Protein polyurethane alloy and layered material containing the same

Abstract

A protein polyurethane alloy containing one or more proteins dissolved in one or more polyurethanes may have one or more mechanical properties superior to those of polyurethanes in the absence of the protein. The protein polyurethane alloy may be incorporated into a layered material containing one or more protein polyurethane alloy layers.

Description

[Technical Field]

[0001] (Reference to electronically submitted sequence listings) The contents of the sequence listing (name: 4431_068PC03_Seqlisting_ST25.txt, size: 4,936 bytes, and date of creation: April 22, 2021), submitted electronically as an ASCII text file with this application, are incorporated herein by reference in their entirety.

[0002] (Field of Invention) This disclosure relates to protein polyurethane alloys comprising one or more proteins dissolved in polyurethane. In certain embodiments, this disclosure relates to protein polyurethane alloys comprising one or more proteins dissolved only in the rigid phase of the polyurethane. In some embodiments, the protein polymer alloys may have an appearance, feel, and aesthetic and / or mechanical properties similar to natural leather and may be used to produce articles and items previously 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 an interior decoration material, the apparel industry where leather is used to manufacture trousers and jackets, the footwear industry where leather is used to prepare casual and dress shoes, the luggage industry, the handbag and accessories industry, and the automotive industry. Global trade in leather is high, and there is a continuing and increasing demand for leather products. However, there are various costs, constraints, and social concerns associated with the production of natural leather. First and foremost, natural leather is produced from animal hides, and therefore requires the raising and slaughter of livestock. Raising livestock requires vast amounts of feed, pastureland, water, and fossil fuels, contributing to the pollution of the air and waterways by greenhouse gases such as methane. Leather production also raises social concerns related to the processing of animals. In recent years, there has also been a decline in the availability of conventionally high-quality hides, which has been fairly well-established. For at least these reasons, alternative means of meeting the demand for leather are desirable. [Overview of the project] [Means for solving the problem]

[0004] This disclosure provides a protein polyurethane alloy suitable for use in a variety of applications, including as a substitute for natural leather.

[0005] The first embodiment (1) of this disclosure relates to a protein polyurethane alloy containing a protein dissolved in polyurethane, wherein the protein is a protein other than soy protein.

[0006] In the second embodiment (2), the protein polyurethane alloy of the first embodiment (1) has a dynamic mechanical analysis (DMA) tan(δ) peak at temperatures ranging from about -60°C to about 30°C, and a second DMA modulus transition onset temperature ranging from about 120°C to about 200°C.

[0007] In the third embodiment (3), the protein polyurethane alloy of the first embodiment (1) or the second embodiment (2) is transparent.

[0008] In the fourth embodiment (4), the polyurethane of the protein polyurethane alloy described in any one of embodiments (1) to (3) has a Young's modulus in the absence of protein, and the protein polyurethane alloy has a Young's modulus that is greater than the Young's modulus of polyurethane in the absence of protein, ranging from about 10% to about 600%.

[0009] In the fifth embodiment (5), the polyurethane of the protein polyurethane alloy described in any one of embodiments (1) to (3) has a Young's modulus in the absence of protein, and the protein polyurethane alloy has a Young's modulus that is about 40% to about 600% greater than the Young's modulus of the polyurethane in the absence of protein.

[0010] In the sixth embodiment (6), the polyurethane of the protein polyurethane alloy described in any one of embodiments (1) to (5) has a Young's modulus in the absence of protein, and the protein polyurethane alloy has a Young's modulus greater than that of the polyurethane in the absence of protein, in the range of about 10 MPa to about 350 MPa.

[0011] In the seventh embodiment (7), the polyurethane of the protein polyurethane alloy described in any one of embodiments (1) to (5) has a Young's modulus in the absence of protein, and the protein polyurethane alloy has a Young's modulus that is greater than the Young's modulus of the polyurethane in the absence of protein, in the range of about 25 MPa to about 350 MPa.

[0012] In the eighth embodiment (8), the polyurethane of the protein polyurethane alloy described in any one of embodiments (1) to (5) has a Young's modulus in the absence of protein, and the protein polyurethane alloy has a Young's modulus greater than that of the polyurethane in the absence of protein, in the range of about 100 MPa to about 350 MPa.

[0013] In the ninth embodiment (9), the protein polyurethane alloy described in any one of embodiments (1) to (8) has a Young's modulus in the range of about 50 MPa to about 450 MPa.

[0014] In the tenth embodiment (10), the protein polyurethane alloy described in any one of embodiments (1) to (8) has a Young's modulus in the range of about 75 MPa to about 450 MPa.

[0015] In the eleventh embodiment (11), the polyurethane of the protein polyurethane alloy described in any one of embodiments (1) to (10) has a second DMA modulus transition onset temperature in the absence of protein, and the protein polyurethane alloy has a second DMA modulus transition onset temperature in a range of Celsius that is about 5% to about 70% greater than the second DMA modulus transition onset temperature of the polyurethane in the absence of protein.

[0016] In the twelfth embodiment (12), the polyurethane of the protein polyurethane alloy described in any one of embodiments (1) to (10) has a second DMA modulus transition onset temperature in the absence of protein, and the protein polyurethane alloy has a second DMA modulus transition onset temperature in a range of Celsius that is about 15% to about 70% greater than the second DMA modulus transition onset temperature of the polyurethane in the absence of protein.

[0017] In the 13th embodiment (13), the polyurethane of the protein polyurethane alloy described in any one of embodiments (1) to (12) has a second DMA modulus transition onset temperature in the absence of protein, and the protein polyurethane alloy has a second DMA modulus transition onset temperature in a range that is greater 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.

[0018] In the 14th embodiment (14), the polyurethane of the protein polyurethane alloy described in any one of embodiments (1) to (12) has a second DMA modulus transition onset temperature in the absence of protein, and the protein polyurethane alloy has a second DMA modulus transition onset temperature in a range of about 20°C to about 80°C that is greater than the second DMA modulus transition onset temperature of the polyurethane in the absence of protein.

[0019] In the 15th embodiment (15), the polyurethane of the protein polyurethane alloy described in any one of embodiments (1) to (12) has a second DMA modulus transition onset temperature in the absence of protein, and the protein polyurethane alloy has a second DMA modulus transition onset temperature in a range of about 40°C to about 80°C that is greater than the second DMA modulus transition onset temperature of the polyurethane in the absence of protein.

[0020] In the sixteenth embodiment (16), the protein polyurethane alloy described in any one of embodiments (1) to (15) has a second DMA modulus transition onset temperature in the range of about 130°C to about 200°C.

[0021] In the 17th embodiment (17), the protein polyurethane alloy described in any one of embodiments (1) to (15) has a second DMA modulus transition onset temperature in the range of about 165°C to about 200°C.

[0022] In the eighteenth embodiment (18), the protein of the protein polyurethane alloy described in any one of embodiments (1) to (17) has an isoelectric point in the range of about 4 to about 5 and a lysine weight percent in the range of about 1% to about 100% by weight.

[0023] In the 19th embodiment (19), the polyurethane of the protein polyurethane alloy described in any one of embodiments (1) to (18) has a tensile strength in the absence of protein, and the protein polyurethane alloy has a tensile strength that is about 5% to about 55% greater than the tensile strength of polyurethane in the absence of protein.

[0024] In the 20th embodiment (20), the polyurethane of the protein polyurethane alloy described in any one of embodiments (1) to (18) has a tensile strength in the absence of protein, and the protein polyurethane alloy has a tensile strength that is about 15% to about 55% greater than the tensile strength of the polyurethane in the absence of protein.

[0025] In the 21st embodiment (21), the polyurethane of the protein polyurethane alloy described in any one of embodiments (1) to (20) has a tensile strength in the absence of protein, and the protein polyurethane alloy has a tensile strength in the range of about 2 MPa to about 8 MPa that is greater than the tensile strength of polyurethane in the absence of protein.

[0026] In the 22nd embodiment (22), the polyurethane of the protein polyurethane alloy described in any one of embodiments (1) to (20) has a tensile strength in the absence of protein, and the protein polyurethane alloy has a tensile strength in the range of about 5 MPa to about 8 MPa that is greater than the tensile strength of polyurethane in the absence of protein.

[0027] In the 23rd embodiment (23), the protein polyurethane alloy described in any one of embodiments (1) to (22) has a tensile strength in the range of about 7 MPa to about 21 MPa.

[0028] In the 24th embodiment (24), the protein polyurethane alloy described in any one of embodiments (1) to (23) comprises about 10% to about 50% by weight of protein and about 50% to about 90% by weight of polyurethane.

[0029] In the 25th embodiment (25), the protein polyurethane alloy described in any one of embodiments (1) to (23) comprises about 20% to about 35% by weight of protein and about 65% to about 80% by weight of polyurethane.

[0030] In the 26th embodiment (26), the protein of the protein polyurethane alloy described in any one of embodiments (1) to (25) is a protein other than collagen.

[0031] In the 27th embodiment (27), the polyurethane of the protein polyurethane alloy described in any one of embodiments (1) to (26) has a water vapor permeability in the absence of protein, and the protein polyurethane alloy has a water vapor permeability that is greater than the water vapor permeability of the polyurethane in the absence of protein, ranging from about 20% to about 600%.

[0032] In the 28th embodiment (28), the polyurethane of the protein polyurethane alloy described in any one of embodiments (1) to (27) has a water vapor permeability in the absence of protein, and the protein polyurethane alloy has a water vapor permeability about 30 g / m² higher than that of the polyurethane in the absence of protein. 2 / 24 hours ~ approx. 500g / m 2 It has a high water vapor transmission rate over a 24-hour period.

[0033] In the 29th embodiment (29), the protein polyurethane alloy described in any one of embodiments (1) to (28) is approximately 30 g / m² / 24 hours to approximately 1000 g / m² 2 It has a water vapor transmission rate over a 24-hour period.

[0034] The 30th embodiment (30) relates to a soy protein polyurethane alloy containing soy protein dissolved in polyurethane, wherein the soy protein polyurethane alloy has a dynamic mechanical analysis (DMA) tan(δ) peak at temperatures in the range of about -60°C to about 30°C and a second DMA modulus transition onset temperature in the range of about 130°C to about 200°C.

[0035] In the 31st embodiment (31), the soy protein polyurethane alloy of the 30th embodiment (30) is transparent.

[0036] In the 32nd embodiment (32), the polyurethane of the soy protein polyurethane alloy of the 30th embodiment (30) or the 31st embodiment (31) has a Young's modulus in the absence of soy protein, and the soy protein polyurethane alloy has a Young's modulus that is greater than that of polyurethane in the absence of soy protein, ranging from about 60% to about 570%.

[0037] In the 33rd embodiment (33), the polyurethane of the soy protein polyurethane alloy described in any one of embodiments (30) to (32) has a Young's modulus in the absence of soy protein, and the soy protein polyurethane alloy has a Young's modulus that is greater than the Young's modulus of the polyurethane in the absence of soy protein, in the range of about 35 MPa to about 340 MPa.

[0038] In the 34th embodiment (34), the soy protein polyurethane alloy described in any one of embodiments (30) to (33) has a Young's modulus in the range of about 90 MPa to about 400 MPa.

[0039] In the 35th embodiment (35), the polyurethane of the soy protein polyurethane alloy described in any one of embodiments (30) to (34) has a second DMA modulus transition onset temperature in the absence of soy protein, and the second DMA modulus transition onset temperature of the soy protein polyurethane alloy is in the range of 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.

[0040] In the 36th embodiment (36), the polyurethane of the soy protein polyurethane alloy described in any one of embodiments (30) to (35) has a tensile strength in the absence of soy protein, and the soy protein polyurethane alloy has a tensile strength that is about 10% to about 45% greater than the tensile strength of the polyurethane in the absence of soy protein.

[0041] In the 37th embodiment (37), the polyurethane of the soy protein polyurethane alloy described in any one of embodiments (30) to (36) has a tensile strength in the absence of soy protein, and the soy protein polyurethane alloy has a tensile strength in the range of about 1.5 MPa to about 5.5 MPa that is greater than the tensile strength of polyurethane in the absence of soy protein.

[0042] In the 38th embodiment (38), the soy protein polyurethane alloy described in any one of embodiments (30) to (37) has a tensile strength in the range of about 14 MPa to about 19 MPa.

[0043] In the 39th embodiment (39), the soy protein polyurethane alloy described in any one of embodiments (30) to (38) comprises about 10% to about 50% by weight of soy protein and about 50% to about 90% by weight of polyurethane.

[0044] In the 40th embodiment (40), the soy protein polyurethane alloy described in any one of embodiments (30) to (38) comprises about 20% to about 35% by weight of soy protein and about 65% to about 80% by weight of polyurethane.

[0045] In the 41st embodiment (41), the polyurethane of the soy protein polyurethane alloy described in any one of embodiments (30) to (40) has a water vapor permeability in the absence of protein, and the soy protein polyurethane alloy has a water vapor permeability that is greater than the water vapor permeability of the polyurethane in the absence of protein, ranging from about 20% to about 600%.

[0046] In the 42nd embodiment (42), the polyurethane of the soy protein polyurethane alloy described in any one of embodiments (30) to (41) has a water vapor permeability in the absence of protein, and the soy protein polyurethane alloy has a water vapor permeability about 30 g / m² higher than the water vapor permeability of the polyurethane in the absence of protein. 2 / 24 hours ~ approx. 500g / m 2 It has a high water vapor transmission rate over a 24-hour period.

[0047] In the 43rd embodiment (43), the soy protein polyurethane alloy described in any one of embodiments (30) to (42) is approximately 30 g / m². 2 / 24 hours ~ approx. 1000g / m 2 It has a water vapor transmission rate over a 24-hour period.

[0048] In the 44th embodiment (44), the protein of the soy protein polyurethane alloy described in any one of embodiments (30) to (43) is a soy protein isolate.

[0049] In the 45th embodiment (45), the protein of the soy protein polyurethane alloy described in any one of embodiments (40) to (43) is a chemically modified soy protein isolate. [Brief explanation of the drawing]

[0050] The accompanying drawings incorporated herein form part of this specification and illustrate embodiments of the disclosure. Together with this specification, the drawings further help to illustrate the principles of embodiments of the disclosure and enable a person skilled in the art to construct and use embodiments of the disclosure. These drawings are intended to be illustrative and not limiting. While this disclosure is generally described in the context of these embodiments, it should be understood that the scope of this disclosure is not intended to be limited to these specific embodiments. In the drawings, similar reference numerals indicate identical or functionally similar elements. [Figure 1] Figure 1 shows dynamic mechanical analysis (DMA) graphs of storage modulus versus temperature for various materials. [Figure 2] Figure 2 is a graph showing the relationship between the maximum tensile stress and the weight percentage of gelatin in gelatin polyurethane alloys according to several embodiments. [Figure 3] Figure 3 is a graph showing the relationship between the Young's modulus and the weight percentage of gelatin in gelatin polyurethane alloys according to several embodiments. [Figure 4] Figure 4 shows the DMA graph of storage modulus versus temperature for various materials. [Figure 5] Figure 5 is a graph showing the relationship between the maximum tensile stress of SPI polyurethane alloy and the weight percentage of soy protein isolate (SPI) in several embodiments. [Figure 6] Figure 6 is a graph showing the relationship between the Young's modulus and the SPI weight percentage of SPI polyurethane alloys in several embodiments. [Figure 7] Figure 7 shows the DMA graph of storage modulus versus temperature for various materials. [Figure 8A] Figure 8A is a graph comparing the maximum tensile stress of various protein polyurethane alloys in several embodiments. [Figure 8B]Figure 8B is a graph comparing the Young's moduli of various protein polyurethane alloys according to several embodiments. [Figure 9] Figure 9 is a DMA thermogram comparing L3360 and gelatin L3360 alloy according to several embodiments. [Figure 10] Figure 10 is a DMA thermogram comparing Hauthane HD-2001 polyurethane and gelatin Hauthane HD-2001 polyurethane alloy according to several embodiments. [Figure 11] Figure 11 is a DMA thermogram comparing SANCURE® 20025F polyurethane and gelatin SANCURE® 20025F polyurethane alloy in several embodiments. [Figure 12] Figure 12 is a DMA thermogram comparing IMPRANIL® DLS polyurethane and gelatin IMPRANIL® DLS polyurethane alloy in several embodiments. [Figure 13] Figure 13 is a DMA thermogram comparing BONDTHANE® UD-108 polyurethane and gelatin BONDTHANE® UD-108 polyurethane alloy in several embodiments. [Figure 14] Figure 14 is a DMA thermogram comparing BONDTHANE® UD-303 polyurethane and gelatin BONDTHANE® UD-303 polyurethane alloy in several embodiments. [Figure 15] Figure 15 is a DMA thermogram comparing BONDTHANE® UD-250 polyurethane and gelatin BONDTHANE® UD-250 polyurethane alloy in several embodiments. [Figure 16] Figure 16 is a typical DMA graph illustrating the methodology for measuring the transition initiation temperatures of the first and second DMA modulus transitions. [Figure 17] Figure 17 shows layered materials according to several embodiments. [Figure 18] Figure 18 shows layered materials according to several embodiments. [Figure 19] Figure 19 is a block diagram showing methods for producing layered materials according to several embodiments. [Figure 20A] Figures 20A to 20F show methods for producing layered materials according to several embodiments. [Figure 20B] Figures 20A to 20F show methods for producing layered materials according to several embodiments. [Figure 20C] Figures 20A to 20F show methods for producing layered materials according to several embodiments. [Figure 20D] Figures 20A to 20F show methods for producing layered materials according to several embodiments. [Figure 20E] Figures 20A to 20F show methods for producing layered materials according to several embodiments. [Figure 20F] Figures 20A to 20F show methods for producing layered materials according to several embodiments. [Figure 21] Figure 21 shows spacer cloth according to several embodiments. [Figure 22] Figure 22 is a DMA thermogram comparing IMPRAPERM® DL 5249 polyurethane and soy protein isolate IMPRAPERM® DL 5249 alloy in several embodiments. [Figure 23] Figure 23 is a graph showing the weight change versus time of the weight of water transported through a multilayer protein polyurethane alloy in several embodiments. [Modes for carrying out the invention]

[0051] The indefinite articles "a," "an," and "the" refer to multiple objects unless they are clearly contradictory or otherwise explicitly specified in the context.

[0052] The term “comprising” is an open-ended transitional clause. The list of elements following the “comprising” transitional clause is a non-exclusive list, allowing for elements to exist in addition to those specifically enumerated in the list. The phrase “essentially consisting of” limits the composition of the constituents to those that do not substantially affect the specific materials and the basic and novel properties (plural) of the constituents. The phrase “consisting of” limits the composition of the constituents to specific materials and excludes any unspecified materials.

[0053] Where numerical ranges, including upper and lower values, are enumerated herein, unless otherwise specified in particular circumstances, the range is intended to include its endpoints, as well as all integers and fractions within the range. This disclosure is not intended to be limited to specific values ​​enumerated when defining a range. Furthermore, where a quantity, 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 as specifically disclosing all ranges formed from any pair of any upper range limit or value and any lower range limit or value, regardless of whether such pairs are disclosed separately. Finally, where the term “approximately” is used when describing a range value or endpoint, this disclosure should be understood to include the specific value or endpoint referred to. Whether or not a numerical range or endpoint describes “approximately,” the numerical range or endpoint is intended to include two embodiments: one modified by “approximately” and one not modified by “approximately.”

[0054] As used herein, the term "approximately" refers to a value that is within ±10% of the stated value. For example, approximately 3 MPa may include any number between 2.7 MPa and 3.3 MPa.

[0055] As used herein, the first layer described as "bonded" to the second layer means that the layers are bonded to each other either by direct contact or by bonding, either between the two layers or through one or more intermediate adhesive layers. The intermediate adhesive layer may be any layer that helps to bond the first layer to the second layer.

[0056] As used herein, the phrase “placed on top of” means that a first component (e.g., a layer) is in direct contact with a second component. A first component “placed on top of” a second component can be directly deposited, formed, positioned, or otherwise applied on top of the second component. In other words, if a first component is placed on top of a second component, there is no component between the first and second components.

[0057] As used herein, the phrase “placed on top of” means that other components (e.g., layers or substrates) may or may not be present between the first component and the second component.

[0058] As used herein, "bio-based polyurethane" refers to polyurethane in which the building blocks of polyols such as diols and diacides are derived from biomaterials such as cornstarch.

[0059] As used herein, the term “substantially absent” means that the constituent is present in a detectable amount not exceeding about 0.1% by weight.

[0060] As used herein, the term “not containing” means that the constituent element is not present in the blend or material (e.g., protein polyurethane alloy) even in trace amounts.

[0061] 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 technology. The term collagen includes collagen, collagen fragments, collagen-like proteins, triple-helical collagen, alpha chains, monomers, gelatin, trimers, and combinations thereof. Recombinant expression of collagen and collagen-like proteins is known in the art (for example, Bell, European Patent No. 1232182(B1), Bovine collagen and method for producing recombinant gelatin; Olsen, et al., U.S. Patent No. 6,428,978, and VanHeerde, et al., U.S. Patent No. 8,188,230, which are incorporated herein by reference in their entirety). Unless otherwise specified, any type of collagen, whether naturally occurring or prepared using recombinant techniques, can be used in any of the embodiments described herein. That is, in some embodiments, the collagen described herein can be prepared using bovine type I collagen. Collagen is characterized by a repeating amino acid triplet, -(Gly-XY)n-, where approximately one-third of the amino acid residues in collagen are glycine. X is often proline, and Y is often hydroxyproline. Therefore, the structure of collagen may 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).

[0062] In some embodiments, collagen may be chemically modified to enhance its solubility in water.

[0063] Any type of collagen, including cleaved collagen, unmodified or post-translationally modified collagen, or amino acid sequence-modified collagen, can be used as part of a protein polyurethane alloy.

[0064] In some embodiments, the collagen may be plant-derived collagen. For example, the collagen may be plant-derived collagen produced by CollPlant.

[0065] In some embodiments, a collagen solution may be fibrillated into collagen microfibrils. As used herein, collagen microfibrils refer to nanofibers composed of tropocollagen or tropocollagen-like structures (having a triple helix structure). In some embodiments, triple helix collagen may be fibrillated to form collagen nanofibrils.

[0066] In some embodiments, recombinant collagen may comprise a collagen fragment of the amino acid sequence of a native collagen molecule capable of forming tropocollagen (trimeric collagen). Recombinant collagen may also comprise modified or cleaved collagen having at least 70, 80, 90, 95, 96, 97, 98, or 99% identical or similar amino acid sequences to the native collagen amino acid sequence (or its fibril-forming region, or a segment substantially containing [Gly-XY]n). In some embodiments, the collagen fragment may be a 50 kDa portion of native collagen. The native collagen sequence may include the amino acid sequences of CollAl, CollA2, and Col3Al, as described by accession numbers NP_001029211.1, NP_776945.1, and NP_001070299.1, which are incorporated by reference. In some embodiments, the collagen fragment may be a portion of human collagen alpha-1(III) (Col3A1, Uniprot#P02461, Entrez Gene ID#1281). In some embodiments, the collagen fragment may include the amino acid sequence listed as SEQ ID NO: 1.

[0067] Methods for producing recombinant collagen and recombinant collagen fragments are known in the art. For example, U.S. Provisional Patent Applications 2019 / 0002893, 2019 / 0040400, 2019 / 0093116, and 2019 / 0092838 provide methods for producing collagen and collagen fragments that can be used to produce the recombinant collagen and recombinant collagen fragments disclosed herein. The contents of these four publications are incorporated in their entirety by reference.

[0068] The protein polyurethane alloys described herein may comprise a protein that is miscible with only one of several phases of polyurethane, or several polyurethanes into which it is blended. For example, in some embodiments, the protein polyurethane alloy may comprise a protein that is miscible with only the rigid phase of polyurethane, or with several polyurethanes having both rigid and flexible phases. The protein polyurethane alloys described herein may not contain, or substantially contain, protein in the form of particles dispersed in the polyurethane. For example, in some embodiments, the protein polyurethane alloy may not contain, or substantially contain, protein particles having an average diameter greater than 1 micron (μm).

[0069] In some embodiments, the protein polyurethane alloy may not contain, or substantially contain, soy protein particles having an average diameter greater than 1 micron (μm). In some embodiments, the protein polyurethane alloy may not contain, or substantially contain, collagen particles having an average diameter greater than 1 micron (μm). In some embodiments, the protein polyurethane alloy may not contain, or substantially contain, gelatin particles having an average diameter greater than 1 micron (μm). In some embodiments, the protein polyurethane alloy may not contain, or substantially contain, bovine serum albumin particles having an average diameter greater than 1 micron (μm). In some embodiments, the protein polyurethane alloy may not contain, or substantially contain, pea protein particles having an average diameter greater than 1 micron (μm). In some embodiments, the protein polyurethane alloy may not contain, or substantially contain, egg white albumin particles having an average diameter greater than 1 micron (μm). In some embodiments, the protein polyurethane alloy may not contain, or substantially contain, casein protein particles having an average diameter greater than 1 micron (μm). In some embodiments, the protein polyurethane alloy may not contain, or substantially contain, peanut protein particles having an average diameter greater than 1 micron (μm). In some embodiments, the protein polyurethane alloy may not contain, or substantially contain, edestin protein particles having an average diameter greater than 1 micron (μm). In some embodiments, the protein polyurethane alloy may not contain, or substantially contain, whey protein particles having an average diameter greater than 1 micron (μm). In some embodiments, the protein polyurethane alloy may not contain, or substantially contain, karanja protein particles having an average diameter greater than 1 micron (μm). In some embodiments, the protein polyurethane alloy may not contain, or substantially contain, cellulase particles having an average diameter greater than 1 micron (μm).In some embodiments, the protein polyurethane alloy may not contain, or substantially not contain, recombinant collagen fragment particles having an average diameter greater than 1 micron (μm).

[0070] In certain embodiments, the Disclosure provides specific combinations of a protein and a polyurethane in which the protein dissolves only in the rigid phase of the polyurethane. The Disclosure also provides a method for producing the protein polyurethane alloys described herein. The Disclosure also provides a layered material comprising one or more protein polyurethane alloy layers, and a method for producing the layered material. The protein polyurethane alloys and protein polyurethane alloy layers may comprise one or more types of protein and one or more polyurethanes.

[0071] The proteins suitable for use in the alloys disclosed herein may be unmodified or chemically modified. In some embodiments, the proteins may be modified to promote miscibility between the protein and the rigid phase of the polyurethane. In some embodiments, the proteins may be chemically modified to promote solubility in water. In such embodiments, the chemical modification to promote solubility in water may promote miscibility between the protein and the rigid phase of the polyurethane. In some embodiments, the chemically modified protein may be a partially hydrolyzed protein. In some embodiments, the chemically modified protein may be a protein modified by covalent bonding of hydrophilic polymer chains, such as polyethylene glycol (PEG) chains, to the protein.

[0072] The polyurethanes suitable for use in the protein polyurethane alloys described herein include those comprising at least two phases, including a "flexible phase" and a "rigid phase." The flexible phase is formed from polyol segments within the polyurethane, separate from the urethane-containing phase, due to differences in polarity. The urethane-containing phase is referred to as the rigid phase. This phase separation is well known in the art and is based on the properties of many polyurethanes.

