Protein polyurethane alloys and layered materials including the same

Abstract

To provide protein polyurethane alloys including proteins dissolved in polyurethanes.SOLUTION: A soy protein polyurethane alloy comprises a soy protein dissolved in a polyurethane. The soy protein polyurethane alloy has a Dynamic Mechanical Analysis (DMA) tan(δ) peak at a temperature ranging from about -60°C to about 30°C and a second DMA modulus transition onset temperature ranging from about 130°C to about 200°C.SELECTED DRAWING: None

Description

[Technical Field]

[0001] (Reference to electronically submitted sequence listing) Sequence Listing submitted electronically in an ASCII text file with this application (Name: 4431_068PC03_Seqlisting_ST25.txt, Size The entire contents of the document (4,936 bytes, and date of creation: April 22, 2021) are available by reference. The body is incorporated herein.

[0002] FIELD OF THE INVENTION The present disclosure provides a protein polymer comprising one or more proteins dissolved in a polyurethane. In certain embodiments, the present disclosure relates to urethane alloys. The present invention relates to a protein polyurethane alloy containing one or more proteins dissolved therein. In some embodiments, the protein polymer alloy has the same look, feel, and texture as natural leather. and aesthetic and / or mechanical properties, which are comparable to those previously prepared from natural leather. It can be used to make articles and goods. [Background technology]

[0003] Leather is used in the furniture industry, where leather is regularly used as an upholstery material, and in the bread industry, where leather is used as a the clothing industry, where leather is used to make pants and jackets; Used in the shoe industry, luggage industry, handbags, and accessories It is a versatile product used across many industries, including the automotive industry as well as the automotive industry. The global trade value of 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 skins and therefore contributes to the farming and Raising livestock requires huge amounts of feed, pasture, water, and fossil fuels. necessary and contributes to the pollution of the air and waterways by greenhouse gases such as methane. Leather production also raises social concerns related to the treatment of animals. There is also a decline in the availability of proven traditional high-quality hides. For these reasons, alternatives to meet the demand for leather are desirable. Summary of the Invention [Means for solving the problem]

[0004] The present disclosure provides protein polymers suitable for use in a variety of applications, including as a substitute for natural leather. We provide urethane alloys.

[0005] The first embodiment (1) of the present disclosure is a protein-containing polyurethane. A modified polyurethane alloy, wherein the protein is a protein other than soy protein. This is aimed at protein polyurethane alloys.

[0006] In the second embodiment (2), the protein polyurethane alloy of the first embodiment (1) is Dynamic Mechanical Analysis (DMA) at temperatures ranging from about -60°C to about 30°C lysis (DMA) tan(δ) peak and a second peak over the range of about 120 °C to about 200 °C. and DMA modulus transition onset temperature.

[0007] In the third embodiment (3), the tamper-proof function of the first embodiment (1) or the second embodiment (2) is The crystalline polyurethane alloy is transparent.

[0008] In the fourth embodiment (4), a protein according to any one of the embodiments (1) to (3) is used. The polyurethane of the modified polyurethane alloy has a Young's modulus in the absence of protein. The protein polyurethane alloy exhibits the same properties as polyurethane in the absence of protein. The Young's modulus is greater than the Young's modulus by about 10% to about 600%.

[0009] In the fifth embodiment (5), a protein according to any one of the embodiments (1) to (3) is used. The polyurethane of the modified polyurethane alloy has a Young's modulus in the absence of protein. The protein polyurethane alloy exhibits the same properties as polyurethane in the absence of protein. The Young's modulus is greater than the Young's modulus by about 40% to about 600%.

[0010] In the sixth embodiment (6), a protein according to any one of the embodiments (1) to (5) is used. The polyurethane of the modified polyurethane alloy has a Young's modulus in the absence of protein. The protein polyurethane alloy exhibits the same properties as polyurethane in the absence of protein. The Young's modulus is greater than the Young's modulus in the range of about 10 MPa to about 350 MPa.

[0011] In the seventh embodiment (7), a protein according to any one of the embodiments (1) to (5) is used. The polyurethane of the modified polyurethane alloy has a Young's modulus in the absence of protein. The protein polyurethane alloy exhibits the same properties as polyurethane in the absence of protein. The Young's modulus is greater than the Young's modulus in the range of about 25 MPa to about 350 MPa.

[0012] In the eighth embodiment (8), a protein according to any one of the embodiments (1) to (5) is used. The polyurethane of the modified polyurethane alloy has a Young's modulus in the absence of protein. The protein polyurethane alloy exhibits the same properties as polyurethane in the absence of protein. The Young's modulus is greater than the Young's modulus in the range of about 100 MPa to about 350 MPa.

[0013] In the ninth embodiment (9), a protein according to any one of the embodiments (1) to (8) is used. The modified polyurethane alloy has a Young's modulus ranging from about 50 MPa to about 450 MPa. do.

[0014] In the tenth embodiment (10), the tank according to any one of the embodiments (1) to (8) is The porous polyurethane alloy has a Young's modulus ranging from approximately 75 MPa to approximately 450 MPa. Has.

[0015] In the eleventh embodiment (11), the temperature sensor according to any one of the embodiments (1) to (10) is used. The polyurethane of the protein polyurethane alloy exhibits a second D The MA elastic modulus transition temperature is The temperature ranges from about 5% to about 70% below the second DMA modulus transition onset temperature of polyurethane. The second DMA modulus transition has an onset temperature over a large range of degrees Celsius.

[0016] In the twelfth embodiment (12), the terminal according to any one of the embodiments (1) to (10) is The polyurethane of the protein polyurethane alloy exhibits a second D The MA elastic modulus transition temperature is The second DMA modulus transition temperature of polyurethane is about 15% to about 70% below the onset temperature. The second DMA modulus transition has an onset temperature over a large range of degrees Celsius.

[0017] In the thirteenth embodiment (13), the terminal according to any one of the embodiments (1) to (12) is The polyurethane of the protein polyurethane alloy exhibits a second D The MA elastic modulus transition temperature is The second DMA modulus transition temperature of polyurethane is about 5°C to about 100°C below the onset temperature. The second DMA modulus transition onset temperature is in a large range over the range.

[0018] In the fourteenth embodiment (14), the terminal according to any one of the embodiments (1) to (12) is The polyurethane of the protein polyurethane alloy exhibits a second D The MA elastic modulus transition temperature is The second DMA modulus transition temperature of polyurethane is about 20°C to about 80°C below the starting temperature. The second DMA modulus transition onset temperature is in a large range over the range.

[0019] In the fifteenth embodiment (15), the terminal according to any one of the embodiments (1) to (12) is The polyurethane of the protein polyurethane alloy exhibits a second D The MA elastic modulus transition temperature is The second DMA modulus transition temperature of polyurethane is about 40°C to about 80°C below the onset temperature. The second DMA modulus transition onset temperature is in a large range over the range.

[0020] In the sixteenth embodiment (16), the temperature sensor according to any one of the embodiments (1) to (15) is The polypropylene alloy is a second DMA type polymer that can withstand temperatures ranging from approximately 130°C to approximately 200°C. It has a thermal conductivity transition temperature.

[0021] In the seventeenth embodiment (17), the terminal according to any one of the embodiments (1) to (15) is The high-quality polyurethane alloy is a second DMA type that can be used in a temperature range of approximately 165°C to approximately 200°C. It has a thermal conductivity transition temperature.

[0022] In the eighteenth embodiment (18), the temperature sensor according to any one of the embodiments (1) to (17) is Proteins in the protein polyurethane alloy have isoelectric points ranging from about 4 to about 5 and about 1. and a lysine weight percentage ranging from about 100% by weight to about 100% by weight.

[0023] In the nineteenth embodiment (19), the terminal according to any one of the embodiments (1) to (18) is The polyurethane of the protein polyurethane alloy has a tensile strength in the absence of protein. The protein polyurethane alloy has a viscosity of 1000 MPa, and the ... polyurethane alloy has a viscosity of 1000 MPa, and the polyurethane alloy has a viscosity of 1000 MPa. The tensile strength of the polyimide is about 5% to about 55% greater than that of the polyimide.

[0024] In the twentieth embodiment (20), the terminal according to any one of the embodiments (1) to (18) is The polyurethane of the protein polyurethane alloy has a tensile strength in the absence of protein. The protein polyurethane alloy has a viscosity of 1000 MPa, and the ... polyurethane alloy has a viscosity of 1000 MPa, and the polyurethane alloy has a viscosity of 1000 MPa. The tensile strength of the polyimide is about 15% to about 55% greater than that of the polyimide.

[0025] In the twenty-first embodiment (21), the temperature sensor according to any one of the embodiments (1) to (20) is used. The polyurethane of the protein polyurethane alloy has a tensile strength in the absence of protein. The protein polyurethane alloy has a viscosity of 1000 MPa, and the ... polyurethane alloy has a viscosity of 1000 MPa, and the polyurethane alloy has a viscosity of 1000 MPa. It has a tensile strength in the range of about 2 MPa to about 8 MPa greater than that of the .

[0026] In the twenty-second embodiment (22), the temperature sensor according to any one of the embodiments (1) to (20) is The polyurethane of the protein polyurethane alloy has a tensile strength in the absence of protein. The protein polyurethane alloy has a viscosity of 1000 MPa, and the ... polyurethane alloy has a viscosity of 1000 MPa, and the polyurethane alloy has a viscosity of 1000 MPa. It has a tensile strength in the range of about 5 MPa to about 8 MPa greater than that of the .

[0027] In the twenty-third embodiment (23), the temperature sensor according to any one of the embodiments (1) to (22) is The polypropylene polyurethane alloy has a tensile strength ranging from approximately 7 MPa to approximately 21 MPa. Has.

[0028] In the twenty-fourth embodiment (24), the temperature sensor according to any one of the embodiments (1) to (23) is Protein polyurethane alloys are made of approximately 10% to 50% protein by weight and approximately 50% polyurethane. % to about 90% by weight of polyurethane.

[0029] In the twenty-fifth embodiment (25), the terminal according to any one of the embodiments (1) to (23) is Protein polyurethane alloys contain approximately 20% to 35% by weight of protein and approximately 65% ​​by weight of % to about 80% by weight of polyurethane.

[0030] In the twenty-sixth embodiment (26), the temperature sensor according to any one of the embodiments (1) to (25) is The protein in the protein polyurethane alloy is a protein other than collagen.

[0031] In the twenty-seventh embodiment (27), the terminal according to any one of the embodiments (1) to (26) is The polyurethane of the protein polyurethane alloy has a water vapor permeability in the absence of protein. The protein polyurethane alloy has a passivation coefficient similar to that of polyurethane in the absence of protein. It has a water vapor permeability that is approximately 20% to 600% greater than that of the tan. do.

[0032] In the twenty-eighth embodiment (28), the terminal according to any one of the embodiments (1) to (27) is The polyurethane of the protein polyurethane alloy has a water vapor permeability in the absence of protein. The protein polyurethane alloy has a passivation coefficient similar to that of polyurethane in the absence of protein. The water vapor permeability rate of the tongue is approximately 30g / m 2 / 24 hours ~ approx. 500g / m 2 / 24-hour range It has a high water vapor transmission rate over a wide range.

[0033] In the twenty-ninth embodiment (29), the terminal according to any one of the embodiments (1) to (28) is The weight of the porous polyurethane alloy is approximately 30g / m² / 24 hours to approximately 1000g / m². 2 / twenty four It has a water vapor transmission rate over a range of times.

[0034] A thirtieth embodiment (30) is a soy protein containing soy protein dissolved in polyurethane. The soy protein polyurethane alloy is about -60 Dynamic mechanical analysis (DMA) tan(δ) peaks at temperatures ranging from about 10°C to about 30°C and a second DMA modulus transition onset temperature ranging from 130°C to about 200°C; Targeted at soy protein polyurethane alloy.

[0035] In a thirty-first embodiment (31), the soy protein polyurethane of the thirtieth embodiment (30) is Tanalloy is transparent.

[0036] In the thirty-second embodiment (32), the thirtieth embodiment (30) or the thirty-first embodiment (3 1) The polyurethane of the soy protein polyurethane alloy is The soy protein polyurethane alloy has a Young's modulus of 100% at 100% in the absence of soy protein. The Young's modulus is approximately 60% to 570% larger than that of polyurethane under ambient conditions. It has a Young's modulus.

[0037] In the thirty-third embodiment (33), the method according to any one of the embodiments (30) to (32) is The polyurethane of the soy protein polyurethane alloy is The soy protein polyurethane alloy has a Young's modulus of 100% in the absence of soy protein. The Young's modulus is larger than that of polyurethane in the range of about 35 MPa to about 340 MPa. It has a high Young's modulus.

[0038] In the thirty-fourth embodiment (34), the method according to any one of the embodiments (30) to (33) is Soy protein polyurethane alloys have a range of tensile strength from about 90 MPa to about 400 MPa. It has a quenching rate.

[0039] In the thirty-fifth embodiment (35), the method according to any one of the embodiments (30) to (34) is The polyurethane of the soy protein polyurethane alloy is and a second DMA modulus transition onset temperature of the soy protein polyurethane alloy. The DMA modulus transition onset temperature was measured in the absence of soy protein. The temperature is in the range of about 15°C to about 100°C higher than the DMA elastic modulus transition onset temperature.

[0040] In the thirty-sixth embodiment (36), the method according to any one of the embodiments (30) to (35) is The polyurethane of the soy protein polyurethane alloy exhibits the same properties as that of the soy protein in the absence of soy protein. The soy protein polyurethane alloy has a tensile strength of 100% in the absence of soy protein. The tensile strength is about 10% to about 45% greater than that of polyurethane at It has strength.

[0041] In the thirty-seventh embodiment (37), the method according to any one of the embodiments (30) to (36) The polyurethane of the soy protein polyurethane alloy exhibits the same properties as that of the soy protein in the absence of soy protein. The soy protein polyurethane alloy has a tensile strength of 100% in the absence of soy protein. The tensile strength of polyurethane is in the range of about 1.5 MPa to about 5.5 MPa. It has a higher tensile strength.

[0042] In the thirty-eighth embodiment (38), the method according to any one of the embodiments (30) to (37) The soy protein polyurethane alloy has a tensile strength ranging from about 14 MPa to about 19 MPa. It has strength.

[0043] In the thirty-ninth embodiment (39), the method according to any one of the embodiments (30) to (38) is The soy protein polyurethane alloy contains about 10% by weight to about 50% by weight of soy protein. and about 50% to about 90% by weight of polyurethane.

[0044] In the fortieth embodiment (40), the method according to any one of the embodiments (30) to (38) is The soy protein polyurethane alloy contains about 20% by weight to about 35% by weight of soy protein. and about 65% to about 80% by weight of polyurethane.

[0045] In the forty-first embodiment (41), the method according to any one of the embodiments (30) to (40) is The polyurethane of the soy protein polyurethane alloy is water-soluble in the absence of protein. The soy protein polyurethane alloy has a vapor permeability of 100% in the absence of protein. The water vapor permeability is approximately 20% to 600% higher than that of polyurethane. It has transmittance.

[0046] In the forty-second embodiment (42), the method according to any one of the embodiments (30) to (41) is The polyurethane of the soy protein polyurethane alloy is water-soluble in the absence of protein. The soy protein polyurethane alloy has a vapor permeability of 100% in the absence of protein. The water vapor permeability of polyurethane is approximately 30g / m 2 / 24 hours ~ approx. 500g / m 2 / 2 It has a high water vapor transmission rate over a 4-hour range.

[0047] In the forty-third embodiment (43), the method according to any one of the embodiments (30) to (42) is Soy protein polyurethane alloy is approximately 30g / m 2 / 24 hours ~ approx. 1000g / m 2 / 24 hour range of water vapor transmission rate.

[0048] In the forty-fourth embodiment (44), the method according to any one of the embodiments (30) to (43) is The protein in the soy protein polyurethane alloy is soy protein isolate.

[0049] In the forty-fifth embodiment (45), the method according to any one of the embodiments (40) to (43) is The protein in the soy protein polyurethane alloy is chemically modified soy protein isolate. It is a thing. [Brief explanation of the drawings]

[0050] The accompanying drawings, which are incorporated herein and form a part of this specification, illustrate embodiments of the present disclosure. Together with the specification, the drawings further serve to explain the principles of embodiments of the present disclosure. and enable one skilled in the relevant art(s) to make and use embodiments of the present disclosure. These diagrams are intended to be illustrative and not limiting. Although the present disclosure has generally been described in the context of these embodiments, it is not intended to limit the scope of the present disclosure to these embodiments. It should be understood that the present invention is not intended to be limited to the particular embodiment shown. In aspects, like reference numbers indicate identical or functionally similar elements. [Figure 1] FIG. 1 is a dynamic mechanical analysis (DMA) graph of storage modulus versus temperature for various materials. [Figure 2] FIG. 2 is a graph illustrating the relationship between maximum tensile stress and gelatin weight percentage for gelatin polyurethane alloys, according to some embodiments. [Figure 3] FIG. 3 is a graph showing the relationship between Young's modulus and gelatin weight percentage for gelatin polyurethane alloys, according to some embodiments. [Figure 4] FIG. 4 is a DMA graph of storage modulus versus temperature for various materials. [Figure 5]FIG. 5 is a graph showing the relationship between maximum tensile stress and soy protein isolate (SPI) weight percent of SPI polyurethane alloys, according to some embodiments. [Figure 6] FIG. 6 is a graph showing the relationship between Young's modulus and SPI weight percent for SPI polyurethane alloys, according to some embodiments. [Figure 7] FIG. 7 is a DMA graph of storage modulus versus temperature for various materials. [Figure 8A] FIG. 8A is a graph comparing the maximum tensile stress of various protein polyurethane alloys, according to some embodiments. [Figure 8B] FIG. 8B is a graph comparing the Young's modulus of various protein polyurethane alloys, according to some embodiments. [Figure 9] FIG. 9 is a DMA thermogram comparing L3360 and gelatin L3360 alloy, according to some embodiments. [Figure 10] FIG. 10 is a DMA thermogram comparing Hauthane HD-2001 polyurethane and gelatin Hauthane HD-2001 polyurethane alloy, according to some embodiments. [Figure 11] FIG. 11 is a DMA thermogram comparing SANCURE™ 20025F polyurethane and gelatin SANCURE™ 20025F polyurethane alloy, according to some embodiments. [Figure 12] FIG. 12 is a DMA thermogram comparing IMPRANIL® DLS polyurethane and a gelatin IMPRANIL® DLS polyurethane alloy, according to some embodiments. [Figure 13] FIG. 13 is a DMA thermogram comparing BONDTHANE™ UD-108 polyurethane and a gelatin BONDTHANE™ UD-108 polyurethane alloy, according to some embodiments. [Figure 14]FIG. 14 is a DMA thermogram comparing BONDTHANE™ UD-303 polyurethane and a gelatin BONDTHANE™ UD-303 polyurethane alloy, according to some embodiments. [Figure 15] FIG. 15 is a DMA thermogram comparing BONDTHANE™ UD-250 polyurethane and a gelatin BONDTHANE™ UD-250 polyurethane alloy, according to some embodiments. [Figure 16] FIG. 16 is a representative DMA graph showing the methodology for measuring the first and second DMA modulus transition onset temperatures. [Figure 17] FIG. 17 illustrates a layered material according to some embodiments. [Figure 18] FIG. 18 illustrates a layered material according to some embodiments. [Figure 19] FIG. 19 is a block diagram illustrating a method of making a layered material, according to some embodiments. [Figure 20A] 20A-20F illustrate methods of making layered materials according to some embodiments. [Figure 20B] 20A-20F illustrate methods of making layered materials according to some embodiments. [Figure 20C] 20A-20F illustrate methods of making layered materials according to some embodiments. [Figure 20D] 20A-20F illustrate methods of making layered materials according to some embodiments. [Figure 20E] 20A-20F illustrate methods of making layered materials according to some embodiments. [Figure 20F] 20A-20F illustrate methods of making layered materials according to some embodiments. [Figure 21] FIG. 21 illustrates a spacer fabric according to some embodiments. [Figure 22]FIG. 22 is a DMA thermogram comparing IMPRAPERM® DL 5249 polyurethane and soy protein isolate IMPRAPERM® DL 5249 alloy, according to some embodiments. [Figure 23] FIG. 23 is a graph measuring the weight of water transported through the construct as weight change versus time for a multilayer protein polyurethane alloy, according to some embodiments. DETAILED DESCRIPTION OF THE INVENTION

[0051] The indefinite articles "a," "an," and "the" are used interchangeably unless clearly contradictory or the context requires otherwise. Unless expressly provided otherwise in the text, a word or phrase includes multiple referents.

[0052] The term "comprising" is an open-ended transitional phrase. The list of elements following "comprising" is in addition to those specifically enumerated in the list. "Consists essentially of" is a non-exclusive list, so that elements can be present in addition to the list. The phrase "composition of components" refers to the specific materials and basic and novel properties of the components. The phrase "consisting of" is limited to those that do not substantially affect the specific material. This limits the composition of the components to the above and excludes any materials not specified.

[0053] Where numerical ranges, including upper and lower values, are recited herein, it is understood that certain limits may be exceeded in certain circumstances. Unless otherwise stated, ranges include their endpoints, and all integers and fractions within the range. It is intended that this disclosure be limited to the specific values ​​recited when defining ranges. Furthermore, it is not intended that amounts, concentrations, or other values ​​or parameters be expressed in a range, When given as one or more ranges or a list of upper and lower values, this Any upper range limit or value and any and (iii) specifically disclose all ranges formed by any pairing of a lower range limit or value. Finally, when the term "about" is used to describe a value or an end point of a range, When used herein, the disclosure should be understood to include the specific value or endpoint referred to. Regardless of whether the numerical value or endpoint of a range is described as "about," The endpoints distinguish two embodiments, those modified by "about" and those not modified. It is intended to include.

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

[0055] As used herein, a first layer described as "bonded" to a second layer refers to a layer that is bonded to two either by direct contact and bonding between the two layers or through one or more intermediate adhesive layers. The intermediate adhesive layer bonds the first layer to the second layer. The layer may be any layer that helps to improve the

[0056] As used herein, the phrase "disposed on" refers to a first component (e.g., The term "layer" means that the second component is in direct contact with the second component. The first component is deposited, formed, or positioned directly on the second component. In other words, the first component may be added to the second component, or may be otherwise applied. When disposed on top, there are no components between the first and second components.

[0057] As used herein, the phrase "disposed on" refers to a component that is not part of another component (e.g., A layer or substrate may or may not be present between the first and second components. This means that it is not necessary.

[0058] As used herein, "bio-based polyurethane" refers to a polymeric material such as a diol and a diacid. Polyurethanes in which the polyol building blocks are derived from biomaterials such as cornstarch. be.

[0059] As used herein, the term "substantially free" means that the component is present in an amount of about 0. It means present in a detectable amount not exceeding 1% by weight.

[0060] As used herein, the term "free" means that a component is present in even trace amounts. Means not present in blends or materials (e.g., protein polyurethane alloys) do.

