural fibers, such as fibers made from cotton, linen, silk, wool, kenaf, flax, cashmere, angora, bamboo, leather, hemp, soy, seacell, milk or milk protein, spider silk, chitosan, mycelium, cellulose (including bacterial cellulose), or wood.

In some embodiments, the textile 110 may be made of one or more synthetic fibers, such as polyester, nylon, aramid, polyolefin fibers (such as polyethylene, polypropylene), rayon, lyocell, viscose, antimicrobial yarn (AMY), Sorbtek, nylon, elastomer (such as ^Lycra® , spandex, or ^Elastane® ), polyester-polyurethane copolymers, polyaramid, carbon (including carbon fibers and fullerene), glass, silicon, minerals, metals or metal blends (including those containing iron, steel, lead, gold, silver, platinum, copper, zinc, and titanium), or a mixture thereof.

In some embodiments, the nonwoven textile 110 may be a staple nonwoven, a melt-blown nonwoven, a spun nonwoven, a flashspun nonwoven, or a combination thereof.

In some embodiments, the textile 110 can be colored with a colorant. In some embodiments, the colorant can be a colored dye, such as an acid dye, a fiber reactive dye, a direct dye, a sulfur dye, an alkaline dye, a reactive dye, or a vat dye. In some embodiments, the colorant can be a pigment, such as a color pigment.

In some embodiments, as shown in, for example, FIG. 2A , material 100 may include a protein polyurethane blend film 120 attached to one surface of textile 110 with an adhesive. In some embodiments, material 100 may include a protein polyurethane blend film 120 attached to a top surface 114 of textile 110 with an adhesive. In some embodiments, material 100 may include a protein polyurethane blend film 120 attached to a bottom surface 112 of textile 110 with an adhesive. In some embodiments, the material 100 may include a first protein polyurethane blend film 120 attached to a bottom surface 112 of a textile surface 110 with an adhesive and a second protein polyurethane blend film 120 attached to a top surface 114 of the textile surface 110.

In such embodiments, the adhesive may include an adhesive layer 150, which includes a bottom surface 152, a top surface 154, and a thickness 156 measured between the bottom surface 152 and the top surface 154. In some embodiments, the thickness 156 may be in the range of about 5 microns to about 50 microns, including sub-ranges. For example, the thickness 156 may be in the range of: about 5 microns to about 50 microns, about 10 microns to about 50 microns, about 20 microns to about 50 microns, about 30 microns to about 50 microns, or about 20 microns to about 40 microns. In some embodiments, the adhesive layer 150 may have a dry weight in the range of about 5 g/ ^m2 to about 50 g/ ^m2 (including sub-ranges). For example, the adhesive layer 150 may have a dry weight in the range of about 5 g/ ^m2 to about 50 g/ ^m2 , about 10 g/ ^m2 to about 50 g/ ^m2 , about 20 g/ ^m2 to about 50 g/ ^m2 , about 30 g/ ^m2 to about 50 g/ ^m2 , or about ²⁰ g/m2 to about 40 g/ ^m2 .

Adhesives suitable for adhesive layer 150 include, but are not limited to, polyurethane adhesives, hot melt adhesives, emulsion polymer adhesives, dry web adhesives, dry lamination adhesives, or wet lamination adhesives. Hauthane HD-2001 available from CL Hauthaway & Sons Corporation is an exemplary lamination adhesive suitable for adhesive layer 150. Exemplary polyurethane adhesives include, but are not limited to, L-2183, L-2245, L-2255 from Hauthaway and ^Impranil® DAH, DAA from Covestro. Exemplary dry web adhesives include, but are not limited to, 9D8D20 from Protechnic. In some embodiments, the polyurethane adhesive may be a polyurethane reactive adhesive (also known as a reactive hot melt adhesive).

In some embodiments, the adhesive layer 150 can be a continuous layer. In some embodiments, the adhesive layer 150 can be a discontinuous layer comprising adhesive deposited in a regular or irregular pattern. The discontinuous adhesive layer can be deposited using, for example, a rotogravure process. In some embodiments, a discontinuous adhesive layer can include a pattern of adhesive islands (e.g., dots or squares), adhesive lines, or a combination thereof.

In some embodiments, the film 120 may be treated with a water repellent finish 170. In some embodiments, the water repellent finish 170 may include a water repellent spray rating of greater than or equal to about 70 as measured according to AATCC 22. In some embodiments, the film 120 may be treated with a fluorine-free water repellent finish 170. In some embodiments, the fluorine-free water repellent finish 170 may include a water repellent spray rating of greater than or equal to about 70 as measured according to AATCC 22. In some embodiments, the water repellent finish 170 may include a polyurethane finish including a water repellent spray rating of greater than or equal to about 70 as measured according to AATCC 22. In some embodiments, the water repellent finish 170 may include a fluorine-free polyurethane finish comprising a water repellent spray rating of greater than or equal to about 70 as measured according to AATCC 22.

In some embodiments, the water-repellent finish 170 may include polycarbonate polyurethane. In some embodiments, the water-repellent finish 170 may include aliphatic polycarbonate polyurethane. In some embodiments, the polyurethane used for the water-repellent finish 170 may include an aqueous aliphatic polycarbonate polyurethane dispersion. In some embodiments, the aqueous aliphatic polycarbonate polyurethane dispersion may have a solid content of about 34% and a viscosity of 5 to 1000 mPa.s.

In some embodiments, as shown in, for example, FIG. 2B , the material 100 may include a first textile 110, a second textile 110, and a protein polyurethane blend film 120 disposed between the first textile 110 and the second textile 110. In such embodiments, the protein polyurethane blend film 120 may be attached to a bottom surface of the first textile 110 with a first adhesive layer 150 and to a top surface of the second textile 110 with a second adhesive layer 150.