[0073] The soft phase is typically an elastomer at room temperature and typically has a softening point or glass transition temperature (Tg) below room temperature. Tg can be measured by dynamic mechanical analysis (DMA) and quantified by either a tan(δ) peak or the onset of storage modulus decrease. Alternatively, Tg can be measured by differential scanning calorimetry (DSC). In some cases, crystallinity may be present in the soft phase, which can typically be seen as a melting point between 0°C and approximately 60°C. For example, the peak in the tan(δ) curve at approximately 35°C for UD-108 polyurethane in Figure 13 indicates the crystallinity in the soft phase of the polyurethane.

[0074] The hard phase typically has a Tg or melting point higher than room temperature, more typically around 80°C. The softening of the hard phase can be measured by determining the onset of the decrease in the storage modulus (sometimes called stiffness), which is measured by DMA.

[0075] The "soft phase" of polyurethane or a polyurethane-containing protein polyurethane alloy contains the polyol components of the polyurethane. Its function is to become soft and pliable at temperatures above its Tg in order to impart toughness, extensibility, and flexibility to the polyurethane. Typical soft segments may include polyether polyols, polyester polyols, polycarbonate polyols, and mixtures thereof. These typically have molecular weights ranging from about 250 daltons to over 5 kilodaltons. The "hard phase" of polyurethane or a polyurethane-containing protein polyurethane alloy contains a polymeric urethane segment, imparted by isocyanates used to link the polyols together with short-chain diols such as butanediol and propanediol. Typical isocyanates useful for this polyurethane 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. Therefore, the hard segment is more rigid and has a higher softening point compared to the soft segment. The function of the hard phase is to provide polyurethane with other properties such as strength, heat resistance, and abrasion resistance.

[0076] In some embodiments described herein, the protein may be miscible only with the hard phase, leaving the transition to the soft phase substantially unchanged. While we do not wish to be bound by any particular theory, it is thought that when the protein dissolves in the hard phase, it significantly increases the temperature at which the hard phase begins to soften, and therefore increases the heat resistance of the alloys described herein. The protein polyurethane alloys described herein may also have increased stiffness and increased strength relative to the base polyurethane (i.e., the polyurethane itself in the absence of protein).

[0077] 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 aqueous 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 aqueous polyurethane dispersions in a liquid state and drying the blend. In some embodiments, the polyurethane dispersions can be ionic and may be either anionic or cationic. In some embodiments, the polyurethane dispersions can be nonionic. In some embodiments, the blended proteins and polyurethanes can be formed into sheets and, in certain embodiments, can be bonded to a substrate layer using a preferred bonding process such as direct coating, a lamination process, or a thermoforming process. In certain embodiments, the lamination process may include bonding the sheet to the substrate layer using an adhesive layer. In some embodiments, the blended proteins and polyurethanes can be coated onto a substrate layer or otherwise deposited in order to bond the blended proteins and polyurethanes to the substrate layer. In some embodiments, a portion of the blended protein and polyurethane can be integrated into a portion of the substrate layer by bonding the blended protein and polyurethane to the substrate layer.

[0078] In a protein-polyurethane alloy comprising one or more miscible proteins and polyurethane, one or more proteins can be dissolved within one or more rigid polyurethane phases. A protein-polyurethane alloy may contain at least one protein that is miscible with one or more rigid polyurethane phases in the alloy. In some embodiments, a protein-polyurethane alloy may contain multiple proteins and / or multiple rigid polyurethane phases that are miscible with each other. In all of these embodiments, while we do not wish to be bound by any particular theory, it is assumed that the protein or multiple proteins are dissolved within the polyurethane or multiple rigid polyurethane phases.

[0079] One or more proteins dissolved in the rigid phase of one or more polyurethanes can form a homogeneous mixture when blended. In some embodiments, a protein polyurethane alloy may contain multiple proteins dissolved in one or more polyurethanes so that when the protein and polyurethane(s) are blended and dried, they form a homogeneous mixture. Typically, a protein polyurethane alloy containing a homogeneous mixture of protein and polyurethane does not contain a substantial amount of protein that does not dissolve in the polyurethane. That is, in some embodiments, a protein polyurethane alloy may contain protein fragments dispersed within the polyurethane.

[0080] In the embodiments described herein, the miscibility between the protein and the rigid phase of the polyurethane can increase the DMA modulus transition softening onset temperature of the rigid phase in the protein-polyurethane alloy without significantly altering one or more other thermomechanical properties of the alloy relative to the thermomechanical properties of the polyurethane itself. For example, the miscibility between the protein and the rigid phase of the polyurethane can increase the DMA modulus transition onset temperature of the rigid phase in the protein-polyurethane alloy without significantly altering 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.

[0081] 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 can 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 can be measured by the onset of storage modulus decrease of the polyurethane or polyurethane protein alloy and can 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.

[0082] For example, many protein types are intended for use in the protein polyurethane alloys described herein, which include collagen and soy protein; however, it is understood that in all embodiments disclosed herein, the protein may be a protein other than collagen and / or a protein other than soy protein. Therefore, in some embodiments, the protein dissolved in the protein polyurethane alloy may be a protein other than collagen. In other embodiments, the protein dissolved in the protein polyurethane alloy may be a protein other than soy protein. In some embodiments, the protein dissolved in the protein polyurethane alloy may be a protein other than collagen and a protein other than soy protein. In some embodiments, the protein polyurethane alloy may not contain collagen or may be substantially free of collagen. In some embodiments, the protein polyurethane alloy may not contain soy protein or may be substantially free of soy protein. In some embodiments, the protein polyurethane alloy may not contain soy protein and collagen or may be substantially free of soy protein and collagen.

[0083] As described above, the soft and hard phases of polyurethane can be measured using dynamic mechanical analysis (DMA). Therefore, one or more polyurethanes contained in the protein polyurethane alloy described herein may have at least two DMA transition temperatures, one corresponding to the soft phase and the other to the hard phase. The DMA transition temperature of the soft phase can be quantified as the "first DMA modulus transition onset temperature" or 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 DMA tan(δ) peak temperature is a lower DMA transition temperature, and the second DMA modulus transition onset temperature is a higher DMA transition temperature.

[0084] Similarly, the protein polyurethane alloys described herein may have at least two phases. These at least two phases may include a soft phase and a hard phase. Different phases of the alloy can be measured and quantified in the same manner as described above for polyurethane.

[0085] 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.

[0086] In some embodiments, the first DMA modulus transition onset temperature of polyurethane may be less than 30°C. In some embodiments, the first DMA modulus transition onset temperature of polyurethane may be in the range of about -65°C to about 30°C, including a partial range. For example, in some embodiments, the first DMA modulus transition onset temperature of polyurethane may be in the range 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 any two of these values ​​as endpoints, including the endpoints. In some embodiments, the first DMA modulus transition onset temperature of polyurethane may 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 about 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.

[0087] Figures 9-15 show DMA thermograms of various exemplary polyurethanes. The first DMA modulus transition onset temperature (T) for each exemplary polyurethane. onset1 ) is the temperature at which the slope of the storage modulus (E') curve begins to decrease significantly in the first time. A methodology for measuring this value is illustrated in Figure 16. DMA instruments such as the DMA-850 from TA Instruments can be programmed to automatically calculate this temperature. Table 4 lists the first DMA modulus transition onset temperatures automatically calculated from the DMA graphs in Figures 9 to 15 (see Examples 1 to 7).

[0088] In some embodiments, the DMA tan(δ) peak temperature corresponding to the flexible phase of polyurethane may be less than 30°C. In some embodiments, the DMA tan(δ) peak temperature corresponding to the flexible phase of polyurethane may be in the range of about -60°C to about 30°C, including a partial range. For example, in some embodiments, the DMA tan(δ) peak temperature corresponding to the flexible phase of polyurethane may be in the range of 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 any two of these values ​​as endpoints, including the endpoints. In some embodiments, the DMA tan(δ) peak temperature corresponding to the flexible phase of polyurethane may be approximately -60°C to approximately 30°C, approximately -60°C to approximately 25°C, approximately -60°C to approximately 20°C, approximately -60°C to approximately 15°C, approximately -60°C to approximately 10°C, approximately -60°C to approximately 5°C, approximately -60°C to approximately 1°C, approximately -60°C to approximately 0°C, approximately -60°C to approximately -1°C, approximately -60°C to approximately -5°C, approximately -60°C to approximately -10°C, approximately -60°C to approximately -15°C, approximately -60°C to approximately -20°C, approximately -60°C to approximately -25°C, approximately -60°C to approximately -30°C, approximately -60°C to approximately -35°C, or approximately -60°C to approximately -40°C.

[0089] The DMA thermograms in Figures 9 to 15 show the DMA tan(δ) peak temperatures corresponding to various exemplary polyurethane soft phases. Similar to 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 to 15 (see Examples 1 to 7).

[0090] In some embodiments, the second DMA elastic modulus transition onset temperature of the polyurethane can be higher than 30°C. In some embodiments, the second DMA elastic modulus transition onset temperature of the polyurethane can range from about 45°C to about 165°C. For example, in some embodiments, the second DMA elastic modulus transition onset temperature of the polyurethane is 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 can be within any range defined by any two of these values as endpoints, inclusive of the endpoints. In some embodiments, the second DMA elastic 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.

[0091] The DMA thermograms of FIGS. 9 to 15 show the second DMA elastic modulus transition onset temperature of various exemplary polyurethanes. The second DMA elastic modulus transition onset temperature (T onset2 ) is the temperature at which the slope of the storage modulus (E') curve begins to decrease significantly at the second instance. The methodology for measuring this value is illustrated in FIG. 16. A DMA instrument such as a DMA-850 manufactured by TA Instruments can be programmed to automatically calculate this temperature. Table 3 lists the second DMA elastic modulus transition onset temperatures automatically calculated from the DMA graphs of FIGS. 9 to 15 (see Examples 1 to 7).

[0092] In some embodiments, polyurethanes may exhibit crystallineity 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: Tg of the soft phase, melting point of the soft phase, and modulus transition of the hard phase. Such melting in the soft phase typically occurs between 0°C and about 60°C, if present. In embodiments exhibiting crystallineity in the soft phase, protein polyurethane alloys typically still exhibit melting in the soft phase, as the protein is miscible with the hard phase and does not substantially alter the mechanical properties of the soft phase.

[0093] In the typical embodiments described herein, a protein polyurethane alloy may have a second DMA transition onset temperature higher than the second DMA transition temperature of the polyurethane in the absence of protein (i.e., the polyurethane itself). This increase in the second DMA transition onset temperature in the alloy is thought to be due to the miscibility of the protein with the rigid phase of the polyurethane. This selective miscibility of the protein is indicated by the increase in the second DMA transition onset temperature without a similar increase in the DMA transition temperature of the soft phase (quantified by the first DMA transition onset temperature or DMA tan(δ) peak temperature corresponding to the soft phase). This selective miscibility can be utilized to control the properties of the protein polyurethane alloy, for example, for mechanical and thermal properties.

[0094] In some embodiments, the protein polyurethane alloys and / or layered materials described herein may have an appearance and feel similar to natural leather, as well as mechanical properties. For example, a protein polyurethane alloy layer or a layered material containing a protein polyurethane alloy layer may, among other things, have tactile, aesthetic, mechanical / performance, manufacturability, and / or thermal properties similar 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 cohesiveness, water resistance, breathability (quantified by water vapor transmission rate measurement in some embodiments), 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 compressive modulus. Aesthetic properties that may be similar to natural leather may include, but are not limited to, dyeability, embossability, aging, color, color intensity, and color pattern. Manufacturing properties that may be similar to those of natural leather include, but are not limited to, the ability to be stitched, cut, skived, and split. Thermal properties that may be similar to those of natural leather include, but are not limited to, heat resistance and resistance to hardening or softening over a remarkably wide temperature range, for example, 25°C to 100°C.

[0095] Desired properties of the protein polyurethane alloy described herein include, but are not limited to, optical properties, tactile properties, aesthetic properties, thermal properties, mechanical properties, and / or permeability properties. Exemplary thermal properties include heat resistance and melt resistance, for example, the transition temperature (T) of the material to the second modulus of elasticity. onset2 This can be quantified by measuring the following: Exemplary mechanical properties include abrasion resistance, maximum tensile stress (also referred to as "tensile strength"), and Young's modulus. Unless otherwise specified, the maximum tensile stress and Young's modulus values ​​disclosed herein are measured according to the method provided by ASTM D638. Exemplary permeability properties include g / m 2This includes moisture vapor transmission rate (MVTR) measured over 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.

[0096] In some embodiments, protein polyurethane alloys may be transparent. In some embodiments, transparent protein polyurethane alloys may indicate that the protein is miscible with the rigid polyurethane phase in the alloy. As used herein, “transparent” material means 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 (“overwhite Y”) by reflectance using a spectrometer with a D65 10-degree light source. The same sample is then placed on a black background and the measurement is repeated to obtain “overblack Y”. The opacity percentage is calculated as “overblack Y” ÷ “overwhite Y” × 100. An opacity of 100% is defined as the lowest transparency, and an opacity of 0% is defined as the highest transparency.

[0097] In some embodiments, the protein polyurethane alloy may be transparent and may have opacity ranging from 0% to about 50%, including a partial range. For example, a transparent protein polyurethane alloy may have 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 staining or coloring the protein polyurethane alloy by other means.

[0098] Transparent protein polyurethane alloys can be produced by selecting and blending appropriate combinations of one or more proteins and one or more polyurethanes. Not all combinations of proteins and polyurethanes result in transparent protein polyurethane alloys, but determining whether a given blend results in a transparent protein polyurethane alloy in light of this disclosure is within the scope of the art of the art. In embodiments relating to layered materials comprising a transparent protein polyurethane alloy layer as described herein, the transparent protein polyurethane alloy layer can provide properties inherent to the layered material. For example, compared to a non-transparent layer, a transparent protein polyurethane alloy layer can provide an inherent color intensity when dyed. Similarly, a transparent protein polyurethane alloy layer can provide the layered material with mechanical properties without significantly affecting the aesthetic properties of the material.

[0099] In some embodiments, the protein polyurethane alloy may contain one or more colorants. In some embodiments, the colorants may be dyes, such as fiber-reactive dyes, direct dyes, or natural dyes. Exemplary dyes include, but are not limited to, azo structure acid dyes, metal complex structure acid dyes, anthraquinone structure acid dyes, and azo / diazo direct dyes. In some embodiments, the colorants may be pigments, such as lake pigments.

[0100] Suitable polyurethanes for blending with one or more proteins according to the embodiments described herein include, but are not limited to, aliphatic polyurethanes, aromatic polyurethanes, bio-based polyurethanes, or acrylic acid-modified polyurethanes. Suitable polyurethanes are commercially available from manufacturers including Lubrizol, Hautaway, and Stahl. In some embodiments, the polyurethane of the protein polyurethane alloy may be a bio-polyurethane. In some embodiments, the polyurethane is a water-dispersible polyurethane. In some embodiments, the polyurethane may be a polyester polyurethane. In some embodiments, the polyurethane may be a polyether polyurethane. In some embodiments, the polyurethane may be a polycarbonate-based polyurethane. In some embodiments, the polyurethane may be an aliphatic polyester polyurethane. In some embodiments, the polyurethane may be an aliphatic polyether polyurethane. In some embodiments, the polyurethane may be an aliphatic polycarbonate polyurethane. In some embodiments, the polyurethane may be an aromatic polyester polyurethane. In some embodiments, the polyurethane may be an aromatic polyether polyurethane. In some embodiments, the polyurethane may be an aromatic polycarbonate polyurethane.

[0101] In some embodiments, the polyurethane may have a flexible segment selected from the group consisting of polyether polyols, polyester polyols, polycarbonate polyols, and mixtures thereof. In some embodiments, the polyurethane may have a rigid segment containing diisocyanates and optionally short-chain diols. Suitable diisocyanates can 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, crosslinking agents such as polyfunctional alcohols such as trimethylolpropanetriol, or diamines such as ethylenediamine or 4,4'-diamino or diphenyldiamine.

[0102] Examples of commercially available polyurethanes include, but are not limited to, L3360 and Hauthane HD-2001 available from CL Hauthaway & Sons Corporation, SANCURE® polyurethane available from Lubrizol Corporation, BONDTHANE® polyurethane available from Bond Polymers International, e.g., UD-108, UD-250, and UD-303, and EPOTAL® ECO 3702 and EPOTAL® P100 ECO from BASF. L3360 is an aqueous dispersion of aliphatic polyester polyurethane polymer with a solids content of 35%, a viscosity of 50–500 cps (centipoise), and a density of approximately 8.5 lb / gal (pounds per gallon). HD-2001 is an aqueous dispersion of aliphatic polyester polyurethane polymer with a solids content of 40%, a viscosity of 50–500 cps, and a density of approximately 8.9 lb / gal. BONDTHANE® UD-108 is an aqueous dispersion of aliphatic polyether polyurethane polymer with a solid content of 33%, a viscosity of 300 cps, and a density of 8.7 lb / gal. BONDTHANE® UD-250 is an aqueous dispersion of aliphatic polyester polyurethane polymer with a solid content of 35%, a viscosity of 200 cps, and a density of 8.8 lb / gal. BONDTHANE® UD-303 is an aqueous dispersion of aliphatic polyether polyurethane polymer with a solid content of 35%, a viscosity of less than 500 cps, and a density of 8.7 lb / gal. EPTOAL® P100 ECO is an aqueous dispersion of polyester polyurethane elastomer with a solid content of approximately 40% and a viscosity of approximately 40 mPas.

[0103] Examples of bio-based polyurethanes include, but are not limited to, L3360 available from CLHauthaway & Sons Corporation, and IMPRANIL® Eco DLS, IMPRANIL® Eco DL 519, IMPRANIL® Eco DLP-R, and IMPRAPERM® DL 5249 available from Covestro. IMPRANIL® Eco DLS is an aqueous dispersion of an anionic aliphatic polyester polyurethane polymer with a solid content of approximately 50%, a viscosity of less than 1,200 MPa·s, and a density of approximately 1.1 g / cc. IMPRANIL® Eco DL 519 is an aqueous dispersion of anionic aliphatic polyester polyurethane polymer. IMPRANIL® Eco DLP-R is an aqueous dispersion of anionic aliphatic polyester polyurethane polymer. IMPRAPERM® DL 5249 is an aqueous dispersion of anionic aliphatic polyester-polyurethane polymer.

[0104] In some embodiments, the polyurethane may contain reactive groups that can be crosslinked with proteins. Examples of reactive groups include, but are not limited to, sulfonates, aldehydes, carboxylic acids or esters, or blocked isocyanates, and combinations thereof. In such embodiments, the polyurethane can be crosslinked with proteins in a protein-polyurethane alloy through a reaction between reactive groups on the protein and reactive groups present in the polyurethane.

[0105] Suitable proteins for blending with one or more polyurethanes according to the embodiments described herein include, but are not limited to, collagen, gelatin, bovine serum albumin (BSA), soy protein, pea protein, ovalbumin, casein, peanut protein, edestin protein, whey protein, callanjan 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.

[0106] Table 1 below lists some exemplary proteins and their properties. Gelatin is type A (Sigma Aldrich G2500), which is gelatin from pig skin. Collagen is extracted from bovine collagen purchased from Wuxi BIOT Biology-technology Company. Bovine serum albumin is Sigma Aldrich 5470. 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 white albumin protein is albumin from chicken egg white (Sigma Aldrich A5253). Casein protein is casein from bovine milk (Sigma Aldrich C7078). Peanut protein is peanut protein powder purchased from Tru-Nut. The whey protein is whey from bovine milk (Sigma Aldrich W1500). Other suitable soy protein isolates include, but are not limited to, soy protein 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).

[0107] Karanja protein is a protein found in karanja seeds harvested from the Pongamia pinnata tree (also known as Pongamia glabra). 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); and also Mandal et al., "Nutritional Evaluation of Proteins from three Non-traditional Seeds with or without Amino Acids Supplementation in Albino Rats," Proc.Indian natn.Sci.Acad., B50, Vol. 1, pp. 48-56 (1984). The protein can be extracted from karanja seeds using a solvent extraction process. Id. In some embodiments, the karanja protein may 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).

[0108] Suitable cellulase proteins are listed in Table 1 below. The "Cellulase-RG" protein is a natural Trichoderma cellulase available from CREATIVE ENZYMES®. The "Cellulase-IG" protein is a laboratory-grade cellulase available from Carolina Biological Supply Company.

[0109] The 50 kDa recombinant collagen fragments (50 kDa r-collagen fragments) in Table 1 are collagen fragments containing the amino acid sequence listed as Sequence ID No. 1.

[0110] The “dissolution methods” listed in Table 1 are exemplary aqueous solvents in which the protein can be dissolved in a solution that is miscible with the rigid phase of the polyurethane described herein. Proteins that are at least partially soluble in aqueous solution are suitable for forming protein polyurethane alloys in polyurethane dispersions.

[0111] [Table 1]

[0112] In some embodiments, the protein may have one or more of the following properties: (i) molecular weight within the range described herein, (ii) isoelectric point within the range described below, (iii) amino acid composition measured in grams of lysine per 100 grams of protein within the range described below, and (iv) thermal stability of the protein up to 200°C.

[0113] Protein molecular weight In some embodiments, the protein may have a molecular weight ranging from about 1 kDa (kilodalton) to about 700 kDa, including a partial range. For example, the protein may have molecular weights of about 1 kDa to about 700 kDa, about 10 kDa to about 700 kDa, about 20 kDa to about 700 kDa, about 50 kDa to about 700 kDa, about 100 kDa to about 700 kDa, about 200 kDa to about 700 kDa, about 300 kDa to about 700 kDa, about 400 kDa to about 700 kDa, about 500 kDa to about 700 kDa, about 600 kDa to about 700 kDa, and about 1 kD The molecular weight may be in the range of a to approximately 600 kDa, approximately 1 kDa to approximately 500 kDa, approximately 1 kDa to approximately 400 kDa, approximately 1 kDa to approximately 300 kDa, approximately 1 kDa to approximately 200 kDa, approximately 1 kDa to approximately 100 kDa, approximately 1 kDa to approximately 50 kDa, approximately 1 kDa to approximately 20 kDa, or approximately 1 kDa to approximately 10 kDa, or within a range having any two of these values ​​as endpoints, including the endpoints.

[0114] Protein isoelectric point In some embodiments, a protein may have an isoelectric point in a range of about 4 to about 10, including a partial range. For example, a protein may have an isoelectric point in a range of about 4 to about 10, about 4.5 to about 9.5, about 5 to about 9, about 5.5 to about 8.5, about 6 to about 8, about 6.5 to about 7.5, or about 6.5 to about 7, or in a range having any two of these values ​​as endpoints, including the endpoints. In some embodiments, a protein may have an isoelectric point in a range of about 4 to about 5.

[0115] 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 a partial range. For example, the protein may have lysine weight percent in the range of 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 in a range having any two of these values ​​as endpoints, including the endpoints. In some embodiments, the protein may be polylysine.

[0116] In some embodiments, the protein may have a lysine weight percentage in the range of about 0.5% to about 20% by weight, including a partial range. For example, the protein may have a lysine weight percentage in the range of about 0.5% to about 20%, about 1% to about 19%, about 2% to about 18%, about 3% to about 17%, about 4% to about 16%, about 5% to about 15%, about 6% to about 14%, about 7% to about 13%, about 8% to about 12%, about 9% to about 11%, or about 9% to about 10%, or in a range having any two of these values ​​as endpoints, including the endpoints. In some embodiments, the protein may have a lysine weight percentage in the range of about 1% to about 20% by weight. In some embodiments, the protein may have a lysine weight percentage in the range of about 5% to about 20% by weight. In some embodiments, the protein may have a lysine weight percentage ranging from about 1% by weight to about 12% by weight. In some embodiments, the protein may have a lysine weight percentage ranging from about 5% by weight to about 12% by weight. In some embodiments, the protein may have a lysine weight percentage ranging from about 1% by weight to about 15% by weight. In some embodiments, the protein may have a lysine weight percentage ranging from about 5% by weight to about 15% by weight.

[0117] In some embodiments, proteins may be thermally stable. In some embodiments, proteins may be non-thermally stable. Protein thermal stability is determined by differential scanning calorimetry (DSC), scanning pre-dried protein powder (with less than 3% moisture) from 0°C to 200°C, as described herein. In the DSC curve of a protein, an endothermic peak greater than 10 mW / mg is determined to be a “denaturation peak,” and the temperature corresponding to the endothermic “denaturation peak” is defined as the protein’s “denaturation temperature.” A protein being “thermally stable” means that the protein has a denaturation temperature of 200°C or higher. For the purposes of this disclosure, proteins with a denaturation temperature below 200°C are considered “non-thermally stable.” For example, whey from bovine milk listed in Table 1 has a denaturation temperature of 158°C by DSC, and therefore, whey is considered non-thermally stable.

[0118] Protein dissolution In some embodiments, one or more proteins can be dissolved in an aqueous solution to form an aqueous protein mixture before blending with one or more polyurethanes. In some embodiments, dissolving the proteins in an aqueous solution before blending with one or more polyurethanes can improve the miscibility between the proteins and the rigid phases of one or more polyurethanes. For example, dissolving the proteins in an aqueous solution before blending with the polyurethane(s) can improve the miscibility between the proteins and the rigid phases of one or more polyurethanes. Not all proteins are naturally miscible with any phase of polyurethane. For example, as illustrated in Examples 33 and 34, casein is not necessarily miscible with polyurethane. When casein, water, and L3360 are mixed as shown in these two examples, casein is miscible with L3360. The resulting film had an opaque appearance with numerous optically visible granules in the film. However, casein is miscible with the rigid phase of L3360 when casein is dissolved in a sodium hydroxide solution before mixing with L3360. The film obtained by blending these components had a transparent and uniform appearance, free from optically visible granules within the film.

[0119] Suitable aqueous solutions include, but are not limited to, water, alkaline aqueous solutions, aqueous acid solutions, aqueous solutions containing organic solvents, urea solutions, and mixtures thereof. In some embodiments, the alkaline aqueous solution may be a basic solution such as sodium hydroxide, ammonia, or ammonium hydroxide solution. In some embodiments, an example of an acidic aqueous solution may be 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 may range from about 10 g / L to about 300 g / L, including a partial range. For example, the protein concentration in an aqueous protein mixture may be approximately 10 g / L, approximately 20 g / L, approximately 30 g / L, approximately 40 g / L, approximately 50 g / L, approximately 60 g / L, approximately 70 g / L, approximately 80 g / L, approximately 90 g / L, approximately 100 g / L, approximately 150 g / L, approximately 200 g / L, approximately 250 g / L, or approximately 300 g / L, or within a range having any two of these values ​​as endpoints, including the endpoint. In some embodiments, the protein concentration in the aqueous protein mixture may be in the range of about 10 g / L to about 300 g / L, about 20 g / L to about 250 g / L, about 30 g / L to about 200 g / L, about 40 g / L to about 150 g / L, about 50 g / L to about 100 g / L, about 60 g / L to about 90 g / L, or about 70 g / L to about 80 g / L.

[0120] In some embodiments, proteins can be pretreated and / or purified to improve their solubility in water. Preferred pretreatments include, but are not limited to, acid treatment, alkali treatment, enzymatic hydrolysis, and salt treatment. An exemplary acid treatment is acid hydrolysis using a preferred acid such as acetic acid or HCl. An exemplary alkali treatment is alkaline hydrolysis having a preferred 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 proteases. Preferred purification treatments include, but are not limited to, removal of phytates with calcium salts, diafiltration, ultrafiltration, and centrifugation.