[0061] As used herein, "collagen" refers to collagen types I, II, III, IV ,V,VI,VII,VIII,IX,X,XI,XII,XIII,XIV,XV,X A few examples include, but are not limited to, VI, XVII, XVIII, XIX, and XX. As used herein, "collagen type" refers to a family of at least 28 distinct naturally occurring collagen types. The term collagen also refers to collagen prepared using recombinant techniques. The term collagen can refer to collagen, collagen fragments, collagen-like proteins, Triple helix collagen, alpha chain, monomer, gelatin, trimer, and combinations thereof Recombinant expression of collagen and collagen-like proteins is well known in the art. are known (see, for example, Bell, European State Patent No. 1232182 (B1), Bovine collagen and met hod for producing recombinant gelatin;Ol sen, et al., U.S. Patent No. 6,428,978, and VanHeerde, e t al., id. 8,188,230) Unless otherwise specified, naturally occurring or Any type of collagen, whether prepared using recombinant techniques or not, is included herein. In other words, in some embodiments, The collagen described herein can be prepared using bovine type I collagen. Collagen is made up of repeating triplets of amino acids, -(Gly-XY)n-. 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 can lead to This may result in different properties (and different resulting leathers).

[0062] In some embodiments, the collagen is chemically modified to enhance its solubility in water. obtain.

[0063] Collagen, truncated collagen, unmodified or post-translationally modified, or amino acid sequence modified collagen Any type of collagen can be used as part of the protein polyurethane alloy. do.

[0064] In some embodiments, the collagen can be plant-based collagen. The protein can be plant-based collagen made by CollPlant.

[0065] In some embodiments, the collagen solution can be fibrillated into collagen fibrils. As used herein, collagen fibrils are referred to as tropocollagen or tropocollagen. It refers to nanofibers that are composed of a protein-like structure (having a triple helix structure). In some embodiments, the triple helix collagen is used to form collagen nanofibrils. It can be fibrillated for this purpose.

[0066] In some embodiments, the recombinant collagen is tropocollagen (trimeric collagen). ) may comprise collagen fragments of the amino acid sequence of a natural collagen molecule capable of forming Recombinant collagen also contains the amino acid sequence of natural collagen (or its fibril-forming region). a region, or a segment substantially containing [Gly-X-Y]n) and at least 70, 80, Modifications with 90, 95, 96, 97, 98, or 99% identical or similar amino acid sequences It may comprise collagen or truncated collagen. In some embodiments, collagen fragments. may be the 50 kDa portion of native collagen. Native collagen sequences are listed by reference. Incorporated accession numbers NP_001029211.1, NP_776945. CollAl, CollA, as described by NP_001070299.1, and 2, and Col3Al. In some embodiments, collagen The fragment was human collagen alpha-1(III) (Col3A1, Uniprot#P0 2461, Entrez Gene ID#1281). In embodiments, the collagen fragment may comprise 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 Application Nos. 2019 / 0002893 and 2019 / 0040 No. 400, No. 2019 / 0093116, and No. 2019 / 0092838, Uses for producing the recombinant collagen and recombinant collagen fragments disclosed herein These four methods provide methods for producing collagen and collagen fragments that can be used in various ways. The contents of these publications are incorporated by reference in their entireties.

[0068] The protein polyurethane alloys described herein are made of a polyurethane having multiple phases. Contains a protein that is miscible with only one or more polyurethanes with which it is blended. For example, in some embodiments, the protein polyurethane alloy may be It is compatible with several polyurethanes, including those with only the hard phase of the rubber or both the hard and soft phases. The protein polyurethane alloys described herein may contain a protein. Protein-free or substantially protein-free in the form of particles dispersed in urethane For example, in some embodiments, the protein polyurethane alloy may comprise 1 micron free or substantially free of protein particles having an average diameter greater than 1 μm Good too.

[0069] In some embodiments, the protein polyurethane alloy has a particle size of greater than 1 micron (μm). It may be free or substantially free of soy protein particles having an average diameter In some embodiments, the protein polyurethane alloy has an average particle size of greater than 1 micron (μm). The collagen particles may be free or substantially free of collagen particles having a diameter of some In embodiments, the protein polyurethane alloy has an average diameter of greater than 1 micron (μm). In some embodiments, the gelatin particles may be free or substantially free of gelatin particles. The protein polyurethane alloy is made of bovine blood granules having an average diameter of more than 1 micron (μm). In some embodiments, the serum may be free or substantially free of albumin particles. The protein polyurethane alloy has an end having an average diameter of more than 1 micron (μm). The composition may be free or substantially free of soy protein particles. In the protein polyurethane alloy, egg white having an average diameter of more than 1 micron (μm) In some embodiments, the composition may be free or substantially free of albumin particles. The protein polyurethane alloy is made of casein having an average diameter of more than 1 micron (μm). It may be free or substantially free of protein particles. The protein polyurethane alloy is made of peanuts having an average diameter of more than 1 micron (μm). In some embodiments, the composition may be free or substantially free of protein particles. The protein polyurethane alloy is made of edes having an average diameter of more than 1 micron (μm). The composition may be free or substantially free of protein particles. In the present study, the protein polyurethane alloy was found to be effective in preventing whey having an average diameter of more than 1 micron (μm). In some embodiments, the composition may be free or substantially free of protein particles. The protein polyurethane alloy is formed by dissolving granules having an average diameter of more than 1 micron (μm). The composition may be free or substantially free of protein particles. In the protein polyurethane alloy, cells with an average diameter of more than 1 micron (μm) It may be free or substantially free of enzyme particles. The protein polyurethane alloy is composed of recombinant collagen with an average diameter of more than 1 micron (μm). The polymer may be free or substantially free of gen fragment particles.

[0070] In certain embodiments, the present disclosure provides a method for preparing a polyurethane composition comprising a protein and a polyurethane hard phase. The present disclosure also provides a unique combination of polyurethanes that are only soluble in water. The present disclosure also provides a method for producing the protein polyurethane alloy. and a method for making the layered material. The protein polyurethane alloy and the protein polyurethane alloy layer are one It may contain the above types of proteins and one or more polyurethanes.

[0071] Proteins suitable for use in the alloys disclosed herein may be unmodified or chemically modified. In some embodiments, the protein may be present in a rigid phase of protein and polyurethane. In some embodiments, the protein may be modified to promote miscibility with water. In such embodiments, the compound may be chemically modified to enhance its solubility in water. Chemical modifications to enhance the compatibility of proteins with the polyurethane hard phase. In some embodiments, the chemically modified protein may be partially hydrolyzed. In some embodiments, the chemically modified protein may be a polyethylene glycol-based protein. by covalent attachment of hydrophilic polymer chains, such as ethylene glycol (PEG) chains, to proteins. It may be a modified protein.

[0072] Suitable polyurethanes for use in the protein polyurethane alloys described herein are The soft phase is a very thin, rigid phase. Due to the difference in the molecular weight, the polyol segments within the polyurethane are separate from the urethane-containing phase. The urethane-containing phase is referred to as the hard phase. This phase separation is well known in the art. and is based on many of the properties of polyurethanes.

[0073] The soft phase is typically elastomeric at room temperature and typically has a softening point or gustomeric phase below room temperature. It has a glass transition temperature (Tg). Tg is determined by dynamic mechanical analysis. Measured by DMA (Dielectric Constants), either the peak in tan(δ) or the onset of the drop in storage modulus Alternatively, the Tg can be quantified by differential scanning calorimetry. This can be measured by differential scanning calorimetry (DSC). There may be some crystallinity present in the polymer, which is typically seen as a melting point between 0°C and about 60°C. For example, the tan(δ) of UD-108 polyurethane in FIG. The peaks in the ) curve indicate the crystallinity in the soft phase of the polyurethane.

[0074] The hard phase typically has a Tg or melting point above room temperature, more typically about 80°C. The softening of the hard phase is related to the storage modulus (sometimes called stiffness) measured by DMA. ) can be measured by measuring the onset of drop.

[0075] The "soft phase" of a polyurethane or a protein polyurethane alloy containing polyurethane is It contains the polyol component of polyurethane. Its function is to give the polyurethane toughness and elongation. and to impart flexibility, the polymer must be soft and flexible at temperatures above its Tg. Typical soft segments are polyether polyols, polyester polyols, These may include polyols such as olefin polyols, olefin polyols, and mixtures thereof. These typically have a molecular weight of about The molecular weight ranges from 250 Daltons to greater than about 5 kilodaltons. The "hard phase" of the protein polyurethane alloy containing tungsten is a polyol containing butanediol. isocyanates used in conjunction with short chain diols such as diol and propanediol The polyurethane comprises a urethane segment of the polymer provided by the urethane segment(s). Typical isocyanates useful in tanning include hexamethylene diisocyanate, isocyanate, phoron diisocyanate, methylene diisocyanate, and phenyl diisocyanate These molecules include, but are not limited to, those that create soft segments. The hard segments are more polar and rigid than the polyols used for It is stiffer and has a higher softening point compared to the soft segment. The function of the hard phase is to: Other properties that provide polyurethanes include strength, heat resistance, and abrasion resistance.

[0076] In some embodiments described herein, the protein is miscible only with the rigid phase. Without being bound by any particular theory, the soft phase transition may be left substantially unchanged. However, if the protein dissolves in the hard phase, the temperature at which the hard phase begins to soften is This is believed to significantly increase the heat resistance of the alloys described herein. The protein polyurethane alloys described herein may also be used in combination with the base polyurethane (i.e., In other words, the polyurethane itself in the absence of protein exhibits increased stiffness and increased It may have a strength of

[0077] The protein polyurethane alloys and layers described herein may comprise one or more proteins, Blending the mixture in a liquid state with one or more waterborne polyurethane dispersions and drying the blend. In some embodiments, the proteins described herein can be formed by The porous polyurethane alloy and layer contain one or more proteins dissolved or dispersed in an aqueous solution. the polyurethane resin is blended with one or more waterborne polyurethane dispersions in a liquid state, and the blend is dried. In some embodiments, the polyurethane The dispersion may be ionic, either anionic or cationic. In some embodiments, the polyurethane dispersion may be non-ionic. In this case, the blended protein and polyurethane can be formed into a sheet, and in certain embodiments In embodiments, the adhesive is bonded using a suitable bonding process such as direct coating, lamination process, or thermoforming process. In certain embodiments, the lamination process may be performed using an adhesive. In some embodiments, the sheet may be bonded to a substrate layer using a layer. The blended protein and polyurethane may be coated or otherwise deposited on the substrate layer to bond the In some embodiments, the blended protein and polyurethane is applied to a substrate layer. By bonding, a portion of the blended protein and polyurethane is bonded to one side of the substrate layer. The device may be integrated into a single unit.

[0078] Protein polyurethane alloys comprising one or more miscible proteins and polyurethanes. can dissolve one or more proteins within the rigid phase of one or more polyurethanes. Protein polyurethane alloys are mixed with one or more polyurethane hard phases in the alloy. In some embodiments, the protein may include at least one protein that is compatible with the protein. The modified polyurethane alloy is a mixture of multiple proteins and / or multiple polyurethanes that are miscible with each other. In all of these embodiments, without being bound to any particular theory, However, it is not desirable to use a protein or proteins in a polyurethane or polyurethanes. It is believed to be dissolved in the hard phase of the ethane.

[0079] One or more proteins dissolved within the hard phase of one or more polyurethanes are blended In some embodiments, a homogenous mixture can be formed when the protein polymer is mixed with the water. The polyurethane alloy is a mixture of protein and polyurethane(s) that has been blended and dried. A plurality of types of polyurethanes dissolved in one or more polyurethanes to form a homogeneous mixture when Typically, the polyurethane contains a homogeneous mixture of protein and polyurethane. Protein polyurethane alloys contain significant amounts of protein that are not soluble in the polyurethane. That is, in some embodiments, the protein polyurethane alloy is It may contain protein fragments dispersed within the tongue.

[0080] In the embodiments described herein, the miscibility of the protein with the polyurethane hard phase is significantly alter one or more other thermomechanical properties of the alloy relative to the thermomechanical properties of the urethane itself. DMA modulus transition of the hard phase in protein polyurethane alloys without softening For example, the polymerization temperature can be increased by increasing the temperature of the hard phase of the protein and the polyurethane. Miscibility is determined by 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. The hardness of the protein polyurethane alloy was improved without significantly changing the DMA transition temperature. The DMA modulus transition onset temperature of the polymer phase can be increased.

[0081] The DMA transition temperature of the soft phase is the glass transition temperature of polyurethane or protein polyurethane alloy. The DMA transition temperature of the soft phase or Tg can be referred to as the transition temperature (Tg). MA storage modulus transition onset temperature (referred to herein as "first DMA storage modulus transition onset temperature") (ii) quantified as the DMA tan(δ) peak temperature corresponding to the soft phase The DMA transition temperature of the hard phase can be calculated by the The DMA modulus transition of the hard phase can be measured by the onset of the storage modulus drop of the hard alloy. The onset temperature of the second DMA modulus transition can be quantified as the onset temperature (referred to herein as the "second DMA modulus transition onset"). In some embodiments, the second D The MA modulus transition onset temperature can be greater than about 80°C or greater than about 130°C.

[0082] For example, the protein polyurethanes described herein, including collagen and soy protein, Many protein types are contemplated for use in the alloys disclosed herein. For all of the embodiments described, the protein may be a protein other than collagen and / or a large It is understood that the protein may be other than soy protein. In an embodiment, the protein dissolved in the protein polyurethane alloy is a protein other than collagen. In another embodiment, the protein may be dissolved in the polyurethane alloy. The protein may be a protein other than soy protein. The proteins dissolved in the protein polyurethane alloy are proteins other than collagen. In some embodiments, the protein may be a protein other than protein and soy protein. The collagen polyurethane alloy is collagen-free or substantially collagen-free. In some embodiments, the protein polyurethane alloy may be a polyurethane containing soy protein. The soy protein may be free or substantially free of soy protein. In this case, the protein polyurethane alloy does not contain soy protein and collagen. , or may be substantially free of soy protein and collagen.

[0083] As previously mentioned, the soft and hard phases of polyurethanes can be distinguished using dynamic mechanical analysis (DMA). Therefore, the protein polyurethane alloys described herein The one or more polyurethanes included may have at least two DMA transition temperatures, one of which is One corresponds to the soft phase and one corresponds to the hard phase. The DMA transition temperature of the soft phase corresponds to the The temperature is defined as the "first DMA modulus transition onset temperature" or the DMA tan(δ) peak temperature. The DMA transition temperature of the hard phase can be quantified as the "second DMA modulus transition onset temperature" The first DMA modulus transition onset temperature or DMA ta The n(δ) peak temperature is the lower DMA transition temperature and the onset temperature of the second DMA modulus transition. The higher the DMA transition temperature.

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

[0085] Polyurethane or protein polyurethane alloy having first and second DMA transition temperatures 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 could occur between the first and second transitions.

[0086] In some embodiments, the polyurethane has a first DMA modulus transition onset temperature of 30° C. In some embodiments, the onset of the first DMA modulus transition of the polyurethane may be less than The temperature may range from about -65°C to about 30°C, including subranges. For example, some In embodiments, the polyurethane has a first DMA modulus transition onset temperature of about -65°C, about -6 0℃, approx. -55℃, approx. -50℃, approx. -45℃, approx. -40℃, approx. -35℃, approx. -30℃, approx. -25℃, approx. -20℃, approx. -15℃, approx. -10℃, approx. -5℃, approx. -1℃, 0℃, approx. 1℃, about 5°C, about 10°C, about 15°C, about 20°C, about 25°C, or about 30°C, or endpoints included It may be within a range having any two of these values ​​as endpoints. The first DMA modulus transition temperature of polyurethane is about -65°C to about 30°C, 5℃ to approximately 25℃, approximately -65℃ to approximately 20℃, approximately -65℃ to approximately 15℃, approximately -65℃ to approximately 10℃ , about -65℃ to about 5℃, about -65℃ to about 1℃, about -65℃ to 0℃, about -65℃ to about -1℃ , about -65℃ to about -5℃, about -65℃ to about -10℃, about -65℃ to about -15℃, about -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, about -65°C to about -35°C, about -65°C to about -40°C, or about -65°C to about -45°C °C.

[0087] 9-15 show the DMA thermograms of various exemplary polyurethanes. The first DMA modulus transition temperature (T onset1 ) is the storage modulus (E') This is the temperature at which the slope of the curve begins to decrease significantly over the first hour. The methodology for determining this value is shown in Figure 1. 16. DMA devices such as the DMA-850 manufactured by TA Instruments The device can be programmed to automatically calculate this temperature. Table 4 shows the temperature in Figures 9-10. Lists the first DMA modulus transition onset temperatures automatically calculated from 15 DMA graphs. (See Examples 1-7).

[0088] In some embodiments, the DMA tan(δ) peak corresponding to the soft phase of the polyurethane The hardening temperature may be less than 30° C. In some embodiments, the hardening temperature may be less than 30° C. for the soft phase of the polyurethane. The corresponding DMA tan(δ) peak temperatures range from about -60°C to about 30°C, including subranges. For example, in some embodiments, the DM corresponding to the soft phase of the polyurethane may be A tan(δ) peak temperatures are about -60°C, about -55°C, about -50°C, about -45°C, and about -40℃, approx. -35℃, approx. -30℃, approx. -25℃, approx. -20℃, approx. -15℃, approx. -10℃ , about -5℃, about -1℃, 0℃, about 1℃, about 5℃, about 10℃, about 15℃, about 20℃, about 25 °C, or about 30 °C, or a range having any two of these values ​​as endpoints inclusive. In some embodiments, the DMA t an(δ) peak temperature is about -60℃ to about 30℃, about -60℃ to about 25℃, about -60℃ to Approximately 20℃, approximately -60℃ to approximately 15℃, approximately -60℃ to approximately 10℃, approximately -60℃ to approximately 5℃, approximately -6 0℃~approx. 1℃, approx. -60℃~0℃, approx. -60℃~approx. -1℃, approx. -60℃~approx. -5℃, approx. -6 0℃ to approximately -10℃, approximately -60℃ to approximately -15℃, approximately -60℃ to approximately -20℃, approximately -60℃ to approximately -25°C, about -60°C to about -30°C, about -60°C to about -35°C, or about -60°C to about -4 It may be 0°C.

[0089] The DMA thermograms in Figures 9-15 correspond to the soft phases of various exemplary polyurethanes. The DMA tan(δ) peak temperature is shown. DMA devices, such as the DMA-850 from Instruments, measure this temperature automatically. Table 4 is automatically calculated from the DMA graphs in Figures 9 to 15. Dynamically calculated DMA tan(δ) peak temperatures are listed (Examples 1 to 7). See the reference.

[0090] In some embodiments, the polyurethane has a second DMA modulus transition onset temperature of 30° C. In some embodiments, the second DMA modulus transition onset temperature of the polyurethane may be greater than 100°C. The temperature may range from about 45° C. to about 165° C. For example, in some embodiments, The second DMA modulus transition temperature of the urethane is about 45°C, about 50°C, about 55°C, about 60°C. °C, about 65 °C, about 70 °C, about 75 °C, about 80 °C, about 85 °C, about 90 °C, about 95 °C, about 10 0℃, approx. 105℃, approx. 110℃, approx. 115℃, approx. 120℃, approx. 125℃, approx. 130℃, approx. 135°C, about 140°C, about 145°C, about 150°C, about 155°C, about 160°C, or about 165°C, or any range between any two of these values ​​inclusive. In some embodiments, the polyurethane has a second DMA modulus transition onset temperature of about 4 5℃ to approx. 165℃, approx. 50℃ to approx. 160℃, approx. 55℃ to approx. 155℃, approx. 60℃ to approx. 150 °C, about 65°C to about 145°C, about 70°C to about 140°C, about 75°C to about 135°C, about 80°C Approximately 130℃, approximately 85℃ to approximately 125℃, approximately 90℃ to approximately 120℃, approximately 95℃ to approximately 115℃, Alternatively, the temperature may be about 100°C to about 110°C.

[0091] The DMA thermograms in Figures 9-15 show the second DMA results for various exemplary polyurethanes. The second DMA modulus transition onset temperature (T onset2 ) is the temperature at which the slope of the storage modulus (E') curve begins to decrease significantly in the second The methodology for measuring this value is illustrated in Figure 16. TA Instrument DMA instruments, such as the DMA-850 from Sigma, can be programmed to calculate this temperature automatically. Table 3 shows the second-order DMA values ​​automatically calculated from the DMA graphs in Figures 9 to 15. The DMA modulus transition onset temperatures are listed below (see Examples 1 to 7).

[0092] In some embodiments, polyurethanes may exhibit crystallinity in the soft phase. Polyethers containing tetramethylene glycol and some polyester polyols In such embodiments, the polyurethane may be at least May exhibit at least three transitions: soft phase Tg, soft phase melting point, and hard phase modulus transition Such melting in the soft phase, if present, typically occurs between 0°C and about 60°C. In embodiments that exhibit crystallinity in the soft phase, the protein polyurethane alloy may be The protein is miscible with the hard phase and leaves the mechanical properties of the soft phase substantially unchanged. Therefore, they typically still exhibit melting in the soft phase.

[0093] In exemplary embodiments described herein, the protein polyurethane alloy is The second DMA elasticity of polyurethane in the absence of a polymer (i.e., polyurethane itself) The alloy may have a second DMA modulus transition onset temperature higher than the first DMA modulus transition temperature. This increase in the DMA modulus transition onset temperature is due to the miscibility of the protein with the polyurethane hard phase. This selective miscibility of proteins is thought to be due to the soft phase DMA transition. indicated by an increase in the onset temperature of the second DMA modulus transition, without a similar increase in temperature. (The first DMA elastic modulus transition onset temperature or DMA tan(δ) peak corresponds to the soft phase.) (Quantified by temperature). This selective miscibility can be attributed to differences in mechanical and thermal properties, e.g. , can be utilized to control the properties of protein polyurethane alloys.

[0094] In some embodiments, the protein polyurethane alloys and / or The layered material may have the same appearance, feel, and mechanical properties as natural leather. For example, The protein polyurethane alloy layer or the layered material including the protein polyurethane alloy layer is , among other things, with tactile, aesthetic, mechanical / performance and manufacturability properties similar to those of natural leather. Mechanical / performance properties that may be similar to natural leather include: , tensile strength, tear strength, elongation at break, abrasion resistance, internal cohesion, water resistance, breathability (several in some embodiments quantified by water vapor transmission rate measurements) and dyed with reactive dyes; These include, but are not limited to, the ability to retain color when rubbed (color fastness). Tactile properties that may be similar to natural leather include softening, stiffness, coefficient of friction, and compressive modulus. Aesthetic properties that may be similar to natural leather include, but are not limited to, dyeing. These may include, but are not limited to, texture, embossability, aging, color, color depth, and color pattern. Manufacturing characteristics that may be similar to natural leather include, but are not limited to, stitching, cutting, These include, but are not limited to, the ability to be archived and split. Possible thermal properties include heat resistance and a significantly wide temperature range, e.g., from 25°C to 100°C. These include, but are not limited to, resistance to hardening or softening.