In some embodiments, as shown in, for example, FIG2B , the textile 110 may be treated with a water-repellent finish 170. In some embodiments, the material 100 may include a protein polyurethane blend film 120 disposed between a first textile 110 and a second textile 110, and the first textile 110, the second textile 110, or both may be treated with a water-repellent finish 170.

The material 100 can be made by attaching one or more protein polyurethane blend films 120 to a textile 110. In some embodiments, the protein polyurethane blend film(s) can be laminated over a sacrificial layer that is removed after lamination and before or after attaching the one or more films 120 to the textile 110. The protein polyurethane blend film 120 may be deposited using any suitable coating technique, including but not limited to knife over roll, gravure coating, slot die coating, multi-layer slot die coating, or curtain coating. Multi-layer slot die coating may allow for the simultaneous coating of multiple adjacent films or layers.

In some embodiments, the textile 110 may be coated with an adhesive layer 150, and one or more films 120 may be formed over the adhesive layer 150. In such embodiments, the film(s) 120 may be formed over the adhesive layer 150 in the same manner as described below for method 300, wherein the films 120 are formed over the adhesive layer 150 rather than over a sacrificial layer.

To prepare the protein polyurethane precursor formulation, one or more aqueous polyurethane dispersions may be blended with one or more proteins to form a blended mixture. Suitable blending equipment includes, but is not limited to, a blender, a stand mixer, an inline mixer, or a high shear mixer.

In some embodiments, the protein(s) may be dispersed or dissolved in an aqueous solution prior to blending with one or more aqueous polyurethane dispersions. Suitable aqueous solutions include, but are not limited to, water, alkaline aqueous solutions, acidic aqueous solutions, aqueous solutions including organic solvents, urea solutions, and mixtures thereof. In some embodiments, the alkaline aqueous solution may be an alkaline solution, such as sodium hydroxide, ammonia, or ammonium hydroxide solution. In some embodiments, an example of an acidic aqueous solution may be an acetic acid or hydrochloric acid (HCl) solution. Suitable organic solvents include, but are not limited to, ethanol, isopropanol, acetone, ethyl acetate, isopropyl acetate, glycerol, and the like.

In some embodiments, the protein polyurethane precursor formulation may include one or more additives. Suitable additives include, but are not limited to, fillers, pigments, plasticizers, waxes, rheology modifiers, flame retardants, antimicrobial agents, antifungal agents, antioxidants, UV stabilizers, hand modifiers, levelers, and the like. Suitable antimicrobial/antifungal agents include Ultra-Fresh DW-56. Suitable flame retardants include Cetaflam ^® DB9 (organophosphorus compound of a polymer with a carbon chain containing C-PO(OH) ₂ or C-PO(OR) ₂ groups), Cetaflam ^® PD3300 (organophosphorus compound of a polymer with a carbon chain containing C-PO(OH) ₂ or C-PO(OR) ₂ groups), or other flame retardants used for coating textiles. Suitable fillers include, but are not limited to, thermoplastic microspheres, such as Expancel ^® microspheres. Suitable rheology modifiers include, but are not limited to, alkali-swellable rheology modifiers, hydrophobically-modified ethylene oxide-based urethane (HEUR) rheology modifiers, and volume exclusion thickeners. Exemplary alkali-swellable rheology modifiers include, but are not limited to, Acrysol ^™ DR-106, Acrysol ^™ ASE-60 from Dow Chemicals, and ^Texicryl® 13-3131, and ^Texicryl® 13-308 from Scott-Bader. Exemplary HEUR modifiers include, but are not limited to, RM-4410 from Stahl and Chemtex 2241-A from HeiQ. Exemplary volume exclusion thickeners include, but are not limited to, Walocel ^™ XM 20000 PV from Dow Chemicals and methyl-hydroxyethyl cellulose from Sigma-Aldrich. HM-13-843 (a water-based modified polysilicone solution feel modifier, available from Stahl Holdings BV) is an exemplary feel modifier.

In some embodiments, the protein polyurethane blend film can be formed on a sacrificial layer and attached to a substrate layer (e.g., textile) after formation. FIG. 3 shows a method 300 for making a material according to some embodiments. The method 300 can be used to attach one or more membranes 120 to one or more surfaces of a textile 110. Unless otherwise specified, the steps of the method 300 do not need to be performed in the order described herein. In addition, unless otherwise specified, the steps of the method 300 do not need to be performed in sequence.

In step 302, the above-described driver formulations may be produced by blending one or more aqueous polyurethane dispersions, one or more proteins, and one or more crosslinking agents to form a blended mixture. In some embodiments, the protein(s) may be dispersed or dissolved in an aqueous solution prior to blending with the polyurethane in step 302. Suitable aqueous solutions include, but are not limited to, water, alkaline aqueous solutions, acidic aqueous solutions, aqueous solutions including organic solvents, urea solutions, and mixtures thereof. In some embodiments, the alkaline aqueous solution may be an alkaline solution, such as sodium hydroxide, ammonia, or ammonium hydroxide solution. In some embodiments, an example of an acidic aqueous solution may be an acetic acid or hydrochloric acid (HCl) solution. Suitable organic solvents include, but are not limited to, ethanol, isopropyl alcohol, acetone, ethyl acetate, isopropyl acetate, glycerol, and the like.

In some embodiments, one or more colored dyes may be added to the mixture in step 302. In some embodiments, one or more additives may be added to the mixture in step 302. Suitable additives include, but are not limited to, fillers, pigments, plasticizers, waxes, rheology modifiers, flame retardants, antimicrobials, antifungals, antioxidants, UV stabilizers, and feel modifiers, as described herein.

In step 304, one or more layers of the blended mixture are disposed over a surface of the sacrificial layer. In step 304, one or more layers of the blended mixture may be coated on the surface of the sacrificial layer. In some embodiments, a layer of the blended mixture may be coated directly on the surface of the sacrificial layer. Coating may include pouring, extrusion, casting, etc. In some embodiments, the mixture may be spread to a desired thickness using, for example, a blade, a scraper, a roller, a roller-lined scraper, curtain coating, and slot die coating.

