Protein polyurethane alloy material

Abstract

A material comprising a protein polyurethane alloy comprising one or more proteins dissolved within one or more polyurethanes. The material can be subjected to various leather and / or textile treatments to produce the described properties. For example, in some embodiments, the material can be dyed. As another example, in some embodiments, the material can be fat-liquidized.

Description

[Technical Field]

[0001] Reference to an electronically submitted sequence listing The contents of the Sequence Listing submitted electronically in an ASCII text file with this application (Name: 4431_091PC01_Seqlisting_ST26.xml; Size: 4,669 bytes; and Creation Date: August 10, 2023) are incorporated herein by reference in their entirety.

[0002] The present disclosure relates to a material comprising a protein polyurethane alloy comprising one or more proteins dissolved in polyurethane. In certain embodiments, the present disclosure relates to a material comprising the protein polyurethane alloy and a textile substrate. In some embodiments, the material can be used to make textiles or fabrics, such as textiles or fabrics typically prepared from natural leather. [Background technology]

[0003] Leather is a versatile product used across many industries, including the furniture industry, where leather is regularly used as upholstery material; the clothing industry, where leather is used to manufacture pants and jackets; the footwear industry, where leather is used to prepare casual and dress shoes; the luggage, handbag, and accessory industries; and the automotive industry. Global trade in leather is high, and there is a continuing and increasing demand for leather products. Despite leather's seemingly widespread popularity, there are various costs, constraints, and societal concerns associated with the production of natural leather. First and foremost, natural leather is produced from animal skins and therefore requires the raising and slaughter of livestock. Raising livestock requires vast amounts of feed, pasture, water, and fossil fuels, contributing to air and waterway pollution from greenhouse gases such as methane. Leather production also raises societal concerns related to animal treatment. In recent years, there has also been a well-documented decline in the availability of traditional, high-quality hides. For at least these reasons, alternative means of satisfying the demand for leather are desirable.

[0004] Additionally, other textile or fabric materials, such as cotton and spandex, are used across many industries, including the furniture and clothing industries. Demand for such materials is high, and there is a continuing need for improved textile and fabric materials. Summary of the Invention

[0005] The present disclosure provides materials comprising protein polyurethane alloys that can be applied in a variety of applications, including as a replacement for natural leather and other applications in textiles and fabrics.

[0006] A first embodiment (1) of the present disclosure relates to a material comprising a textile; a protein polyurethane alloy disposed on the textile, the protein polyurethane alloy comprising a protein dissolved in the polyurethane; and about 1% to about 16% by weight of one or more fatliquoring agents.

[0007] In a second embodiment (2), the protein polyurethane alloy according to the first embodiment (1) comprises more than 50% by weight of protein.

[0008] In a third embodiment (3), the protein polyurethane alloy according to the first embodiment (1) contains about 60% to about 90% by weight of protein.

[0009] In a fourth embodiment (4), the one or more fatliquors according to any one of embodiments (1) to (3) comprise a functionalized oil.

[0010] In a fifth embodiment (5), the one or more fatliquors according to any one of embodiments (1) to (3) are selected from the group consisting of sulfited fatliquors, sulfated fatliquors, or combinations thereof.

[0011] In a sixth embodiment (6), the material according to any one of the embodiments (1) to (5) has an elastic modulus of 9×10̂7 Pa or less.

[0012] In a seventh embodiment (7), the material according to any one of the embodiments (1) to (5) has an elastic modulus of 6×10̂7 Pa or less.

[0013] An eighth embodiment (8) of the present disclosure relates to a material comprising a textile, a protein polyurethane alloy including a protein dissolved in the polyurethane, a first portion having a first protein polyurethane alloy density, and a second portion having a second protein polyurethane alloy density different from the first protein polyurethane alloy density.

[0014] In a ninth embodiment (9), in the material according to the eighth embodiment (8), the density of the first protein polyurethane alloy is at least 5% less than or greater than the density of the second protein polyurethane alloy.

[0015] In a tenth embodiment (10), a first portion of the material according to the eighth embodiment (8) or the ninth embodiment (9) comprises a first protein polyurethane alloy layer, and a second portion of the material according to the eighth embodiment (8) or the ninth embodiment (9) comprises a second protein polyurethane alloy layer.

[0016] In an eleventh embodiment (11), in the material according to the tenth embodiment (10), the textile comprises a top surface and a bottom surface, and a first protein polyurethane alloy layer is disposed on the top surface of the textile and a second protein polyurethane alloy layer is disposed on the bottom surface of the textile.

[0017] In a twelfth embodiment (12), in the material according to the eighth embodiment (8) or the ninth embodiment (9), the first portion comprises a protein polyurethane alloy integrated into the textile at a first protein polyurethane alloy density, and the second portion comprises a protein polyurethane alloy integrated into the textile at a second protein polyurethane alloy density.

[0018] In a thirteenth embodiment (13), in a material according to the eighth embodiment (8) or the ninth embodiment (9), the textile comprises a first textile layer bonded to a second textile layer, the first portion comprising a protein polyurethane alloy integrated into the first textile layer at a first protein polyurethane alloy density, and the second portion comprising a protein polyurethane alloy integrated into the second textile layer at a second protein polyurethane alloy density.

[0019] In a fourteenth embodiment (14), the material according to any one of embodiments (8) to (13) further comprises a crosslinking agent selected from the group consisting of an epoxy-based crosslinking agent, an isocyanate-based crosslinking agent, and a carbodiimide-based crosslinking agent.

[0020] In a fifteenth embodiment (15), the crosslinking agent according to the fourteenth embodiment (14) is a carbodiimide-based crosslinking agent.

[0021] A sixteenth embodiment (16) of the present disclosure is directed to an aqueous formulation including water, an aqueous polyurethane dispersion, a protein, about 4% to about 10% by weight of one or more color dyes, and a foam stabilizer.

[0022] In a seventeenth embodiment (17), the protein according to the sixteenth embodiment (16) is dissolved in the polyurethane of the polyurethane dispersion.

[0023] An eighteenth embodiment (18) of the present disclosure relates to a material comprising: a textile; a protein polyurethane alloy integrated into the textile, the protein polyurethane alloy comprising a protein dissolved in the polyurethane; and about 100% to about 250% by weight of one or more color dyes, wherein the weight % of the one or more color dyes is measured relative to the weight of the protein in the protein polyurethane alloy. [Brief explanation of the drawings]

[0024] The accompanying drawings incorporated herein, form a part of this specification, and illustrate embodiments of the present disclosure. Together with the specification, the drawings further serve to explain the principles of embodiments of the present disclosure and enable one skilled in the relevant art(s) to make and use embodiments of the present disclosure. The figures are intended to be illustrative, not limiting. While the present disclosure has generally been described in the context of these embodiments, it will be understood that it is not intended to limit the scope of the disclosure to these particular embodiments. In the drawings, like reference numbers indicate identical or functionally similar elements.

[0025] [Figure 1] FIG. 1 is a dynamic mechanical analysis (DMA) graph of storage modulus versus temperature for various materials. [Figure 2] FIG. 2 is a graph illustrating the relationship between maximum tensile stress and gelatin weight percentage for gelatin polyurethane alloys, according to some embodiments. [Figure 3] FIG. 3 is a graph showing the relationship between Young's modulus and gelatin weight percentage for gelatin polyurethane alloys, according to some embodiments. [Figure 4] FIG. 4 is a DMA graph of storage modulus versus temperature for various materials. [Figure 5] FIG. 5 is a graph showing the relationship between maximum tensile stress and soy protein isolate (SPI) weight percent of SPI polyurethane alloys, according to some embodiments. [Figure 6] FIG. 6 is a graph showing the relationship between Young's modulus and SPI weight percent for SPI polyurethane alloys, according to some embodiments. [Figure 7] FIG. 7 is a DMA graph of storage modulus versus temperature for various materials. [Figure 8A] FIG. 8A is a graph comparing the maximum tensile stress of various protein polyurethane alloys, according to some embodiments. [Figure 8B]FIG. 8B is a graph comparing the Young's modulus of various protein polyurethane alloys, according to some embodiments. [Figure 9] FIG. 9 is a DMA thermogram comparing L3360 and gelatin L3360 alloy, according to some embodiments. [Figure 10] FIG. 10 is a DMA thermogram comparing Hauthane HD-2001 polyurethane and gelatin Hauthane HD-2001 polyurethane alloy, according to some embodiments. [Figure 11] FIG. 11 is a DMA thermogram comparing SANCURE™ 20025F polyurethane and gelatin SANCURE™ 20025F polyurethane alloy, according to some embodiments. [Figure 12] FIG. 12 is a DMA thermogram comparing IMPRANIL® DLS polyurethane and a gelatin IMPRANIL® DLS polyurethane alloy, according to some embodiments. [Figure 13] FIG. 13 is a DMA thermogram comparing BONDTHANE™ UD-108 polyurethane and a gelatin BONDTHANE™ UD-108 polyurethane alloy, according to some embodiments. [Figure 14] FIG. 14 is a DMA thermogram comparing BONDTHANE™ UD-303 polyurethane and a gelatin BONDTHANE™ UD-303 polyurethane alloy, according to some embodiments. [Figure 15] FIG. 15 is a DMA thermogram comparing BONDTHANE™ UD-250 polyurethane and a gelatin BONDTHANE™ UD-250 polyurethane alloy, according to some embodiments. [Figure 16] FIG. 16 is a representative DMA graph showing the methodology for measuring the first and second DMA modulus transition onset temperatures. [Figure 17A]FIG. 17A shows a material including a protein polyurethane alloy integrated into a textile, according to some embodiments. [Figure 17B] FIG. 17B shows a material including a protein polyurethane alloy integrated into a multi-layer textile, according to some embodiments. [Figure 17C] FIG. 17C shows a material including a protein polyurethane alloy integrated into a foam layer on a textile, according to some embodiments. [Figure 18A] FIG. 18A illustrates a layered material according to some embodiments. [Figure 18B] FIG. 18B shows a layered material including a non-foamed layer and a foamed layer, according to some embodiments. [Figure 19] FIG. 19 is a block diagram illustrating a method of making a layered material, according to some embodiments. [Figure 20A] 20A-20F illustrate a method of making a layered material according to some embodiments. [Figure 20B] 20A-20F illustrate a method of making a layered material according to some embodiments. [Figure 20C] 20A-20F illustrate a method of making a layered material according to some embodiments. [Figure 20D] 20A-20F illustrate a method of making a layered material according to some embodiments. [Figure 20E] 20A-20F illustrate a method of making a layered material according to some embodiments. [Figure 20F] 20A-20F illustrate a method of making a layered material according to some embodiments. [Figure 21] FIG. 21 illustrates a spacer fabric according to some embodiments. [Figure 22] FIG. 22 is a DMA thermogram comparing IMPRAPERM® DL 5249 polyurethane and soy protein isolate IMPRAPERM® DL 5249 alloy, according to some embodiments. [Figure 23] FIG. 23 is a graph measuring the weight of water transported through the construct as weight change versus time for a multilayered protein polyurethane alloy, according to some embodiments. DETAILED DESCRIPTION OF THE INVENTION

[0026] The indefinite articles "a," "an," and "the" include plural referents unless the context clearly dictates otherwise or the context clearly contradicts this.

[0027] The terms "comprising" and "including" are open-ended transitional phrases. The list of elements following the transitional phrase "comprising" or "including" is a non-exclusive list, and therefore, elements may be present in addition to those specifically recited in the list. The phrase "consisting essentially of" limits the component composition to specified materials and to those that do not materially affect the basic and novel property(ies) of the component. The phrase "consisting of" limits the component composition to specified materials and excludes any materials not specified.

[0028] When a range of numerical values, including upper and lower values, is recited herein, unless otherwise specified in specific circumstances, the range is intended to include its endpoints, and all integers and fractions within the range. The present disclosure is not intended to be limited to the specific values ​​recited when defining a range. Furthermore, when an amount, concentration, or other value or parameter is given as a range, one or more ranges, or a list of upper and lower values, this should be understood to specifically disclose all ranges formed from any pairing of any upper range limit or value with any lower range limit or value, regardless of whether such pairs are separately disclosed. Finally, when the term "about" is used in describing a value or endpoint of a range, the disclosure should be understood to include the specific value or endpoint referred to. Regardless of whether a value or endpoint of a range is described as "about," the value or endpoint of the range is intended to include two embodiments: one modified by "about" and one not modified.

[0029] As used herein, the term "about" refers to a value that is within ±10% of the stated value. For example, about 3 MPa can include any number between 2.7 MPa and 3.3 MPa. However, when a percentage is recited and the percentage value cannot exceed 100%, e.g., 100% or 99% by weight, "about" does not modify the percentage to include values ​​greater than 100%.

[0030] As used herein, a first layer described as "bonded" to a second layer means that the layers are bonded to one another either by direct contact and bonding between the two layers or through one or more intermediate adhesive layers. An intermediate adhesive layer can be any layer that serves to bond the first layer to the second layer.

[0031] As used herein, the phrase "disposed on" means that a first component (e.g., a layer, alloy, or textile) is in direct contact with a second component. A first component "disposed on" a second component may be deposited, formed, positioned, or otherwise applied directly onto the second component. In other words, when a first component is disposed on a second component, there are no components between the first and second components.

[0032] As used herein, the phrase "disposed on" means that other components (e.g., layers or substrates) may or may not be present between the first and second components.

[0033] As used herein, a "bio-based polyurethane" is a polyurethane in which the polyol building blocks, such as diols and diacids, are derived from biomaterials, such as cornstarch.

[0034] As used herein, the term "substantially free" means that the component is present in a detectable amount not exceeding about 0.1% by weight.

[0035] As used herein, the term "free" means that the component is not present in the blend or material (e.g., protein polyurethane alloy) even in trace amounts.

[0036] As used herein, "collagen" refers to a family of at least 28 distinct naturally occurring collagen types, including, but not limited to, collagen types I, II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII, XIX, and XX. As used herein, the term collagen also refers to collagen prepared using recombinant techniques. The term collagen includes collagen, collagen fragments, collagen-like proteins, triple helix collagen, alpha chains, monomers, gelatins, trimers, and combinations thereof. Recombinant expression of collagen and collagen-like proteins is known in the art (e.g., Bell, EP 1232182(B1), Bovine collagen and method for producing recombinant gelatin; Olsen, et al., U.S. Pat. No. 6,428,978, and VanHeerde, et al., U.S. Pat. No. 8,188,230, which are incorporated herein by reference in their entireties). 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. Thus, in some embodiments, the collagen described herein can be prepared using bovine type I collagen. Collagen is characterized by a repeating triplet of amino acids, -(Gly-XY)n-, such that approximately one-third of the amino acid residues in collagen are glycine. X is often proline, and Y is often hydroxyproline. Thus, the structure of collagen can consist of three intertwined peptide chains of different lengths. Different animals may produce collagen with different amino acid compositions, which may result in different properties (and differences in the resulting leather).

[0037] In some embodiments, collagen can be chemically modified to enhance its solubility in water.

[0038] Any type of collagen, truncated collagen, unmodified or post-translationally modified, or amino acid sequence modified collagen can be used as part of the protein polyurethane alloy.

[0039] In some embodiments, the collagen can be plant-based collagen, for example, the collagen can be plant-based collagen made by CollPlant.

[0040] In some embodiments, the collagen solution can be fibrillated into collagen fibrils. As used herein, collagen fibrils refer to nanofibers composed of tropocollagen or tropocollagen-like structures (having triple helix structures). In some embodiments, triple helix collagen can be fibrillated to form collagen nanofibrils.

[0041] In some embodiments, recombinant collagen can include collagen fragments of the amino acid sequence of a native collagen molecule capable of forming tropocollagen (trimeric collagen). Recombinant collagen can also include modified collagens or truncated collagens having an amino acid sequence at least 70, 80, 90, 95, 96, 97, 98, or 99% identical or similar to the native collagen amino acid sequence (or to its fibril-forming region, or a segment substantially containing [Gly-XY]n). In some embodiments, the collagen fragment can be a 50 kDa portion of native collagen. Native collagen sequences include the amino acid sequences of CollA1, CollA2, and Col3A1, as described by Accession Nos. NP_001029211.1, NP_776945.1, and NP_001070299.1, which are incorporated by reference. In some embodiments, the collagen fragment can be a portion of human collagen alpha-1(III) (Col3A1; Uniprot #P02461, Entrez Gene ID #1281). In some embodiments, the collagen fragment can be the amino acid sequence listed as SEQ ID NO: 1. In some embodiments, the collagen fragment can be the amino acid sequence listed as SEQ ID NO: 2. In some embodiments, the collagen fragment comprises an amino acid sequence having at least 80% sequence identity to SEQ ID NO: 2. Examples of proteins comprising at least 80% sequence identity to SEQ ID NO: 2 are disclosed in International Application No. PCT / US2022 / 027016, the disclosure of which is incorporated herein by reference.

[0042] Methods for producing recombinant collagen and recombinant collagen fragments are known in the art. For example, U.S. Patent Application Publication Nos. 2019 / 0002893, 2019 / 0040400, 2019 / 0093116, and 2019 / 0092838 describe methods for producing collagen and collagen fragments that can be used to produce the recombinant collagen and recombinant collagen fragments disclosed herein. The contents of these four publications are incorporated by reference in their entirety.

[0043] The protein polyurethane alloys described herein may contain a protein that is miscible with only one of the phases of the polyurethane, or multiple polyurethanes with which it is blended. For example, in some embodiments, the protein polyurethane alloy may contain a protein that is miscible with only the hard phase of the polyurethane, or with multiple polyurethanes having both hard and soft phases. The protein polyurethane alloys described herein may be free or substantially free of protein in the form of particles dispersed in the polyurethane. For example, in some embodiments, the protein polyurethane alloy may be free or substantially free of protein particles having an average diameter greater than 1 micron (μm).

[0044] In some embodiments, the protein polyurethane alloy may be free or substantially free of soy protein particles having an average diameter greater than 1 micron (μm). In some embodiments, the protein polyurethane alloy may be free or substantially free of collagen particles having an average diameter greater than 1 micron (μm). In some embodiments, the protein polyurethane alloy may be free or substantially free of gelatin particles having an average diameter greater than 1 micron (μm). In some embodiments, the protein polyurethane alloy may be free or substantially free of bovine serum albumin particles having an average diameter greater than 1 micron (μm). In some embodiments, the protein polyurethane alloy may be free or substantially free of pea protein particles having an average diameter greater than 1 micron (μm). In some embodiments, the protein polyurethane alloy may be free or substantially free of ovalbumin particles having an average diameter greater than 1 micron (μm). In some embodiments, the protein polyurethane alloy may be free or substantially free of casein protein particles having an average diameter greater than 1 micron (μm). In some embodiments, the protein polyurethane alloy 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 alloy may be free of or substantially free of edestin protein particles having an average diameter greater than 1 micron (μm). In some embodiments, the protein polyurethane alloy 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 alloy 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 alloy may be free of or substantially free of cellulase particles having an average diameter greater than 1 micron (μm).In some embodiments, the protein polyurethane alloy may be free or substantially free of recombinant collagen fragment particles having an average diameter greater than 1 micron (μm).

[0045] In certain embodiments, the present disclosure provides a unique combination of a protein and a polyurethane in which the protein is dissolved only in the rigid phase of the polyurethane. The present disclosure also provides methods for making the protein polyurethane alloys described herein. The present disclosure also provides materials comprising one or more protein polyurethane alloys and methods for making the materials. In some embodiments, the present disclosure provides layered materials comprising one or more protein polyurethane alloy layers and methods for making the layered materials. The protein polyurethane alloys and protein polyurethane alloy layers can comprise one or more types of proteins and one or more polyurethanes.

[0046] Proteins suitable for use in the alloys disclosed herein can be unmodified or chemically modified. In some embodiments, proteins can be modified to promote miscibility of the protein with the polyurethane hard phase. In some embodiments, proteins can be chemically modified to promote solubility in water. In such embodiments, chemical modifications to promote solubility in water can promote miscibility of the protein with the polyurethane hard phase. In some embodiments, chemically modified proteins can be partially hydrolyzed proteins. In some embodiments, chemically modified proteins can be proteins modified by the covalent attachment of hydrophilic polymer chains, such as polyethylene glycol (PEG) chains, to the protein.

[0047] Suitable polyurethanes for use in the protein polyurethane alloys described herein include those that contain at least two phases, including a "soft phase" and a "hard phase." The soft phase is formed from polyol segments within the polyurethane that are 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 for many of the properties of polyurethanes.

[0048] The soft phase is typically elastomeric at room temperature and typically has a softening point or glass transition temperature (Tg) below room temperature. Tg is measured by dynamic mechanical analysis (DMA) and can be quantified by either the peak in tan(δ) or the onset of the drop in storage modulus. Alternatively, Tg can be measured by differential scanning calorimetry (DSC). In some cases, crystallinity may be present in the soft phase, which is typically visible as a melting point between 0°C and about 60°C. For example, the peak in the tan(δ) curve at about 35°C for UD-108 polyurethane in Figure 13 indicates crystallinity in the soft phase of the polyurethane.

[0049] The hard phase typically has a Tg or melting point above room temperature, more typically above about 80° C. The softening of the hard phase can be measured by measuring the onset of drop in storage modulus (sometimes referred to as stiffness) as measured by DMA.

[0050] The "soft phase" of polyurethanes or polyurethane-containing protein polyurethane alloys comprises the polyol component of the polyurethane. Its function is to become soft and flexible above its Tg, imparting toughness, extensibility, and flexibility to the polyurethane. Typical soft segments can include polyether polyols, polyester polyols, polycarbonate polyols, and mixtures thereof. These typically range in molecular weight from about 250 daltons to greater than about 5 kilodaltons. The "hard phase" of polyurethanes or polyurethane-containing protein polyurethane alloys comprises the polymeric urethane segments provided by isocyanates used to connect the polyols with short-chain diols such as butanediol and propanediol. Typical isocyanates useful in the polyurethanes include, but are not limited to, hexamethylene diisocyanate, isophorone diisocyanate, methylene diisocyanate, and phenyl diisocyanate. These molecules are more polar and rigid than the polyols used to create the soft segments. Thus, the hard segments are stiffer and have a higher softening point compared to the soft segments. The function of the hard phase is to provide strength, temperature resistance, and abrasion resistance, among other properties, to the polyurethane.

[0051] In some embodiments described herein, the protein may be miscible only with the hard phase, leaving the soft phase transition substantially unchanged. Without wishing to be bound by any particular theory, it is believed that when the protein dissolves in the hard phase, it significantly increases the temperature at which the hard phase begins to soften, thus increasing the heat resistance of the alloys described herein. The protein polyurethane alloys described herein may also have increased stiffness and strength relative to the base polyurethane (i.e., the polyurethane itself in the absence of the protein).

[0052] The protein polyurethane alloys and layers described herein can be formed by blending one or more proteins in a liquid state with one or more waterborne polyurethane dispersions and drying the blend. In some embodiments, the protein polyurethane alloys and layers described herein can be formed by blending one or more proteins dissolved or dispersed in an aqueous solution with one or more waterborne polyurethane dispersions in a liquid state and drying the blend. In some embodiments, the polyurethane dispersions can be ionic, either anionic or cationic. In some embodiments, the polyurethane dispersions can be nonionic. In some embodiments, the blended protein and polyurethane can be formed into a sheet, which in certain embodiments can be bonded to a substrate layer using a suitable bonding process, such as direct coating, a lamination process, or a thermoforming process. In certain embodiments, the lamination process can include bonding the sheet to the substrate layer using an adhesive layer. In some embodiments, the blended protein and polyurethane can be coated or otherwise deposited onto a substrate layer to bond the blended protein and polyurethane to the substrate layer. In some embodiments, a portion of the blended protein and polyurethane may be integrated into a portion of the substrate layer by binding the blended protein and polyurethane to the substrate layer.

[0053] In protein polyurethane alloys comprising one or more miscible proteins and polyurethanes, the one or more proteins may be dissolved in the hard phase of one or more polyurethanes. The protein polyurethane alloy may include at least one protein that is miscible with the hard phase of one or more polyurethanes in the alloy. In some embodiments, the protein polyurethane alloy may include multiple proteins and / or multiple polyurethane hard phases that are miscible with each other. In all of these embodiments, without wishing to be bound by theory, it is believed that the protein or proteins are dissolved in the hard phase of the polyurethane or polyurethanes.

[0054] One or more proteins dissolved in the hard phase of one or more polyurethanes can form a homogeneous mixture when blended. In some embodiments, a protein polyurethane alloy can include multiple proteins dissolved in one or more polyurethanes such that the proteins and polyurethane(s) form a homogeneous mixture when blended and dried. Typically, a protein polyurethane alloy comprising a homogeneous mixture of protein and polyurethane does not contain a significant amount of protein that is not dissolved in the polyurethane. That is, in some embodiments, a protein polyurethane alloy can include protein fragments dispersed within the polyurethane.

[0055] In embodiments described herein, miscibility of a protein with a polyurethane hard phase can increase the DMA modulus transition softening onset temperature of the hard phase in a protein polyurethane alloy without significantly changing one or more other thermomechanical properties of the alloy relative to the thermomechanical properties of the polyurethane itself. For example, miscibility of a protein with a polyurethane hard phase can increase the DMA modulus transition onset temperature of the hard phase in a protein polyurethane alloy without significantly changing the DMA transition temperature of the soft phase in the alloy compared to the DMA transition temperature of the soft phase of the polyurethane itself.

[0056] The DMA transition temperature of the soft phase may be referred to as the glass transition temperature (Tg) of the polyurethane or protein polyurethane alloy. The DMA transition temperature of the soft phase or Tg may be quantified as (i) the DMA storage modulus transition onset temperature of the soft phase (referred to herein as the "first DMA storage modulus transition onset temperature") or (ii) the DMA tan(δ) peak temperature corresponding to the soft phase. The DMA transition temperature of the hard phase may be measured by the onset of the storage modulus drop of the polyurethane or polyurethane-protein alloy and may be quantified as the DMA modulus transition onset temperature of the hard phase (referred to herein as the "second DMA modulus transition onset temperature"). In some embodiments, the second DMA modulus transition onset temperature of the protein polyurethane alloy may be greater than about 80°C or greater than about 130°C.

[0057] While many protein types are contemplated for use in the protein polyurethane alloys described herein, including, for example, collagen and soy protein, it is understood that for all of the embodiments disclosed herein, the protein can be a protein other than collagen and / or a protein other than soy protein. Thus, in some embodiments, the protein dissolved in the protein polyurethane alloy can be a protein other than collagen. In other embodiments, the protein dissolved in the protein polyurethane alloy can be a protein other than soy protein. In some embodiments, the protein dissolved in the protein polyurethane alloy can be a protein other than collagen and a protein other than soy protein. In some embodiments, the protein polyurethane alloy can be free of collagen or substantially free of collagen. In some embodiments, the protein polyurethane alloy can be free of soy protein or substantially free of soy protein. In some embodiments, the protein polyurethane alloy can be free of soy protein and collagen or substantially free of soy protein and collagen.

[0058] As mentioned above, the soft and hard phases of polyurethanes can be measured using dynamic mechanical analysis (DMA). Accordingly, one or more polyurethanes included in the protein polyurethane alloys described herein may have at least two DMA transition temperatures, one corresponding to the soft phase and one corresponding to the hard phase. The DMA transition temperature of the soft phase can be quantified as the "first DMA modulus transition onset temperature" or the DMA tan(δ) peak temperature corresponding to the soft phase. The DMA transition temperature of the hard phase can be quantified by the "second DMA modulus transition onset temperature." The first DMA modulus transition onset temperature or the DMA tan(δ) peak temperature is the lower DMA transition temperature, and the second DMA modulus transition onset temperature is the higher DMA transition temperature.

[0059] Similarly, the protein polyurethane alloys described herein may have at least two phases. The at least two phases may include a soft phase and a hard phase. The different phases of the alloy may be measured and quantified in the same manner as described above for polyurethanes.

[0060] A polyurethane or protein polyurethane alloy having first and second DMA transition temperatures means that the first DMA transition temperature occurs at a temperature lower than the second DMA transition temperature. However, the first and second transition temperatures do not have to be sequential transition temperatures. Other DMA transition temperatures may occur between the first and second transitions.

[0061] In some embodiments, the polyurethane may have a first DMA modulus transition onset temperature less than 30° C. In some embodiments, the polyurethane may have a first DMA modulus transition onset temperature in the range of about −65° C. to about 30° C., including subranges. For example, in some embodiments, the polyurethane may have a first DMA modulus transition onset temperature of about −65° C., about −60° C., about −55° C., about −50° C., about −45° C., about −40° C., about −35° C., about −30° C., about −25° C., about −20° C., about −15° C., about −10° C., about −5° C., about −1° C., 0° C., about 1° C., about 5° C., about 10° C., about 15° C., about 20° C., about 25° C., or about 30° C., or a range having as endpoints any two of these values ​​inclusive. In some embodiments, the polyurethane's first DMA modulus transition onset temperature can be about -65°C to about 30°C, about -65°C to about 25°C, about -65°C to about 20°C, about -65°C to about 15°C, about -65°C to about 10°C, about -65°C to about 5°C, about -65°C to about 1°C, about -65°C to 0°C, about -65°C to about -1°C, about -65°C to about -5°C, about -65°C to about -10°C, about -65°C to about -15°C, about -65°C to about -20°C, about -65°C to about -25°C, about -65°C to about -30°C, about -65°C to about -35°C, about -65°C to about -35°C, about -65°C to about -40°C, or about -65°C to about -45°C.

[0062] 9-15 show DMA thermograms of various exemplary polyurethanes. The first DMA modulus transition onset temperature (T onset1 ) is the temperature at which the slope of the storage modulus (E') curve begins to decrease significantly over the first time. The methodology for determining this value is illustrated in FIG. 16. DMA instruments, such as the TA Instruments DMA-850, can be programmed to automatically calculate this temperature. Table 4 lists the first DMA modulus transition onset temperatures automatically calculated from the DMA graphs of FIGS. 9-15 (see Examples 1-7).

[0063] In some embodiments, the DMA tan(δ) peak temperature corresponding to the soft phase of the polyurethane may be less than 30° C. In some embodiments, the DMA tan(δ) peak temperature corresponding to the soft phase of the polyurethane may be in the range of about −60° C. to about 30° C., including subranges. For example, in some embodiments, the DMA tan(δ) peak temperature corresponding to the soft phase of the polyurethane may be about −60° C., about −55° C., about −50° C., about −45° C., about −40° C., about −35° C., about −30° C., about −25° C., about −20° C., about −15° C., about −10° C., about −5° C., about −1° C., 0° C., about 1° C., about 5° C., about 10° C., about 15° C., about 20° C., about 25° C., or about 30° C., or a range having as endpoints any two of these values ​​inclusive. In some embodiments, the DMA tan(δ) peak temperature corresponding to the soft phase of the polyurethane can be about -60°C to about 30°C, about -60°C to about 25°C, about -60°C to about 20°C, about -60°C to about 15°C, about -60°C to about 10°C, about -60°C to about 5°C, about -60°C to about 1°C, about -60°C to about 0°C, about -60°C to about -1°C, about -60°C to about -5°C, about -60°C to about -10°C, about -60°C to about -15°C, about -60°C to about -20°C, about -60°C to about -25°C, about -60°C to about -30°C, about -60°C to about -35°C, or about -60°C to about -40°C.

[0064] The DMA thermograms in Figures 9-15 show the DMA tan(δ) peak temperatures corresponding to the soft phase of various exemplary polyurethanes. As with the DMA modulus transition onset temperature, DMA instruments such as the TA Instruments DMA-850 can be programmed to automatically calculate this temperature. Table 4 lists the DMA tan(δ) peak temperatures automatically calculated from the DMA graphs in Figures 9-15 (see Examples 1-7).

[0065] In some embodiments, the second DMA modulus transition onset temperature of the polyurethane may be greater than 30° C. In some embodiments, the second DMA modulus transition onset temperature of the polyurethane may be in the range of about 45° C. to about 165° C. For example, in some embodiments, the second DMA modulus transition onset temperature of the polyurethane may be about 45° C., about 50° C., about 55° C., about 60° C., about 65° C., about 70° C., about 75° C., about 80° C., about 85° C., about 90° C., about 95° C., about 100° C., about 105° C., about 110° C., about 115° C., about 120° C., about 125° C., about 130° C., about 135° C., about 140° C., about 145° C., about 150° C., about 155° C., about 160° C., or about 165° C., or any range defined between any two of these endpoints inclusive. In some embodiments, the second DMA modulus transition onset temperature of the polyurethane can be from about 45°C to about 165°C, from about 50°C to about 160°C, from about 55°C to about 155°C, from about 60°C to about 150°C, from about 65°C to about 145°C, from about 70°C to about 140°C, from about 75°C to about 135°C, from about 80°C to about 130°C, from about 85°C to about 125°C, from about 90°C to about 120°C, from about 95°C to about 115°C, or from about 100°C to about 110°C.