[0121] In some embodiments, miscibility between the protein and the rigid phase of one or more polyurethanes can be improved by adding lysine or other hydrophilic amino acids to the protein before blending it with one or more polyurethanes.

[0122] Protein hydrolysis 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 improve the miscibility of the protein with the rigid phase of the polyurethane. Partial hydrolysis of the protein can be achieved using an enzyme or a base of moderate strength. Following the hydrolysis, a reduction in viscosity and / or a reduction in protein molecular weight may occur. Methods for characterizing the reduction in protein molecular weight, and therefore 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.

[0123] Protein PEG modification In some embodiments, proteins can be chemically modified by covalent bonding of PEG polyethylene glycol (PEG) to the protein. PEG modification of proteins can promote the solubility of proteins in water and / or improve miscibility between the protein and the rigid polyurethane phase. PEG modification of proteins can be achieved by covalently bonding hydrophilic polyethylene glycol (PEG) chains to the protein.

[0124] In some embodiments, the amount of protein in the protein polyurethane alloy may be in the range of about 10% to about 50% by weight, including a partial range. For example, in some embodiments, the amount of protein in the protein polyurethane alloy is in the range of about 10% to about 50%, about 15% to about 50%, about 20% to about 50%, about 25% to about 50%, about 30% to about 50%, about 35% to about 50%, about 40% to about 50%, about 45% to about 50%, about 10% 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%, or a range having any two of these values ​​as endpoints, including the endpoints. In some embodiments, the amount of protein in the protein polyurethane alloy may range from about 20% by weight to about 35% by weight.

[0125] In some embodiments, the amount of polyurethane in the protein polyurethane alloy may be in the range of about 50% to about 90% by weight, including a partial range. For example, in some embodiments, the amount of polyurethane in the protein polyurethane alloy may be in the range of about 50% to about 90%, about 55% to about 90%, about 60% to about 90%, about 65% to about 90%, about 70% to about 90%, about 75% to about 90%, about 80% to about 90%, about 85% to about 90%, about 50% to about 85%, about 50% to about 80%, about 50% to about 75%, about 50% to about 70%, about 50% to about 65%, about 50% to about 60%, or about 50% to about 55%, or a range having any two of these values ​​as endpoints, including the endpoints. In some embodiments, the amount of polyurethane in the protein polyurethane alloy may range from about 65% to about 80% by weight.

[0126] In some embodiments, the above weight percentage values ​​and ranges may be based on the total weight of the protein polyurethane alloy or protein polyurethane alloy layer. In some embodiments, the above weight percentage values ​​and ranges may be based on the total weight of the protein and polyurethane alone in the protein polyurethane alloy or protein polyurethane alloy layer. Unless otherwise specified, the weight percentage values ​​or ranges of polyurethane and protein are based on the total weight of the protein and polyurethane alone in the protein polyurethane alloy or protein polyurethane alloy layer.

[0127] In some embodiments, the sum of the amount of protein plus the amount of polyurethane in the protein polyurethane alloy may be about 80% by weight or more. For example, in some embodiments, the sum of the amount of protein plus the amount of polyurethane in the protein polyurethane alloy may 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.

[0128] In some embodiments, the protein polyurethane alloy may contain water that constitutes a portion of the total weight percentage of the material. In some embodiments, the amount of water in the protein polyurethane alloy may be in the range of about 1% by weight to about 10% by weight, including a partial range. For example, in some embodiments, the amount of water in the protein polyurethane alloy may be in the range of about 1% by weight to about 10% by weight, about 2% by weight to about 10% by weight, about 3% by weight to about 10% by weight, about 4% by weight to about 10% by weight, about 5% by weight to about 10% by weight, about 6% by weight to about 10% by weight, about 7% by weight to about 10% by weight, about 8% by weight to about 10% by weight, about 1% by weight to about 9% by weight, about 1% by weight to about 8% by weight, about 1% by weight to about 7% by weight, about 1% by weight to about 6% by weight, about 1% by weight to about 5% by weight, about 1% by weight to about 4% by weight, or about 1% by weight to about 3% by weight, or in the range having any two of these values ​​as endpoints, including the endpoints.

[0129] The protein polyurethane alloys described herein may have one or more of the following: (i) a second dynamic mechanical analysis (DMA) modulus transition onset temperature higher than the second DMA modulus transition onset temperature of 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 non-alloyed polyurethane; (iii) a DMA tan(δ) peak at substantially the same temperature as the DMA tan(δ) peak corresponding to the soft phase of non-alloyed polyurethane; (iv) a Young's modulus higher than that of non-alloyed polyurethane; (v) a tensile strength higher than that of non-alloyed polyurethane; or (vi) a water vapor transmission rate (MVTR) higher than that of non-alloyed polyurethane.

[0130] Figures 1 to 15 illustrate the effects of forming polyurethane alloys by dissolving different amounts of different proteins in different polyurethanes according to several embodiments. Tables 3 to 6 list the thermal and mechanical properties of various protein polyurethane alloys according to several embodiments, as well as the thermal and mechanical properties of various polyurethanes. The tested samples were prepared by blending the listed proteins with aqueous dispersions of the listed polyurethanes, forming the mixture into a flat film, drying it in an oven at 45°C overnight (16 to 24 hours), and adjusting it for 24 hours in a standard reference atmosphere (23°C, 50% humidity) before testing. The weight percentage values ​​in the figures and Tables 3 to 6 are the relative weight percentages of solids added to the blends used to prepare the samples. For example, sample No. 9 of Example was prepared by blending 0.825 g of gelatin and 5.5 g of L3360 (35 wt% solids) to have 30 wt% gelatin and 70 wt% L3360. The weight percentage values ​​in the drawings and Tables 3-6 can be used to closely approximate the weight percentages of protein and polyurethane in the dried samples of Examples 1-44, based on the total weight of the dried samples. The dried samples contained water, which constituted a small portion (e.g., about 5% to about 10% by weight) of the total weight percentage of the sample.

[0131] Table 7 lists the water vapor permeability of various protein polyurethane alloys according to several embodiments. The samples tested were prepared as described in Examples 45–56. The weight percentage values ​​in Table 7 are the relative weight percentages of the solids added to the blends used to prepare the samples. These weight percentage values ​​can closely approximate the weight percentages of protein and polyurethane in the dry samples of Examples 45–56, based on the total weight of the dry samples. The dry samples contained water, which constituted a small portion (e.g., about 5%–about 10% by weight) of the total weight percentage of the sample.

[0132] The DMA temperatures in Tables 3 and 4 were measured using a TA Instruments DMA-850. For testing, 1 cm × 2.5 cm strips were cut from the sample film using a metal die. The cut film samples were loaded into film and fiber tension clamps for testing. During the test, a preload of 0.01 Newtons (N) was applied to the cut film samples. The instrument was cooled to -80°C and held for 1 minute, then the temperature was increased from 4°C / min to 200°C, or until the sample was too weak to maintain tension. The sample was vibrated at a frequency of 1 Hz with a strain of 0.1% within the temperature gradient. The obtained storage modulus, loss modulus, and tan(δ) values ​​were plotted against temperature for each test. Unless otherwise specified, 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 method provided by ASTM D638. The tensile strength and Young's modulus values ​​are the average of at least three sample specimens that were tested.

[0133] The DMA graph shown in Figure 1 shows the measured storage modulus (E') of 100% L3360 (Example 1), as well as gelatin dissolved in L3360 at various weight percentages, namely 5 wt%, 10 wt%, 15 wt%, 20%, and 30 wt% (Examples 9 and 25-28). This graph shows that blending gelatin with L3360 can produce alloys with a second DMA transition onset temperature higher than that of 100% L3360. While we do not wish to be bound by any particular theory, it is thought that the increase in the second DMA transition onset temperature would be more evident in this test because the hard phase containing gelatin and the hard segment of polyurethane become continuous at higher gelatin content. This trend indicates that gelatin is miscible with the hard phase of L3360.

[0134] This miscibility between gelatin and the hard phase L3360 is further illustrated in the mechanical properties graphs of Figures 2 and 3, which compare two different mechanical properties of Examples 1 and 9 and 25-28. As shown in Figure 2, the maximum tensile stress ("tensile strength") of the tested protein polyurethane alloy is greater than the maximum tensile stress of 100% L3360. This increase in maximum tensile stress is particularly significant at gelatin weight percentages of 10% or more by weight. As shown in Figure 3, the Young's modulus of the tested protein polyurethane alloy is greater than the Young's modulus of 100% L3360. This increase in Young's modulus is particularly significant at gelatin weight percentages of 15% or more by weight.

[0135] The DMA graph shown in Figure 4 shows the measured storage modulus (E') of 100% L3360 (Example 1), as well as SPI dissolved in L3360 at various weight percentages, namely 10 wt%, 20%, and 30 wt% (Examples 21, 30, and 31). This thermogram shows that blending SPI with L3360 can produce a protein polyurethane alloy having a second DMA transition onset temperature higher than that of 100% L3360. With increasing amounts of SPI added, the increase in the second DMA transition onset temperature increases. This trend indicates that SPI is miscible with the hard phase of L3360.

[0136] The miscibility of SPI with the hard phase L3360 is further illustrated in the mechanical properties graphs of Figures 5 and 6, which compare the two different mechanical properties of Examples 1 and 21, 30, and 31. As shown in Figure 5, the maximum tensile stress ("tensile strength") of the tested protein polyurethane alloy is greater than the maximum tensile stress of 100% L3360. This increase in maximum tensile stress is particularly significant at SPI weight percentages of 10 wt% or more. As shown in Figure 6, the Young's modulus of the tested protein polyurethane alloy is greater than the Young's modulus of 100% L3360. This increase in Young's modulus is particularly significant at SPI weight percentages of 15 wt% or more.

[0137] 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% by weight (Examples 9 and 17 to 23). This graph shows that by blending gelatin, SPI, and other proteins with L3360, a protein-polyurethane alloy having a second DMA elastic modulus transition onset temperature higher than the second DMA elastic modulus transition onset temperature of 100% L3360 can be prepared. All proteins except whey produced a protein-polyurethane alloy having a second DMA elastic modulus transition onset temperature higher than the second DMA elastic modulus transition onset temperature of 100% L3360. Whey is considered to be miscible with the hard phase of L3360, due to its ability to improve the mechanical properties of the protein-polyurethane alloy relative to 100% L3360. However, it is considered that whey did not increase the second DMA elastic modulus transition onset temperature because whey has a low denaturation temperature, as determined by DSC.

[0138] Furthermore, the graph in Figure 7 shows that even when various proteins are dissolved in L3360, no protein-polyurethane alloy in which the DMA transition temperature of the soft phase is significantly different from the DMA transition temperature of the soft phase of 100% L3360 was obtained. As shown in Table 4, all delta first elastic modulus transition onsets of Examples 9 and 17 to 23 were less than 10°C. In this connection, all delta Tan (δ) peak temperatures of Examples 9 and 17 to 23 were less than 10°C. These results indicate that the proteins were not miscible with the soft phase of L3360.

[0139] This selective miscibility between proteins and the hard phase of 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 of Figures 8A and 8B compare the tensile strength and Young's modulus of Example 1, Example 9, and Examples 17 to 23. An increase in tensile strength and / or an increase in Young's modulus can 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.

[0140] To further explain the selective miscibility between the hard phase of a polyurethane having both a soft phase and a hard phase and proteins, gelatin was blended with various exemplary polyurethanes. Figures 9 to 15 show DMA thermograms of these exemplary blends, as well as thermograms of the polyurethanes in the absence of gelatin. Figure 9 compares DMA data of a protein-polyurethane alloy made from 30 wt% gelatin and 70 wt% L3360 (Example 9) with 100% L3360 (Example 1). Figure 10 compares DMA data of a protein-polyurethane alloy made from 30 wt% gelatin and 70 wt% HD-2001 (Example 15) with 100% HD-2001 (Example 7). Figure 11 compares DMA data of a protein-polyurethane alloy made from 30 wt% gelatin and 70 wt% Sancure (Example 14) with 100% Sancure (Example 6). Figure 12 compares DMA data of a protein-polyurethane alloy made from 30 wt% gelatin and 70 wt% Impranil DLS (Example 12) with 100% Impranil DLS (Example 5). Figure 13 compares DMA data of a protein-polyurethane alloy made from 30 wt% gelatin and 70 wt% UD-108 (Example 10) with 100% UD-108 (Example 2). Figure 14 compares DMA data of a protein-polyurethane alloy made from 30 wt% gelatin and 70 wt% UD-303 (Example 13) with 100% UD-303 (Example 4). Figure 15 compares DMA data of a protein-polyurethane alloy made from 30 wt% gelatin and 70 wt% UD-250 (Example 11) with 100% UD-250 (Example 3).

[0141] Figure 22 compares the DMA data of protein polyurethane alloys prepared from 30 wt% soy protein isolate (SPI), 70 wt% IMPRAPERM® DL5249, and 100% IMPRAPERM® DL5249 polyurethane samples. 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. 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 and the results of this mechanical test of the protein polyurethane alloys shown in Figure 22 demonstrate the selective miscibility of SPI with the rigid phase of IMPRAPERM® DL5249.

[0142] Tables 3 and 4 report DMA data for various exemplary polyurethanes and the same polyurethanes blended with 30% by weight gelatin. Tables 5 and 6 report tensile strength and Young's modulus data for various exemplary polyurethanes and the same polyurethanes blended with 30% by weight gelatin. The results demonstrate the selective miscibility of the proteins tested in the rigid phase of the tested polyurethanes.

[0143] In some embodiments, the protein polyurethane alloy may include a polyurethane having a second DMA modulus transition onset temperature in the absence of protein. The same protein polyurethane alloy may 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 the second DMA modulus transition onset temperature can be referred to as "second delta modulus transition onset." In some embodiments, the second delta modulus transition onset may be about 5°C or higher. In some embodiments, the transition of the second modulus of elasticity of the delta occurs at approximately 5°C to 100°C, 5°C to 95°C, 5°C to 90°C, 5°C to 85°C, 5°C to 80°C, 5°C to 75°C, 5°C to 70°C, 5°C to 65°C, 5°C to 60°C, 5°C to 55°C, 5°C to 50°C, 5°C to 45°C, 5°C to 40°C, 5°C to 35°C, 5°C to 30°C, 5°C to 25°C, 5°C to 20°C, 5°C to 15°C, 5°C to 10°C, 10°C to 100°C, and 15°C to 100°C. The range may be approximately 20°C to 100°C, approximately 25°C to 100°C, approximately 30°C to 100°C, approximately 35°C to 100°C, approximately 40°C to 100°C, approximately 45°C to 100°C, approximately 50°C to 100°C, approximately 55°C to 100°C, approximately 60°C to 100°C, approximately 65°C to 100°C, approximately 70°C to 100°C, approximately 75°C to 100°C, approximately 80°C to 100°C, approximately 85°C to 100°C, approximately 90°C to 100°C, or approximately 95°C to 100°C, or a range having any two of these values ​​as endpoints, including the endpoint.

[0144] In some embodiments, the onset of the second delta modulus transition may be in the range of about 5°C to about 80°C. In some embodiments, the onset of the second delta modulus transition may be in the range of about 20°C to about 80°C. In some embodiments, the onset of the second delta modulus transition may be in the range of about 40°C to about 80°C. In some embodiments, the onset of the second delta modulus transition may be above about 100°C. For example, the onset of the second delta modulus transition may be in the range of about 100°C to about 150°C.

[0145] 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 higher than the second DMA modulus transition onset temperature of the polyurethane in the absence of soy protein, ranging from about 15°C to about 100°C. In some embodiments, the onset of the second delta modulus transition of the soy protein polyurethane alloy may be about 15°C or higher. In some embodiments, the onset of the delta-2 modulus transition of the soy protein polyurethane alloy occurs at approximately 15°C to 100°C, 15°C to 95°C, 15°C to 90°C, 15°C to 85°C, 15°C to 80°C, 15°C to 75°C, 15°C to 70°C, 15°C to 65°C, 15°C to 60°C, 15°C to 55°C, 15°C to 50°C, 15°C to 45°C, 15°C to 40°C, 15°C to 35°C, 15°C to 30°C, 15°C to 25°C, 15°C to 20°C, and 2°C. The range may be 0°C to approximately 100°C, approximately 25°C to approximately 100°C, approximately 30°C to approximately 100°C, approximately 35°C to approximately 100°C, approximately 40°C to approximately 100°C, approximately 45°C to approximately 100°C, approximately 50°C to approximately 100°C, approximately 55°C to approximately 100°C, approximately 60°C to approximately 100°C, approximately 65°C to approximately 100°C, approximately 70°C to approximately 100°C, approximately 75°C to approximately 100°C, approximately 80°C to approximately 100°C, approximately 85°C to approximately 100°C, approximately 90°C to approximately 100°C, or approximately 95°C to approximately 100°C, or a range having any two of these values ​​as endpoints, including the endpoint.

[0146] In some embodiments, the protein polyurethane alloy may have a second DMA modulus transition onset temperature in a range of about 100°C to about 200°C, including a partial range. For example, in some embodiments, the protein polyurethane alloy is suitable for temperatures of approximately 100°C to 200°C, approximately 100°C to 195°C, approximately 100°C to 190°C, approximately 100°C to 185°C, approximately 100°C to 180°C, approximately 100°C to 175°C, approximately 100°C to 170°C, approximately 100°C to 165°C, approximately 100°C to 160°C, approximately 100°C to 155°C, approximately 100°C to 150°C, approximately 100°C to 145°C, approximately 100°C to 140°C, approximately 100°C to 135°C, approximately 100°C to 130°C, approximately 100°C to 125°C, or approximately 100°C to 120°C, approximately 105°C to 20 The second DMA modulus transition onset temperature may be in the range of 0°C, approximately 110°C to approximately 200°C, approximately 115°C to approximately 200°C, approximately 120°C to approximately 200°C, approximately 125°C to approximately 200°C, approximately 130°C to approximately 200°C, approximately 135°C to approximately 200°C, approximately 140°C to approximately 200°C, approximately 145°C to approximately 200°C, approximately 150°C to approximately 200°C, approximately 155°C to approximately 200°C, approximately 160°C to approximately 200°C, approximately 165°C to approximately 200°C, approximately 170°C to approximately 200°C, approximately 175°C to approximately 200°C, or approximately 180°C to approximately 200°C, or within a range having any two of these values ​​as endpoints, including the endpoints. In some embodiments, the protein polyurethane alloy may have a second DMA modulus transition onset temperature in the range of about 120°C to about 200°C. In some embodiments, the protein polyurethane alloy may have a second DMA modulus transition onset temperature in the range of about 130°C to about 200°C. In some embodiments, the protein polyurethane alloy may have a second DMA modulus transition onset temperature in the range of about 165°C to about 200°C.

[0147] In some embodiments, the soy protein polyurethane alloy may have a second DMA modulus transition onset temperature in a range of about 130°C to about 200°C, including a partial range. For example, in some embodiments, the soy protein polyurethane alloy may have temperatures of about 130°C to about 200°C, about 130°C to about 195°C, about 130°C to about 190°C, about 130°C to about 185°C, about 130°C to about 180°C, about 130°C to about 175°C, about 130°C to about 170°C, about 130°C to about 165°C, about 130°C to about 160°C, about 130°C to about 155°C, about 130°C to about 150°C, about 130°C to about 145°C, about 130°C to about 140°C, and about 135°C to about 20 The second DMA modulus transition onset temperature may be in the range of 0°C, approximately 140°C to approximately 200°C, approximately 145°C to approximately 200°C, approximately 150°C to approximately 200°C, approximately 155°C to approximately 200°C, approximately 160°C to approximately 200°C, approximately 165°C to approximately 200°C, approximately 170°C to approximately 200°C, approximately 175°C to approximately 200°C, approximately 180°C to approximately 200°C, approximately 185°C to approximately 200°C, or approximately 190°C to approximately 200°C, or in a range having any two of these values ​​as endpoints, including the endpoints.

[0148] In some embodiments, the protein polyurethane alloy may have a first DMA modulus transition temperature below 30°C. In some embodiments, the protein polyurethane alloy may have a first DMA modulus transition onset temperature in a range of about -65°C to about 30°C, including a partial range. For example, in some embodiments, the first DMA modulus transition onset temperature of the protein polyurethane alloy may 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 about 0°C, about -65°C to about 1°C, and about -65°C to about -5°C. The range may be approximately -65°C to approximately -10°C, approximately -65°C to approximately -15°C, approximately -65°C to approximately -20°C, approximately -65°C to approximately -25°C, approximately -65°C to approximately -30°C, approximately -65°C to approximately -35°C, approximately -65°C to approximately -35°C, approximately -65°C to approximately -40°C, or approximately -65°C to approximately -45°C, or a range having any two of these values ​​as endpoints, including the endpoint.

[0149] In some embodiments, the protein polyurethane alloy may comprise a polyurethane having a first DMA modulus transition onset temperature in the absence of protein. The same protein polyurethane alloy may have a first DMA modulus transition onset temperature in the absence of protein, which is ±X°C of the polyurethane's first DMA modulus transition onset temperature. This relative increase or decrease in the first DMA modulus transition onset temperature may be referred to as the "first delta modulus transition onset." In some embodiments, X may be 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.

[0150] In some embodiments, the protein polyurethane alloy may have a DMA tan(δ) peak temperature below 30°C. In some embodiments, the protein polyurethane alloy may have a DMA tan(δ) peak temperature in a range of about -60°C to about 30°C, including a partial range. For example, in some embodiments, the DMA tan(δ) peak temperature of the protein polyurethane alloy may be in the range of approximately -60°C to approximately 30°C, approximately -60°C to approximately 25°C, approximately -60°C to approximately 20°C, approximately -60°C to approximately 15°C, approximately -60°C to approximately 10°C, approximately -60°C to approximately 5°C, approximately -60°C to approximately 1°C, approximately -60°C to approximately 0°C, approximately -60°C to approximately 1°C, approximately -60°C to approximately -5°C, approximately -60°C to approximately -10°C, approximately -60°C to approximately -15°C, approximately -60°C to approximately -60°C to approximately -20°C, approximately -60°C to approximately -25°C, approximately -60°C to approximately -30°C, approximately -60°C to approximately -35°C, or approximately -60°C to approximately -40°C, or within a range having any two of these values ​​as endpoints.

[0151] In some embodiments, a 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, a protein polyurethane alloy may have a DMA tan(δ) peak temperature of + / - Y°C corresponding to the soft phase of the polyurethane in the absence of protein. This relative increase or decrease in the DMA tan(δ) peak temperature can 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.

[0152] In some embodiments, the protein polyurethane alloy may include polyurethane having tensile strength in the absence of protein. The same protein polyurethane alloy may have a tensile strength about 5% to about 55% greater than the tensile strength of polyurethane in the absence of protein. This relative increase in tensile strength can be referred to as "delta tensile strength %". In some embodiments, the delta tensile strength % may be 5% or more. In some embodiments, the delta tensile strength % may 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 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 values ​​as endpoints, including the endpoints. In some embodiments, the delta tensile strength % may be in the range of about 15% to about 55%. In some embodiments, the delta tensile strength % may be greater than about 55%. For example, the delta tensile strength % may be in the range of about 55% to about 1000%.

[0153] In some embodiments, the soy protein polyurethane alloy may comprise a polyurethane having tensile strength in the absence of soy protein. This same soy protein polyurethane alloy may have a tensile strength about 10% to about 45% greater than that 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 more. In some embodiments, the delta tensile strength % of the soy protein polyurethane alloy may be in the range 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%, or a range having any two of these values ​​as endpoints, including the endpoints.

[0154] In some embodiments, the protein polyurethane alloy may include polyurethane having tensile strength in the absence of protein. The same protein polyurethane alloy may have a tensile strength greater than that of 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 may be greater than or equal to 2 MPa. In some embodiments, the delta tensile strength may 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 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 in the range having any two of these values ​​as endpoints, including the endpoints. In some embodiments, the delta tensile strength may be in the range of about 5 MPa to about 8 MPa. In some embodiments, the delta tensile strength may be greater than approximately 8 MPa. For example, the delta tensile strength may be in the range of approximately 8 MPa to approximately 15 MPa.

[0155] In some embodiments, the soy protein polyurethane alloy may comprise a polyurethane having tensile strength in the absence of soy protein. The same soy protein polyurethane alloy may 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 may be 1.5 MPa or greater. In some embodiments, the delta tensile strength of the soy protein polyurethane alloy may 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, including the endpoints.

[0156] In some embodiments, the protein polyurethane alloy may have a tensile strength in the range of about 7 MPa to about 21 MPa, including a partial range. For example, in some embodiments, the protein polyurethane alloy may have a tensile strength in the range of about 7 MPa to about 21 MPa, about 10 MPa to about 21 MPa, about 15 MPa to about 21 MPa, about 7 MPa to about 15 MPa, or about 7 MPa to about 10 MPa, or a tensile strength within a range having any of these values ​​as endpoints, including endpoints. 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 in the range of about 21 MPa to about 25 MPa.

[0157] 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.

[0158] In some embodiments, polyurethane in the absence of protein may have a tensile strength of about 2 MPa or more. In some embodiments, polyurethane in the absence of protein may have a tensile strength in the range of about 2 MPa to about 35 MPa, including a partial range. For example, in some embodiments, polyurethane in the absence of protein may have a tensile strength in the range of about 2 MPa to about 35 MPa, about 5 MPa to about 30 MPa, about 10 MPa to about 25 MPa, or about 15 MPa to about 20 MPa, or a range having any two of these values ​​as endpoints, including the endpoints. In some embodiments, polyurethane in the absence of protein may have a tensile strength in the range of about 10 MPa to about 15 MPa. In some embodiments, polyurethane in the absence of protein may have a tensile strength in the range of about 1 MPa to about 35 MPa.

[0159] In some embodiments, the protein polyurethane alloy may comprise a polyurethane having a Young's modulus in the absence of protein. The same protein polyurethane alloy may have a Young's modulus that is approximately 10% to 600% greater than the Young's modulus of the polyurethane in the absence of protein. This relative percentage increase in Young's modulus can be referred to as the "delta Young's modulus %". In some embodiments, the delta Young's modulus % may be approximately 10% or greater. In some embodiments, the delta Young's modulus % may 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%, about 500% to about 600%, or in the range having any two of these values ​​as endpoints, including the endpoints. In some embodiments, the delta Young's modulus % may be in the range of about 40% to about 600%. In some embodiments, the delta Young's modulus % may be greater than about 600%. For example, the delta Young's modulus (%) can range from approximately 600% to approximately 2400%.

[0160] 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 greater than that of polyurethane in the absence of soy protein, ranging from about 60% to about 570%. In some embodiments, the delta Young's modulus % of the soy protein polyurethane alloy may be about 60% or more. 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, including the endpoints.