The sacrificial layer is not defined as a material layer of the material 100. Instead, the sacrificial layer is removed during the manufacturing of the material 100. The sacrificial layer can be removed mechanically (e.g., by peeling) or chemically (e.g., by dissolving the sacrificial layer). In some embodiments, the sacrificial layer can be a release paper.

In step 306, the solvent (e.g., water) in the one or more layers may be removed to form the protein polyurethane blend film 120. Suitable solvent removal methods include, but are not limited to, tunnel drying, vacuum drying, oven drying with hot air, humidity chamber drying, flotation drying with hot air, and an oven with a combination of mid-range IR (infrared) for preheating and then hot air for post drying.

In some embodiments, steps 304 and 306 may be repeated to apply layers of the mixture over the sacrificial layer. For example, in some embodiments, a first layer of the blended mixture may be applied over the sacrificial layer and then completely or partially dried. Then, after completely or partially drying the first layer, a second layer of the blended mixture may be applied over the first layer. In such embodiments, after applying the two layers, the layers may be dried to form the membrane 120.

In step 308, the sacrificial layer is removed. The sacrificial layer may be removed by a mechanical process or a chemical process. For example, the sacrificial layer may be removed by peeling the sacrificial layer from the film 120. As another example, the sacrificial layer may be removed by dissolving the sacrificial layer.

In step 310, film 120 is attached to a substrate layer (e.g., textile 110). In some embodiments, attaching film 120 in step 310 may include a heat press process. In such embodiments, film 120 may be in direct contact with textile 110. Additionally, in such embodiments, film 120 may be partially melted into textile 110, and upon cooling, the two layers may be firmly attached. In some embodiments, attaching film 120 to textile 110 in step 310 may include a lamination process. In such embodiments, lamination may be accomplished with an adhesive layer 150. In such embodiments, the textile 110 and/or film 120 may be coated with an adhesive by known techniques such as slot die casting, kiss coating, drawdown technique, or reverse transfer coating. In some embodiments, the lamination process may include passing the textile 110 and film 120 through a roller under heat.

In some embodiments, step 310 may be omitted from method 300. In such embodiments, film 120 may not be attached to a substrate layer. For example, in such embodiments, film 120 may not be attached to textile 110.

The materials described herein can be used in a variety of applications. For example, the materials can be used in footwear, clothing, gloves, furniture, vehicle interiors, and other goods and products, such as coats, jackets, jackets, shirts, trousers, pants, shorts, swimwear, underwear, uniforms, badges or letters, clothing, ties, skirts, dresses, blouses, leggings, gloves, mittens, shoes, shoe components (such as soles, quarters, tongues, collars, welts, and counters), dress shoes, athletic shoes, running shoes, casual shoes, athletic shoes, running shoes or casual shoe components (such as toe caps, toe boxes, outsoles, midsoles, uppers, laces, eyelets, collars, linings, Achilles tendon notches, etc.) notch), heel, and back), fashion shoes or women's shoes and their components (such as uppers, outer soles, toe caps, toes, decorations, vamps, linings, insoles, midsoles, platforms, backs, and heels or high heels), boots, sandals, buckles, sandals, hats, masks, helmets, headbands, scarves, and belts; jewelry such as bracelets, watchbands, and necklaces; gloves, umbrellas , canes, wallets, cell phone or wearable computer covers, wallets, backpacks, briefcases, handbags, folios, folders, boxes, and other personal items; sports, athletic, hunting, or recreational equipment such as harnesses, leashes, reins, harnesses, belts, mittens, tennis rackets, golf clubs, polo, hockey, or lacrosse equipment, chess and game boards, medicine balls, softballs (kick ball), baseballs, and other types of balls, and toys; book bindings, book covers, picture frames, or artwork; furniture and home, office, or other indoor or outdoor furnishings including chairs, sofas, doors, seats, ottomans, room dividers, coasters, mouse pads, desk organizers or other pads, tables, beds, floor, wall or ceiling coverings, flooring materials, automotive, marine, aircraft, and other vehicular products including seats, headrests, interior trim, trim, steering wheels, joystick or controller covers, and other wrappings or coverings.

The embodiments discussed herein will be further illustrated in the following embodiments. It should be understood that these embodiments are not limited to the above-mentioned embodiments.

100 g of a waterborne aliphatic polyether-based polyurethane dispersion having a solids content of 35%, a specific gravity of 1.02 g/mL, and a Brookfield viscosity of 160 mPa.s ("WPD1"), 0.3 g of AF-715 (antifoam available from Quaker Color), and 5 g of Permutex ^® XR-5577 (polycarbodiimide crosslinker available from Stahl Holdings BV) were added to a 150 mL beaker to prepare the polyurethane formulation. The formulation was mixed in the beaker for 5 minutes at room temperature using a Caframo impeller stirrer. After mixing, 2 g of Permutex ^® EVO-EX-RM-2956 (rheology modifier available from Stahl Holdings BV) was added to the beaker and the combination was mixed for another 5 to 10 minutes. The polyurethane formulation was then filtered through a 190 micron nylon mesh paper filter and degassed in a vacuum oven at room temperature for up to 1 hour to remove air bubbles.

After degassing, a multi-layer polyurethane film was made by coating two layers of the polyurethane formulation each onto a release paper using a Sintex laboratory coater with a doctor blade applicator. When coating, the first layer was applied and then dried at 70°C for 90 seconds. After applying and drying the first layer, the second layer was applied on top of the first layer, and then both layers were dried at 70°C for 90 seconds, at 90°C for 90 seconds, and at 150°C for 90 seconds. After drying, the film was peeled off the release paper. The film had a thickness between 20 and 40 microns. The membranes were then conditioned in a temperature and humidity controlled chamber (Forma ^™ Environmental Chamber, available from Thermo Scientific) at 23°C and 50% relative humidity for up to 24 hours.