[0066] The DMA thermograms in Figures 9-15 show the second DMA modulus transition onset temperatures for various exemplary polyurethanes. The second DMA modulus transition onset temperature (T onset2 ) is the temperature at which the slope of the storage modulus (E') curve begins to decrease significantly in the second hour. The methodology for determining this value is illustrated in FIG. 16. DMA instruments, such as the DMA-850 from TA Instruments, can be programmed to automatically calculate this temperature. Table 3 lists the second DMA modulus transition onset temperatures automatically calculated from the DMA graphs of FIGS. 9-15 (see Examples 1-7).

[0067] In some embodiments, polyurethanes may exhibit crystallinity in the soft phase. This is common in polyether soft segments containing polytetramethylene glycol and some polyester polyols. In such embodiments, polyurethanes may exhibit at least three transitions: a soft-phase Tg, a soft-phase melting point, and a hard-phase modulus transition. Such melting in the soft phase, if present, typically occurs between 0°C and about 60°C. In embodiments exhibiting crystallinity in the soft phase, the protein polyurethane alloy typically still exhibits melting in the soft phase because the protein is miscible with the hard phase, leaving the mechanical properties of the soft phase substantially unchanged.

[0068] In exemplary embodiments described herein, the protein polyurethane alloy may have a second DMA modulus transition onset temperature higher than the second DMA modulus transition temperature of the polyurethane in the absence of the protein (i.e., the polyurethane itself). This increase in the second DMA modulus transition onset temperature in the alloy is believed to be due to miscibility of the protein with the hard phase of the polyurethane. This selective miscibility of the protein is indicated by an increase in the second DMA modulus transition onset temperature (quantified by the first DMA modulus transition onset temperature or DMA tan(δ) peak temperature corresponding to the soft phase) without a corresponding increase in the DMA transition temperature of the soft phase. This selective miscibility can be exploited to control the properties of the protein polyurethane alloy, for example, for mechanical and thermal properties.

[0069] In some embodiments, the protein polyurethane alloys and / or materials described herein may have similar appearance and feel, as well as mechanical properties, to natural leather. For example, protein polyurethane alloys or materials comprising protein polyurethane alloys may have, among other things, similar tactile, aesthetic, mechanical / performance, manufacturability, and / or thermal properties to natural leather. Mechanical / performance properties that may be similar to natural leather include, but are not limited to, tensile strength, tear strength, elongation at break, abrasion resistance, internal cohesion, water resistance, breathability (quantified in some embodiments by water vapor transmission rate measurements), and the ability to retain color when dyed with reactive dyes and rubbed (color fastness). Tactile properties that may be similar to natural leather include, but are not limited to, softening, stiffness, coefficient of friction, and compression modulus. Aesthetic properties that may be similar to natural leather may include, but are not limited to, dyeability, embossability, aging, color, color depth, and color pattern. Manufacturing properties that may be similar to natural leather include, but are not limited to, the ability to stitch, cut, skive, and be split. Thermal properties that may be similar to natural leather include, but are not limited to, heat resistance and resistance to hardening or softening over a significantly wider temperature range, for example, 25°C to 100°C.

[0070] Desirable properties of the protein polyurethane alloys described herein include, but are not limited to, optical, tactile, aesthetic, thermal, mechanical, and / or breathability properties. Exemplary thermal properties include heat resistance and melt resistance, for example, the second modulus transition onset temperature (T onset2 ) can be quantified by measuring the permeability (or permeability) of the material. Exemplary mechanical properties include abrasion resistance, ultimate tensile stress (also referred to as "tensile strength"), and Young's modulus. Unless otherwise specified, ultimate tensile stress and Young's modulus values ​​disclosed herein are measured according to the method provided by ASTM D638. Exemplary breathability properties include permeability (or permeability) in g / m 2The moisture vapor transmission rate (MVTR) is measured in grams per square meter per 24 hours (grams per square meter per 24 hours). Unless otherwise specified, the moisture vapor transmission rates disclosed herein are measured according to the method provided by ASTM E96-Method B.

[0071] In some embodiments, the protein polyurethane alloy may be transparent. In some embodiments, a transparent protein polyurethane alloy may indicate that the protein is miscible with the polyurethane hard phase in the alloy. As used herein, a "transparent" material refers to a material having an opacity of about 50% or less. Opacity is measured by placing a sample of the material on a white background and measuring the Y tristimulus value ("over white Y") in reflectance with a spectrophotometer using a D65 10-degree illuminant. The same sample is then placed on a black background and the measurement is repeated to obtain "over black Y." Percent opacity is calculated as "over black Y" ÷ "over white Y" × 100. 100% opacity is defined as the lowest transparency, and 0% opacity is defined as the highest transparency.

[0072] In some embodiments, the protein polyurethane alloy may be transparent and have an opacity ranging from 0% to about 50%, including subranges. For example, a transparent protein polyurethane alloy may have an opacity ranging from 0% to about 40%, 0% to about 30%, 0% to about 20%, 0% to about 10%, or 0% to about 5%. The transparency of the protein polyurethane alloy is evaluated before dyeing or otherwise coloring the protein polyurethane alloy.

[0073] Transparent protein polyurethane alloys can be produced by selecting and blending an appropriate combination of one or more proteins with one or more polyurethanes. While not all combinations of proteins and polyurethanes result in transparent protein polyurethane alloys, it is within the skill of one of ordinary skill in the art to determine whether a given blend will result in a transparent protein polyurethane alloy in light of the present disclosure. In embodiments directed to materials comprising transparent protein polyurethane alloys described herein, the transparent protein polyurethane alloys can provide unique properties to the material. For example, compared to non-transparent counterparts, transparent protein polyurethane alloys can provide unique color depth when dyed. Similarly, transparent protein polyurethane alloys can provide mechanical properties to a material without significantly affecting the aesthetic properties of the material.

[0074] In some embodiments, the protein polyurethane alloy may include one or more colorants. In some embodiments, the colorant may be a dye, such as a fiber-reactive dye, a direct dye, an acid 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. The colorant may be a pigment, such as a lake pigment.

[0075] Suitable polyurethanes for blending with one or more proteins according to embodiments described herein include, but are not limited to, aliphatic polyurethanes, aromatic polyurethanes, bio-based polyurethanes, or acrylic acid-modified polyurethanes. Suitable polyurethanes are commercially available from manufacturers including Lubrizol, Hauthaway, and Stahl. In some embodiments, the polyurethane of the protein-polyurethane alloy can be a bio-polyurethane. In some embodiments, the polyurethane is a water-dispersible polyurethane. In some embodiments, the polyurethane can be a polyester polyurethane. In some embodiments, the polyurethane can be a polyether polyurethane. In some embodiments, the polyurethane can be a polycarbonate-based polyurethane. In some embodiments, the polyurethane can be an aliphatic polyester polyurethane. In some embodiments, the polyurethane can be an aliphatic polyether polyurethane. In some embodiments, the polyurethane can be an aliphatic polycarbonate polyurethane. In some embodiments, the polyurethane can be an aromatic polyester polyurethane. In some embodiments, the polyurethane can be an aromatic polyether polyurethane. In some embodiments, the polyurethane can be an aromatic polycarbonate polyurethane.

[0076] 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 and isophorone diisocyanate; and aromatic diisocyanates such as 4,4'-diphenylmethylene diisocyanate, toluene diisocyanate, phenyl diisocyanate, and mixtures thereof. Suitable short-chain diols include ethylene glycol, propanediol, butanediol, 2,2-methyl-1,3-propanediol, pentanediol, hexanediol, and mixtures thereof. In some embodiments, the crosslinker may be a polyfunctional alcohol, such as trimethylolpropanetriol, or a diamine, such as ethylenediamine or 4,4'-diaminodiphenyldiamine.

[0077] Exemplary commercially available polyurethanes include, but are not limited to, L3360 and Hauthane HD-2001 available from CL Hauthaway & Sons Corporation, SANCURE™ polyurethanes available from Lubrizol Corporation, BONDTHANE™ polyurethanes such as UD-108, UD-250, and UD-303 available from Bond Polymers International, and EPOTAL® ECO 3702 and EPOTAL® P100 ECO manufactured by BASF. L3360 is an aliphatic polyester polyurethane polymer aqueous dispersion with 35% solids, a viscosity of 50-500 cps (centipoise), and a density of approximately 8.5 lb / gal (pounds per gallon). HD-2001 is an aliphatic polyester polyurethane polymer aqueous dispersion with 40% solids, a viscosity of 50-500 cps, and a density of approximately 8.9 lb / gal. BONDTHANE™ UD-108 is an aliphatic polyether polyurethane polymer aqueous dispersion with 33% solids, a viscosity of 300 cps, and a density of 8.7 lb / gal. BONDTHANE™ UD-250 is an aliphatic polyester polyurethane polymer aqueous dispersion with 35% solids, a viscosity of 200 cps, and a density of 8.8 lb / gal. BONDTHANE™ UD-303 is an aliphatic polyether polyurethane polymer aqueous dispersion with 35% solids, a viscosity of less than 500 cps, and a density of 8.7 lb / gal. EPOTAL™ P100 ECO is a polyester polyurethane elastomer aqueous dispersion with approximately 40% solids and a viscosity of about 40 mPas.

[0078] Further exemplary polyurethanes include, but are not limited to, (i) an aqueous aliphatic polyether-based polyurethane dispersion having a 35% solids content, a specific gravity of 1.02 g / mL, and a Brookfield viscosity of 160 mPa.s, (ii) a nonionic aliphatic polycarbonate-polyether polyurethane dispersion having a 30% solids content, a specific gravity of 1.1 g / mL, and a viscosity of less than 1000 mPa.s, and (iii) an aqueous aliphatic polyether-based polyurethane dispersion having a 35% solids content, a specific gravity of 1.04 g / mL, and a Brookfield viscosity of 30 mPa.s at 25°C.

[0079] Exemplary bio-based polyurethanes include, but are not limited to, L3360 available from CL Hauthaway & Sons Corporation, IMPRANIL® Eco DLS, IMPRANIL® Eco DL519, IMPRANIL® Eco DLP-R, and IMPRAPERM® DL 5249 available from Covestro. IMPRANIL® Eco DLS is an anionic aliphatic polyester polyurethane polymer aqueous dispersion with approximately 50% solids, a viscosity of less than 1,200 MPa·s, and a density of about 1.1 g / cc. IMPRANIL® Eco DL 519 is an anionic aliphatic polyester polyurethane polymer aqueous dispersion. IMPRANIL® Eco DLP-R is an anionic aliphatic polyester polyurethane polymer aqueous dispersion. IMPRAPERM® DL 5249 is an anionic aliphatic polyester-polyurethane polymer aqueous dispersion.

[0080] In some embodiments, the polyurethane may include reactive groups that can be crosslinked with proteins. Exemplary reactive groups include, but are not limited to, sulfonates, aldehydes, carboxylic acids or esters, blocked isocyanates, and the like, and combinations thereof. In such embodiments, the polyurethane may be crosslinked to proteins in the protein-polyurethane alloy through reaction of the reactive groups on the protein with reactive groups present in the polyurethane.

[0081] Suitable proteins for blending with one or more polyurethanes according to embodiments described herein include, but are not limited to, collagen, gelatin, bovine serum albumin (BSA), soy protein, pea protein, egg albumin, casein, peanut protein, edestin protein, whey protein, kalanjiang protein, and cellulase. Suitable collagens include, but are not limited to, recombinant collagen (r-collagen), recombinant collagen fragments, and extracted collagen. Suitable soy proteins include, but are not limited to, soy protein isolate (SPI), soybean meal protein, and soy protein derivatives. In some embodiments, the soy protein isolate may be a partially hydrolyzed soy protein isolate. Suitable pea proteins include, but are not limited to, pea protein isolate and pea protein derivatives. In some embodiments, the pea protein isolate may be a partially hydrolyzed pea protein isolate.

[0082] Table 1 below lists some exemplary proteins and their properties. Gelatin is type A gelatin from pig skin (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). Egg albumin protein is albumin from chicken egg white (Sigma Aldrich A5253). Casein protein is casein from bovine milk (Sigma Aldrich C7078). Peanut protein is pea protein powder purchased from Tru-Nut. The whey protein is whey from bovine milk (Sigma Aldrich W1500). Other suitable soy protein isolates include, but are not limited to, soy protein 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).

[0083] Karanja protein is a protein found in karanja seeds harvested from the Pongamia pinnata tree (also known as the Pongamia glabra tree). See Rahman, M. M., and Netravali, "Green Resin from Forestry Waste Residue 'Karanja (Pongamia pinnata) Seed Cake' for Biobased Composite Structures," ACS Sustainable Chem. Eng., Vol. 2, pp. 2318-2328 (2014); see also Mandal et al., "Nutritional Evaluation of Proteins from Three Non-traditional Seeds with or without Amino Acid Supplementation in Albino Rats," Proc. Indianapolis, Sci. Acad., B50, Vol. 1, pp. 48-56 (1984). Proteins can be extracted from karanja seeds using a solvent extraction process. Id. In some embodiments, the karanja protein can be a karanja protein isolate. In such embodiments, the karanja protein isolate can be obtained by alkaline extraction and acid precipitation of defatted karanja seed cake. See Rahman, M. M., and Netravali, "Green Resin from Forestry Waste Residue 'Karanja (Pongamia pinnata) Seed Cake' for Biobased Composite Structures," ACS Sustainable Chem. Eng., Vol. 2, pp. 2318-2328 (2014);

[0084] Suitable cellulase proteins are listed below in Table 1. "Cellulase-RG" protein is a natural Trichoderma species cellulase available from CREATIVE ENZYMES®. "Cellulase-IG" protein is a laboratory grade cellulase available from Carolina Biological Supply Company.

[0085] The 50 KDa recombinant collagen fragment (50 KDa r-collagen fragment) of Table 1 is a collagen fragment having the amino acid sequence listed as SEQ ID NO:2.

[0086] The "dissolution methods" listed in Table 1 are exemplary aqueous solvents in which proteins can be dissolved into solutions that are miscible with the hard phase of the polyurethanes described herein. Proteins that are at least partially soluble in aqueous solutions are suitable for forming protein polyurethane alloys in polyurethane dispersions. [Table 1]

[0087] In some embodiments, the protein may have one or more of the following characteristics: (i) a molecular weight within the ranges described herein; (ii) an isoelectric point within the ranges described below; (iii) an amino acid composition, measured in grams of lysine per 100 grams of protein, within the ranges described below; and (iv) a thermal stability of the protein up to 200°C.

[0088] Protein molecular weight In some embodiments, the protein may have a molecular weight ranging from about 1 KDa (kilodalton) to about 700 KDa, including subranges. For example, the protein may have a molecular weight ranging from 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 ...100 KDa to about 700 KDa, about 100 KDa to about 700 KDa, about 100 KDa to about 700 KDa, about 100 KDa to about 700 KDa, about 100 KDa to about 700 KDa, about 100 KDa to about 700 KDa, about 100 KDa to about 700 KDa, The molecular weight may range from 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 10 KDa, or within a range having any two of these values ​​as endpoints, inclusive.

[0089] Protein isoelectric point In some embodiments, a protein may have an isoelectric point ranging from about 4 to about 10, including subranges. For example, a protein may have an isoelectric point ranging from about 4 to about 10, from about 4.5 to about 9.5, from about 5 to about 9, from about 5.5 to about 8.5, from about 6 to about 8, from about 6.5 to about 7.5, or from about 6.5 to about 7, or within a range having any two of these values ​​as endpoints, inclusive. In some embodiments, a protein may have an isoelectric point ranging from about 4 to about 5.

[0090] Protein Amino Acid Composition In some embodiments, the protein may have an amino acid composition, measured in grams of lysine per 100 grams of protein (referred to as "lysine weight percent"), ranging from about 0.5% to about 100% by weight, including subranges. For example, the protein may have a lysine weight percent ranging from about 0.5% to about 100% by weight, about 1% to about 100% by weight, about 5% to about 100% by weight, about 10% to about 100% by weight, about 20% to about 100% by weight, about 30% to about 100% by weight, about 40% to about 100% by weight, about 50% to about 100% by weight, about 60% to about 100% by weight, about 70% to about 100% by weight, about 80% to about 100% by weight, or about 90% to about 100% by weight, or a range having any two of these values ​​as endpoints, inclusive. In some embodiments, the protein can be polylysine.

[0091] In some embodiments, the protein may have a lysine weight percent ranging from about 0.5% to about 20% by weight, including subranges. For example, the protein may have a lysine weight percent ranging from about 0.5% to about 20% by weight, about 1% to about 19% by weight, about 2% to about 18% by weight, about 3% to about 17% by weight, about 4% to about 16% by weight, about 5% to about 15% by weight, about 6% to about 14% by weight, about 7% to about 13% by weight, about 8% to about 12% by weight, about 9% to about 11% by weight, or about 9% to about 10% by weight, or within a range having any two of these values ​​as endpoints, inclusive. In some embodiments, the protein may have a lysine weight percent ranging from about 1% to about 20% by weight. In some embodiments, the protein may have a lysine weight percent ranging from about 5% to about 20% by weight. In some embodiments, the protein may have a lysine weight percent ranging from about 1% to about 12% by weight. In some embodiments, the protein may have a lysine weight percent ranging from about 5% to about 12% by weight. In some embodiments, the protein may have a lysine weight percent ranging from about 1% to about 15% by weight. In some embodiments, the protein may have a lysine weight percent ranging from about 5% to about 15% by weight.

[0092] In some embodiments, a protein may be thermostable. In some embodiments, a protein may be non-thermostable. As described herein, protein thermostability is determined by differential scanning calorimetry (DSC), in which pre-dried protein powder (having less than 3% moisture) is scanned from 0°C to 200°C. In a protein's DSC curve, an endothermic peak greater than 10 mW / mg is determined to be the "denaturation peak," and the temperature corresponding to the endothermic "denaturation peak" is defined as the protein's "denaturation temperature." A protein that is "thermostable" means that the protein has a denaturation temperature of 200°C or greater. For purposes of this disclosure, proteins with a denaturation temperature less than 200°C are considered "non-thermostable." For example, it was found that whey from cow's milk listed in Table 1 has a denaturation temperature of 158°C by DSC, and therefore, the whey is considered non-thermostable.

[0093] Protein lysis In some embodiments, one or more proteins can be dissolved in an aqueous solution before blending with one or more polyurethanes to form an aqueous protein mixture. In some embodiments, dissolving the protein in an aqueous solution before blending with one or more polyurethanes can promote miscibility of the protein with the hard phase of one or more polyurethanes. For example, dissolving the protein in an aqueous solution before blending with the polyurethane(s) can promote miscibility of the protein with the hard phase of one or more polyurethanes. Not all proteins are naturally miscible with any phase of a polyurethane. For example, as exemplified in Examples 33 and 34, casein is not necessarily miscible with polyurethanes. As shown in these two examples, when casein, water, and L3360 are mixed, casein is immiscible with L3360. The resulting film had an opaque appearance with numerous optically visible granules in the film. However, casein is miscible with the hard phase of L3360 when casein is dissolved in sodium hydroxide solution before mixing with L3360. The film obtained by blending these components had a clear and uniform appearance with no optically visible granules in the film.

[0094] Suitable aqueous solutions include, but are not limited to, water, alkaline aqueous solutions, acidic aqueous solutions, aqueous solutions containing organic solvents, urea solutions, and mixtures thereof. In some embodiments, the alkaline aqueous solution can be a basic solution such as sodium hydroxide, ammonia, or ammonium hydroxide solution. In some embodiments, an example of an acidic aqueous solution can 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, and glycerol. In some embodiments, the protein concentration in the aqueous protein mixture can range from 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 within a range having any two of these values ​​as endpoints, inclusive. In some embodiments, the protein concentration in the aqueous protein mixture can range from about 10 g / L to about 300 g / L, from about 20 g / L to about 250 g / L, from about 30 g / L to about 200 g / L, from about 40 g / L to about 150 g / L, from about 50 g / L to about 100 g / L, from about 60 g / L to about 90 g / L, or from about 70 g / L to about 80 g / L.

[0095] In some embodiments, proteins can be pretreated and / or purified to improve their solubility in water. Suitable pretreatments include, but are not limited to, acid treatment, alkaline treatment, enzymatic hydrolysis, and salt treatment. An exemplary acid treatment is acid hydrolysis using a suitable acid such as acetic acid or HCl. An exemplary alkaline treatment is 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, bromelain, trypsin, and alkaline protease. Suitable purification processes include, but are not limited to, removal of phytate with calcium salts, diafiltration, ultrafiltration, and centrifugation.

[0096] 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 miscibility of the protein with the hard phase of the one or more polyurethanes. Protein hydrolysis

[0097] In some embodiments, the protein may be partially hydrolyzed. Partial hydrolysis of the protein can promote the dissolution of the protein in water and / or the miscibility of the protein with the rigid phase of the polyurethane. Partial hydrolysis of the protein can be achieved using enzymes or strong to moderate bases. Hydrolysis can be followed by a reduction in viscosity and / or a reduction in protein molecular weight. Characterization methods for determining the reduction in protein molecular weight, and thus the level of protein hydrolysis, include, but are not limited to, light scattering, gel electrophoresis, size exclusion chromatography, solution viscosity measurement, terminal amino group detection using trinitrobenzenesulfonic acid or ninhydrin, or particle size measurement by laser diffraction. Example 21 describes partially hydrolyzed soy protein prepared using sodium hydroxide according to some embodiments.

[0098] PEGylation of proteins In some embodiments, proteins can be chemically modified by covalently attaching PEG (polyethylene glycol) to the protein. PEG modification of proteins can promote the solubility of proteins in water and / or promote miscibility of proteins with the rigid phase of polyurethane. PEG modification of proteins can be achieved using methods that covalently attach hydrophilic polyethylene glycol (PEG) chains to proteins.

[0099] In some embodiments, the amount of protein in the protein polyurethane alloy can range from about 10% to about 50% by weight of protein, including subranges. For example, in some embodiments, the amount of protein in the protein polyurethane alloy is about 10% to about 50% by weight, about 15% to about 50% by weight, about 20% to about 50% by weight, about 25% to about 50% by weight, about 30% to about 50% by weight, about 35% to about 50% by weight, about 40% to about 50% by weight, about 45% to about 50% by weight, about 10% to about 45% by weight, about 10% to about 40% by weight, about 10% to about 35% by weight, about 10% to about 30% by weight, about 10% to about 25% by weight, about 10% to about 20% by weight, or about 10% to about 15% by weight, or a range having any two of these endpoints as endpoints, inclusive. In some embodiments, the amount of protein in the protein polyurethane alloy may range from about 20% to about 35% by weight.

[0100] In some embodiments, the amount of protein in the protein polyurethane alloy may be greater than about 50% by weight, hi some embodiments, the amount of protein in the protein polyurethane alloy may range from about 50% to about 90% by weight protein, including subranges. For example, in some embodiments, the amount of protein in the protein polyurethane alloy is in the range of about 50% to about 90% by weight, about 55% to about 90% by weight, about 60% to about 90% by weight, about 65% to about 90% by weight, about 70% to about 90% by weight, about 75% to about 90% by weight, about 80% to about 90% by weight, about 85% to about 90% by weight, about 50% to about 85% by weight, about 50% to about 80% by weight, about 50% to about 75% by weight, about 50% to about 70% by weight, about 60% to about 85% by weight, about 60% to about 80% by weight, or about 70% to about 90% by weight, or a range having any two of these values ​​as endpoints inclusive.

[0101] In some embodiments, the amount of polyurethane in the protein polyurethane alloy can be in the range of about 50% to about 90% by weight, including subranges. For example, in some embodiments, the amount of polyurethane in the protein polyurethane alloy can be in the range of about 50% to about 90% by weight, about 55% to about 90% by weight, about 60% to about 90% by weight, about 65% to about 90% by weight, about 70% to about 90% by weight, about 75% to about 90% by weight, about 80% to about 90% by weight, about 85% to about 90% by weight, about 50% to about 85% by weight, about 50% to about 80% by weight, about 50% to about 75% by weight, about 50% to about 70% by weight, about 50% to about 65% by weight, about 50% to about 60% by weight, or about 50% to about 55% by weight, or a range having any two of these endpoints as endpoints, inclusive. In some embodiments, the amount of polyurethane in the protein polyurethane alloy can range from about 65% to about 80% by weight.

[0102] In some embodiments, the amount of polyurethane in the protein polyurethane alloy may be less than 50% by weight. In some embodiments, the amount of polyurethane in the protein polyurethane alloy may be in the range of about 10% to about 50% by weight, including subranges. For example, in some embodiments, the amount of polyurethane in the protein polyurethane alloy may be in the range of about 10% to about 50% by weight, about 15% to about 50% by weight, about 20% to about 50% by weight, about 25% to about 50% by weight, about 10% to about 45% by weight, about 10% to about 40% by weight, about 10% to about 35% by weight, about 10% to about 30% by weight, about 10% to about 25% by weight, about 10% to about 20% by weight, about 15% to about 40% by weight, about 20% to about 40% by weight, or about 10% to about 30% by weight, or a range having any two of these values ​​as endpoints, inclusive.

[0103] In some embodiments, the above weight percentages and ranges can be based on the total weight of the protein polyurethane alloy or protein polyurethane alloy layer. In some embodiments, the above weight percentages and ranges can be based on the total weight of only the protein and polyurethane in the protein polyurethane alloy or protein polyurethane alloy layer. Unless otherwise specified, the weight percentages or ranges for polyurethane and protein are based on the total weight of only the protein and polyurethane in the protein polyurethane alloy or protein polyurethane alloy layer.

[0104] In some embodiments, the sum of the amount of protein and the amount of polyurethane in the protein polyurethane alloy can be about 80% by weight or greater. For example, in some embodiments, the sum of the amount of protein and the amount of polyurethane in the protein polyurethane alloy can be in the range of about 80% to 100% by weight, about 82% to 100% by weight, about 84% to 100% by weight, about 86% to 100% by weight, about 88% to 100% by weight, about 90% to 100% by weight, about 92% to 100% by weight, about 94% to 100% by weight, about 96% to 100% by weight, or about 98% to 100% by weight.

[0105] In some embodiments, the protein polyurethane alloy may contain water, which constitutes a portion of the total weight percent of the material. In some embodiments, the amount of water in the protein polyurethane alloy may range from about 1% to about 10% by weight, including subranges. For example, in some embodiments, the amount of water in the protein polyurethane alloy may be from about 1% to about 10% by weight, from about 2% to about 10% by weight, from about 3% to about 10% by weight, from about 4% to about 10% by weight, from about 5% to about 10% by weight, from about 6% to about 10% by weight, from about 7% to about 10% by weight, from about 8% to about 10% by weight, from about 1% to about 9% by weight, from about 1% to about 8% by weight, from about 1% to about 7% by weight, from about 1% to about 6% by weight, from about 1% to about 5% by weight, from about 1% to about 4% by weight, or from about 1% to about 3% by weight, or a range having any two of these values ​​as endpoints, inclusive.

[0106] The protein polyurethane alloys described herein may have one or more of: (i) a second dynamic mechanical analysis (DMA) modulus transition onset temperature higher than the second DMA modulus transition onset temperature of the non-alloyed polyurethane; (ii) a first dynamic mechanical analysis (DMA) modulus transition onset temperature substantially the same as the first DMA modulus transition onset temperature of the non-alloyed polyurethane; (iii) a DMA tan(δ) peak at a temperature substantially the same as the temperature of the DMA tan(δ) peak corresponding to the soft phase of the non-alloyed polyurethane; (iv) a Young's modulus higher than the Young's modulus of the non-alloyed polyurethane; (v) a tensile strength higher than the tensile strength of the non-alloyed polyurethane; or (vi) a moisture vapor transmission rate (MVTR) higher than the MVTR of the non-alloyed polyurethane.

[0107] Figures 1-15 show the effect of dissolving various amounts of different proteins in different polyurethanes to form polyurethane alloys, according to some embodiments. Tables 3-6 list the thermal and mechanical properties of various protein polyurethane alloys, as well as the thermal and mechanical properties of various polyurethanes, according to some embodiments. The tested samples were prepared by blending the listed protein with an aqueous dispersion of the listed polyurethane, casting the mixture into a flat film, drying it in an oven at 45°C overnight (16-24 hours), and conditioning it at a standard reference atmosphere (23°C, 50% humidity) for 24 hours before testing. The weight percentage values ​​in the figures and Tables 3-6 are the relative weight percentages of solids added to the blends used to make the samples. For example, 0.825 grams of gelatin and 5.5 g of L3360 (35% solids by weight) were blended to make Example 9, which had 30% gelatin and 70% L3360 by weight. The weight percentage values ​​in the Figures and Tables 3-6 are based on the total weight of the dried sample and can closely approximate the weight percentage of protein and polyurethane in the dried samples of Examples 1-44. The dried samples contained water, which made up a small portion (e.g., about 5% to about 10% by weight) of the total weight percentage of the sample.

[0108] Table 7 lists the water vapor transmission rates of various protein polyurethane alloys according to some embodiments. The tested samples were prepared as described in Examples 45-56. The weight percentage values ​​in Table 7 are the relative weight percentages of solids added to the blends used to make the samples. These weight percentage values ​​can closely approximate the weight percentages of protein and polyurethane in the dried samples of Examples 45-56, based on the total weight of the dried samples. The dried samples contained water, which made up a small portion of the total weight percentage of the sample (e.g., about 5% to about 10% by weight).

[0109] The DMA temperatures in Tables 3 and 4 were measured using a TA Instruments DMA-850. For testing, 1 cm x 2.5 cm strips were cut from the sample film using a metal die. The cut film sample was loaded into a film and fiber tension clamp for testing. During testing, a preload of 0.01 Newtons (N) was applied to the cut film sample. The instrument was cooled to -80°C, held for 1 minute, and then the temperature was increased at 4°C / min to 200°C, or until the sample was too weak to hold the tension. During the temperature ramp, the sample was oscillated at a frequency of 1 Hz and 0.1% strain. The resulting storage modulus, loss modulus, and tan(δ) values ​​were plotted against temperature for each test. Unless otherwise noted, all DMA test data reported herein were measured using this test method. The tensile strength and Young's modulus values ​​in Tables 5 and 6 were measured according to the methods provided by ASTM D638. Tensile strength and Young's modulus values ​​are the average of at least three sample specimens tested.

[0110] The DMA graph shown in Figure 1 shows the measured storage modulus (E') of 100% L3360 (Example 1) and gelatin dissolved in L3360 at various weight percentages, i.e., 5%, 10%, 15%, 20%, and 30% (Examples 9 and 25-28). This graph demonstrates that blending gelatin with L3360 can produce alloys with a higher second DMA modulus transition onset temperature than that of 100% L3360. While not wishing to be bound by theory, it is believed that the increase in second DMA modulus transition onset temperature becomes more apparent in this test because the gelatin-containing hard phase and polyurethane hard segments become continuous at higher gelatin contents. This trend indicates that gelatin is miscible with the hard phase of L3360.

[0111] This miscibility of gelatin with the hard phase L3360 is further illustrated in the mechanical property graphs of Figures 2 and 3, which compare two different mechanical properties of Examples 1, 9, and 25-28. As shown in Figure 2, the maximum tensile stress ("tensile strength") of the tested protein polyurethane alloys is greater than that of 100% L3360. This increase in maximum tensile stress is particularly significant at gelatin weight percentages of 10 wt% and above. As shown in Figure 3, the Young's modulus of the tested protein polyurethane alloys is greater than that of 100% L3360. This increase in Young's modulus is particularly significant at gelatin weight percentages of 15 wt% and above.

[0112] The DMA graph shown in Figure 4 shows the measured storage modulus (E') of 100% L3360 (Example 1) and SPI dissolved in L3360 at various weight percentages, i.e., 10%, 20%, and 30% (Examples 21, 30, and 31). The thermograms demonstrate that blending SPI with L3360 can produce protein polyurethane alloys with second DMA modulus transition onset temperatures higher than that of 100% L3360. As more SPI is added, the rise in second DMA modulus transition onset temperature increases. This trend indicates that SPI is miscible with the hard phase of L3360.

[0113] This miscibility of SPI with the hard phase L3360 is further illustrated in the mechanical property graphs of Figures 5 and 6, which compare two different mechanical properties of Example 1 and Examples 21, 30, and 31. As shown in Figure 5, the maximum tensile stress ("tensile strength") of the tested protein polyurethane alloys is greater than that of 100% L3360. This increase in maximum tensile stress is particularly significant at SPI weight percentages of 10 wt% and above. As shown in Figure 6, the Young's modulus of the tested protein polyurethane alloys is greater than that of 100% L3360. This increase in Young's modulus is particularly significant at SPI weight percentages of 15 wt% and above.

[0114] The DMA graph shown in Figure 7 shows the measured storage modulus (E') of 100% L3360 (Example 1) and various proteins dissolved in L3360 at 30 wt% (Examples 9 and 17-23). ​​This graph demonstrates that gelatin, SPI, and other proteins can be blended with L3360 to produce protein polyurethane alloys with second DMA modulus transition onset temperatures higher than that of 100% L3360. All proteins except whey produced protein polyurethane alloys with second DMA modulus transition onset temperatures higher than that of 100% L3360. Whey is believed to be miscible with the hard phase of L3360 due to its ability to improve the mechanical properties of the protein polyurethane alloys relative to 100% L3360. However, it is believed that whey did not increase the onset temperature of the second DMA modulus transition because whey has a low denaturation temperature as determined by DSC.