[0095] Desirable properties of the protein polyurethane alloys described herein include optical properties, tactile These may include, but are not limited to, properties, aesthetic properties, thermal properties, mechanical properties, and / or breathability properties. Exemplary thermal properties include, but are not limited to, heat resistance and melt resistance, e.g., the second elastic modulus of the material. Temperature at which sexual rate transition starts (T onset2) can be quantified by measuring Exemplary mechanical properties include abrasion resistance, ultimate tensile stress (also referred to as "tensile strength"). ), and Young's modulus. Unless otherwise specified, the maximum tensile strengths disclosed herein Stress and Young's modulus values ​​were measured according to the method provided by ASTM D638. Exemplary breathability properties include: g / m 2 / 24 hours (per square meter per 24 hours) Moisture vapor transmission rate (MVT) measured in grams per 1000g Unless otherwise specified, the water vapor transmission rates disclosed herein are based on ASTM Measured according to the method provided by E96-Method B.

[0096] In some embodiments, the protein polyurethane alloy may be transparent. In some embodiments, the transparent protein polyurethane alloy is formed by dissolving the protein in the poly(urethane) alloy. It may be shown to be miscible with the hard phase of the urethane. By material is meant a material having an opacity of about 50% or less. Opacity is determined by examining a sample of the material. Placed on a white background, the Y tristimulus value was measured using a D65 10-degree light source and a spectrometer to measure reflectance. ("Over White Y") is measured. Place it on a colored background and repeat the measurement to get "Over Black Y." Opacity Percent The percentage is calculated as "Over Black Y" ÷ "Over White Y" x 100. 0% opacity is defined as the least transparent and 0% opacity is defined as the most transparent. do.

[0097] In some embodiments, the protein polyurethane alloy may be transparent, with a range of The opacity may range from 0% to about 50%, including transparent protein polyurethanes. The alloy is 0% to about 40%, 0% to about 30%, 0% to about 20%, 0% to about 10%, or The transparency of the protein polyurethane alloy can range from 0% to about 5%. The degree of coloring is evaluated before dyeing or otherwise coloring the protein polyurethane alloy. do.

[0098] Transparent protein polyurethane alloys are made by combining one or more proteins with one or more polyurethanes. It can be made by selecting and blending the appropriate combination with tan. All combinations of proteins and polyurethanes result in transparent protein polyurethane alloys. Although not necessarily intended, a given blend may be considered a transparent protein polyurethane alloy in light of the present disclosure. It is within the skill of one of ordinary skill in the art to determine whether the transparency described herein results in a In embodiments directed to layered materials including clear protein polyurethane alloy layers, The protein polyurethane alloy layer can provide unique properties to the layered material. For example, compared to a non-transparent layer, a transparent protein polyurethane alloy layer is more durable when dyed. Similarly, transparent protein polyurethane alloys can provide inherent color intensity. The layer imparts mechanical properties to the layered material without significantly affecting the aesthetic properties of the material. can be provided.

[0099] In some embodiments, the protein polyurethane alloy comprises one or more colorants. In some embodiments, the colorant is a dye, such as a fiber reactive dye, a direct dye, Exemplary dyes include azo-structure acid dyes, metal complex-structure acid dyes, and natural dyes. dyes, anthraquinone acid dyes, and azo / diazo direct dyes. In some embodiments, the colorant may be a pigment, such as a lake pigment. do.

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

[0101] In some embodiments, the polyurethane may be a polyether polyol, a polyester polyol, or a polyols, polycarbonate polyols, and mixtures thereof. In some embodiments, the polyurethane may have a soft segment. The diisocyanates may have hard segments comprising diisocyanates and optionally short chain diols. The diisocyanate is an aliphatic diisocyanate such as hexamethylene diisocyanate or isophorone diisocyanate. Isocyanates: 4,4'-diphenylmethylene diisocyanate, toluene diisocyanate from aromatic diisocyanates such as methyl methyl ether, phenyl diisocyanate, and mixtures thereof; Suitable short chain diols include ethylene glycol. , propanediol, butanediol, 2,2 methyl 1,3 propanediol, pentane In some embodiments, the diols include hexanediol, hexanediol, and mixtures thereof. is a polyfunctional alcohol, such as trimethylolpropanetriol, or ethylene Crosslinking agents such as diamines or diamines such as 4,4' diamino, diphenyldiamine, etc. .

[0102] Exemplary commercially available polyurethanes include those available from CL Hauthaway & Sons Corp. L3360 and Hauthane HD-2001, available from Lu SANCURE™ Polyurethane available from Brizol Corporation Tan, BON available from Bond Polymers International DTHANE™ polyurethanes, such as UD-108, UD-250, and UD- 303, and EPOTAL® ECO 3702 and EPOTA® manufactured by BASF These include, but are not limited to, L® P100 ECO. L3360 35% solids, 50-500 cps (centipoise) viscosity, and approximately 8.5 lb / g Aliphatic polyester polyurethane polymer with density of 1000 psi (pounds per gallon) HD-2001 is an aqueous dispersion with a solid content of 40% and a viscosity of 50-500 cps. and an aliphatic polyester polyurethane polymer waterborne having a density of about 8.9 lb / gal. BONDTHANE™ UD-108 is a 33% solids dispersion. Aliphatic polyether polyurethane with a viscosity of 100 cps and a density of 8.7 lb / gal BONDTHANE™ UD-250 is a 35% solids aqueous polymer dispersion. an aliphatic polyester having a viscosity of 200 cps and a density of 8.8 lb / gal BONDTHANE™ UD-303 is an aqueous dispersion of polyurethane polymer. A fat having a solids content of 35%, a viscosity of less than 500 cps, and a density of 8.7 lb / gal EPTOAL® P is an aqueous dispersion of aliphatic polyether polyurethane polymer. 100 ECO is a polyester with approximately 40% solids and a viscosity of about 40 mPas. It is an aqueous dispersion of polyurethane elastomer.

[0103] Exemplary bio-based polyurethanes include CL Hauthaway & Sons C L3360 available from Covestro, L3360 available from Covestro PRANIL® Eco DLS, IMPRANIL® Eco DL 519, IMPRANIL® Eco DLP-R, and IMPRAPERM ® DL 5249. (registered trademark) Eco DLS is a sol- uid-containing polymer with a solid content of approximately 50% and a sol- uid-containing polymer with a sol-u- tion strength of less than 1,200 MPa·s. An anionic aliphatic polyester polyurethane having a viscosity and a density of about 1.1 g / cc IMPRANIL® Eco DL 519 is an aqueous polymer dispersion. IMPRANIL is an aqueous dispersion of anionic aliphatic polyester polyurethane polymers. Eco DLP-R is an anionic aliphatic polyester polyurethane polymer IMPRAPERM® DL 5249 is an anionic lipid dispersion. It is an aqueous dispersion of an aliphatic polyester-polyurethane polymer.

[0104] In some embodiments, the polyurethane contains reactive groups that can be crosslinked with proteins. Exemplary reactive groups include sulfonates, aldehydes, carboxylic acids, or esters. Examples of suitable isocyanates include, but are not limited to, methyl isocyanate, methyl ... In such an embodiment, the polyurethane is bonded to a reactive group on the protein. Protein in the protein polyurethane alloy through reaction with reactive groups present in the ethylene It can be crosslinked to a solid.

[0105] Suitable polyurethanes for blending with one or more polyurethanes according to embodiments described herein Proteins include collagen, gelatin, bovine serum albumin (BSA), and soy protein. Protein, pea protein, egg albumin, casein, peanut protein, edible Examples include lactic acid bacteria protein, whey protein, karanjian 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 soy protein isolate (SPI), soy protein isolate (SOI), and soy protein isolate (SOI). Proteins and soy protein derivatives are included, but are not limited to: In some embodiments, the soy protein isolate is a partially hydrolyzed soy protein. Suitable pea proteins include pea protein isolates and These include, but are not limited to, pea protein derivatives. In its form, pea protein isolate is a partially hydrolyzed pea protein. It may be a quality isolate.

[0106] Table 1 below lists some exemplary proteins and properties of the proteins. The gelatin was type A (Sigma Aldrich G2500), which is gelatin from pig skin. Collagen is manufactured by Wuxi BIOT Biology-technology C Extract bovine collagen purchased from the company Sigma. Bovine serum albumin Aldrich 5470 Bovine Serum Albumin. r-Collagen is a Modern Mea Recombinant collagen from Dow. Soy protein isolate from MP Medicals (IC90545625) is a soy protein isolate purchased from Pea Protein. The protein was pea protein purchased from Bob's Red Mills (MTX5232). The egg albumin protein is obtained from chicken egg white (Sigma Aldrich A Casein protein was obtained from bovine milk (Sigma Aldrich 5253). Casein from peanut protein (rich C7078). The whey protein was obtained from bovine milk (Sigma). Other suitable soy protein isolates include whey from Aldrich W1500. Examples include AMD (Clarisoy 100, 110, 150, 170, 180), DuPont (SUPRO® XT 55, SUPRO® XT 2 21D, and SOBIND® Balance (a soy protein monohydrate purchased from Other suitable pea protein powders include, but are not limited to, Examples include pea protein powders purchased from Puris (870 and 870H). Examples include, but are not limited to:

[0107] Karanja protein is derived from the Pongamia pinnata tree (Pongamia Karanja seeds harvested from the Aglabra (also known as Pongamia glabra) tree Rahman, M. M. and Netravali, "Gr een Resin from Forestry Waste Residue'Ka ranja(Pongamia pinnata)Seed Cake'for Bio based Composite Structures”, ACS Sustaina See Chem. Eng., Vol. 2, pp. 2318-2328 (2014); Also, Mandal et al., "Nutritional Evaluation of f Proteins from three Non-traditional Se eds with or without Amino Acids Suppleme ntation in Albino Rats”, Proc.Indian natn See also Sci. Acad., B50, Vol. 1, pp. 48-56 (1984). Protein can be extracted from karanja seeds using a solvent extraction process. In some embodiments, the karanjang protein is a karanjang protein isolate. In such an embodiment, the karanji protein isolate may be defatted karanji. It can be obtained by alkaline extraction and acid precipitation of the seed cake. M. and Netravali, "Green Resin from Forestry Waste Residue'Karanja(Pongamia pinnata) Seed Cake'for Biobased Composite Structu res”, ACS Sustainable Chem.Eng., Vol. 2, No. 2318~ See p. 2328 (2014);

[0108] Suitable cellulase proteins are listed in Table 1 below. "Cellulase-RG" Protein The quality is natural trichoderma available from CREATIVE ENZYMES® The "Cellulase-IG" protein is a Trichoderma species cellulase. Laboratory available from lina Biological Supply Company It is a high-grade cellulase.

[0109] The 50 KDa recombinant collagen fragment (50 KDa r-collagen fragment) in Table 1 has the sequence It is a collagen fragment containing the amino acid sequence listed as number 1.

[0110] The "dissolution methods" listed in Table 1 are used to dissolve proteins in the rigid polyurethanes described herein. An exemplary aqueous solvent is one that can be dissolved in a solution that is miscible with the aqueous solution. Proteins that are partially soluble in polyurethane dispersions are also known as protein polyurethane alloys. It is suitable for forming a

[0111] [Table 1]

[0112] In some embodiments, the protein has the following characteristics: (i) within the ranges described herein; (ii) a molecular weight within the ranges set forth below; (iii) a tangent point within the ranges set forth below; (iv) amino acid composition measured in grams of lysine per 100 grams of protein; and The protein may have one or more of the following thermostabilities up to 200°C.

[0113] Protein molecular weight In some embodiments, the protein is about 1 KDa (kilodalton), including subranges. For example, the protein may have a molecular weight ranging from about 1 KDa to about 700 KDa. ~700KDa, approx. 10KDa ~ approx. 700KDa, approx. 20KDa ~ approx. 700KDa, approx. 50KDa ~ approx. 700KDa, approx. 100KDa ~ approx. 700KDa, approx. 200KDa ~ approx. 7 00KDa, about 300KDa to about 700KDa, about 400KDa to about 700KDa, about 5 00KDa ~ approx. 700KDa, approx. 600KDa ~ approx. 700KDa, approx. 1KDa ~ approx. 600 KDa, about 1KDa to about 500KDa, about 1KDa to about 400KDa, about 1KDa to about 3 00KDa, about 1KDa~about 200KDa, about 1KDa~about 100KDa, about 1KDa~ In the range of about 50KDa, about 1KDa to about 20KDa, or about 1KDa to about 10KDa The molecular weight is within a range having any two of these values ​​as endpoints, including the endpoints. It is possible.

[0114] Protein isoelectric point In some embodiments, the protein ranges from about 4 to about 10, including subranges. For example, the protein may have an isoelectric point of about 4 to about 10, about 4.5 to about 9.5, about 5 to about 10, or about 10 to about 10. 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 within a range having any two of these values ​​as endpoints, inclusive In some embodiments, the protein may have an isoelectric point ranging from about 4 to about 5. It may have an isoelectric point.

[0115] Protein Amino Acid Composition In some embodiments, the protein is present in an amount ranging from about 0.5% to about 100% by weight, including subranges. The grams of lysine per 100 grams of protein ("Lysine weight percent") across a range of weight percents For example, a protein may have an amino acid composition measured in , about 0.5% to about 100% by weight, about 1% to about 100% by weight, about 5% to about 10% by weight 0% by weight, about 10% to about 100% by weight, about 20% to about 100% by weight, about 30% by weight % to about 100% by weight, about 40% to about 100% by weight, about 50% to about 100% by weight, Approximately 60% to approximately 100% by weight, approximately 70% to approximately 100% by weight, approximately 80% to approximately 10% by weight 0% by weight, or ranging from about 90% to about 100% by weight, inclusive of endpoints. The lysine weight percentage may be within a range having any two of these values ​​as endpoints. In some embodiments, the protein can be polylysine.

[0116] In some embodiments, the protein is present in an amount ranging from about 0.5% to about 20% by weight, including subranges. For example, the protein may have a lysine weight percentage ranging from about 0.5 to about 1.5. Amount%~20wt%, approx.1wt%~approx.19wt%, approx.2wt%~approx.18wt%, approx.3wt % ~ approx. 17% by weight, approx. 4% ~ approx. 16% by weight, approx. 5% ~ approx. 15% by weight, approx. 6% by weight ~14% by weight, approximately 7% by weight~13% by weight, approximately 8% by weight~12% by weight, approximately 9% by weight~ about 11% by weight, or in the range of about 9% to about 10% by weight, inclusive of endpoints thereof. The lysine weight percentage may be within a range having any two of these values ​​as endpoints. In some embodiments, the protein contains lysine ranging from about 1% to about 20% by weight. In some embodiments, the protein may have a weight percent of about 5% to about 2%. In some embodiments, the lysine weight percentage may range from 0 to 100%. The protein may have a lysine weight percentage ranging from about 1% to about 12% by weight. In some embodiments, the protein ranges from about 5% to about 12% by weight. In some embodiments, the protein may have a weight percent of about 1% to about 1% by weight. In some embodiments, the lysine weight percentage may range from about 15% by weight. The protein has a lysine weight percentage ranging from about 5% to about 15% by weight. obtain.

[0117] In some embodiments, the protein may be thermostable. Alternatively, the protein may be non-thermostable. Protein powder (with less than 3% moisture) scanned from 0°C to 200°C to determine protein thermal stability The activity is determined by differential scanning calorimetry (DSC). The DSC curve for a protein shows The endothermic peak exceeding 0 mW / mg was determined to be the "denaturation peak" and the endothermic "denaturation peak" The temperature corresponding to this is defined as the "denaturation temperature" of the protein. Protein means that the protein has a denaturation temperature of 200°C or higher. For purposes of this study, proteins with a denaturation temperature below 200°C are considered "non-thermostable." For example, the whey from bovine milk listed in Table 1 has a denaturation temperature of 158°C by DSC. and therefore whey is considered to be non-thermostable.

[0118] Protein lysis In some embodiments, one or more tartaric acid salts may be added prior to blending with one or more polyurethanes. Proteins can be dissolved in an aqueous solution to form an aqueous protein mixture. In some embodiments, the protein is dissolved in an aqueous solution before being blended with one or more polyurethanes. By dissolving the protein in the For example, the protein can be mixed with the polyurethane(s) to promote miscibility. Proteins and one or more polymers can be mixed by dissolving the protein in an aqueous solution before application. It can promote miscibility with the hard phase of the urethane. For example, the examples in Examples 33 and 34 are not naturally miscible with any phase of the As shown, casein is not necessarily miscible with polyurethane. As shown in the examples, when casein, water, and L3360 are mixed, the casein The resulting film is immiscible with L3360. It had an opaque appearance with some granules. However, the casein was mixed with L3360. When casein is dissolved in sodium hydroxide solution before use, the hard phase of L3360 is formed. The film obtained by blending these components is miscible. The film had a clear and uniform appearance with no optically visible granules.

[0119] Suitable aqueous solutions include water, alkaline solutions, aqueous acid solutions, aqueous solutions containing organic solvents, and urine. Examples of suitable solubility include, but are not limited to, solubility in water ... In this embodiment, the alkaline solution is a sodium hydroxide, ammonia, or ammonium hydroxide solution. In some embodiments, an example of an acidic aqueous solution is acetic acid or It may be a hydrochloric acid (HCl) solution. Suitable organic solvents include ethanol, isopropanol, acetone, ethyl acetate, isopropyl acetate, and glycerol. In some embodiments, the protein in the aqueous protein mixture is The concentration can range from about 10 g / L to about 300 g / L, including subranges. The protein concentration in the protein mixture is about 10 g / L, about 20 g / L, about 30 g / L, Approx. 40g / L, Approx. 50g / L, Approx. 60g / L, Approx. 70g / L, Approx. 80g / L, Approx. 90g / L, about 100g / L, about 150g / L, about 200g / L, about 250g / L, or about 3 00g / L, or within a range having any two of these values ​​as endpoints, inclusive In some embodiments, the protein concentration in the aqueous protein mixture is about 10 g / L ~ approx. 300g / L, approx. 20g / L ~ approx. 250g / L, approx. 30g / L ~ approx. 200g / L , about 40g / L to about 150g / L, about 50g / L to about 100g / L, about 60g / L to about 9 It can be 0 g / L or in the range of about 70 g / L to about 80 g / L.

[0120] In some embodiments, the protein is pretreated and / or purified to reduce its solubility in water. Suitable pretreatments include acid treatment, alkali treatment, enzymatic hydrolysis, and Exemplary acid treatments include, but are not limited to, acetic acid or HCl treatments. An exemplary alkaline treatment is acid hydrolysis using a suitable acid such as ammonium hydroxide, Alkaline hydrolysis with a suitable base such as NaOH, KOH, or mixtures thereof. Exemplary enzymes for hydrolysis include papain, bromelain, trypsin, and Suitable purification methods include, but are not limited to, alkaline proteases and the like. These include phytate removal with calcium salts, diafiltration, ultrafiltration, and centrifugation, etc.

[0121] In some embodiments, lysine or other additives may be added prior to blending with one or more polyurethanes. By adding hydrophilic amino acids to the protein, the protein and one or more polyurethanes can be This can promote compatibility with the hard phase of the tongue.

[0122] Protein hydrolysis In some embodiments, the protein may be partially hydrolyzed. Hydrolysis can facilitate the dissolution of proteins in water and / or Partial hydrolysis of proteins can promote miscibility with the hard phase of polyurethane. This can be achieved using enzymes or strong to moderate bases. A reduction in viscosity and / or a reduction in protein molecular weight may occur. Therefore, a characterization method to determine the level of protein hydrolysis is photodiffusion. Turbulence, gel electrophoresis, size exclusion chromatography, solution viscosity measurement, trinitrobenzene Detection of terminal amino groups using sulfonic acid or ninhydrin, or particle size measurement by laser diffraction Examples of the invention include, but are not limited to, the following: Example 21 illustrates, according to some embodiments, Partially hydrolyzed soy protein prepared using sodium hydroxide is described.

[0123] PEGylation of proteins In some embodiments, the protein is PEG-polyethylene glycol (PEG)-coated. The PEG modification of proteins can be achieved by covalent attachment to the proteins. It can promote the dissolution of proteins and / or the hard phase of proteins and polyurethane. The PEG modification of proteins can promote miscibility with hydrophilic polyethylene. This can be achieved using a method to covalently attach PEG chains to proteins. Cut.

[0124] In some embodiments, the amount of protein in the protein polyurethane alloy is The protein content may range from about 10% to about 50% by weight, including the range. In some embodiments, the amount of protein in the protein polyurethane alloy is about 10 wt. % ~ approx. 50% by weight, approx. 15% ~ approx. 50% by weight, approx. 20% ~ approx. 50% by weight, approx. 25 Weight% ~ Approx. 50% by weight, Approx. 30% ~ Approx. 50%, Approx. 35% ~ Approx. 50%, Approx. 40% to approximately 50% by weight, approximately 45% to approximately 50% by weight, approximately 10% to approximately 45% by weight , about 10% to about 40% by weight, about 10% to about 35% by weight, about 10% to about 30% by weight %, about 10% by weight to about 25% by weight, about 10% by weight to about 20% by weight, or about 10% by weight to about 15%, or a range having any two of these values ​​as endpoints, inclusive. In some embodiments, the amount of protein in the protein polyurethane alloy is about It can range from 20% to about 35% by weight.

[0125] In some embodiments, the amount of polyurethane in the protein polyurethane alloy is The range may be from about 50% to about 90% by weight, including the full range. In this embodiment, the amount of polyurethane in the protein polyurethane alloy is about 50% by weight to about 90% by weight. 0% by weight, about 55% to about 90% by weight, about 60% to about 90% by weight, about 65% by weight Approximately 90% by weight, approximately 70% to approximately 90% by weight, approximately 75% to approximately 90% by weight, approximately 80% by weight % ~ approx. 90% by weight, approx. 85% ~ approx. 90% by weight, approx. 50% ~ approx. 85%, approx. 50 Weight% ~ Approx. 80% by weight, Approx. 50% ~ Approx. 75% by weight, Approx. 50% ~ Approx. 70% by weight, Approx. 50% by weight to about 65% by weight, about 50% by weight to about 60% by weight, or about 50% by weight to about 5 5% by weight, or within a range having any two of these values ​​as endpoints, inclusive. In some embodiments, the polyurethane in the protein polyurethane alloy may Amounts may range from about 65% to about 80% by weight.

[0126] In some embodiments, the above weight percentages and ranges are for protein polyurethanes. The total weight of the polyurethane alloy or protein alloy layer may be based on the total weight of the polyurethane alloy or protein alloy layer. In certain embodiments, the weight percentages and ranges above are for protein polyurethane alloys or is the total weight of the sole protein and polyurethane in the protein-polyurethane alloy layer Unless otherwise specified, the weight percentages of polyurethane and protein are The value or range is based on the protein polyurethane alloy or the protein polyurethane alloy layer. Based on the total weight of only the protein and polyurethane in the composition.