The waterproofness of different samples cut from the film was measured using a hydrostatic head tester (Hydro Tester MK4, available from Ardmel) according to JIS L 1092. The air permeability of different samples cut from the film was measured using a custom-made test fixture according to the JIS L 1099 B1 hydrostatic pressure test.

The custom test fixture was constructed according to the JIS L 1099 B1 test method. The fixture has a base that can hold water, a lid with a hole of 89-mm diameter in the center, and a cylindrical tube with an outer diameter of 89 mm, an inner diameter of 80 mm, and a length of 50 mm. The tube was fixed to the lid, and the sample membrane was mounted on the tube using a rubber band. The lid was placed on the base, and the sample membrane was immersed 10 mm below the water line. One end of the desiccant cup with a 75-mm tube length and a diameter of 56 mm was sealed with an acrylic sheet. The cup was then filled to 2/3 of its volume with potassium acetate desiccant solution and sealed with a PTFE microporous membrane and further secured with tape. All parts of the test fixture are made of acrylic plastic sheets and acrylic tubes.

During the waterproofness test and air permeability test, the temperature and relative humidity of the membrane samples were controlled using an Espec BTL-433 temperature and humidity chamber. The air permeability and waterproofness measurements of the membrane samples (Samples 1A, 1B, 1C, and 1D) are shown in Table 4 below. Examples 2 to 12

A soy protein isolate (SPI) solution was prepared by adding 176.47 g of soy protein isolate (SUPRO ^® XT 221D, manufactured by DuPont, available from Solae LLC) to 1 L of a 0.05 mol/L aqueous sodium hydroxide solution preheated to 50°C. After addition, the solution was mixed at 50°C and 250 rpm for 30 minutes using a Caframo impeller stirrer to completely dissolve the SPI. The SPI solution was then cooled to room temperature. After cooling, 24 g of Ultra-Fresh Dw-56 (aqueous antimicrobial dispersion) was added and the solution was mixed at 250 rpm for 5 to 10 minutes at room temperature.

The protein polyurethane blend films were prepared by adding the following to a 150 mL beaker: (a) SPI solution, the mass of which is detailed in Tables 2 to 3, (b) waterborne polyurethane dispersion (WPD), the mass of which is detailed in Tables 2 to 3, (c) 0.3 g of defoamer (AF-715, available from Quaker Color), and (d) crosslinker, the amount of which is detailed in Tables 2 to 3. Each formulation was mixed in its respective beaker at room temperature for 5 minutes using a Caframo impeller mixer. The aqueous polyurethane dispersions are WPD1, nonionic aliphatic polycarbonate-polyether polyurethane dispersion (having a solid content of 30%, a specific gravity of 1.1 g/mL, and a viscosity of <1000 mPa.s) ("WPD2"), or both. The crosslinking agent is WH-PZ5150 (aziridine functionalized branched polyester crosslinker, available from An Fong Development Co., Ltd.), Permutex ^® XR-5577, or XR-13-820 (isocyanate crosslinker available from Stahl Holdings BV).

After mixing, 2 g of ^Permutex® EVO-EX-RM-2956 (Stahl Holdings BV) was added to the beaker and the combination was mixed for an additional 5 to 10 minutes. Each formulation was filtered through a 190 micron nylon mesh filter paper filter and degassed in a vacuum oven at room temperature for up to 1 hour to remove air bubbles.

After degassing, multi-layer polyurethane films were made from each formulation by coating two layers of the formulation onto a release paper using a Sintex laboratory coater with a doctor blade applicator. When coating, the first layer was applied and then dried at 70°C for 90 seconds. After applying and drying the first layer, the second layer was applied on top of the first layer, and then both layers were dried at 70°C for 90 seconds, at 90°C for 90 seconds, and at 150°C for 90 seconds. After drying, the film was peeled off the release paper. Each film had a thickness between 20 and 40 microns. Prior to testing, the membranes were conditioned in a temperature and humidity controlled chamber (Forma ^™ Environmental Chamber, available from Thermo Scientific) at 23°C and 50% relative humidity for up to 24 hours.

Examples 11 and 12 were prepared using the same method as Examples 2 to 10, except that no crosslinking agent was included, as detailed in Table 3 below.

The air permeability and water resistance of different samples cut from the membrane were measured using the method described in Example 1. The air permeability and water resistance values of different membrane samples (samples 2A, 2B, 2C, etc.) of each membrane type are shown in Table 4 below. Example 13

100 g of WPD1 and 0.3 g of AF-715 were added to a 150 mL beaker to prepare the polyurethane formulation. The formulation was mixed in the beaker using a Caframo impeller stirrer at room temperature for 5 minutes. After mixing, 1 g of Permutex ^® EVO-EX-RM-2956 was added to the beaker and the combination was mixed for another 5 to 10 minutes. The polyurethane formulation was then filtered through a 190 micron nylon mesh filter paper filter and degassed in a vacuum oven at room temperature for up to 1 hour to remove air bubbles.

After degassing, a multi-layer polyurethane film was made by coating two layers of the polyurethane formulation each onto a release paper using a Sintex laboratory coater with a doctor blade applicator and the same procedure as described in Example 1 above. The air permeability and water resistance of samples cut from the film were measured using the methods described in Example 1. The air permeability and water resistance measurements of the film samples are shown in Table 4 below. Example 14

100 g of WPD2 and 0.3 g of AF-715 were added to a 150 mL beaker to prepare a polyurethane formulation. The formulation was mixed in the beaker using a Caframo impeller stirrer at room temperature for 5 minutes. After mixing, 1 g of HM-13-843 (a water-based modified polysilicone solution feel modifier, available from Stahl Holdings B.V.) was added to the beaker and the combination was mixed for another 5 to 10 minutes. The polyurethane formulation was then filtered through a 190 micron nylon mesh filter paper filter and degassed in a vacuum oven at room temperature for up to 1 hour to remove air bubbles.