[0115] Furthermore, the graph in Figure 7 shows that dissolving various proteins in L3360 did not result in protein polyurethane alloys in which the DMA transition temperature of the soft phase was significantly different from that of 100% L3360. As shown in Table 4, the delta first modulus transition onset for Examples 9 and 17-23 was all below 10°C. Correspondingly, the delta Tan (δ) peak temperatures for Examples 9 and 17-23 were all below 10°C. These results indicate that the proteins were not miscible with the soft phase of L3360.

[0116] This selective miscibility of the protein with the hard phase L3360 is further illustrated in the mechanical property test results plotted in the graphs of Figures 8A and 8B and reported in Tables 5 and 6. The graphs in Figures 8A and 8B compare the tensile strength and Young's modulus of Example 1, Example 9, and Example 17-23. An increase in tensile strength and / or an increase in Young's modulus may indicate that the protein is miscible with the hard phase of L3360. Tables 5 and 6 report the tensile strength and Young's modulus of the materials.

[0117] To further illustrate the selective miscibility of proteins with the hard phase of polyurethanes having both soft and hard phases, gelatin was blended with various exemplary polyurethanes. Figures 9-15 show DMA thermograms of these exemplary blends, as well as thermograms of the polyurethanes in the absence of gelatin. Figure 9 compares the DMA data for protein polyurethane alloys made with 30 wt% gelatin and 70 wt% L3360 (Example 9) and 100% L3360 (Example 1). Figure 10 compares the DMA data for protein polyurethane alloys made with 30 wt% gelatin and 70 wt% HD-2001 (Example 15) and 100% HD-2001 (Example 7). Figure 11 compares the DMA data for protein polyurethane alloys made with 30 wt% gelatin and 70 wt% Sancure (Example 14) and 100% Sancure (Example 6). Figure 12 compares the DMA data for protein polyurethane alloys made with 30 wt% gelatin and 70 wt% Impranil DLS (Example 12) and 100% Impranil DLS (Example 5). Figure 13 compares the DMA data for protein polyurethane alloys made with 30 wt% gelatin and 70 wt% UD-108 (Example 10) and 100% UD-108 (Example 2). Figure 14 compares the DMA data for protein polyurethane alloys made with 30 wt% gelatin and 70 wt% UD-303 (Example 13) and 100% UD-303 (Example 4). FIG. 15 compares the DMA data for protein polyurethane alloys made with 30% by weight gelatin and 70% by weight UD-250 (Example No. 11) and 100% UD-250 (Example No. 3).

[0118] Figure 22 compares the DMA data for protein polyurethane alloys made with 30 wt% soy protein isolate (SPI) and 70 wt% IMPRAPERM® DL 5249 and 100% IMPRAPERM® DL 5249 polyurethane samples. The three samples of 30 wt% soy protein isolate (SPI) and 70 wt% IMPRAPERM® DL 5249 alloy in Figure 22 with an average thickness of 0.44 mm had an average Young's modulus of 65.80 MPa. The three samples of 100% IMPRAPERM® DL 5249 polyurethane in Figure 22 with an average thickness of 0.7 mm had an average Young's modulus of 10.13 MPa. The DMA data shown in Figure 22 and the results of this mechanical testing of the protein polyurethane alloys demonstrate the selective miscibility of SPI with the hard phase of IMPRAPERM® DL 5249.

[0119] Tables 3 and 4 report DMA data for various exemplary polyurethanes and those same polyurethanes blended with 30 wt% gelatin. Tables 5 and 6 report tensile strength and Young's modulus data for various exemplary polyurethanes and those same polyurethanes blended with 30 wt% gelatin. The results demonstrate the selective miscibility of the tested proteins in the hard phase of the tested polyurethanes.

[0120] In some embodiments, a protein polyurethane alloy can include a polyurethane having a second DMA modulus transition onset temperature in the absence of protein. The same protein polyurethane alloy can have a second DMA modulus transition onset temperature that is higher than the second DMA modulus transition onset temperature of the polyurethane in the absence of protein, ranging from about 5°C to about 100°C. This relative increase in second DMA modulus transition onset temperature can be referred to as the "second delta modulus transition onset." In some embodiments, the second delta modulus transition onset can be about 5°C or higher. In some embodiments, the onset of the second delta modulus transition occurs at a temperature between about 5°C and about 100°C, about 5°C and about 95°C, about 5°C and about 90°C, about 5°C and about 85°C, about 5°C and about 80°C, about 5°C and about 75°C, about 5°C and about 70°C, about 5°C and about 65°C, about 5°C and about 60°C, about 5°C and about 55°C, about 5°C and about 50°C, about 5°C and about 45°C, about 5°C and about 40°C, about 5°C and about 35°C, about 5°C and about 30°C, about 5°C and about 25°C, about 5°C and about 20°C, about 5°C and about 15°C, about 5°C and about 10°C, about 10°C and about 100°C, or about 15°C and about 100°C. , about 20°C to about 100°C, about 25°C to about 100°C, about 30°C to about 100°C, about 35°C to about 100°C, about 40°C to about 100°C, about 45°C to about 100°C, about 50°C to about 100°C, about 55°C to about 100, about 60°C to about 100°C, about 65°C to about 100°C, about 70°C to about 100°C, about 75°C to about 100°C, about 80°C to about 100°C, about 85°C to about 100°C, about 90°C to about 100°C, or about 95°C to about 100°C, or a range having any two of these values ​​as endpoints inclusive.

[0121] In some embodiments, the second delta modulus transition onset can range from about 5°C to about 80°C. In some embodiments, the second delta modulus transition onset can range from about 20°C to about 80°C. In some embodiments, the second delta modulus transition onset can range from about 40°C to about 80°C. In some embodiments, the second delta modulus transition onset can be greater than about 100°C. For example, the second delta modulus transition onset can range from about 100°C to about 150°C.

[0122] In some embodiments, the soy protein polyurethane alloy may comprise a polyurethane having a second DMA modulus transition onset temperature in the absence of soy protein. The same soy protein polyurethane alloy may have a second DMA modulus transition onset temperature that is about 15°C to about 100°C higher than the second DMA modulus transition onset temperature of the polyurethane in the absence of soy protein. In some embodiments, the second delta modulus transition onset of the soy protein polyurethane alloy may be about 15°C or higher. In some embodiments, the onset of the second delta modulus transition of the soy protein polyurethane alloy occurs between about 15°C and about 100°C, about 15°C and about 95°C, about 15°C and about 90°C, about 15°C and about 85°C, about 15°C and about 80°C, about 15°C and about 75°C, about 15°C and about 70°C, about 15°C and about 65°C, about 15°C and about 60°C, about 15°C and about 55°C, about 15°C and about 50°C, about 15°C and about 45°C, about 15°C and about 40°C, about 15°C and about 35°C, about 15°C and about 30°C, about 15°C and about 25°C, about 15°C and about 20°C, or about 25°C. The temperature may be in the range of 0°C to about 100°C, about 25°C to about 100°C, about 30°C to about 100°C, about 35°C to about 100°C, about 40°C to about 100°C, about 45°C to about 100°C, about 50°C to about 100°C, about 55°C to about 100, about 60°C to about 100°C, about 65°C to about 100°C, about 70°C to about 100°C, about 75°C to about 100°C, about 80°C to about 100°C, about 85°C to about 100°C, about 90°C to about 100°C, or about 95°C to about 100°C, or a range having any two of these values ​​as endpoints, inclusive.

[0123] In some embodiments, the protein polyurethane alloy may have a second DMA modulus transition onset temperature ranging from about 100° C. to about 200° C., including any subrange. For example, in some embodiments, the protein polyurethane alloy may be heated to a temperature of about 100°C to about 200°C, about 100°C to about 195°C, about 100°C to about 190°C, about 100°C to about 185°C, about 100°C to about 180°C, about 100°C to about 175°C, about 100°C to about 170°C, about 100°C to about 165°C, about 100°C to about 160°C, about 100°C to about 155°C, about 100°C to about 150°C, about 100°C to about 145°C, about 100°C to about 140°C, about 100°C to about 135°C, about 100°C to about 130°C, about 100°C to about 125°C, or about 100°C to about 120°C, about 105°C to about 2 The second DMA modulus transition onset temperature may be in the range of about 100°C, about 110°C to about 200°C, about 115°C to about 200°C, about 120°C to about 200°C, about 125°C to about 200°C, about 130°C to about 200°C, about 135°C to about 200°C, about 140°C to about 200°C, about 145°C to about 200°C, about 150°C to about 200°C, about 155°C to about 200°C, about 160°C to about 200°C, about 165°C to about 200°C, about 170°C to about 200°C, about 175°C to about 200°C, or about 180°C to about 200°C, or in a range having any two of these values ​​as endpoints, inclusive of the endpoints. In some embodiments, the protein polyurethane alloy may have a second DMA modulus transition onset temperature ranging from about 120° C. to about 200° C. In some embodiments, the protein polyurethane alloy may have a second DMA modulus transition onset temperature ranging from about 130° C. to about 200° C. In some embodiments, the protein polyurethane alloy may have a second DMA modulus transition onset temperature ranging from about 165° C. to about 200° C.

[0124] In some embodiments, the soy protein polyurethane alloy may have a second DMA modulus transition onset temperature ranging from about 130° C. to about 200° C., including subranges. For example, in some embodiments, the soy protein polyurethane alloy may have a second DMA modulus transition onset temperature ranging from about 130° C. to about 200° C., from about 130° C. to about 195° C., from about 130° C. to about 190° C., from about 130° C. to about 185° C., from about 130° C. to about 180° C., from about 130° C. to about 175° C., from about 130° C. to about 170° C., from about 130° C. to about 165° C., from about 130° C. to about 160° C., from about 130° C. to about 155° C., from about 130° C. to about 150° C., from about 130° C. to about 145° C., from about 130° C. to about 140° C., from about 135° C. to about 20° C. The second DMA modulus transition onset temperature may be in the range of 0°C, about 140°C to about 200°C, about 145°C to about 200°C, about 150°C to about 200°C, about 155°C to about 200°C, about 160°C to about 200°C, about 165°C to about 200°C, about 170°C to about 200°C, about 175°C to about 200°C, about 180°C to about 200°C, about 185°C to about 200°C, or about 190°C to about 200°C, or in a range having any two of these values ​​as endpoints, inclusive.

[0125] In some embodiments, the protein polyurethane alloy may have a first DMA modulus transition temperature of less than 30° C. In some embodiments, the protein polyurethane alloy may have a first DMA modulus transition onset temperature ranging from about −65° C. to about 30° C., including subranges. For example, in some embodiments, the protein polyurethane alloy may have a first DMA modulus transition onset temperature ranging from about −65° C. to about 30° C., from about −65° C. to about 25° C., from about −65° C. to about 20° C., from about −65° C. to about 15° C., from about −65° C. to about 10° C., from about −65° C. to about 5° C., from about −65° C. to about 1° C., from about −65° C. to 0° C., from about −65° C. to about 1° C., or from about −65° C. to about −5° C. , about −65°C to about −10°C, about −65°C to about −15°C, about −65°C to about −20°C, about −65°C to about −25°C, about −65°C to about −30°C, about −65°C to about −35°C, about −65°C to about −35°C, about −65°C to about −40°C, or about −65°C to about −45°C, or a range having any two of these values ​​as endpoints, inclusive.

[0126] In some embodiments, a protein polyurethane alloy can include a polyurethane having a first DMA modulus transition onset temperature in the absence of protein. That same protein polyurethane alloy can have a first DMA modulus transition onset temperature in the absence of protein that is + / - X°C above the first DMA modulus transition onset temperature of the polyurethane. This relative increase or decrease in the first DMA modulus transition onset temperature can be referred to as the "delta first modulus transition onset." In some embodiments, X can be 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.

[0127] In some embodiments, the protein polyurethane alloy may have a DMA tan(δ) peak temperature of less than 30° C. In some embodiments, the protein polyurethane alloy may have a DMA tan(δ) peak temperature ranging from about −60° C. to about 30° C., including subranges. For example, in some embodiments, the DMA tan(δ) peak temperature of the protein polyurethane alloy may be in the range of about -60°C to about 30°C, about -60°C to about 25°C, about -60°C to about 20°C, about -60°C to about 15°C, about -60°C to about 10°C, about -60°C to about 5°C, about -60°C to about 1°C, about -60°C to 0°C, about -60°C to about 1°C, about -60°C to about -5°C, about -60°C to about -10°C, about -60°C to about -15°C, about -60°C to about -20°C, about -60°C to about -25°C, about -60°C to about -30°C, about -60°C to about -35°C, or about -60°C to about -40°C, or a range having any two of these values ​​as endpoints.

[0128] In some embodiments, the protein polyurethane alloy may comprise a polyurethane having a DMA tan(δ) peak temperature corresponding to the soft phase of the polyurethane in the absence of protein. Similarly, the protein polyurethane alloy may have a DMA tan(δ) peak temperature that is + / - Y°C above the DMA tan(δ) peak temperature corresponding to the soft phase of the polyurethane in the absence of protein. This relative increase or decrease in DMA tan(δ) peak temperature may be referred to as the "delta tan(δ) peak temperature." In some embodiments, Y may be 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.

[0129] In some embodiments, a protein polyurethane alloy can include a polyurethane that has a tensile strength in the absence of protein. The same protein polyurethane alloy can have a tensile strength that is about 5% to about 55% greater than the tensile strength of the polyurethane in the absence of protein. This relative increase in tensile strength can be referred to as the "delta tensile strength %." In some embodiments, the delta tensile strength % can be 5% or greater. In some embodiments, the % delta tensile strength can be in the range of about 5% to about 55%, about 10% to about 55%, about 15% to about 55%, about 20% to about 55%, about 25% to about 55%, about 30% to about 55%, about 35% to about 55%, about 40% to about 55%, about 45% to about 55%, about 50% to about 55%, about 5% to about 50%, about 5% to about 45%, about 5% to about 40%, about 5% to about 35%, about 5% to about 30%, about 5% to about 25%, about 5% to about 20%, about 5% to about 15%, or about 5% to about 10%, or a range having any two of these endpoints inclusive. In some embodiments, the % delta tensile strength can be in the range of about 15% to about 55%. In some embodiments, the % Delta Tensile Strength can be greater than about 55%. For example, the % Delta Tensile Strength can range from about 55% to about 1000%.

[0130] In some embodiments, the soy protein polyurethane alloy may comprise a polyurethane that has a tensile strength in the absence of soy protein. The same soy protein polyurethane alloy may have a tensile strength that is about 10% to about 45% greater than the tensile strength of the polyurethane in the absence of soy protein. In some embodiments, the delta tensile strength % of the soy protein polyurethane alloy may be 10% or greater. In some embodiments, the soy protein polyurethane alloys can have a delta tensile strength % of about 10% to about 45%, about 15% to about 45%, about 20% to about 45%, about 25% to about 45%, about 30% to about 45%, about 35% to about 45%, about 40% to about 45%, about 10% to about 40%, about 10% to about 35%, about 10% to about 30%, about 10% to about 25%, about 10% to about 20%, or about 10% to about 15% by weight, or a range having any two of these values ​​as endpoints, inclusive.

[0131] In some embodiments, a protein polyurethane alloy can include a polyurethane that has a tensile strength in the absence of protein. The same protein polyurethane alloy can have a tensile strength greater than the tensile strength of the polyurethane in the absence of protein, ranging from about 2 MPa (megapascals) to about 8 MPa. This relative increase in tensile strength can be referred to as "delta tensile strength." In some embodiments, the delta tensile strength can be 2 MPa or greater. In some embodiments, the delta tensile strength can be in the range of about 2 MPa to about 8 MPa, about 3 MPa to about 8 MPa, about 4 MPa to about 8 MPa, about 5 MPa to about 8 MPa, about 6 MPa to about 8 MPa, about 7 MPa to about 8 MPa, about 2 MPa to about 7 MPa, about 2 MPa to about 6 MPa, about 2 MPa to about 5 MPa, about 2 MPa to about 4 MPa, or about 2 MPa to about 3 MPa, or a range having any two of these values ​​as endpoints, inclusive. In some embodiments, the delta tensile strength can be in the range of about 5 MPa to about 8 MPa. In some embodiments, the delta tensile strength can be greater than about 8 MPa. For example, the delta tensile strength can range from about 8 MPa to about 15 MPa.

[0132] In some embodiments, a soy protein polyurethane alloy can include a polyurethane that has a tensile strength in the absence of soy protein. The same soy protein polyurethane alloy can have a tensile strength in the range of about 1.5 MPa to about 5.5 MPa greater than the tensile strength of the polyurethane in the absence of soy protein. In some embodiments, the delta tensile strength of the soy protein polyurethane alloy can be 1.5 MPa or greater. In some embodiments, the delta tensile strength of the soy protein polyurethane alloy can be in the range of about 1.5 MPa to about 5.5 MPa, about 2 MPa to about 5.5 MPa, about 3 MPa to about 5.5 MPa, about 4 MPa to about 5.5 MPa, about 1.5 MPa to about 5 MPa, about 1.5 MPa to about 4 MPa, or about 1.5 MPa to about 3 MPa, or a range having any two of these values ​​as endpoints, inclusive.

[0133] In some embodiments, the protein polyurethane alloy may have a tensile strength ranging from about 7 MPa to about 21 MPa, including subranges. For example, in some embodiments, the protein polyurethane alloy may have a tensile strength ranging from about 7 MPa to about 21 MPa, from about 10 MPa to about 21 MPa, from about 15 MPa to about 21 MPa, from about 7 MPa to about 15 MPa, or from about 7 MPa to about 10 MPa, or within a range having any of these values ​​as endpoints, inclusive. In some embodiments, the protein polyurethane alloy may have a tensile strength greater than about 21 MPa. For example, the protein polyurethane alloy may have a tensile strength ranging from about 21 MPa to about 25 MPa.

[0134] In some embodiments, the soy protein polyurethane alloy may have a tensile strength ranging from about 14 MPa to about 19 MPa or from about 16 MPa to about 19 MPa.

[0135] In some embodiments, polyurethanes in the absence of protein may have a tensile strength of about 2 MPa or greater. In some embodiments, polyurethanes in the absence of protein may have a tensile strength ranging from about 2 MPa to about 35 MPa, including subranges. For example, in some embodiments, polyurethanes in the absence of protein may have a tensile strength ranging from about 2 MPa to about 35 MPa, from about 5 MPa to about 30 MPa, from about 10 MPa to about 25 MPa, or from about 15 MPa to about 20 MPa, or a range having any two of these values ​​as endpoints, inclusive. In some embodiments, polyurethanes in the absence of protein may have a tensile strength ranging from about 10 MPa to about 15 MPa. In some embodiments, polyurethanes in the absence of protein may have a tensile strength ranging from about 1 MPa to about 35 MPa.

[0136] In some embodiments, a protein polyurethane alloy can include a polyurethane having a Young's modulus in the absence of protein. The same protein polyurethane alloy can have a Young's modulus in the range of about 10% to about 600% greater than the Young's modulus of the polyurethane in the absence of protein. This relative percent increase in Young's modulus can be referred to as "delta Young's modulus %." In some embodiments, the delta Young's modulus % can be about 10% or greater. In some embodiments, the % delta Young's modulus can be in the range of about 10% to about 600%, about 20% to about 600%, about 30% to about 600%, about 40% to about 600%, about 50% to about 600%, about 60% to about 600%, about 70% to about 600%, about 80% to about 600%, about 90% to about 600%, about 100% to about 600%, about 200% to about 600%, about 300% to about 600%, about 400% to about 600%, or about 500% to about 600%, or a range having any two of these endpoints, inclusive. In some embodiments, the % delta Young's modulus can be in the range of about 40% to about 600%. In some embodiments, the % delta Young's modulus can be greater than about 600%. For example, the delta Young's modulus % can range from about 600% to about 2400%.

[0137] In some embodiments, the soy protein polyurethane alloy may comprise a polyurethane having a Young's modulus in the absence of soy protein. The same soy protein polyurethane alloy may have a Young's modulus in the range of about 60% to about 570% greater than the Young's modulus of the polyurethane in the absence of soy protein. In some embodiments, the delta Young's modulus % of the soy protein polyurethane alloy may be about 60% or greater. In some embodiments, the delta Young's modulus % of the soy protein polyurethane alloy may be in the range of about 60% to about 570%, about 100% to about 570%, about 200% to about 570%, about 300% to about 570%, about 400% to about 570%, or about 500% to about 570%, or a range having any two of these values ​​as endpoints, inclusive.

[0138] In some embodiments, a protein polyurethane alloy can include a polyurethane having a Young's modulus in the absence of protein. The same protein polyurethane alloy can have a Young's modulus greater than the Young's modulus of the polyurethane in the absence of protein, ranging from about 10 MPa to about 350 MPa. This relative increase in Young's modulus can be referred to as the "delta Young's modulus." In some embodiments, the delta Young's modulus can be greater than 10 MPa. In some embodiments, the delta Young's modulus can be in the range of about 10 MPa to about 350 MPa, about 25 MPa to about 350 MPa, about 50 MPa to about 350 MPa, about 100 MPa to about 350 MPa, about 150 MPa to about 350 MPa, about 200 MPa to about 350 MPa, about 250 MPa to about 350 MPa, about 300 MPa to about 350 MPa, about 10 MPa to about 300 MPa, about 10 MPa to about 250 MPa, about 10 MPa to about 200 MPa, about 10 MPa to about 150 MPa, about 10 MPa to about 100 MPa, about 10 MPa to about 50 MPa, or about 10 MPa to about 25 MPa, or a range having any two of these values ​​as endpoints, inclusive. In some embodiments, the delta Young's modulus can be in the range of about 25 MPa to about 350 MPa. In some embodiments, the delta Young's modulus can be in the range of about 100 MPa to about 350 MPa.

[0139] In some embodiments, the soy protein polyurethane alloy may comprise a polyurethane having a Young's modulus in the absence of soy protein. The same soy protein polyurethane alloy may have a Young's modulus in the range of about 35 MPa to about 340 MPa greater than the Young's modulus of the polyurethane in the absence of soy protein. In some embodiments, the delta Young's modulus of the soy protein polyurethane alloy may be greater than 35 MPa. In some embodiments, the delta Young's modulus of the soy protein polyurethane alloy can be in the range of about 35 MPa to about 340 MPa, about 50 MPa to about 340 MPa, about 100 MPa to about 340 MPa, about 150 MPa to about 340 MPa, about 200 MPa to about 340 MPa, about 250 MPa to about 340 MPa, about 300 MPa to about 340 MPa, about 35 MPa to about 300 MPa, about 35 MPa to about 250 MPa, about 35 MPa to about 200 MPa, about 35 MPa to about 150 MPa, about 35 MPa to about 100 MPa, or about 35 MPa to about 50 MPa, or a range having any two of these values ​​as endpoints, inclusive.

[0140] In some embodiments, the protein polyurethane alloy may have a Young's modulus in the range of about 50 MPa to about 450 MPa, including subranges. For example, in some embodiments, the protein polyurethane alloy may have a Young's modulus ranging from about 50 MPa to about 450 MPa, from about 75 MPa to about 450 MPa, from about 100 MPa to about 450 MPa, from about 150 MPa to about 450 MPa, from about 200 MPa to about 450 MPa, from about 250 MPa to about 450 MPa, from about 300 MPa to about 450 MPa, from about 350 MPa to about 450 MPa, from about 400 MPa to about 450 MPa, from about 50 MPa to about 400 MPa, from about 50 MPa to about 350 MPa, from about 50 MPa to about 300 MPa, from about 50 MPa to about 250 MPa, from about 50 MPa to about 200 MPa, from about 50 MPa to about 150 MPa, from about 50 MPa to about 100 MPa, or from about 50 MPa to about 75 MPa, or within a range having any two of these values ​​as endpoints, inclusive. In some embodiments, the protein polyurethane alloy may have a Young's modulus ranging from about 75 MPa to about 450 MPa. In some embodiments, the protein polyurethane alloy may have a Young's modulus greater than about 450 MPa. For example, the protein polyurethane alloy may have a Young's modulus ranging from about 450 MPa to about 580 MPa.

[0141] In some embodiments, the soy protein polyurethane alloy may have a Young's modulus ranging from about 90 MPa to about 400 MPa, including subranges. For example, in some embodiments, the soy protein polyurethane alloy may have a Young's modulus ranging from about 90 MPa to about 400 MPa, from about 100 MPa to about 400 MPa, from about 150 MPa to about 400 MPa, from about 200 MPa to about 400 MPa, from about 250 MPa to about 400 MPa, from about 300 MPa to about 400 MPa, from about 350 MPa to about 400 MPa, from about 90 MPa to about 350 MPa, from about 90 MPa to about 300 MPa, from about 90 MPa to about 250 MPa, from about 90 MPa to about 200 MPa, from about 90 MPa to about 150 MPa, or from about 90 MPa to about 100 MPa, or a range having any two of these values ​​as endpoints, inclusive.

[0142] In some embodiments, polyurethanes in the absence of protein may have a Young's modulus of about 10 MPa or greater. In some embodiments, polyurethanes in the absence of protein may have a Young's modulus ranging from about 10 MPa to about 600 MPa, including subranges. For example, in some embodiments, polyurethanes in the absence of protein may have a Young's modulus ranging from about 10 MPa to about 600 MPa, about 10 MPa to about 500 MPa, about 10 MPa to about 400 MPa, about 10 MPa to about 300 MPa, about 10 MPa to about 200 MPa, about 10 MPa to about 100 MPa, or about 10 MPa to about 50 MPa, or a range having any two of these values ​​as endpoints, inclusive. In some embodiments, polyurethanes in the absence of protein may have a Young's modulus ranging from about 50 MPa to about 100 MPa.

[0143] In some embodiments, a protein polyurethane alloy can include a polyurethane that has a water vapor transmission rate in the absence of protein. The same protein polyurethane alloy can have a water vapor transmission rate that is about 20% or greater than the water vapor transmission rate in the absence of protein. In some embodiments, the protein polyurethane alloy can have a water vapor transmission rate that is about 20% to about 600% greater than the water vapor transmission rate of polyurethane in the absence of protein. This relative percentage increase in water vapor transmission rate can be referred to as "delta MVTR%." In some embodiments, the delta MVTR% can be about 20% or greater. In some embodiments, the delta MVTR% can be in the range of about 20% to about 600%, about 30% to about 600%, about 40% to about 600%, about 50% to about 600%, about 75% to about 600%, about 100% to about 600%, about 125% to about 600%, about 150% to about 600%, about 200% to about 600%, about 20% to about 500%, about 20% to about 400%, about 20% to about 300%, about 20% to about 200%, about 20% to about 150%, about 20% to about 125%, or about 20% to about 100%, or a range having any two of these values ​​as endpoints, inclusive.

[0144] In some embodiments, the soy protein polyurethane alloy may have a delta MVTR% of about 20% or greater. In some embodiments, the delta MVTR% of the soy protein polyurethane alloy may be in the range of about 20% to about 600%, about 30% to about 600%, about 40% to about 600%, about 50% to about 600%, about 75% to about 600%, about 100% to about 600%, about 125% to about 600%, about 150% to about 600%, about 200% to about 600%, about 20% to about 500%, about 20% to about 400%, about 20% to about 300%, about 20% to about 200%, about 20% to about 150%, about 20% to about 125%, or about 20% to about 100%, or a range having any two of these endpoints inclusive.

[0145] In some embodiments, the protein polyurethane alloy can include a polyurethane that has a water vapor transmission rate in the absence of protein that is about 30 g / m 2 higher than the water vapor transmission rate of polyurethane in the absence of protein. 2 / 24 hours ~ approx. 500g / m 2 This relative increase in moisture vapor transmission rate can be referred to as "delta MVTR." In some embodiments, the delta MVTR is greater than or equal to 30 g / m². 2 In some embodiments, the delta MVTR is about 30 g / m 2 / 24 hours ~ approx. 500g / m 2 / 24 hours, approximately 40g / m 2 / 24 hours ~ approx. 500g / m 2 / 24 hours, approximately 50g / m 2 / 24 hours ~ approx. 500g / m 2 / 24 hours, approximately 75g / m 2 / 24 hours ~ approx. 500g / m 2 / 24 hours, approximately 100g / m 2 / 24 hours ~ approx. 500g / m 2 / 24 hours, approximately 150g / m 2 / 24 hours ~ approx. 500g / m 2 / 24 hours, approx. 200g / m 2 / 24 hours ~ approx. 500g / m 2 / 24 hours, approx. 300g / m 2 / 24 hours ~ approx. 500g / m 2 / 24 hours, approximately 30g / m 2 / 24 hours ~ approx. 400g / m 2 / 24 hours, approximately 30g / m 2 / 24 hours ~ approx. 300g / m 2 / 24 hours, approximately 30g / m 2 / 24 hours ~ approx. 200g / m 2 / 24 hours, approximately 30g / m 2 / 24 hours ~ approx. 150g / m 2 / 24 hours, approximately 30g / m 2 / 24 hours ~ approx. 100g / m 2 / 24 hours, approx. 30MPa ~ approx. 75g / m 2 / 24 hours, or approximately 30g / m 2 / 24 hours ~ approx. 50g / m 2 The range may be a 24 hour range, or a range having as endpoints any two of these values ​​inclusive.

[0146] In some embodiments, the soy protein polyurethane alloy has a density of 30 g / m 2 In some embodiments, the soy protein polyurethane alloy may have a delta MVTR of about 30 g / m 2 / 24 hours ~ approx. 500g / m 2 / 24 hours, approximately 40g / m 2 / 24 hours ~ approx. 500g / m 2 / 24 hours, approximately 50g / m 2 / 24 hours ~ approx. 500g / m 2 / 24 hours, approximately 75g / m 2 / 24 hours ~ approx. 500g / m 2 / 24 hours, approximately 100g / m 2 / 24 hours ~ approx. 500g / m 2 / 24 hours, approximately 150g / m 2 / 24 hours ~ approx. 500g / m 2 / 24 hours, approx. 200g / m 2 / 24 hours ~ approx. 500g / m 2 / 24 hours, approx. 300g / m 2 / 24 hours ~ approx. 500g / m 2 / 24 hours, approximately 30g / m 2 / 24 hours ~ approx. 400g / m 2 / 24 hours, approximately 30g / m 2 / 24 hours ~ approx. 300g / m 2 / 24 hours, approximately 30g / m 2 / 24 hours ~ approx. 200g / m 2 / 24 hours, approximately 30g / m 2 / 24 hours ~ approx. 150g / m 2 / 24 hours, approximately 30g / m 2 / 24 hours ~ approx. 100g / m 2 / 24 hours, approx. 30MPa ~ approx. 75g / m 2 / 24 hours, or about 30g / m 2 / 24 hours ~ approx. 50g / m 2 The range may be a 24 hour range, or a range having as endpoints any two of these values ​​inclusive.

[0147] In some embodiments, the protein polyurethane alloy has a viscosity of about 30 g / m, including subranges. 2 / 24 hours ~ approx. 1000g / m 2 For example, in some embodiments, the protein polyurethane alloy may have a water vapor transmission rate over a range of about 30 g / m 2 / 24 hours ~ approx. 1000g / m 2 / 24 hours, approximately 60g / m 2 / 24 hours ~ approx. 1000g / m 2 / 24 hours, approximately 100g / m 2 / 24 hours ~ approx. 1000g / m 2 / 24 hours, approx. 200g / m 2 / 24 hours ~ approx. 1000g / m 2 / 24 hours, approx. 250g / m 2 / 24 hours ~ approx. 1000g / m 2 / 24 hours, approx. 300g / m 2 / 24 hours ~ approx. 1000g / m 2 / 24 hours, approx. 400g / m 2 / 24 hours ~ approx. 1000g / m 2 / 24 hours, approximately 500g / m 2 / 24 hours ~ approx. 1000g / m 2 / 24 hours, approximately 30g / m 2 / 24 hours ~ approx. 900g / m 2 / 24 hours, approximately 30g / m 2 / 24 hours ~ approx. 800g / m 2 / 24 hours, approximately 30g / m 2 / 24 hours ~ approx. 700g / m 2 / 24 hours, approximately 30g / m 2 / 24 hours ~ approx. 600g / m 2 / 24 hours, approximately 30g / m 2 / 24 hours ~ approx. 500g / m 2 / 24 hours, approximately 30g / m 2 / 24 hours ~ approx. 400g / m 2 / 24 hours, approximately 30g / m 2 / 24 hours ~ approx. 300g / m 2 / 24 hours, approximately 30g / m 2 / 24 hours ~ approx. 250g / m 2 / 24 hours, approximately 30g / m 2 / 24 hours ~ approx. 200g / m 2 / 24 hours, or approximately 30g / m 2 / 24 hours ~ approx. 100g / m 2 In some embodiments, the protein polyurethane alloy may have a moisture vapor transmission rate of about 250 g / m / 24 hours, or within a range having any two of these values ​​as endpoints, inclusive. 2 For example, in some embodiments, the protein polyurethane alloy may have a water vapor transmission rate of about 250 g / m 2 / 24 hours ~ approx. 1000g / m 2 / 24 hours, approx. 250g / m 2 / 24 hours ~ approx. 700g / m 2 / 24 hours, or approximately 250g / m 2 / 24 hours ~ approx. 500g / m 2 The moisture vapor transmission rate may include a 24 hour range.