[0161] In some embodiments, the protein-polyurethane alloy may comprise a polyurethane having a Young's modulus in the absence of the protein. The same protein-polyurethane alloy may have a Young's modulus that is greater over a range of from about 10 MPa to about 350 MPa than the Young's modulus of the polyurethane in the absence of the protein. This relative increase in Young's modulus may be referred to as "delta Young's modulus". In some embodiments, the delta Young's modulus may be greater than 10 MPa. In some embodiments, the delta Young's modulus ranges from about 10 MPa to about 350 MPa, from about 25 MPa to about 350 MPa, from about 50 MPa to about 350 MPa, from about 100 MPa to about 350 MPa, from about 150 MPa to about 350 MPa, from about 200 MPa to about 350 MPa, from about 250 MPa to about 350 MPa, from about 300 MPa to about 350 MPa, from about 10 MPa to about 300 MPa, from about 10 MPa to about 250 MPa, from about 10 MPa to about 200 MPa, from about 10 MPa to about 150 MPa, from about 10 MPa to about 100 MPa, from about 10 MPa to about 50 MPa, or from about 10 MPa to about 25 MPa, or within a range having as endpoints any two of these values, inclusive of the endpoints. In some embodiments, the delta Young's modulus may range from about 25 MPa to about 350 MPa. In some embodiments, the delta Young's modulus may range from about 100 MPa to about 350 MPa.

[0162] 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 greater than that of polyurethane in the absence of soy protein, ranging from about 35 MPa to about 340 MPa. 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 may be in the range of approximately 35 MPa to approximately 340 MPa, approximately 50 MPa to approximately 340 MPa, approximately 100 MPa to approximately 340 MPa, approximately 150 MPa to approximately 340 MPa, approximately 200 MPa to approximately 340 MPa, approximately 250 MPa to approximately 340 MPa, approximately 300 MPa to approximately 340 MPa, approximately 35 MPa to approximately 300 MPa, approximately 35 MPa to approximately 250 MPa, approximately 35 MPa to approximately 200 MPa, approximately 35 MPa to approximately 150 MPa, approximately 35 MPa to approximately 100 MPa, or approximately 35 MPa to approximately 50 MPa, or a range having any two of these values ​​as endpoints, including the endpoints.

[0163] 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 a partial range. For example, in some embodiments, the protein polyurethane alloy may have a Young's modulus in the range of approximately 50 MPa to approximately 450 MPa, approximately 75 MPa to approximately 450 MPa, approximately 100 MPa to approximately 450 MPa, approximately 150 MPa to approximately 450 MPa, approximately 200 MPa to approximately 450 MPa, approximately 250 MPa to approximately 450 MPa, approximately 300 MPa to approximately 450 MPa, approximately 350 MPa to approximately 450 MPa, approximately 400 MPa to approximately 450 MPa, approximately 50 MPa to approximately 400 MPa, approximately 50 MPa to approximately 350 MPa, approximately 50 MPa to approximately 300 MPa, approximately 50 MPa to approximately 250 MPa, approximately 50 MPa to approximately 200 MPa, approximately 50 MPa to approximately 150 MPa, approximately 50 MPa to approximately 100 MPa, or approximately 50 MPa to approximately 75 MPa, or a range having any two of these values ​​as endpoints, including the endpoints. In some embodiments, the protein polyurethane alloy may have a Young's modulus in the range of 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 in the range of about 450 MPa to about 580 MPa.

[0164] In some embodiments, the soy protein polyurethane alloy may have a Young's modulus in the range of about 90 MPa to about 400 MPa, including a partial range. For example, in some embodiments, the soy protein polyurethane alloy may have a Young's modulus in the range of about 90 MPa to about 400 MPa, about 100 MPa to about 400 MPa, about 150 MPa to about 400 MPa, about 200 MPa to about 400 MPa, about 250 MPa to about 400 MPa, about 300 MPa to about 400 MPa, about 350 MPa to about 400 MPa, about 90 MPa to about 350 MPa, about 90 MPa to about 300 MPa, about 90 MPa to about 250 MPa, about 90 MPa to about 200 MPa, about 90 MPa to about 150 MPa, or about 90 MPa to about 100 MPa, or in a range having any two of these values ​​as endpoints, including the endpoints.

[0165] In some embodiments, polyurethane in the absence of protein may have a Young's modulus of about 10 MPa or more. In some embodiments, polyurethane in the absence of protein may have a Young's modulus in the range of about 10 MPa to about 600 MPa, including a partial range. For example, in some embodiments, polyurethane in the absence of protein, such as thermoplastic collagen elastomer composites, may have a Young's modulus in the range of 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, including the endpoints. In some embodiments, polyurethane in the absence of protein may have a Young's modulus in the range of about 50 MPa to about 100 MPa.

[0166] In some embodiments, the protein polyurethane alloy may comprise a polyurethane having a water vapor permeability in the absence of protein. The same protein polyurethane alloy may have a water vapor permeability about 20% or more greater than its water vapor permeability in the absence of protein. In some embodiments, the protein polyurethane alloy may have a water vapor permeability about 20% to about 600% greater than the water vapor permeability of the polyurethane in the absence of protein. This relative percentage increase in water vapor permeability can be referred to as "delta MVTR%". In some embodiments, delta MVTR% may be about 20% or more. In some embodiments, the delta MVTR% 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 values ​​as endpoints, including the endpoints.

[0167] In some embodiments, the soy protein polyurethane alloy may contain a delta MVTR% of about 20% or more. 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 values ​​as endpoints, including the endpoints.

[0168] In some embodiments, the protein polyurethane alloy may comprise a polyurethane having a water vapor permeability in the absence of protein. This same protein polyurethane alloy has a water vapor permeability about 30 g / m² higher than that of the polyurethane in the absence of protein. 2 / 24 hours ~ approx. 500g / m 2 It may include a high water vapor transmission rate over a range of 24 hours. This relative increase in water vapor transmission rate can be referred to as "delta MVTR". In some embodiments, delta MVTR is 30 g / m³. 2 / This can be 24 hours or more. In some embodiments, the delta MVTR is approximately 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 This could be within the range of / 24 hours, or within the range having any two of these values ​​as endpoints, including the endpoints.

[0169] In some embodiments, the soy protein polyurethane alloy is 30 g / m². 2 It may contain a delta MVTR of 24 hours or more. In some embodiments, the delta MVTR of the soy protein polyurethane alloy is about 30 g / m². 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 h to about 500 g / m 2 / 24 h, about 30 g / m 2 / 24 h to about 400 g / m 2 / 24 h, about 30 g / m 2 / 24 h to about 300 g / m 2 / 24 h, about 30 g / m 2 / 24 h to about 200 g / m 2 / 24 h, about 30 g / m 2 / 24 h to about 150 g / m 2 / 24 h, about 30 g / m 2 / 24 h to about 100 g / m 2 / 24 h, about 30 MPa to about 75 g / m 2 / 24 h, or about 30 g / m 2 / 24 h to about 50 g / m 2 may be within the range of / 24 h, or a range having any two of these values, including endpoints, as endpoints.

[0170] In some embodiments, the protein polyurethane alloy is about 30 g / m including subranges 2 / / 24 h to about 1000 g / m 2 may include a water vapor transmission rate over the range of / 24 h. For example, in some embodiments, the protein polyurethane alloy is about 30 g / m 2 / 24 h to about 1000 g / m 2 / 24 h, about 60 g / m 2 / 24 h to about 1000 g / m 2 / 24 h, about 100 g / m 2 / 24 h to about 1000 g / m 2 / 24 h, about 200 g / m 2 / 24 h to about 1000 g / m 2 / 24 h, about 250 g / m 2 / 24 h to about 1000 g / m 2 / 24 h, about 300 g / m 2 / 24 h to about 1000 g / m 2 / 24 h, about 400 g / m 2 / 24 h to about 1000 g / m 2 / 24 h, about 500 g / m 2 / 24 h to about 1000 g / m 2 / 24 h, about 30 g / m 2 / 24 h to about 900 g / m 2 / 24 h, about 30 g / m 2 / 24 h to about 800 g / m 2 / 24 h, about 30 g / m 2 / 24 h to about 700 g / m 2 / 24 h, about 30 g / m 2 / 24 h to about 600 g / m 2 / 24 h, about 30 g / m 2 / 24 h to about 500 g / m 2 / 24 h, about 30 g / m 2 / 24 h to about 400 g / m 2 / 24 h, about 30 g / m 2 / 24 h to about 300 g / m 2 / 24 h, about 30 g / m 2 / 24 h to about 250 g / m 2 / 24 h, about 30 g / m 2 / 24 h to about 200 g / m 2 / 24 h, or about 30 g / m 2 / 24 h to about 100 g / m 2 It may comprise a water vapor transmission rate within a range having, as endpoints, any two of these values, including the endpoints, spanning the range over 24 hours. In some embodiments, the protein polyurethane alloy has about 250 g / m 2 / 24 h or higher water vapor transmission rate. For example, in some embodiments, the protein polyurethane alloy has about 250 g / m 2 / 24 h to about 1000 g / m 2 / 24 h, about 250 g / m 2 / 24 h to about 700 g / m 2 / 24 h, or about 250 g / m 2 / 24 h to about 500 g / m 2 It may comprise a water vapor transmission rate spanning the range over 24 hours.

[0171] In some embodiments, the soy protein polyurethane alloy comprises about 30 g / m, including subranges, 2 / 24 h to about 1000 g / m 2This may include water vapor transmission rates over a range of 24 hours. For example, in some embodiments, the soy protein polyurethane alloy is approximately 30 g / m². 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 ~ approximately 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 2The water vapor transmission rate may include a range of / 24 hours, or a range having any two of these values ​​as endpoints, including the endpoints. In some embodiments, the soy protein polyurethane alloy is approximately 250 g / m². 2 This may include a water vapor transmission rate of 24 hours or more. For example, in some embodiments, the soy protein polyurethane alloy has a transmission rate of approximately 250 g / m². 2 / 24 hours ~ approx. 1000g / m 2 / 24 hours, approx. 250g / m 2 / 24 hours ~ approx. 700g / m 2 / 24 hours, or approximately 250g / m² 2 / 24 hours ~ approx. 500g / m 2 This may include water vapor transmission rates over a 24-hour period.

[0172] Figure 17 shows layered material 1700 according to several embodiments. The layered material 1700 includes a polyurethane protein alloy layer 1720 bonded to a base layer 1710. The polyurethane protein alloy layer 1720 can be directly bonded to the surface of the base layer 1710, or it can be bonded to the surface of the base layer 1710 via an intermediate layer, such as an adhesive layer. Direct bonding can be achieved, for example, by a thermal bonding process or stitching. The polyurethane protein alloy layer 1720 may be referred to as the "first polyurethane protein alloy layer".

[0173] The polyurethane protein alloy layer 1720 may contain one or more protein types and one or more polyurethanes. In some embodiments, the polyurethane protein alloy layer 1720 may contain one or more proteins dissolved within one or more polyurethanes. In some embodiments, the polyurethane protein alloy layer 1720 may be transparent. The transparency of the polyurethane protein alloy layer is evaluated before staining or coloring the polyurethane protein alloy layer by other means.

[0174] A transparent protein polyurethane alloy layer can provide inherent properties to layered materials. For example, compared to an opaque layer, a transparent protein polyurethane alloy layer can provide a unique color intensity when dyed. Similarly, a transparent protein polyurethane alloy layer can provide the mechanical properties of a layered material without significantly affecting its aesthetic properties.

[0175] The protein polyurethane alloy layer 1720 includes a bottom surface 1722, a top surface 1724, and a thickness 1726 measured between the bottom surface 1722 and the top surface 1724. In some embodiments, the thickness 1726 may be in the range of about 25 microns to about 400 microns (micrometers, μm), including a partial range. For example, the thickness 1726 may be in the range of 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, including the endpoints. In some embodiments, the thickness 1726 may be in the range of approximately 50 microns to approximately 350 microns, approximately 75 microns to approximately 300 microns, approximately 100 microns to approximately 250 microns, approximately 125 microns to approximately 200 microns, or approximately 150 microns to approximately 175 microns.

[0176] The protein polyurethane alloy layer 1720 has a density of approximately 25 g / m², including in partial areas. 2 ~Approx. 125g / m 2 The number of grams per square meter (gsm, g / m²) over the range 2 It may have a dry weight measured at ). For example, the protein polyurethane alloy layer 1720 has a dry weight of approximately 25 g / m². 2 , about 50g / m 2 , about 75g / m 2 , about 100g / m 2 , or approximately 125g / m 2 The dry weight may be , or within a range having any two of these values ​​as endpoints, including the endpoint. In some embodiments, the protein polyurethane alloy layer 1720 is approximately 25 g / m²2 ~Approx. 125g / m 2 , about 25g / m 2 ~about 100g / m 2 , or approximately 50g / m 2 ~about 100g / m 2 It may have a dry weight in the range of [a certain range].

[0177] Unless otherwise specified, the dry weight of a layer is measured during the material preparation process using the following method: First, before applying the layer in question to the material, a first sample of the material (approximately 10 centimeters in diameter) is cut, and its weight and dimensions are measured to calculate the first dry weight. If a sacrificial layer exists, it is removed before measuring its weight and dimensions. Next, after applying and drying the layer in question, a second sample of the same size is cut from the material, and its weight and dimensions are measured to calculate the second dry weight. If a sacrificial layer exists, it is removed before measuring its weight and dimensions. Third, the dry weight of the layer in question is obtained by subtracting the first dry weight from the second dry weight. All weight and dimensional measurements are performed at the same humidity level, typically the humidity level of the manufacturing environment in which the material is produced. Three separate dry weight tests are performed for the purpose of calculating the dry weight, and the average dry weight is reported as the dry weight of the layer.

[0178] In some embodiments, the protein polyurethane alloy layer 1720 may be a non-foamed layer. A “non-foamed” layer means a layer having a density measured by the void percentage of the layer, such as 0% to 5% voids, or less. In some embodiments, the protein polyurethane alloy layer 1720 may be a foamed layer. In such embodiments, the protein polyurethane alloy layer 1720 may have a density measured by the void percentage of the layer 1720, including a partial range of about 5% to about 70% voids. For example, the protein polyurethane alloy layer 1720 may have voids in the range of approximately 5%, approximately 10%, approximately 20%, approximately 30%, approximately 35%, approximately 40%, approximately 45%, approximately 50%, approximately 55%, approximately 60%, approximately 65%, or approximately 70%, or any two of these values ​​with endpoints. In some embodiments, the protein polyurethane alloy layer 1720 may have percentage voids in the range of approximately 10% to approximately 65%, approximately 20% to approximately 60%, approximately 30% to approximately 55%, approximately 35% to approximately 50%, or approximately 40% to approximately 45%.

[0179] The void percentage (also referred to as "percent porosity") can be measured by image analysis of the cross-section of the layer or by measuring the bulk density of the layer sample using a hydrometer. Unless otherwise specified, the void percentages reported herein are measured by image analysis of the cross-section of the layer. Images are analyzed at 37x magnification using ImageJ software (or equivalent software). The ImageJ software calculates the void percentage within the layer using a trainable Weka segmentation classifier. For the purpose of calculating the void percentage, 3 to 5 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 1720 may contain one or more blowing agents and / or foam stabilizers. Suitable blowing agents and foam stabilizers include those discussed herein for layers 1730 and 1740.

[0180] The base layer 1710 includes a bottom surface 1712, a top surface 1714, and a thickness 1716 measured between the bottom surface 1712 and the top surface 1714. In some embodiments, the thickness 1716 may be in the range of about 50 microns to about 1000 microns, including a partial range. For example, the thickness 1716 may be in the range of 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, including the endpoints. In some embodiments, the thickness 1716 may be in the range of approximately 100 microns to approximately 900 microns, approximately 150 microns to approximately 800 microns, approximately 200 microns to approximately 700 microns, approximately 250 microns to approximately 600 microns, approximately 300 microns to approximately 500 microns, or approximately 350 microns to approximately 400 microns.

[0181] The base layer 1710 has a density of approximately 50 g / m², including in partial areas. 2 ~about 600g / m 2 The number of grams per square meter (g / m²) within the range 2 It may have a dry weight measured at ). For example, the base layer 110 may have a dry weight of approximately 50 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 approximately 600g / m 2 The dry weight may be 75 g / m², or within a range having any two of these values ​​as endpoints. In some embodiments, the base layer 1710 is about 75 g / m² 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 approximately 175g / m 2 ~about 200g / m 2 It may have a dry weight in the range of [a certain range].

[0182] The base layer 1710 may include one or more textile layers. One or more textile layers may be, for example, a woven layer, a nonwoven layer, a knitted layer, a mesh fabric layer, or a leather layer. One or more textile layers may consist of recycled or unused fibers, filaments, or yarns. In some embodiments, the base layer 1710 may be or include a polyester knitted layer, a polyester-cotton-spandex blended knitted layer, or a suede layer. In some embodiments, the base layer 1710 may be made from one or more natural fibers, for example, cotton, linen, silk, wool, kenaf, flax, cashmere, angora, bamboo, bast, hemp, soybean, sea cell, milk or milk protein, spider silk, chitosan, mycelium, cellulose containing bacterial cellulose, or fibers made from wood. Mycelium is the nutrient-rich part of a fungal or fungal-like bacterial colony, consisting of a mass of branched filamentous hyphae. Fungi are primarily composed of cell walls that are constantly elongating at the apex of the hyphae. Unlike the structural components of plant cells, which are mainly composed of cellulose, or animal cells, which depend on collagen, the structural oligosaccharides of fungal cell walls are mainly dependent on chitin and beta-glucan. Chitin is a strong, hard substance also found in the exoskeleton of arthropods.

[0183] In some embodiments, the base layer 1710 may be made from one or more synthetic fibers, such as polyester, nylon, aromatic polyamide, polyolefin fibers, such as polyethylene, polypropylene, rayon, liocell, viscose, antimicrobial yarn (AMY), Sorbtek, nylon, elastomers, such as LYCRA®, spandex, or ELASTANE®, polyester-polyurethane copolymer, aramid, carbon fiber, and fullerenes, or metals or metal alloys containing carbon, glass, silicon, minerals, iron, steel, lead, gold, silver, platinum, copper, zinc, and titanium, or mixtures thereof.

[0184] In some embodiments, the nonwoven base layer 1710 may be a stapled nonwoven, a meltblown nonwoven, a spunlaid nonwoven, a flashspun nonwoven, or a combination thereof. In some embodiments, the nonwoven base layer 1710 may be made by carding, which may be airlaid or wetlaid. In some embodiments, the carded, airlaid, or wetlaid bases may be bonded together, for example, by needle punching, water entanglement, lamination, or thermal bonding. In some embodiments, the nonwoven base layer 1710 may contain one or more natural fibers, such as cotton, linen, silk, wool, kenaf, flax, cashmere, angora, bamboo, bast, hemp, soybean, sea cell, milk or milk protein, spider silk, chitosan, mycelium, cellulose including bacterial cellulose, or fibers made from wood.

[0185] In some embodiments, the nonwoven base layer 1710 may contain polymer fibers having functional particles in the polymer. Exemplary functional particles include ceramic particles mixed into the polymer resin during the extrusion process for producing polymer fibers. Such ceramic particles can provide polymer fibers with desirable heat dissipation and flame resistance properties. In some embodiments, the nonwoven base layer 1710 may contain fibers made from fruit pulp (e.g., grape pulp or apple pulp) or pineapple fibers. In some embodiments, the nonwoven base layer 1710 may contain fibers made from recycled materials, such as recycled plastics. In some embodiments, the nonwoven base layer 1710 may contain algae fibers. In some embodiments, the nonwoven base layer 1710 may contain cork fibers.

[0186] In some embodiments, the base layer 1710 may be or include a spacer cloth, for example, a spacer cloth 2100 shown in Figure 21. The spacer cloth 2100 includes a first cloth layer 2110 and a second cloth layer 2120 connected by one or more spacer yarns 2130. The spacer yarns 2130 are positioned between the first cloth layer 2110 and the second cloth layer 2120 and define the distance between the inner surface 2114 of the first cloth layer 2110 and the inner surface 2124 of the second cloth layer 2120. The outer surface 2112 of the first cloth layer 2110 and the outer surface 2122 of the second cloth layer 2120 may define the top surface 1714 and the bottom surface 1712 of the base layer 1710, respectively.

[0187] 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 fiber” refers to a fiber having a short length of about 0.2 mm to about 5 centimeters (cm). Staple fibers may be naturally occurring or cut filaments. As used herein, “filament” refers to a long fiber 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.

[0188] 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, soybean, sea cell, milk or milk protein, spider silk, chitosan, mycelium, cellulose including bacterial cellulose, or fibers made from wood. In some embodiments, the first fabric layer 2110 and the second fabric layer 2120 may be made from one or more synthetic fibers, such as polyester, nylon, aromatic polyamide, polyolefin fibers, such as polyethylene, polypropylene, rayon, liocell, viscose, antimicrobial yarn (AMY), Sorbtek, nylon, elastomers, such as LYCRA®, spandex, or ELASTANE®, polyester-polyurethane copolymer, aramid, carbon fiber, and fullerenes, including metals or metal alloys containing carbon, glass, silicon, minerals, iron, steel, lead, gold, silver, platinum, copper, zinc, and titanium, or mixtures thereof. The spacer yarn(s) 2130 may include monofilament yarn(s) made from any of the natural or synthetic materials listed above for the first fabric layer 2110 and the second fabric layer 2120.

[0189] In some embodiments, the base layer 1710 may be colored with a colorant. In some embodiments, the colorant may be a dye, such as an acid dye, a fiber reactive dye, a direct dye, a sulfur dye, a basic dye, or a reactive dye. In some embodiments, the colorant may be a pigment, such as a lake pigment. In some embodiments, depending on the desired aesthetics of the layered material, a first colorant may be incorporated into one or more protein polyurethane alloy layers, and a second colorant may be incorporated into the base layer 1710.

[0190] Fiber reactive dyes contain one or more chromophores containing pendant groups that can form covalent bonds with nucleophilic sites in fibrous cellulose substrates in the presence of an alkaline pH and high temperature. These dyes can achieve high wash fastness 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 that can dye cellulose fibers or protein fibers. In the presence of an electrolyte such as sodium chloride or sodium sulfate, the closer the boiling point, the greater the affinity these dyes may have for cellulose. Exemplary direct dyes include, but are not limited to, azo, stilbene, phthalocyanine, and dioxazine.

[0191] In some embodiments, the layered material 1700 may include a protein polyurethane alloy layer 1720 bonded to the upper surface 1714 of the base layer 1710. In some embodiments, the bottom surface 1722 of the protein polyurethane alloy layer 1720 may be in direct contact with the upper surface 1714 of the base layer 1710. In some embodiments, the bottom surface 1722 of the protein polyurethane alloy layer 1720 may be bonded to the upper surface 1714 of the base layer 1710 via an adhesive layer (e.g., adhesive layer 1750). In some embodiments, the layered material 1700 may include a protein polyurethane alloy layer 1720 bonded to the bottom surface 1712 of the base layer 1710. In some embodiments, the upper surface 1724 of the protein polyurethane alloy layer 1720 may be in direct contact with the bottom surface 1712 of the base layer 1710. In some embodiments, the upper surface 1724 of the protein polyurethane alloy layer 1720 may be bonded to the bottom surface 1712 of the base layer 1710 via an adhesive layer (e.g., adhesive layer 1750). In some embodiments, the layered material 1700 may include a protein polyurethane alloy layer 1720 bonded to the upper surface 1714 of the base layer 1710 and a protein polyurethane alloy layer 1720 bonded to the bottom surface 1712 of the base layer 1710. In such embodiments, the layered material 1700 includes protein polyurethane alloy layers 1720 disposed on opposing surfaces of the base layer 1710.

[0192] In some embodiments, as shown, for example in Figure 18, the layered material 1700 may include a second protein polyurethane alloy layer 1730 positioned between the protein polyurethane alloy layer 1720 and the substrate layer 1710. In such embodiments, the second protein polyurethane alloy layer 1730 is bonded to the protein polyurethane alloy layer 1720. In some embodiments, the bottom surface 1722 of the protein polyurethane alloy layer 1720 may be in direct contact with the top surface 1734 of the second protein polyurethane alloy layer 1730.

[0193] The second protein polyurethane alloy layer 1730 includes a bottom surface 1732, a top surface 1734, and a thickness 1736 measured between the bottom surface 1732 and the top surface 1734. In some embodiments, the thickness 1736 may be in the range of about 25 microns to about 600 microns, including a partial range. For example, the thickness 1736 may be in the range of 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, including the endpoints. In some embodiments, the thickness 1736 may be in the range of about 50 to about 500 microns, about 75 to about 400 microns, about 100 to about 300 microns, about 125 to about 275 microns, about 150 to about 250 microns, about 175 to about 225 microns, or about 200 to about 225 microns. In some embodiments, the thickness 1736 may be greater than the thickness 1726. In some embodiments, the thickness 1736 may be less than the thickness 1726. In some embodiments, the thickness 1736 may be 5 microns or more greater than the thickness 1726, or 5 microns or more less than the thickness 1726.

[0194] The second protein polyurethane alloy layer 1730 has a density of approximately 30 g / m², including in a partial area. 2 ~about 600g / m 2 The number of grams per square meter (g / m²) within the range 2 It may have a dry weight measured at ). For example, the second protein polyurethane alloy layer 1730 may have a dry weight of approximately 30 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 approximately 600g / m 2 The dry weight may be , or within a range having any two of these values ​​as endpoints, including the endpoint. In some embodiments, the second protein polyurethane alloy layer 1730 is about 40 g / m² 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 approximately 140g / m 2 ~Approx. 150g / m 2 The dry weight may range from 1 to 2. In some embodiments, the protein polyurethane alloy layer 1720 may have a first weight, the second protein polyurethane alloy layer 1730 may have a second weight, and the first weight may be less than the second weight. In some embodiments, the first weight is 5 g / m² less than the second weight. 2 It can be even smaller than that.

[0195] In some embodiments, the second protein polyurethane alloy layer 1730 may contain a foaming agent. In some embodiments, the second protein polyurethane alloy layer 1730 may contain a foam stabilizer. The foaming agent or foam stabilizer can promote the formation of spaces within the second protein polyurethane alloy layer 1730 during blending. Suitable foam stabilizers include, but are not limited to, HeiQ Chemtex 2216-T (a stabilizing blend of nonionic and anionic surfactants), HeiQ Chemtex 2241-A (a modified HEUR (hydrophobic 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. When used, the foam stabilizer helps stabilize mechanically produced foams (bubbles). Mechanically produced foams can be created, for example, by a rotor and / or compressed air. When used, the foaming agent can create foam (bubbles) within the layer by chemical reaction and / or through heat generation within the layer.

[0196] In some embodiments, the second protein polyurethane alloy layer 1730 can be referred to as a "foamed protein polyurethane alloy layer" because (i) layer 1730 contains one or more foaming agents or foam stabilizers, and / or (ii) layer 1730 has a lower density than the protein polyurethane alloy layer 1720.

[0197] The second protein polyurethane alloy layer 1730 may have a density measured by the void percentage of layer 1730, ranging from approximately 5% voids to approximately 70% voids, including a partial range. For example, the second protein polyurethane alloy layer 1730 may have voids in the range of approximately 5%, approximately 10%, approximately 20%, approximately 30%, approximately 35%, approximately 40%, approximately 45%, approximately 50%, approximately 55%, approximately 60%, approximately 65%, or approximately 70%, or any two of these values ​​with endpoints. In some embodiments, the second protein polyurethane alloy layer 1730 may have percentage 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 1720 may have a first density, and the second protein polyurethane alloy layer 1730 may have a second density, with the first density being greater than the second density. In some embodiments, the first density may be greater than the second density with voids of 5% or more.