After degassing, a multi-layer polyurethane film was made by coating two layers of the polyurethane formulation each onto a release paper using a Sintex laboratory coater with a doctor blade applicator and the same procedure as described in Example 1 above. The air permeability and water resistance of samples cut from the film were measured using the methods described in Example 1. The air permeability and water resistance measurements of the film samples are shown in Table 4 below. Example 15

Three different articles (articles A, B, and C) were prepared, which included a protein polyurethane blend film on different textile substrates. Article A was made by applying the formulation of Example 3 directly to a 100% polyester textile substrate. Article B was made by applying the formulation of Example 3 directly to a 100% cotton textile substrate. Article C was made by applying the formulation of Example 15 shown in Table 3 below to a 100% polyester textile substrate. The formulation of Example 15 was made using the same procedure as Examples 2 to 12. The other aqueous polyurethane dispersion used was an aqueous aliphatic nonionic polyurethane dispersion having a solid content of about 32%, a specific gravity of 1.03 g/mL, and a Brookfield viscosity of about 200 mPa.s ("WPD3").

The formulations were coated on articles A to C using the following procedure. After degassing the formulations, the textile substrate of each article A to C was coated with a layer of the corresponding formulation using a Sintex laboratory coater with a doctor blade applicator. After coating, the layers were dried at 70° C. for 90 seconds, then at 90° C. for 90 seconds, and finally at 150° C. for 90 seconds. After drying, the coatings on all three articles had a thickness between 17 and 50 microns as measured on one of the cross sections of the articles using a scanning electron microscope (Phenom Pro X, NanoScience Instruments). The coated articles were then conditioned in a temperature and humidity controlled chamber (FORMA ^™ Environmental Chamber, Thermo Scientific) at 23°C and 50% relative humidity for up to 24 hours before testing.

The air permeability and water resistance of different samples cut from articles A to C were measured using the method described in Example 1. The air permeability and water resistance measurements of different film samples (A1, A2, A3, etc.) of the article are shown in Table 5 below. Example 16

A sample of Item A from Example 15 was dyed with 0.5% to 5% (w/w) reactive dye (Reactive Navy 1143 - cas 86024-59-1 vinyl sulfide, chloro-triphosphine, and copper metal complex) in an aqueous dye bath at a weight ratio of 1:10 textile to dye bath. The dye bath also included soda ash at a concentration of 10 mg/mL dye bath solution. After placing the sample in the dye bath, the pH of the dye bath solution was raised to above 10 using sodium hydroxide. After raising the pH, the sample was dyed in an infrared dyer (Pyrotec ⁴ dyer, Roaches International) at 60°C for four hours. After dyeing, the sample was washed in DI water at 60°C for 15 minutes. The color properties of the sample of Article A and the undyed sample were measured using a spectrophotometer (Ultra Scan Pro, HunterLab) in reflectance (including specular reflectance) mode. Table 6 below shows the color properties of the two samples. The color properties of the dyed sample show significant dye absorption in the coating formulation. Example 17

An article comprising a protein polyurethane blend film made with the recipe of Example 3 was laminated onto a knitted textile with a polyurethane reactive adhesive. After lamination, the article was conditioned in a temperature and humidity controlled box (FORMA ^™ environmental box, Thermo Scientific) at 23°C and 50% relative humidity for up to 24 hours. After conditioning, the abrasion performance of the article was then tested under dry conditions at 9 kPa pressure using a Martindale Abrader (James Heal Martindale Abrasion And Pilling Tester, Model 1605-181114). Multiple samples of the article were tested until failure, and failure was checked every 20,000 cycles. The sample failed at 200,000 cycles. Example 18

A protein polyurethane formulation according to Example 3 was prepared. A polyurethane formulation for use as a finishing agent was then prepared according to Example 1, except that the aqueous aliphatic polycarbonate polyurethane dispersion had a solid content of about 34% and a viscosity of 5 to 1000 mPa.s. ("WPD4") was used instead of WPD1 and 1 g of WH-PZ5150 was used instead of XR-5577 (see Table 3, Example 18).

After degassing, the polyurethane formulation and the protein polyurethane formulation were applied to a release paper using a Sintex laboratory coater with a doctor blade applicator. First, a baseline sample 18A was prepared using the protein polyurethane formulation using the same procedure as Examples 2 to 12. Second, sample 18B was prepared by depositing the polyurethane formulation in two layers on a release paper. The first layer of the polyurethane formulation was applied to give a wet thickness of less than 20 microns. The desired coating thickness was achieved by doctoring the release paper to achieve the lowest possible thickness or positioning the doctor blade height above the surface of the release paper to give the desired wet coating thickness. The first layer of the polyurethane formulation was then dried at 70°C for 90 seconds. After the first layer was applied and dried, a second layer of the polyurethane formulation was applied on top of the first layer using the same method. Both layers were then dried at 70°C for 90 seconds, 90°C for 90 seconds, and 150°C for 90 seconds. After the polyurethane layer was dried, two layers of the protein polyurethane formulation were applied and dried using the same procedure. After the protein polyurethane formulation layer was dried, the four-layer sample was peeled off the release paper.

Samples 18A and 18B both have a thickness between 20 and 40 microns. Prior to testing, the samples were conditioned at 23°C and 50% relative humidity for up to 24 hours in a temperature and humidity controlled chamber (FORMA ^™ Environmental Chamber, available from Thermo Scientific). The air permeability and water resistance of the samples from the two samples were measured using the method described in Example 1. The air permeability and water resistance measurements of the samples are shown in Table 7 below. The spray rating of the samples of the two samples was also measured according to AATCC 22. The spray rating results are also shown in Table 7. Sample 18A has a spray rating of 0. Sample 18B has a spray rating of ≥80. Examples 19 to 22

The same method as in Examples 2 to 12 was used to prepare a soy protein isolate (SPI) solution.