[0148] In some embodiments, the soy protein polyurethane alloy has a density of about 30 g / m, including subranges. 2 / 24 hours ~ approx. 1000g / m 2For example, in some embodiments, the soy protein polyurethane alloy may have a moisture vapor transmission rate over a range of about 30 g / m 2 / 24 hours ~ approx. 1000g / m 2 / 24 hours, approximately 60g / m 2 / 24 hours ~ approx. 1000g / m 2 / 24 hours, approximately 100g / m 2 / 24 hours ~ approx. 1000g / m 2 / 24 hours, approx. 200g / m 2 / 24 hours ~ approx. 1000g / m 2 / 24 hours, approx. 250g / m 2 / 24 hours ~ approx. 1000g / m 2 / 24 hours, approx. 300g / m 2 / 24 hours ~ approx. 1000g / m 2 / 24 hours, approx. 400g / m 2 / 24 hours ~ approx. 1000g / m 2 / 24 hours, approximately 500g / m 2 / 24 hours ~ approx. 1000g / m 2 / 24 hours, approximately 30g / m 2 / 24 hours ~ approx. 900g / m 2 / 24 hours, approximately 30g / m 2 / 24 hours ~ approx. 800g / m 2 / 24 hours, approximately 30g / m 2 / 24 hours ~ approx. 700g / m 2 / 24 hours, approximately 30g / m 2 / 24 hours ~ approx. 600g / m 2 / 24 hours, approximately 30g / m 2 / 24 hours ~ approx. 500g / m 2 / 24 hours, approximately 30g / m 2 / 24 hours ~ approx. 400g / m 2 / 24 hours, approximately 30g / m 2 / 24 hours ~ approx. 300g / m 2 / 24 hours, approximately 30g / m 2 / 24 hours ~ approx. 250g / m 2 / 24 hours, approximately 30g / m 2 / 24 hours ~ approx. 200g / m 2 / 24 hours, or approximately 30g / m 2 / 24 hours ~ approx. 100g / m 2In some embodiments, the soy protein polyurethane alloy may comprise a moisture vapor transmission rate of about 250 g / m / 24 hours, or within a range having any two of these values ​​as endpoints, inclusive. 2 For example, in some embodiments, the soy protein polyurethane alloy may have a water vapor transmission rate of about 250 g / m 2 / 24 hours ~ approx. 1000g / m 2 / 24 hours, approx. 250g / m 2 / 24 hours ~ approx. 700g / m 2 / 24 hours, or approximately 250g / m 2 / 24 hours ~ approx. 500g / m 2 The moisture vapor transmission rate may include a 24 hour range.

[0149] 17A shows a material 1700 according to some embodiments. Material 1700 includes a substrate layer 1710 and a protein polyurethane alloy 1720 that includes one or more proteins dissolved in one or more polyurethanes.

[0150] Protein polyurethane alloy 1720 may be coated or otherwise deposited on substrate layer 1710. In some embodiments, all or a portion of protein polyurethane alloy 1720 may be integrated into substrate layer 1710. In some embodiments, protein polyurethane alloy 1720 may be disposed on substrate layer 1710. In some embodiments, protein polyurethane alloy 1720 may be disposed on top surface 1714 of substrate layer 1710. In some embodiments, protein polyurethane alloy 1720 may be disposed on bottom surface 1712 of substrate layer 1710. In some embodiments, protein polyurethane alloy 1720 may be disposed on top surface 1714 of substrate layer 1710. In some embodiments, protein polyurethane alloy 1720 may be disposed on bottom surface 1712 of substrate layer 1710.

[0151] Substrate layer 1710 includes a bottom surface 1712, a top surface 1714, and a thickness 1716 measured between bottom surface 1712 and top surface 1714. In some embodiments, thickness 1716 can be in the range of about 50 microns to about 1000 microns, including subranges. For example, thickness 1716 can be about 50 microns, about 100 microns, about 150 microns, about 200 microns, about 250 microns, about 300 microns, about 350 microns, about 400 microns, about 500 microns, about 600 microns, about 700 microns, about 800 microns, about 900 microns, or about 1000 microns, or a range having any two of these values ​​as endpoints, inclusive. In some embodiments, the thickness 1716 can range from about 100 microns to about 900 microns, from about 150 microns to about 800 microns, from about 200 microns to about 700 microns, from about 250 microns to about 600 microns, from about 300 microns to about 500 microns, or from about 350 microns to about 400 microns.

[0152] The substrate layer 1710 has a thickness of about 50 g / m 2 ~about 600g / m 2 Grams per square meter (g / m) ranges from 2 For example, the substrate layer 110 may have a dry weight measured in g / m². 2 , about 75g / m 2 , about 100g / m 2 , about 125g / m 2 , about 150g / m 2 , about 175g / m 2 , about 200g / m 2 , about 300g / m 2 , about 400g / m 2 , about 500g / m 2 , or about 600 g / m 2 or a range having any two of these values ​​as endpoints. In some embodiments, the substrate layer 1710 has a dry weight of about 75 g / m 2 ~about 500g / m 2 , about 100g / m 2 ~about 400g / m 2 , about 125g / m 2 ~about 300g / m2 , about 150g / m 2 ~about 200g / m 2 , or about 175 g / m 2 ~about 200g / m 2 The dry weight may range from 1000 to 10 ...

[0153] The substrate layer 1710 may include one or more textiles. The substrate layer 1710 may include one or more textile layers. The one or more textile layers may be, for example, a woven fabric layer, a nonwoven fabric layer, a knitted layer, a mesh fabric layer, or a leather layer. The one or more textile layers may be composed of recycled or virgin fibers, filaments, or yarns. In some embodiments, the substrate layer 1710 may be or include a polyester knit layer, a polyester-cotton blend, a polyester-cotton-spandex blend knit layer, or a suede layer. In some embodiments, the substrate layer 1710 may be made from one or more natural fibers, such as cotton, linen, silk, wool, kenaf, flax, cashmere, angora, bamboo, bast, hemp, soy, seaweed, milk or milk protein, spider silk, chitosan, mycelium, cellulose including bacterial cellulose, or fibers made from wood. Mycelium is the vegetative part of a fungus or fungus-like bacterial colony, consisting of a mass of branching, thread-like hyphae. Fungi are primarily composed of a cell wall that continually elongates at the apex of the hyphae. Unlike the structural components of plants, which are primarily cellulose, or animal cells, which rely on collagen, the structural oligosaccharides of fungal cell walls are primarily chitin and beta-glucan. Chitin is a strong, rigid substance also found in the exoskeletons of arthropods.

[0154] In some embodiments, the substrate layer 1710 may be made from fibers made from one or more synthetic fibers, such as polyester, nylon, aromatic polyamide, polyolefin fibers such as polyethylene, polypropylene, rayon, lyocell, viscose, antimicrobial yarn (AMY), Sorbtek, nylon, elastomers such as LYCRA®, spandex, or ELASTANE®, polyester-polyurethane copolymers, aramid, carbon including carbon fibers and fullerenes, glass, silicon, minerals, metals or metal alloys including those containing iron, steel, lead, gold, silver, platinum, copper, zinc, and titanium, or mixtures thereof.

[0155] In some embodiments, the nonwoven substrate layer 1710 can be a staple nonwoven, a meltblown nonwoven, a spunlaid nonwoven, a flashspun nonwoven, or a combination thereof. In some embodiments, the nonwoven substrate layer 1710 can be made by carding, can be airlaid, or can be wetlaid. In some embodiments, carded, airlaid, or wetlaid substrates can be bonded by, for example, needlepunching, hydroentanglement, lamination, or thermal bonding. In some embodiments, the nonwoven substrate layer 1710 can comprise one or more natural fibers, such as cotton, linen, silk, wool, kenaf, flax, cashmere, angora, bamboo, bast, hemp, soy, seaweed, milk or milk protein, spider silk, chitosan, mycelium, cellulose, including bacterial cellulose, or fibers made from wood.

[0156] In some embodiments, the nonwoven substrate layer 1710 can include polymer fibers with functional particles in the polymer. Exemplary functional particles include ceramic particles mixed into the polymer resin during the extrusion process to create the polymer fibers. Such ceramic particles can provide the polymer fibers with desirable heat dissipation and flame resistance properties. In some embodiments, the nonwoven substrate layer 1710 can include fibers made from fruit pulp (e.g., grape pulp or apple pulp) or pineapple fibers. In some embodiments, the nonwoven substrate layer 1710 can include fibers made from recycled materials, such as recycled plastics. In some embodiments, the nonwoven substrate layer 1710 can include algae fibers. In some embodiments, the nonwoven substrate layer 1710 can include cork fibers.

[0157] In some embodiments, the substrate layer 1710 can be or include a spacer fabric, such as the spacer fabric 2100 shown in FIG. 21 . The spacer fabric 2100 includes a first fabric layer 2110 and a second fabric layer 2120 connected by one or more spacer yarns 2130. The spacer yarn(s) 2130 are disposed between the first fabric layer 2110 and the second fabric layer 2120 and define the distance between the inner surface 2114 of the first fabric layer 2110 and the inner surface 2124 of the second fabric layer 2120. The outer surface 2112 of the first fabric layer 2110 and the outer surface 2122 of the second fabric layer 2120 can define the top surface 1714 and the bottom surface 1712 of the substrate layer 1710, respectively.

[0158] The first fabric layer 2110 and the second fabric layer 2120 may comprise one or more layers of fabric material. In some embodiments, the first fabric layer 2110 and the second fabric layer 2120 may comprise one or more textile layers made from staple fibers, filaments, or mixtures thereof. As used herein, "staple fibers" are fibers having a short length of about 0.2 mm to about 5 centimeters (cm). Staple fibers may be naturally occurring or may be cut filaments. As used herein, "filaments" are long fibers having a length of 5 cm or more. In some embodiments, the first fabric layer 2110 and the second fabric layer 2120 may comprise one or more layers of woven or knitted material. In some embodiments, the outer surface 2112 of the first fabric layer 2110 may be defined by a woven or knitted fabric layer. In some embodiments, the outer surface 2122 of the second fabric layer 2120 may be defined by a woven or knitted fabric layer.

[0159] In some embodiments, the first fabric layer 2110 and the second fabric layer 2120 may be made from one or more natural fibers, such as cotton, linen, silk, wool, kenaf, flax, cashmere, angora, bamboo, bast, hemp, soy, seaweed, milk or milk protein, spider silk, chitosan, mycelium, cellulose including bacterial cellulose, or fibers made from wood. In some embodiments, the first 2110 and second 2120 fabric layers may be made from one or more synthetic fibers, such as polyester, nylon, aromatic polyamide, polyolefin fibers such as polyethylene, polypropylene, rayon, lyocell, viscose, antimicrobial yarn (AMY), Sorbtek, nylon, elastomers such as LYCRA®, spandex, or ELASTANE®, polyester-polyurethane copolymers, aramid, carbon, including carbon fibers and fullerenes, glass, silicon, minerals, metals or metal alloys, including those containing iron, steel, lead, gold, silver, platinum, copper, zinc, and titanium, or mixtures thereof. The spacer yarn(s) 2130 may include monofilament yarn(s) composed of any of the natural or synthetic materials listed above for the first 2110 and second 2120 fabric layers.

[0160] In some embodiments, the substrate layer 1710 can be colored with a colorant. In some embodiments, the colorant can be a color dye, such as an acid dye, a fiber reactive dye, a direct dye, a sulfur dye, a basic dye, a reactive dye, or a vat dye. In some embodiments, the colorant can be a pigment, such as a lake pigment. In some embodiments, a first colorant can be incorporated into the protein polyurethane alloy and a second colorant can be incorporated into the substrate layer 1710, depending on the desired aesthetics of the material.

[0161] Fiber-reactive dyes contain one or more chromophores containing pendant groups capable of forming covalent bonds with nucleophilic sites in fibrous cellulosic substrates under alkaline pH and elevated temperatures. These dyes can achieve high washfastness and a wide range of brilliant colors. Exemplary reactive dyes include, but are not limited to, sulfatoethylsulfone (Remazol), triazine, vinyl sulfone, and acrylamide dyes. These dyes can dye protein fibers such as silk, wool, and nylon by reacting with fiber nucleophiles via Michael addition. Direct dyes are anionic dyes capable of dyeing cellulose or protein fibers. In the presence of electrolytes such as sodium chloride or sodium sulfate, these dyes may have an affinity for cellulose due to the proximity of their boiling points. Exemplary direct dyes include, but are not limited to, azo, stilbene, phthalocyanine, and dioxazine.

[0162] In some embodiments, material 1700 can include a first portion 1730 having a first protein polyurethane alloy density and a second portion 1740 having a second protein polyurethane alloy density that is different from the first protein polyurethane alloy density. As used herein, "protein polyurethane alloy density" refers to the mass of protein polyurethane alloy in grams per unit volume in a particular component (e.g., material, textile, or layer).

[0163] In some embodiments, the density of the first protein polyurethane alloy may be 5% or more less than or greater than the density of the second protein polyurethane alloy. In some embodiments, the density of the first protein polyurethane alloy may be 10% or more less than or greater than the density of the second protein polyurethane alloy. In some embodiments, the density of the first protein polyurethane alloy may be 20% or more less than or greater than the density of the second protein polyurethane alloy.

[0164] In some embodiments, the density of the first protein polyurethane alloy can range from about 0.001 g / cc (grams per cubic centimeter) to about 1 g / cc. For example, in some embodiments, the density of the first protein polyurethane alloy can be in the range of about 0.001 g / cc to about 0.9 g / cc, about 0.001 g / cc to about 0.8 g / cc, about 0.001 g / cc to about 0.7 g / cc, about 0.001 g / cc to about 0.6 g / cc, about 0.001 g / cc to about 0.5 g / cc, about 0.001 g / cc to about 0.4 g / cc, about 0.001 g / cc to about 0.3 g / cc, about 0.001 g / cc to about 0.2 g / cc, about 0.001 g / cc to about 0.1 g / cc, about 0.01 g / cc to about 1 g / cc, about 0.05 g / cc to about 1 g / cc, about 0.1 g / cc to about 1 g / cc, or about 0.5 g / cc to about 1 g / cc. In some embodiments, the density of the first protein polyurethane alloy can range from about 0.05 g / cc to about 0.9 g / cc. For example, in some embodiments, the density of the first protein polyurethane alloy can range from about 0.05 g / cc to about 0.8 g / cc, from about 0.05 g / cc to about 0.7 g / cc, from about 0.05 g / cc to about 0.6 g / cc, from about 0.05 g / cc to about 0.5 g / cc, from about 0.05 g / cc to about 0.4 g / cc, from about 0.05 g / cc to about 0.3 g / cc, or from about 0.05 g / cc to about 0.5 g / cc. .05g / cc ~ approx. 0.2g / cc, approx. 0.1g / cc ~ approx. 0.9g / cc, approx. 0.2g / cc ~ approx. 0.9g / cc, approx. 0.3g / cc ~ approx. 0.9g / cc, approx. 0.4g / cc to about 0.9 g / cc, about 0.5 g / cc to about 0.9 g / cc, about 0.6 g / cc to about 0.9 g / cc, or about 0.7 g / cc to about 0.9 g / cc.

[0165] In some embodiments, the density of the second protein polyurethane alloy can range from about 0.001 g / cc to about 1 g / cc. For example, in some embodiments, the density of the second protein polyurethane alloy can be in the range of about 0.001 g / cc to about 0.9 g / cc, about 0.001 g / cc to about 0.8 g / cc, about 0.001 g / cc to about 0.7 g / cc, about 0.001 g / cc to about 0.6 g / cc, about 0.001 g / cc to about 0.5 g / cc, about 0.001 g / cc to about 0.4 g / cc, about 0.001 g / cc to about 0.3 g / cc, about 0.001 g / cc to about 0.2 g / cc, about 0.001 g / cc to about 0.1 g / cc, about 0.01 g / cc to about 1 g / cc, about 0.05 g / cc to about 1 g / cc, about 0.1 g / cc to about 1 g / cc, or about 0.5 g / cc to about 1 g / cc. In some embodiments, the density of the second protein polyurethane alloy can range from about 0.05 g / cc to about 0.9 g / cc. For example, in some embodiments, the density of the second protein polyurethane alloy can range from about 0.05 g / cc to about 0.8 g / cc, from about 0.05 g / cc to about 0.7 g / cc, from about 0.05 g / cc to about 0.6 g / cc, from about 0.05 g / cc to about 0.5 g / cc, from about 0.05 g / cc to about 0.4 g / cc, from about 0.05 g / cc to about 0.3 g / cc, or from about 0.05 g / cc to about 0.5 g / cc. .05g / cc ~ approx. 0.2g / cc, approx. 0.1g / cc ~ approx. 0.9g / cc, approx. 0.2g / cc ~ approx. 0.9g / cc, approx. 0.3g / cc ~ approx. 0.9g / cc, approx. 0.4g / cc to about 0.9 g / cc, about 0.5 g / cc to about 0.9 g / cc, about 0.6 g / cc to about 0.9 g / cc, or about 0.7 g / cc to about 0.9 g / cc.

[0166] In some embodiments, the first portion 1730 may include a protein polyurethane alloy 1720 integrated into the substrate layer 1710 at a first protein polyurethane alloy density, and the second portion 1740 may include a protein polyurethane alloy 1720 integrated into the substrate layer 1710 at a second protein polyurethane alloy density.

[0167] 17B, ​​the substrate layer 1710 can include a first layer 1750 (e.g., a first textile layer) bonded to a second layer 1760 (e.g., a second textile layer). In such embodiments, a first portion 1730 of the material 1700 can include a protein polyurethane alloy 1720 integrated into the first layer 1750 at a first protein polyurethane alloy density, and a second portion 1740 of the material 1700 can include a protein polyurethane alloy 1720 integrated into the second layer 1760 at a second protein polyurethane alloy density.

[0168] 17C , material 1700 may include a first protein polyurethane alloy layer 1770 disposed on top surface 1714 of substrate layer 1710, a second protein polyurethane layer 1780 disposed on bottom surface 1712 of substrate layer 1710, or both. In some embodiments, first portion 1730 of material 1700 may include first protein polyurethane alloy layer 1770 and second portion 1740 of material 1700 may include second protein polyurethane alloy layer 1780. In some embodiments, first portion 1730 of material 1700 may be first protein polyurethane alloy layer 1770 and second portion 1740 of material 1700 may be second protein polyurethane alloy layer 1780.

[0169] First protein polyurethane alloy layer 1770 includes bottom surface 1772, top surface 1774, and thickness 1776 measured between bottom surface 1772 and top surface 1774. In some embodiments, thickness 1776 can range from about 25 microns to about 400 microns (micrometers, μm). For example, in some embodiments, thickness 1776 can range from about 50 microns to about 350 microns, from about 75 microns to about 300 microns, from about 100 microns to about 250 microns, from about 125 microns to about 200 microns, or from about 150 microns to about 175 microns.

[0170] Similarly, second protein polyurethane alloy layer 1780 includes bottom surface 1782, top surface 1784, and thickness 1786 measured between bottom surface 1782 and top surface 1784. In some embodiments, thickness 1786 can be in the range of about 25 microns to about 400 microns (micrometers, μm), including subranges. For example, in some embodiments, thickness 1786 can be in the range of about 50 microns to about 350 microns, about 75 microns to about 300 microns, about 100 microns to about 250 microns, about 125 microns to about 200 microns, or about 150 microns to about 175 microns.

[0171] In some embodiments, the protein polyurethane alloy 1720 can include a foaming agent. In some embodiments, the protein polyurethane alloy 1720 can include a foam stabilizer. Suitable foam stabilizers include, but are not limited to, UNIFROTH® 0520 (a nonionic surfactant available from Unichem Specialty Chemicals), or HeiQ Chemtex 2216-T (a stabilized blend of nonionic and anionic surfactants), HeiQ Chemtex 2241-A (a modified HEUR (hydrophobically modified ethylene oxide urethane) thickener), HeiQ Chemtex 2243 (a nonionic silicone dispersion), or HeiQ Chemtex 2317 (a nonionic and anionic surfactant) foam stabilizer available from HeiQ Chemtex.

[0172] In some embodiments, material 1700 can include one or more colorants. In some embodiments, the colorant can be a colored dye, such as a fiber-reactive dye, a direct dye, an acid 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 colorant can be a pigment, such as a lake pigment.

[0173] In some embodiments, material 1700 can include one or more color dyes. In some embodiments, material 1700 can include about 100% to about 250% by weight of one or more color dyes, where the weight percent of the one or more color dyes is measured relative to the weight of the protein in protein polyurethane alloy 1720. For example, for a material including an alloy containing 10 grams of protein and 10 grams of color dye, the color dyes are present at 100% by weight. As another example, for a material including 10 grams of protein and an alloy containing 5 grams of a first color dye and 5 grams of a second color dye, the color dyes are present at 100% by weight. In some embodiments, the one or more color dyes can include two color dyes. In some embodiments, the one or more color dyes can include three color dyes. In some embodiments, the one or more color dyes can include four color dyes.

[0174] In some embodiments, material 1700 comprises from about 100% to about 250% by weight of one or more coloring dyes, from about 100% to about 245% by weight of one or more coloring dyes, from about 100% to about 240% by weight of one or more coloring dyes, from about 100% to about 235% by weight of one or more coloring dyes, from about 100% to about 230% by weight of one or more coloring dyes, from about 100% to about 225% by weight of one or more coloring dyes, from about 100% to about 220% by weight of one or more coloring dyes, from about 100% to about 215% by weight of one or more coloring dyes, from about 100% to about 210% by weight of one or more coloring dyes. one or more coloring dyes, about 100% to about 205% by weight of one or more coloring dyes, about 100% to about 200% by weight of one or more coloring dyes, about 100% to about 195% by weight of one or more coloring dyes, about 100% to about 190% by weight of one or more coloring dyes, about 100% to about 185% by weight of one or more coloring dyes, about 100% to about 180% by weight of one or more coloring dyes, about 100% to about 175% by weight of one or more coloring dyes, about 100% to about 170% by weight of one or more coloring dyes, about 100% to about 165% by weight of one or more coloring dyes, about 1 00% to about 160% by weight of one or more coloring dyes, about 100% to about 155% by weight of one or more coloring dyes, about 100% to about 150% by weight of one or more coloring dyes, about 100% to about 145% by weight of one or more coloring dyes, about 100% to about 140% by weight of one or more coloring dyes, about 100% to about 135% by weight of one or more coloring dyes, about 100% to about 130% by weight of one or more coloring dyes, about 100% to about 125% by weight of one or more coloring dyes, about 100% to about 120% by weight of one or more coloring dyes, 100% to about 115% by weight % of one or more coloring dyes, about 100% to about 110% by weight of one or more coloring dyes, about 100% to about 105% by weight of one or more coloring dyes, about 105% to about 250% by weight of one or more coloring dyes, about 110% to about 250% by weight of one or more coloring dyes, about 115% to about 250% by weight of one or more coloring dyes, about 120% to about 250% by weight of one or more coloring dyes, about 125% to about 250% by weight of one or more coloring dyes, about 130% to about 250% by weight of one or more coloring dyes, about 135% to about 250% by weight of one or more coloring dyes,About 140% to about 250% by weight of one or more coloring dyes, about 145% to about 250% by weight of one or more coloring dyes, about 150% to about 250% by weight of one or more coloring dyes, about 155% to about 250% by weight of one or more coloring dyes, about 160% to about 250% by weight of one or more coloring dyes, about 165% to about 250% by weight of one or more coloring dyes, about 170% to about 250% by weight of one or more coloring dyes, about 175% to about 250% by weight of one or more coloring dyes, about 180% to about 250% by weight of one or more coloring dyes, about 185% to about 250% by weight of one or more coloring dyes, about 190% to about 250% by weight of one or more coloring dyes, about 195% to about 250% by weight of one or more coloring dyes , about 200% to about 250% by weight of one or more coloring dyes, about 205% to about 250% by weight of one or more coloring dyes, about 210% to about 250% by weight of one or more coloring dyes, about 215% to about 250% by weight of one or more coloring dyes, about 220% to about 250% by weight of one or more coloring dyes, about 225% to about 250% by weight of one or more coloring dyes, about 230% to about 250% by weight of one or more coloring dyes, about 235% to about 250% by weight of one or more coloring dyes, about 240% to about 250% by weight of one or more coloring dyes, or about 245% to about 250% by weight of one or more coloring dyes, or one or more coloring dyes within a range having any two of these values ​​as endpoints, inclusive.

[0175] The protein in the alloy of material containing about 100% to about 250% by weight of one or more color dyes can be collagen, gelatin, bovine serum albumin (BSA), soy protein, pea protein, egg albumin, casein, peanut protein, edestin protein, whey protein, karanja protein, cellulase, or a combination thereof. Suitable collagens include, but are not limited to, recombinant collagen (r-collagen), recombinant collagen fragments, and extracted collagen. In some embodiments, the collagen can be a collagen fragment comprising an amino acid sequence having at least 80% sequence identity to SEQ ID NO:2.

[0176] In some embodiments, the protein polyurethane alloy 1720 may include one or more colorants. In some embodiments, the colorant may be a color dye, such as a fiber-reactive dye, a direct dye, an acid 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 colorant may be a pigment, such as a lake pigment. In some embodiments, the one or more color dyes may include two color dyes. In some embodiments, the one or more color dyes may include three color dyes. In some embodiments, the one or more color dyes may include four color dyes.

[0177] In some embodiments, protein polyurethane alloy 1720 can include one or more color dyes, where the weight percent of the one or more color dyes is measured relative to the weight of the protein in protein polyurethane alloy 1720. In some embodiments, protein polyurethane alloy 1720 can include between about 100% and about 250% by weight of one or more color dyes, between about 100% and about 245% by weight of one or more color dyes, between about 100% and about 240% by weight of one or more color dyes, between about 100% and about 235% by weight of one or more color dyes, between about 100% and about 230% by weight of one or more color dyes, between about 100% and about 225% by weight of one or more color dyes, between about 100% and about 220% by weight of one or more color dyes, ...50% by weight of one or more color dyes, between about 100% and about 250% by weight of one or more color dyes, between about 100% and about 250% by weight of one or more color dyes, between about 100% and about 250 About 215% by weight of one or more coloring dyes, about 100% to about 210% by weight of one or more coloring dyes, about 100% to about 205% by weight of one or more coloring dyes, about 100% to about 200% by weight of one or more coloring dyes, about 100% to about 195% by weight of one or more coloring dyes, about 100% to about 190% by weight of one or more coloring dyes, about 100% to about 185% by weight of one or more coloring dyes, about 100% to about 180% by weight of one or more coloring dyes, about 100% to about 175% by weight of one or more coloring dyes Color dye, about 100% to about 170% by weight of one or more color dyes, about 100% to about 165% by weight of one or more color dyes, about 100% to about 160% by weight of one or more color dyes, about 100% to about 155% by weight of one or more color dyes, about 100% to about 150% by weight of one or more color dyes, about 100% to about 145% by weight of one or more color dyes, about 100% to about 140% by weight of one or more color dyes, about 100% to about 135% by weight of one or more color dyes, about 100% to about 1 30% by weight of one or more coloring dyes, about 100% to about 125% by weight of one or more coloring dyes, about 100% to about 120% by weight of one or more coloring dyes, 100% to about 115% by weight of one or more coloring dyes, about 100% to about 110% by weight of one or more coloring dyes, about 100% to about 105% by weight of one or more coloring dyes, about 105% to about 250% by weight of one or more coloring dyes, about 110% to about 250% by weight of one or more coloring dyes, about 115% to about 250% by weight of one or more coloring dyes,About 120% to about 250% by weight of one or more coloring dyes, about 125% to about 250% by weight of one or more coloring dyes, about 130% to about 250% by weight of one or more coloring dyes, about 135% to about 250% by weight of one or more coloring dyes, about 140% to about 250% by weight of one or more coloring dyes, about 145% to about 250% by weight of one or more coloring dyes, about 150% to about 250% by weight of one or more coloring dyes , about 155% to about 250% by weight of one or more coloring dyes, about 160% to about 250% by weight of one or more coloring dyes, about 165% to about 250% by weight of one or more coloring dyes, about 170% to about 250% by weight of one or more coloring dyes, about 175% to about 250% by weight of one or more coloring dyes, about 180% to about 250% by weight of one or more coloring dyes, about 185% to about 250% by weight of one or more coloring dyes , about 190% to about 250% by weight of one or more coloring dyes, about 195% to about 250% by weight of one or more coloring dyes, about 200% to about 250% by weight of one or more coloring dyes, about 205% to about 250% by weight of one or more coloring dyes, about 210% to about 250% by weight of one or more coloring dyes, about 215% to about 250% by weight of one or more coloring dyes, and about 220% to about 250% by weight of one or more coloring dyes. , about 225% to about 250% by weight of one or more coloring dyes, about 230% to about 250% by weight of one or more coloring dyes, about 235% to about 250% by weight of one or more coloring dyes, about 240% to about 250% by weight of one or more coloring dyes, or about 245% to about 250% by weight of one or more coloring dyes, or one or more coloring dyes within a range having any two of these values ​​as endpoints, inclusive.

[0178] The protein in the protein polyurethane alloy containing about 100% to about 250% by weight of one or more color dyes can be collagen, gelatin, bovine serum albumin (BSA), soy protein, pea protein, egg albumin, casein, peanut protein, edestin protein, whey protein, karanja protein, cellulase, or a combination thereof. Suitable collagens include, but are not limited to, recombinant collagen (r-collagen), recombinant collagen fragments, and extracted collagen. In some embodiments, the collagen can be a collagen fragment comprising an amino acid sequence having at least 80% sequence identity to SEQ ID NO:2.

[0179] In some embodiments, one or more color dyes can be incorporated into material 1700 and protein polyurethane alloy 1720 by dyeing material 1700 with one or more color dyes. In some embodiments, one or more color dyes can be incorporated into material 1700 by blending one or more color dyes into the formulation before applying the formulation to substrate layer 1710. In some embodiments, one or more color dyes can be incorporated into material 1700 and protein polyurethane alloy 1720 by dyeing material 1700 with one or more color dyes and blending one or more color dyes into the formulation before applying the one or more color dyes to substrate layer 1710.

[0180] In some embodiments, material 1700 can include a base coat layer (e.g., base coat layer 1860). In some embodiments, material 1700 can include a top coat layer (e.g., top coat layer 1870).

[0181] 18A shows a layered material 1800 according to some embodiments. The layered material 1800 includes a polyurethane-protein alloy layer 1820 bonded to a substrate layer 1710. The polyurethane-protein alloy layer 1820 may be bonded directly to the surface of the substrate layer 1710 or may be bonded to the surface of the substrate layer 1710 via an intermediate layer, such as an adhesive layer. Direct bonding may be achieved using, for example, a thermal bonding process or stitching. The polyurethane-protein alloy layer 1820 may be referred to as a "first polyurethane-protein alloy layer."

[0182] Polyurethane-protein alloy layer 1820 may include one or more types of proteins and one or more polyurethanes. In some embodiments, polyurethane-protein alloy layer 1820 may include one or more proteins dissolved in one or more polyurethanes. In some embodiments, polyurethane-protein alloy layer 1820 may be transparent. The transparency of the polyurethane-protein alloy layer is evaluated before dyeing or otherwise coloring the polyurethane-protein alloy layer.

[0183] The transparent protein polyurethane alloy layer can provide unique properties to the layered material. For example, compared to a non-transparent layer, the transparent protein polyurethane alloy layer can provide unique color depth when dyed. Similarly, the transparent protein polyurethane alloy layer can provide mechanical properties to the layered material without significantly affecting the aesthetic properties of the material.

[0184] Protein polyurethane alloy layer 1820 includes a bottom surface 1822, a top surface 1824, and a thickness 1826 measured between bottom surface 1822 and top surface 1824. In some embodiments, thickness 1826 can be in the range of about 25 microns to about 400 microns (micrometers, μm), including subranges. For example, thickness 1826 can be about 25 microns, about 50 microns, about 100 microns, about 125 microns, about 150 microns, about 175 microns, about 200 microns, about 250 microns, about 300 microns, about 350 microns, or about 400 microns, or a range having any two of these values ​​as endpoints, inclusive. In some embodiments, thickness 1826 can range from about 50 microns to about 350 microns, from about 75 microns to about 300 microns, from about 100 microns to about 250 microns, from about 125 microns to about 200 microns, or from about 150 microns to about 175 microns.

[0185] The protein polyurethane alloy layer 1820 has a thickness of about 25 g / m 2 ~Approx. 125g / m 2 Grams per square meter (gsm, g / m) ranges from 2 For example, the protein polyurethane alloy layer 1820 may have a dry weight measured in g / m². 2 , about 50g / m 2 , about 75g / m 2 , about 100g / m 2 , or about 125 g / m 2 or a range between any two of these values ​​inclusive of the endpoints. In some embodiments, the protein polyurethane alloy layer 1820 has a dry weight of about 25 g / m 2 ~Approx. 125g / m 2 , about 25g / m 2 ~about 100g / m 2 , or about 50 g / m 2 ~about 100g / m 2 The dry weight may range from 1000 to 10 ...