[0127] In some embodiments, the amount of protein plus the amount of polyurethane in the protein polyurethane alloy The total amount of ethane may be about 80% by weight or greater. For example, in some embodiments, The total amount of protein and polyurethane in the protein polyurethane alloy is approximately 80 Weight% ~ 100% by weight, approx. 82% ~ 100% by weight, approx. 84% ~ 100% by weight, approx. 86%~100% by weight, approximately 88%~100% by weight, approximately 90%~100% by weight , about 92% to 100% by weight, about 94% to 100% by weight, about 96% to 100% by weight % by weight, or in the range of about 98% to 100% by weight.

[0128] In some embodiments, the protein polyurethane alloy comprises a total weight percent of the material. In some embodiments, the protein polyurethane alloy may comprise water, which forms part of the polyurethane. The amount of water in the solution may range from about 1% to about 10% by weight, including subranges. For example, In some embodiments, the amount of water in the protein polyurethane alloy is about 1% by weight to About 10% by weight, about 2% to about 10% by weight, about 3% to about 10% by weight, about 4% to about 10% by weight, about 5% to about 10% by weight, about 6% to about 10% by weight, about 7% to about 1 0% by weight, about 8% to about 10% by weight, about 1% to about 9% by weight, about 1% to about 8% by weight %, about 1% to about 7% by weight, about 1% to about 6% by weight, about 1% to about 5% by weight, about 1 % to about 4% by weight, or about 1% to about 3% by weight, or any of these values ​​inclusive of the endpoints. It can be a range within a range having any two of the endpoints.

[0129] The protein polyurethane alloys described herein are (i) non-alloyed polyurethanes A second dynamic mechanical analysis (DMA) modulus transition onset temperature higher than the second DMA modulus transition onset temperature. (ii) a temperature substantially equal to the onset temperature of the first DMA modulus transition of the non-alloyed polyurethane; (iii) the same first dynamic mechanical analysis (DMA) modulus transition onset temperature; DMA at a temperature substantially the same as that of the DMA tan(δ) peak corresponding to the soft phase of the tan. tan(δ) peak, (iv) Young's modulus higher than that of unalloyed polyurethane (v) a tensile strength greater than that of non-alloyed polyurethane, or (vi) a tensile strength greater than that of non-alloyed polyurethane. It has one or more of the following moisture vapor transmission rates (MVTR) higher than the MVTR of hydroxylated polyurethane. possible.

[0130] 1-15 show various amounts of different polyurethanes according to some embodiments. Tables 3 to 6 show the effect of dissolving proteins to form polyurethane alloys. , Thermal and Mechanical Properties of Various Protein Polyurethane Alloys According to Some Embodiments The thermal and mechanical properties of various polyurethanes are listed. The protein was blended with an aqueous dispersion of the listed polyurethane and the mixture was applied to a flat plate. Formed into a film, dried in an oven at 45°C overnight (16 to 24 hours), and tested Prepare by conditioning in a standard reference atmosphere (23°C, 50% humidity) for 24 hours prior to The weight percentage values ​​in the figures and Tables 3 to 6 are based on the blends used to prepare the samples. The relative weight percentage of solids added to the gelatin. For example, 0.825 grams of gelatin and 5.5 g of L3360 (35% solids by weight) to give a gelatin content of 30% by weight. A sample of Example No. 9 was prepared containing 100% L3360 and 70% by weight of L3360. The weight percentage values ​​in 6 are based on the total weight of the dried sample. The weight percent of protein and polyurethane in the sample can be closely approximated. , water, which constitutes a small portion of the total weight percent of the sample (e.g., about 5% to about 10% by weight) It included:

[0131] Table 7 shows the water vapor permeability of various protein polyurethane alloys, according to some embodiments. The tested samples were prepared as described in Examples 45-56. The weight percentage values ​​in Table 7 represent the solids added to the blends used to make the samples. These weight percentages are based on the total weight of the dry sample. The weight percentages of protein and polyurethane in the dried samples of Examples 45 to 56 were A dry sample may be a small fraction (e.g., 1 / 2 of the total weight percent) of the sample. The water content was about 5% to about 10% by weight.

[0132] The DMA temperatures in Tables 3 and 4 were measured using a TA Instruments DMA-850. For the test, a metal die was used to cut a 1 cm x 2.5 cm strip from the sample film. The cut film samples were then placed in the film and fiber tension clamp for testing. During the test, a preload of 0.01 Newtons (N) was applied to the cut film sample. The instrument was cooled to -80°C, held for 1 minute, and then the temperature was increased at a rate of 4°C / min to 200°C. or until the sample was too weak to hold the tension. The sample was vibrated at a frequency of 1 Hz with a strain of 0.1%. The activity and tan(δ) values ​​were plotted against temperature for each test. All DMA test data reported herein was measured using this test method. The tensile strength and Young's modulus values ​​in Tables 5 and 6 are based on the values ​​provided by ASTM D638. The tensile strength and Young's modulus values ​​were measured according to the method. The mean of the sample.

[0133] The DMA graph shown in Figure 1 shows the measured storage modulus (E '), as well as various weight percentages, namely 5 wt%, 10 wt%, 15 wt%, 20 wt%, %, and 30% by weight (Example 9 and Examples 25 to 28) of L3360 This graph shows the gelatin dissolved in the gelatin blended with L3360. However, the second DMA elastic modulus transition temperature is higher than that of 100% L3360. This indicates that it is possible to produce alloys with a specific transition temperature. While not wishing to be bound by theory, it is believed that the hard phase comprising gelatin and polyurethane The second DMA modulus transition occurs because the hard segments of the The increase in the transition temperature is thought to be more evident in this test. This indicates that the hard phase of L3360 is miscible with the hard phase of L3360.

[0134] This miscibility of gelatin with the hard phase L3360 is demonstrated in Examples 1 and 9. The mechanical property graphs in Figures 2 and 3 compare two different mechanical properties of Nos. 25 to 28. As shown in Figure 2, the best of the protein polyurethane alloys tested The maximum tensile stress ("tensile strength") 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% by weight and above. As shown in Figure 3, the Young's modulus of the tested protein polyurethane alloy is 10 This increase in Young's modulus is greater than that of L3360 with 0% zeolite. This is particularly significant in the platinum weight percent.

[0135] The DMA graph shown in Figure 4 shows the measured storage modulus (E '), and various weight percentages, namely 10 wt%, 20%, and 30 wt% (actual Examples 21, 30, and 31 show SPI dissolved in L3360. The thermograms show that blending SPI with L3360 is significantly superior to the first-order thermogram of pure L3360. A tank having a second DMA modulus transition onset temperature higher than the second DMA modulus transition onset temperature. This shows that it is possible to prepare a porous polyurethane alloy. The addition of SPI increases the onset temperature of the second DMA modulus transition. This indicates that SPI is miscible with the hard phase of L3360.

[0136] This miscibility of SPI with the hard phase L3360 is demonstrated in Examples 1 and 21, 3 and 4. The mechanical properties of No. 0 and No. 31 are compared in the mechanical property graphs in Figures 5 and 6. This is further exemplified in the following figure. As shown in Figure 5, the protein polyurethane alloys tested The maximum tensile stress ("tensile strength") is greater than that of 100% L3360. This increase in maximum tensile stress is particularly significant at SPI weight percentages above 10 wt.%. As shown in Figure 6, the Young's modulus of the tested protein polyurethane alloy is 10 This increase in Young's modulus is greater than that of L3360 with 0% S. This is particularly significant for PI weight percent.

[0137] The DMA graph shown in Figure 7 shows the measured storage modulus (E '), and 30% by weight (Examples 9 and 17 to 23) dissolved in L3360. This graph shows the various proteins that were analyzed using gelatin, SPI, and other proteins. Blended with L3360, the second DMA modulus transition temperature was higher than that of 100% L3360. To prepare a protein polyurethane alloy with the highest second DMA modulus transition onset temperature, All proteins except whey are 100% Second DMA elastic modulus transition onset temperature higher than that of L3360 The whey was used in the production of a protein polyurethane alloy with a 100% L3360 Due to its ability to improve the mechanical properties of protein polyurethane alloys, L33 It is believed to be miscible with the hard phase of 60. However, as determined by DSC As whey has a low denaturation temperature, the second DMA modulus transition onset temperature It is believed that this did not increase

[0138] Furthermore, the graph in Figure 7 shows that even when various proteins are dissolved in L3360, the soft phase DM Proteins whose A transition temperature is significantly different from the DMA transition temperature of the soft phase of 100% L3360 As shown in Table 4, Example 9 and Example 10 were not obtained. The onset of the delta first modulus transition for all samples 17 to 23 was below 10°C. In connection with this, the delta Tan (δ) peak temperatures of all Examples 9 and 17 to 23 are These results indicate that the protein was immiscible with the soft phase of L3360. This indicates that

[0139] This selective miscibility of the protein with the hard phase L3360 is shown in the graphs of Figures 8A and 8B. This is further illustrated in the plotted mechanical property test results and reported in Tables 5 and 6. The graphs in FIG. 8A and FIG. 8B show the results of Example 1, Example 9, and Example 17 to Example 23. The tensile strength and Young's modulus of the specimens are compared. The increase in tensile strength and / or the increase in Young's modulus are This indicates that the protein is miscible with the hard phase of L3360. The tensile strength and Young's modulus of the material are reported.

[0140] Selective miscibility of proteins with the hard phase of polyurethanes containing both soft and hard phases To further illustrate, gelatin was blended with various exemplary polyurethanes. 15 shows the DMA thermograms of these exemplary blends, as well as the DMA thermograms in the absence of gelatin. Figure 9 shows the thermograms of polyurethanes containing 30% by weight gelatin and 70% by weight gelatin. % L3360 (Example No. 9) and 100% L3360 (Example 1). Figure 10 compares the DMA data for 30 wt% gelatinized polyurethane alloys. and 70% by weight HD-2001 (Example 15) and 100% HD-2001 ( The DMA data of the protein polyurethane alloys prepared in Example No. 7 are compared. FIG. 11 shows the results of a mixture of 30% gelatin and 70% Sancure (Example 14) and and a protein polyurethane alloy made of 100% Sancure (Example No. 6). Figure 12 compares the DMA data for 30% gelatin and 70% Imp. Impranil DLS (Example 12) and 100% Impranil DLS (Example The DMA data of the protein polyurethane alloy prepared in Example 5 are compared. 3 is 30% by weight gelatin and 70% by weight UD-108 (Example 10) and 10 DM of protein polyurethane alloy made with 0% UD-108 (Example No. 2) Figure 14 compares the data for 30% by weight gelatin and 70% by weight UD-303 ( Proteins made with 100% UD-303 (Example No. 4) and 100% UD-303 (Example No. 13). Figure 15 compares the DMA data for polyurethane alloys containing 30 wt% gelatin and 7 wt% gelatin. 0% by weight of UD-250 (Example No. 11) and 100% of UD-250 (Example No. 3) ) and compare the DMA data of protein polyurethane alloys prepared by

[0141] Figure 22 shows the results for 30% by weight soy protein isolate (SPI) and 70% by weight IMP. RAPERM® DL5249 and 100% IMPRAPERM® DMA data of protein polyurethane alloys made from DL5249 polyurethane samples 22 with an average thickness of 0.44 mm. (SPI) and 70 wt. % IMPRAPERM® DL 5249 alloy The three samples had an average Young's modulus of 65.80 MPa and an average thickness of 0.7 mm. 22 100% IMPRAPERM® DL 5249 polyurethane The three samples had an average Young's modulus of 10.13 MPa. The results of this mechanical testing of the PET and protein polyurethane alloys were obtained by SPI and IMPRA. PERM® DL5249 demonstrates selective miscibility with hard phases.

[0142] Tables 3 and 4 show various exemplary polyurethanes and blends with 30% by weight gelatin. Tables 5 and 6 report the DMA data for the same polyurethanes tested. Typical polyurethanes and those same polyurethanes blended with 30% by weight gelatin. The tensile strength and Young's modulus data for the tongue are reported. The results indicate the rigidity of the polyurethanes tested. The results show the selective miscibility of the proteins tested in the phases.

[0143] In some embodiments, the protein polyurethane alloy may be The polyurethane may include a polyurethane having a second DMA modulus transition onset temperature. The polyurethane alloy exhibits the second DMA elongation of polyurethane in the absence of protein. The second DMA modulus transition occurs over a temperature range from about 5°C to about 100°C higher than the modulus transition onset temperature. This relative increase in the second DMA modulus transition onset temperature is referred to as the "second DMA onset temperature." In some embodiments, the second delta modulus transition may be referred to as the "onset of the second delta modulus transition." The modulus transition onset can be about 5° C. or greater. In some embodiments, the delta second modulus transition The temperature range is from about 5℃ to about 100℃, from about 5℃ to about 95℃, from about 5℃ to about 90℃, and from about 5℃ to about 85℃. °C, about 5°C to about 80°C, about 5°C to about 75°C, about 5°C to about 70°C, about 5°C to about 65°C, about 5 ℃ to about 60℃, about 5℃ to about 55℃, about 5℃ to about 50℃, about 5℃ to about 45℃, about 5℃ to about 4 0℃, 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℃, about 5℃ to about 10℃, about 10℃ to about 100℃, about 15℃ to about 100℃, about 20℃ to approx. 100℃, approx. 25℃ to approx. 100℃, approx. 30℃ to approx. 100℃, approx. 35℃ to approx. 10 0℃, approx. 40℃ to approx. 100℃, approx. 45℃ to approx. 100℃, approx. 50℃ to approx. 100℃, approx. 55℃ ~ about 100, about 60℃ ~ about 100℃, about 65℃ ~ about 100℃, about 70℃ ~ about 100℃, about 75℃~approx. 100℃, approx. 80℃~approx. 100℃, approx. 85℃~approx. 100℃, approx. 90℃~approx. 10 0°C, or about 95°C to about 100°C, or any two of these values ​​inclusive of the endpoints The range may be within the range having the formula:

[0144] In some embodiments, the onset of the second delta modulus transition is in the range of about 5°C to about 80°C. In some embodiments, the onset of the second delta modulus transition is between about 20°C and about 80°C. In some embodiments, the onset of the second delta modulus transition can range from about 40° C. to about In some embodiments, the onset of the second delta modulus transition can be in the range of about 1.80°C. For example, the onset of the second delta modulus transition may be between about 100°C and about 150°C. It can be a range.

[0145] In some embodiments, the soy protein polyurethane alloy is a non- In the presence of the polyurethane, the polyurethane may have a second DMA modulus transition onset temperature. Soy protein polyurethane alloys are polyurethanes that are produced in the absence of soy protein. The second DMA modulus transition temperature is higher than the second DMA modulus transition temperature in the range of about 15°C to about 100°C. In some embodiments, the soy protein polyolefin may have a DMA modulus transition onset temperature of 0.15 to 1.005°C. The onset of the second delta modulus transition for urethane alloys can be about 15°C or higher. In an embodiment, the delta second modulus transition onset of the soy protein polyurethane alloy is about 1 5℃ to approximately 100℃, approximately 15℃ to approximately 95℃, approximately 15℃ to approximately 90℃, approximately 15℃ to approximately 85℃, approximately 15℃ to approximately 80℃, approximately 15℃ to approximately 75℃, approximately 15℃ to approximately 70℃, approximately 15℃ to approximately 65℃, approximately 15℃ to approximately 60℃, approximately 15℃ to approximately 55℃, approximately 15℃ to approximately 50℃, approximately 15℃ to approximately 45℃, approximately 15℃ to about 40℃, about 15℃ to about 35℃, about 15℃ to about 30℃, about 15℃ to about 25℃, about 15℃ to approx. 20℃, approx. 20℃ to approx. 100℃, approx. 25℃ to approx. 100℃, approx. 30℃ to approx. 100 °C, approx. 35°C to approx. 100°C, approx. 40°C to approx. 100°C, approx. 45°C to approx. 100°C, approx. 50°C Approximately 100°C, approximately 55°C to approximately 100, approximately 60°C to approximately 100°C, approximately 65°C to approximately 100°C, approximately 7 0℃ to approx. 100℃, approx. 75℃ to approx. 100℃, approx. 80℃ to approx. 100℃, approx. 85℃ to approx. 100 °C, about 90°C to about 100°C, or about 95°C to about 100°C, or these values ​​inclusive of the endpoints The range may be within a range having any two of the following as endpoints:

[0146] In some embodiments, the protein polyurethane alloy comprises a polyurethane having a viscosity of about 10,000 psi, including subranges. It may have a second DMA modulus transition onset temperature ranging from 0° C. to about 200° C. For example, In some embodiments, the protein polyurethane alloy is heated at about 100° C. to about 200° C. Approximately 100℃ to approximately 195℃, approximately 100℃ to approximately 190℃, approximately 100℃ to approximately 185℃, approximately 100 ℃ to about 180℃, about 100℃ to about 175℃, about 100℃ to about 170℃, about 100℃ to about 1 65℃, approximately 100℃ to approximately 160℃, approximately 100℃ to approximately 155℃, approximately 100℃ to approximately 150℃, Approximately 100℃ to approximately 145℃, approximately 100℃ to approximately 140℃, approximately 100℃ to approximately 135℃, approximately 100 ℃ to about 130℃, about 100℃ to about 125℃, or about 100 to about 120℃, about 105℃ to about 200℃, approx. 110℃ to approx. 200℃, approx. 115℃ to approx. 200℃, approx. 120℃ to approx. 200℃ , about 125℃ to about 200℃, about 130℃ to about 200℃, about 135℃ to about 200℃, about 14 0℃ to approximately 200℃, approximately 145℃ to approximately 200℃, approximately 150℃ to approximately 200℃, approximately 155℃ to approximately 200℃, approx. 160℃~approx. 200℃, approx. 165℃~approx. 200℃, approx. 170℃~approx. 200℃ , about 175°C to about 200°C, or about 180°C to about 200°C, or A second DMA modulus transition opening within a range having any two of these values ​​as endpoints, inclusive, is In some embodiments, the protein polyurethane alloy may have an initial temperature of about 12 It may have a second DMA modulus transition onset temperature ranging from 0°C to about 200°C. In this embodiment, the protein polyurethane alloy is heat-resistant in the range of about 130°C to about 200°C. In some embodiments, the protein may have a second DMA modulus transition onset temperature. The polyurethane alloy exhibits a second DMA modulus transition over the range of about 165°C to about 200°C. It may have an onset temperature.

[0147] In some embodiments, the soy protein polyurethane alloy comprises a polyurethane having a molecular weight of about 1000 to about 15000, including subranges thereof. It may have a second DMA modulus transition onset temperature ranging from 130°C to about 200°C. For example, in some embodiments, the soy protein polyurethane alloy is heated to about 130°C to about 2 00℃, about 130℃ to about 195℃, about 130℃ to about 190℃, about 130℃ to about 185℃, Approximately 130℃ to approximately 180℃, approximately 130℃ to approximately 175℃, approximately 130℃ to approximately 170℃, approximately 130 ℃ to about 165℃, about 130℃ to about 160℃, about 130℃ to about 155℃, about 130℃ to about 1 50℃, approximately 130℃ to approximately 145℃, approximately 130℃ to approximately 140℃, approximately 135℃ to approximately 200℃, Approximately 140℃ to approximately 200℃, approximately 145℃ to approximately 200℃, approximately 150℃ to approximately 200℃, approximately 155 ℃ to approximately 200℃, approximately 160℃ to approximately 200℃, approximately 165℃ to approximately 200℃, approximately 170℃ to approximately 2 00℃, about 175℃ to about 200℃, about 180℃ to about 200℃, about 185℃ to about 200℃, or any of these values ​​ranging from about 190°C to about 200°C, inclusive. It may have a second DMA modulus transition onset temperature within a range having two endpoints.

[0148] In some embodiments, the protein polyurethane alloy is In some embodiments, the protein polyurethane alloy may have a modulus transition temperature of 1. is the onset of the first DMA modulus transition over the range of about -65°C to about 30°C, including the subrange. For example, in some embodiments, the first temperature of the protein polyurethane alloy may be The DMA elastic modulus transition onset temperature of 1 is about -65°C to about 30°C, about -65°C to about 25°C, and about - 65℃ to approximately 20℃, approximately -65℃ to approximately 15℃, approximately -65℃ to approximately 10℃, approximately -65℃ to approximately 5℃ , about -65℃ to about 1℃, about -65℃ to 0℃, about -65℃ to about 1℃, about -65℃ to about -5℃ , about -65℃ to about -10℃, about -65℃ to about -15℃, about -65℃ to about -20℃, about -6 5℃ to approximately -25℃, approximately -65℃ to approximately -30℃, approximately -65℃ to approximately -35℃, approximately -65℃ to approximately -35°C, a range of about -65°C to about -40°C, or a range of about -65°C to about -45°C, or an end point The range may be within a range having any two of these values ​​as endpoints, inclusive.

[0149] In some embodiments, the protein polyurethane alloy may be The polyurethane may include a polyurethane having a first DMA modulus transition onset temperature in that same temperature range. Protein polyurethane alloys exhibit the first D of polyurethane in the absence of protein. It may have a first DMA modulus transition onset temperature that is + / - X°C of the MA modulus transition onset temperature. This relative increase or decrease in the first DMA modulus transition onset temperature is referred to as the "first delta modulus transition." In some embodiments, X is 1, 2, 3, 4, 5, It can be 6, 7, 8, 9, or 10.

[0150] In some embodiments, the protein polyurethane alloy has a DMA t of less than 30° C. In some embodiments, the protein polyurethane adhesive may have a peak temperature of an(δ). Roy has a DMA tan(δ) peak over the range of about -60°C to about 30°C, including subranges. For example, in some embodiments, the protein polyurethane alloy The DMA tan(δ) peak temperature is about -60°C to about 30°C, about -60°C to about 25°C, Approximately -60℃ to approximately 20℃, approximately -60℃ to approximately 15℃, approximately -60℃ to approximately 10℃, approximately -60℃ to approximately 5℃, approx. -60℃ to approx. 1℃, approx. -60℃ to 0℃, approx. -60℃ to approx. 1℃, approx. -60℃ to approx. - 5℃, approx. -60℃ to approx. -10℃, approx. -60℃ to approx. -15℃, approx. -60℃ to approx. -20℃, approx. -60°C to about -25°C, about -60°C to about -30°C, about -60°C to about -35°C, or about A range of -60°C to approximately -40°C, or a range having any two of these values ​​as endpoints It could be.

[0151] In some embodiments, the protein polyurethane alloy may be The DMA tan(δ) peak temperature corresponds to the soft phase of the polyurethane. Similarly, the protein polyurethane alloy may contain a protein DMA tan(δ) peak temperature corresponding to the soft phase of polyurethane in the absence of -Y °C. DMA tan(δ) peak temperature This relative increase or decrease in temperature may be referred to as the "Delta Tan (δ) Peak Temperature." In some embodiments, Y is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 1. It can be 0.