The protein polyurethane blend film was prepared by adding the following to a 150 mL beaker: (a) SPI solution, the mass of which is detailed in Table 8 below, (b) waterborne polyurethane dispersion (WPD), the mass of which is detailed in Table 8 below, (c) 0.3 g of defoamer (AF-715, available from Quaker Color), and (d) 4 g of Imprafix ^® AH (a water-based, co-solvent-free, blocked aliphatic isocyanate crosslinker). Each formulation was mixed in its own beaker at room temperature for 5 minutes using a Caframo impeller mixer. The aqueous polyurethane dispersions are WPD2, WPD3, an aqueous aliphatic anionic polyester polyurethane dispersion having a solid content of about 50%, a specific gravity of 1.1 g/mL, a Brookfield viscosity of less than or equal to 1200 mPa.s, a biocontent of about 50% as measured according to ASTM D6866, a tensile strength of 30 MPa, and an elongation at break of 1000% ("WPD5"), and an aqueous aliphatic anionic polyester polyurethane dispersion having a solid content of about 50%, a specific gravity of 1.1 g/mL, a Brookfield viscosity of less than or equal to 1200 mPa.s, a biocontent of about 56% as measured according to ASTM D6866, a tensile strength of 12 MPa, and an elongation at break of 800% ("WPD6").

After mixing, 0.3 g of a solvent-free, polyurethane oligomer-based rheology modifier (having approximately 50% solids content) was added to the beaker and the combination was mixed for an additional 5 to 10 minutes. Each formulation was filtered through a 190 micron nylon mesh filter paper filter and degassed in a vacuum oven at room temperature for up to 1 hour to remove air bubbles.

After degassing, multiple protein polyurethane membranes were made from each formulation using the same method as Examples 2 to 12.

The air permeability and water resistance of different samples cut from the membrane were measured using the method described in Example 1. The air permeability and water resistance values of different membrane samples (samples 19A, 19B, 19C, etc.) of each membrane type are shown in Table 9 below. Instance Number 1 2 3 4 5 6 7 SPI solution (g) - 21.11 50.79 50.79 50.79 48.41 48.41 WPD1 (g) 100.00 78.89 49.21 49.21 49.21 18.76 18.76 WPD2 (g) - - - - - 32.83 32.83 Permutex ^® XR-5577 (g) 5 5 - 5 - - 5 XR-13-820 (g) - - - - 1 - - WH-PZ5150 (g) - - 1 - - 1 - Table 3 Instance Number 8 9 10 11 12 13 14 15 16 18 SPI solution (g) 48.41 61.62 61.62 50.79 61.62 - - 50.3 50.3 - WPD1 (g) 18.76 38.38 38.38 49.21 38.38 100 - 44 44 - WPD2 (g) 32.83 - - - - - 100 - - - WPD3 (g) - - - - - - - 5.7 5.7 - WPD4 (g) - - - - - - - - - 100 Permutex ^® XR-5577 (g) - - 5 - - - - - - XR-13-820 (g) 1 - - - - - - - - WH-PZ5150 (g) - 1 - - - - - 1 1 1 Table 4 Instance Number Sample Number Static water pressure head (mm H ₂ O) [JIS L 1092] Air permeability (g/m ² /24hr) [JIS L 1099 B1] Approximate biomass content (%) 1 1A 12237 62% 1B 11217 62% 1C 4287 62% 1D 4326 62% 2 2A 11217 64% 2B 9687 64% 2C 3586 64% 2D 4287 64% 3 3A 5099 72% 3B 7138 72% 3C 15122 72% 4 4A 14480 69% 4B 6628 69% 4C 10197 69% 4D 20151 69% 4E 36599 69% 5 5A 9687 72% 5B 10197 72% 5C 24360 72% 5D 26426 72% 6 6A 6118 45% 6B 1530 45% 6C 67078 45% 6D 71171 45% 7 7A 4079 44% 7B 3059 44% 7C 80526 44% 7D 86333 44% 8 8A 3875 46% 8B 4079 46% 8C 68404 46% 8D 95103 46% 9 9A 3059 74% 9B 8158 74% 9C 29115 74% 9D 31376 74% 10 10A 5608 72% 10B 6424 72% 10C 41315 72% 11 11A 4079 74% 11B 5099 74% 11C 68365 74% 11D 53008 74% 12 12A 3773 78% 12B 5812 78% 12C 54723 78% 12D 58776 78% 13 13A 11217 64% 13B 10197 64% 13C 2767 64% 13D 5418 64% 14 14A 1734 0% 14B 3059 0% 14C 122465 0% Table 5 thing Sample Number Approximate biomass content (%) (coating) Static water pressure head (mm H ₂ O) [JIS L 1092] Coating thickness(µm) Air permeability (g/m ² /24hr) [JIS L 1099 B1] Example 15 Item A A1 71 19884 20-35 A2 71 18865 20-35 A3 71 20-35 15365 A4 71 20-35 16521 Example 15 Item B B1 71 29572 17-25 B2 71 20394 17-25 B3 71 17-25 68783 B4 71 17-25 94119 Example 15 Item C C1 64 13256 17-50 C2 64 17-50 112759 Table 6 L* a* b* YI E313 [D65/10] WI E313 [D65/10] Item A, undyed 92.82 -3.02 10.57 17.32 33.22 Item A, Dye (Navy) 33.76 6.75 -34.31 -203.15 313.59 Table 7 membrane Approximate biomass content (%) (coating) Static water pressure head (mm H ₂ O) [JIS L 1092] Thickness(µm) Air permeability (g/m ² /24hr) [JIS L 1099 B1] Spray level Sample 18A 66 10000 30 5000 0 Sample 18B 50-58 12000 30 20000 ≥80 Table 8 Instance Number 19 20 twenty one twenty two SPI solution (g) 57.59 57.59 51.36 51.36 WPD2 (g) - 6.63 - 7.6 WPD3 (g) 6.63 - 7.6 - WPD5 (g) 35.79 35.79 - - WPD6 (g) - - 41.038 41.038 Imprafix ^® AH (g) 4 4 4 4 Table 9 Instance Number Sample Number Static water pressure head (mm H ₂ O) [JIS L 1092] Air permeability (g/m ² /24hr) [JIS L 1099 B1] Approximate biomass content (%) 19 19A 12237 55% 19B 16315 55% 19C 30008 55% 19D 36655 55% 20 20A 11217 55% 20B 12237 55% 20C 16136 55% 20D 29816 55% twenty one 21A 13766 57% 21B 12237 57% 21C 43158 57% 21D 43495 57% twenty two 22A 14786 57% 22B 15296 57% 22C 30249 57% 22D 32368 57%