[0186] Unless otherwise specified, the dry weight of a layer is measured during the process of making the material using the following method. First, before applying the layer of interest to the material, a first sample of the material (approximately 10 centimeters in diameter) is cut and weighed and measured to calculate the first dry weight. If a sacrificial layer is present, it is removed before measuring the weight and dimensions. Next, after the layer of interest has been applied and dried, a second sample of the same size is cut from the material and weighed and measured to calculate the second dry weight. If a sacrificial layer is present, it is removed before measuring the weight and dimensions. Third, the first dry weight is subtracted from the second dry weight to obtain the dry weight of the layer of interest. All weight and dimension measurements are performed at the same humidity level, typically the humidity level of the manufacturing environment in which the material is made. For the purpose of calculating the dry weight, three separate dry weight tests are performed, and the average dry weight is reported as the dry weight of the layer.

[0187] In some embodiments, protein polyurethane alloy layer 1820 can be a non-foamed layer. By "non-foamed" layer, we mean a layer having a density measured in terms of the void percentage of the layer of 5% or less voids, e.g., 0% voids to 5% voids. In some embodiments, protein polyurethane alloy layer 1820 can be a foamed layer. In such embodiments, protein polyurethane alloy layer 1820 can have a density measured in terms of the void percentage of layer 1820 ranging from about 5% voids to about 70% voids, including sub-ranges. For example, protein polyurethane alloy layer 1820 can have a void percentage of about 5%, about 10%, about 20%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, or about 70%, or a range of void percentages between any two of these values, inclusive. In some embodiments, protein polyurethane alloy layer 1820 can have a void percentage ranging from about 10% to about 65%, from about 20% to about 60%, from about 30% to about 55%, from about 35% to about 50%, or from about 40% to about 45%.

[0188] The void percentage (which may also be referred to as "percent porosity") can be measured by image analysis of a cross-section of the layer or by measuring the bulk density of a sample of the layer using a hydrometer. Unless otherwise specified, the void percentage reported herein is measured by image analysis of a cross-section of the layer. Images are analyzed using ImageJ software (or equivalent software) at 37x magnification. The ImageJ software uses a trainable Weka segmentation classifier to calculate the void percentage within the layer. For purposes of calculating the void percentage, three to five separate images of the cross-section are evaluated, and the average void space percentage is reported as the void percentage of the layer. In some embodiments, the protein polyurethane alloy layer 1820 can include one or more foaming agents and / or foam stabilizers. Suitable foaming agents and foam stabilizers include those discussed herein for layers 1830 and 1840.

[0189] In some embodiments, layered material 1800 may include a protein polyurethane alloy layer 1820 bonded to the top surface 1714 of substrate layer 1710. In some embodiments, a bottom surface 1822 of protein polyurethane alloy layer 1820 may be in direct contact with the top surface 1714 of substrate layer 1710. In some embodiments, the bottom surface 1822 of protein polyurethane alloy layer 1820 may be bonded to the top surface 1714 of substrate layer 1710 via an adhesive layer (e.g., adhesive layer 1850). In some embodiments, layered material 1800 may include a protein polyurethane alloy layer 1820 bonded to the bottom surface 1712 of substrate layer 1710. In some embodiments, the top surface 1824 of protein polyurethane alloy layer 1820 may be in direct contact with the bottom surface 1712 of substrate layer 1710. In some embodiments, the top surface 1824 of the protein polyurethane alloy layer 1820 may be bonded to the bottom surface 1712 of the substrate layer 1710 via an adhesive layer (e.g., adhesive layer 1850). In some embodiments, the layered material 1800 may include a protein polyurethane alloy layer 1820 bonded to the top surface 1714 of the substrate layer 1710 and a protein polyurethane alloy layer 1820 bonded to the bottom surface 1712 of the substrate layer 1710. In such embodiments, the layered material 1800 includes the protein polyurethane alloy layers 1820 disposed on opposing surfaces of the substrate layer 1710.

[0190] 18B, layered material 1800 can include a second protein polyurethane alloy layer 1830 disposed between protein polyurethane alloy layer 1820 and substrate layer 1710. In such embodiments, second protein polyurethane alloy layer 1830 is bonded to protein polyurethane alloy layer 1820. In some embodiments, bottom surface 1822 of protein polyurethane alloy layer 1820 can be in direct contact with top surface 1834 of second protein polyurethane alloy layer 1830.

[0191] Second protein polyurethane alloy layer 1830 includes a bottom surface 1832, a top surface 1834, and a thickness 1836 measured between bottom surface 1832 and top surface 1834. In some embodiments, thickness 1836 can be in the range of about 25 microns to about 600 microns, including subranges. For example, thickness 1836 can be about 25 microns, about 50 microns, about 100 microns, about 125 microns, about 150 microns, about 175 microns, about 200 microns, about 225 microns, about 250 microns, about 275 microns, about 300 microns, about 400 microns, about 500 microns, or about 600 microns, or a range having any two of these values ​​as endpoints, inclusive. In some embodiments, thickness 1836 can range from about 50 microns to about 500 microns, from about 75 microns to about 400 microns, from about 100 microns to about 300 microns, from about 125 microns to about 275 microns, from about 150 microns to about 250 microns, from about 175 microns to about 225 microns, or from about 200 microns to about 225 microns. In some embodiments, thickness 1836 can be greater than thickness 1826. In some embodiments, thickness 1836 can be less than thickness 1826. In some embodiments, thickness 1836 can be 5 microns or more greater or less than thickness 1826.

[0192] The second protein polyurethane alloy layer 1830 has a thickness of about 30 g / m 2 ~about 600g / m 2 Grams per square meter (g / m) ranges from 2 For example, the second protein polyurethane alloy layer 1830 may have a dry weight measured in g / m². 2 , about 40g / m 2 , about 60g / m 2 , about 80g / m 2 , about 100g / m 2 , about 120g / m 2 , about 140g / m 2 , about 150g / m 2 , about 200g / m 2 , about 300g / m 2 , about 400g / m 2, about 500g / m 2 , or about 600 g / m 2 or a range between any two of these values ​​inclusive. In some embodiments, the second protein polyurethane alloy layer 1830 may have a dry weight of about 40 g / m 2 ~about 500g / m 2 , about 60g / m 2 ~about 400g / m 2 , about 80g / m 2 ~about 300g / m 2 , about 100g / m 2 ~about 200g / m 2 , about 120g / m 2 ~Approx. 150g / m 2 , or about 140 g / m 2 ~Approx. 150g / m 2 In some embodiments, the protein polyurethane alloy layer 1820 may have a first weight and the second protein polyurethane alloy layer 1830 may have a second weight, and the first weight may be less than the second weight. In some embodiments, the first weight may be 5 g / m or more less than the second weight. 2 It may be smaller than this.

[0193] In some embodiments, the second protein polyurethane alloy layer 1830 can include a foaming agent. In some embodiments, the second protein polyurethane alloy layer 1830 can include a foam stabilizer. The foaming agent or foam stabilizer can promote the formation of voids in the second protein polyurethane alloy layer 1830 during blending of the second protein polyurethane alloy layer 1830. Suitable foam stabilizers include, but are not limited to, UNIFROTH® 0520 (a nonionic surfactant available from Unichem Specialty Chemicals), or HeiQ Chemtex 2216-T (a stabilized blend of nonionic and anionic surfactants), HeiQ Chemtex 2241-A (a modified HEUR (hydrophobically modified ethylene oxide urethane) thickener), HeiQ Chemtex 2243 (a nonionic silicone dispersion), or HeiQ Chemtex 2317 (a nonionic and anionic surfactant) foam stabilizers available from HeiQ Chemtex. When used, foam stabilizers help stabilize mechanically generated foams (cells). Mechanically generated foams can be generated, for example, by a rotor and / or compressed air. When used, blowing agents can generate foams (cells) within the layer by chemical reaction and / or through heat generation within the layer.

[0194] In some embodiments, second protein polyurethane alloy layer 1830 can be referred to as a "foamed protein polyurethane alloy layer" because either (i) layer 1830 comprises one or more foaming agents or foam stabilizers, and / or (ii) layer 1830 comprises a lower density than protein polyurethane alloy layer 1820.

[0195] The second protein polyurethane alloy layer 1830 can have a density, measured in percent voids, ranging from about 5% voids to about 70% voids, including subranges, of the layer 1830. For example, the second protein polyurethane alloy layer 1830 can have about 5% voids, about 10% voids, about 20% voids, about 30% voids, about 35% voids, about 40% voids, about 45% voids, about 50% voids, about 55% voids, about 60% voids, about 65% voids, or about 70% voids, or a range having any two of these values ​​as endpoints, inclusive. In some embodiments, second protein polyurethane alloy layer 1830 can have a percent voids ranging from about 10% to about 65%, about 20% to about 60%, about 30% to about 55%, about 35% to about 50%, or about 40% to about 45%. In some embodiments, protein polyurethane alloy layer 1820 can have a first density and second protein polyurethane alloy layer 1830 can have a second density, where the first density can be greater than the second density. In some embodiments, the first density can be greater than the second density by 5% or more voids.

[0196] Layering multiple protein polyurethane alloy layers with different weights and / or densities can be used to adjust the material properties of the layered material. For example, using a layer with a lower weight and / or density can increase the softness and / or flexibility of the layered material. Meanwhile, a layer with a higher weight and / or density can increase the strength of the layered material. In addition, using one or more layers with a relatively low weight and / or density can increase the ease with which cutting, stitching, and / or forming process steps (e.g., skiving) can be performed on the layered material. Layering multiple protein polyurethane alloy layers allows for greater flexibility in material design.

[0197] In some embodiments, second protein polyurethane alloy layer 1830 may further include a foaming agent, a foam stabilizer, one or more colorants, or the like, in addition to any other components that may be present. The type and content of colorant in second protein polyurethane alloy layer 1830 may be any of the types and amounts described herein for protein polyurethane alloy layer 1820. In some embodiments, second protein polyurethane alloy layer 1830 may be free of colorants or substantially free of colorants.

[0198] 18B, the layered material 1800 can include a third protein polyurethane alloy layer 1840 disposed between the second protein polyurethane alloy layer 1830 and the substrate layer 1710. In such embodiments, the third protein polyurethane alloy layer 1840 is bonded to the second protein polyurethane alloy layer 1830. In some embodiments, the bottom surface 1832 of the second protein polyurethane alloy layer 1830 can be in direct contact with the top surface 1844 of the third protein polyurethane alloy layer 1840.

[0199] Third protein polyurethane alloy layer 1840 includes a bottom surface 1842, a top surface 1844, and a thickness 1846 measured between bottom surface 1842 and top surface 1844. In some embodiments, thickness 1846 can be in the range of about 25 microns to about 600 microns, including subranges. For example, thickness 1846 can be about 25 microns, about 50 microns, about 100 microns, about 125 microns, about 150 microns, about 175 microns, about 200 microns, about 225 microns, about 250 microns, about 275 microns, about 300 microns, about 400 microns, about 500 microns, or about 600 microns, or a range having any two of these values ​​as endpoints, inclusive. In some embodiments, thickness 1846 can range from about 50 microns to about 500 microns, from about 75 microns to about 400 microns, from about 100 microns to about 300 microns, from about 125 microns to about 275 microns, from about 150 microns to about 250 microns, from about 175 microns to about 225 microns, or from about 175 microns to about 200 microns. In some embodiments, thickness 1846 can be greater than thickness 1826. In some embodiments, thickness 1846 can be less than thickness 1826. In some embodiments, thickness 1846 can be 5 microns or more greater or less than thickness 1826. In some embodiments, thickness 1846 can be the same as thickness 1836. In some embodiments, thickness 1846 can be greater or less than thickness 1836. In some embodiments, thickness 1846 can be 5 microns or more greater or less than thickness 1836.

[0200] The third protein polyurethane alloy layer 1840 has a thickness of about 30 g / m 2 ~about 600g / m 2 Grams per square meter (g / m) ranges from 2 For example, the third protein polyurethane alloy layer 1840 may have a dry weight measured in g / m². 2 , about 40g / m 2 , about 60g / m 2 , about 80g / m 2 , about 100g / m 2, about 120g / m 2 , about 140g / m 2 , about 150g / m 2 , about 200g / m 2 , about 300g / m 2 , about 400g / m 2 , about 500g / m 2 , or about 600 g / m 2 or a range between any two of these values ​​inclusive. In some embodiments, the third protein polyurethane alloy layer 1840 may have a dry weight of about 40 g / m 2 ~about 500g / m 2 , about 60g / m 2 ~about 400g / m 2 , about 80g / m 2 ~about 300g / m 2 , about 100g / m 2 ~about 200g / m 2 , about 120g / m 2 ~about 150g / m 2 , or about 120 g / m 2 ~Approx. 140g / m 2 In some embodiments, the protein polyurethane alloy layer 1820 may have a first weight, and the third protein polyurethane alloy layer 1840 may have a third weight, where the first weight is less than the third weight. In some embodiments, the protein polyurethane alloy layer 1820 may have a first weight, the second protein polyurethane alloy layer 1830 may have a second weight, and the third protein polyurethane alloy layer 1840 may have a third weight, where the first weight may be less than the second weight and the third weight. In some embodiments, the first weight may be 5 g / m or more less than the second weight and / or the third weight. 2 It may be smaller than this.

[0201] In some embodiments, the third protein polyurethane alloy layer 1840 can include a foaming agent. In some embodiments, the third protein polyurethane alloy layer 1840 can include a foam stabilizer. The foaming agent and / or foam stabilizer can promote the formation of voids in the third protein polyurethane alloy layer 1840 during blending of the third protein polyurethane alloy layer 1840. Suitable foaming agents include, but are not limited to, UNIFROTH® 0520 (a nonionic surfactant available from Unichem Specialty Chemicals), or HeiQ Chemtex 2216-T (a stabilized blend of nonionic and anionic surfactants), HeiQ Chemtex 2241-A (a modified HEUR (hydrophobically modified ethylene oxide urethane) thickener), HeiQ Chemtex 2243 (a nonionic silicone dispersion), or HeiQ Chemtex 2317 (a nonionic and anionic surfactant) foam stabilizer available from HeiQ Chemtex.

[0202] In some embodiments, the third protein polyurethane alloy layer 1840 can be referred to as a “foamed protein polyurethane alloy layer” because either (i) layer 1840 comprises one or more foaming agents or foam stabilizers, and / or (ii) layer 1840 comprises a lower density than protein polyurethane alloy layer 1820.

[0203] The third protein polyurethane alloy layer 1840 can have a density, measured in percent voids, ranging from about 5% voids to about 70% voids, including subranges, of the layer 1840. For example, the third protein polyurethane alloy layer 1840 can have about 5% voids, about 10% voids, about 20% voids, about 30% voids, about 35% voids, about 40% voids, about 45% voids, about 50% voids, about 55% voids, about 60% voids, about 65% voids, or about 70% voids, or a range having any two of these values ​​as endpoints, inclusive. In some embodiments, the third protein polyurethane alloy layer 1840 can have a percent voids ranging from about 10% to about 65%, about 20% to about 60%, about 30% to about 55%, about 35% to about 50%, or about 40% to about 45%. In some embodiments, the protein polyurethane alloy layer 1820 can have a first density and the third protein polyurethane alloy layer 1840 can have a third density, where the first density can be greater than the third density. In some embodiments, the protein polyurethane alloy layer 1820 can have a first density, the second protein polyurethane alloy layer 1830 can have a second density, and the third protein polyurethane alloy layer 1840 can have a third density, where the first density can be greater than the second and third densities. In some embodiments, the first density can be greater than the second and / or third density with 5% or more voids.

[0204] In some embodiments, layered material 1800 can include multiple protein polyurethane alloy layers having the same protein and polyurethane, hi some embodiments, layered material 1800 can include multiple protein polyurethane alloy layers, with different layers having different proteins and / or different polyurethanes.

[0205] In some embodiments, third protein polyurethane alloy layer 1840 may further include a foaming agent, a foam stabilizer, one or more colorants, and the like, in addition to any other components that may be present. The type and content of colorant in third protein polyurethane alloy layer 1840 may be any of the types and amounts described herein for protein polyurethane alloy layer 1820. In some embodiments, third protein polyurethane alloy layer 1840 may be free of colorants or substantially free of colorants.

[0206] 18B , for example, layered material 1800 can include base coat layer 1860. Base coat layer 1860 can be disposed on top surface 1824 of protein polyurethane alloy layer 1820. Base coat layer 1860 can be directly or indirectly bonded to protein polyurethane alloy layer 1820. In some embodiments, base coat layer 1860 can be disposed on top surface 1824 of protein polyurethane alloy layer 1820. In some embodiments, bottom surface 1862 of base coat layer 1860 can be in direct contact with top surface 1824 of protein polyurethane alloy layer 1820.

[0207] Base coat layer 1860 includes a bottom surface 1862, a top surface 1864, and a thickness 1866 measured between bottom surface 1862 and top surface 1864. In some embodiments, thickness 1866 can be in the range of about 20 microns to about 200 microns, including subranges. For example, thickness 1866 can be about 20 microns, about 30 microns, about 40 microns, about 50 microns, about 60 microns, about 70 microns, about 80 microns, about 90 microns, about 100 microns, about 150 microns, or about 200 microns, or a range having any two of these values ​​as endpoints, inclusive. In some embodiments, thickness 1866 can be in the range of about 30 microns to about 150 microns, about 40 microns to about 100 microns, about 50 microns to about 90 microns, about 60 microns to about 80 microns, or about 60 microns to about 70 microns.

[0208] In embodiments that include a base coat layer 1860, the base coat layer 1860 can provide one or more of the following properties to the layered material 1800: (i) abrasion resistance, color fastness, or hydrolysis resistance. The base coat layer 1860 can also, in embodiments that include a top coat layer, help adhere the top coat layer to the layered material 1800. In some embodiments, the base coat layer 1860 can include one or more polymeric materials. Suitable materials for the base coat layer 1860 include, but are not limited to, polyether polyurethane, polycarbonate polyurethane, polyester polyurethane, acrylic polymers, and crosslinkers such as isocyanates or carbodiimides. In some embodiments, the layered material 1800 can include multiple base coat layers 1860. In some embodiments, the base coat layer 1860 can be absent from the layered material 1800.

[0209] The base coat layer 1860 is approximately 20 g / m 2 ~about 100g / m 2 Grams per square meter (g / m) ranges from 2 For example, the base coat layer 1860 may have a dry weight measured in g / m². 2 , about 30g / m 2 , about 40g / m 2 , about 50g / m 2 , about 60g / m 2 , about 70g / m 2 , about 80g / m 2 , about 90g / m 2 , or about 100 g / m 2 or a range between any two of these values ​​as endpoints, inclusive. In some embodiments, the base coat layer 1860 may have a dry weight of about 30 g / m 2 ~about 90g / m 2 , about 40g / m 2 ~about 80g / m 2 , or about 50 g / m 2 ~about 70g / m 2 The dry weight may range from 1000 to 10 ...

[0210] In some embodiments, as shown in FIG. 18B , for example, layered material 1800 can include a top coat layer 1870. Top coat layer 1870 can be disposed on top surface 1824 of protein polyurethane alloy layer 1820. Top coat layer 1870 can be directly or indirectly bonded to protein polyurethane alloy layer 1820. In some embodiments, bottom surface 1872 of top coat layer 1870 can be in direct contact with top surface 1824 of protein polyurethane alloy layer 1820. In embodiments including base coat layer 1860, top coat layer 1870 can be disposed on top surface 1864 of base coat layer 1860. In some embodiments, top coat layer 1870 can be disposed on top surface 1864 of base coat layer 1860. In some embodiments, bottom surface 1872 of top coat layer 1870 can be in direct contact with top surface 1864 of base coat layer 1860.

[0211] Topcoat layer 1870 includes a bottom surface 1872, a top surface 1874, and a thickness 1876 measured between bottom surface 1872 and top surface 1874. In some embodiments, thickness 1876 can be in the range of about 10 microns to about 80 microns, including subranges. For example, thickness 1876 can be about 10 microns, about 20 microns, about 30 microns, about 40 microns, about 50 microns, about 60 microns, about 70 microns, or about 80 microns, or a range having any two of these values ​​as endpoints, inclusive. In some embodiments, thickness 1876 can be in the range of about 20 microns to about 70 microns, about 30 microns to about 60 microns, or about 30 microns to about 50 microns.

[0212] In embodiments including a topcoat layer 1870, the topcoat layer 1870 can provide one or more of the following properties to the layered material 1800: surface feel, stain resistance, flame resistance, gloss level, or color appearance. In some embodiments, the topcoat layer 1870 can include one or more polymeric materials. Suitable materials for the topcoat layer 1870 include, but are not limited to, polyurethane, acrylic, silicone-based feel agents, matte agents, and gloss agents. In some embodiments, the layered material 1800 can include multiple topcoat layers 1870. In some embodiments, the topcoat layer 1870 can be absent from the layered material 1800. In some embodiments, the topcoat layer 1870 can be transparent or translucent. In some embodiments, the topcoat layer 1870 can include one or more dyes, one or more pigments, and / or one or more reflective agents to affect appearance.

[0213] The topcoat layer 1870 is approximately 10 g / m 2 ~about 80g / m 2 Grams per square meter (g / m) ranges from 2 For example, the topcoat layer 1870 may have a dry weight measured in g / m². 2 , about 20g / m 2 , about 30g / m 2 , about 40g / m 2 , about 50g / m 2 , about 60g / m 2 , about 70g / m 2 , or about 80 g / m 2 or a range between any two of these values ​​inclusive of the endpoints. In some embodiments, the top coat layer 1870 has a dry weight of about 20 g / m 2 ~about 70g / m 2 , about 30g / m 2 ~about 60g / m 2 , or about 30 g / m 2 ~about 50g / m 2 The dry weight may range from 1000 to 10 ...

[0214] Protein polyurethane alloy layer(s) 1820, protein polyurethane alloy layer 1830, protein polyurethane alloy layer 1840, base coat layer(s) 1860, and / or top coat layer(s) 1870 can together define a layered assembly 1880 of layered material 1800. Layered assembly 1880 can include any number of protein polyurethane alloy layers described herein. For example, layered assembly 1880 can include 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 protein polyurethane alloy layers. In some embodiments, layered material 1800 can include layered assembly 1880 bonded to bottom surface 1712 of substrate layer 1710. The layered assembly 1880 bonded to the bottom surface 1712 of the substrate layer 1710 may include any of the layers and materials described herein for the layered assembly 1880 bonded to the top surface 1714 of the substrate layer 1710. In some embodiments, the layered material 1700 may include a layered assembly 1880 bonded to the top surface 1714 of the substrate layer 1710 and a layered assembly 1880 bonded to the bottom surface 1712 of the substrate layer 1710. In such embodiments, the layered material 1800 includes layered assemblies 1880 disposed on opposing surfaces 1712 and 1714 of the substrate layer 1710.

[0215] In some embodiments, the protein polyurethane alloy layer of layered material 1800 is bonded to the surface of substrate layer 1710 by adhesive layer 1850. In such embodiments, adhesive layer 1850 includes a bottom surface 1852, a top surface 1854, and a thickness 1856 measured between bottom surface 1852 and top surface 1854. In some embodiments, thickness 1856 can be in the range of about 10 microns to about 50 microns, including subranges. For example, thickness 1856 can be about 10 microns, about 20 microns, about 30 microns, about 40 microns, or about 50 microns, or a range having any two of these values ​​as endpoints, inclusive. In some embodiments, thickness 1856 can be in the range of about 20 microns to about 40 microns. Suitable adhesives for adhesive layer 1850 include, but are not limited to, polyurethane adhesives, hot melt adhesives, emulsion polymer adhesives, dry web adhesives, dry laminating adhesives, or wet laminating adhesives. Hauthane HD-2001, available from CL Hauthaway & Sons Corporation, is an exemplary laminating adhesive suitable for adhesive layer 1850. Exemplary polyurethane adhesives include, but are not limited to, L-2183, L-2245, and L-2255 manufactured by Hauthaway, and IMPRANIL® DAH and DAA manufactured by Covestro. Exemplary dry web adhesives include, but are not limited to, 9D8D20 manufactured by Protechnic. In some embodiments, layered material 1800 does not include adhesive layer 1850.

[0216] The adhesive layer 1850 has a thickness of about 10 g / m 2 ~about 50g / m 2 Grams per square meter (g / m) ranges from 2 For example, adhesive layer 1850 may have a dry weight measured in g / m². 2 , about 20g / m 2 , about 30g / m 2 , about 40g / m 2 , or about 50 g / m 2or a range between any two of these values ​​inclusive. In some embodiments, adhesive layer 1850 has a dry weight of about 20 g / m 2 ~about 40g / m 2 The dry weight may range from 1000 to 10 ...

[0217] The layered material 1800 can be made by bonding one or more protein polyurethane alloy layers described herein and one or more base coat and / or top coat layers to a substrate layer 1710. In some embodiments, the layer(s) can be subsequently laminated onto the surface of the substrate layer. The layer(s) can be bonded to either the top surface 1714 and / or the bottom surface 1712 of the substrate layer 1710. In some embodiments, the layer(s) can be laminated onto a sacrificial layer that is removed after lamination and before or after bonding one or more layers to the substrate layer 1710. Each protein polyurethane alloy layer of the layered material can be deposited using any suitable coating technique, including, but not limited to, knife-over-roll coating, gravure coating, slot-die coating, multi-layer slot-die coating, or curtain coating. Multi-layer slot-die coating can allow for simultaneous coating of multiple adjacent layers.

[0218] In some embodiments, substrate layer 1710 can be coated with adhesive layer 1850, and additional layers (e.g., layer 1820, layer 1830, layer 1840, layer 1860, and / or layer 1870) can be formed on adhesive layer 1850 in any suitable order. In such embodiments, layers can be formed on adhesive layer 1850 in the same manner as described below for method 1900, with layers formed on adhesive layer 1850 rather than a sacrificial layer. In some embodiments, the blended mixture described herein can be applied directly to the surface of substrate layer 1710, for example, using a coating or injection process. In such embodiments, the blended mixture can penetrate at least a portion of substrate layer 1710. After application, the blended mixture can be dried to form a protein polyurethane alloy layer (e.g., layer 1820). In some embodiments, after drying, the protein polyurethane alloy layer and substrate layer 1710 can be heated (e.g., heat pressed) to help the layers bond together. Other layers (e.g., layer 1830, layer 1840, layer 1860, and / or layer 1870) can be applied in any suitable order over the protein polyurethane alloy layer before or after drying and / or before or after bonding the protein polyurethane alloy layer to substrate layer 1710. In such embodiments, the other layers can be formed over the protein polyurethane alloy layer in the same manner as described below for method 1900, with the layers being formed over the protein polyurethane alloy layer rather than as sacrificial layers.

[0219] In some embodiments, a decorative layer can be applied between layers of layered material during manufacturing. For example, a logo, artistic pattern, drawing, or symbol can be applied to a first layer before placing another layer on top of the first layer. The decorative layer can be applied using, for example, screen printing, digital printing, or transfer printing.

[0220] The protein polyurethane alloys described herein can be made by blending one or more proteins and one or more polyurethanes into an aqueous protein polyurethane formulation and drying the formulation. In some embodiments, the protein can be dissolved within the polyurethane of the polyurethane dispersion. In some embodiments, the formulation can include water, one or more polyurethanes, one or more proteins, and one or more additives.

[0221] To make an aqueous protein polyurethane formulation, one or more polyurethanes dispersed or dissolved in an aqueous solution can be blended with one or more proteins to form a blended mixture in the aqueous solution. In some embodiments, the one or more polyurethanes can be dispersed or dissolved in the aqueous solution before blending with the protein(s). In some embodiments, the one or more polyurethanes can be dispersed or dissolved in the aqueous solution while blending with the protein(s). In some embodiments, the one or more polyurethanes and the one or more proteins can be blended in a suitable container until a homogeneous blend is formed. Suitable blending equipment includes, but is not limited to, a blender, a stand mixer, an in-line mixer, or a high-shear mixer.

[0222] In some embodiments, the protein(s) can be dispersed or dissolved in an aqueous solution prior to blending with one or more polyurethanes. Suitable aqueous solutions include, but are not limited to, water, alkaline aqueous solutions, acidic aqueous solutions, aqueous solutions containing organic solvents, urea solutions, and mixtures thereof. In some embodiments, alkaline aqueous solutions can be basic solutions such as sodium hydroxide, ammonia, or ammonium hydroxide solutions. In some embodiments, an example of an acidic aqueous solution can be acetic acid or hydrochloric acid (HCl) solutions. Suitable organic solvents include, but are not limited to, ethanol, isopropanol, acetone, ethyl acetate, isopropyl acetate, and glycerol. In some embodiments, the protein concentration in the aqueous protein polyurethane formulation can range from about 10 g / L to about 300 g / L, including subranges. For example, the protein concentration can range from about 10 g / L to about 300 g / L, from about 20 g / L to about 250 g / L, from about 30 g / L to about 200 g / L, from about 40 g / L to about 150 g / L, from about 50 g / L to about 100 g / L, from about 60 g / L to about 90 g / L, or from about 70 g / L to about 80 g / L.

[0223] In some embodiments, the amount of protein in the aqueous protein polyurethane formulation can range from about 5% to about 90% by weight, based on the weight of the protein and polyurethane, including subranges. For example, in some embodiments, the amount of protein in the formulation can be in the range of about 5% to about 90% by weight, about 10% to about 90% by weight, about 15% to about 90% by weight, about 20% to about 90% by weight, about 30% to about 90% by weight, about 40% to about 90% by weight, about 50% to about 90% by weight, about 60% to about 90% by weight, about 70% to about 90% by weight, about 5% to about 85% by weight, about 5% to about 80% by weight, about 5% to about 70% by weight, about 5% to about 60% by weight, about 5% to about 50% by weight, about 5% to about 40% by weight, about 5% to about 30% by weight, or about 5% to about 20% by weight, or a range having any two of these values ​​as endpoints, inclusive. In some embodiments, the amount of protein in the formulation may range from about 20% to about 40% by weight.

[0224] In some embodiments, the amount of polyurethane(s) in the aqueous protein polyurethane formulation can range from about 10% to about 95% by weight, including subranges, based on the weight of the protein and polyurethane. For example, in some embodiments, the amount of polyurethane(s) in the formulation can be in the range of about 10% to about 95% by weight, about 10% to about 90% by weight, about 10% to about 85% by weight, about 10% to about 80% by weight, about 10% to about 70% by weight, about 10% to about 60% by weight, about 10% to about 50% by weight, about 10% to about 40% by weight, about 10% to about 30% by weight, about 20% to about 95% by weight, about 30% to about 95% by weight, about 40% to about 95% by weight, about 50% to about 95% by weight, about 60% to about 95% by weight, about 70% to about 95% by weight, or about 80% to about 95% by weight, or a range having any two of these values ​​as endpoints, inclusive.

[0225] In some embodiments, the blending temperature can range, inclusive of subranges, from about room temperature (18° C.) to about 100° C. For example, the blending temperature can range from about 18° C. to about 90° C., from about 18° C. to about 80° C., from about 18° C. to about 70° C., from about 18° C. to about 60° C., from about 18° C. to about 50° C., from about 18° C. to about 40° C., or from about 18° C. to about 30° C.

[0226] In some embodiments, the protein polyurethane formulation may contain one or more additives. The additive(s) may affect the final properties of the protein polyurethane alloy, and therefore the final properties of the material. For example, the added additive(s) may affect one or more of the following material properties: stiffness, elasticity, film tensile strength, tear strength, flame retardancy, chemical stability, or wet stability. Suitable additives include, but are not limited to, crosslinkers, fillers, dyes, pigments, plasticizers, waxes, rheology modifiers, flame retardants, antimicrobial agents, antifungal agents, antioxidants, UV stabilizers, mechanical blowing agents, chemical blowing agents, and foam stabilizers. Suitable dyes include, but are not limited to, fiber-reactive dyes or natural dyes. Suitable crosslinkers include, but are not limited to, epoxy-based crosslinkers (e.g., poly(ethylene glycol) diglycidyl ether (PEGDE) available from Sigma Aldrich), isocyanate-based crosslinkers (e.g., X-TAN® available from Lanxess), and carbodiimide-based crosslinkers (e.g., PERMUTEX® XR-5577 (a carbodiimide crosslinker available from Stahl)). Suitable foaming agents include, but are not limited to, UNIFROTH® 0520 (a nonionic surfactant available from Unichem Specialty Chemicals), or HeiQ Chemtex 2216-T (a stabilized blend of nonionic and anionic surfactants), HeiQ Chemtex 2241-A (a modified HEUR (hydrophobically modified ethylene oxide urethane) thickener), HeiQ Chemtex 2243 (a nonionic silicone dispersion), or HeiQ Chemtex 2317 (a nonionic and anionic surfactant) foam stabilizer available from HeiQ Chemtex. Suitable antimicrobial / antifungal agents include Ultra-Fresh DW-56 or other antimicrobial / antifungal agents used in the leather industry.Suitable flame retardants include CETAFLAM® DB9 (an organophosphorus compound containing C-PO(OH)2 or C-PO(OR)2 groups with a carbon chain-containing polymer), CETAFLAM® PD3300 (an organophosphorus compound containing C-PO(OH)2 or C-PO(OR)2 groups with a carbon chain-containing polymer), or other flame retardants used in coated 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-excluding thickeners. Exemplary alkali-swellable rheology modifiers include, but are not limited to, ACRYSOL™ DR-106 and ACRYSOL™ ASE-60 manufactured by Dow Chemicals, TEXICRYL® 13-3131 and TEXICRYL® 13-308 manufactured by Scott-Bader. Exemplary HEUR modifiers include, but are not limited to, RM-4410 manufactured by Stahl and Chemtex 2241-A manufactured by HeiQ. Exemplary volume-excluding thickeners include, but are not limited to, WALOCEL™ XM 20000 PV manufactured by Dow Chemicals and methyl-hydroxyethyl cellulose manufactured by Sigma-Aldrich.