[0152] In some embodiments, the protein polyurethane alloy may be The same protein polyurethane alloy may contain polyurethane having tensile strength in the range of 1000 to 15000 kJ / cm. is about 5% to about 55% greater than the tensile strength of polyurethane in the absence of protein. This relative increase in tensile strength is referred to as the "delta tensile strength," In some embodiments, the delta tensile strength % is 5% or greater. In some embodiments, the delta tensile strength % can be from about 5% to about 55%, about 10 % to approximately 55%, approximately 15% to approximately 55%, approximately 20% to approximately 55%, approximately 25% to approximately 55%, approximately 30 % to approximately 55%, approximately 35% to approximately 55%, approximately 40% to approximately 55%, approximately 45% to approximately 55%, approximately 50 % to approximately 55%, approximately 5% to approximately 50%, approximately 5% to approximately 45%, approximately 5% to approximately 40%, approximately 5% to approximately 3 5%, about 5% to about 30%, about 5% to about 25%, about 5% to about 20%, about 5% to about 15%, or a range of about 5% to about 10%, or any two of these values ​​inclusive In some embodiments, the delta tensile strength % can be in the range of about 15% to In some embodiments, the delta tensile strength % can be in the range of about 55%. For example, the delta tensile strength % can range from about 55% to about 1000%. do.

[0153] In some embodiments, the soy protein polyurethane alloy is a non- The same soy protein polyurethane may be used in the present invention. The polyurethane alloy has a tensile strength greater than that of polyurethane in the absence of soy protein. In some embodiments, the soy protein may have a tensile strength that is about 10% to about 45% greater than that of the soy protein. The delta tensile strength of some polymeric polyurethane alloys can be 10% or greater. In an embodiment, the delta tensile strength % of the soy protein polyurethane alloy is about 10% to Approximately 45%, approximately 15% to approximately 45%, approximately 20% to approximately 45%, approximately 25% to approximately 45%, approximately 30% or more Approximately 45%, approximately 35% to approximately 45%, approximately 40% to approximately 45%, approximately 10% to approximately 40%, approximately 10% or more About 35%, about 10% to about 30%, about 10% to about 25%, about 10% to about 20%, or about A range of 10% to about 15%, or any two of these values ​​inclusive, as endpoints It can be in the range.

[0154] In some embodiments, the protein polyurethane alloy may be The same protein polyurethane alloy may contain polyurethane having tensile strength in the range of 1000 to 15000 kJ / cm. The tensile strength of polyurethane is approximately 2 MPa (megapascals) higher than that of polyurethane in the absence of protein. The tensile strength of the sintered body can be increased over a range of 1000 psi to about 8 MPa. The relative increase can be referred to as the "delta tensile strength." In some embodiments, The delta tensile strength may be 2 MPa or greater. In some embodiments, the delta tensile strength may be Strength: Approximately 2MPa to 8MPa, approximately 3MPa to 8MPa, approximately 4MPa to 8MPa a, about 5MPa to about 8MPa, about 6MPa to about MPa, about 7MPa to about 8MPa, about 2M Pa ~ approx. 7MPa, approx. 2MPa ~ approx. 6MPa, approx. 2MPa ~ approx. 5MPa, approx. 2MPa ~ approx. 4 MPa, or in the range of about 2 MPa to about 3 MPa, or any of these values ​​inclusive of the endpoints. In some embodiments, the delta tensile strength may be in a range having one or two of the end points. The delta tension may range from about 5 MPa to about 8 MPa. For example, the delta tensile strength may be between about 8 MPa and about 15 MPa. The pressure may be in the range of MPa.

[0155] In some embodiments, the soy protein polyurethane alloy is a non- The same soy protein polyurethane may be used in the present invention. The polyurethane alloy has a tensile strength greater than that of polyurethane in the absence of soy protein. The tensile strength of the cellulose acylate polymer may be large, ranging from about 1.5 MPa to about 5.5 MPa. In some embodiments, the soy protein polyurethane alloy has a delta tensile strength of 1.5M In some embodiments, the density of the soy protein polyurethane alloy may be 100 Pa or more. The tensile strength is approximately 1.5MPa to 5.5MPa, approximately 2MPa to 5.5MPa, approximately 3MPa to approx. 5.5MPa, approx. 4MPa to approx. 5.5MPa, approx. 1.5MPa to approx. 5MPa , about 1.5 MPa to about 4 MPa, or about 1.5 MPa to about 3 MPa, or an end point The range may be inclusive, having as endpoints any two of these values.

[0156] In some embodiments, the protein polyurethane alloy has a viscosity of about 7 MP, including subranges. For example, in some embodiments, the tensile strength may range from about 100 psi to about 21 MPa. The protein polyurethane alloy has a compressive strength of about 7 MPa to about 21 MPa and about 10 MPa to about 2 1 MPa, about 15 MPa to about 21 MPa, about 7 MPa to about 15 MPa, or about 7 MPa Tensile strengths ranging from about 10 MPa to about 10 MPa, or any of these values ​​as inclusive endpoints In some embodiments, the tensile strength of the protein polymer may be within a range having any of the following: The polyurethane alloy may have a tensile strength of greater than about 21 MPa. The polyurethane alloy may have a tensile strength ranging from about 21 MPa to about 25 MPa. do.

[0157] In some embodiments, the soy protein polyurethane alloy has a modulus of about 14 MPa to about 1 It may have a tensile strength of 9 MPa or ranging from about 16 MPa to about 19 MPa.

[0158] In some embodiments, the polyurethane in the absence of protein has a viscosity of about 2 MPa. In some embodiments, the tensile strength in the absence of protein may be greater than or equal to 1000 kJ / cm. Polyurethanes have tensile strengths ranging from about 2 MPa to about 35 MPa, including subranges. For example, in some embodiments, the polyurethane in the absence of protein The pressure ranges from about 2MPa to about 35MPa, from about 5MPa to about 30MPa, and from about 10MPa to about 25MPa. Pa, or ranging from about 15 MPa to about 20 MPa, inclusive of these endpoints. The tensile strength may be within a range having any two of the following endpoints: In the form of polyurethane, in the absence of protein, the viscosity is about 10 MPa to about 15 MPa In some embodiments, the tensile strength of the polymer may range from 0.01 to 0.01 in the absence of protein. The polyurethanes in this example may have tensile strengths ranging from about 1 MPa to about 35 MPa. do.

[0159] In some embodiments, the protein polyurethane alloy may be The same protein polyurethane alloy may include a polyurethane having a Young's modulus of , which is about 10% to about 600% higher than the Young's modulus of polyurethane in the absence of protein. This relative percentage increase in Young's modulus can be expressed as " In some embodiments, the delta Young's modulus % can be about 10% or more. In some embodiments, the delta Young's modulus % is about 10% ~approx. 600%, ~approx. 20%~approx. 600%, ~approx. 30%~approx. 600%, ~approx. 40%~approx. 600%, Approximately 50% to approximately 600%, approximately 60% to approximately 600%, approximately 70% to approximately 600%, approximately 80% to approximately 6 00%, approx. 90% to approx. 600%, approx. 100% to approx. 600%, approx. 200% to approx. 600%, approx. 300% to about 600%, about 400% to about 600%, about 500% to about 600%, or The range may be any two of these values ​​inclusive. In embodiments, the delta Young's modulus % may range from about 40% to about 600%. In some embodiments, the Delta Young's Modulus % may be greater than about 600%. The % ratio can range from about 600% to about 2400%.

[0160] In some embodiments, the soy protein polyurethane alloy is a non- The same soy protein polyurethane may contain a polyurethane having a Young's modulus in the presence of Tanalloy exhibits a Young's modulus approximately 60 times higher than that of polyurethane in the absence of soy protein. In some embodiments, the Young's modulus may be large, ranging from about 570% to about 570%. The delta Young's modulus % of the pea protein polyurethane alloy may be about 60% or greater. In some embodiments, the soy protein polyurethane alloy has a delta Young's modulus of about 60 % to approximately 570%, approximately 100% to approximately 570%, approximately 200% to approximately 570%, approximately 300% to approximately 5 70%, about 400% to about 570%, or about 500% to about 570%, or the end points It may be in a range having as endpoints any two of these values ​​inclusive.

[0161] In some embodiments, the protein polyurethane alloy may be The same protein polyurethane alloy may include a polyurethane having a Young's modulus of , which is about 10 MPa to about 350 MPa higher than the Young's modulus of polyurethane in the absence of protein. The Young's modulus can be large over a range of MPa. In some embodiments, the delta Young's modulus is 1 In some embodiments, the delta Young's modulus can be from about 10 MPa to about 100 MPa. 350MPa, about 25MPa to about 350MPa, about 50MPa to about 350MPa, about 10 0MPa ~ approx. 350MPa, approx. 150MPa ~ approx. 350MPa, approx. 200MPa ~ approx. 35 0MPa, approx. 250MPa ~ approx. 350MPa, approx. 300MPa ~ approx. 350MPa, approx. 10 MPa ~ approx. 300MPa, approx. 10MPa ~ approx. 250MPa, approx. 10MPa ~ approx. 200MPa a, about 10MPa to about 150MPa, about 10MPa to about 100MPa, about 10MPa to about 50 MPa, or a range of about 10 MPa to about 25 MPa, or any of these values ​​inclusive of the endpoints. It may be within a range having any two of these as endpoints. The compression rate can range from about 25 MPa to about 350 MPa. The delta Young's modulus can range from about 100 MPa to about 350 MPa.

[0162] In some embodiments, the soy protein polyurethane alloy is a non- The same soy protein polyurethane may contain a polyurethane having a Young's modulus in the presence of Tanalloy has a Young's modulus approximately 35% higher than that of polyurethane in the absence of soy protein. In some embodiments, the Young's modulus may be large, ranging from about 340 MPa to about 340 MPa. In this case, the delta Young's modulus of the soy protein polyurethane alloy can be greater than 35 MPa. In some embodiments, the delta Young's modulus of the soy protein polyurethane alloy is about 35MPa ~ approx. 340MPa, approx. 50MPa ~ approx. 340MPa, approx. 100MPa ~ approx. 34 0MPa, approx. 150MPa ~ approx. 340MPa, approx. 200MPa ~ approx. 340MPa, approx. 25 0MPa ~ approx. 340MPa, approx. 300MPa ~ approx. 340MPa, approx. 35MPa ~ approx. 300 MPa, approx. 35MPa ~ approx. 250MPa, approx. 35MPa ~ approx. 200MPa, approx. 35MPa up to about 150 MPa, about 35 MPa to about 100 MPa, or about 35 MPa to about 50 MPa a, or a range having any two of these values ​​as endpoints, inclusive do.

[0163] In some embodiments, the protein polyurethane alloy comprises a polyurethane having a viscosity of about 50 M, including subranges thereof. For example, in some embodiments, the Young's modulus may range from about 450 MPa to about 450 MPa. Protein polyurethane alloys have a strength of about 50 MPa to about 450 MPa, and about 75 MPa to about 4 50MPa, approx. 100MPa to approx. 450MPa, approx. 150MPa to approx. 450MPa, approx. 2 00MPa to about 450MPa, about 250MPa to about 450MPa, about 300MPa to about 4 50MPa, approx. 350MPa to approx. 450MPa, approx. 400MPa to approx. 450MPa, approx. 5 0MPa to approximately 400MPa, approximately 50MPa to approximately 350MPa, approximately 50MPa to approximately 300MPa Pa, approx. 50 MPa ~ approx. 250 MPa, approx. 50 MPa ~ approx. 200 MPa, approx. 50 MPa ~ Approximately 150 MPa, approximately 50 MPa to approximately 100 MPa, or approximately 50 MPa to approximately 75 MPa or within a range having any two of these values ​​as endpoints, inclusive In some embodiments, the protein polyurethane alloy may have a Young's modulus of about 7 In some embodiments, the Young's modulus may range from 5 MPa to about 450 MPa. The porous polyurethane alloy may have a Young's modulus greater than about 450 MPa. The polypropylene polyurethane alloy has a Young's modulus ranging from about 450 MPa to about 580 MPa. The rate may be:

[0164] In some embodiments, the soy protein polyurethane alloy comprises a polyisoprene copolymer having a viscosity of about 900 MPa, including subranges thereof. The Young's modulus may range from 0 MPa to about 400 MPa. In the form, the soy protein polyurethane alloy has a compressive strength of about 90 MPa to about 400 MPa, about 1 00MPa to about 400MPa, about 150MPa to about 400MPa, about 200MPa to about 4 00MPa, approx. 250MPa to approx. 400MPa, approx. 300MPa to approx. 400MPa, approx. 3 50MPa to approximately 400MPa, approximately 90MPa to approximately 350MPa, approximately 90MPa to approximately 300 MPa, approx. 90MPa ~ approx. 250MPa, approx. 90MPa ~ approx. 200MPa, approx. 90MPa to about 150 MPa, or about 90 MPa to about 100 MPa, or The Young's modulus may lie within a range having any two of these values ​​as endpoints, inclusive.

[0165] In some embodiments, the polyurethane in the absence of protein has a viscosity of about 10 MP In some embodiments, the Young's modulus in the absence of protein may be greater than or equal to a. Polyurethanes have a Young's modulus ranging from about 10 MPa to about 600 MPa, including subranges. For example, in some embodiments, the polyurea in the absence of protein may have Tan said that the thermoplastic collagen elastomer composite has a strength of about 10 MPa to about 600 MPa. Approximately 10MPa to approximately 500MPa, approximately 10MPa to approximately 400MPa, approximately 10MPa to approximately 30 0 MPa, about 10 MPa to about 200 MPa, about 10 MPa to about 100 MPa, or about Any two of these values ​​ranging from 10 MPa to approximately 50 MPa, including the endpoints In some embodiments, the protein may have a Young's modulus within a range having as endpoints In the absence of hydroxybenzoates, polyurethanes have a Young's modulus ranging from about 50 MPa to about 100 MPa. The rate may be:

[0166] In some embodiments, the protein polyurethane alloy may be The same protein polyurethane may include a polyurethane having a water vapor transmission rate of 100%. The alloy has a water vapor transmission rate that is approximately 20% greater than that in the absence of protein. In some embodiments, the protein polyurethane alloy may have a protein permeability. Water vapor transmission rates are approximately 20% to 600% greater than those of polyurethane in the absence of cellulose. This relative percentage increase in water vapor transmission rate is called the "Delta MV" In some embodiments, the delta MVTR% is about 20 In some embodiments, the delta MVTR% can be from about 20% to about 600%. %, approx. 30% to approx. 600%, approx. 40% to approx. 600%, approx. 50% to approx. 600%, approx. 75% Approximately 600%, approximately 100% to approximately 600%, approximately 125% to approximately 600%, approximately 150% to approximately 600 %, approx. 200% to approx. 600%, approx. 20% to approx. 500%, approx. 20% to approx. 400%, approx. 20% ~approximately 300%, approximately 20% to approximately 200%, approximately 20% to approximately 150%, approximately 20% to approximately 125%, Or a range of about 20% to about 100%, or any two of these values ​​inclusive of the endpoints The range may be within the range having the formula:

[0167] In some embodiments, the soy protein polyurethane alloy comprises about 20% or more delta In some embodiments, the soy protein polyurethane alloy may comprise % MVTR. The delta MVTR% is approximately 20% to approximately 600%, approximately 30% to approximately 600%, approximately 40% to approximately 6 00%, approx. 50% to approx. 600%, approx. 75% to approx. 600%, approx. 100% to approx. 600%, approx. 25% to approx. 600%, approx. 150% to approx. 600%, approx. 200% to approx. 600%, approx. 20% to approx. 500%, approx. 20% to approx. 400%, approx. 20% to approx. 300%, approx. 20% to approx. 200%, approx. a range of 0% to about 150%, about 20% to about 125%, or about 20% to about 100%, or It may be in a range having as endpoints any two of these values ​​inclusive.

[0168] In some embodiments, the protein polyurethane alloy may be The same protein polyurethane may include a polyurethane having a water vapor transmission rate of 100%. The alloy has a water vapor transmission rate approximately 30 g / cm2 higher than that of polyurethane in the absence of protein. m 2 / 24 hours ~ approx. 500g / m 2 / 24-hour range with high water vapor transmission rate This relative increase in moisture vapor transmission rate can be referred to as "Delta MVTR." In some embodiments, the delta MVTR is 30 g / m 2 / It can be more than 24 hours. In some embodiments, the delta MVTR is about 30 g / m 2 / 24 hours ~ approx. 500g / m 2 / 24 hours, approximately 40g / m 2 / 24 hours ~ approx. 500g / m 2 / 24 hours, approximately 50g / m 2 / 24 hours ~ approx. 500g / m 2 / 24 hours, approximately 75g / m 2 / 24 hours ~ approx. 500g / m 2 / 24 hours, approximately 100g / m 2 / 24 hours ~ approx. 500g / m 2 / 24 hours, approx. 15 0g / 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 , about 30g / m 2 / 24 hours ~ approx. 400g / m 2 / 24 hours, approximately 30g / m 2 / 24 hours ~about 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 / 24 hour range or these including endpoints It may be within a range having any two of the values ​​as endpoints.

[0169] In some embodiments, the soy protein polyurethane alloy has a density of 30 g / m 2 / twenty four In some embodiments, the soy protein polyester may comprise a delta MVTR of 1 hour or more. The Delta MVTR of Letan Alloy is approximately 30 g / m 2 / 24 hours ~ approx. 500g / m 2 / twenty four time, about 40g / m 2 / 24 hours ~ approx. 500g / m 2 / 24 hours, approximately 50g / m2 / twenty four Time ~ approx. 500g / m 2 / 24 hours, approximately 75g / m 2 / 24 hours ~ approx. 500g / m 2 / 2 4 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. 300 g / m 2 / 24 hours, approximately 30g / m 2 / 24 hours ~ approx. 200g / m 2 / 24 hours, approx. 30 g / m 2 / 24 hours ~ approx. 150g / m 2 / 24 hours, approximately 30g / m 2 / 24 hours ~ approx. 10 0g / m 2 / 24 hours, approx. 30MPa ~ approx. 75g / m 2 / 24 hours, or about 30g / m 2 / 24 hours ~ approx. 50g / m 2 / 24 hour range or any two of these values ​​inclusive The range may be within a range having one of the two endpoints.

[0170] In some embodiments, the protein polyurethane alloy comprises about 30 g, including subranges. / m 2 / 24 hours ~ approx. 1000g / m 2 / 24 hour range of water vapor transmission rate For example, in some embodiments, the protein polyurethane alloy has a density of about 30 g / m 2 / 24 hours ~ approx. 1000g / m 2 / 24 hours, approximately 60g / m 2 / 24 hours ~ approx. 1000 g / 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, approx. 500g / m 2 / 24 hours ~ approx. 1000g / m 2 / 24 hours, approximately 30g / m 2 / 24 hours ~ approx. 90 0g / m 2 / 24 hours, approximately 30g / m 2 / 24 hours ~ approx. 800g / m 2 / 24 hours, approx. 0g / m 2 / 24 hours ~ approx. 700g / m 2 / 24 hours, approximately 30g / m 2 / 24 hours ~ approx. 6 00g / m 2 / 24 hours, approximately 30g / m 2 / 24 hours ~ approx. 500g / m 2 / 24 hours, approx. 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 / 2 4 hours ~ approx. 100g / m 2 Any of these values ​​over a 24-hour range or including the endpoints In some embodiments, the moisture vapor transmission rate may be within a range having any two of the endpoints. , protein polyurethane alloy is about 250g / m 2 / More than 24 hours of water vapor transmission For example, in some embodiments, the protein polyurethane alloy may comprise about 25 0g / m 2 / 24 hours ~ approx. 1000g / m 2 / 24 hours, approx. 250g / m 2 / 24 hours~ Approximately 700g / m 2 / 24 hours, or approximately 250g / m 2 / 24 hours ~ approx. 500g / m 2 / 2 The moisture vapor transmission rate may include a 4 hour range.

[0171] In some embodiments, the soy protein polyurethane alloy comprises a polyisoprene copolymer having a viscosity of about 300 MPa, including subranges thereof. 0g / m 2 / 24 hours ~ approx. 1000g / m 2 Includes water vapor transmission rates over a 24-hour range. For example, in some embodiments, the soy protein polyurethane alloy may have a viscosity of about 300 MPa. 0g / m 2 / 24 hours ~ approx. 1000g / m 2 / 24 hours, approximately 60g / m 2 / 24 hours ~ approx. 1000g / m 2 / 24 hours, approximately 100g / m 2 / 24 hours ~ approx. 1000g / m 2 / twenty four time, about 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. 1000 g / m 2 / 24 hours, approx. 400g / m 2 / 24 hours ~ approx. 1000g / m 2 / 24 hours, approx. 500g / m 2 / 24 hours ~ approx. 1000g / m 2 / 24 hours, approximately 30g / m 2 / 24 hours ~about 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 ~about 600g / m 2 / 24 hours, approximately 30g / m 2 / 24 hours ~ approx. 500g / m 2 / twenty four time, about 30g / m 2 / 24 hours ~ approx. 400g / m 2 / 24 hours, approximately 30g / m 2 / twenty four Time ~ approx. 300g / m 2 / 24 hours, approximately 30g / m 2 / 24 hours ~ approx. 250g / m 2 / 2 4 hours, approximately 30g / m 2 / 24 hours ~ approx. 200g / m 2 / 24 hours or about 30g / m 2 / 24 hours ~ approx. 100g / m 2 These ranges span a 24-hour period or include the endpoints. The moisture vapor transmission rate may fall within a range having any two of the values ​​as endpoints. In form, soy protein polyurethane alloy is about 250 g / m 2 / Water for more than 24 hours For example, in some embodiments, soy protein polyurethanes may include a vapor transmission rate. The alloy is approximately 250 g / m 2 / 24 hours ~ approx. 1000g / m 2 / 24 hours, approx. 250g / m 2 / 24 hours ~ approx. 700g / m 2 / 24 hours, or approximately 250g / m 2 / 24 hours ~ about 5 00g / m 2 / 24 hour range of water vapor transmission rates.

[0172] Figure 17 illustrates a layered material 1700 according to some embodiments. The layered material 1700 comprises a substrate The polyurethane-protein alloy layer 1720 is bonded to the material layer 1710. The protein alloy layer 1720 can be directly bonded to the surface of the substrate layer 1710 or Alternatively, it can be bonded to the surface of the base layer 1710 via an intermediate layer, such as an adhesive layer. Bonding can be achieved, for example, using a thermal bonding process or stitching. The urethane protein alloy layer 1720 is referred to as the "first polyurethane protein alloy layer." It can be called.

[0173] The polyurethane-protein alloy layer 1720 may comprise one or more protein types and one or more In some embodiments, the polyurethane-protein alloy layer 1 720 may include one or more proteins dissolved in one or more polyurethanes. In some embodiments, the polyurethane-protein alloy layer 1720 can be transparent. The transparency of the polyurethane protein alloy layer is determined by dyeing the polyurethane protein alloy layer. The color is evaluated before it is applied or otherwise colored.