Although various embodiments have been described herein, they are presented by way of example and not limitation. It is apparent that, based on the teachings and guidance presented herein, adjustments and modifications are intended to fall within the meaning and range of equivalents of the disclosed embodiments. Therefore, it will be apparent to those of ordinary skill in the art that various changes in form and detail may 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 are interchangeable to satisfy various circumstances that will be understood by those of ordinary skill in the art.

The embodiments of the present disclosure are described in detail herein with reference to the embodiments thereof as illustrated in the accompanying drawings, where reference numbers are used to indicate identical or functionally similar elements. Reference to "one embodiment," "an embodiment," "some embodiments," and "in certain embodiments" indicates that the described embodiments may include a specific feature, structure, or characteristic, but each embodiment may not necessarily include the specific feature, structure, or characteristic. In addition, such phrases do not necessarily refer to the same embodiment. In addition, when a specific feature, structure, or characteristic is described in conjunction with an embodiment, it is believed that a person of ordinary skill in the art will be able to implement such feature, structure, or characteristic in conjunction with other embodiments, whether or not explicitly described.

These examples are illustrative rather than limiting of the present disclosure. Other suitable modifications and adjustments of the various conditions and parameters normally encountered in the art will be obvious to those skilled in the art and are within the spirit and scope of the present disclosure.

It should be understood that the phraseology or terminology used herein is for the purpose of description and not limitation. The breadth and scope of the present disclosure should not be limited to any of the above exemplary embodiments, but should only be defined in accordance with the following claims and their equivalents. Sequence SEQ ID NO: 1: Collagen fragment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

without

The accompanying drawings incorporated herein form a part of this specification and illustrate embodiments of the present invention. These drawings, together with the specification, are further used to explain the principles of the disclosed embodiments and enable those with ordinary knowledge in the relevant technical field to make and use the disclosed embodiments. These drawings are intended to illustrate rather than limit. 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 specific embodiments. In these drawings, similar reference numbers indicate identical or functionally similar elements. [Figure 1A] shows a material comprising a protein polyurethane blend membrane according to some embodiments. [Figure 1B] shows a material comprising a protein polyurethane blend membrane according to some embodiments. [FIG. 2A] shows a material comprising a protein polyurethane blend film attached to a textile according to some embodiments. [FIG. 2B] shows a material comprising a protein polyurethane blend film disposed between two textiles according to some embodiments. [FIG. 3] shows a block diagram of a method for making a material according to some embodiments.

TW202500672A_113122885_SEQL.xml

Claims (39)