[0227] In some embodiments, the crosslinker can be a crosslinker selected from the group consisting of an epoxy-based crosslinker, an isocyanate-based crosslinker, and a carbodiimide-based crosslinker. In some embodiments, the crosslinker can be a carbodiimide-based crosslinker.

[0228] In some embodiments, the formulation may include one or more colorants. In some embodiments, the colorant may be a colored dye, such as a fiber-reactive dye, a direct dye, an acid dye, or a natural dye. Exemplary dyes include, but are not limited to, azo-structure acid dyes, metal complex-structure acid dyes, anthraquinone-structure acid dyes, azo / diazo-direct dyes, sulfur dyes, and vat dyes. In some embodiments, the colorant may be a pigment, such as a lake pigment.

[0229] In some embodiments, the formulation may comprise from about 4% to about 10% by weight of one or more color dyes, including subranges. For example, in some embodiments, the concentration of one or more color dyes in the formulation may be from about 4% to about 10%, from about 5% to about 10%, from about 6% to about 10%, from about 7% to about 10%, from about 4% to about 9%, from about 4% to about 8%, or from about 4% to about 7%, or a range having any two of these values ​​as endpoints, inclusive. In some embodiments, the formulation may comprise from about 0.5% to about 8% by weight of one or more color dyes.

[0230] In some embodiments, the formulation may comprise from about 100% to about 250% by weight of one or more color dyes, where the weight percent of the one or more color dyes is measured relative to the weight of protein in the formulation. In some embodiments, the one or more color dyes may comprise two color dyes. In some embodiments, the one or more color dyes may comprise three color dyes. In some embodiments, the one or more color dyes may comprise four color dyes.

[0231] In some embodiments, the formulation comprises from about 100% to about 250% by weight of one or more color dyes, from about 100% to about 245% by weight of one or more color dyes, from about 100% to about 240% by weight of one or more color dyes, from about 100% to about 235% by weight of one or more color dyes, from about 100% to about 230% by weight of one or more color dyes, from about 100% to about 225% by weight of one or more color dyes, from about 100% to about 220% by weight of one or more color dyes, from about 100% to about 215% by weight of one or more color dyes, or from about 1 00% to about 210% by weight of one or more coloring dyes, about 100% to about 205% by weight of one or more coloring dyes, about 100% to about 200% by weight of one or more coloring dyes, about 100% to about 195% by weight of one or more coloring dyes, about 100% to about 190% by weight of one or more coloring dyes, about 100% to about 185% by weight of one or more coloring dyes, about 100% to about 180% by weight of one or more coloring dyes, about 100% to about 175% by weight of one or more coloring dyes, about 100% to about 170% by weight of one or more coloring dyes, about 100% to about 165% by weight of one or more coloring dyes or more coloring dyes, about 100% by weight to about 160% by weight of one or more coloring dyes, about 100% by weight to about 155% by weight of one or more coloring dyes, about 100% by weight to about 150% by weight of one or more coloring dyes, about 100% by weight to about 145% by weight of one or more coloring dyes, about 100% by weight to about 140% by weight of one or more coloring dyes, about 100% by weight to about 135% by weight of one or more coloring dyes, about 100% by weight to about 130% by weight of one or more coloring dyes, about 100% by weight to about 125% by weight of one or more coloring dyes, about 100% by weight to about 120% by weight of one or more coloring dyes, 100% by weight to about 115% by weight of one or more coloring dyes, about 100% to about 110% by weight of one or more coloring dyes, about 100% to about 105% by weight of one or more coloring dyes, about 105% to about 250% by weight of one or more coloring dyes, about 110% to about 250% by weight of one or more coloring dyes, about 115% to about 250% by weight of one or more coloring dyes, about 120% to about 250% by weight of one or more coloring dyes, about 125% to about 250% by weight of one or more coloring dyes, about 130% to about 250% by weight of one or more coloring dyes, about 135% to about 250% by weight of one or more coloring dyes,About 140% to about 250% by weight of one or more coloring dyes, about 145% to about 250% by weight of one or more coloring dyes, about 150% to about 250% by weight of one or more coloring dyes, about 155% to about 250% by weight of one or more coloring dyes, about 160% to about 250% by weight of one or more coloring dyes, about 165% to about 250% by weight of one or more coloring dyes, about 170% to about 250% by weight of one or more coloring dyes, about 175% to about 250% by weight of one or more coloring dyes, about 180% to about 250% by weight of one or more coloring dyes, about 185% to about 250% by weight of one or more coloring dyes, about 190% to about 250% by weight of one or more coloring dyes, about 195% to about 250% by weight of one or more coloring dyes , about 200% to about 250% by weight of one or more coloring dyes, about 205% to about 250% by weight of one or more coloring dyes, about 210% to about 250% by weight of one or more coloring dyes, about 215% to about 250% by weight of one or more coloring dyes, about 220% to about 250% by weight of one or more coloring dyes, about 225% to about 250% by weight of one or more coloring dyes, about 230% to about 250% by weight of one or more coloring dyes, about 235% to about 250% by weight of one or more coloring dyes, about 240% to about 250% by weight of one or more coloring dyes, or about 245% to about 250% by weight of one or more coloring dyes, or one or more coloring dyes within a range having any two of these values ​​as endpoints, inclusive.

[0232] In some embodiments, the protein polyurethane formulation may include a foam stabilizer content of about 0.1% to about 10% by weight. For example, the formulation may include about 0.1% to about 10% by weight, about 1% to about 7.5% by weight, about 2.5% to about 5% by weight, about 0.1% to about 5% by weight, or about 0.1% to about 2.5% by weight of foam stabilizer. Suitable foam stabilizers include, but are not limited to, UNIFROTH® 0520 (a nonionic surfactant available from Unichem Specialty Chemicals), or HeiQ Chemtex 2216-T (a stabilized blend of nonionic and anionic surfactants), HeiQ Chemtex 2241-A (a modified HEUR (hydrophobically modified ethylene oxide urethane) thickener), HeiQ Chemtex 2243 (a nonionic silicone dispersion), or HeiQ Chemtex 2317 (a nonionic and anionic surfactant) foam stabilizer available from HeiQ Chemtex.

[0233] In some embodiments, the protein polyurethane formulation may comprise a crosslinker content of about 0.1% to about 10% by weight. For example, the formulation may comprise about 0.1% to about 10% by weight, about 1% to about 7.5% by weight, about 2.5% to about 5% by weight, about 0.1% to about 5% by weight, or about 0.1% to about 2.5% by weight of crosslinker. In some embodiments, the protein polyurethane formulation may comprise a crosslinker content of about 0.5% to about 10% by weight. In some embodiments, the weight percent of the crosslinker may be based on the solid weight of the polyurethane in the protein polyurethane formulation.

[0234] In some embodiments, the protein polyurethane formulation may have a pH ranging from about 8 to about 9. In some embodiments, the protein polyurethane formulation may have a pH of about 8. In some embodiments, a base, such as sodium hydroxide, may be blended into the formulation to adjust the pH to a desired value.

[0235] In some embodiments, the formulation can be foamed to form a protein polyurethane formulation. The formulation can be foamed, for example, using a mechanical foaming process or a chemical foaming process. Exemplary mechanical foaming equipment includes a Hansa Mixer or a GEMAT® foaming agent. Blending and foaming of the formulation can be performed separately or simultaneously.

[0236] In some embodiments, the foamed protein polyurethane alloy formulation, before the solvent is removed, may have a liquid density ranging from about 300 g / L to about 900 g / L, including subranges. For example, in some embodiments, the formulation may have a liquid density ranging from about 300 g / L to about 1000 g / L, from about 300 g / L to about 800 g / L, from about 400 g / L to about 600 g / L, from about 300 g / L to about 500 g / L, or from about 300 g / L to about 600 g / L.

[0237] The protein polyurethane formulation can be applied to the substrate layer 1710 using any suitable application technique, including but not limited to, spray coating, dip coating, or pouring. In some embodiments, the foamed protein polyurethane formulation can be applied to the substrate layer 1710 using any suitable application technique, including but not limited to, spray coating, dip coating, or pouring.

[0238] In some embodiments, the temperature of the formulation during coating can be about 40° C. or higher. For example, the temperature of the formulation can range from about 40° C. to about 100° C., including subranges. For example, in some embodiments, the temperature of the formulation during coating can range from about 40° C. to about 90° C., from about 40° C. to about 80° C., from about 40° C. to about 70° C., from about 40° C. to about 60° C., or from about 40° C. to about 50° C.

[0239] After the formulation is applied to the substrate layer 1710, the solvent (e.g., water) can be removed from the formulation to form the protein polyurethane alloy 1720. Suitable solvent removal methods include, but are not limited to, tunnel drying, vacuum drying, hot air oven drying, humidity chamber drying, flotation drying with hot air, and ovens using a combination of mid-range IR (infrared) for preheating and then hot air for subsequent drying. Suitable solvent removal temperatures can range from about room temperature (18°C) to about 210°C, including subranges. For example, in some embodiments, the solvent can be removed at temperatures ranging from about 18°C ​​to about 35°C, about 18°C ​​to about 50°C, about 18°C ​​to about 75°C, about 18°C ​​to about 100°C, about 18°C ​​to about 150°C, about 18°C ​​to about 200°C, or about 18°C ​​to about 210°C.

[0240] In some embodiments, layers of layered material can be formed on a sacrificial layer and then bonded to a substrate layer after formation. FIG. 19 illustrates a method 1900 for making a layered material 1800, according to some embodiments. FIGS. 20A-20F illustrate the steps of method 1900. Unless otherwise specified, the steps of method 1900 need not be performed in the order described herein. Additionally, unless otherwise specified, the steps of method 1900 need not be performed sequentially. Steps can be performed simultaneously. As an example, method 1900 need not include a solvent removal step after deposition of each individual protein polyurethane alloy layer. Rather, solvent (e.g., water) from multiple protein polyurethane alloy layers can be removed in a single step. Method 1900 can be used to bond layers to one or both sides of substrate layer 1710.

[0241] In step 1902, a topcoat layer 1870 can be disposed on the upper surface 2002 of the sacrificial layer 2000, as shown, for example, in FIG. 20A . The topcoat layer 1870 can be disposed on the sacrificial layer 2000 using any suitable coating technique, such as knife-over-roll, spraying, or roller coating using reverse transfer paper. The sacrificial layer 2000 is a layer of material that does not define a layer of the layered material 1800. Rather, the sacrificial layer 2000 is removed during the fabrication of the layered material 1800. The sacrificial layer 2000 can be removed mechanically, for example, by peeling the sacrificial layer 2000, or chemically, for example, by dissolving the sacrificial layer 2000. In some embodiments, the sacrificial layer 2000 can be a release liner. Suitable materials for the sacrificial layer 2000 include, but are not limited to, grained release paper. Exemplary grained release papers include Sappi papers, such as those available from Matte Freeport 189, Freeport 123, or Expresso 904. In some embodiments, method 1900 does not include step 1902, i.e., step 1902 is optional. In some embodiments, topcoat layer 1870 can be applied to layered material 1800 after sacrificial layer 2000 is removed in step 1918. In some embodiments, topcoat layer 1870 can be applied to layered material 1800 after protein polyurethane alloy layer(s) are bonded to substrate layer 1710 in step 1920.

[0242] In step 1904, a base coat layer 1860 can be disposed on the sacrificial layer 2000, as shown, for example, in FIG. 20B . In embodiments including a top coat layer 1870, the base coat layer 1860 can be disposed on the top coat layer 1870. The base coat layer 1860 can be disposed on the sacrificial layer 2000 using any suitable coating technique, such as knife-over-roll, spray, or roller coating with reverse transfer paper. In some embodiments, the method 1900 does not include step 1904. Step 1904 is optional. In some embodiments, the base coat layer 1860 can be applied to the layered material 1800 after removing the sacrificial layer 2000 in step 1918. In some embodiments, the base coat layer 1860 can be applied to the layered material 1800 after bonding the protein polyurethane alloy layer(s) to the substrate layer 1710 in step 1920.

[0243] In step 1906, one or more polyurethanes dispersed or dissolved in an aqueous solution can be blended with one or more proteins to form a blended mixture in the aqueous solution. In some embodiments, the one or more polyurethanes can be dispersed or dissolved in the aqueous solution before blending with the protein(s). In some embodiments, the one or more polyurethanes can be dispersed or dissolved in the aqueous solution while blending with the protein(s). In some embodiments, the one or more polyurethanes and the one or more proteins can be blended in a suitable container until a homogeneous blend is formed. Suitable blending equipment includes, but is not limited to, a blender, a stand mixer, an in-line mixer, or a high-shear mixer.

[0244] In some embodiments, the protein(s) may be dispersed or dissolved in an aqueous solution prior to blending with the polyurethane in step 1906. Suitable aqueous solutions include, but are not limited to, water, alkaline aqueous solutions, acidic aqueous solutions, aqueous solutions containing organic solvents, urea solutions, and mixtures thereof. In some embodiments, alkaline aqueous solutions may be basic solutions such as sodium hydroxide, ammonia, or ammonium hydroxide solutions. In some embodiments, an example of an acidic aqueous solution 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, and glycerol. In some embodiments, the protein concentration in the aqueous protein mixture may range from 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 within a range having any two of these values ​​as endpoints, inclusive. In some embodiments, the protein concentration in the aqueous protein mixture can range from about 10 g / L to about 300 g / L, from about 20 g / L to about 250 g / L, from about 30 g / L to about 200 g / L, from about 40 g / L to about 150 g / L, from about 50 g / L to about 100 g / L, from about 60 g / L to about 90 g / L, or from about 70 g / L to about 80 g / L.

[0245] The amount of protein in a protein / polyurethane blend can range from about 5% to about 60% by weight, including subranges, based on the weight of the protein and polyurethane. For example, the amount of protein in the blend can be about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, or about 60% by weight, or a range having any two of these values ​​as endpoints. In some embodiments, the amount of protein in the blend can be about 10% to about 55%, about 15% to about 50%, about 20% to about 45%, about 25% to about 40%, or about 30% to about 35% by weight. In some embodiments, the amount of protein in a protein / polyurethane alloy blend can range from about 20% to about 40% by weight.

[0246] The amount of polyurethane(s) in the protein / polyurethane blend can range from about 10% to about 85% by weight, based on the weight of the protein and polyurethane, including subranges. For example, the amount of polyurethane(s) in the blend can be about 10%, about 15%, about, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, or about 85% by weight, or a range having any two of these values ​​as endpoints, inclusive. In some embodiments, the amount of polyurethane(s) in the blend can range from about 20% to about 75%, about 30% to about 65%, or about 40% to about 55% by weight.

[0247] In some embodiments, the blending temperature can range from about room temperature (18°C) to about 100°C, inclusive of subranges. For example, the blending temperature can be about 18°C, about 30°C, about 40°C, about 50°C, about 60°C, about 70°C, about 80°C, about 90°C, or about 100°C, or a range having any two of these endpoints, inclusive. In some embodiments, the blending temperature can range from about 18°C ​​to about 90°C, about 18°C ​​to about 80°C, about 18°C ​​to about 70°C, about 18°C ​​to about 60°C, about 18°C ​​to about 50°C, about 18°C ​​to about 40°C, or about 18°C ​​to about 30°C.

[0248] In some embodiments, the blending time in step 1906 can range from about 15 minutes to about 3 hours, inclusive of subranges. For example, the blending time can be about 30 minutes, about 1 hour, about 90 minutes, about 2 hours, about 150 minutes, or about 3 hours, or any range having any two of these endpoints, inclusive. In some embodiments, the blending time can range from about 15 minutes to about 150 minutes, about 15 minutes to about 2 hours, about 15 minutes to about 90 minutes, or about 15 minutes to about 1 hour. In some embodiments, the blending speed in step 1906 can range from about 150 rpm to about 250 rpm, inclusive of subranges. For example, the blending speed can be about 150 rpm, about 175 rpm, about 200 rpm, about 225 rpm, or about 250 rpm. In some embodiments, the blending speed can range from about 150 rpm to about 225 rpm, about 150 rpm to about 200 rpm, or about 150 rpm to about 225 rpm. The blending speed may depend on the size of the blending equipment (eg, impeller size) and / or the size of the container in which the components are blended.

[0249] In some embodiments, one or more additives can be added to the blend in step 1906. The additive(s) can affect the final properties of the protein polyurethane alloy layer, and therefore the final properties of the layered material 1800. For example, the added additive(s) can affect one or more of the following material properties: stiffness, elasticity, film tensile strength, tear strength, flame retardancy, chemical stability, or wet stability. Suitable additives include, but are not limited to, crosslinkers, fillers, dyes, pigments, plasticizers, waxes, rheology modifiers, flame retardants, antimicrobial agents, antifungal agents, antioxidants, UV stabilizers, mechanical blowing agents, chemical blowing agents, and foam stabilizers. Suitable dyes include, but are not limited to, fiber-reactive dyes or natural dyes. Suitable crosslinkers include, but are not limited to, epoxy-based crosslinkers (e.g., poly(ethylene glycol) diglycidyl ether (PEGDE) available from Sigma Aldrich), isocyanate-based crosslinkers (e.g., X-TAN® available from Lanxess), and carbodiimide-based crosslinkers (e.g., PERMUTEX® XR-5577 (a carbodiimide crosslinker available from Stahl)). Suitable foaming agents include HeiQ Chemtex 2216-T (a stabilized blend of nonionic and anionic surfactants), HeiQ Chemtex 2241-A (a modified HEUR (hydrophobically modified ethylene oxide urethane) thickener), HeiQ Chemtex 2243 (a nonionic silicone dispersion), or HeiQ Chemtex 2317 (a nonionic and anionic surfactant) foam stabilizer, all available from HeiQ Chemtex. Suitable antimicrobial / antifungal agents include Ultra-Fresh DW-56 or other antimicrobial / antifungal agents used in the leather industry.Suitable flame retardants include CETAFLAM® DB9 (an organophosphorus compound containing C-PO(OH)2 or C-PO(OR)2 groups with a carbon chain-containing polymer), CETAFLAM® PD3300 (an organophosphorus compound containing C-PO(OH)2 or C-PO(OR)2 groups with a carbon chain-containing polymer), or other flame retardants used in coated 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-excluding thickeners. Exemplary alkali-swellable rheology modifiers include, but are not limited to, ACRYSOL™ DR-106 and ACRYSOL™ ASE-60 manufactured by Dow Chemicals, TEXICRYL® 13-3131 and TEXICRYL® 13-308 manufactured by Scott-Bader. Exemplary HEUR modifiers include, but are not limited to, RM-4410 manufactured by Stahl and Chemtex 2241-A manufactured by HeiQ. Exemplary volume-excluding thickeners include, but are not limited to, WALOCEL™ XM 20000 PV manufactured by Dow Chemicals and methyl-hydroxyethyl cellulose manufactured by Sigma-Aldrich.

[0250] In some embodiments, material 1800 may include from about 0.5% to about 5% by weight of one or more rheology modifiers, where the weight percentage is based on the total weight of material 1800.

[0251] In some embodiments, the blend may include one or more colorants. In some embodiments, the colorant may be a dye, such as a fiber-reactive dye, a direct dye, an acid 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 colorant may be a pigment, such as a lake pigment. In some embodiments, the blend may include a colorant content of about 2% by weight or less. For example, the blend may include about 0.1%, about 0.5%, about 1%, about 1.5%, or about 2% by weight of colorant. In some embodiments, the blend may include about 0.1% to about 2%, about 0.5% to about 1.5%, or about 0.1% to about 1% by weight of colorant. In some embodiments, the blend may be free of colorants or substantially free of colorants. In such embodiments, the protein polyurethane alloy layer made from the blend may be free of colorants or substantially free of colorants.

[0252] In step 1908, a layer of the blended mixture is disposed on the top surface 2002 of the sacrificial layer 2000. The blended mixture may be coated on the top surface 2002 of the sacrificial layer 2000. In embodiments that do not include steps 1902 and 1904, the blended mixture may be coated directly on the top surface 2002 of the sacrificial layer 2000. In embodiments that include step 1904, the blended mixture may be coated directly on the surface of the base coat layer 1860. In embodiments that include step 1902 but not step 1904, the blended mixture may be coated directly on the surface of the top coat layer 1870. In some embodiments, the blended mixture may be formed into a sheet by coating the blended mixture on a surface to a desired thickness. Coating may include pouring, extrusion, molding, and the like. In some embodiments, the sheet may be spread to a desired thickness using, for example, a blade, a knife, a roller, a knife over roll, curtain coating, and slot die coating.

[0253] In some embodiments, the temperature of the blended mixture during coating can be about 40°C or higher. For example, the temperature of the blended mixture can be in the range of about 40°C to about 100°C, including subranges. For example, the temperature can be about 40°C, about 50°C, about 60°C, about 70°C, about 80°C, about 90°C, or about 100°C, or a range having any two of these values ​​as endpoints, inclusive. In some embodiments, the temperature of the blended mixture during coating can be in the range of about 40°C to about 90°C, about 40°C to about 80°C, about 40°C to about 70°C, about 40°C to about 60°C, or about 40°C to about 50°C. Coating at a temperature below about 40°C can make the blended mixture excessively viscous, making it difficult to form a layer of uniform thickness.

[0254] In step 1910, solvent (e.g., water) can be removed from the coated blend mixture to form a protein polyurethane alloy layer 1820, as shown, for example, in Figure 20C. Suitable solvent removal methods include, but are not limited to, tunnel drying, vacuum drying, hot air oven drying, humidity chamber drying, flotation drying with hot air, and ovens with a combination of mid-range IR (infrared) for preheating followed by hot air for subsequent drying.

[0255] Suitable solvent removal temperatures in step 1910 can range from about room temperature (18°C) to about 100°C, inclusive of subranges. For example, the solvent may be removed at a temperature of about 18°C, about 35°C, about 50°C, about 60°C, about 70°C, about 80°C, about 90°C, or about 100°C, or a temperature within a range having any two of these values ​​as endpoints, inclusive. In some embodiments, the solvent may be removed at a temperature ranging from about 18°C ​​to about 35°C, about 18°C ​​to about 50°C, about 18°C ​​to about 60°C, about 18°C ​​to about 70°C, about 18°C ​​to about 80°C, about 18°C ​​to about 90°C, or about 18°C ​​to about 100°C. Suitable humidity values ​​for solvent removal in step 1910 include humidity levels ranging from 0% RH (relative humidity) to about 65% RH, inclusive of subranges. For example, the humidity can be about 10% RH, about 20% RH, about 40% RH, about 50% RH, or about 65% RH, or a range having any two of these values ​​as endpoints, inclusive. In some embodiments, the humidity can be between 0% RH and about 50% RH, between 0% RH and about 40% RH, between 0% RH and about 20% RH, or between 0% RH and about 10% RH. The solvent removal temperature and / or humidity can affect the final properties of the protein polyurethane alloy layer and, therefore, the layered material. The solvent removal temperature and / or humidity in step 1910 can affect one or more of the following material properties: stiffness, elasticity, film tensile strength, tear strength, flame retardancy, chemical stability, and wet stability. For example, a relatively high humidity and a relatively low temperature can result in a softer, more elastic material. Conversely, a relatively low humidity and a relatively high temperature can result in a stiffer, less elastic material.

[0256] In some embodiments, steps 1906-1910 can be repeated multiple times to form multiple protein polyurethane alloy layers 1820 on sacrificial layer 2000. In some embodiments, steps 1906-1910 can be repeated sequentially to form multiple protein polyurethane alloy layers 1820 on sacrificial layer 2000. In some embodiments, steps 1906-1910 can be repeated after steps 1912-1916 to form one or more protein polyurethane alloy layers 1820 on one or more foamed protein polyurethane alloy layers 1830 / 1840. In some embodiments, method 1900 may not include steps 1906-1910.

[0257] In step 1912, one or more polyurethanes dispersed or dissolved in an aqueous solution can be blended with the protein(s) and foamed to form a foamed blend mixture in the aqueous solution. In some embodiments, the one or more polyurethanes can be dispersed or dissolved in the aqueous solution before blending with the protein(s) and foam. In some embodiments, the one or more polyurethanes can be dispersed or dissolved in the aqueous solution while blending with the protein(s) and foam. In some embodiments, the one or more polyurethanes and the one or more proteins can be blended in a suitable container until a homogeneous blend is formed. Suitable blending equipment includes, but is not limited to, a blender, a stand mixer, an in-line mixer, or a high-shear mixer. The blend can be foamed, for example, using a mechanical foaming process or a chemical foaming process. Exemplary mechanical foaming equipment includes a Hansa Mixer or GEMAT® foaming agent. Blending and foaming can be performed separately or simultaneously.

[0258] Suitable polyurethane(s) for blending and foaming in step 1912 are those discussed herein for the protein polyurethane alloy layer. In some embodiments, one or more foaming agents and / or foam stabilizers may be added to the blend in step 1912. Suitable foaming agents and foam stabilizers include those discussed herein for the protein polyurethane alloy layer 1830 / 1840.

[0259] In some embodiments, the blend may contain a foaming agent or foam stabilizer content of about 10% by weight or less. For example, the blend may contain about 0.1%, about 1%, about 2.5%, about 5%, about 7.5%, or about 10% by weight of the foaming agent or foam stabilizer. In some embodiments, the blend may contain about 0.1% to about 10%, about 1% to about 7.5%, about 2.5% to about 5%, about 0.1% to about 5%, or about 0.1% to about 2.5% by weight of the foaming agent or foam stabilizer. In some embodiments, the blend may be substantially free of, or free of, foaming agents and / or foam stabilizers. In such embodiments, a protein polyurethane alloy layer made from the blend may be substantially free of, or free of, foaming agents and / or foam stabilizers.

[0260] Foaming in step 1912 can be used to impart a desired density to the foamed protein polyurethane alloy layer. In some embodiments, the foamed blend mixture can have a liquid density ranging from about 300 g / L to about 900 g / L, including subranges, before the solvent is removed in step 1916. For example, the foamed blend mixture formed in step 1912 can have a liquid density of about 300 g / L, about 400 g / L, about 500 g / L, about 600 g / L, about 700 g / L, about 800 g / L, or about 900 g / L, or a liquid density within a range having any two of these values ​​as endpoints. In some embodiments, the foamed blended mixture may have a liquid density ranging from about 300 g / L to about 800 g / L, from about 300 g / L to about 700 g / L, from about 400 g / L to about 600 g / L, from about 300 g / L to about 500 g / L, or from about 300 g / L to about 600 g / L. In some embodiments, the blended mixture formed in step 1906, before the solvent is removed from the blended mixture in step 1910, may have a liquid density that is higher than the liquid density of the foamed blended mixture formed in step 1912 before the solvent is removed in step 1916.

[0261] In some embodiments, the protein(s) can be dispersed or dissolved in an aqueous solution prior to blending with the polyurethane and foam in step 1912. Suitable aqueous solutions include those discussed above for step 1906. The protein concentration in the aqueous solution can be any value or range discussed above for step 1906. The amount of protein in the protein / polyurethane blend in step 1912 can be any value or range discussed above for step 1906. The blending temperature in step 1912 can be any temperature or temperature range discussed above for step 1906. The blending time in step 1912 can be any time or range of times discussed above for step 1906. The blending speed in step 1912 can be any speed or range of speeds discussed above for step 1906. In some embodiments, one or more additives can be added to the blend in step 1912. The additive(s) added in step 1912 can be any of the additives discussed above for step 1906.

[0262] In step 1914, a layer of foaming blend mixture is disposed on sacrificial layer 2000. In some embodiments, the layer of foaming blend mixture is disposed on the surface of protein polyurethane alloy layer 1820. In some embodiments, the blend and foaming mixture can be coated directly onto the surface of protein polyurethane alloy layer 1820. In some embodiments, the foaming blend mixture can be formed into a sheet by coating the blend mixture onto a surface to a desired thickness. Coating can include injection, extrusion, molding, and the like. In some embodiments, the sheet can be spread to a desired thickness using, for example, a blade, a knife, a roller, a knife over roll, curtain coating, and slot die coating.

[0263] In step 1916, solvent (e.g., water) can be removed from the coated foamed blend mixture to form a foamed protein polyurethane alloy layer 1830, as shown, for example, in FIG. 20D. Suitable solvent removal methods include, but are not limited to, tunnel drying, vacuum drying, hot air oven drying, humidity chamber drying, flotation drying with hot air, and ovens with a combination of mid-range IR for preheating followed by hot air for subsequent drying. Suitable solvent removal temperatures for step 1916 can be any of the temperatures or temperature ranges discussed above for step 1910. Humidity values ​​for step 1916 can be any of the humidity values ​​or humidity ranges discussed above for step 1910.

[0264] In some embodiments, steps 1912 through 1916 can be repeated multiple times to form foamed protein polyurethane alloy layers, such as foamed protein polyurethane alloy layer 1830 and foamed protein polyurethane alloy layer 1840, on sacrificial layer 2000. In such embodiments, the foamed blend mixtures formed in separate steps 1912 can have different liquid densities. For example, the liquid density of one foamed blend mixture can be 10 g / L to 300 g / L more or less than the liquid density of another foamed blend mixture. For example, in some embodiments, a first blend mixture can have a liquid density ranging from about 300 g / L to about 500 g / L, and a second blend mixture can have a liquid density ranging from about 600 g / L to about 700 g / L. As another example, a first blend mixture can have a liquid density ranging from about 300 g / L to about 400 g / L, and a second blend mixture can have a liquid density ranging from about 500 g / L to about 700 g / L.

[0265] In some embodiments, steps 1912-1916 can be sequentially repeated to form multiple foamed protein polyurethane alloy layers on sacrificial layer 2000. In some embodiments, the foamed and blended mixture formed in step 1912 can be used to form multiple foamed protein polyurethane alloy layers in steps 1914-1916. In some embodiments, steps 1912-1916 can be performed before performing the sequence of steps 1906-1910 to form one or more foamed protein polyurethane alloy layers between protein polyurethane alloy layer 1820 and sacrificial layer 2000. In some embodiments, method 1900 does not include steps 1912-1916.

[0266] In step 1918, the sacrificial layer 2000 is removed from the layer(s) formed in steps 1902-1916, as shown, for example, in FIG. 20E. The sacrificial layer 2000 can be removed by a mechanical process or a chemical process. For example, the sacrificial layer 2000 can be removed by peeling the sacrificial layer 2000 from the other layers. As another example, the sacrificial layer 2000 can be removed by dissolving the sacrificial layer 2000. In some embodiments, the sacrificial layer 2000 can be removed in step 1918 before the layer(s) formed in steps 1902-1916 are bonded to the substrate layer 1710 in step 1920. In some embodiments, the sacrificial layer 2000 can be removed after step 1920.

[0267] In step 1920, the layer(s) formed in steps 1902-1916 are bonded to substrate layer 1710, as shown, for example, in FIG. 20F. In step 1920, protein polyurethane alloy layer 1820, and any other protein polyurethane alloy layers formed in steps 1906-1916, are bonded to substrate layer 1710. In some embodiments, bonding one or more protein polyurethane alloy layers (e.g., protein polyurethane alloy layer 1820) to substrate layer 1710 in step 1920 comprises a thermocompression bonding process. In such embodiments, the protein polyurethane alloy layer (e.g., protein polyurethane alloy layer 1820) may be in direct contact with substrate layer 1710. Also, in such embodiments, the protein polyurethane alloy layer may be partially melted into substrate layer 1710, such that upon cooling, the two layers are firmly bonded. In some embodiments, bonding one or more protein polyurethane alloy layers (e.g., protein polyurethane alloy layer 1820) to substrate layer 1710 in step 1920 comprises a lamination process. In such embodiments, lamination can be achieved with adhesive layer 1850. In such embodiments, substrate layer 1710 and / or protein polyurethane alloy layer(s) can be coated with adhesive by known techniques such as slot die molding, kiss coating, drawdown techniques, or reverse transfer coating. In some embodiments, the lamination process can include passing substrate layer 1710 and other layer(s) through rollers under heat.

[0268] In some embodiments, step 1920 can be omitted from method 1900. In such embodiments, the layer(s) formed in steps 1902 through 1916 define a layered material that does not have a protein polyurethane alloy layer or substrate layer 1710.

[0269] In some embodiments, the protein polyurethane alloy layers described herein can have a tear strength in the range of about 2 N to about 30 N, including subranges. For example, the tear strength of the protein polyurethane alloy layer can be about 2 N, about 4 N, about 5 N, about 10 N, about 15 N, about 20 N, about 25 N, or about 30 N, or a range having any two of these values ​​as endpoints, inclusive. In some embodiments, the tear strength can be in the range of about 4 N to about 25 N, about 5 N to about 20 N, or about 10 N to about 15 N.