[0198] The material properties of a layered material can be adjusted by layering multiple protein polyurethane alloy layers having different weights and / or densities. For example, using layers with lower weight and / or density can increase the softening and / or flexibility of the layered material. On the other hand, layers with higher weight and / or density can increase the strength of the layered material. In addition, using one or more layers with relatively low weight and / or density can increase the ease with which cutting, stitching, and / or forming processes (e.g., skyving) can be performed on the layered material. Layering multiple protein polyurethane alloy layers increases the degree of freedom in material design.

[0199] In some embodiments, the second protein polyurethane alloy layer 1730 may further include any other components that may be present, such as foaming agents, foaming stabilizers, or one or more colorants. The type and amount of colorant in the second protein polyurethane alloy layer 1730 may be any of the types and amounts described herein for the protein polyurethane alloy layer 1720. In some embodiments, the second protein polyurethane alloy layer 1730 may be colorant-free or substantially colorant-free.

[0200] In some embodiments, as shown, for example in Figure 18, the layered material 1700 may include a third protein polyurethane alloy layer 1740 positioned between a second protein polyurethane alloy layer 1730 and a substrate layer 1710. In such embodiments, the third protein polyurethane alloy layer 1740 is bonded to the second protein polyurethane alloy layer 1730. In some embodiments, the bottom surface 1732 of the second protein polyurethane alloy layer 1730 may be in direct contact with the top surface 1744 of the third protein polyurethane alloy layer 1740.

[0201] The third protein polyurethane alloy layer 1740 includes a bottom surface 1742, a top surface 1744, and a thickness 1746 measured between the bottom surface 1742 and the top surface 1744. In some embodiments, the thickness 1746 may be in the range of about 25 microns to about 600 microns, including a partial range. For example, the thickness 1746 may be in the range of 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, including the endpoints. In some embodiments, the thickness 1746 may be in the range of approximately 50 to 500 microns, approximately 75 to 400 microns, approximately 100 to 300 microns, approximately 125 to 275 microns, approximately 150 to 250 microns, approximately 175 to 225 microns, or approximately 175 to 200 microns. In some embodiments, the thickness 1746 may be greater than the thickness 1726. In some embodiments, the thickness 1746 may be less than the thickness 1726. In some embodiments, the thickness 1746 may be 5 microns or more greater than the thickness 1726, or 5 microns or more less than the thickness 1726. In some embodiments, the thickness 1746 may be the same as the thickness 1736. In some embodiments, the thickness 1746 may be greater than or less than the thickness 1736. In some embodiments, the thickness 1746 may be 5 microns or more greater than the thickness 1736, or 5 microns or more less than the thickness 1736.

[0202] The third protein polyurethane alloy layer 1740 has a density of approximately 30 g / m², including in a partial area. 2 ~about 600g / m 2 The number of grams per square meter (g / m²) within the range 2 It may have a dry weight measured at ). For example, the third protein polyurethane alloy layer 1740 may have a dry weight of approximately 30 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 approximately 600g / m 2 The dry weight may be , or within a range having any two of these values ​​as endpoints, including the endpoint. In some embodiments, the third protein polyurethane alloy layer 1740 is about 40 g / m² 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 approximately 120g / m 2 ~Approx. 140g / m 2 The dry weight may range from 1 to 2. In some embodiments, the protein polyurethane alloy layer 1720 may have a first weight, the third protein polyurethane alloy layer 1740 may have a third weight, and the first weight may be less than the third weight. In some embodiments, the protein polyurethane alloy layer 1720 may have a first weight, the second protein polyurethane alloy layer 1730 may have a second weight, the third protein polyurethane alloy layer 1740 may have a third weight, and the first weight may be less than the second and third weights. In some embodiments, the first weight is 5 g / m² more than the second and / or third weights. 2 It can be even smaller than that.

[0203] In some embodiments, the third protein polyurethane alloy layer 1740 may contain a foaming agent. In some embodiments, the third protein polyurethane alloy layer 1740 may contain a foam stabilizer. The foaming agent and / or foam stabilizer can promote the formation of spaces in the third protein polyurethane alloy layer 1740 during blending. Suitable foaming agents include, but are not limited to, HeiQ Chemtex 2216-T (a stabilizing blend of nonionic and anionic surfactants), HeiQ Chemtex 2241-A (a modified HEUR (hydrophobic 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.

[0204] In some embodiments, the third protein polyurethane alloy layer 1740 can be referred to as a "foamed protein polyurethane alloy layer" because (i) layer 1740 contains one or more foaming agents or foam stabilizers, and / or (ii) layer 1740 has a lower density than the protein polyurethane alloy layer 120.

[0205] The third protein polyurethane alloy layer 1740 may have a density measured by the void percentage of layer 1740, ranging from approximately 5% voids to approximately 70% voids, including a partial range. For example, the third protein polyurethane alloy layer 1740 may have voids in the range of approximately 5%, approximately 10%, approximately 20%, approximately 30%, approximately 35%, approximately 40%, approximately 45%, approximately 50%, approximately 55%, approximately 60%, approximately 65%, or approximately 70%, or any two of these values ​​with endpoints. In some embodiments, the third protein polyurethane alloy layer 1740 may have percentage 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 1720 may have a first density, the third protein polyurethane alloy layer 1740 may have a third density, and the first density may be greater than the third density. In some embodiments, the protein polyurethane alloy layer 1720 may have a first density, the second protein polyurethane alloy layer 1730 may have a second density, the third protein polyurethane alloy layer 1740 may have a third density, and the first density may be greater than the second and third densities. In some embodiments, the first density may be greater than the second and / or third density with 5% or more voids.

[0206] In some embodiments, the layered material 1700 may comprise multiple protein-polyurethane alloy layers having the same protein and polyurethane. In some embodiments, the layered material 1700 may comprise multiple protein-polyurethane alloy layers, and different layers may have different proteins and / or different polyurethanes.

[0207] In some embodiments, the third protein polyurethane alloy layer 1740 may further include any other components that may be present, such as foaming agents, foaming stabilizers, and one or more colorants. The type and amount of colorants in the third protein polyurethane alloy layer 1740 may be any of the types and amounts described herein for the protein polyurethane alloy layer 1720. In some embodiments, the third protein polyurethane alloy layer 1740 may be colorant-free or substantially colorant-free.

[0208] In some embodiments, the layered material 1700 may include a base coat layer 1760, as shown, for example, in Figure 18. The base coat layer 1760 may be positioned on the upper surface 1724 of the protein polyurethane alloy layer 1720. The base coat layer 1760 may be bonded directly or indirectly to the protein polyurethane alloy layer 1720. In some embodiments, the base coat layer 1760 may be positioned on the upper surface 1724 of the protein polyurethane alloy layer 1720. In some embodiments, the bottom surface 1762 of the base coat layer 1760 may be in direct contact with the upper surface 1724 of the protein polyurethane alloy layer 1720.

[0209] The base coat layer 1760 includes a bottom surface 1762, a top surface 1764, and a thickness 1766 measured between the bottom surface 1762 and the top surface 1764. In some embodiments, the thickness 1766 may be in the range of about 20 microns to about 200 microns, including a partial range. For example, the thickness 1766 may be in the range of 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 having any two of these values ​​as endpoints, including the endpoints. In some embodiments, the thickness 1766 may 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.

[0210] In embodiments including a base coat layer 1760, the base coat layer 1760 can provide one or more of the following properties of the layered material 1700: (i) abrasion resistance, color fastness, or hydrolysis resistance. The base coat layer 1760 may also help to adhere the layered material 1700 to the top coat layer in embodiments including a top coat layer. In some embodiments, the base coat layer 1760 may comprise one or more polymer materials. Suitable materials for the base coat layer 1760 include, but are not limited to, polyether polyurethane, polycarbonate polyurethane, polyester polyurethane, acrylic polymers, and crosslinking agents such as isocyanates or carbodiimides. In some embodiments, the layered material 1700 may comprise multiple base coat layers 1760. In some embodiments, the base coat layer 1760 may not be present in the layered material 1700.

[0211] The base coat layer 1760 has a density of approximately 20 g / m², including partial areas. 2 ~about 100g / m 2 The number of grams per square meter (g / m²) within the range 2 It may have a dry weight measured at ). For example, the base coat layer 1760 may have a dry weight of approximately 20 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 approximately 100g / m 2 The dry weight may be , or within a range having any two of these values ​​as endpoints, including the endpoint. In some embodiments, the base coat layer 1760 is about 30 g / m² 2 ~about 90g / m 2 , about 40g / m 2 ~about 80g / m 2 , or approximately 50g / m 2 ~about 70g / m 2 It may have a dry weight in the range of [a certain range].

[0212] In some embodiments, the layered material 1700 may include a topcoat layer 1770, as shown, for example, in Figure 18. The topcoat layer 1770 may be positioned on the upper surface 1724 of the protein polyurethane alloy layer 1720. The topcoat layer 1770 may be directly or indirectly bonded to the protein polyurethane alloy layer 1720. In some embodiments, the bottom surface 1772 of the topcoat layer 1770 may be in direct contact with the upper surface 1724 of the protein polyurethane alloy layer 1720. In embodiments including a basecoat layer 1760, the topcoat layer 1770 may be positioned on the upper surface 1764 of the basecoat layer 1760. In some embodiments, the topcoat layer 1770 may be positioned on the upper surface 1764 of the basecoat layer 1760. In some embodiments, the bottom surface 1772 of the topcoat layer 1770 may be in direct contact with the upper surface 1764 of the basecoat layer 1760.

[0213] The topcoat layer 1770 includes a bottom surface 1772, a top surface 1774, and a thickness 1776 measured between the bottom surface 1772 and the top surface 1774. In some embodiments, the thickness 1776 may be in the range of about 10 microns to about 80 microns, including a partial range. For example, the thickness 1776 may be in the range of 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 having any two of these values ​​as endpoints, including the endpoints. In some embodiments, the thickness 1776 may 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.

[0214] In embodiments including a topcoat layer 1770, the topcoat layer 1770 can provide one or more of the following properties of the layered material 1700: surface feel, stain resistance, flame resistance, gloss level, or color appearance. In some embodiments, the topcoat layer 1770 may comprise one or more polymer materials. Suitable materials for the topcoat layer 1770 include, but are not limited to, polyurethane, acrylic, silicone-based tactile agents, matting agents, and glossing agents. In some embodiments, the layered material 1700 may comprise multiple topcoat layers 1770. In some embodiments, the topcoat layer 1770 may not be present in the layered material 1700. In some embodiments, the topcoat layer 1770 may be transparent or translucent. In some embodiments, the topcoat layer 1770 may comprise one or more dyes, one or more pigments, and / or one or more reflective agents to affect the appearance.

[0215] The top coat layer 1770 has a density of approximately 10 g / m², including partial areas. 2 ~about 80g / m 2 The number of grams per square meter (g / m²) within the range 2 It may have a dry weight measured at ). For example, the topcoat layer 1770 may have a dry weight of approximately 10 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 approximately 80g / m 2 The dry weight may be 1, or within a range having any two of these values ​​as endpoints, including the endpoint. In some embodiments, the topcoat layer 1770 is about 20 g / m² 2 ~about 70g / m 2 , about 30g / m 2 ~about 60g / m 2 , or approximately 30g / m 2 ~about 50g / m 2 It may have a dry weight in the range of [a certain range].

[0216] Together, the protein polyurethane alloy layers 1720, 1730, 1740, the base coat layer 1760, and / or the top coat layer 1770 can define a layered assembly 1780 of the layered material 1700. The layered assembly 1780 may comprise any number of protein polyurethane alloy layers as described herein. For example, the layered assembly 1780 may comprise 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, the layered material 1700 may comprise a layered assembly 1780 bonded to the bottom surface 1712 of the substrate layer 1710. A layered assembly 1780 bonded to the bottom surface 1712 of the base layer 1710 may include any of the layers and materials described herein with respect to a layered assembly 1780 bonded to the top surface 1714 of the base layer 1710. In some embodiments, the layered material 1700 may include a layered assembly 1780 bonded to the top surface 1714 of the base layer 1710 and a layered assembly 1780 bonded to the bottom surface 1712 of the base layer 1710. In such embodiments, the layered material 1700 includes a layered assembly 1780 disposed on opposing surfaces 1712 and 1714 of the base layer 1710.

[0217] In some embodiments, a protein polyurethane alloy layer of the layered material 1700 is bonded to the surface of the substrate layer 1710 by an adhesive layer 1750. In such embodiments, the adhesive layer 1750 includes a bottom surface 1752, a top surface 1754, and a thickness 1756 measured between the bottom surface 1752 and the top surface 1754. In some embodiments, the thickness 1756 may be in the range of about 10 microns to about 50 microns, including a partial range. For example, the thickness 1756 may be in the range of about 10 microns, about 20 microns, about 30 microns, about 40 microns, or about 50 microns, or any two of these values ​​with endpoints. In some embodiments, the thickness 1756 may be in the range of about 20 microns to about 40 microns. Suitable adhesives for the adhesive layer 1750 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 CLHauthaway & Sons Corporation, is an exemplary laminate adhesive suitable for the adhesive layer 1750. Exemplary polyurethane adhesives include, but are not limited to, Hauthane's L-2183, L-2245, L-2255, and Covestro's IMPRANIL® DAH, DAA. An exemplary dry web adhesive is, but is not limited to, Protechnic's 9D8D20. In some embodiments, the layered material 1700 may not include the adhesive layer 1750.

[0218] The adhesive layer 1750 has a density of approximately 10 g / m², including in partial areas. 2 ~about 50g / m 2 The number of grams per square meter (g / m²) within the range 2 It may have a dry weight measured at ). For example, adhesive layer 1750 may have a dry weight of approximately 10 g / m². 2 , about 20g / m 2 , about 30g / m 2 , about 40g / m 2 , or approximately 50g / m 2The dry weight may be 1, or within a range having any two of these values ​​as endpoints, including the endpoint. In some embodiments, the adhesive layer 1750 is about 20 g / m² 2 ~about 40g / m 2 It may have a dry weight in the range of [a certain range].

[0219] The layered material 1700 can be produced by bonding one or more protein polyurethane alloy layers and one or more basecoat and / or topcoat layers as described herein to a substrate layer 1710. In some embodiments, the layers(s) may subsequently be laminated onto the surface of the substrate layer. The layers(s) may be bonded to either the top surface 1714 and / or bottom surface 1712 of the substrate layer 1710. In some embodiments, the layers(s) may 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 preferred coating technique, including but not limited to knife-over-roll coating, gravure coating, slot-die coating, multilayer slot-die coating, or curtain coating. Multilayer slot-die coating can enable simultaneous coating of multiple adjacent layers.

[0220] In some embodiments, the substrate layer 1710 may be coated with an adhesive layer 1750, and additional layers (e.g., layers 1720, 1730, 1740, 1760, and / or 1770) may be formed on the adhesive layer 1750 in any suitable order. In such embodiments, the layers may be formed on the adhesive layer 1750 in the same manner as described below for method 1900, with the layers being formed on the adhesive layer 1750 rather than as sacrificial layers. In some embodiments, the blend mixture described herein may be applied directly to the surface of the substrate layer 1710, for example, by a coating or injection process. In such embodiments, the blend mixture may penetrate at least a portion of the substrate layer 1710. After application, the blend mixture can be dried to form a protein polyurethane alloy layer (e.g., layer 1720). In some embodiments, after drying, the protein polyurethane alloy layer and the substrate layer 1710 may be heated (e.g., by hot pressing) to help the layers bond together. Other layers (e.g., layers 1730, 1740, 1760, and / or 1770) can be applied to the protein polyurethane alloy layer in any suitable order before or after drying, and / or before or after bonding the protein polyurethane alloy layer and the substrate layer 1710. In such embodiments, the other layers may be formed on the protein polyurethane alloy layer in the same manner as described below for method 1900, and these layers are formed on the protein polyurethane alloy layer rather than as sacrificial layers.

[0221] In some embodiments, decorative layers can be applied between layers of a layered material during manufacturing. For example, a logo, artistic pattern, drawing, or symbol can be applied to a first layer before another layer is placed on top of it. The decorative layer can be applied, for example, using screen printing, digital printing, or transfer printing.

[0222] In some embodiments, layers of the layered material can be formed on a sacrificial layer and then bonded to a substrate layer. Figure 19 shows a method 1900 for producing a layered material 1700 according to some embodiments. Figures 20A to 20F show the steps of method 1900. Unless otherwise specified, the steps of method 1900 do not need to be performed in the order described herein. In addition, unless otherwise specified, the steps of method 1900 do not need to be performed sequentially. The steps can be performed simultaneously. As an example, method 1900 does not need to include a solvent removal step after the deposition of each individual protein polyurethane alloy layer. Rather, the 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 a substrate layer 1710.

[0223] In step 1902, a topcoat layer 1770 can be placed on the upper surface 2002 of the sacrificial layer 2000, for example, as shown in Figure 20A. The topcoat layer 1770 can be placed on the sacrificial layer 2000 using any suitable coating technique, such as roll knife, spray, or roller coating on reverse transfer paper. The sacrificial layer 2000 is a layer of material that does not define the layers of the layered material 1700. Rather, the sacrificial layer 2000 is removed during the manufacturing of the layered material 1700. The sacrificial layer 2000 can be removed mechanically, for example by peeling off the sacrificial layer 2000, or chemically, for example by dissolving the sacrificial layer 2000. In some embodiments, the sacrificial layer 2000 may be a release liner. Suitable materials for the sacrificial layer 2000 include, but are not limited to, granular release paper. Examples of granular release papers include release papers available from Sappi paper, such as 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, after removing the sacrificial layer 2000 in step 1918, the topcoat layer 1770 can be applied to the layered material 1700. In some embodiments, after bonding the protein polyurethane alloy layer(s) to the substrate layer 1710 in step 1920, the topcoat layer 1770 can be applied to the layered material 1700.

[0224] In step 1904, the base coat layer 1760 can be placed on the sacrificial layer 2000, for example, as shown in Figure 20B. In embodiments including a top coat layer 1770, the base coat layer 1760 can be placed on the top coat layer 1770. The base coat layer 1760 can be placed on the sacrificial layer 2000 using any preferred coating technique, such as roll knife, spray, or roller coating on reverse transfer paper. In some embodiments, method 1900 does not include step 1904. Step 1904 is optional. In some embodiments, the base coat layer 1760 can be applied to the layered material 1700 after the sacrificial layer 2000 has been removed in step 1918. In some embodiments, the base coat layer 1760 can be applied to the layered material 1700 after the protein polyurethane alloy layer(s) have been bonded to the substrate layer 1710 in step 1920.

[0225] 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 blend mixture in the aqueous solution. In some embodiments, one or more polyurethanes can be dispersed or dissolved in the aqueous solution before blending with the protein(s). In some embodiments, one or more polyurethanes can be dispersed or dissolved in the aqueous solution while blending with the protein(s). In some embodiments, one or more polyurethanes and 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, stand mixer, inline mixer, or high-shear mixer.

[0226] In some embodiments, the protein(s) may be dispersed or dissolved in an aqueous solution before being blended with the polyurethane in step 1906. Suitable aqueous solutions include, but are not limited to, water, alkaline aqueous solutions, aqueous acid solutions, aqueous solutions containing organic solvents, urea solutions, and mixtures thereof. In some embodiments, the alkaline aqueous solution may be a basic solution such as sodium hydroxide, ammonia, or ammonium hydroxide solution. In some embodiments, an example of an acidic aqueous solution may be 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 may range from about 10 g / L to about 300 g / L, including a partial range. For example, the protein concentration in an aqueous protein mixture may be approximately 10 g / L, approximately 20 g / L, approximately 30 g / L, approximately 40 g / L, approximately 50 g / L, approximately 60 g / L, approximately 70 g / L, approximately 80 g / L, approximately 90 g / L, approximately 100 g / L, approximately 150 g / L, approximately 200 g / L, approximately 250 g / L, or approximately 300 g / L, or within a range having any two of these values ​​as endpoints, including the endpoint. In some embodiments, the protein concentration in the aqueous protein mixture may be in the range of about 10 g / L to about 300 g / L, about 20 g / L to about 250 g / L, about 30 g / L to about 200 g / L, about 40 g / L to about 150 g / L, about 50 g / L to about 100 g / L, about 60 g / L to about 90 g / L, or about 70 g / L to about 80 g / L.

[0227] The amount of protein in a protein / polyurethane blend may range from about 5% by weight to about 60% by weight, based on the weights of protein and polyurethane, including a partial range. For example, the amount of protein in a blend may be in the range of about 5% by weight, about 10% by weight, about 15% by weight, about 20% by weight, about 25% by weight, about 30% by weight, about 35% by weight, about 40% by weight, about 45% by weight, about 50% by weight, about 55% by weight, or about 60% by weight, or any two of these values ​​as endpoints. In some embodiments, the amount of protein in a blend may be about 10% by weight to about 55% by weight, about 15% by weight to about 50% by weight, about 20% by weight to about 45% by weight, about 25% by weight to about 40% by weight, or about 30% by weight to about 35% by weight. In some embodiments, the amount of protein in a protein / polyurethane blend may be in the range of 20% by weight to 40% by weight.

[0228] The amount of polyurethane(s) in a protein / polyurethane blend may range from about 10% to about 85% by weight, based on the weights of protein and polyurethane, including partial ranges. For example, the amount of polyurethane(s) in the blend may be about 10% by weight, about 15% by weight, about 20% by weight, about 25% by weight, about 30% by weight, about 35% by weight, about 40% by weight, about 45% by weight, about 50% by weight, about 55% by weight, about 60% by weight, about 65% by weight, about 70% by weight, about 75% by weight, about 80% by weight, or about 85% by weight, or within a range having any two of these values ​​as endpoints, including the endpoints. In some embodiments, the amount of polyurethane(s) in the blend may range from about 20% to about 75% by weight, about 30% to about 65% by weight, or about 40% to about 55% by weight.

[0229] In some embodiments, the blend temperature may be in the range of about room temperature (18°C) to about 100°C, including a partial range. For example, the blend temperature may be in the range of 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 values ​​as endpoints, including the endpoints. In some embodiments, the blend temperature may be in the range of 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.

[0230] In some embodiments, the blending time of step 1906 may be in the range of about 15 minutes to about 3 hours, including a partial range. For example, the blending time may be in the range of about 30 minutes, about 1 hour, about 90 minutes, about 2 hours, about 150 minutes, or about 3 hours, or a range having any two of these values ​​as endpoints, including the endpoint. In some embodiments, the blending time may be in the range of 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 of step 1906 may be in the range of about 150 rpm to about 250 rpm, including a partial range. For example, the blending speed may be about 150 rpm, about 175 rpm, about 200 rpm, about 225 rpm, or about 250 rpm. In some embodiments, the blending speed may be in the range of 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 device (e.g., the size of the impeller) and / or the size of the container in which the components are blended.

[0231] In some embodiments, one or more additives may be added to the blend in step 1906. The additive(s) may affect the final properties of the protein polyurethane alloy layer, and therefore the final properties of the layered material 1700. For example, the additive(s) added 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, crosslinking agents, fillers, dyes, pigments, plasticizers, waxes, rheological modifiers, flame retardants, antimicrobial agents, antifungal agents, antioxidants, UV stabilizers, mechanical foaming agents, chemical foaming agents, and foam stabilizers. Suitable dyes include, but are not limited to, fiber-reactive dyes or natural dyes. Suitable crosslinking agents include, but are not limited to, epoxy crosslinking agents (e.g., poly(ethylene glycol) diglycidyl ether (PEGDE) available from Sigma Aldridge), isocyanate crosslinking agents (e.g., X-TAN® available from Lanxess), and carbodiimide crosslinking agents. Suitable foaming agents include HeiQ Chemtex 2216-T (a stabilizing blend of nonionic and anionic surfactants), HeiQ Chemtex 2241-A (a modified HEUR (hydrophobic 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 rheological modifiers include, but are not limited to, alkali-swelling rheological modifiers, hydrophobic modified ethylene oxide-based urethane (HEUR) rheological modifiers, and volume-excluding thickeners. Exemplary alkali-swelling rheological modifiers include, but are not limited to, ACRYSOL® DR-106 and ACRYSOL® ASE-60 from Dow Chemicals, and TEXICRYL® 13-3131 and TEXICRYL® 13-308 from Scott-Bader. Exemplary HEUR modifiers include, but are not limited to, RM-4410 from Stahl and Chemtex 2241-A from HeiQ. Examples of volume-excluded thickeners include, but are not limited to, WALOCEL®XM 20000 PV from Dow Chemicals and methylhydroxyethylcellulose from Sigma-Aldrich.

[0232] In some embodiments, the blend may contain one or more colorants. In some embodiments, the colorants may be dyes, such as fiber-reactive dyes, direct dyes, or natural dyes. Exemplary dyes include, but are not limited to, azo-structured acid dyes, metal-complex-structured acid dyes, anthraquinone-structured acid dyes, and azo / diazo direct dyes. In some embodiments, the colorants may be pigments, such as lake pigments. In some embodiments, the blend may contain a colorant content of about 2% by weight or less. For example, the blend may contain about 0.1% by weight, about 0.5% by weight, about 1% by weight, about 1.5% by weight, or about 2% by weight of colorants. In some embodiments, the blend may contain about 0.1% to about 2% by weight, about 0.5% to about 1.5% by weight, or about 0.1% to about 1% by weight of colorants. In some embodiments, the blend may contain no colorants or be substantially colorant-free. In such embodiments, the protein polyurethane alloy layer made from the blend may be colorant-free or substantially colorant-free.

[0233] In step 1908, a layer of the blend mixture is placed on the upper surface 2002 of the sacrificial layer 2000. The blend mixture can be coated onto the upper surface 2002 of the sacrificial layer 2000. In embodiments that do not include steps 1902 and 1904, the blend mixture can be directly coated onto the upper surface 2002 of the sacrificial layer 2000. In embodiments that include step 1904, the blend mixture can be directly coated onto the surface of the base coat layer 1760. In embodiments that include step 1902 but do not include step 1904, the blend mixture can be directly coated onto the surface of the top coat layer 1770. In some embodiments, the blend mixture can be formed into a sheet by coating the blend mixture onto a surface to a desired thickness. Coating may include injection, extrusion, and molding. In some embodiments, the sheet can be spread to a desired thickness using, for example, blades, knives, rollers, roll knives, curtain coating, and slot die coating.

[0234] In some embodiments, the temperature of the blend mixture during coating may be about 40°C or higher. For example, the temperature of the blend mixture may be in the range of about 40°C to about 100°C, including a partial range. For example, the temperature may be in the range of about 40°C, about 50°C, about 60°C, about 70°C, about 80°C, about 90°C, or about 100°C, or any two of these values ​​with endpoints. In some embodiments, the temperature of the blend mixture during coating may 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 temperatures below about 40°C may make the blend mixture excessively viscous, making it difficult to form a layer of uniform thickness.

[0235] In step 1910, the solvent (e.g., water) can be removed from the coated blend mixture to form the protein polyurethane alloy layer 1720, for example, as shown in Figure 20C. Suitable solvent removal methods include, but are not limited to, tunnel drying, vacuum drying, hot air oven drying, humidity chamber drying, hot air flotation drying, and oven drying with a combination of intermediate-range IR (infrared) for preheating and hot air for subsequent drying.