[0174] The transparent protein polyurethane alloy layer can provide unique properties to the layered material. For example, compared to a non-transparent layer, a transparent protein polyurethane alloy layer has a higher viscosity when dyed. It can provide inherent color intensity. Similarly, transparent protein polyurethane alloys The layers provide the layered material with its mechanical properties without significantly affecting the aesthetic properties of the material. It can be provided.

[0175] The protein polyurethane alloy layer 1720 has a bottom surface 1722, a top surface 1724, and a bottom surface 1726. 1722 and the upper surface 1724. The thickness 1726 is between about 25 microns and about 400 microns (micrometers), inclusive. For example, the thickness 1726 may be in the range of about 25 microns, about 50 mm, or about 100 mm. Cron, approximately 100 microns, approximately 125 microns, approximately 150 microns, approximately 175 microns, about 200 microns, about 250 microns, about 300 microns, about 350 microns, or About 400 microns, or within a range having any two of these values ​​as endpoints, inclusive In some embodiments, the thickness 1726 can be between about 50 microns and about 350 microns. Ron, about 75 microns to about 300 microns, about 100 microns to about 250 microns, about 1 The range is from 25 microns to about 200 microns, or from about 150 microns to about 175 microns. It is possible.

[0176] The protein polyurethane alloy layer 1720 has a thickness of about 25 g / m 2 ~about 12 5g / m 2 Grams per square meter (gsm, g / m) ranges from 2 ) measured For example, the protein polyurethane alloy layer 1720 may have a dry weight of about 2 5g / m 2 , about 50g / m 2 , about 75g / m 2 , about 100g / m 2 , or about 125g / m 2 or a range having any two of these values ​​as endpoints, inclusive of the endpoints. In some embodiments, the protein polyurethane alloy layer 17 may have a dry weight of 20 is approximately 25g / m 2 ~Approx. 125g / m 2 , about 25g / m 2 ~about 100g / m 2 , or Approximately 50g / m 2 ~about 100g / m 2 The dry weight may range from 1000 to 10 ...

[0177] Unless otherwise specified, the dry weight of the layers is calculated during the process of making the material using the following method: First, a first sample of the material (approximately 10 mm in diameter) is prepared before the layer in question is applied to the material. The sacrificial layer is cut into pieces (approximately 1 / 4 inch) and weighed and measured to calculate the initial dry weight. If present, remove it before measuring the weight and dimensions. Then apply and dry the layer in question. After allowing to stand, a second sample of the same size is cut from the material and the weight and dimensions are measured to determine the second Calculate the dry weight. If a sacrificial layer is present, remove it before measuring the weight and dimensions. 3. Subtract the dry weight of the first from the dry weight of the second to get the dry weight of the layer in question. All weight and dimensional measurements are taken at the same humidity level, typically that of the manufacturing environment in which the material is made. For the purpose of calculating dry weight, three separate dry weight tests are performed: The average dry weight is reported as the dry weight of the layer.

[0178] In some embodiments, the protein polyurethane alloy layer 1720 is a non-foamed layer. A "non-foamed" layer may have a void percentage of 5% or less, for example, a layer with 0% void to 5% void. In some embodiments, the layer has a density measured in micrometers. The polyethylene alloy layer 1720 may be a foam layer. The polyurethane alloy layer 1720 has a void ratio ranging from about 5% to about 70%. The density may be measured by the percent voids in the layer 1720. For example, The polyurethane alloy layer 1720 has about 5% voids, about 10% voids, about 20% voids, and about 3% voids. 0% void, about 35% void, about 40% void, about 45% void, about 50% void, about 5 5% voids, about 60% voids, about 65% voids, or about 70% voids, or including the end points The gap may be within a range having any two of these values ​​as endpoints. In an embodiment, the protein polyurethane alloy layer 1720 is 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% The percent voids may range from 0.01 to 0.01.

[0179] The percent voids (which may also be referred to as "percent porosity") are determined by image analysis of the cross section of the layer. This can be measured by measuring the bulk density of a sample of the layer using a hydrometer. Unless otherwise specified, the void percentages reported herein are based on images of cross sections of layers. Images were analyzed at 37x magnification using ImageJ software (or equivalent). The analysis is performed using ImageJ software, which is a trainable Weka A segmentation classifier is used to calculate the void percentage in the layer. Three to five separate images of the cross section are evaluated to calculate the average percent void space. is reported as the percent voids of the layer. In some embodiments, the protein polyurethane The tan alloy layer 1720 may include one or more foaming agents and / or foam stabilizers. The foam stabilizers and foam stabilizers include those discussed herein for layers 1730 and 1740.

[0180] The base layer 1710 has a bottom surface 1712, a top surface 1714, and a bottom surface 1712, a top surface 1714, and a In some embodiments, the thickness 1716 is measured between the portions For example, the thickness 171 6 is about 50 microns, about 100 microns, about 150 microns, about 200 microns, about 2 50 microns, approximately 300 microns, approximately 350 microns, approximately 400 microns, approximately 500 microns Ron, about 600 microns, about 700 microns, about 800 microns, about 900 microns, or about 1000 microns, or any two of these values ​​inclusive. In some embodiments, the thickness 1716 can be in a range from about 100 microns to about 900 microns, approximately 150 microns to approximately 800 microns, approximately 200 microns to approximately 700 microns Chron, about 250 microns to about 600 microns, about 300 microns to about 500 microns, Or it may be in the range of about 350 microns to about 400 microns.

[0181] The substrate layer 1710 has a thickness of about 50 g / m 2 ~about 600g / m 2 ranging from , grams per square meter (g / m 2) may have a dry weight measured at 1000 kJ / kg. For example, , the base layer 110 is approximately 50 g / m 2 , about 75g / m 2 , about 100g / m 2 , about 125g / m 2 , about 150g / m 2 , about 175g / m 2 , about 200g / m 2 , about 300g / m 2 ,about 400g / m 2 , about 500g / m 2 , or about 600 g / m 2 Dry weight or end point The dry weight may be within a range having any two of these values. In this embodiment, the substrate layer 1710 has a weight of about 75 g / m 2 ~about 500g / m 2 , about 100g / m 2 ~about 400g / m 2 , about 125g / m 2 ~about 300g / m 2 , about 150g / m 2 ~About 200g / m 2 , or about 175 g / m 2 ~about 200g / m 2 The dry weight may range from 1000 to 10 ...

[0182] The substrate layer 1710 may include one or more textile layers. For example, the layer may be a woven fabric layer, a nonwoven fabric layer, a knitted layer, a mesh fabric layer, or a leather layer. One or more textile layers are made of recycled or virgin fibers, filaments, or yarns. In some embodiments, the substrate layer 1710 may be made of polyester knit. a polyester cotton spandex blend knit layer, or a suede layer; or In some embodiments, the substrate layer 1710 may include one or more natural fibers, For example, cotton, linen, silk, wool, kenaf, flax, cashmere, angora, bamboo, bast, and hemp , soybeans, seaweed, milk or milk protein, spider silk, chitosan, mycelium It may be made from fibers made from cellulose, including bacterial cellulose, or wood. A filament is the vegetative part of a fungus or fungus-like bacterial colony, consisting of a mass of branching, filamentous hyphae. Fungi consist mainly of a cell wall that is constantly elongating at the apex of the hyphae. Unlike the structural components of plants, which consist of cellulose, or animal cells, which depend on collagen, The structural oligosaccharides of fungal cell walls are mainly composed of chitin and beta-glucans. is a strong, hard substance also found in the exoskeleton of arthropods.

[0183] In some embodiments, the substrate layer 1710 is made of one or more synthetic fibers, such as polyester. ester, nylon, aromatic polyamide, polyolefin fibers, e.g., polyethylene, poly Propylene, rayon, lyocell, viscose, antimicrobial yarn (AMY), S orbtek, nylon, elastomers such as LYCRA®, spandex or ELASTANE®, a polyester-polyurethane copolymer , aramid, carbon including carbon fiber and fullerenes, glass, silicon, minerals, iron, steel, lead , metals or metal alloys, including those containing gold, silver, platinum, copper, zinc and titanium; It may be made from fibers made from a mixture thereof.

[0184] In some embodiments, the nonwoven substrate layer 1710 is a staple nonwoven, meltblown The nonwoven may be a spun-laid nonwoven, a spun-laid nonwoven, a flash-spun nonwoven, or a combination thereof. In some embodiments, the nonwoven substrate layer 1710 is made by carding. It can be air laid or wet laid. In some configurations, carded, airlaid, or wetlaid substrates may be, for example, needle-pasted. The fibers may be bonded by punching, hydroentanglement, lamination, or thermal bonding. The woven substrate layer 1710 is made of one or more natural fibers, such as cotton, linen, silk, wool, or kenaf. Fu, flax, cashmere, angora, bamboo, bast, hemp, soybean, seaweed, milk or milk tan Cellulose, including protein, spider silk, chitosan, mycelium, bacterial cellulose, or It may include fibers made from wood.

[0185] In some embodiments, the nonwoven substrate layer 1710 has functional particles in the polymer. Exemplary functional particles include polymer fibers. These include ceramic particles mixed into a polymer resin during the extrusion process. Ceramic particles can provide polymer fibers with desirable heat dissipation and flame resistance properties. In some embodiments, the nonwoven substrate layer 1710 is made of fruit pulp (e.g., grape pulp). Some embodiments may include fiber made from pineapple fiber or apple pulp. In this embodiment, the nonwoven substrate layer 1710 is made from recycled materials, such as recycled plastic. In some embodiments, the nonwoven substrate layer 1710 may include fibers made from In some embodiments, the nonwoven substrate layer 1710 may comprise cork fibers. may include:

[0186] In some embodiments, the substrate layer 1710 may be a spacer fabric, such as the one shown in FIG. The spacer fabric 2100 may be or include one or more The first fabric layer 2110 and the second fabric layer 21 are connected by spacer yarns 2130 above. 20. The spacer yarn(s) 2130 are spaced apart from the first fabric layer 2110 and the second fabric layer 2110. 120, and the inner surface 2114 of the first fabric layer 2110 and the inner surface 2120 of the second fabric layer 2120. defines the distance between the outer surface 2112 of the first fabric layer 2110 and the surface 2124 of the second fabric layer The outer surfaces 2122 of 2120 are respectively connected to the top surface 1714 and bottom surface 1712 of the substrate layer 1710. can be defined.

[0187] The first fabric layer 2110 and the second fabric layer 2120 may include one or more layers of fabric material. In some embodiments, the first fabric layer 2110 and the second fabric layer 2120 are made of staple fibers. , filaments, or mixtures thereof. As used herein, "staple fibers" refers to fibers having a length of from about 0.2 mm to about 5 centimeters. Staple fibers are fibers with a short length of about 1 / 4 inch (0.5 cm). Staple fibers can occur in nature. As used herein, "filament" may be a cut filament. "long fibers" refers to fibers having a length of 5 cm or more. In some embodiments, the first fabric layer 2110 and 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 is a woven fabric layer or a knit fabric. In some embodiments, the outer surface of the second fabric layer 2120 2122 can be defined by a woven or knitted fabric layer.

[0188] In some embodiments, the first fabric layer 2110 and the second fabric layer 2120 are made of one or more Natural fibers, such as cotton, linen, silk, wool, kenaf, flax, cashmere, angora, bamboo , bast, hemp, soybean, seaweed, milk or milk protein, spider silk, chitosan Fibers made from cellulose, including cellulose, mycelium, bacterial cellulose, or wood. In some embodiments, the first fabric layer 2110 and the second fabric layer 2120 may be a single The above synthetic fibers, for example, polyester, nylon, aromatic polyamide, polyolefin Fibers, such as polyethylene, polypropylene, rayon, lyocell, viscose, anti-fungal Bio-based yarn (AMY), Sorbtek, nylon, elastomers, e.g., L YCRA®, spandex, or ELASTANE®, poly Ester-polyurethane copolymer, aramid, carbon fiber and fullerene-containing carbon, gas containing lath, silicon, minerals, iron, steel, lead, gold, silver, platinum, copper, zinc and titanium or a mixture thereof. The spacer yarn(s) 2130 are attached to the first fabric layer 2110 and the second fabric layer 2120. Monofilament yarns made from any of the natural or synthetic materials listed above. It may include (several).

[0189] In some embodiments, the substrate layer 1710 may be colored with a colorant. In the form, the colorant may be a dye, for example, an acid dye, a fiber-reactive dye, a direct dye, a sulfur dye, It can be a basic dye or a reactive dye. In some embodiments, the colorant is a pigment, e.g. In some embodiments, depending on the desired aesthetics of the layered material, A first colorant can be incorporated into one or more protein polyurethane alloy layers, and Two colorants can be incorporated into the substrate layer 1710.

[0190] Fiber reactive dyes react with fibrous cellulosic substrates in the presence of alkaline pH and elevated temperatures. one or more pendant groups capable of forming a covalent bond with a nucleophilic site in These dyes are capable of achieving high washfastness and a wide range of brilliant shades. Exemplary reactive dyes include sulfatoethyl sulfone (Remazol), trimethylsilyl sulfone (Trimethylsilyl sulfone), Includes, but is not limited to, azine, vinyl sulfone, and acrylamide dyes These dyes are capable of reacting with fiber nucleophiles via Michael addition to form dyes on silk, wool, and other fibers. Direct dyes can dye protein fibers such as cellulose, polyester, and nylon. It is an anionic dye that can dye carbon fibers or protein fibers. In the presence of electrolytes such as ammonium hydroxide or sodium sulfate, the closer the boiling points, the more readily these dyes can be dissolved. Exemplary direct dyes include azo, stilbene, fluoro, and fluoroisopropyl dyes. These include, but are not limited to, phthalocyanines and dioxazines.

[0191] In some embodiments, the layered material 1700 is bonded to the top surface 1714 of the substrate layer 1710. In some embodiments, the layer may include a protein polyurethane alloy layer 1720. The bottom surface 1722 of the porous polyurethane alloy layer 1720 is in contact with the top surface 171 of the substrate layer 1710. In some embodiments, the protein polyurethane alloy layer 172 The bottom surface 1722 of the substrate 1710 is connected to the top surface of the substrate 1710 via an adhesive layer (e.g., adhesive layer 1750). In some embodiments, the layered material 1700 may be bonded to a substrate layer 1710. The bottom surface 1712 of the casing 1700 may include a protein polyurethane alloy layer 1720 bonded thereto. In some embodiments, the top surface 1724 of the protein polyurethane alloy layer 1720 is In some embodiments, the protein polyimide may be in direct contact with the bottom surface 1712 of the protein polyimide. The upper surface 1724 of the ethylene alloy layer 1720 is bonded to the adhesive layer (e.g., adhesive layer 1750) via an adhesive layer. The layered material 170 may be bonded to the bottom surface 1712 of the substrate layer 1710. 17.0 is a protein polyurethane alloy layer 172 bonded to the top surface 1714 of the substrate layer 1710. 0 and a protein polyurethane alloy layer 172 bonded to the bottom surface 1712 of the substrate layer 1710. In such an embodiment, the layered material 1700 may include a pair of substrate layers 1710. The membrane includes a protein polyurethane alloy layer 1720 disposed on the facing surface.

[0192] In some embodiments, for example as shown in FIG. 18, the layered material 1700 may be A second tamper-evident layer is disposed between the porous polyurethane alloy layer 1720 and the substrate layer 1710. In such an embodiment, the second tamper-evident layer 1730 may include a hard polyurethane alloy layer 1730. Protein polyurethane alloy layer 1730 is bonded to protein polyurethane alloy layer 1720 In some embodiments, the bottom surface 1720 of the protein polyurethane alloy layer 1720 22 may be in direct contact with the top surface 1734 of the second protein polyurethane alloy layer 1730. do.

[0193] The second protein polyurethane alloy layer 1730 has a bottom surface 1732, a top surface 1734, and and a thickness 1736 measured between the bottom surface 1732 and the top surface 1734. In some embodiments, the thickness 1736 ranges from about 25 microns to about 600 microns, including subranges. For example, the thickness 1736 can be about 25 microns, about 50 microns, about 100 microns, or about 100 microns. 125 microns, 150 microns, 175 microns, 200 microns, 2 25 microns, approximately 250 microns, approximately 275 microns, approximately 300 microns, approximately 400 microns about 500 microns, or about 600 microns, or any of these values ​​inclusive. In some embodiments, the thickness 1736 may be in a range having any two of these as endpoints. is about 50 microns to about 500 microns, about 75 microns to about 400 microns, about 100 Microns to approximately 300 microns, approximately 125 microns to approximately 275 microns, approximately 150 microns about 250 microns, about 175 microns to about 225 microns, or about 200 microns to about In some embodiments, the thickness 1736 may be in the range of 225 microns. In some embodiments, thickness 1736 is less than thickness 1726. In some embodiments, thickness 1736 may be less than 5 microns thicker than thickness 1726. It may be 5 microns or more larger than thickness 1726 or 5 microns or more smaller than thickness 1726.

[0194] The second protein polyurethane alloy layer 1730 has a thickness of about 30 g / m 2 ~ Approximately 600g / m 2 Grams per square meter (g / m) ranges from 2 ) measured For example, the second protein polyurethane alloy layer 1730 may have a dry weight of Approximately 30g / m 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 30 0g / m 2 , about 400g / m 2 , about 500g / m 2 , or about 600 g / m 2 Dry weight of or a range having any two of these values ​​as endpoints, inclusive. In some embodiments, the second protein polyurethane alloy layer 1730 may be Approximately 40g / m 2 ~about 500g / m 2 , about 60g / m 2 ~about 400g / m 2 , about 80g / m 2 ~about 300g / m 2 , about 100g / m 2 ~about 200g / m 2 , about 120g / m 2 ~about 1 50g / m 2 , or about 140 g / m 2 ~about 150g / m 2 having a dry weight ranging from In some embodiments, the protein polyurethane alloy layer 1720 has a first weight the second protein polyurethane alloy layer 1730 may have a second weight, and the first The first weight can be less than the second weight. In some embodiments, the first weight is less than the second weight. Amount less than 5g / m 2 It may be smaller than this.

[0195] In some embodiments, the second protein polyurethane alloy layer 1730 comprises a blowing agent In some embodiments, the second protein polyurethane alloy layer 1730 The foaming agent or foam stabilizer may comprise a second protein polyurethane alloy. The space in the second protein polyurethane alloy layer 1730 is formed during blending of the polyurethane layer 1730. Suitable foam stabilizers include HeiQ from Chemtex Available in HeiQ Chemtex 2216-T (nonionic and anionic) Stabilized blend of surfactants), HeiQ Chemtex 2241-A (modified HEU R (hydrophobically modified ethylene oxide urethane) thickener), HeiQ Chemtex 22 43 (non-ionic silicone dispersion), or HeiQ Chemtex 2317 (non-ionic Foam stabilizers include, but are not limited to, ionic and anionic surfactants. When used, foam stabilizers help stabilize mechanically produced foams (cells). Mechanically produced foams can be produced, for example, by a rotor and / or compressed air. When used, the blowing agent may be formed by a chemical reaction and / or through heat generation within the layer. Foam (air bubbles) can be created within the layer.

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

[0197] The second protein polyurethane alloy layer 1730 has a void volume of about 5% to about 10%. The layer 1730 may have a density measured in percent voids ranging from 70% voids to 100% voids. For example, the second protein polyurethane alloy layer 1730 may have about 5% voids, about 10% Void, about 20% void, about 30% void, about 35% void, about 40% void, about 45% void, about 50% void, about 55% void, about 60% void, about 65% void, or about 70% voids or voids within a range having any two of these values ​​as endpoints, inclusive In some embodiments, the second protein polyurethane alloy layer 173 0 is approximately 10% to approximately 65%, approximately 20% to approximately 60%, approximately 30% to approximately 55%, approximately 35% to approximately 5 The percent voids may range from about 40% to about 45%. In an embodiment, the protein polyurethane alloy layer 1720 may have a first density and a second density. The porous polyurethane alloy layer 1730 can have a second density, and the first density can be In some embodiments, the first density may be greater than the second density with 5% or more voids. The density may be greater than that of the

[0198] Layering of multiple protein polyurethane alloy layers having different weights and / or densities is used. can be used to tailor the material properties of the layered material, e.g., to achieve lower weight and / or Layers having density can be used to increase the softening and / or flexibility of the layered material. On the other hand, layers with greater weight and / or density can increase the strength of the layered material. Additionally, using one or more layers with a relatively low weight and / or density can improve cutting performance. Cutting, stitching, and / or forming process steps (e.g., skiving) This increases the ease with which the method can be performed on layered materials. Layering of the polyurethane alloy layer increases the degree of freedom in material design.

[0199] In some embodiments, the second protein polyurethane alloy layer 1730 comprises a blowing agent In addition to any other components that may be present, such as a foam stabilizer, or one or more colorants, The type and content of the colorant in the second protein polyurethane alloy layer 1730 The protein polyurethane alloy layer 1720 may be of any of the types and amounts described herein. In some embodiments, the second protein polyurethane alloy layer 1 730 may be free or substantially free of colorants.

[0200] In some embodiments, for example as shown in FIG. 18, the layered material 1700 comprises a second a third layer disposed between the protein polyurethane alloy layer 1730 and the substrate layer 1710; In such an embodiment, the third The protein polyurethane alloy layer 1740 is a second protein polyurethane alloy layer 1 730. In some embodiments, the second protein polyurethane alloy layer The bottom surface 1732 of 1730 is connected to the top surface 1740 of the third protein polyurethane alloy layer 1740. 44 may come into direct contact with

[0201] The third protein polyurethane alloy layer 1740 has a bottom surface 1742, a top surface 1744, and and a thickness 1746 measured between the bottom surface 1742 and the top surface 1744. In some embodiments, the thickness 1746 ranges from about 25 microns to about 600 microns, including subranges. For example, the thickness 1746 can be about 25 microns, about 50 microns, about 100 microns, or about 100 microns. 125 microns, 150 microns, 175 microns, 200 microns, 2 25 microns, approximately 250 microns, approximately 275 microns, approximately 300 microns, approximately 400 microns about 500 microns, or about 600 microns, or any of these values ​​inclusive. In some embodiments, the thickness 1746 is about 50 microns to about 500 microns, about 75 microns to about 400 microns, about 100 Microns to approximately 300 microns, approximately 125 microns to approximately 275 microns, approximately 150 microns about 250 microns, about 175 microns to about 225 microns, or about 175 microns to about In some embodiments, the thickness 1746 can be in the range of 200 microns. In some embodiments, thickness 1746 is less than thickness 1726. In some embodiments, thickness 1746 is 5 microns greater than thickness 1726. It may be 5 microns or more larger than thickness 1726, or 5 microns or more smaller than thickness 1726. In some embodiments, thickness 1746 may be the same as thickness 1736. In this case, thickness 1746 may be greater than thickness 1736 or less than thickness 1736. In some embodiments, thickness 1746 is at least 5 microns greater than thickness 1736. or may be 5 microns or more less than thickness 1736.