[0270] Tear strength or tear resistance is a measure of how well a material can withstand the effects of tearing. Tear resistance can be measured by various methods, such as those provided by ASTM D412 or ISO 3377 (also known as "Baumann tear"). The method provided by ASTM D624 can also be used to measure resistance to tear formation and tear propagation. Regardless of the method used, a cut is first made in the tested material sample to induce a tear. The sample is then held between two grips and a uniform pulling force is applied until the sample breaks into two pieces. Tear resistance is then calculated by dividing the applied force by the thickness of the material. Unless otherwise specified, tear strength values ​​reported herein are measured according to ISO 3377.

[0271] In some embodiments, the materials described herein can have a tensile strength in the range of about 1 kPa (kilopascal) to about 100 MPa (megapascal), including subranges. For example, the materials can have a tensile strength of about 1 kPa, about 50 kPa, about 100 kPa, about 200 kPa, about 300 kPa, about 400 kPa, about 500 kPa, about 600 kPa, about 700 kPa, about 800 kPa, about 900 kPa, about 1 MPa, about 5 MPa, about 10 MPa, about 20 MPa, about 30 MPa, about 40 MPa, about 50 MPa, about 60 MPa, about 70 MPa, about 80 MPa, about 90 MPa, or about 100 MPa, or within a range having any two of these values ​​as endpoints, inclusive. In some embodiments, the tensile strength can range from about 50 kPa to about 90 MPa, from about 100 kPa to about 80 MPa, from about 200 kPa to about 70 MPa, from about 300 kPa to about 60 MPa, from about 400 kPa to about 50 MPa, from about 500 kPa to about 40 MPa, from about 600 kPa to about 30 MPa, from about 700 kPa to about 20 MPa, from about 800 kPa to about 10 MPa, or from about 1 MPa to about 5 MPa.

[0272] The softening property, also referred to as the "hand" of a material, can be determined according to ISO 17235. In some embodiments, the outer surface of a material described herein can have a softening property ranging from about 2 mm to about 12 mm, including subranges. For example, the outer surface of a material can have a softening property of about 2 mm, about 3 mm, about 4 mm, about 5 mm, about 6 mm, about 7 mm, about 8 mm, about 9 mm, about 10 mm, about 11 mm, or about 12 mm, or within a range having any two of these values ​​as endpoints, inclusive. In some embodiments, the softening property can be about 3 mm to about 11 mm, about 4 mm to about 10 mm, about 5 mm to about 9 mm, about 6 mm to about 8 mm, or about 6 mm to about 7 mm. Unless otherwise specified, softening property values ​​disclosed herein are determined according to ISO 17235.

[0273] The flexibility or strain of a material can be determined by measuring its elongation at break when a tensile force is applied, for example, using the equation: ΔL / L, where ΔL is the change in length of the material after the tensile force is applied and L is the original length of the material. Flexibility can also be measured according to the method provided by ASTM D412. In some embodiments, the materials described herein can have a flexibility in the range of about 100% to about 400%, including subranges. For example, the materials can have a flexibility of about 100%, about 200%, about 300%, or about 400%, or within a range having any two of these values ​​as endpoints, inclusive. In some embodiments, the flexibility can be about 100% to about 200%, about 100% to about 300%, about 200% to about 300%, or about 200% to about 400%. Unless otherwise specified, flexibility values ​​disclosed herein are measured according to ASTM D412. In some embodiments, the protein polyurethane alloy layers described herein can have flexibility values ​​or ranges as described above for the layered materials.

[0274] In some embodiments, the materials described herein may have a permanent set of about 8% or less in a hysteresis experiment. In some embodiments, the materials may have a permanent set of about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, or about 8%, or a range having any two of these values ​​as endpoints. In some embodiments, the materials may have a permanent set of about 1% to about 8%, about 2% to about 7%, about 3% to about 6%, or about 4% to about 5%.

[0275] Unless otherwise specified, permanent set values ​​are measured by the following method: Cut the material into a dogbone-shaped tensile specimen and measure the original length of the specimen. The specimen is cut to have a dogbone shape with a length of approximately 110 mm and a width of 10 mm (gauge length 75-100 mm). The specimen is then stretched along its length using an INSTRON® machine, both at a constant rate of 3 millimeters per second, to 15% strain and returned to 0% strain. This is repeated five times. The distance between the original specimen length and the specimen length where the load is zero on the final return cycle is then measured. The percent difference between the measured length and the original length after repeatedly straining the material is the % permanent set. For purposes of calculating permanent set values, three separate specimens of the material are evaluated, and the average permanent set value is reported as the permanent set value of the material.

[0276] In some embodiments, the materials described herein have a mass of about 75 g / m 2 / hour or greater. In some embodiments, the materials described herein may have a moisture vapor transmission rate (MVTR) of about 75 g / m², including subranges. 2 / hour~about 200g / m 2 For example, the material may have an MVTR in the range of about 80 g / m 2 / hour ~ approx. 190g / m 2 / hour, about 90g / m 2 / hour ~ approx. 180g / m 2 / hour, about 100g / m 2 / hour ~ approx. 170g / m 2 / hour, approx. 110g / m 2 / hour ~ approx. 160g / m 2 / hour, about 120g / m 2 / hour~about 150g / m 2 / hour, or approximately 130g / m 2 / hour ~ approx. 140g / m 2Unless otherwise specified, the MVTR values ​​disclosed herein are measured using ASTM E96 ("Standard Test Method for Moisture Vapor Transmission Testing of Materials") - Procedure B, Water Method, at about 74.3°F, about 50% relative humidity, and a ¾ inch air gap.

[0277] Materials having water vapor transmission rates as reported herein may be suitable for use in a variety of applications where breathability of the material is a desirable property. Exemplary applications where breathability may be desirable include, but are not limited to, footwear, clothing, and upholstery materials. The layered materials described herein may have significantly higher water vapor transmission rates than layered polymeric materials having the same number of layers with the same thickness and made of the same polymeric material(s), but in which the polymeric material(s) are not blended with a protein.

[0278] In some embodiments, the materials described herein may have a colorfastness of 4 or higher when measured according to the ISO 11640 ("Leather - Color fastness test - Color fastness to back and forth rubbing cycles") wet rub fastness test. In some embodiments, the materials described herein may have a colorfastness of 4, 4.5, or 5 when measured according to the ISO 11640 wet rub fastness test. A colorfastness of 4 or higher may provide the materials described herein with desirable abrasion resistance for various applications.

[0279] The materials described herein can achieve a color fastness of grade 4 or higher, or any other color characteristic described herein, without the inclusion of pigments in the material. This is a unique property compared to polyurethane materials made with the same polyurethane(s) without the protein(s) blended into the polyurethane(s). The proteins in the materials described herein can provide good adhesion to the dyes used to color the material. To achieve high color fastness, polyurethane materials are typically colored with pigments, as dyes generally do not adhere well to polyurethanes. Poor adhesion between the dye and polyurethane results in relatively poor color fastness. The dyed materials described herein can have improved color strength and other aesthetic features not achievable with polyurethanes colored with pigments.

[0280] In some embodiments, dyed materials according to embodiments described herein may have a wet crock value of 3 or greater. In some embodiments, dyed materials according to embodiments described herein may have a wet crock value of 4 or greater. In some embodiments, dyed materials according to embodiments described herein may have a dry crock value of 3 or greater. In some embodiments, dyed materials according to embodiments described herein may have a dry crock value of 4 or greater. Unless otherwise specified, wet crock and dry crock are measured according to ISO 105-X12(2016):Textiles-Tests for color fastness-Part X12:Color fastness to rubbing.

[0281] In some embodiments, dyed materials according to embodiments described herein may have a waterfastness value of 3 or greater. In some embodiments, dyed materials according to embodiments described herein may have a waterfastness value of 4 or greater. In some embodiments, dyed materials according to embodiments described herein may have a sweatfastness value of 3 or greater. In some embodiments, dyed materials according to embodiments described herein may have a sweatfastness value of 4 or greater. Unless otherwise specified, waterfastness is measured according to ISO 11642 IULTCS / IUF 421(2012):Leather—Tests for color fastness—Color fastness to water. Unless otherwise specified, sweat fastness is measured according to ISO 105-E04(2013):Textiles—Tests for color fastness—Part E04:Color fastness to perspiration.

[0282] In some embodiments, dyed materials according to embodiments described herein may have a migration value of 2 or greater. In some embodiments, dyed materials according to embodiments described herein may have a migration value of 4 or greater. In some embodiments, dyed materials according to embodiments described herein may have a migration value of 5 or greater. Unless otherwise specified, migration is measured according to ISO 15701 IULTCS / IUF 442(2015):Leather—Tests for color fastness—Color fastness to migration into polymeric material.

[0283] In some embodiments, dyed materials according to embodiments described herein may have a dry Martindale value of greater than or equal to 2. In some embodiments, dyed materials according to embodiments described herein may have a dry Martindale value of greater than or equal to 3. Unless otherwise specified, dry Martindale is measured according to ISO 12947-4:1998: Textiles—Determination of the abrasion resistance of fabrics by the Martindale method—Part 4:Assessment of appearance change.

[0284] In some embodiments, dyed materials according to embodiments described herein may have a light fastness value of 3 or greater. In some embodiments, dyed materials according to embodiments described herein may have a light fastness value of 4 or greater. Unless otherwise specified, light fastness is measured according to ISO 105-B02(2014):Textiles-Tests for color fastness-Part B02:Color fastness to artificial light:Xenon arc fading lamp test.

[0285] In some embodiments, dyeing materials according to embodiments described herein may have a K / S color intensity value of greater than or equal to 6. In some embodiments, dyeing materials according to embodiments described herein may have a K / S color intensity value of greater than or equal to 7. Unless otherwise specified, K / S color intensity values ​​are measured using a spectrophotometer at the wavelength of the lowest R / T (reflectance to transmittance) value.

[0286] In some embodiments, the materials described herein (e.g., material 1700 or material 1800), or individual layers of the materials described herein, can be subjected to finishing processes the same as or similar to those used to treat natural leather. In some embodiments, the materials described herein can be tumbled or staked to adjust the properties of the material, such as the feel of the material. In such embodiments, traditional textile tumbling and staking methods can be used. In some embodiments, the materials described herein can be tanned. In some embodiments, the materials described herein can be fatliquored. In some embodiments, the materials described herein can be re-tanned.

[0287] In some embodiments, a material described herein (e.g., material 1700 or material 1800), or an individual layer of a material described herein, can have an elastic modulus of 9x10^7 Pa or less. In some embodiments, a material described herein (e.g., material 1700 or material 1800), or an individual layer of a material described herein, can have an elastic modulus of 8x10^7 Pa or less, 7x10^7 Pa or less, 6x10^7 Pa or less, 5x10^7 Pa or less, 4x10^7 Pa or less, 3x10^7 Pa or less, 2x10^7 Pa or less, or 1x10^7 Pa or less. In some embodiments, a material described herein (e.g., Material 1700 or 1800), or an individual layer of a material described herein, can have a modulus of elasticity in the range of 1 x 10^5 Pa to 9 x 10^7 Pa, 5 x 10^5 Pa to 9 x 10^7 Pa, 1 x 10^6 Pa to 9 x 10^7 Pa, 5 x 10^6 Pa to 9 x 10^7 Pa, or 1 x 10^7 Pa to 9 x 10^7 Pa. Unless otherwise specified, modulus values ​​disclosed herein are measured in accordance with ASTM D5934-02 (Determination of Modulus of Elasticity for Rigid and Semi-Rigid Plastic Specimens by Controlled Rate of Loading Using Three-Point Bending) with the following modifications to the test specifications: Rather than using a dual cantilever fixture to collect and average single modulus data points across five different samples as recommended by ASTM D5934-02, an oscillating three-point bending fixture was used with a DMA 850 Dynamic Mechanical Analyzer to apply 37 data points at preset strain percentages and a 1 Hz frequency for 2 minutes to a single sample. The average modulus value of the 37 data points was obtained and reported. To determine the strain percentages of the 37 data points, an amplitude sweep was performed on a sample of the same material to identify the region of stress and strain where the modulus is linear. All 37 data points were taken within the linear region.

[0288] Tanning can be carried out in any number of well-understood ways, including contacting the material with vegetable tanning agents, blocked isocyanate compounds, chromium compounds, aldehydes, syntans, natural resins, tanning oils, or modified oils. Blocked isocyanate compounds may include X-tans. Vegetable tannins may include pyrogallol- or pyrocatechin-based tannins, such as those from valonea, mimosa, marten, tara, oak, pine, sumac, quebracho, and chestnut. Chrome tanning agents may include chromium salts, such as chromium sulfate. Aldehyde tanning agents may include glutaraldehyde and oxazolidine compounds. Syntans may include aromatic polymers, polyacrylates, polymethacrylates, copolymers of maleic anhydride and styrene, condensation products of formaldehyde with melamine or dicyandiamide, lignin, and natural flour.

[0289] To tan a material, the pH of the material can be adjusted, for example, to a pH in the range of about 2.5 to about 3.0 in the presence of 10% salt (e.g., sodium chloride, sodium sulfate, or a sodium salt) to allow penetration of the tanning agent. Following penetration, the pH of the material can be adjusted again, for example, to a pH in the range of about 3.5 to about 4.0 to fix the tanning agent. In some embodiments, the material can be immersed in a bath containing 2 wt. % chromium(III) sulfate (based on the weight of the protein polyurethane alloy in the material), and the pH can be adjusted as needed for penetration and fixation. The material can then be placed in a container, and the container can be agitated, for example, with an orbital shaker at 50 rpm. Agitation can be carried out at a pH of about 2.8 to about 3.2 for a time sufficient to allow penetration of the chromium(III) sulfate into the material. After penetration, the pH of the bath can be increased, and fixation of the chromium(III) sulfate can be carried out at a pH of about 3.8 to about 4.2. The duration of the fixing step can be selected so that the desired color of the material is achieved.

[0290] In some embodiments, the material can be tanned by crosslinking the protein polyurethane alloy. The crosslinking reaction can stabilize the alloy structure. Any suitable crosslinking agent known in the art can be used to crosslink the alloy, such as inorganic salts (such as those based on chromium), formaldehyde, hexamethylene diisocyanate, glutaraldehyde, polyepoxy compounds, gamma irradiation, and ultraviolet irradiation using riboflavin. Other suitable crosslinking agents include isocyanates, carbodiimides, poly(aldehydes), poly(aziridines), inorganic salts, poly(epoxies), enzymes, thiiranes, phenols, novolacs, resoles, and other compounds with chemistries that react with amino acid side chains such as lysine, arginine, aspartic acid, glutamic acid, hydroxyproline, or hydroxylysine. In some embodiments, the crosslinking agent can be selected from the group consisting of epoxy-based crosslinkers, isocyanate-based crosslinkers, and carbodiimide-based crosslinkers. In some embodiments, the crosslinking agent can be a carbodiimide-based crosslinker.

[0291] In some embodiments, after tanning, the material can be re-tanned. Re-tanning refers to post-tanning treatments. Such treatments can include second tanning, wetting (rehydrating the semi-finished material), squeezing (squeezing 45-55% of the water out of the material), dewatering, neutralizing (adjusting the pH of the material to, for example, about 4.5 to about 6.5), adding colorants such as dyes, fatliquoring, fixing unbound chemicals, setting (flattening the grain and removing excess water), seasoning (adding moisture to the material, for example, to a level of about 18-28%), softening (physically softening the material by separating the fibers), buffing (sanding the surface of the material to reduce fuzz and grain defects), shaving (thinning the material), filling (increasing the material's hardness and weight with high-density / high-specific-gravity chemicals), and / or stuffing (adding fats, oils, or waxes).

[0292] In some embodiments, the material may be subjected to a surface coating process, which may include any one or combination of the following processes: oiling (coating the material with one or more raw oils or oils), buffing, spraying, roller coating, curtain coating, sanding, plating, embossing, ironing, or glazing.

[0293] In some embodiments, the fatliquor used during fatliquor addition may comprise a functionalized oil. Suitable fatliquors include anionic fatliquors, cationic fatliquors, nonionic fatliquors, emulsion-based fatliquors, or non-emulsion fatliquors. In some embodiments, the fatliquor may comprise a sulfite fatliquor, a sulfated fatliquor, or a combination thereof.

[0294] In some embodiments, additional lubricants can be incorporated into materials according to embodiments described herein. Additional lubricants include, but are not limited to, fats, biological oils, mineral or synthetic oils, cod oil, polymers, organofunctional siloxanes, or other hydrophobic compounds or agents used to lubricate traditional leathers, or mixtures thereof. Other lubricants can include surfactants, anionic surfactants, cationic surfactants, cationic polymeric surfactants, anionic polymeric surfactants, amphiphilic polymers, fatty acids, modified fatty acids, nonionic hydrophilic polymers, nonionic hydrophobic polymers, polyacrylic acid, polymethacrylic acid, acrylics, natural rubber, synthetic rubber, resins, amphiphilic anionic polymers and copolymers, amphiphilic cationic polymers and copolymers, and mixtures thereof, as well as emulsions or suspensions thereof in water, alcohols, ketones, and other solvents.

[0295] In some embodiments, after fatliquoring, the material may comprise from about 1% to about 16% by weight of one or more fatliquoring agents, including subranges. For example, in some embodiments, the material may comprise from about 1% to about 16%, from about 2% to about 16%, from about 3% to about 16%, from about 4% to about 16%, from about 5% to about 16%, from about 6% to about 16%, from about 7% to about 16%, from about 8% to about 16%, from about 9% to about 16%, or from about 10% to about 16% by weight of one or more fatliquoring agents.

[0296] Surprisingly, materials comprising the protein polyurethane alloys applied to textiles described herein can receive fatliquoring agents at weight percentages ranging from about 1% to about 16% by weight to achieve desired mechanical properties such as softening and flexibility. This is surprising, especially at high protein concentrations, because the addition of protein to a material generally increases the stiffness and rigidity of the material.

[0297] In some embodiments, after fatliquoring, the protein polyurethane alloy may comprise from about 1% to about 16% by weight of one or more fatliquoring agents, including subranges. For example, in some embodiments, the protein polyurethane alloy may comprise from about 1% to about 16% by weight, from about 2% to about 16% by weight, from about 3% to about 16% by weight, from about 4% to about 16% by weight, from about 5% to about 16% by weight, from about 6% to about 16% by weight, from about 7% to about 16% by weight, from about 8% to about 16% by weight, from about 9% to about 16% by weight, or from about 10% to about 16% by weight of one or more fatliquoring agents.

[0298] Surprisingly, the protein polyurethane alloys applied to textiles described herein can accept fatliquoring agents at weight percentages ranging from about 1% to about 16% by weight to achieve desired mechanical properties such as softening and flexibility. This is surprising, especially at high protein concentrations, because adding protein to a material generally increases the stiffness and rigidity of the material.

[0299] In some embodiments, during dehydration, water may be removed by filtration, evaporation, freeze-drying, solvent exchange, vacuum drying, convection drying, heating, irradiation, microwaves, or other known methods for removing water. In some embodiments, the water content of the material after dehydration is about 60% or less by weight of the material, e.g., about 5% or less, about 10% or less, about 15% or less, about 20% or less, about 30% or less, about 35% or less, about 40% or less, about 50% or less, or about 60% or less. Unless otherwise specified, water content is measured by equilibration at 25°C and 1 atm at 65% relative humidity.

[0300] In some embodiments, the tanned material can be mechanically or chemically finished. For example, mechanical finishing can include sanding the material to obtain a glossy surface, ironing and plating the material to achieve a flat and smooth surface, embossing the material to create a three-dimensional print or pattern on the surface of the material, or tumbling the material to provide a more defined grain and smooth surface. Chemical finishing can involve the application of a film, natural or synthetic coating, or other treatment. Chemical treatments can be applied, for example, by spraying, curtain coating, or roller coating.

[0301] In some embodiments, the materials described herein can be used as a substitute for natural leather in a variety of applications. For example, the materials can be used in footwear, clothing, gloves, furniture, vehicle interiors, and other articles and products, such as overcoats, coats, jackets, shirts, trousers, pants, shorts, swimwear, underwear, uniforms, insignia or lettering, costumes, ties, skirts, dresses, blouses, leggings, gloves, mittens, shoes, shoe components, such as soles, waist caps, tongues, cuffs, slits, and cleats, dress shoes, athletic shoes, running shoes, casual shoes, athletic shoe, running shoe or casual shoe components, such as trims, toe caps, outerwear, and other articles and products. Fashion shoes or women's shoes and their components, such as uppers, outer soles, toe springs, toe caps, decorations, toe caps, linings, socks, insoles, platforms, moon shapes, and heels, or high heels, boots, sandals, buttons, sandals, hats, masks, headgear, headbands, head wraps, and belts; jewelry, such as bracelets, watch bands, and necklaces; gloves, umbrellas, canes, wallets, cell phone or wearable computer covers, purses, backpacks, suitcases, handbags, folios, folders, boxes, and other personal objects; athletic, sports, hunting, or recreational equipment, such as saddlery, bridles, reins, bits, thongs, mitts, tennis rackets, golf clubs, polo, hockey, or lacrosse equipment, chess and game boards, medicine balls, kick balls, baseballs, and other types of balls, and toys; bookbindings, book covers, picture frames, or crafts; furniture and home, office, or other indoor or outdoor furnishings, including chairs, sofas, doors, seats, ottomans, screens, coasters, mouse pads, desk blotters, or other pads, tables, beds, floors, wallpaper, or ceiling coverings, flooring, automobile, boat, aircraft, and other vehicle products, including seats, headrests, upholstery, paneling, steering wheel, joystick, or control covers, and other wraps or coverings.

[0302] In some embodiments, a material, a layered material, or an individual layer of a layered material can have a rough exterior surface. For example, the top surface 1824 of protein polyurethane alloy layer 1820 can have a rough surface, the top surface 1874 of top coat layer 1870 can have a rough surface, the top surface 1864 of base coat layer 1860 can have a rough surface, the top surface 1834 of protein polyurethane alloy layer 1830 can have a rough surface, and the top surface 1844 of protein polyurethane alloy layer 1840 can have a rough surface. The rough exterior surface can create a surface texture similar in appearance and feel to that of natural leather (e.g., pebble-grained natural leather). In some embodiments, the top surface 2002 of sacrificial layer 2000 can have a rough surface that is transferred onto the surface of a layer disposed directly on top surface 2002 during method 1900.

[0303] Rough surface is 1 in 2 In other words, in some embodiments, a 1 square inch sample of a material including a layer with a rough exterior surface (e.g., material 1700 or layered material 1800) may have a surface area per square inch that is at least about 1% greater than a 1 square inch sample of a material with a completely smooth surface. In some embodiments, the rough exterior surface may have a surface area per square inch that is at least about 1% greater than a 1 square inch sample of a material with a completely smooth surface. 2 At least about 1% larger than 1 in 2 Approximately 10% larger than 1 in 2 Approximately 20% larger than 1in 2 Approximately 30% larger than 1in 2 Approximately 40% larger than 1in 2 Approximately 50% larger than 1in 2 Approximately 60% larger than 1in 2 Approximately 70% larger than 1in 2 Approximately 80% larger than 1in 2 Approximately 90% larger than 1in 2 Approximately 100% larger than 1in 2 Approximately 150% larger than 1in 2 Approximately 200% larger than 1in 2 Approximately 250% larger than 1in 2 Approximately 300% larger than 1in 2 Approximately 350% larger than 1in2 Approximately 400% larger than 1in 2 Approximately 450% larger than or 1 in 2 In some embodiments, the roughened surface may have a surface area per square inch that is about 500% greater than 1 in , or a surface area per square inch within a range having any two of these values ​​as endpoints, inclusive. 2 Approximately 1% to 1 inch 2 Approximately 500% more than 1 in 2 Approximately 10% more than ~1 inch 2 Approximately 450% more than 1 in 2 Approximately 20% more than ~1 inch 2 Approximately 400% more than 1in 2 Approximately 30% more than ~1 inch 2 Approximately 350% more than 1 in 2 Approximately 40% more than ~1 inch 2 Approximately 300% more than 1 in 2 Approximately 50% more than ~1 inch 2 Approximately 250% more than 1 in 2 Approximately 60% more than ~1 inch 2 Approximately 200% more than 1 in 2 Approximately 70% more than ~1 inch 2 Approximately 150% more than or 1 in 2 Approximately 80% more than ~1 inch 2 The surface area of ​​the materials disclosed herein may be about 100% greater than the surface area per square inch. Unless otherwise specified, the surface area of ​​the materials disclosed herein is measured using profilometry. For opaque materials, optical profilometry is used. In some embodiments, the layered material, or individual layers of the layered material, may have a smooth outer surface. A smooth surface is defined as a surface area per square inch that is greater than or equal to 1 in. 2 For example, a smooth surface has a surface area per square inch that is less than 1% larger than the surface area per square inch of a 2 ~1.01in 2 In some embodiments, the top surface 2002 of the sacrificial layer 2000 may have a smooth surface that is transferred onto the surface of a layer disposed directly on the top surface 2002 during the method 1900.

[0304] In some embodiments, the layered material, or individual layers of the layered material, may have a textured exterior surface. In some embodiments, the top surface 2002 of the sacrificial layer 2000 may have a textured surface that is transferred onto the surface of a layer disposed directly on top surface 2002 during method 1900. In some embodiments, the textured exterior surface may be a surface area per square inch or a range of surface areas per square inch, as described above for rough surfaces.

[0305] In some embodiments, the texture can be a macroscale texture, such as any of the many textures used in Sappi / Warren release paper, commercially available under the trademark ULTRACAST® or the trade name Classic, manufactured by SD Warren Company d / b / a Sappi North America. An example of a macroscale texture is a natural leather grain repeat having a feature depth of about 50 to about 300 microns. Any other desired macroscale texture may be used. In some embodiments, the macroscale texture can be a "leather grain texture." As used herein, the term "leather grain texture" refers to a texture that mimics the look and feel of natural leather. Exemplary "leather grain textures" include, but are not limited to, Sappi Matte Freeport 189, Sappi Freeport 123, or Sappi Expresso 904.

[0306] In some embodiments, the texture can be a microscale texture. In some embodiments, the texture can be a microscale texture with surface features having a feature size of less than 50 microns, e.g., between 1000 nanometers and less than 50 microns. An example of a microscale texture is referred to in the art as a "sharklet." Sharklet textures can be applied to provide products with surfaces configured to inhibit bacterial growth. The surface microscale texture has repeating sharkskin projections arranged in a diamond-shaped pattern with millions of tiny ridges. Sharklet materials are described, for example, in U.S. Patent Nos. 7,650,848 and 8,997,672, the disclosures of which are incorporated herein by reference.

[0307] In some embodiments, the texture can be a nanoscale texture with surface features having a feature size of less than 1000 nanometers, for example, between 10 nanometers and less than 1000 nanometers. An example of a nanoscale texture is a diffraction grating having a series of ridges about 400 nanometers wide, spaced approximately 800 nanometers apart, and having a depth of approximately 100 nanometers.

[0308] The embodiments discussed herein will be further clarified by the following examples, which should be understood to be in no way limiting of the above embodiments.

[0309] Example 1 Samples were prepared by mixing 5.5 g of Hauthaway's waterborne polyurethane dispersion L3360 with 10 mL of deionized water and stirring at 1000 rpm (revolutions per minute) for 30 minutes at 50°C. The solution was then pipetted into a 10 cm diameter Teflon evaporating dish. The dish was dried overnight in a 45°C oven. After drying, the dried sample was conditioned at a standard reference atmosphere (23°C, 50% humidity) for 24 hours to obtain a polyurethane film.

[0310] The films were tested using a TA Instruments DMA-850. A metal die was used to cut 1 cm x 2.5 cm strips from each film. The cut film samples were loaded into film and fiber tension clamps for testing. During testing, a preload of 0.01 N was applied to the cut film samples. The instrument was cooled to -80°C, held for 1 minute, and then the temperature was increased at 4°C / min to 200°C, or until the sample was too weak to hold the tension. During the temperature ramp, the samples were oscillated at a frequency of 1 Hz and 0.1% strain. The storage modulus, loss modulus, and tan(δ) were plotted against temperature for both films. The resulting second storage modulus transition (taken as the onset of the last decrease in measured storage modulus, i.e., the second DMA modulus transition onset temperature) was 114.9°C for the control sample.

[0311] Additionally, five tensile specimens (per ASTM D638) were cut from each dried and conditioned sample film using a metal die. The cut film samples were placed in an INSTRON® 5960 series machine and pulled at a tension of 100 millimeters per minute until failure. The average Young's modulus, average tensile strength (maximum tensile stress), and average elongation at break were recorded. The Young's modulus was 59 MPa, the maximum tensile stress was 12.9 MPa, and the elongation at break was 402%.

[0312] Examples 2 to 8 Examples 2 to 8 were carried out using the same method as Example 1 to demonstrate a range of polyurethane dispersions. The polyurethanes used and the resulting properties are listed in Tables 3 to 6.

[0313] Example 9 Samples were prepared by dissolving 0.825 g (grams) of gelatin from pig skin in 10 mL (milliliters) of deionized water and stirring with a magnetic stir bar at 1000 rpm (revolutions per minute) at 50°C for 1 hour. After complete dissolution of the gelatin, the pH of the solution was adjusted to 7.0 with 0.1 N sodium hydroxide. 5.5 g of L3360 was then added to the solution and stirred at 1000 rpm for 30 minutes. The polyurethane and gelatin solution was then pipetted into a 10 cm diameter Teflon evaporating dish. The dish was dried overnight in a 45°C oven. After drying, the dried sample was conditioned at a standard reference atmosphere (23°C, 50% humidity) for 24 hours to produce a gelatin-polyurethane alloy film.

[0314] Upon pipetting, the gelatin polyurethane solution was milky white in appearance, with no visible particulates. After drying, the gelatin polyurethane solution produced a transparent film with a uniform appearance and no optically visible granules. The combined results of Example 33 and Example 34 demonstrate that when the protein is miscible with the hard phase, the protein polyurethane alloy can be transparent and have enhanced properties.

[0315] DMA testing was performed as outlined in Example 1. The second storage modulus transition (taken as the onset of the last measured decrease in storage modulus, i.e., the second DMA modulus transition onset temperature) obtained for the gelatin polyurethane alloy was 180.6°C, a 65.7°C increase over the control sample described in Example 1.

[0316] Tensile testing was performed as outlined in Example 1. The average Young's modulus was 344 MPa, the average tensile stress measured was 19.8 MPa, and the average elongation at break was 197% for the gelatin polyurethane alloy.

[0317] The increase in the second DMA modulus transition onset temperature for this example, along with the increase in modulus and strength and decrease in extensibility compared to the polyurethane alone in Example 1, indicates that the dissolved gelatin in the gelatin polyurethane alloy is miscible with the hard phase of the polyurethane.

[0318] Examples 10 to 19 Examples 10-19 were carried out using the same method as used in Example 9 to demonstrate a range of polyurethane dispersions from different manufacturers and different proteins. The resulting properties of these alloys are listed in Tables 3-6.

[0319] Example 20 The sample was prepared by dissolving 0.825 g (grams) of Sigma-Aldrich bovine serum albumin (BSA) in 10 mL (milliliters) of deionized water and stirring with a magnetic stir bar at 1000 rpm (revolutions per minute) for 1 hour at 20°C. 5.5 g of L3360 was then added to the solution, which was then stirred at 1000 rpm for 30 minutes. The polyurethane and BSA solution was then pipetted into a 10 cm diameter Teflon evaporating dish. The dish was allowed to dry overnight on a benchtop at 25°C. After drying, the dried sample was conditioned at a standard reference atmosphere (23°C, 50% humidity) for 24 hours to produce a BSA-polyurethane alloy film.

[0320] DMA testing was performed as outlined in Example 1. The second storage modulus transition (taken as the onset of the last measured decrease in storage modulus, i.e., the second DMA modulus transition onset temperature) obtained for the BSA polyurethane alloy was 184.9°C, a 70°C increase over the control sample described in Example 1.

[0321] Tensile testing was performed as outlined in Example 1. The average Young's modulus was 174 MPa, the average tensile stress measured was 11.7 MPa, and the average elongation at break was 123% for the BSA polyurethane alloy.

[0322] Example 21 Soy protein isolate (SPI) was dispersed at a concentration of 0.05 mol / L by adding 0.75 g of SPI to 15 mL of sodium hydroxide solution. The dispersion was stirred with a magnetic stir bar at 600 rpm for 3 hours at 80°C. 5 g of L3360 was then added to the solution and stirred at 600 rpm for 30 minutes. The SPI polyurethane solution was then pipetted into a 10 cm diameter Teflon evaporating dish. The dish was dried overnight in an oven at 45°C. After drying, the dried sample was conditioned at a standard reference atmosphere (23°C, 50% humidity) for 24 hours to produce an SPI polyurethane alloy film.

[0323] DMA testing was performed as outlined in Example 1. The second storage modulus transition obtained for the SPI polyurethane alloy (taken as the onset of the last decrease in measured storage modulus, i.e., the second DMA modulus transition onset temperature) was 186.6°C, a 72°C increase over the Example 1 control.

[0324] Tensile testing was performed as outlined in Example 1. The average Young's modulus was 396 MPa, the average tensile stress measured was 18 MPa, and the average elongation at break was 151% for the SPI polyurethane alloy.