A membrane comprising: a protein polyurethane blend comprising: a protein dissolved in a polyurethane prepared from an aqueous polyurethane dispersion, a crosslinking agent, and having a thickness ranging from about 5 microns to about 200 microns; wherein the protein polyurethane blend has a water resistance greater than 3,000 mm _H2O measured by a hydrostatic pressure test according to JIS L 1092 and an air permeability greater than 3,000 g/ ^m2 /24hr measured according to JIS L 1099 B1. The film of claim 1, wherein the crosslinking agent is selected from the group consisting of epoxy crosslinking agents, aziridine crosslinking agents, isocyanate crosslinking agents, carbodiimide crosslinking agents, melamine crosslinking agents, and combinations thereof. A membrane as claimed in claim 1 or claim 2, wherein the protein polyurethane blend further comprises a second polyurethane. A membrane as claimed in claim 3, wherein the protein is dissolved in the second polyurethane. The membrane of any one of claims 1 to 4, wherein the membrane has a dry weight greater than or equal to about 5 g/m ² . The membrane of any one of claims 1 to 5, wherein the protein polyurethane blend has an air permeability greater than 5,000 g/m ² /24hr as measured according to JIS L 1099 B1. The membrane of any one of claims 1 to 5, wherein the protein polyurethane blend has an air permeability greater than 3,000 g/m ² /24hr as measured according to JIS L 1099 A1. The membrane of any one of claims 1 to 5, wherein the protein polyurethane blend has an air permeability greater than 250 g/m ² /24hr measured according to ASTM E 96 B. The film of any one of claims 1 to 8, wherein the protein polyurethane blend has a water repellency of greater than 10,000 mm H ₂ O measured according to JIS L 1092. A membrane as in any one of claims 1 to 9, wherein the protein polyurethane blend comprises greater than or equal to about 5 wt % of the protein. A membrane as in any of claims 1 to 10, wherein the polyurethane comprises a biocontent greater than or equal to about 15% as measured according to ASTM D6866. A membrane as in any one of claims 1 to 11, wherein the protein polyurethane blend comprises a biocontent greater than or equal to about 35% as measured according to ASTM D6866. A membrane as claimed in any one of claims 1 to 12, wherein the protein polyurethane blend is dyed with an acidic or reactive dye. A membrane as claimed in any one of claims 1 to 13, wherein the membrane is non-porous or microporous. A film as in any one of claims 1 to 14, wherein the film is treated with a water repellent finish and comprises a water repellency spray rating of greater than or equal to about 70 as measured according to AATCC 22. A film as in any of claims 1 to 14, wherein the film is treated with a polyurethane finish and comprises a water repellency spray rating of greater than or equal to about 70 as measured according to AATCC 22. A membrane as in any of claims 1 to 14, wherein the membrane has a dry Martindale abrasion of greater than or equal to about 20,000 cycles as measured according to the Martindale Abrasion Test using a 9 kPa load. A membrane as claimed in any one of claims 1 to 17, wherein the protein is soy protein isolate. The film of claim 1 to 18, wherein the aqueous polyurethane dispersion has a water resistance of greater than 10,000 mm H ₂ O as measured by the JIS L 1092 hydrostatic pressure test when cured in the absence of a protein and a crosslinking agent. The membrane of claim 1 to 18, wherein the aqueous polyurethane dispersion comprises an aqueous aliphatic polyether-based polyurethane having a solid content of about 35% and a specific gravity of about 1.02 g/mL; a nonionic aliphatic polycarbonate-polyether polyurethane dispersion having a solid content of about 30% and a specific gravity of about 1.1 g/mL; an aqueous aliphatic nonionic polyurethane dispersion having a solid content of about 32%, a specific gravity of 1.03 g/mL, and a Brookfield viscosity of about 200 mPa.s; an aqueous aliphatic nonionic polyurethane dispersion having a solid content of about 50%, a specific gravity of 1.1 g/mL, a Brookfield viscosity of less than or equal to 1200 mPa.s, a biocontent of about 50% as measured according to ASTM D6866, a specific gravity of 30 An aqueous aliphatic anionic polyester polyurethane dispersion having a tensile strength of about 12 MPa, and an elongation at break of 1000%; an aqueous aliphatic anionic polyester polyurethane dispersion having a solids content of about 50%, a specific gravity of 1.1 g/mL, a Brookfield viscosity of less than or equal to 1200 mPa.s, a biocontent of about 56% as measured according to ASTM D6866, a tensile strength of 12 MPa, and an elongation at break of 800%, or a combination thereof. A precursor formulation comprising: water; protein; aqueous polyurethane dispersion; and one or more crosslinking agents present in a weight percentage ranging from about 0.1 wt % to about 5 wt % relative to the total weight of water, protein, and aqueous polyurethane dispersion in the formulation. The driver formulation as claimed in claim 21, wherein the protein is dissolved in the polyurethane in the polyurethane dispersion. The formulation of claim 21 or claim 22, wherein the one or more crosslinking agents are selected from the group consisting of epoxy crosslinking agents, aziridine crosslinking agents, isocyanate crosslinking agents, carbodiimide crosslinking agents, melamine crosslinking agents, and combinations thereof. The formulation of any one of claims 21 to 23, further comprising an acid dye or a reactive dye. The formulation of any one of claims 21 to 24, further comprising a defoaming agent or an antifoaming agent. As in the formulation of claim 25, wherein the defoaming agent is a mineral oil-based defoaming agent. The formulation of claims 21 to 26, wherein the aqueous polyurethane dispersion has a water resistance of greater than 3,000 mm H ₂ O as measured by the JIS L 1092 hydrostatic pressure test when cured in the absence of a protein and a crosslinking agent. The formulation of any one of claims 21 to 26, wherein the aqueous polyurethane dispersion comprises an aqueous aliphatic polyether-based polyurethane having a solid content of about 35% and a specific gravity of about 1.02 g/mL; a nonionic aliphatic polycarbonate-polyether polyurethane dispersion having a solid content of about 30% and a specific gravity of about 1.1 g/mL; an aqueous aliphatic nonionic polyurethane dispersion having a solid content of about 32%, a specific gravity of 1.03 g/mL, and a Brookfield viscosity of about 200 mPa.s; an aqueous aliphatic nonionic polyurethane dispersion having a solid content of about 50%, a specific gravity of 1.1 g/mL, a Brookfield viscosity of less than or equal to 1200 mPa.s, a biocontent of about 50% as measured according to ASTM D6866, a specific gravity of 30 MPa, and an elongation at break of 1000%; an aqueous aliphatic anionic polyester polyurethane dispersion having a solids content of about 50%, a specific gravity of 1.1 g/mL, a Brookfield viscosity of less than or equal to 1200 mPa.s, a biocontent of about 56% as measured according to ASTM D6866, a tensile strength of 12 Mpa, and an elongation at break of 800%; or a combination thereof. An article comprising: a textile; and a film as claimed in any one of claims 1 to 20 attached to the textile. An article as in claim 29, wherein the film is attached to the textile with an adhesive. The article of claim 29 or 30, wherein the textile comprises a first textile layer and a second textile layer, and wherein the film is disposed between the first textile layer and the second textile layer. An article as claimed in claim 29 or 30, wherein the film is attached to an exterior surface of the textile. An article comprising: a textile; and a coating comprising the formulation of any one of claims 21 to 28, the coating being attached to the textile. An article as in claim 33, wherein the coating is directly attached to a surface of the textile. An article as claimed in claim 33 or claim 34, wherein the coating is attached to a front surface of the textile. An article as claimed in claim 33 to 35, wherein the coating is attached to a back surface of the textile. An article as in any one of claims 33 to 36, wherein the article is dyed with an acid dye, a reactive dye, or a combination thereof. The article of claim 37, wherein the textile is dyed with the acid dye, the reactive dye, or a combination thereof. An article as claimed in claim 37 or claim 38, wherein the coating is dyed with the acid dye, the reactive dye, or a combination thereof.