[0202] The third protein polyurethane alloy layer 1740 has a thickness of about 30 g / m 2 ~ Approximately 600g / m 2 Grams per square meter (g / m) ranges from 2 ) measured For example, the third protein polyurethane alloy layer 1740 may have a dry weight of Approximately 30g / m 2 , about 40g / m 2 , about 60g / m2 , 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 30 0g / m 2 , about 400g / m 2 , about 500g / m 2 , or about 600 g / m 2 Dry weight of or a range having any two of these values ​​as endpoints, inclusive. In some embodiments, the third protein polyurethane alloy layer 1740 may be Approximately 40g / m 2 ~about 500g / m 2 , about 60g / m 2 ~about 400g / m 2 , about 80g / m 2 ~about 300g / m 2 , about 100g / m 2 ~about 200g / m 2 , about 120g / m 2 ~about 1 50g / m 2 , or about 120 g / m 2 ~Approx. 140g / m 2 having a dry weight ranging from In some embodiments, the protein polyurethane alloy layer 1720 has a first weight the third protein polyurethane alloy layer 1740 may have a third weight, and the first The weight of the protein polyurethane may be less than the third weight. The alloy layer 1720 may have a first weight and the second protein polyurethane alloy layer 173 0 may have a second weight, and the third protein polyurethane alloy layer 1740 may have a third weight and the first weight may be less than the second weight and the third weight. In this embodiment, the first weight is 5 g / m 2 or more thicker than the second weight and / or the third weight. 2 It's smaller than that Good too.

[0203] In some embodiments, the third protein polyurethane alloy layer 1740 comprises a blowing agent In some embodiments, the third protein polyurethane alloy layer 1740 The foaming agent and / or foam stabilizer may comprise a third protein polyurethane. The third protein polyurethane alloy layer 1740 is blended with the third protein polyurethane alloy layer 1740. It can promote the formation of voids. Suitable foaming agents include HeiQ Chemtex HeiQ Chemtex 2216-T (nonionic and anionic) available from HeiQ Chemtex 2241-A (modified H EUR (Hydrophobic Modified Ethylene Oxide Urethane) Thickener), HeiQ Chemtex 2243 (non-ionic silicone dispersion), or HeiQ Chemtex 2317 ( Nonionic and anionic surfactants) foam stabilizers, including but not limited to .

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

[0205] The third protein polyurethane alloy layer 1740 has a void volume of about 5% to about 10%. The layer 1740 may have a density measured in percent voids ranging from 70% voids to 100% voids. For example, the third protein polyurethane alloy layer 1740 may have about 5% voids, about 10% Void, about 20% void, about 30% void, about 35% void, about 40% void, about 45% void, about 50% void, about 55% void, about 60% void, about 65% void, or about 70% voids or voids within a range having any two of these values ​​as endpoints, inclusive In some embodiments, the third protein polyurethane alloy layer 174 0 is approximately 10% to approximately 65%, approximately 20% to approximately 60%, approximately 30% to approximately 55%, approximately 35% to approximately 5 The percent voids may range from about 40% to about 45%. In an embodiment, the protein polyurethane alloy layer 1720 may have a first density and a third density. The porous polyurethane alloy layer 1740 can have a third density, and the first density can be In some embodiments, the protein polyurethane alloy layer 17 20 may have a first density and 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 third protein polyurethane alloy layer 1740 may have a third density. The first density may be greater than the second density and the third density. The first density may be greater than the second density and / or the third density by 5% or more voids. .

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

[0207] In some embodiments, the third protein polyurethane alloy layer 1740 comprises a blowing agent In addition to any other components that may be present, such as a foam stabilizer, one or more colorants, etc. The type and content of the colorant in the third protein polyurethane alloy layer 1740 are as follows: Any of the types and amounts described herein for the protein polyurethane alloy layer 1720 In some embodiments, the third protein polyurethane alloy layer 174 0 may be free or substantially free of colorants.

[0208] In some embodiments, for example as shown in FIG. 18, the layered material 1700 may be a base The base coat layer 1760 may include a protein polyurethane adhesive. The base coat layer 1760 may be disposed on the top surface 1724 of the Roy layer 1720. The protein-polyurethane alloy layer 1720 may be directly or indirectly bonded to the protein-polyurethane alloy layer 1720. In an embodiment, the base coat layer 1760 is a layer of the protein polyurethane alloy layer 1720. In some embodiments, the base coat layer 17 The bottom surface 1762 of the 60 is directly in contact with the top surface 1724 of the protein polyurethane alloy layer 1720. Can come into contact.

[0209] The base coat layer 1760 has a bottom surface 1762, a top surface 1764, and a bottom surface 1762 and a top surface 1765. 764. In some embodiments, thickness 1766 can range from about 20 microns to about 200 microns, including subranges. For example, 1766 is approximately 20 microns, approximately 30 microns, approximately 40 microns, approximately 50 microns, approximately 6 0 microns, approximately 70 microns, approximately 80 microns, approximately 90 microns, approximately 100 microns, approximately 150 microns, or about 200 microns, or any two of these values ​​inclusive In some embodiments, the thickness 1766 can be in a range having as endpoints about 3 0 microns to approximately 150 microns, approximately 40 microns to approximately 100 microns, approximately 50 microns and above About 90 microns, about 60 microns to about 80 microns, or about 60 microns to about 70 microns The range can be as low as 1000 sq m.

[0210] In embodiments that include a base coat layer 1760, the base coat layer 1760 is made of layered material 1 700, and provide one or more of the following properties: (i) abrasion resistance, color fastness, or hydrolysis resistance. The base coat layer 1760 may also be used in embodiments that include a top coat layer. In some embodiments, this can help adhere layered material 1700 to the topcoat layer. In some embodiments, the base coat layer 1760 may include one or more polymeric materials. Suitable materials for the adhesive layer 1760 include polyether polyurethane, polycarbonate polyurethane, and the like. Urethane, polyester polyurethane, acrylic polymer, and isocyanate or chlorine In some embodiments, crosslinking agents include, but are not limited to, benzodiimides. Alternatively, the layered material 1700 may include 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 is approximately 20 g / m 2 ~about 100g / m 2 Range Grams per square meter (g / m 2 ) may have a dry weight measured at For example, the base coat layer 1760 may have a thickness of about 20 g / m 2 , about 30g / m 2 , about 40g / m 2 , about 50g / m 2 , about 60g / m 2 , about 70g / m 2 , about 80g / m 2 , about 90g / m 2 , or about 100 g / m 2 or any two of these values, including the end points In some embodiments, the base coat may have a dry weight within a range having as endpoints: Layer 1760 is approximately 30 g / m 2 ~about 90g / m 2 , about 40g / m 2 ~about 80g / m 2 ,also is about 50g / m 2 ~about 70g / m 2 The dry weight may range from 1000 to 10 ...

[0212] In some embodiments, for example as shown in FIG. 18, the layered material 1700 includes a top The topcoat layer 1770 may include a protein polyurethane adhesive. The topcoat layer 1770 may be disposed on the upper surface 1724 of the Roy layer 1720. The protein-polyurethane alloy layer 1720 may be directly or indirectly bonded to the protein-polyurethane alloy layer 1720. In an embodiment, the bottom surface 1772 of the topcoat layer 1770 is made of a protein polyurethane alloy. The base coat layer 1760 may be in direct contact with the top surface 1724 of the base coat layer 1720. , a topcoat layer 1770 is disposed on the upper surface 1764 of the basecoat layer 1760. In some embodiments, the top coat layer 1770 is formed by applying a coating of the base coat layer 1760. In some embodiments, the bottom of the topcoat layer 1770 may be disposed on the top surface 1764. The surface 1772 may be in direct contact with the top surface 1764 of the base coat layer 1760 .

[0213] The topcoat layer 1770 has a bottom surface 1772, a top surface 1774, and a bottom surface 1772 and a top surface 1775. 774. In some embodiments, thickness 1776 The thickness may range from about 10 microns to about 80 microns, including subranges. 776 is approximately 10 microns, approximately 20 microns, approximately 30 microns, approximately 40 microns, approximately 50 microns, about 60 microns, about 70 microns, or about 80 microns, or including endpoints It may be within a range having any two of these values ​​as endpoints. The thickness 1776 is about 20 microns to about 70 microns, about 30 microns to about 60 microns The thickness may be in the range of about 100 microns to about 50 microns.

[0214] In embodiments that include a topcoat layer 1770, the topcoat layer 1770 may be formed from a layered material 1 700 of the following properties: surface feel, stain resistance, flame resistance, gloss level, or color appearance In some embodiments, the topcoat layer 1770 may be provided in one or more layers. Suitable materials for the topcoat layer 1770 may include one or more polymeric materials. These include polyurethane, acrylic, and silicone feel agents, matting agents, and gloss agents. In some embodiments, the layered material 1700 may include a plurality of top coats. In some embodiments, the topcoat layer 1770 may comprise a layer of material. In some embodiments, the topcoat layer 1770 may be absent from the material 1700. In some embodiments, the topcoat layer 1770 may be an outer One or more dyes, one or more pigments, and / or one or more reflectors to affect the appearance The agent may include:

[0215] The topcoat layer 1770 is approximately 10 g / m 2 ~about 80g / m 2 In the range of Grams per square meter (g / m 2 ) may have a dry weight measured at 1000 kJ / kg. For example, the topcoat layer 1770 may have a thickness of about 10 g / m 2 , about 20g / m 2 , about 30g / m 2 , about 40g / m 2 , about 50g / m 2 , about 60g / m 2 , about 70g / m 2 , or about 80 g / m 2 or a range having any two of these values ​​as endpoints, inclusive. In some embodiments, the topcoat layer 1770 may have a dry weight of about 20 g / m 2 ~about 70g / m 2 , about 30g / m 2 ~about 60g / m 2 , or about 30 g / m 2 ~about 50g / m 2 The dry weight may range from 1000 to 10 ...

[0216] together, protein polyurethane alloy layer(s) 1720, 1730, 1740, The base coat layer(s) 1760 and / or top coat layer(s) 1770 may be: A layered assembly 1780 of the layered material 1700 can be defined. The layered assembly 1780 It may include any number of protein polyurethane alloy layers as described herein. For example, layered Aggregate 1780 is 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, It may contain 15, 16, 17, 18, 19, or 20 protein polyurethane alloy layers. In some embodiments, the layered material 1700 is bonded to the bottom surface 1712 of the substrate layer 1710. The layered assembly 1780 may include a layered assembly bonded to the bottom surface 1712 of the substrate layer 1710. The coalescence 1780 is about a layered assembly 1780 bonded to the top surface 1714 of the substrate layer 1710. It may include any of the layers and materials described herein. In some embodiments, the layered material 1700 includes a layered assembly 1780 bonded to the top surface 1714 of a substrate layer 1710 and a substrate layer 1710. and a layered assembly 1780 coupled to the bottom surface 1712 of the substrate 710. In this state, the layered material 1700 is formed on opposing surfaces 1712 and 1714 of the substrate layer 1710. The layered assembly 1780 includes a layered assembly 1780 arranged in a layered manner.

[0217] In some embodiments, the protein polyurethane alloy layer of the layered material 1700 is In such an embodiment, the adhesive layer 1750 is bonded to the surface of the substrate layer 1710. The deposition layer 1750 has a bottom surface 1752, a top surface 1754, and a layer between the bottom surface 1752 and the top surface 1754. In some embodiments, the thickness 1756 is measured in the subrange For example, the thickness 1756 can range from about 10 microns to about 50 microns, inclusive. 10 microns, about 20 microns, about 30 microns, about 40 microns, or about 50 microns The range may be any value between 0 and 100, or between any two of these values ​​inclusive. In some embodiments, the thickness 1756 ranges from about 20 microns to about 40 microns. Suitable adhesives for the adhesive layer 1750 include polyurethane adhesives, hot melt adhesives, and the like. adhesive, emulsion polymer adhesive, dry web adhesive, dry laminating adhesive, or wet Examples of suitable laminating adhesives include, but are not limited to, acrylic and acrylic laminating adhesives. Hauthane HD-200 available from Y&Sons Corporation 1 is an exemplary laminating adhesive suitable for adhesive layer 1750. An exemplary polyurethane adhesive The adhesives used were Hauthaway's L-2183, L-2245, L-2255, and and IMPRANIL® DAH and DAA manufactured by Covestro. Exemplary dry web adhesives include, but are not limited to, those manufactured by Protechnic In some embodiments, layered materials include, but are not limited to, 9D8D20. 1700 may not include adhesive layer 1750.

[0218] The adhesive layer 1750 has a thickness of about 10 g / m 2 ~about 50g / m 2 ranging from Grams per square meter (g / m 2 ) may have a dry weight measured at 1000 kJ / kg. For example, The adhesive layer 1750 is approximately 10 g / m 2 , about 20g / m 2 , about 30g / m 2 , about 40g / m 2 , or about 50 g / m 2 or any two of these values ​​including the end points In some embodiments, adhesive layer 1750 may have a dry weight within a range of , about 20g / m 2 ~about 40g / m 2 The dry weight may range from 1000 to 10 ...

[0219] The layered material 1700 comprises one or more protein polyurethane alloy layers and a The one or more base coat and / or top coat layers are bonded to the substrate layer 1710. In some embodiments, the layer(s) can be subsequently , may be laminated onto the surface of the substrate layer. The layer(s) may be laminated onto the top surface 1714 of the substrate layer 1710 and and / or bottom surface 1712. In some embodiments, the layer(s) is a sacrificial material 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 laminated onto the roll knife. Coating (knife over roll coating), gravure coating, slot die coating coating, multi-layer slot die coating, or curtain coating It can be deposited using any suitable coating technique, including but not limited to. Hot die coating can allow for simultaneous coating of multiple adjacent layers. .

[0220] In some embodiments, the substrate layer 1710 may be coated with an adhesive layer 1750, Additional layers (e.g., layers 1720, 1730, 1740, 1760, and / or 1770) may be formed on adhesive layer 1750 in any suitable order. In such an embodiment, the layers The following description of method 1900 is given with the substrate 1700 being formed on the adhesive layer 1750 rather than the sacrificial layer. It may be formed on adhesive layer 1750 in the same manner as described below. The blended mixtures described herein can be applied to various applications, for example, using a coating or injection process. , may be applied directly to the surface of the substrate layer 1710. In such an embodiment, the blend mixture The blended mixture may be dried and then at least partially applied to the substrate layer 1710. A protein polyurethane alloy layer (eg, layer 1720) can be formed. In some embodiments, after drying, the protein polyurethane alloy layer and the substrate layer 1710 can be heated (e.g., heat pressed) to help the layers bond together. After drying, and / or bonding the protein polyurethane alloy layer and the substrate layer 1710 Before or after combining, other layers (e.g., layers 1730, 1740, 1760, and / or 1770) can be applied onto the protein polyurethane alloy layer in any suitable order. In such an embodiment, the other layers may be The protein polyurethane alloy layer can be formed in the same manner as the sacrificial layer. It is formed on the protein polyurethane alloy layer without any adhesive.

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

[0222] In some embodiments, a layer of layered material is formed on a sacrificial layer and subsequently bonded to a substrate layer. FIG. 19 illustrates a method for making a layered material 1700, according to some embodiments. 20A-20F show the steps of the method 1900. Unless otherwise specified, the steps of method 1900 do not have to be performed in the order described herein. Additionally, unless otherwise specified, the steps of method 1900 do not have to be performed sequentially. can be performed simultaneously. In one example, method 1900 can be performed by analyzing each individual protein polypeptide. It is not necessary to include a solvent removal step after deposition of the urethane alloy layer. The solvent (e.g., water) from the polyurethane alloy layer can be removed in a single step. The method 1900 may be used to bond layers to one or both sides of the substrate layer 1710. can be done.

[0223] In step 1902, the topcoat layer 1770 is sacrificially removed, for example, as shown in FIG. 20A. The topcoat layer 1770 may be disposed on the top surface 2002 of the layer 2000. Any suitable coating technique, such as knife-on-roll with reverse transfer paper, spray, or roll. A glass coating can be used to place the sacrificial layer 2000 on the sacrificial layer 200. 0 is a layer of material that does not define a layer of layered material 1700. Rather, sacrificial layer 2000 is The sacrificial layer 2000 is removed during the fabrication of the layered material 1700. The sacrificial layer 2000 can be removed mechanically, e.g., by removing the sacrificial layer 2 2000 or chemically, for example by dissolving the sacrificial layer 2000. In some embodiments, the sacrificial layer 2000 can be removed by a release liner. Suitable materials for the sacrificial layer 2000 include granular release paper, which Exemplary granular release papers include, but are not limited to, Sappi paper, e.g., Matte F Reeport 189, Freeport 123, or Expresso 904 In some embodiments, the method 1900 includes step 19 In some embodiments, step 1902 is not included. After removing the sacrificial layer 2000 in step 1918, the topcoat layer 1770 is applied to the layered material 1700. In some embodiments, the protein polyurethane in step 1920 After the tan alloy layer(s) are bonded to the substrate layer 1710, a topcoat layer 1770 is applied. The material 1700 can be applied to the adhesive.

[0224] In step 1904, for example, as shown in FIG. 20B, the base coat layer 1760 is sacrificially In embodiments including a topcoat layer 1770, the base The base coat layer 1760 can be disposed on the top coat layer 1770. The coating layer 1760 may be applied by any suitable coating technique, such as knife-on-roll with reverse transfer paper. , spray, or roller coating onto the sacrificial layer 2000. In some embodiments, the method 1900 does not include step 1904. 4 is optional. In some embodiments, the sacrificial layer 2000 is removed in step 1918. Afterwards, a base coat layer 1760 can be applied to the layered material 1700. In an embodiment, in step 1920, the protein polyurethane alloy layer(s) are attached to the substrate layer 17. After bonding to the layered material 1700, a basecoat layer 1760 can be applied to the layered material 1700. do.

[0225] In step 1906, one or more polyurethanes dispersed or dissolved in an aqueous solution are mixed with one or more It can be blended with proteins to form a blended mixture in aqueous solution. In some embodiments, the one or more polyurethanes may be mixed prior to blending with the protein(s). In some embodiments, one or more polysaccharides may be dispersed or dissolved in an aqueous solution. The urethane is dispersed or dissolved in an aqueous solution while blending with the protein(s). In some embodiments, one or more polyurethanes and one or more tan The proteins can be blended in a suitable container until a homogeneous blend is formed. Suitable blending equipment includes a blender, stand mixer, in-line mixer, or high-pressure mixer. Examples of suitable mixers include, but are not limited to, shear mixers.

[0226] In some embodiments, the protein(s) are added to the polyurethane in step 1906. The hydroxybenzoates may be dispersed or dissolved in an aqueous solution before blending with the hydroxybenzoates. Suitable aqueous solutions include water, Alkaline aqueous solutions, aqueous acid solutions, aqueous solutions containing organic solvents, urea solutions, and mixtures thereof In some embodiments, the alkaline aqueous solution includes, but is not limited to, water. It can be a basic solution such as sodium oxide, ammonia, or ammonium hydroxide solution In some embodiments, examples of acidic aqueous solutions can be acetic acid or hydrochloric acid (HCl) solutions. Suitable organic solvents include ethanol, isopropanol, acetone, ethyl acetate, and vinegar. Examples of suitable glycerol include, but are not limited to, isopropyl alcohol, and glycerol. In some embodiments, the protein concentration in the aqueous protein mixture is about 10, including subranges. For example, the protein content in the aqueous protein mixture may range from about 300 g / L to about 300 g / L. The concentrations are approximately 10g / L, 20g / L, 30g / L, 40g / L, 50g / L, Approx. 60g / L, Approx. 70g / L, Approx. 80g / L, Approx. 90g / L, Approx. 100g / L, Approx. 150 g / L, about 200 g / L, about 250 g / L, or about 300 g / L, or endpoints. In some embodiments, the range may be between any two of these values ​​as endpoints. The protein concentration in the aqueous protein mixture is about 10 g / L to about 300 g / L, about 20 g / L ~ approx. 250g / L, approx. 30g / L ~ approx. 200g / L, approx. 40g / L ~ approx. 150g / L, about 50g / L to about 100g / L, about 60g / L to about 90g / L, or about 70g / L It may be in the range of about 80 g / L.

[0227] The amount of protein in the protein / polyurethane blend includes subranges and The amount may range from about 5% to about 60% by weight based on the weight of the material and polyurethane. The amount of protein in the blend may be about 5% by weight, about 10% by weight, about 15% by weight, about 20% by weight, or about 30% by weight. Amount%, about 25% by weight, about 30% by weight, about 35% by weight, about 40% by weight, about 45% by weight, about 5 0% by weight, about 55% by weight, or about 60% by weight, or any of these values ​​as endpoints In some embodiments, the amount of protein in the blend may be in the range of 2. , about 10% to about 55% by weight, about 15% to about 50% by weight, about 20% to about 45% by weight %, about 25% to about 40% by weight, or about 30% to about 35% by weight. In some embodiments, the amount of protein in the protein / polyurethane blend is 20 times The amount may range from 10% to 40% by weight.

[0228] The amount of polyurethane(s) in the protein / polyurethane blend may include subranges. In the range of about 10% by weight to about 85% by weight based on the weight of the protein and polyurethane. For example, the amount of polyurethane(s) in the blend can be about 10% by weight, about 1 5% by weight, approximately 20% by weight, approximately 25% by weight, approximately 30% by weight, approximately 35% by weight, approximately 40% by weight, Approximately 45% by weight, approximately 50% by weight, approximately 55% by weight, approximately 60% by weight, approximately 65% ​​by weight, approximately 70% by weight %, about 75% by weight, about 80% by weight, or about 85% by weight, or endpoints of these values ​​inclusive. The range may be within any two of the endpoints. In some embodiments, the blend The amount of polyurethane(s) in the composition may range from about 20% to about 75% by weight, from about 30% to about 60% by weight, or It may be 5% by weight, or in the range of about 40% to about 55% by weight.

[0229] In some embodiments, the blending temperature ranges from about room temperature (18° C.) to about 1 For example, the blending temperature can range from 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 any of the endpoints. The range may be inclusive of any two of these values ​​as endpoints. The blending temperature is about 18℃ to about 90℃, about 18℃ to about 80℃, about 18℃ to about 70℃. , 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 3 The temperature may be in the range of 0°C.

[0230] In some embodiments, the blending time in step 1906 is about 15 minutes, including subranges. For example, blending times can range from about 30 minutes, about 1 hour, about 90 minutes, to about 3 hours. minutes, about 2 hours, about 150 minutes, or about 3 hours, or any of these values ​​inclusive of the endpoints. In some embodiments, the blending time can be within a range having one or two of the end points. , about 15 minutes to about 150 minutes, about 15 minutes to about 2 hours, about 15 minutes to about 90 minutes, or about The range may be from 15 minutes to about 1 hour. The rotation speed may range from about 150 rpm to about 250 rpm, including subranges. , Blending speed: about 150 rpm, about 175 rpm, about 200 rpm, about 225 rpm In some embodiments, the blending speed may be about 150 rpm, or about 250 rpm. rpm to about 225 rpm, about 150 rpm to about 200 rpm, or about 150 rpm to about 2 The blending speed may be in the range of 25 rpm. The blending speed may vary depending on the size of the blending device (e.g., impeller). The amount of mixing may depend on the size of the container and / or the size of the vessel in which the components are blended.