[0325] The increase in the onset temperature of the second DMA modulus transition, along with the increase in modulus and strength and the decrease in elongation, indicates that the dissolved SPI in the SPI polyurethane alloy is miscible with the hard phase of the polyurethane.

[0326] Examples 22 and 23 Examples 22-23 were preformed using the same method as Example 21. The proteins used and the resulting properties of these protein polymer alloys are listed in Tables 3-6.

[0327] Examples 24 to 29 The samples were prepared by the same method as in Example 9. The amounts of gelatin and L3360 were varied to achieve various mass ratios of the two components in the alloy samples. The masses of gelatin and PU dispersion and the resulting mass fractions are summarized in Table 2 below. [Table 2]

[0328] Tensile and DMA tests were performed as outlined in Example 1. The resulting properties of the alloys are listed in Tables 3-6.

[0329] Example 30 Soy protein isolate (SPI) was dispersed by adding 0.25 g of SPI to 15 mL of deionized water. The dispersion was stirred with a magnetic stir bar at 600 rpm for 3 hours at 80°C. 6.42 g of L3360 was then added to the solution and stirred at 600 rpm for 30 minutes. The SPI polyurethane solution was then pipetted into a 10 cm diameter Teflon evaporating dish. The dish was dried overnight in a 45°C oven. After drying, the dried sample was conditioned at a standard reference atmosphere (23°C, 50% humidity) for 24 hours to produce an SPI polyurethane alloy film.

[0330] Tensile and DMA tests were performed as outlined in Example 1. The resulting properties of the alloys are listed in Tables 3-6.

[0331] Example 31 Soy protein isolate (SPI) was dispersed in 15 mL of sodium hydroxide solution at a concentration of 0.05 mol / L by adding 0.5 g of SPI. The dispersion was stirred with a magnetic stir bar at 600 rpm for 3 hours at 80°C. 6.42 g of L3360 was then added to the solution and stirred at 600 rpm for 30 minutes. The SPI polyurethane solution was then pipetted into a 10 cm diameter Teflon evaporating dish. The dish was dried overnight in an oven at 45°C. After drying, the dried sample was conditioned at a standard reference atmosphere (23°C, 50% humidity) for 24 hours to produce an SPI polyurethane alloy film.

[0332] Tensile and DMA tests were performed as outlined in Example 1. The resulting properties of the alloys are listed in Tables 3-6.

[0333] Example 32 Whey protein (Sigma Bovine Whey W1500) was dispersed at a concentration of 0.05 mol / L by adding 0.75 g of whey to 15 mL of sodium hydroxide solution. The dispersion was stirred with a magnetic stir bar at 600 rpm for 3 hours at 80°C. 5 g of L3360 was then added to the solution and stirred at 600 rpm for 30 minutes. The whey polyurethane solution was then pipetted into a 10 cm diameter Teflon evaporating dish. The dish was dried overnight in an oven at 45°C. After drying, the dried sample was conditioned at a standard reference atmosphere (23°C, 50% humidity) for 24 hours to prepare a whey polyurethane alloy film.

[0334] DMA testing was performed as outlined in Example 1. The second storage modulus transition (taken as the onset of the last measured decrease in storage modulus, i.e., the second DMA modulus transition onset temperature) obtained for the whey polyurethane alloy was 100.9°C, a decrease of 14°C compared to the control in Example 1.

[0335] Tensile testing was performed as outlined in Example 1. The average Young's modulus was 105 MPa, the average tensile stress measured was 7.6 MPa, and the average elongation at break was 224% for the whey polyurethane alloy.

[0336] Although whey appears to be miscible with the rigid phase of polyurethane, the second DMA modulus transition temperature was not increased due to the poor thermal stability of the protein itself. As mentioned above, whey has a denaturation temperature of 158°C and is therefore considered non-thermostable.

[0337] Example 33 0.75 g of casein (from bovine milk, Sigma, C7078) was added to 15 mL of deionized water (pH=7) in a 20 mL glass vial without any other additives, stirred at 600 rpm, heated to 90°C, and maintained for 3 hours.

[0338] Next, 5 g of L3360 was added to a 20 mL glass vial. The vial was capped and vortexed at maximum speed for 1 minute. The mixed casein polyurethane solution was then transferred to a 10 cm Teflon dish. The dish was dried in a 45°C oven overnight (16-24 hours).

[0339] After drying, the casein polyurethane alloy film had an opaque appearance with numerous optically visible granules in the film. The tensile properties of this film were measured by measuring five tensile specimens using an INSTRON® 5960 series machine. The samples were pulled at a tension of 100 millimeters per minute until failure. The average tensile strength of the films was 4.96 MPa. The average elongation at break of the films was 12.03%. The average Young's modulus of the films was 158 MPa. These results, along with those of Example 34, indicate that casein is insoluble and does not disperse in water at pH 7, and therefore does not dissolve in L3360 when mixed.

[0340] Example 34 0.75 g of casein (from bovine milk, Sigma, C7078) was dispersed in 15 mL of 0.05 mol / L NaOH deionized water solution in a 20 mL glass vial, stirred at 600 rpm, heated to 90° C., and maintained for 3 hours. A uniform dispersion was obtained.

[0341] Next, 5 g of L3360 was added to a 20 mL glass vial. The vial was then capped and vortexed at maximum speed for 1 minute. The mixed casein polyurethane solution was then transferred to a 10 cm Teflon dish. The dish was dried in a 45°C oven overnight (16-24 hours).

[0342] After drying, the casein polyurethane alloy film had a clear and uniform appearance with no optically visible granules in the film. The tensile properties of this film were measured by measuring five tensile specimens using an INSTRON® 5960 series machine. The samples were pulled at a tension of 100 millimeters per minute until failure. The average tensile strength of the films was 15.5 MPa. The average elongation at break of the films was 160%. The average Young's modulus of the films was 160 MPa. The increased modulus, strength, and extensibility compared to Example 33 indicate that the modified casein is dissolved in the polyurethane and is miscible with the rigid phase of the polyurethane.

[0343] Example 35 0.375 g of soy protein isolate (SPI) and 0.375 g of r-collagen were added to 15 mL of sodium hydroxide solution at a concentration of 0.05 mol / L in a 20 mL glass vial. The soy protein isolate was a soy protein isolate purchased from MP Medicals (IC90545625). The r-collagen was a recombinant collagen from Modern Meadow. The solution in the vial was mixed with a magnetic stir bar at 600 rpm for 2 hours at 80°C.

[0344] Five grams of L3360 was then added to a 20 mL glass vial. The vial was capped and vortexed at maximum speed for 1 minute. The mixed SPI / r-col polyurethane solution was then transferred to a 10 cm Teflon dish. The dish was dried overnight in an oven at 45°C. After drying, the dried sample was conditioned at a standard reference atmosphere (23°C, 50% humidity) for 24 hours to produce an SPI / r-col polyurethane alloy film.

[0345] The tensile properties of this film were measured by measuring five tensile specimens using an INSTRON® 5960 series machine. The samples were pulled to break at a tension of 100 millimeters per minute. The average tensile strength of the films was 15.71 MPa. The average elongation at break of the films was 175.9%. The average Young's modulus of the films was 247.1 MPa. The films were also tested using a TA Instruments DMA-850 according to the method described in Example 1. The resulting second storage modulus transition (taken as the onset of the last decrease in the measured storage modulus, i.e., the second DMA modulus transition onset temperature) for the SPI / r-col polyurethane alloy was 184.9°C.

[0346] Compared to Examples 1 and 9, these results show an increase in the onset temperature of the second DMA modulus transition, along with an increase in modulus and strength and a decrease in elongation, indicating that blends of SPI and r-col in polyurethane alloys are miscible with the hard phase of the polyurethane and show corresponding enhancements in properties.

[0347] Example 36 Using the same method as in Example 35, a film was made with 0.375 g of pea protein MTX5232 from Bobs Red Mills, 0.375 g of r-collagen (recombinant collagen from Modern Meadow), and 5 g of L3360 polyurethane dispersion.

[0348] The resulting protein polyurethane alloy films were tested using the same tensile and DMA test methods as described for Example 35. The average tensile strength of the films was 15.36 MPa. The average elongation at break of the films was 183.17%. The average Young's modulus of the films was 231.13 MPa. The second DMA modulus transition onset temperature of the pea protein / r-col polyurethane alloy was 189.65°C.

[0349] Compared to Example 1 and Example 9, these results show an increase in the onset temperature of the second DMA modulus transition, along with an increase in modulus and strength, indicating that blends of pea protein and r-col in protein polyurethane alloys are miscible with the hard phase of the polyurethane and show a corresponding enhancement in properties.

[0350] Example 37 A gelatin solution was prepared by dissolving 0.825 g (grams) of gelatin from pig skin (Sigma Aldrich G2500) in 10 mL (milliliters) of deionized water and stirring with a magnetic stir bar at 1000 rpm (revolutions per minute) for 1 hour at 50°C. After complete dissolution of the gelatin, the pH of the solution was adjusted to 7.0 with 0.1 N sodium hydroxide. Navy Black #1684 fiber-reactive dye was added to the gelatin solution at 4.05 parts per 100 parts of gelatin and mixed for 15 minutes at 45°C. 5.5 g of L3360 was then added to the solution and stirred at 1000 rpm for 30 minutes. The polyurethane and gelatin solution was then pipetted into a 10 cm diameter Teflon evaporating dish. The dish was dried overnight in a 45°C oven. The resulting film was uniformly dyed, with no phase separation or color differences throughout the sample. A comparable film of the same polyurethane dispersion without protein could not be dyed uniformly.

[0351] Example 38 Chemically modified soy protein solutions (chemically modified SUPRO® XT55 soy protein isolate and chemically modified SUPRO® XT221D soy protein isolate) were prepared by preparing two 5 mL aliquots of 0.1 mol / L sodium hydroxide solution. Once prepared, 40 milligrams (mg) of DABCO (1,4-diazabicyclo[2.2.2]octane) was added to each solution and allowed to dissolve. Once the DABCO was dissolved, 300 mg of poly(ethylene glycol) monoglycidyl ether-550Mn was added to each solution, followed by the addition of 0.75 g of SUPRO® XT55 soy protein isolate to one solution and 0.75 g of SUPRO® XT221D soy protein isolate to the other solution. The solution was stirred at 600 rpm at 65°C for 45 minutes to produce a chemically modified soy protein with much higher solubility in aqueous solution compared to the individual soy proteins in 0.1 mol / L sodium hydroxide alone without modification. The poly(ethylene glycol) monoglycidyl ether-modified protein solution was significantly clearer than the same protein solution without poly(ethylene glycol) monoglycidyl ether, indicating increased solubility. In addition, size exclusion chromatography (SEC) data showed minimal hydrolysis in the soluble modified protein solution, indicating that the protein solubility was due to the protein modification and not hydrolysis caused by the basic conditions used.

[0352] Example 39 Chemically modified soy protein solutions (chemically modified SUPRO® XT55 soy protein isolate and chemically modified SUPRO® XT221D soy protein isolate) were prepared by preparing two 5 mL aliquots of 0.1 mol / L sodium hydroxide solution. Once prepared, 40 mg of DABCO (1,4-diazabicyclo[2.2.2]octane) was added to each solution and allowed to dissolve. Once the DABCO was dissolved, 300 mg of poly(ethylene glycol) diglycidyl ether-550Mn was added to the solutions, followed by 0.75 g of SUPRO® XT55 soy protein isolate to one solution and 0.75 g of SUPRO® XT221D soy protein isolate to the other solution. The solution was stirred at 600 rpm at 65°C for 45 minutes to produce a soy protein with much higher solubility in aqueous solution compared to the individual soy proteins in 0.1 mol / L sodium hydroxide alone without modification. The poly(ethylene glycol) diglycidyl ether-modified protein solution was significantly clearer than the same protein solution without poly(ethylene glycol) diglycidyl ether, indicating increased solubility. In addition, SEC data showed minimal hydrolysis in the soluble modified soy protein solution, indicating that the protein solubility was due to the protein modification and not hydrolysis caused by the basic conditions used.

[0353] Example 40 SUPRO® XT55 soy protein isolate (SPI) was dispersed in 5 mL of sodium hydroxide solution at a concentration of 0.1 mol / L by adding 0.75 g of SPI. The dispersion was stirred with a magnetic stir bar at 600 rpm at 65°C for 2 hours. HeiQ Chemtex 2317 (anionic surfactant) was added at 5 parts per 100 parts by weight of protein. 5 g of L3360 was then added to the solution and stirred at 600 rpm for 30 minutes. The SPI polyurethane solution was then pipetted into a 10 cm diameter Teflon evaporating dish. The dish was dried overnight in a 45°C oven. After drying, the dried sample was conditioned at a standard reference atmosphere (23°C, 50% humidity) for 24 hours to produce an SPI polyurethane alloy film.

[0354] Example 41 The gelatin solution was prepared by dissolving 3.885 g of gelatin from pig skin (Sigma Aldrich G2500) in 22 mL of deionized water and stirring at 450 rpm with an overhead impeller mixer at 50°C for 1 hour. After complete dissolution of the gelatin, the pH of the solution was adjusted to 7.0 with 1 N sodium hydroxide. After pH adjustment, antimicrobial Ultra-Fresh DW-56 was added at 1.2 parts per 100 parts by weight of the gelatin solution. The solution was then mixed at 50°C for 10 minutes to ensure good dispersion of all components. After 10 minutes, 15 mL of the solution was aliquoted and Antifoam 204 (a mixture of organic polyether dispersions from Sigma Aldrich) was added at 0.5 parts per 100 parts of estimated final solution weight. The aliquoted solution was mixed at 50°C for 10 minutes to ensure good dispersion of all components. 25.885 g of L3360 was then added to the solution. After the addition of L3360, the solution was mixed until it reached a temperature of 43°C to 45°C.

[0355] To another aliquot of the solution was added 5.5 parts per 100 parts of solution weight of HeiQ Chemtex 2216-T (a stabilizing blend of nonionic and anionic surfactants), and 2.2 parts per 100 parts of HeiQ Chemtex 2317 (a stabilizing blend of nonionic and anionic surfactants), along with 0.1 parts per 100 parts of HeiQ Chemtex 2243 (a nonionic silicone dispersion). The solution was then mechanically whipped and frozen at a temperature of 43° C. to 45° C. until a wet density of 650 g / L to 850 g / L was reached, thereby forming a foamed blend mixture.

[0356] Surface finishes including topcoats and basecoats were prepared to create press skins of protein polyurethane alloys. The topcoat blend was made by blending 9.74 parts Stahl Melio WF-5227.A LIQ, 100 parts Stahl WT-42-511, 30 parts Stahl DI-17-701, 30 parts Stahl XR-13-820, and 25 parts water. The basecoat blend was made by blending 450 parts Stahl RC-43-023, 50 parts Stahl RU-3901, 150 parts Stahl RA-30, 50 parts Stahl FI-1208, 30 parts Stahl XR-13-820, and 100 parts Stahl RA-22-063.

[0357] The blended non-foamed solution was deposited onto the dried press skin using a drawdown device at a target wet thickness of 200 gsm, and dried in a Mathis LTE-S Labcoater at 75 ° C, 2000 rpm, and 70% air blown from below the sample for 15 minutes to form a protein polyurethane alloy layer. After this first layer was dried, a second layer of the blended foamed solution was deposited onto the first layer at a target wet thickness of 350 gsm, and dried in a Mathis LTE-S Labcoater at 75 ° C for 5 minutes, then 100 ° C for 5 minutes, and finally 120 ° C for 5 minutes, with an air speed of 700 rpm, and 70% air blown from below for 15 minutes in a gradient drying procedure to form a first foamed protein polyurethane alloy layer. After the foam layer was dried, a third layer of the blended foam solution was deposited onto the first foam layer at a target wet thickness of 350 gsm and dried in a Mathis LTE-S Labcoater at 75°C for 5 minutes, then 100°C for 5 minutes, and finally at 120°C for 15 minutes at an air speed of 700 rpm with 70% air blown from below in a gradient drying procedure to form a second foamed protein polyurethane alloy layer.

[0358] After the samples were thoroughly dried and conditioned in a conditioning chamber at 23°C and 50% humidity for 24 hours, they were cut and tested according to the DMA and tensile mechanical property tests described herein. The resulting second storage modulus transition (taken as the onset of the last measured decrease in storage modulus, i.e., the second DMA modulus transition onset temperature) was 190°C, with a Young's modulus of 88.9 MPa, a tensile stress of 5.4 MPa, and an elongation at break of 110%.

[0359] Example 42 The sample was prepared by dissolving 1 g of 50 kDa rCol in 5 mL of deionized water and stirring with a magnetic stir bar at 1000 rpm for 1 hour at 20 °C. The 50 kDa rCol protein was a collagen fragment prepared by Modern Meadow, with the amino acid sequence listed as SEQ ID NO:2. After stirring for 1 hour, 6.7 g of L3360 was added to the solution and stirred at 1000 rpm for 30 minutes. The polyurethane and 50 kDa rCol solution was then pipetted into a 10 cm diameter Teflon evaporating dish. The dish was dried overnight in a 45 °C oven. After drying, the dried sample was conditioned at a standard reference atmosphere (23 °C, 50% humidity) for 24 hours to produce a 50 kDa rCol polyurethane alloy film.

[0360] DMA testing was performed as outlined in Example 1. The second storage modulus transition (taken as the onset of the last decrease in measured storage modulus, i.e., the second DMA modulus transition onset temperature) obtained for the 50 KDa rCol polyurethane alloy was 177.8°C, a 62.9°C increase over the control sample described in Example 1.

[0361] Tensile testing was carried out as outlined in Example 1. The average Young's modulus was 161 MPa, the average measured tensile stress was 17 MPa, and the average elongation at break was 173% for the 50 KDa rCol polyurethane alloy.

[0362] Example 43 Samples were prepared by dissolving 1 g of native Trichoderma species cellulase (Cellulase-RG) available from CREATIVE ENZYMES® in 5 mL of deionized water and stirring with a magnetic stir bar at 1000 rpm for 1 hour at 20°C. After stirring for 1 hour, 11.4 g of L3360 was added to the solution and stirred at 1000 rpm for 30 minutes. The polyurethane and cellulase solution was then pipetted into a 10 cm diameter Teflon evaporating dish. The dish was dried overnight in a 45°C oven. After drying, the dried sample was conditioned at a standard reference atmosphere (23°C, 50% humidity) for 24 hours to produce a cellulase-polyurethane alloy film.

[0363] DMA testing was performed as outlined in Example 1. The second storage modulus transition (taken as the onset of the last decrease in measured storage modulus, i.e., the second DMA modulus transition onset temperature) obtained for the Celluase-RG polyurethane alloy was 153.1°C, a 38.2°C increase over the control sample described in Example 1.

[0364] Tensile testing was performed as outlined in Example 1. The average Young's modulus was 184 MPa, the average tensile stress measured was 14.7 MPa, and the average elongation at break was 252% for the cellulase polyurethane alloy.

[0365] Example 44 Samples were prepared by dissolving 1 g of laboratory-grade cellulase (Cellulase-IG) available from Carolina Biological Supply Company in 5 mL of deionized water and stirring with a magnetic stir bar at 1000 rpm for 1 hour at 20°C. After stirring for 1 hour, 11.4 g of L3360 was added to the solution and stirred at 1000 rpm for 30 minutes. The polyurethane and cellulase solution was then pipetted into a 10 cm diameter Teflon evaporating dish. The dish was dried overnight in a 45°C oven. After drying, the dried sample was conditioned at a standard reference atmosphere (23°C, 50% humidity) for 24 hours to produce a cellulase-polyurethane alloy film.

[0366] DMA testing was performed as outlined in Example 1. The second storage modulus transition (taken as the onset of the last measured decrease in storage modulus, i.e., the second DMA modulus transition onset temperature) obtained for the Cellulase-IG polyurethane alloy was 122.1°C, a 7.2°C increase over the control sample described in Example 1.

[0367] Tensile testing was performed as outlined in Example 1. The average Young's modulus was 84 MPa, the average tensile stress measured was 15.1 MPa, and the average elongation at break was 286% for the cellulase polyurethane alloy.

[0368] Example 45 Two control samples (Example 45a and Example 45b) were each prepared according to the following process: 0.4 g of AF-715 (a defoamer available from Quaker Color) was mixed into 38 g of a water-borne polyurethane dispersion, Hauthane HD-2001, manufactured by CL Hauthaway & Sons Corporation. The mixture was mixed using an impeller at a speed of 500 rpm and allowed to stir at room temperature for 5 minutes. After the mixture was properly mixed, 0.6 g of BORCHI® Gel L 75 N was added to increase the viscosity of the mixture, and the mixture was allowed to mix for 5 minutes. The mixture was then coated onto release paper using a Mathis LTE-S Labcoater coater and dried at 75°C for 10 minutes and 100°C for 10 minutes. The coating was then removed from the release paper to produce a protein-free polyurethane film.

[0369] After drying, the thickness of the sample of Example 45a was 0.4 mm and the thickness of the sample of Example 45b was 0.4 mm. As reported in Table 7, the polyurethane film of Example 45a had a thickness of 30 g / m 2 / 24 hour water vapor transmission rate, and the polyurethane film of Example 45b has a water vapor transmission rate of 38 g / m 2 It had a water vapor transmission rate of 1 / 24 hours.

[0370] Example 46 Two samples (Example 46a and Example 46b) were each prepared according to the following process. 13.25 g of gelatin from pig skin was dissolved in a solution of 2 g of antimicrobial Ultra-Fresh DW-56, 0.8 g of AF-715 (an antifoaming agent available from Quaker Color), and 75 mL of water at 50°C. The solution was stirred with an impeller at 500 rpm until the gelatin was completely dissolved. The pH of the solution was then increased with 1 M NaOH until a pH of 8-9 was achieved. After adjusting the pH, 77 g of water-borne polyurethane dispersion Hauthane HD-2001 (manufactured by CL Hauthaway & Sons Corporation) was added to the gelatin solution and stirred for 15 minutes. After the gelatin and polyurethane solution were properly mixed, 1 g of RM-4410 (manufactured by Stahl) was added to increase the viscosity of the solution, and the solution was mixed for 5 minutes. This solution was then coated onto a 0.35 mm thick microsuede textile, the surface of which was coated with a thin IMPRANIL® DLS coating layer (0.03 mm thick). The gelatin-polyurethane solution was coated onto the thin IMPRANIL® DLS coating layer using a handheld drawdown device and dried under standard ambient conditions (23°C and 50% humidity) to produce a gelatin-polyurethane film with a textile backing. The thin IMPRANIL® DLS coating was used to prevent the gelatin-polyurethane coating from penetrating too deeply into the microsuede textile.

[0371] After drying, the thickness of the sample of Example 46a was 0.77 mm (which was the sum of the thicknesses of the gelatin-polyurethane film, the thin IMPRANIL® DLS coating, and the microsuede textile), and the thickness of the sample of Example 46b was 0.82 mm (which was the sum of the thicknesses of the gelatin-polyurethane film, the thin IMPRANIL® DLS coating, and the microsuede textile).

[0372] As reported in Table 7, the sample of Example No. 46a was 180 g / m 2 / 24 hour water vapor transmission rate, which is 150 g / m compared to the sample of Example No. 45a 2 / 24 hour increase of 142 g / m compared to the sample of Example No. 45b 2 Also as reported in Table 7, the sample of Example No. 46b had an increase of 138 g / m 2 / 24 hour water vapor transmission rate, which is 108 / m compared to the sample of Example No. 45a. 2 / 24 hour increase of 100 g / m compared to the sample of Example No. 45b 2 / 24 hour increase.

[0373] Neither the thin IMPRANIL® DLS coating nor the microsuede textile significantly affected the water vapor transmission rate of Samples No. 46a or No. 46b. In other words, the water vapor transmission rates reported in Table 7 reflect the water vapor transmission rate of the gelatin-polyurethane film alone.

[0374] Example 47 Two control samples (Example 47a and Example 47b) were each prepared according to the following process: 0.4 g of AF-715 (a defoamer available from Quaker Color) was mixed into 38 g of Hauthaway's water-borne polyurethane dispersion L3360. The mixture was mixed using an impeller at a speed of 500 rpm and stirred at room temperature for 5 minutes. After the mixture was properly mixed, 0.6 g of BORCHI® Gel L 75 N was added to increase the viscosity of the mixture, and the mixture was mixed for 5 minutes. The mixture was then coated onto release paper using a Mathis LTE-S Labcoater coater and dried at 75°C for 10 minutes and 100°C for 10 minutes. The coating was then removed from the release paper to produce a protein-free polyurethane film.

[0375] After drying, the sample of Example 47a had a thickness of 0.32 mm and the sample of Example 47b had a thickness of 0.36 mm. As reported in Table 7, the polyurethane film of Example 47a had a thickness of 23 g / m 2 / 24 hour water vapor transmission rate, and the polyurethane film of Example 47b has a water vapor transmission rate of 27 g / m 2 It had a water vapor transmission rate of 1 / 24 hours.

[0376] Example 48 Two samples (Example 48a and Example 48b) were each prepared according to the following process. 13.25 g of gelatin from pig skin was dissolved in a solution of 2 g of antimicrobial Ultra-Fresh DW-56, 0.8 g of AF-715 (an antifoaming agent available from Quaker Color), and 75 mL of water at 50°C. The solution was stirred with an impeller at 500 rpm until the gelatin was completely dissolved. The pH of the solution was then increased with 1 M NaOH until a pH of 8-9 was achieved. After adjusting the pH, 77 g of water-borne polyurethane dispersion L3360 from Hauthaway was added to the gelatin solution and stirred for 15 minutes. After the gelatin and polyurethane solution were properly mixed, 1 g of RM-4410 from Stahl was added to increase the viscosity of the solution, and the solution was mixed for 5 minutes. This solution was then coated onto a 0.35 mm thick microsuede textile, the surface of which was coated with a thin IMPRANIL® DLS coating layer (0.03 mm thick). The gelatin and polyurethane solution was coated onto the thin IMPRANIL® DLS coating layer using a handheld drawdown device and dried under standard ambient conditions (23°C and 50% humidity) to produce a gelatin-polyurethane film with a textile backing. The thin IMPRANIL® DLS coating was used to prevent the gelatin-polyurethane coating from penetrating too deeply into the microsuede textile.

[0377] After drying, the thickness of the sample of Example 48a was 0.77 mm (which was the sum of the thicknesses of the gelatin-polyurethane film, the thin Impranil® DLS coating, and the microsuede textile), and the thickness of the sample of Example 48b was 0.84 mm (which was the sum of the thicknesses of the gelatin-polyurethane film, the thin Impranil® DLS coating, and the microsuede textile).

[0378] As reported in Table 7, the sample of Example No. 48a had a viscosity of 117 g / m 2 / 24 hour water vapor transmission rate, which is 94 g / m compared to the sample of Example No. 47a. 2 / 24 hour increase of 90 g / m compared to the sample of Example No. 47b 2 Also reported in Table 7, the sample of Example 48b had an increase of 74 g / m 2 / 24 hour water vapor transmission rate, which is 51 g / m compared to the sample of Example No. 47a. 2 / 24 hour increase of 47 g / m compared to the sample of Example No. 47b 2 / 24 hour increase.

[0379] Neither the thin IMPRANIL® DLS coating nor the microsuede textile significantly affected the water vapor transmission rate of Samples No. 46a or No. 46b. In other words, the water vapor transmission rates reported in Table 7 reflect the water vapor transmission rate of the gelatin-polyurethane film alone.

[0380] Example 49 Two control samples (Example 49a and Example 49b) were each prepared according to the following process: 0.2 g of AF-715 (a defoamer available from Quaker Color) was mixed into 38 g of Hauthaway's water-borne polyurethane dispersion L3360. The mixture was mixed for 5 minutes at 500 rpm using an impeller. After the mixture was properly mixed, 0.6 g of BORCHI® Gel L 75 N was added to increase the viscosity of the mixture, and the mixture was mixed again for 5 minutes. The polyurethane mixture was then coated onto release paper using a Mathis LTE-S Labcoater and dried at 75°C for 10 minutes and 100°C for 10 minutes.

[0381] A foam solution was then prepared by mixing Hauthaway's waterborne polyurethane dispersion L3360 with HeiQ Chemtex 2216-T (3% by solution weight), HeiQ Chemtex 2317 (3% by solution weight), HeiQ Chemtex 2241-A (1% by solution weight), and HeiQ Chemtex 2243 (0.1% by solution weight). The mixture was stirred at 500 rpm for 5 minutes at room temperature using an impeller. The mixture was then foamed to create a foam mixture with a wet density of 700 g / L to 900 g / L. The foam mixture was coated onto the previously coated polyurethane layer using a Mathis LTE-S Labcoater and dried at 75°C for 10 minutes and 100°C for 10 minutes. After this first foam coating was dried, a second foam coating layer made from the same foam mixture was coated onto the first foam coating using the same conditions. After the second foam layer dried, the three-layer sample was removed from the release paper.

[0382] The three-layer sample of Example 49a had a thickness of 0.23 mm, and the three-layer sample of Example 49b had a thickness of 0.24 mm. As reported in Table 7, the three-layer sample of Example 49a had a thickness of 83 g / m 2 / 24 hour moisture vapor transmission rate, and the three-layer sample of Example 49b had a moisture vapor transmission rate of 87 g / m 2It had a water vapor transmission rate of 1 / 24 hours.

[0383] Example 50 Two samples (Example 50a and Example 50b) were each prepared according to the following process: 5.3 g of SUPRO® XT221D soy protein isolate was mixed with 30 g of water. The pH of the mixture was then increased with 1 M NaOH until a pH of 8-9 was achieved. After adjusting the pH, Ultra-Fresh DW-56 (15 wt. % based on the amount of soy protein isolate material) and AF-715 antifoam agent (1 wt. % based on the solution weight) were added to the mixture, and the mixture was stirred at 500 rpm with an impeller until the soy protein isolate was completely dissolved. Once the soy protein isolate was completely dissolv...

Claims

1. Textiles and, A protein polyurethane alloy arranged on a textile, comprising a protein polyurethane alloy containing protein dissolved within the polyurethane, One or more fatliquoring agents in an amount of approximately 1% to 16% by weight, Materials, including.

2. The material according to claim 1, wherein the protein polyurethane alloy contains more than 50% by weight of the protein.

3. The material according to claim 1, wherein the protein polyurethane alloy contains about 60% to about 90% by weight of the protein.

4. The material according to any one of claims 1 to 3, wherein the one or more fatliquoring agents include a functionalized oil.

5. The material according to any one of claims 1 to 3, wherein the one or more fatliquoring agents are selected from the group consisting of sulfite-containing fatliquoring agents, sulfite-containing fatliquoring agents, or combinations thereof.

6. A material according to any one of claims 1 to 3, having an elastic modulus of 9 × 10^7 Pa or less.

7. A material according to any one of claims 1 to 3, having an elastic modulus of 6 × 10^7 Pa or less.

8. Textiles and, A protein polyurethane alloy containing proteins dissolved within polyurethane, A first portion having a first protein polyurethane alloy density, A second portion having a second protein polyurethane alloy density different from the first protein polyurethane alloy density, Materials, including.

9. The material according to claim 8, wherein the density of the first protein polyurethane alloy is 5% or more less or greater than the density of the second protein polyurethane alloy.

10. The material according to claim 8 or 9, wherein the first portion comprises a first protein polyurethane alloy layer, and the second portion comprises a second protein polyurethane alloy layer.

11. The material according to claim 10, The textile includes a top surface and a bottom surface, The first protein polyurethane alloy layer is disposed on the upper surface of the textile, The second protein polyurethane alloy layer is placed on the bottom surface of the textile. material.

12. A material according to claim 8 or claim 9, The first portion comprises the protein polyurethane alloy integrated into the textile at the first protein polyurethane alloy density, The second portion includes the protein polyurethane alloy integrated into the textile at the second protein polyurethane alloy density, material.

13. A material according to claim 8 or claim 9, The textile includes a first textile layer bonded to a second textile layer. The first portion comprises the protein polyurethane alloy integrated into the first textile layer at the first protein polyurethane alloy density, The second portion comprises the protein polyurethane alloy integrated into the second textile layer at the second protein polyurethane alloy density, material.

14. The material according to claim 8 or 9, further comprising a crosslinking agent selected from the group consisting of epoxy crosslinking agents, isocyanate crosslinking agents, and carbodiimide crosslinking agents.

15. The material according to claim 14, wherein the crosslinking agent is a carbodiimide-based crosslinking agent.

16. Water and, Aqueous polyurethane dispersion and Proteins and, One or more coloring dyes in an amount of approximately 4% to 10% by weight, Foam stabilizer and Aqueous formulations containing the above.

17. The formulation according to claim 16, wherein the protein is dissolved in the polyurethane of the polyurethane dispersion.

18. Textiles and, A protein polyurethane alloy integrated into the aforementioned textile, comprising a protein polyurethane alloy containing protein dissolved within the polyurethane, A coloring dye comprising one or more coloring dyes in an amount of approximately 100% to approximately 250% by weight, wherein the weight percentage of the one or more coloring dyes is measured relative to the weight of the protein in the protein polyurethane alloy, Materials, including.

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