[0236] The preferred solvent removal temperature for step 1910 may be in the range of about room temperature (18°C) to about 100°C, including a partial range. For example, the solvent may be removed at temperatures 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 within a range having any two of these values ​​as endpoints, including the endpoints. In some embodiments, the solvent may be removed at temperatures spanning the ranges of 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. The preferred humidity values ​​for solvent removal in step 1910 include humidity in the range of 0%RH (relative humidity) to about 65%RH, including a partial range. For example, humidity may be approximately 10%RH, approximately 20%RH, approximately 40%RH, approximately 50%RH, or approximately 65%RH, or within a range having any two of these values ​​as endpoints, including the endpoint. In some embodiments, humidity may be 0%RH to approximately 50%RH, 0%RH to approximately 40%RH, 0%RH to approximately 20%RH, or 0%RH to approximately 10%RH. Solvent removal temperature and / or humidity may affect the final properties of the protein polyurethane alloy layer, and thus the layered material. The solvent removal temperature and / or humidity in step 1910 may 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, relatively high humidity and relatively low temperature may result in a softer and more elastic material. Conversely, relatively low humidity and relatively high temperature may result in a harder and less elastic material.

[0237] In some embodiments, steps 1906 to 1910 can be repeated multiple times to form multiple protein polyurethane alloy layers 1720 on the sacrificial layer 2000. In some embodiments, steps 1906 to 1910 can be repeated sequentially to form multiple protein polyurethane alloy layers 1720 on the sacrificial layer 2000. In some embodiments, steps 1906 to 1910 can be repeated after steps 1912 to 1916 to form one or more protein polyurethane alloy layers 1720 on one or more foamed protein polyurethane alloy layers 1730 / 1740. In some embodiments, method 1900 may not include steps 1906 to 1910.

[0238] In step 1912, one or more polyurethanes dispersed or dissolved in an aqueous solution may be blended with a protein(s) and foamed to form a foamed blend mixture in the aqueous solution. In some embodiments, one or more polyurethanes may be dispersed or dissolved in the aqueous solution before blending with the protein(s) and foam. In some embodiments, one or more polyurethanes may be dispersed or dissolved in the aqueous solution while blending with the protein(s) and foam. In some embodiments, one or more polyurethanes and one or more proteins may be blended in a suitable container until a homogeneous blend is formed. Suitable blending equipment includes, but is not limited to, blenders, stand mixers, inline mixers, or high-shear mixers. The blend may be foamed using, for example, a mechanical foaming process or a chemical foaming process. Exemplary mechanical foaming equipment includes Hansa Mixer or GEMTA® foaming agents. Blending and foaming may be performed separately or simultaneously.

[0239] Suitable polyurethanes 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 1730 / 1740.

[0240] 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% by weight, about 1% by weight, about 2.5% by weight, about 5% by weight, about 7.5% by weight, or about 10% by weight of a foaming agent or foam stabilizer. In some embodiments, the blend may contain 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 a foaming agent or foam stabilizer. In some embodiments, the blend may be substantially free of foaming agents and / or foam stabilizers, or may not contain foaming agents and / or foam stabilizers. In such embodiments, the protein polyurethane alloy layer made from the blend may be substantially free of foaming agents and / or foam stabilizers, or may not contain foaming agents and / or foam stabilizers.

[0241] The 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 may have a liquid density ranging from about 300 g / L to about 900 g / L, including a partial range, before the solvent is removed in step 1916. For example, the foamed blend mixture formed in step 1912 may 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 blend mixture may have a liquid density in the range of about 300 g / L to about 800 g / L, about 300 g / L to about 700 g / L, about 400 g / L to about 600 g / L, about 300 g / L to about 500 g / L, or about 300 g / L to about 600 g / L. In some embodiments, the blend mixture formed in step 1906 may have a higher liquid density than the foamed blend mixture formed in step 1912 before the solvent is removed in step 1916, before the solvent is removed from the blend mixture in step 1910.

[0242] In some embodiments, the protein(s) may be dispersed or dissolved in an aqueous solution before 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 may be any value or range discussed above for step 1906. The amount of protein in the protein / polyurethane blend in step 1912 may be any value or range discussed above for step 1906. The blending temperature in step 1912 may be any temperature or temperature range discussed above for step 1906. The blending time in step 1912 may be any time or time range discussed above for step 1906. The blending rate in step 1912 may be any rate or rate range discussed above for step 1906. In some embodiments, one or more additives may be added to the blend in step 1912. The additive(s) added in step 1912 may be any of the additives discussed above for step 1906.

[0243] In step 1914, a layer of the foamed blend mixture is placed on top of the sacrificial layer 2000. In some embodiments, the layer of the foamed blend mixture is placed on the surface of the protein polyurethane alloy layer 1720. In some embodiments, the blend and foamed mixture can be directly coated onto the surface of the protein polyurethane alloy layer 1720. In some embodiments, the foamed blend mixture can be formed into a sheet by coating the blend mixture onto the surface to a desired thickness. Coating may include injection, extrusion, and molding. In some embodiments, the sheet can be spread to a desired thickness using, for example, blades, knives, rollers, roll knives, curtain coating, and slot die coating.

[0244] In step 1916, the solvent (e.g., water) can be removed from the coated foam blend mixture to form the foamed protein polyurethane alloy layer 1730, for example, as shown in Figure 20D. Suitable solvent removal methods include, but are not limited to, tunnel drying, vacuum drying, hot air oven drying, humidity chamber drying, hot air flotation drying, and oven drying with a combination of intermediate-range IR for preheating and hot air for subsequent drying. The suitable solvent removal temperature for step 1916 may be any of the temperatures or temperature ranges discussed above for step 1910. The humidity value for step 1916 may be any of the humidity values ​​or humidity ranges discussed above for step 1910.

[0245] In some embodiments, steps 1912 to 1916 can be repeated multiple times to form multiple foamed protein polyurethane alloy layers on the sacrificial layer 2000, for example, foamed protein polyurethane alloy layer 1730 and foamed protein polyurethane alloy layer 1740. In such embodiments, the foamed blend mixtures formed in separate steps 1912 may have different liquid densities. For example, the liquid density of one foamed blend mixture may be 10 g / L to 300 g / L or more or less than the liquid density of another foamed blend mixture. For example, in some embodiments, the first blend mixture may have a liquid density in the range of about 300 g / L to about 500 g / L, and the second blend mixture may have a liquid density in the range of about 600 g / L to about 700 g / L. Another example is that the first blend mixture may have a liquid density in the range of about 300 g / L to about 400 g / L, and the second blend mixture may have a liquid density in the range of about 500 g / L to about 700 g / L.

[0246] In some embodiments, steps 1912 to 1916 can be repeated sequentially to form multiple foamed protein polyurethane alloy layers on the sacrificial layer 2000. In some embodiments, the foamed mixture and blend mixture formed in step 1912 can be used to form multiple foamed protein polyurethane alloy layers in steps 1914 to 1916. In some embodiments, steps 1912 to 1916 may be performed before performing the set of steps 1906 to 1910 to form one or more foamed protein polyurethane alloy layers between the protein polyurethane alloy layer 1720 and the sacrificial layer 2000. In some embodiments, method 1900 may not include steps 1912 to 1916.

[0247] In step 1918, the sacrificial layer 2000 is removed from the layer(s) formed in steps 1902 to 1916, for example, as shown in Figure 20E. The sacrificial layer 2000 can be removed by a mechanical or chemical process. For example, the sacrificial layer 2000 can be removed by peeling it from the other layers. Alternatively, the sacrificial layer 2000 can be removed by dissolving it. In some embodiments, the sacrificial layer 2000 can be removed in step 1918 before the layer(s) formed in steps 1902 to 1916 are bonded to the substrate layer 1710 in step 1920. In some embodiments, the sacrificial layer 2000 can be removed after step 1920.

[0248] In step 1920, the layer(s) formed in steps 1902 to 1916 are bonded to the substrate layer 1710, for example, as shown in Figure 20F. In step 1920, the protein polyurethane alloy layer 1720 and any other protein polyurethane alloy layers formed in steps 1906 to 1916 are bonded to the substrate layer 1710. In some embodiments, bonding one or more protein polyurethane alloy layers (e.g., protein polyurethane alloy layer 1720) to the substrate layer 1710 in step 1920 includes a hot pressing process. In such embodiments, the protein polyurethane alloy layer (e.g., protein polyurethane alloy layer 1720) may be in direct contact with the substrate layer 1710. Also in such embodiments, the protein polyurethane alloy layer may be partially melted into the substrate layer 1710, and the two layers will be firmly bonded upon cooling. In some embodiments, the process of bonding one or more protein polyurethane alloy layers (e.g., protein polyurethane alloy layer 1720) to the substrate layer 1710 in step 1920 includes a lamination process. In such embodiments, lamination can be achieved with an adhesive layer 1750. In such embodiments, the substrate layer 1710 and / or the protein polyurethane alloy layer can be coated with an adhesive by known techniques such as slot die molding, kiss coating, drawdown technique, or reverse transfer coating. In some embodiments, the lamination process may include passing the substrate layer 1710 and other layers(s) through rollers under heating.

[0249] In some embodiments, step 1920 can be omitted from method 1900. In such embodiments, the layer(s) formed in steps 1902 to 1916 define a layered material that does not have a protein polyurethane alloy layer or a substrate layer 1710.

[0250] In some embodiments, the layered materials described herein may have a tear strength at least about 1% greater than the tear strength of natural leather of the same thickness. For example, the layered materials may have a tear strength about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 100%, about 150%, or about 200% greater than the tear strength of natural leather of the same thickness. In some embodiments, the layered materials may have a tear strength in the range of about 20 N to about 300 N, including a partial range. For example, the tear strength of a layered material may be in the range of about 20N, about 30N, about 40N, about 50N, about 60N, about 70N, about 80N, about 90N, about 100N, about 125N, about 150N, about 175N, about 200N, about 225N, about 250N, about 275N, or about 300N, or a range having any two of these values ​​as endpoints, including the endpoint. In some embodiments, the tear strength may be in the range of about 30N to about 275N, about 40N to about 250N, about 50N to about 225N, about 60N to about 200N, or about 75N to about 175N, about 80N to about 150N, about 90N to about 125N, or about 100N to about 125N.

[0251] In some embodiments, the protein polyurethane alloy layers described herein may have a tear strength in the range of about 2N to about 30N, including a partial range. For example, the tear strength of the protein polyurethane alloy layer may be in the range of about 2N, about 4N, about 5N, about 10N, about 15N, about 20N, about 25N, or about 30N, or any two of these values ​​with endpoints. In some embodiments, the tear strength may be in the range of about 4N to about 25N, about 5N to about 20N, or about 10N to about 15N.

[0252] 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, for example, the methods provided by ASTM D412 or ISO 3377 (also known as the “Baumann tear”). The method provided by ASTM D624 may also be used to measure resistance to tear formation and resistance to tear expansion. Regardless of the method used, first, a cut is made in the material sample to be tested to induce tearing. Then, the sample is held between two grips and a uniform tensile force is applied until the sample splits in two. The tear resistance is then calculated by dividing the applied force by the thickness of the material. Unless otherwise specified, the tear strength values ​​reported herein are measured according to ISO 3377.

[0253] In some embodiments, the layered materials described herein may have tensile strengths in the range of about 1 kPa (kilopascals) to about 100 MPa (megapascals), including a partial range. For example, the layered materials may have tensile strengths in the range 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 any two of these values ​​with endpoints. In some embodiments, the tensile strength may be in the range of approximately 50 kPa to approximately 90 MPa, approximately 100 kPa to approximately 80 MPa, approximately 200 kPa to approximately 70 MPa, approximately 300 kPa to approximately 60 MPa, approximately 400 kPa to approximately 50 MPa, approximately 500 kPa to approximately 40 MPa, approximately 600 kPa to approximately 30 MPa, approximately 700 kPa to approximately 20 MPa, approximately 800 kPa to approximately 10 MPa, or approximately 1 MPa to approximately 5 MPa.

[0254] The softness of a material, also known as its "feel," can be determined by ISO 17235. In some embodiments, the outer surface of the layered material described herein may have softness in the range of about 2 mm to about 12 mm, including partial ranges. For example, the outer surface of the layered material may have softness in the range 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 any two of these values ​​with endpoints. In some embodiments, the softness may 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, the softness values ​​disclosed herein are determined by ISO 17235.

[0255] The flexibility or strain of a material can be determined, for example, by measuring its elongation at break when a tensile force is applied, using the equation: ΔL / L, where ΔL is the change in the 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 layered materials described herein may have a flexibility in the range of about 100% to about 400%, including a partial range. For example, a layered material may have a flexibility in the range of about 100%, about 200%, about 300%, or about 400%, or having any two of these values ​​as endpoints, including the endpoints. In some embodiments, flexibility may 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, the flexibility values ​​disclosed herein are measured according to ASTM D412. In some embodiments, the protein polyurethane alloy layers described herein may have the above-described flexibility values ​​or ranges for the layered material.

[0256] In some embodiments, the layered materials described herein may have a permanent strain of about 8% or less in hysteresis experiments. In some embodiments, the layered materials may have a permanent strain in the range of about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, or about 8%, or having any two of these values ​​as endpoints. In some embodiments, the layered materials may have a permanent strain of about 1% to about 8%, about 2% to about 7%, about 3% to about 6%, or about 4% to about 5%.

[0257] Unless otherwise specified, permanent strain is measured by the following method: A tensile specimen of dogbone-shaped material is cut, and the original length of the specimen is measured. 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 at a constant speed of 3 mm per second in both directions to 15% strain, and then returned to 0% strain. This is repeated 5 times. The distance between the original specimen length and the specimen length at which the load becomes zero in the last return cycle is then measured. The percentage difference between the length measured after repeatedly straining the material and the original length is the permanent strain %. Three separate specimens of the material are evaluated for the purpose of calculating permanent strain, and the average permanent strain value is reported as the permanent strain value of the material.

[0258] In some embodiments, the layered material described herein is approximately 75 g / m² 2 It may have a water vapor transmission rate (MVTR) of more than / hour. In some embodiments, the layered material described herein has a partial range of about 75 g / m² 2 / hour~about 200g / m 2 It may have an MVTR in the range of / time. For example, a layered material may have 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 / m2 / hour, about 120g / m 2 / hour~about 150g / m 2 / hour, or approximately 130g / m 2 / hour ~ approx. 140g / m 2 It may have an MVTR of / hour. Unless otherwise specified, the MVTR values ​​disclosed herein are measured using ASTM E96 ("Standard Test Methods for Water Vapor Permeation Testing of Materials") - Procedure B, water method, approximately 74.3°F, approximately 50% relative humidity, and a 3 / 4-inch air gap.

[0259] Layered materials having water vapor permeability as reported herein may be suitable for use in a variety of applications where breathability of the material is a desirable property. Examples of 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 permeability compared to layered polymer materials having the same number of layers of the same thickness and consisting of the same polymer material(s), but without the blending of proteins into the polymer material(s).

[0260] In some embodiments, the layered materials described herein may have a color fastness of Class 4 or higher when measured according to the ISO 11640 ("Leather - Tests for color fastness - Fastness to reciprocating friction cycles") wet friction fastness test. In some embodiments, the layered materials described herein may have a color fastness of Class 4, Class 4.5, or Class 5 when measured according to the ISO 11640 wet friction fastness test. A color fastness of Class 4 or higher can provide the layered materials described herein with desirable abrasion resistance for a variety of applications.

[0261] The layered materials described herein can achieve a colorfastness of Class 4 or higher without containing pigments in the material. This is a unique property compared to layered polyurethane materials made from the same polyurethane(s) without the protein(s) blended into the polyurethane(s). The proteins in the layered materials described herein can adhere well to the dyes used to color the material. To achieve high colorfastness, polyurethane materials are usually colored with pigments because dyes generally do not adhere well to polyurethane. Poor adhesion between the dye and polyurethane results in relatively low colorfastness. The dyed layered materials described herein may have improved color intensity and other aesthetic characteristics that cannot be achieved with polyurethane colored using pigments.

[0262] In some embodiments, the layered material described herein, or individual layers of the layered material described herein, may be subjected to the same or similar finishing treatments used for processing natural leather. In some embodiments, the layered material described herein may be tumbling or staking to adjust the material properties, such as the feel of the material. In such embodiments, conventional textile tumbling and staking methods may be used.

[0263] In some embodiments, the layered material, or individual layers of the layered material, may have a rough outer surface. For example, the top surface 1724 of the protein polyurethane alloy layer 1720 may have a rough surface, the top surface 1774 of the topcoat layer 1770 may have a rough surface, the top surface 1764 of the basecoat layer 1760 may have a rough surface, the top surface 1734 of the protein polyurethane alloy layer 1730 may have a rough surface, and the top surface 1744 of the protein polyurethane alloy layer 1740 may have a rough surface. The rough outer surface can create a surface texture that is similar in appearance and feel to that of natural leather (e.g., stone-textured natural leather). In some embodiments, the top surface 2002 of the sacrificial layer 2000 may have a rough surface that is transferred onto the surface of a layer placed directly on the top surface 2002 during method 1900.

[0264] The rough surface is 1 inch 2 It has a surface area per square inch that is at least about 1% larger than that of the other material. In other words, in some embodiments, a 1-square-inch sample of the layered material 1700 containing a layer with a rough outer surface may have a surface area at least about 1% larger than a 1-square-inch sample of the material containing a perfectly smooth surface. In some embodiments, the rough outer surface has a surface area per square inch that is at least about 1% larger than that of the other material containing a layer with a rough outer surface. 2 At least about 1% larger, 1 in 2 Approximately 10% larger, 1 inch 2 Approximately 20% larger, 1 inch 2 Approximately 30% larger, 1 inch 2 Approximately 40% larger, 1 inch 2 Approximately 50% larger, 1 inch 2 Approximately 60% larger, 1 inch 2 Approximately 70% larger, 1 inch 2 Approximately 80% larger, 1 inch 2 Approximately 90% larger, 1 inch 2 Approximately 100% larger, 1 inch 2 Approximately 150% larger, 1 inch 2 Approximately 200% larger, 1 inch 2 Approximately 250% larger, 1 inch 2 Approximately 300% larger, 1 inch 2 Approximately 350% larger, 1 inch 2 Approximately 400% larger, 1 inch 2 Approximately 450% larger, or 1 inch 2 A surface area per square inch may be approximately 500% larger, or have a surface area per square inch within a range that includes any two of these values ​​as endpoints. In some embodiments, a rough surface may have a surface area per square inch of 1 in 2 Approximately 1% more than 1 in 2 Over 500% more, 1 in 2 Approximately 10% more than 1 in 2 Over 450% more, 1 in 2 Approximately 20% more than 1 inch 2 Over 400% more, 1 in 2 Approximately 30% more than 1 in 2 Approximately 350% more, 1 in 2Approximately 40% more than 1 inch 2 Over 300% more, 1 in 2 Approximately 50% more than 1 inch 2 Approximately 250% more, 1 in 2 Approximately 60% more than 1 inch 2 Approximately 200% more, 1 in 2 Approximately 70% more than 1 inch 2 More than approximately 150%, or 1 in 2 Approximately 80% more than 1 inch 2 They may have a surface area of ​​more than approximately 100% 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, layered materials, or individual layers of layered materials, may have a smooth outer surface. The smooth surface may have a surface area of ​​1 inch. 2 It has a surface area per square inch that is less than 1% larger than [a certain value]. For example, a smooth surface has a surface area per square inch of 1 inch. 2 ~1.01in 2 It may have a surface area of ​​less than a square inch. In some embodiments, the top surface 2002 of the sacrificial layer 2000 may have a smooth surface that is transported onto the surface of a layer placed directly on the top surface 2002 during method 1900.

[0265] In some embodiments, the layered material, or individual layers of the layered material, may have a textured outer 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 placed directly on the top surface 2002 during Method 1900. In some embodiments, the textured outer surface may be a surface area per square inch, or a range of surface areas per square inch, as described above for rough surfaces.

[0266] In some embodiments, the texture may be a macroscale texture, for example, one of the many textures used in Sappi / Warren release papers manufactured by the SD Warren Company under the designation Sappi North America and marketed under the trademarks ULTRACAST® or Classic. An example of a macroscale texture is a repeating natural leather grain with a feature depth of about 50 to about 300 microns. Any other desired macroscale texture may be used. In some embodiments, the macroscale texture may be a “leather grain texture.” As used herein, the term “leather grain texture” refers to a texture that mimics the appearance 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.

[0267] In some embodiments, the texture may be a microscale texture. In some embodiments, the texture may be a microscale texture with surface features having a feature size of less than 50 microns, for example, 1000 nanometers to less than 50 microns. An example of a microscale texture is referred to in the art as “sharklet”. Sharklet textures may be applied to provide products having a surface configured to inhibit bacterial growth. The microscale texture of the surface repeats sharkskin protrusions arranged in a rhomboid 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.

[0268] In some embodiments, the texture may 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 raised sections about 400 nanometers wide, spaced about 800 nanometers apart, and with a depth of about 100 nanometers.

[0269] The embodiments discussed herein will become even clearer in the following examples. It should be understood that these examples are not limited to the embodiments described above. [Example 1]

[0270] The sample was prepared by mixing 5.5 g of Hauthaway's water-mediated 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 adjusted in a standard reference atmosphere (23°C, 50% humidity) for 24 hours to obtain a polyurethane film.

[0271] The films were tested using a TA Instruments DMA-850. 1 cm × 2.5 cm strips were cut from each film using a metal die. The cut film samples were loaded into film and fiber tension clamps for testing. During the test, a preload of 0.01 N was applied to the cut film samples. The instrument was cooled to -80°C and held for 1 minute, then the temperature was increased from 4°C / min to 200°C, or until the sample was too weak to maintain tension. The sample was vibrated at a frequency of 1 Hz with a strain of 0.1% within the temperature gradient. The storage modulus, loss modulus, and tan(δ) were plotted against temperature for both films. The obtained second storage modulus transition (taken as the starting point of the final decrease in the measured storage modulus, i.e., the second DMA modulus transition onset temperature) was 114.9°C for the control sample.

[0272] In addition, five tensile specimens (according to ASTM D638) were cut from dried and prepared sample films using a metal die. The cut film samples were placed in an INSTRON® 5960 series machine and pulled under tension at 100 mm / min until fracture. 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%. [Examples 2-8]

[0273] Examples 2 to 8 were carried out using the same method as in Example 1 to illustrate the range of polyurethane dispersions. The polyurethanes used and the properties obtained are listed in Tables 3 to 6. [Example 9]

[0274] The sample was prepared by dissolving 0.825 g of gelatin from pig skin in 10 mL of deionized water and stirring with a magnetic stirring rod at 1000 rpm for 1 hour at 50°C. After the gelatin was completely dissolved, the pH of the solution was adjusted to 7.0 with 0.1 N sodium hydroxide. Next, 5.5 g of L3360 was added to the solution and stirred at 1000 rpm for 30 minutes. Then, the polyurethane and gelatin solution was pipetteed into a 10 cm diameter Teflon® evaporating dish. The dish was dried overnight in a 45°C oven. After drying, the dried sample was adjusted in a standard reference atmosphere (23°C, 50% humidity) for 24 hours to prepare a gelatin polyurethane alloy film.

[0275] During pipetting, the gelatin polyurethane solution was milky white in appearance, and no fine particles were visible. After drying, the gelatin polyurethane solution formed a transparent film with a uniform appearance that did not contain optically visible granules. Combining Examples 33 and 34, these results indicate that when the protein is miscible with the rigid phase, the protein polyurethane alloy can be transparent and its properties can be enhanced.

[0276] The DMA test was performed as outlined in Example 1. The second storage modulus transition obtained for the gelatin polyurethane alloy (acquired as the starting point of the final decrease in the measured storage modulus, i.e., the second DMA modulus transition onset temperature) was 180.6°C, which was 65.7°C higher than that of the control sample described in Example 1.

[0277] Tensile tests were performed as outlined in Example 1. The average Young's modulus was 344 MPa, the measured average tensile stress was 19.8 MPa, and the average elongation at break was 197% for the gelatin polyurethane alloy.

[0278] The increase in the second DMA modulus transition onset temperature in this embodiment, compared to polyurethane alone in Example 1, indicates that the dissolved gelatin in the gelatin polyurethane alloy is miscible with the rigid phase of the polyurethane, along with an increase in modulus and strength, and a decrease in elongation. [Examples 10-19]

[0279] Examples 10 to 19 were carried out using the same method as in Example 9 to demonstrate a range of polyurethane dispersions from different manufacturers and different proteins. The properties obtained for these alloys are listed in Tables 3 to 6. [Example 20]

[0280] The sample was prepared by dissolving 0.825 g of Sigma bovine serum albumin (BSA) in 10 mL of deionized water and stirring with a magnetic stirring rod at 1000 rpm for 1 hour at 20°C. Next, 5.5 g of L3360 was added to the solution and stirred at 1000 rpm for 30 minutes. Then, the polyurethane and BSA solution was pipetteed into a 10 cm diameter Teflon® evaporating dish. The dish was dried overnight on a benchtop at 25°C. After drying, the dried sample was adjusted in a standard reference atmosphere (23°C, 50% humidity) for 24 hours to prepare a BSA polyurethane alloy film.

[0281] The DMA test was performed as outlined in Example 1. The second storage modulus transition obtained for the BSA polyurethane alloy (acquired as the starting point of the final decrease in the measured storage modulus, i.e., the second DMA modulus transition onset temperature) was 184.9°C, which was 70°C higher than that of the control sample described in Example 1.

[0282] Tensile tests were performed as outlined in Example 1. The average Young's modulus was 174 MPa, the measured average tensile stress was 11.7 MPa, and the average elongation at break was 123% for the BSA polyurethane alloy. [Example 21]

[0283] Soy protein isolate (SPI) was dispersed by adding 0.75 g of SPI to 15 mL of a 0.05 mol / L sodium hydroxide solution. The dispersion was stirred at 600 rpm for 3 hours at 80°C using a magnetic stirring rod. Next, 5 g of L3360 was added to the solution and stirred at 600 rpm for 30 minutes. Then, the SPI polyurethane solution was pipetteed into a 10 cm diameter Teflon® evaporating dish. The dish was dried overnight in a 45°C oven. After drying, the dried sample was adjusted in a standard reference atmosphere (23°C, 50% humidity) for 24 hours to prepare an SPI polyurethane alloy film.

[0284] The DMA test was performed as outlined in Example 1. The second storage modulus transition obtained for the SPI polyurethane alloy (acquired as the starting point of the final decrease in the measured storage modulus, i.e., the second DMA modulus transition onset temperature) was 186.6°C, which was 72°C higher than the control in Example 1.

[0285] Tensile tests were performed as outlined in Example 1. The average Young's modulus was 396 MPa, the measured average tensile stress was 18 MPa, and the average elongation at break was 151% for the SPI polyurethane alloy.

[0286] The increase in the second DMA modulus transition onset temperature, along with the increase in modulus and strength, and the decrease in tensile strength, indicates that the dissolved SPI in the SPI polyurethane alloy is miscible with the hard phase of the polyurethane. [Examples 22-23]

[0287] Examples 22 and 23 were pre-formed using the same method as in Example 21. The proteins used and the properties obtained for these protein polymer alloys are listed in Tables 3 to 6. [Examples 24-29]

[0288] The samples were prepared by the same method as in Example 9. By varying the amounts of gelatin and L3360, various mass ratios of the two components in the alloy samples were achieved. The masses of gelatin and PU dispersions, as well as the resulting mass fractions, are summarized in Table 2 below.

[0289] [Table 2]

[0290] Tensile and DMA tests were performed as outlined in Example 1. The obtained properties of the alloy are listed in Tables 3 to 6. [Example 30]

[0291] Soy protein isolate (SPI) was dispersed by adding 0.25 g of SPI to 15 mL of deionized water. The dispersion was stirred at 600 rpm for 3 hours at 80°C using a magnetic stirring rod. Next, 6.42 g of L3360 was added to the solution and stirred at 600 rpm for 30 minutes. Then, the SPI polyurethane solution was pipetteed into a 10 cm diameter Teflon® evaporating dish. The dish was dried overnight in a 45°C oven. After drying, the dried sample was adjusted in a standard reference atmosphere (23°C, 50% humidity) for 24 hours to prepare an SPI polyurethane alloy film.

[0292] Tensile and DMA tests were performed as outlined in Example 1. The obtained properties of the alloy are listed in Tables 3 to 6. [Example 31]

[0293] Soy protein isolate (SPI) was dispersed by adding 0.5 g of SPI to 15 mL of a 0.05 mol / L sodium hydroxide solution. The dispersion was stirred at 600 rpm for 3 hours at 80°C using a magnetic stirring rod. Next, 6.42 g of L3360 was 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 adjusted in a standard reference atmosphere (23°C, 50% humidity) for 24 hours to prepare an SPI polyurethane alloy film.

[0294] Tensile and DMA tests were performed as outlined in Example 1. The obtained properties of the alloy are listed in Tables 3 to 6. [Example 32]

[0295] Whey protein (Sigma bovine whey W1500) was dispersed by adding 0.75 g of whey to 15 mL of sodium hydroxide solution at a concentration of 0.05 mol / L. The dispersion was stirred at 600 rpm for 3 hours at 80°C using a magnetic stirring rod. Next, 5 g of L3360 was added to the solution and stirred at 600 rpm for 30 minutes. Then, the whey polyurethane solution was pipetteed 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 adjusted in a standard reference atmosphere (23°C, 50% humidity) for 24 hours to prepare a whey polyurethane alloy film.

[0296] The DMA test was performed as outlined in Example 1. The second storage modulus transition obtained for the whey polyurethane alloy (acquired as the starting point of the final decrease in the measured storage modulus, i.e., the second DMA modulus transition onset temperature) was 100.9°C, which is 14°C lower than the control in Example 1.

[0297] Tensile tests were performed as outlined in Example 1. The average Young's modulus was 105 MPa, the measured average tensile stress was 7.6 MPa, and the average elongation at break was 224% for the whey polyurethane alloy.

[0298] Although whey appears to be miscible with the rigid polyurethane phase, the second DMA modulus transition temperature did not increase due to the poor thermal stability of the protein itself. As mentioned above, whey has a denaturation temperature of 158°C and was therefore considered non-thermally stable. [Example 33]

[0299] 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 containing no other additives, stirred at 600 rpm, heated to 90°C, and maintained for 3 hours.

[0300] Next, 5 g of L3360 was added to a 20 mL glass vial. The glass 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).

[0301] After drying, the casein polyurethane alloy film had an opaque appearance with numerous optically visible granules within the film. The tensile properties of this film were measured by measuring five tensile samples using an INSTRON® 5960 series instrument. The samples were pulled with a tension of 100 mm / min until they broke. The average tensile strength of the film was 4.96 MPa. The average elongation at break of the film was 12.03%. The average Young's modulus of the film was 158 MPa. These results, along with the results of Example 39, indicate that casein is insoluble, does not disperse in water at pH 7, and therefore does not dissolve in L3360 when mixed. [Example 34]

[0302] 0.75 g of casein (from bovine milk, Sigma, C7078) was dispersed in 15 mL of 0.05 mol / L NaOH deionized aqueous solution in a 20 mL glass vial, stirred at 600 rpm, heated to 90 °C, and maintained for 3 hours. A homogeneous dispersion was obtained.

[0303] Next, 5 g of L3360 was added to a 20 mL glass vial. The glass 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).

[0304] After drying, the casein polyurethane alloy film had a transparent and uniform appearance without any optically visible granules in the film. The tensile properties of this film were measured by measuring five tensile samples using an INSTRON® 5960 series machine. The samples were pulled with a tension of 100 mm / min until they broke. The average tensile strength of the film was 15.5 MPa. The average elongation at break of the film was 160%. The average Young's modulus of the film was 160 MPa. The increased modulus, strength, and elongation compared to Example 33 indicate that the modified casein dissolved in the polyurethane and was miscible with the rigid phase of the polyurethane. [Example 35]

[0305] 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 purchased from MP Medicals (IC90545625). The r-collagen was recombinant collagen from Modern Meadow. The solution in the vial was mixed using a magnetic stirring rod at 600 rpm for 2 hours at 80°C.

[0306] Next, 5 g of L3360 was added to a 20 mL glass vial. The glass 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 a 45°C oven. After drying, the dried sample was adjusted in a standard reference atmosphere (23°C, 50% humidity) for 24 hours to prepare an SPI / r-col polyurethane alloy film.

[0307] The tensile properties of this film were measured by measuring five tensile samples using an INSTRON® 5960 series machine. The samples were pulled with a tension of 100 mm / min until they broke. The average tensile strength of the film was 15.71 MPa. The average elongation at break of the film was 175.9%. The average Young's modulus of the film was 247.1 MPa. The film was also tested using a TA Instruments DMA-850 according to the method described in Example 1. The resulting second storage modulus transition (obtained as the starting point of the final 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.

[0308] Compared to Examples 1 and 9, these results show an increase in the second DMA modulus transition onset temperature, along with an increase in elastic modulus and strength and a decrease in elongation, indicating that the blend of SPI and r-col in the polyurethane alloy is miscible with the rigid phase of the polyurethane and exhibits a corresponding enhancement of properties. [Example 37]

[0309] Using the same method as in Example 36, a film was prepared using 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.

[0310] The obtained protein polyurethane alloy film was tested using the same tensile and DMA test methods as described in Example 36. The average tensile strength of the film was 15.36 MPa. The average elongation at break of the film was 183.17%. The average Young's modulus of the film was 231.13 MPa. The second DMA modulus transition onset temperature of the pea protein / r-col polyurethane alloy was 189.65°C.

[0311] Compared to Examples 1 and 9, these results show an increase in the second DMA modulus transition onset temperature, along with an increase in elastic modulus and strength, indicating that the blend of pea protein and r-col in the protein polyurethane alloy is miscible with the rigid phase of the polyurethane and exhibits a corresponding enhancement of properties. [Example 38]

[0312] The gelatin solution was prepared by dissolving 0.825 g of gelatin in 10 mL of deionized water from pig skin (Sigma Aldrich G2500) and stirring with a magnetic stirring rod at 1000 rpm for 1 hour at 50°C. After the gelatin was completely dissolved, 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 a rate of 4.05 parts per 100 parts of gelatin and mixed at 45°C for 15 minutes. Then, 5.5 g of L3360 was added to the solution and stirred at 1000 rpm for 30 minutes. The polyurethane and gelatin solutions were then pipetted into a 10 cm diameter Teflon® evaporating dish. The dish was dried overnight in an oven at 45°C. The resulting film was uniformly dyed, and there was no phase separation or color difference throughout the sample. Equivalent films using the same polyurethane dispersion without protein were not uniformly stained. [Example 39A]

[0313] 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 0.1 mol / L sodium hydroxide solutions. After preparation, 40 mg of DABCO (1,4-diazabicyclo[2.2.2]octane) was added to each solution and dissolved. After dissolving the DABCO, 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 chemically modified soy proteins that exhibited significantly higher solubility in aqueous solution compared to 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 and showed increased solubility compared to the same protein solution without poly(ethylene glycol) monoglycidyl ether. In addition, size exclusion chromatography (SEC) data showed minimal hydrolysis in the soluble modified protein solution, indicating that the protein solubility was due to protein modification and not hydrolysis due to the basic conditions used. [Example 39B]

[0314] 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 0.1 mol / L sodium hydroxide solutions. After preparation, 40 mg of DABCO (1,4-diazabicyclo[2.2.2]octane) was added to each solution and dissolved. After dissolving the DABCO, 300 mg of poly(ethylene glycol) diglycidyl ether-550Mn was added to the 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 soy protein with significantly higher solubility in aqueous solution compared to individual soy proteins with 0.1 mol / L sodium hydroxide alone without modification. The poly(ethylene glycol) diglycidyl ether modified protein solution was significantly clearer and showed increased solubility compared to the same protein solution without poly(ethylene glycol) diglycidyl ether. In addition, SEC data showed minimal hydrolysis in the soluble modified soy protein solution, indicating that the protein solubility was due to protein modification and not hydrolysis due to the basic conditions used. [Example 40]

[0315] SUPRO® XT55 soy protein isolate (SPI) was dispersed by adding 0.75 g of SPI to 5 mL of a 0.1 mol / L sodium hydroxide solution. The dispersion was stirred at 600 rpm for 2 hours at 65°C using a magnetic stirring rod. HeiQ Chemtex 2317 (anionic surfactant) was added at a rate of 5 parts per 100 parts by mass of protein. Next, 5 g of L3360 was 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 adjusted in a standard reference atmosphere (23°C, 50% humidity) for 24 hours to prepare an SPI polyurethane alloy film. [Example 41]

[0316] 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 using 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 1N sodium hydroxide. After pH adjustment, antimicrobial Ultra-Fresh DW-56 was added at a rate of 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 divided equally, and Antifoam 204 (a mixture of organic polyether dispersions from Sigma Aldrich) was added at a rate of 0.5 parts per 100 parts of the estimated final solution weight. The divided solutions were mixed at 50°C for 10 minutes to ensure good dispersion of all components. Next, 25.885 g of L3360 was added to the solution. After adding L3360, the solution was mixed until it reached a temperature of 43°C to 45°C.

[0317] To the other aliquot of the solution, 5.5 parts of HeiQ Chemtex 2216-T (stabilized blend of nonionic and anionic surfactants) and 2.2 parts of HeiQ Chemtex 2317 (stabilized blend of nonionic and anionic surfactants) per 100 parts of the solution weight were added together with 0.1 parts of HeiQ Chemtex 2243 (nonionic silicone dispersion) per 100 parts. The solution was then mechanically foamed at a temperature of 43°C to 45°C until a wet density of 650 g / L to 850 g / L was reached, and the mixture was frozen to form a foamed blend mixture.

[0318] Preskin of protein polyurethane alloy was prepared by preparing surface finishes including a topcoat and a basecoat. The topcoat blend was prepared by blending 9.74 parts of Stahl Melio WF-5227.A LIQ, 100 parts of Stahl WT-42-511, 30 parts of Stahl DI-17-701, 30 parts of Stahl XR-13-820, and 25 parts of water. The basecoat blend was prepared by blending 450 parts of Stahl RC-43-023, 50 parts of Stahl RU-3901, 150 parts of Stahl RA-30, 50 parts of Stahl FI-1208, 30 parts of Stahl XR-13-820, and 100 parts of Stahl RA-22-063.

[0319] A blended non-foaming solution was deposited onto a dried presskin to a target wet thickness of 200 gsm using a drawdown apparatus. The sample was then dried in a Mathis LTE-S Labcoater at 75°C, an air velocity of 2000 rpm, and 70% air was blown from below the sample for 15 minutes to form a protein polyurethane alloy layer. After drying this first layer, a second layer of the blended foaming solution was deposited on top of the first layer to a target wet thickness of 350 gsm. The sample was then dried in a Mathis LTE-S Labcoater for 15 minutes using a gradient drying procedure: 75°C for 5 minutes, then 100°C for 5 minutes, and finally 120°C for 5 minutes, with an air velocity of 700 rpm and 70% air blown from below to form a first foamed protein polyurethane alloy layer. After drying the foam layer, a third layer of the blended foam solution was deposited on the first foam layer to a target wet thickness of 350 gsm. The second foamed protein polyurethane alloy layer was then formed by drying in a Mathis LTE-S Labcoater using a gradient drying procedure: 75°C for 5 minutes, then 100°C for 5 minutes, and finally 120°C for 15 minutes with an air velocity of 700 rpm and 70% air blown from below.

[0320] The sample was completely dried and conditioned for 24 hours in a conditioned chamber at 23°C and 50% humidity. After this, the sample was cut and tested according to the DMA and tensile mechanical property tests described herein. The obtained second storage modulus transition (obtained as the starting point of the final decrease in the measured storage modulus, i.e., the second DMA modulus transition onset temperature) was 190°C, the Young's modulus was 88.9 MPa, the tensile stress was 5.4 MPa, and the elongation at break was 110%. [Example 42]

[0321] The sample was prepared by dissolving 1 g of 50 kDa rCol in 5 mL of deionized water and stirring with a magnetic stirring rod at 1000 rpm for 1 hour at 20°C. The 50 kDa rCol protein was a collagen fragment prepared by Modern Meadow containing the amino acid sequence listed as SEQ ID NO: 1. 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 solutions were 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 adjusted in a standard reference atmosphere (23°C, 50% humidity) for 24 hours to produce a 50 kDa rCol polyurethane alloy film.

[0322] The DMA test was performed as outlined in Example 1. The second storage modulus transition obtained for the 50 kDa rCol polyurethane alloy (acquired as the starting point of the final decrease in the measured storage modulus, i.e., the second DMA modulus transition onset temperature) was 177.8°C, which was 62.9°C higher than that of the control sample described in Example 1.

[0323] Tensile tests were performed as outlined in Example 1. The average Young's modulus was 161 MPa, the measured average tensile stress was 17 MPa, and the average elongation at break was 173% for the 50 kDa rCol polyurethane alloy. [Example 43]

[0324] The sample was prepared by dissolving 1 g of natural Trichoderma cellulase-RG (available from CREATIVE ENZYMES®) in 5 mL of deionized water and stirring with a magnetic stirring rod at 1000 rpm at 20°C for 1 hour. 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 were 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 adjusted in a standard reference atmosphere (23°C, 50% humidity) for 24 hours to produce a cellulase polyurethane alloy film.

[0325] The DMA test was performed as outlined in Example 1. The second storage modulus transition obtained for the Celluase-RG polyurethane alloy (acquired as the starting point of the final decrease in the measured storage modulus, i.e., the second DMA modulus transition onset temperature) was 153.1°C, which was 38.2°C higher than that of the control sample described in Example 1.

[0326] Tensile tests were performed as outlined in Example 1. The average Young's modulus was 184 MPa, the measured average tensile stress was 14.7 MPa, and the average elongation at break was 252% for the cellulase polyurethane alloy. [Example 44]

[0327] The sample was 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 stirring rod at 1000 rpm at 20°C for 1 hour. 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 adjusted in a standard reference atmosphere (23°C, 50% humidity) for 24 hours to produce a cellulase polyurethane alloy film.

[0328] The DMA test was performed as outlined in Example 1. The second storage modulus transition obtained for the Cellulase-IG polyurethane alloy (acquired as the starting point of the final decrease in the measured storage modulus, i.e., the second DMA modulus transition onset temperature) was 122.1°C, which was 7.2°C higher than that of the control sample described in Example 1.

[0329] Tensile tests were performed as outlined in Example 1. The average Young's modulus was 84 MPa, the measured average tensile stress was 15.1 MPa, and the average elongation at break was 286% for the cellulase polyurethane alloy. [Example 45]

[0330] Two control samples (Example 45a and Example 45b) were prepared according to the following process: 0.4 g of AF-715 (an antifoaming agent available from Quaker Color) was mixed with 38 g of a water-mediated polyurethane dispersion, HauthaneHD-2001, manufactured by CLHauthaway & Sons Corporation. 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 then at 100°C for 10 minutes. The coating was then removed from the release paper to prepare a protein-free polyurethane film.

[0331] After drying, the thickness of the sample in Example 45a was 0.4 mm, and the thickness of the sample in Example 45b was also 0.4 mm. As reported in Table 7, the polyurethane film of Example 45a was 30 g / m². 2 The polyurethane film of Example 45b has a water vapor transmission rate of 38 g / m² over 24 hours. 2 It had a water vapor transmission rate of / 24 hours. [Example 46]

[0332] Two samples (Example 46a and Example 46b) were prepared according to the following process. 13.25 g of gelatin from porcine skin was dissolved in 2 g of the 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-mediated polyurethane dispersion Hauthane HD-2001 from CL Hauthane & Sons Corporation was added to the gelatin solution and stirred for 15 minutes. After the gelatin and polyurethane solutions were properly mixed, 1 g of Stahl RM-4410 was added to increase the viscosity of the solution, and the solution was mixed for 5 minutes. Next, this solution was coated onto a 0.35 mm thick microsuede textile whose surface was coated with a thin IMPRANIL® DLS coating layer (0.03 mm thick). The gelatin polyurethane solution was then coated onto the thin IMPRANIL® DLS coating layer using a handheld drawdown device and dried in a standard ambient atmosphere (23°C and 50% humidity) to produce a gelatin-polyurethane film with a textile backing. The thin IMPRANIL® DLS coating prevented the gelatin polyurethane coating from penetrating too deeply into the microsuede textile.

[0333] After drying, the thickness of the sample in Example 46a was 0.77 mm (this 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 in Example 46b was 0.82 mm (this was the sum of the thicknesses of the gelatin-polyurethane film, the thin Impranil® DLS coating, and the microsuede textile).

[0334] As reported in Table 7, the sample for Example 46a was 180 g / m².2 It has a water vapor transmission rate of 150 g / m² over 24 hours, which is compared to the sample in Example 45a. 2 This represents an increase of 142 g / m² per 24 hours compared to sample No. 45b of Example. 2 The increase was over 24 hours. Also, as reported in Table 7, the sample for Example 46b was 138 g / m². 2 It has a water vapor transmission rate of 108 / m³ / 24 hours, which is compared to the sample of Example 45a. 2 This represents an increase of 100 g / m² per 24 hours compared to the sample in Example 45b. 2 This was an increase over a 24-hour period.

[0335] Neither the thin IMPRANIL® DLS coating nor the microsuede textile had a significant effect on the water vapor transmission rate of the samples in Example 46a or 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. [Example 47]

[0336] Two control samples (Example 47a and Example 47b) were prepared according to the following process: 0.4 g of AF-715 (an antifoaming agent available from Quaker Color) was mixed into 38 g of Hauthaway's water-mediated 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 then at 100°C for 10 minutes. The coating was then removed from the release paper to prepare a protein-free polyurethane film.

[0337] After drying, the thickness of the sample in Example 47a was 0.32 mm, and the thickness of the sample in Example 47b was 0.36 mm. As reported in Table 7, the polyurethane film of Example 47a was 23 g / m². 2 The polyurethane film of Example 47b has a water vapor transmission rate of 27 g / m² over 24 hours. 2 It had a water vapor transmission rate of / 24 hours. [Example 48]

[0338] Two samples (Example 48a and Example 48b) were prepared according to the following process. 13.25 g of gelatin from porcine skin was dissolved in 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-mediated polyurethane dispersion L3360 from Hauthawayy was added to the gelatin solution and stirred for 15 minutes. After the gelatin and polyurethane solutions 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. Next, this solution was coated onto a 0.35 mm thick microsuede textile whose surface 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 in a standard ambient atmosphere (23°C and 50% humidity) to produce a gelatin-polyurethane film with a textile backing. The thin IMPRANIL® DLS coating prevented the gelatin-polyurethane coating from penetrating too deeply into the microsuede textile.

[0339] After drying, the thickness of the sample in Example 48a was 0.77 mm (this 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 in Example 48b was 0.84 mm (this was the sum of the thicknesses of the gelatin-polyurethane film, the thin Impranil® DLS coating, and the microsuede textile).

[0340] As reported in Table 7, the sample for Example 48a was 117 g / m². 2 It has a water vapor transmission rate of 94 g / m² over 24 hours, which is 94 g / m² compared to the sample in Example 47a. 2 This represents an increase of 90 g / m² over 24 hours, compared to sample No. 47b of Example. 2 The increase was over 24 hours. Also, as reported in Table 7, the sample for Example 48b was 74 g / m². 2 It has a water vapor transmission rate of 51 g / m² over 24 hours, which is compared to the sample in Example 47a. 2 This represents an increase of 47 g / m² per 24 hours, compared to sample No. 47b of Example. 2 This was an increase over a 24-hour period.

[0341] Neither the thin IMPRANIL® DLS coating nor the microsuede textile had a significant effect on the water vapor transmission rate of the samples in Example 46a or 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. [Example 49]

[0342] Two control samples (Example 49a and Example 49b) were prepared according to the following process: 0.2 g of AF-715 (an antifoaming agent available from Quaker Color) was mixed into 38 g of Hauthaway's water-mediated polyurethane dispersion L3360. The mixture was mixed using an impeller at a speed of 500 rpm 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 again for another 5 minutes. This polyurethane mixture was then coated onto release paper using a Mathis LTE-S Labcoater and dried at 75°C for 10 minutes and then at 100°C for 10 minutes.

[0343] Next, a foaming solution was prepared by mixing Hauthaway's water-mediated polyurethane dispersion L3360 with HeiQ Chemtex 2216-T (3% based on solution weight), HeiQ Chemtex 2317 (3% based on solution weight), HeiQ Chemtex 2241-A (1% based on solution weight), and HeiQ Chemtex 2243 (0.1% based on solution weight). This mixture was stirred at room temperature using an impeller at 500 rpm for 5 minutes. The mixture was then foamed to produce a foamed mixture with a wet density of 700 g / L to 900 g / L. The foamed mixture was coated onto a pre-coated polyurethane layer using a Mathis LTE-S Labcoater and dried at 75°C for 10 minutes and then at 100°C for 10 minutes. After drying this first foamed coating, a second foamed coating layer made from the same foamed mixture was coated onto the first foamed coating under the same conditions. After the second foam layer dried, the three-layer sample was removed from the release paper.

[0344] The thickness of the three-layer sample in Example 49a was 0.23 mm, and the thickness of the three-layer sample in Example 49b was 0.24 mm. As reported in Table 7, the three-layer sample in Example 49a was 83 g / m². 2 It has a water vapor transmission rate of / 24 hours, and the three-layer sample of Example 49b is 87 g / m². 2It had a water vapor transmission rate of / 24 hours. [Example 50]

[0345] Two samples (Example 50a and Example 50b) were 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% by weight based on the amount of soy protein isolate) and AF-715 defoamer (1% by weight based on the weight of the solution) 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 dissolved, 32 g of Hauthaway's water-mediated polyurethane dispersion L3360 was added to the protein solution, and the solution was stirred at 500 rpm with an impeller for 10 minutes at room temperature. Next, this protein solution was coated onto release paper using a Mathis LTE-S Labcoater and dried at 75°C for 10 minutes and then at 100°C for 10 minutes.

[0346] Next, a foaming solution was prepared by mixing 5.3 g of SUPRO® XT221D soy protein isolate with 30 g of water. The pH of the mixture was increased with 1 M NaOH until a pH of 8-9 was achieved. After adjusting the pH and ensuring the soy protein isolate was completely dissolved, Ultra-Fresh DW-56 (15% by weight based on soy protein mass), HeiQ Chemtex 2216-T (3% by weight based on solution weight), HeiQ Chemtex 2317 (3% based on solution weight), HeiQ Chemtex 2241-A (1% based on solution weight), HeiQ Chemtex 2243 (0.1% based on solution weight), and 32 g of Hauthaway's water-mediated polyurethane dispersion L3360 were added to the solution, and the solution was stirred at 500 rpm using an impeller at room temperature for 5 minutes. The solution was then foamed to produce a foaming solution with a wet density of 700 g / L to 900 g / L. The foaming solution was coated onto a pre-coated protein solution layer using a Mathis LTE-S Labcoater and dried at 75°C for 10 minutes and then at 100°C for 10 minutes. After drying the first foaming solution coating, a second foaming layer was coated onto the first foaming coating under the same conditions. After drying the second foaming solution layer, the three-layer sample was removed from the release paper.

[0347] The thickness of the three-layer sample in Example 50a was 0.24 mm, and the thickness of the three-layer sample in Example 50b was 0.25 mm. As reported in Table 7, the sample in Example 50a was 268 g / m². 2 It has a water vapor transmission rate of 185 g / m² over 24 hours, compared to the sample in Example 49a. 2 This represents an increase of 181 g / m² per 24 hours, compared to sample No. 49b of Example. 2 The increase was over 24 hours. Also, as reported in Table 7, the sample for Example 50b was 277 g / m². 2 It has a water vapor transmission rate of 194 g / m² over 24 hours, compared to the sample in Example 49a. 2 This represents an increase of 190 g / m² per 24 hours compared to the sample in Example 49b. 2This was an increase over a 24-hour period. [Example 51]

[0348] A control sample was prepared by mixing 0.4 g of AF-715 (an antifoaming agent available from Quaker Color) with 38 g of Covestro's water-mediated polyurethane dispersion IMPRAPERM® DL5249. 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 then at 100°C for 10 minutes. The coating was then removed from the release paper to prepare a protein-free polyurethane film.

[0349] After drying, the thickness of the sample was 0.08 mm. As reported in Table 7, the polyurethane film was 338 g / m². 2 It had a water vapor transmission rate of / 24 hours. [Example 52]

[0350] Two samples (Example 52a and Example 52b) were 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% by weight based on the amount of soy protein isolate) and AF-715 defoamer (1% by weight based on the weight of the solution) 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 dissolved, 32 g of Covestro's water-mediated polyurethane dispersion IMPRAPERM® DL 5249 was added to the protein solution, and the solution was stirred at 500 rpm with an impeller for 10 minutes at room temperature. Next, this protein solution was coated onto release paper using a Mathis LTE-S Labcoater and dried at 75°C for 10 minutes and then at 100°C for 10 minutes.

[0351] Next, a foaming solution was prepared by mixing 5.3 g of SUPRO® XT221D soy protein isolate with 30 g of water. The pH of the mixture was increased with 1 M NaOH until a pH of 8-9 was achieved. After adjusting the pH and ensuring the soy protein isolate was completely dissolved, Ultra-Fresh DW-56 (15% by weight based on soy protein mass), HeiQ Chemtex 2216-T (3% by weight based on solution weight), HeiQ Chemtex 2317 (3% based on solution weight), HeiQ Chemtex 2241-A (1% based on solution weight), HeiQ Chemtex 2243 (0.1% based on solution weight), and 32 g of Covestro's water-mediated polyurethane dispersion IMPRAPERM® DL 5249 were added to the solution, and the solution was stirred at 500 rpm using an impeller for 5 minutes at room temperature. Next, this solution was foamed to prepare a foamed solution with a wet density of 700 g / L to 900 g / L. The foamed solution was coated onto a pre-coated protein solution layer using a Mathis LTE-S Labcoater and dried at 75°C for 10 minutes and then at 100°C for 10 minutes. After drying the first foamed coating, a second foamed layer was coated onto the first foamed coating under the same conditions. After drying the second foamed solution layer, the three-layer sample was removed from the release paper.

[0352] The thickness of the three-layer sample in Example 52a was 0.22 mm, and the thickness of the three-layer sample in Example 52b was 0.23 mm. As reported in Table 7, the sample in Example 52a was 626 g / m². 2 The sample for Example 52b has a water vapor transmission rate of 644 g / m² over 24 hours. 2The water vapor transmission rates were measured over 24 hours. Since all three samples contained a non-foamed layer of substantially the same thickness prepared using IMPRAPERM(registered trademark) DL5249, the water vapor transmission rates of Examples 52a and 52b can be compared with those of Example 51 to evaluate the change in water vapor transmission rate. The foamed layers of Examples 52a and 52b did not significantly affect the water vapor transmission rates of these samples due to their high porosity. Compared to the sample of Example 51, the sample of Example 52a had a water vapor transmission rate of 288 g / m². 2 The increase over 24 hours was observed, and the sample in Example 52b showed 306 g / m³ in water vapor permeability. 2 This showed an increase over a 24-hour period. [Example 53]

[0353] A control sample was prepared by mixing 0.2 g of AF-715 (an antifoaming agent available from Quaker Color) with 38 g of Covestro's water-mediated polyurethane dispersion IMPRAPERM® DL5249. The mixture was mixed using an impeller at a speed of 500 rpm 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 again for another 5 minutes. This polyurethane mixture was then coated onto release paper using a Mathis LTE-S Labcoater and dried at 75°C for 10 minutes and then at 100°C for 10 minutes.

[0354] Next, a foaming solution was prepared by mixing Hauthaway's water-mediated polyurethane dispersion L3360 with HeiQ Chemtex 2216-T (3% based on solution weight), HeiQ Chemtex 2317 (3% based on solution weight), HeiQ Chemtex 2241-A (1% based on solution weight), and HeiQ Chemtex 2243 (0.1% based on solution weight). This mixture was stirred at room temperature using an impeller at 500 rpm for 5 minutes. The mixture was then foamed to produce a foamed mixture with a wet density of 700 g / L to 900 g / L. The foamed mixture was coated onto a pre-coated polyurethane layer using a Mathis LTE-S Labcoater and dried at 75°C for 10 minutes and then at 100°C for 10 minutes. After drying this first foamed coating, a second foamed coating layer made from the same L3360 foamed mixture was coated onto the first foamed coating under the same conditions. After the second foam layer dried, the three-layer sample was removed from the release paper.

[0355] The thickness of the three-layer sample in Example 53 was 0.32 mm. As reported in Table 7, the three-layer sample in Example 53 had a water vapor transmission rate of 84 g / m². 2 It was 24 hours. [Example 54]

[0356] A sample was prepared by mixing 5.3 g of SUPRO® XT221D soy protein isolate with 30 g of water. The pH of the mixture was increased with 1 M NaOH until a pH of 8–9 was achieved. After adjusting the pH, Ultra-Fresh DW-56 (15% by weight based on the amount of soy protein isolate) and AF-715 defoamer (1% by weight based on the weight of the solution) 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 dissolved, 53.7 g of Covestro's water-mediated polyurethane dispersion IMPRAPERM® DL 5249 was added to the protein solution, and the solution was stirred at 500 rpm with an impeller for 10 minutes at room temperature. This protein solution was then coated onto release paper using Mathis LTE-S Labcoater and dried at 75°C for 10 minutes and at 100°C for 10 minutes.

[0357] Next, a foaming solution was prepared by mixing 5.3 g of SUPRO® XT221D soy protein isolate with 30 g of water. The pH of the mixture was increased with 1 M NaOH until a pH of 8-9 was achieved. After adjusting the pH and ensuring the soy protein isolate was completely dissolved, Ultra-Fresh DW-56 (15% by weight based on soy protein mass), HeiQ Chemtex 2216-T (3% by weight based on solution weight), HeiQ Chemtex 2317 (3% based on solution weight), HeiQ Chemtex 2241-A (1% based on solution weight), HeiQ Chemtex 2243 (0.1% based on solution weight), and 53.7 g of Hauthaway's water-mediated polyurethane dispersion L3360 were added to the solution, and the solution was stirred at 500 rpm using an impeller at room temperature for 5 minutes. The solution was then foamed to produce a foaming solution with a wet density of 700 g / L to 900 g / L. The foaming solution was coated onto a pre-coated protein solution layer using a Mathis LTE-S Labcoater and dried at 75°C for 10 minutes and then at 100°C for 10 minutes. After drying this first foaming solution coating, a second foamed L3360 layer was coated onto the first foaming coating under the same conditions. After drying the second foaming solution layer, the three-layer sample was removed from the release paper.

[0358] The thickness of the three-layer sample in Example 54 was 0.32 mm. As reported in Table 7, the sample in Example 54 was 166 g / m². 2 It has a water vapor transmission rate of 82 g / m² over 24 hours, compared to the sample in Example 53. 2 The increase was over 24 hours. The graph in Figure 23 shows that the permeability of sample No. 54 was consistent over time. The amount of water transported through the sample increased linearly with time during the permeability test. The graph in Figure 23 shows that the protein in the protein polyurethane alloy did not cause any significant fluctuations in the permeability of the alloy over time. [Example 55]

[0359] A control sample was prepared by mixing 0.4 g of AF-715 (an antifoaming agent manufactured by Quaker Color) with 38 g of a water-mediated polyurethane dispersion consisting of 25% by weight of IMPRAPERM® DL5249 manufactured by Covestro and 75% by weight of L3360 manufactured by Hautaway. 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 at 100°C for 10 minutes. The coating was then removed from the release paper to prepare a protein-free polyurethane film.

[0360] After drying, the thickness of the sample was 0.07 mm. As reported in Table 7, the polyurethane film was 168 g / m². 2 It had a water vapor transmission rate of / 24 hours. [Example 56]

[0361] A sample was prepared by mixing 5.3 g of SUPRO® XT221D soy protein isolate with 30 g of water. The pH of the mixture was increased with 1 M NaOH until a pH of 8-9 was achieved. After pH adjustment, Ultra-Fresh DW-56 (15 wt% based on the amount of soy protein isolate) and AF-715 defoamer (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 dissolved, 53.7 g of a water-mediated polyurethane dispersion consisting of 25 wt% IMPRAPERM® DL 5249 from Covestro and 75 wt% L3360 from Hauthaway were added to the protein solution, and the solution was stirred at 500 rpm with an impeller for 10 minutes at room temperature. Next, this protein solution was coated onto release paper using a Mathis LTE-S Labcoater and dried at 75°C for 10 minutes and then at 100°C for 10 minutes.

[0362] After drying, the sample thickness was 0.05 mm. As reported in Table 7, the sample was 266 g / m². 2 It has a water vapor transmission rate of 98 g / m² over 24 hours, compared to sample No. 55 of Example. 2 This was an increase over a 24-hour period.

[0363] Exemplary table Tables 3 to 6 below report the DMA and mechanical property test results for Examples 1 to 31. In the tables, "Sancure" polyurethane refers to SANCURE® 20025F, an aliphatic polyester polyurethane dispersion with 47% solids in water manufactured by Lubrizol. "Impranil DLS" polyurethane refers to IMPRANIL® DLS, an aliphatic polyester polyurethane with 50% solids in water manufactured by Covestro. "L2996" polyurethane refers to an aliphatic polycarbonate polyurethane dispersion with 35% solids in water manufactured by Hauthaway. "Gelatin" protein refers to Sigma's Type A porcine skin gelatin G2500. "SPI" protein refers to MP Medicals' soy protein isolate IC90545625. "Collagen" protein refers to bovine collagen from Wuxi BIOT biology technology in China. "BSA" protein refers to Sigma's bovine serum albumin 5470. The "rCol" protein is recombinant bovine collagen prepared with yeast from Modern Meadow. The "albumin" protein is chicken egg white albumin A5253 from Sigma. The "pea" protein is pea protein powder MTX5232 from Bobs Red Mills. The "peanut" protein is peanut protein powder from Tru-Nut. Table 7 reports the results of the water vapor transmission rate tests for Examples 45 to 56.

[0364] [Table 3]

[0365] [Table 4]

[0366] [Table 5]

[0367] [Table 6]

[0368] [Table 7]

[0369] While various embodiments have been described herein, they are presented as examples and not as limitations. It is clear that any adaptations and modifications are intended to be within the meaning and scope of the equivalent embodiments disclosed herein, based on the teachings and guidance presented herein. Therefore, it will be apparent to those skilled in the art that various changes in form and detail can be made to the embodiments disclosed herein without departing from the spirit and scope of this disclosure. The elements of the embodiments presented herein are not necessarily mutually exclusive, but can be interchanged to satisfy various circumstances, as will be understood by those skilled in the art.

[0370] Embodiments of the Disclosure are described in detail herein with reference to such embodiments as shown in the accompanying drawings, and similar reference numerals are used to indicate identical or functionally similar elements. References such as “one embodiment,” “a certain embodiment,” “several embodiments,” and “a particular embodiment” indicate that the described embodiments may include certain features, structures, or characteristics, but not all embodiments necessarily include such features, structures, or characteristics. Furthermore, such phrases do not necessarily refer to the same embodiments. Furthermore, where certain features, structures, or characteristics are described in relation to a particular embodiment, whether explicitly stated or not, any impact on such features, structures, or characteristics in relation to other embodiments shall be known to those skilled in the art.

[0371] The examples provided are illustrative but not limiting to the present disclosure. Other suitable modifications and adaptations of various conditions and parameters commonly encountered in the art, as will be apparent to those skilled in the art, are within the spirit and scope of this disclosure.

[0372] It should be understood that any expressions or technical terms used herein are for illustrative purposes only and not to limit them. The scope and breadth of this disclosure should not be limited by any of the exemplary embodiments described above, but should be defined in accordance with the following claims and their equivalents.

[0373] array Sequence ID 1: Human collagen alpha-1(III) chain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he present invention includes the following embodiments. [Claim 1] A protein polyurethane alloy containing a protein dissolved within polyurethane, wherein the protein is a protein other than soy protein. [Claim 2] The aforementioned protein polyurethane alloy is as follows: Dynamic Mechanical Analysis (DMA) tan(δ) peaks at temperatures ranging from approximately -60°C to approximately 30°C, The second DMA modulus transition onset temperature is in the range of approximately 120°C to approximately 200°C, A protein polyurethane alloy according to claim 1, having the following characteristics. [Claim 3] The protein polyurethane alloy according to claim 1 or claim 2, wherein the protein polyurethane alloy is transparent. [Claim 4] The protein polyurethane alloy according to any one of claims 1 to 3, wherein the polyurethane has a Young's modulus in the absence of protein, and the protein polyurethane alloy has a Young's modulus in the absence of protein that is greater than the Young's modulus of the polyurethane in the range of about 10% to about 600%. [Claim 5] The protein polyurethane alloy according to any one of claims 1 to 3, wherein the polyurethane has a Young's modulus in the absence of protein, and the protein polyurethane alloy has a Young's modulus in the absence of protein that is greater than the Young's modulus of the polyurethane in the range of about 40% to about 600%. [Claim 6] The protein polyurethane alloy according to any one of claims 1 to 5, wherein the polyurethane has a Young's modulus in the absence of protein, and the protein polyurethane alloy has a Young's modulus in the absence of protein that is greater than the Young's modulus of the polyurethane in the range of about 10 MPa to about 350 MPa. [Claim 7] The protein polyurethane alloy according to any one of claims 1 to 5, wherein the polyurethane has a Young's modulus in the absence of protein, and the protein polyurethane alloy has a Young's modulus in the absence of protein that is greater than the Young's modulus of the polyurethane in the range of about 25 MPa to about 350 MPa. [Claim 8] The protein polyurethane alloy according to any one of claims 1 to 5, wherein the polyurethane has a Young's modulus in the absence of protein, and the protein polyurethane alloy has a Young's modulus in the absence of protein that is greater than the Young's modulus of the polyurethane in the range of about 100 MPa to about 350 MPa. [Claim 9] The protein polyurethane alloy according to any one of claims 1 to 8, wherein the protein polyurethane alloy has a Young's modulus in the range of about 50 MPa to about 450 MPa. [Claim 10] The protein polyurethane alloy according to any one of claims 1 to 8, wherein the protein polyurethane alloy has a Young's modulus in the range of about 75 MPa to about 450 MPa. [Claim 11] The protein polyurethane alloy according to any one of claims 1 to 10, wherein the polyurethane has a second DMA modulus transition onset temperature in the absence of protein, and the protein polyurethane alloy has a second DMA modulus transition onset temperature in a range of Celsius that is about 5% to about 70% greater than the second DMA modulus transition onset temperature of the polyurethane in the absence of protein. [Claim 12] The protein polyurethane alloy according to any one of claims 1 to 10, wherein the polyurethane has a second DMA modulus transition onset temperature in the absence of protein, and the protein polyurethane alloy has a second DMA modulus transition onset temperature in a range of Celsius that is about 15% to about 70% greater than the second DMA modulus transition onset temperature of the polyurethane in the absence of protein. [Claim 13] The protein polyurethane alloy according to any one of claims 1 to 12, wherein the polyurethane has a second DMA modulus transition onset temperature in the absence of protein, and the protein polyurethane alloy has a second DMA modulus transition onset temperature in a range greater than the second DMA modulus transition onset temperature of the polyurethane in the absence of protein, in a range of about 5°C to about 100°C. [Claim 14] The protein polyurethane alloy according to any one of claims 1 to 12, wherein the polyurethane has a second DMA modulus transition onset temperature in the absence of protein, and the protein polyurethane alloy has a second DMA modulus transition onset temperature in a range greater than the second DMA modulus transition onset temperature of the polyurethane in the absence of protein, in a range of about 20°C to about 80°C. [Claim 15] The protein polyurethane alloy according to any one of claims 1 to 12, wherein the polyurethane has a second DMA modulus transition onset temperature in the absence of protein, and the protein polyurethane alloy has a second DMA modulus transition onset temperature in a range greater than the second DMA modulus transition onset temperature of the polyurethane in the absence of protein, in the range of about 40°C to about 80°C. [Claim 16] The protein polyurethane alloy according to any one of claims 1 to 15, wherein the protein polyurethane alloy has a second DMA modulus transition onset temperature in the range of about 130°C to about 200°C. [Claim 17] The protein polyurethane alloy according to any one of claims 1 to 15, wherein the protein polyurethane alloy has a second DMA modulus transition onset temperature in the range of about 165°C to about 200°C. [Claim 18] The aforementioned protein is as follows: (a) The isoelectric point in the range of approximately 4 to approximately 5, (b) Lysine weight percentages ranging from approximately 1% to approximately 100% by weight, A protein polyurethane alloy according to any one of claims 1 to 17, having the following characteristics. [Claim 19] The protein polyurethane alloy according to any one of claims 1 to 18, wherein the polyurethane has a tensile strength in the absence of protein, and the protein polyurethane alloy has a tensile strength that is about 5% to about 55% greater than the tensile strength of the polyurethane in the absence of protein. [Claim 20] The protein polyurethane alloy according to any one of claims 1 to 18, wherein the polyurethane has a tensile strength in the absence of protein, and the protein polyurethane alloy has a tensile strength that is about 15% to about 55% greater than the tensile strength of the polyurethane in the absence of protein. [Claim 21] The protein polyurethane alloy according to any one of claims 1 to 20, wherein the polyurethane has a tensile strength in the absence of protein, and the protein polyurethane alloy has a tensile strength in the range of about 2 MPa to about 8 MPa that is greater than the tensile strength of the polyurethane in the absence of protein. [Claim 22] The protein polyurethane alloy according to any one of claims 1 to 20, wherein the polyurethane has a tensile strength in the absence of protein, and the protein polyurethane alloy has a tensile strength in the range of about 5 MPa to about 8 MPa that is greater than the tensile strength of the polyurethane in the absence of protein. [Claim 23] The protein polyurethane alloy according to any one of claims 1 to 22, wherein the protein polyurethane alloy has a tensile strength in the range of about 7 MPa to about 21 MPa. [Claim 24] A protein polyurethane alloy according to any one of claims 1 to 23, comprising approximately 10% to approximately 50% by weight of the protein and approximately 50% to approximately 90% by weight of the polyurethane. [Claim 25] A protein polyurethane alloy according to any one of claims 1 to 23, comprising approximately 20% to approximately 35% by weight of the protein and approximately 65% ​​to approximately 80% by weight of the polyurethane. [Claim 26] The protein polyurethane alloy according to any one of claims 1 to 25, wherein the protein is a protein other than collagen. [Claim 27] The protein polyurethane alloy according to any one of claims 1 to 26, wherein the polyurethane has a water vapor permeability in the absence of protein, and the protein polyurethane alloy has a water vapor permeability that is greater in the range of about 20% to about 600% than the water vapor permeability of the polyurethane in the absence of protein. [Claim 28] The polyurethane has a water vapor permeability in the absence of protein, and the protein polyurethane alloy has a water vapor permeability of approximately 30 g / m² higher than the water vapor permeability of the polyurethane in the absence of protein. 2 / 24 hours ~ approx. 500g / m 2 A protein polyurethane alloy according to any one of claims 1 to 27, having a high water vapor permeability over a range of 24 hours. [Claim 29] The aforementioned protein polyurethane alloy is approximately 30 g / m² 2 / 24 hours ~ approx. 1000g / m 2 A protein polyurethane alloy according to any one of claims 1 to 28, having a water vapor permeability over a range of 24 hours. [Claim 30] A soy protein polyurethane alloy comprising soy protein dissolved within polyurethane, wherein the soy protein polyurethane alloy has a dynamic mechanical analysis (DMA) tan(δ) peak at temperatures in the range of about -60°C to about 30°C, and a second DMA modulus transition onset temperature in the range of about 130°C to about 200°C. [Claim 31] The soy protein polyurethane alloy according to claim 30, wherein the soy protein polyurethane alloy is transparent. [Claim 32] The soy protein polyurethane alloy according to claim 30 or claim 31, wherein the polyurethane has a Young's modulus in the absence of soy protein, and the soy protein polyurethane alloy has a Young's modulus in the absence of soy protein that is greater than the Young's modulus of the polyurethane in the range of about 60% to about 570%. [Claim 33] The soy protein polyurethane alloy according to any one of claims 30 to 32, wherein the polyurethane has a Young's modulus in the absence of soy protein, and the soy protein polyurethane alloy has a Young's modulus in the absence of soy protein that is greater than the Young's modulus of the polyurethane in the range of about 35 MPa to about 340 MPa. [Claim 34] The soy protein polyurethane alloy according to any one of claims 30 to 33, wherein the soy protein polyurethane alloy has a Young's modulus in the range of about 90 MPa to about 400 MPa. [Claim 35] The soy protein polyurethane alloy according to any one of claims 30 to 34, wherein the polyurethane has a second DMA modulus transition onset temperature in the absence of soy protein, and the second DMA modulus transition onset temperature of the soy protein polyurethane alloy is in the range of 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. [Claim 36] The soy protein polyurethane alloy according to any one of claims 30 to 35, wherein the polyurethane has a tensile strength in the absence of soy protein, and the soy protein polyurethane alloy has a tensile strength in the range of about 10% to about 45% greater than the tensile strength of the polyurethane in the absence of soy protein. [Claim 37] The soy protein polyurethane alloy according to any one of claims 30 to 36, wherein the polyurethane has a tensile strength in the absence of soy protein, and the soy protein polyurethane alloy has a tensile strength in the range of about 1.5 MPa to about 5.5 MPa that is greater than the tensile strength of the polyurethane in the absence of soy protein. [Claim 38] The soy protein polyurethane alloy according to any one of claims 30 to 37, wherein the soy protein polyurethane alloy has a tensile strength in the range of about 14 MPa to about 19 MPa. [Claim 39] A soy protein polyurethane alloy according to any one of claims 30 to 38, comprising approximately 10% to approximately 50% by weight of the soy protein and approximately 50% to approximately 90% by weight of the polyurethane. [Claim 40] A soy protein polyurethane alloy according to any one of claims 30 to 38, comprising approximately 20% to approximately 35% by weight of the soy protein and approximately 65% ​​to approximately 80% by weight of the polyurethane. [Claim 41] The soy protein polyurethane alloy according to any one of claims 30 to 40, wherein the polyurethane has a water vapor permeability in the absence of protein, and the soy protein polyurethane alloy has a water vapor permeability that is greater in the range of about 20% to about 600% than the water vapor permeability of the polyurethane in the absence of protein. [Claim 42] The polyurethane has a water vapor permeability in the absence of protein, and the soy protein polyurethane alloy has a water vapor permeability of approximately 30 g / m² higher than the water vapor permeability of the polyurethane in the absence of protein. 2 / 24 hours ~ approx. 500g / m 2 A soy protein polyurethane alloy according to any one of claims 30 to 41, having a high water vapor permeability over a range of 24 hours. [Claim 43] The aforementioned soy protein polyurethane alloy is approximately 30 g / m². 2 / 24 hours ~ approx. 1000g / m 2 A soy protein polyurethane alloy according to any one of claims 30 to 42, having a water vapor permeability over a range of 24 hours. [Claim 44] The soy protein polyurethane alloy according to any one of claims 30 to 43, wherein the soy protein is a soy protein isolate. [Claim 45] The soy protein polyurethane alloy according to any one of claims 30 to 43, wherein the soy protein is a chemically modified soy protein isolate.

Claims

1. A protein polyurethane alloy comprising a protein dissolved in polyurethane, wherein the protein is a protein other than soy protein, the polyurethane has a second DMA modulus transition onset temperature in the absence of the protein, and the protein polyurethane alloy has a second DMA modulus transition onset temperature at a temperature in degrees Celsius that is about 5% to about 70% higher than the second DMA modulus transition onset temperature of the polyurethane in the absence of the protein.

2. The protein polyurethane alloy exhibits a tan(δ) peak in dynamic mechanical analysis (DMA) at temperatures ranging from approximately -60°C to approximately 30°C. The protein polyurethane alloy according to claim 1, wherein the second DMA modulus transition onset temperature of the protein polyurethane alloy is in the range of about 120°C to about 200°C.

3. The protein polyurethane alloy according to claim 1 or claim 2, wherein the protein polyurethane alloy is transparent.

4. The protein polyurethane alloy according to any one of claims 1 to 3, wherein the polyurethane has a Young's modulus in the absence of protein, and the protein polyurethane alloy has a Young's modulus that is about 10% to about 600% greater than the Young's modulus of the polyurethane in the absence of protein.

5. The protein polyurethane alloy according to any one of claims 1 to 3, wherein the polyurethane has a Young's modulus in the absence of protein, and the protein polyurethane alloy has a Young's modulus that is about 40% to about 600% greater than the Young's modulus of the polyurethane in the absence of protein.

6. The protein polyurethane alloy according to any one of claims 1 to 5, wherein the polyurethane has a Young's modulus in the absence of protein, and the protein polyurethane alloy has a Young's modulus that is about 10 MPa to about 350 MPa greater than the Young's modulus of the polyurethane in the absence of protein.

7. The protein polyurethane alloy according to any one of claims 1 to 5, wherein the polyurethane has a Young's modulus in the absence of protein, and the protein polyurethane alloy has a Young's modulus that is about 25 MPa to about 350 MPa greater than the Young's modulus of the polyurethane in the absence of protein.

8. The protein polyurethane alloy according to any one of claims 1 to 5, wherein the polyurethane has a Young's modulus in the absence of protein, and the protein polyurethane alloy has a Young's modulus that is about 100 MPa to about 350 MPa greater than the Young's modulus of the polyurethane in the absence of protein.

9. The protein polyurethane alloy according to any one of claims 1 to 8, wherein the protein polyurethane alloy has a Young's modulus in the range of about 50 MPa to about 450 MPa.

10. The protein polyurethane alloy according to any one of claims 1 to 8, wherein the protein polyurethane alloy has a Young's modulus in the range of about 75 MPa to about 450 MPa.

11. The protein polyurethane alloy according to any one of claims 1 to 10, wherein the second DMA modulus transition onset temperature in degrees Celsius is about 15% to about 70% greater than the second DMA modulus transition onset temperature of the polyurethane in the absence of protein.

12. The protein polyurethane alloy according to any one of claims 1 to 11, wherein the second DMA modulus transition onset temperature is about 5°C to about 100°C greater than the second DMA modulus transition onset temperature of the polyurethane in the absence of protein.

13. The protein polyurethane alloy according to any one of claims 1 to 11, wherein the second DMA modulus transition onset temperature is about 20°C to about 80°C greater than the second DMA modulus transition onset temperature of the polyurethane in the absence of protein.

14. The protein polyurethane alloy according to any one of claims 1 to 11, wherein the second DMA modulus transition onset temperature is about 40°C to about 80°C greater than the second DMA modulus transition onset temperature of the polyurethane in the absence of protein.

15. The protein polyurethane alloy according to any one of claims 1 to 14, wherein the second DMA modulus transition onset temperature of the protein polyurethane alloy is in the range of about 130°C to about 200°C.

16. The protein polyurethane alloy according to any one of claims 1 to 14, wherein the second DMA modulus transition onset temperature of the protein polyurethane alloy is in the range of about 165°C to about 200°C.

17. The aforementioned protein, (a) Isoelectric point in the range of approximately 4 to approximately 5, (b) Lysine weight percentages in the range of approximately 1% to approximately 100% by weight, A protein polyurethane alloy according to any one of claims 1 to 16, having the features described herein.

18. The protein polyurethane alloy according to any one of claims 1 to 17, wherein the polyurethane has a tensile strength in the absence of protein, and the protein polyurethane alloy has a tensile strength that is about 5% to about 55% greater than the tensile strength of the polyurethane in the absence of protein.

19. The protein polyurethane alloy according to any one of claims 1 to 17, wherein the polyurethane has a tensile strength in the absence of protein, and the protein polyurethane alloy has a tensile strength that is about 15% to about 55% greater than the tensile strength of the polyurethane in the absence of protein.

20. The protein polyurethane alloy according to any one of claims 1 to 19, wherein the polyurethane has a tensile strength in the absence of protein, and the protein polyurethane alloy has a tensile strength about 2 MPa to about 8 MPa greater than the tensile strength of the polyurethane in the absence of protein.

21. The protein polyurethane alloy according to any one of claims 1 to 19, wherein the polyurethane has a tensile strength in the absence of protein, and the protein polyurethane alloy has a tensile strength about 5 MPa to about 8 MPa greater than the tensile strength of the polyurethane in the absence of protein.

22. The protein polyurethane alloy according to any one of claims 1 to 21, wherein the protein polyurethane alloy has a tensile strength in the range of about 7 MPa to about 21 MPa.

23. A protein polyurethane alloy according to any one of claims 1 to 22, comprising approximately 10% to approximately 50% by weight of the protein and approximately 50% to approximately 90% by weight of the polyurethane.

24. A protein polyurethane alloy according to any one of claims 1 to 22, comprising approximately 20% to approximately 35% by weight of the protein and approximately 65% ​​to approximately 80% by weight of the polyurethane.

25. The protein polyurethane alloy according to any one of claims 1 to 24, wherein the protein is a protein other than collagen.

26. The protein polyurethane alloy according to any one of claims 1 to 25, wherein the polyurethane has a water vapor permeability in the absence of protein, and the protein polyurethane alloy has a water vapor permeability that is about 20% to about 600% greater than the water vapor permeability of the polyurethane in the absence of protein.

27. The polyurethane has a water vapor permeability in the absence of protein, and the protein polyurethane alloy has a water vapor permeability of about 30 g / m² higher than the water vapor permeability of the polyurethane in the absence of protein. ２ / 24 hours ~ approx. 500g / m ２ A protein polyurethane alloy according to any one of claims 1 to 26, having a high water vapor permeability over 24 hours.

28. The aforementioned protein polyurethane alloy is approximately 30 g / m ２ / 24 hours ~ approx. 1000g / m ２ A protein polyurethane alloy according to any one of claims 1 to 27, having a water vapor permeability in the range of 24 hours.

Images