[0231] In some embodiments, in step 1906, one or more additives are added to the blend. The additive(s) can affect the final properties of the protein polyurethane alloy layer, This can affect the final properties of the layered material 1700. For example, the additives added The following material properties are measured: stiffness, elasticity, film tensile strength, tear strength, flame retardancy, Suitable additives include: , crosslinkers, fillers, dyes, pigments, plasticizers, waxes, rheology modifiers, flame retardants, antimicrobial 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 crosslinkers include, but are not limited to, epoxy-based crosslinkers. Agents, (e.g., poly(ethylene glycol) available from Sigma Aldridge) ) diglycidyl ether (PEGDE)), isocyanate-based crosslinkers (e.g., Lanx X-TAN® available from Ess, and carbodiimide-based crosslinkers. Suitable blowing agents include, but are not limited to, HeiQ from Chemtex. Available in HeiQ Chemtex 2216-T (nonionic and anionic) Stabilized blend of surfactants), HeiQ Chemtex 2241-A (modified HEU R (hydrophobically modified ethylene oxide urethane) thickener), HeiQ Chemtex 22 43 (non-ionic silicone dispersion), or HeiQ Chemtex 2317 (non-ionic Suitable antimicrobial / antifungal agents include foam stabilizers (ionic and anionic surfactants). Examples include Ultra-Fresh DW-56 or other antimicrobial agents used in the leather industry. Suitable flame retardants include CETAFLAM®, DB9 (carbon chain-containing polymer with C-PO(OH)2 or C-PO(OR)2 group) CETAFLAM (registered trademark) PD3300 (containing carbon chains) Organic polymers containing C-PO(OH)2 or C-PO(OR)2 groups phosphorus compounds), or other flame retardants used in coated textiles. Suitable fillers include thermoplastic microspheres, such as EXPANCEL® Suitable rheological agents include, but are not limited to, Microspheres. Rheology modifiers include alkali-swellable rheology modifiers, hydrophobically modified ethylene oxides, and oxide-based urethane (HEUR) rheology modifiers, and volume-excluding thickeners, Exemplary alkali swellable rheology modifiers include, but are not limited to, Dow C Chemicals' ACRYSOL™ DR-106, ACRYSOL™ A SE-60, TEXICRYL® 13-3131 manufactured by Scott-Bader and TEXICRYL® 13-308. Exemplary HEUR modifiers include RM-4410 manufactured by Stahl and RM-4410 manufactured by HeiQ. Exemplary volumetric exhaust sorbents include, but are not limited to, Chemtex 2241-A. The dethickening agent is WALOCEL™ XM 20 manufactured by Dow Chemicals. 000 PV and methylhydroxyethyl cellulose from Sigma-Aldrich These include, but are not limited to:

[0232] In some embodiments, the blend may include one or more colorants. In form, the colorant may be a dye, for example, a fiber reactive dye, a direct dye, or a natural dye. Exemplary dyes include azo-structure acid dyes, metal complex-structure acid dyes, and anthraquinone dyes. These include, but are not limited to, structural acid dyes, and azo / diazo direct dyes. In some embodiments, the colorant may be a pigment, such as a lake pigment. In some embodiments, the blend may contain a colorant content of about 2% by weight or less. about 0.1%, about 0.5%, about 1%, about 1.5%, or about 2% by weight of coloring In some embodiments, the blend may include from about 0.1% to about 2% by weight of an agent. It may contain from 0.5% to about 1.5% by weight, or from about 0.1% to about 1% by weight of colorant. In some embodiments, the blend is free of colorants or substantially free of colorants. In such an embodiment, the protein polyurethane made from the blend The alloy layer may be free of colorants or substantially free of colorants.

[0233] In step 1908, a layer of the blend mixture is disposed on the top surface 2002 of the sacrificial layer 2000. The blend mixture may be coated onto the top surface 2002 of the sacrificial layer 2000. In an embodiment that does not include step 1902 and step 1904, the blended mixture is 0. In an embodiment including step 1904, The blend mixture can be coated directly onto the surface of the base coat layer 1760. In embodiments including step 902 but not step 1904, the blended mixture may be The blend may be coated directly onto the surface of layer 1770. The blend can be formed into a sheet by coating the blend mixture onto a surface to a desired thickness. Coatings can include injection, extrusion, molding, and the like. In some embodiments, the sheet may be, for example, a blade, knife, roller, or knife-on-roll. Spread to desired thickness using curtain coating, and slot die coating. It is possible.

[0234] In some embodiments, the temperature of the blend mixture during coating is about 40° C. or higher. For example, the temperature of the blended mixture may range from about 40°C to about 100°C, including subranges. 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 endpoints inclusive In some embodiments, the blended mixture in the coating may be in a range having a viscosity of 1000 MPa or less. Temperature: about 40℃ to about 90℃, about 40℃ to about 80℃, about 40℃ to about 70℃, about 40℃ to about 60°C, or in the range of about 40°C to about 50°C. The adhesive may make the blend mixture too viscous, making it difficult to form a layer of uniform thickness. do.

[0235] In step 1910, a solvent (e.g., water) is added to the coating, as shown, for example, in FIG. 20C. The protein polyurethane alloy layer 1720 is removed from the blended mixture. Suitable methods for removing the solvent include tunnel drying, vacuum drying, hot air drying, and the like. Mid-range IR for oven drying, humidity chamber drying, hot air flotation drying, and preheating ) followed by hot air for drying. Not determined.

[0236] Suitable solvent removal temperatures for step 1910 include subranges from about room temperature (18° C.) to about 100° C. For example, the solvent may be in the range of about 18°C, about 35°C, about 50°C, about 60°C, about 70°C, or about 80°C. °C, about 80°C, about 90°C, or about 100°C, or any of these values ​​inclusive of the endpoints. In some embodiments, the temperature may be removed at any two of the temperatures within a range having any two of the temperatures as endpoints. The solvent is heated at about 18°C ​​to about 35°C, about 18°C ​​to about 50°C, about 18°C ​​to about 60°C, or about 18°C ​​to about 60°C. About 70°C, about 18°C ​​to about 80°C, about 18°C ​​to about 90°C, or about 18°C ​​to about 100°C Suitable humidity values ​​for solvent removal in step 1910 includes humidity in the range of 0% RH (relative humidity) to about 65% RH, including subranges. For example, Humidity: about 10%RH, about 20%RH, about 40%RH, about 50%RH, or about 65% The range may be within the range having as endpoints any two of these values, inclusive. In some embodiments, the humidity is 0% RH to about 50% RH, 0% RH to about 40% RH, The temperature may be 0% RH to about 20% RH, or 0% RH to about 10% RH. Humidity or humidity can affect the protein polyurethane alloy layer and therefore the final properties of the layered material. The solvent removal temperature and / or humidity in step 1910 may affect the following material properties: rigidity Among the properties of tensile strength, elasticity, film tensile strength, tear strength, flame retardancy, chemical stability, and wet stability For example, higher humidity and lower temperatures may affect softer Conversely, lower humidity and higher temperatures may result in a more elastic material. This can result in a harder, less elastic material.

[0237] In some embodiments, steps 1906 through 1910 may be repeated multiple times to form sacrificial layer 2. A plurality of protein polyurethane alloy layers 1720 can be formed on the surface of the 1720. In some embodiments, steps 1906 through 1910 are repeated sequentially to form a sacrificial layer 2000. A plurality of protein polyurethane alloy layers 1720 can be formed on the surface. In this embodiment, steps 1906 to 1910 are repeated after steps 1912 to 1916. One or more foamed protein polyurethane alloy layers 1730 / 1740 on top The protein polyurethane alloy layer 1720 can be formed in several ways. In some embodiments, the method 1900 may not include steps 1906 through 1910.

[0238] In step 1912, one or more polyurethanes dispersed or dissolved in an aqueous solution are treated with a protein. and foaming to form a foamed blend mixture in aqueous solution. In some embodiments, the one or more polyurethanes may be ) and can be dispersed or dissolved in an aqueous solution before blending with the foam. In embodiments, one or more polyurethanes are blended with the protein(s) and foam. In some embodiments, one or more The polyurethane and one or more proteins are mixed together until a homogeneous blend is formed. The blending can be carried out in any suitable container. Suitable blending equipment includes a blender, a stirrer, a Mixers that can be used include, but are not limited to, a dome mixer, an in-line mixer, or a high shear mixer. The blends may be foamed using, for example, mechanical or chemical foaming processes. Exemplary mechanical foaming equipment is a Hansa Mixer or a GEMAT® ) a blowing agent. Blending and foaming can be carried out separately or simultaneously.

[0239] The polyurethane(s) suitable for blending and foaming in step 1912 may be a protein The polyurethane alloy layer is discussed herein. In step 1912, one or more foaming agents and / or foam stabilizers are added to the blend. Suitable foaming agents and foam stabilizers are those used in the protein polyurethane alloy layer 1730 / 17 40, including those discussed herein.

[0240] In some embodiments, the blend contains no more than about 10% by weight of a foaming agent or foam stabilizer. For example, the blend may contain about 0.1 wt.%, about 1 wt.%, about 2.5 wt.%, about 5 wt.%, %, about 7.5%, or about 10% by weight of a foaming agent or foam stabilizer. In embodiments, the blend may comprise from about 0.1% to about 10% by weight, from about 1% to about 7.5% by weight. %, about 2.5% by weight to about 5% by weight, about 0.1% by weight to about 5% by weight, or about 0.1% by weight In some embodiments, the blend may include up to about 2.5% by weight of a foaming agent or foam stabilizer. is substantially free of foaming agents and / or foam stabilizers, or In such an embodiment, the protein produced from the blend may be stabilizer-free. The polyurethane alloy layer is substantially free of foaming agents and / or foam stabilizers, or It may be free of foaming agents and / or foam stabilizers.

[0241] The foaming in step 1912 provides the foamed protein polyurethane alloy layer with the desired density. In some embodiments, the foam blend can be used to before being removed in step 1916, in the range of about 300 g / L to about 900 g / L, inclusive. For example, the foam blend mixture formed in step 1912 may have a liquid density ranging from 0.01 to 0.01. is approximately 300g / L, approximately 400g / L, approximately 500g / L, approximately 600g / L, approximately 700g / a liquid density of about 800 g / L, about 800 g / L, or about 900 g / L, or these values ​​as endpoints In some embodiments, the liquid density may be within a range having any two of the above. The blended mixture is about 300g / L to about 800g / L, about 300g / L to about 700g / L , about 400g / L to about 600g / L, about 300g / L to about 500g / L, or about 300g In some embodiments, the process may have a liquid density ranging from about 600 g / L to about 600 g / L. The blended mixture formed in step 1906 is subjected to step 1910 where the solvent is removed from the blended mixture. The foamed blend formed in step 1912 before the solvent is removed in step 1916 is then removed. The granulated cellulose may have a liquid density greater than the liquid density of the blend.

[0242] In some embodiments, the protein(s) are mixed with polyurethane and It may be dispersed or dissolved in an aqueous solution prior to blending with the foam. Suitable aqueous solutions include those prepared in step 1. The protein concentration in the aqueous solution can be determined by steps 1906 and 1908, including those discussed above. The protein / polyurethane of step 1912 can be any value or range discussed above. The amount of protein in the tan blend may be any of the values ​​or ranges discussed above for step 1906. The blending temperature of step 1912 can be any of the temperatures discussed above for step 1906. The blending time in step 1912 can be any temperature range or temperature range as described above for step 1906. The blending speed of step 1912 can be any of the times or ranges of times discussed. The rate may be any of the rates or ranges of rates discussed above for 6. In step 1912, one or more additives can be added to the blend. The additive(s) added in step 2 may be any of the additives discussed above for step 1906. It could be either one.

[0243] In step 1914, a layer of foam blend mixture is placed on the sacrificial layer 2000. In some embodiments, the foam blend layer comprises a protein polyurethane alloy layer 1. 720. In some embodiments, the blend and foam mixture is placed on the surface of the It can be coated directly onto the surface of the porous polyurethane alloy layer 1720. In this embodiment, the foaming blended mixture is applied to a surface by coating the blended mixture to a desired thickness. The coating can be formed into a sheet by pouring, pressing, or In some embodiments, the sheet may be formed by, for example, blades, extrusion, and molding. Knife, roller, roll knife, curtain coating, and slot die coating A gag can be used to spread it to the desired thickness.

[0244] In step 1916, a solvent (e.g., water) is added to the coating, as shown, for example, in FIG. 20D. The foamed protein polyurethane alloy layer 1 is removed from the foamed blend mixture. 730. Suitable methods for removing the solvent include tunnel drying and vacuum drying. , hot air oven drying, humidity chamber drying, hot air flotation drying, and mid-range IR for preheating and subsequent drying with hot air. Suitable solvent removal temperatures for step 1916 are the temperatures discussed above for step 1910. The humidity value in step 1916 can be either the temperature range or the humidity range. The humidity value or range can be any of those discussed above.

[0245] In some embodiments, steps 1912 to 1916 may be repeated multiple times to form sacrificial layer 2. 000, for example, a foamed protein polyurethane alloy layer 1730 and a foamed protein polyurethane forming a plurality of foamed protein polyurethane alloy layers on the polyurethane alloy layer 1740; In such an embodiment, the foam blend formed in the separate step 1912 may be The mixtures may have different liquid densities. For example, the liquid density of one foaming blend mixture may be: The liquid density of another foam blend mixture is 10g / L to 300g / L or more or less. For example, in some embodiments, the first blended mixture may have a concentration of from about 300 g / L to about The second blend mixture may have a liquid density ranging from about 600 g / L to about 500 g / L. The first blend may have a liquid density ranging from about 100 g / L to about 700 g / L. The mixture may have a liquid density ranging from about 300 g / L to about 400 g / L, and the second The blended mixture may have a liquid density ranging from about 500 g / L to about 700 g / L. .

[0246] In some embodiments, steps 1912 through 1916 are repeated sequentially to form sacrificial layer 20 Multiple foamed protein polyurethane alloy layers can be formed on the 00. In an embodiment, the foam mixture and blended mixture formed in step 1912 are used to Steps 1914 to 1916 form a plurality of foamed protein polyurethane alloy layers. In some embodiments, steps 1912 to 1916 can be performed by steps 1906 to 1916. 1910 sets of protein polyurethane alloy layers 1720 and sacrificial layers 2000 Before forming one or more foamed protein polyurethane alloy layers between In some embodiments, the method 1900 does not include steps 1912 through 1916. Good too.

[0247] In step 1918, the sacrificial layer 2000 is removed, for example, as shown in FIG. 20E. The sacrificial layer 2000 is mechanically removed from the layer(s) formed in steps 902 through 1916. For example, the sacrificial layer 2000 can be removed by thermal or chemical processes. Alternatively, the sacrificial layer 2000 can be removed by peeling it away from the other layers. The sacrificial layer 2000 can be removed by dissolving the sacrificial layer 2000. In some embodiments, the layer(s) formed in steps 1902 through 1916 are The sacrificial layer 2000 is removed in step 1918 before being bonded to the substrate layer 1710 in step 920. In some embodiments, the sacrificial layer 2000 is removed after step 1920. It is possible.

[0248] In step 1920, the layer(s) formed in steps 1902 through 1916 are, for example, As shown in Figure 20F, the substrate layer 1710 is bonded to the substrate layer 1710. The rubber polyurethane alloy layer 1720 and the rubber polyurethane alloy layer formed in steps 1906 to 1916 Any other protein polyurethane alloy layers are bonded to the substrate layer 1710. In some embodiments, step 1920 comprises forming one or more protein polyurethane alloy layers (e.g., Bonding the protein polyurethane alloy layer 1720 to the substrate layer 1710 is accomplished by thermal In such an embodiment, the protein polyurethane alloy layer (e.g., For example, the protein polyurethane alloy layer 1720 may be in direct contact with the substrate layer 1710. In such an embodiment, the protein polyurethane alloy layer may be formed on the substrate layer 1710. The two layers can be partially melted into a solid layer, and upon cooling, the two layers bond tightly together. In some embodiments, step 1920 comprises forming one or more protein polyurethane alloy layers (e.g., Bonding the protein polyurethane alloy layer 1720 to the substrate layer 1710 is In such an embodiment, lamination may be accomplished with adhesive layer 1750. In such an embodiment, the backing layer 1710 and / or the protein polyurethane adhesive may The alloy layer can be applied by slot die molding, kiss coating, drawdown techniques, or reverse transfer coating. The adhesive can be coated by known techniques such as coating. In an embodiment, the lamination process involves rolling the substrate layer 1710 and other layer(s) under heat. This may include passing the data through a filter.

[0249] In some embodiments, step 1920 may be omitted from method 1900. In such an embodiment, the layer(s) formed in steps 1902 through 1916 may be This defines a layered material that does not have a porous polyurethane alloy layer or a substrate layer 1710.

[0250] In some embodiments, the layered materials described herein may be fabricated with a thickness equivalent to that of natural leather. For example, the layered material may have a tear strength that is at least about 1% greater than the tear strength. The tear strength is approximately 1%, 2%, 3%, 4%, 5%, and 6% higher than that of natural leather of the same thickness. 6%, approximately 7%, approximately 8%, approximately 9%, approximately 10%, approximately 15%, approximately 20%, approximately 25%, approximately 30%, Approximately 35%, approximately 40%, approximately 45%, approximately 50%, approximately 100%, approximately 150%, or approximately 200% larger In some embodiments, the layered material may have a tear strength of about 100 MPa, including subranges thereof. The tear strength may range from 20 N to about 300 N. For example, the tear strength of the layered material may be approx. 20N, approx. 30N, approx. 40N, approx. 50N, approx. 60N, approx. 70N, approx. 80N, approx. 90N, Approx. 100N, Approx. 125N, Approx. 150N, Approx. 175N, Approx. 200N, Approx. 225N, Approx. 250 N, about 275N, or about 300N, or any two of these values ​​inclusive In some embodiments, the tear strength may be in the range of about 30 N to about 50 N. 275N, about 40N to about 250N, about 50N to about 225N, about 60N to about 200N, or Approximately 75N to approximately 175N, approximately 80N to approximately 150N, approximately 90N to approximately 125N, or approximately 100N can range from about 125N.

[0251] In some embodiments, the protein polyurethane alloy layers described herein comprise a For example, the protein polyimide may have a tear strength in the range of about 2 N to about 30 N, including the range of about 2 N to about 30 N. The tear strength of the urethane alloy layer is approximately 2N, approximately 4N, approximately 5N, approximately 10N, approximately 15N, approximately 2 0N, about 25N, or about 30N, or any two of these values ​​inclusive, as endpoints. In some embodiments, the tear strength may be in the range of about 4 N to about 25 N. N, about 5N to about 20N, or about 10N to about 15N.

[0252] Tear strength or tear resistance is how well a material can withstand the effects of tearing. Tear resistance is a measure of the strength of a material. or the method provided by ISO 3377 (also known as "Baumann tear"). The method provided by ASTM D624 can also be used to measure the It is used to measure the resistance to tear formation and tear extension. Regardless of the method used, first, the material sample is tested to induce tearing. The specimen is then held between the two grips and cut until it separates into two pieces. A uniform pulling force is applied. The tear resistance is then calculated by dividing the applied force by the thickness of the material. Unless otherwise specified, tear strength values ​​reported herein are calculated by I Measured by SO 3377.

[0253] In some embodiments, the layered materials described herein have a molecular weight of about 1 kJ / cm, including subranges. It can have a tensile strength ranging from 100 Pa (kilopascals) to about 100 MPa (megapascals). For example, the layered material may be applied at pressures of about 1 kPa, about 50 kPa, about 100 kPa, about 200 kPa, Approximately 300kPa, approximately 400kPa, approximately 500kPa, approximately 600kPa, approximately 700kPa, Approximately 800kPa, approximately 900kPa, approximately 1MPa, approximately 5MPa, approximately 10MPa, approximately 20MPa a, approx. 30MPa, approx. 40MPa, approx. 50MPa, approx. 60MPa, approx. 70MPa, approx. 80 MPa, about 90 MPa, or about 100 MPa, or any of these values ​​inclusive. The tensile strength may be within a range having two endpoints. The strength is about 50kPa to about 90MPa, about 100kPa to about 80MPa, and about 200kPa. a ~ approx. 70 MPa, approx. 300 kPa ~ approx. 60 MPa, approx. 400 kPa ~ approx. 50 MPa, approx. 500kPa to approximately 40MPa, approximately 600kPa to approximately 30MPa, approximately 700kPa to approximately 20 MPa, about 800 kPa to about 10 MPa, or about 1 MPa to about 5 MPa .

[0254] The softening property, also called the "handle" of a material, is determined according to ISO 17235 In some embodiments, the outer surface of the layered materials described herein can include subranges. For example, the outer surface of the layered material may have a softening property ranging from about 2 mm to about 12 mm. Approximately 2mm, approximately 3mm, approximately 4mm, approximately 5mm, approximately 6mm, approximately 7mm, approximately 8mm, approximately 9mm, About 10 mm, about 11 mm, or about 12 mm, or any two of these values ​​inclusive In some embodiments, the softening property may be within a range having one of the following endpoints: Approximately 3mm to approximately 11mm, approximately 4mm to approximately 10mm, approximately 5mm to approximately 9mm, approximately 6mm to approximately 8m Unless otherwise specified, the thickness of the cellulose membrane disclosed herein may be about 6 mm to about 7 mm. The softening value is determined according to ISO 17235.

[0255] The flexibility or strain of a material can be calculated, for example, by using the equation: ΔL / L can be determined by measuring its elongation at break when The change in length of a material after tension is applied, where L is the original length of the material. can also be measured according to the method provided by ASTM D412. In some embodiments, the layered materials described herein comprise from about 100% to about 40% inclusive of subranges. For example, the layered material may have a flexibility ranging from about 100%, about 200%, about 300%, 00%, or approximately 400%, or any two of these values ​​inclusive as endpoints. In some embodiments, the flexibility may range from about 100% to about 2 00%, about 100% to about 300%, about 200% to about 300%, or about 200% to about 400 Unless otherwise specified, flexibility values ​​disclosed herein are based on ASTM D4 In some embodiments, the protein polypeptides described herein are The ethylene alloy layer may have a flexibility value or range as described above for the layered material.

[0256] In some embodiments, the layered materials described herein have a hysteresis loop of about 8% or less. In some embodiments, the layered material may have a permanent deformation of about 1%, about 2%, or , about 3%, about 4%, about 5%, about 6%, about 7%, or about 8%, or endpoints thereof In some embodiments, the permanent set may be within a range having any two of the values: The layered material may be about 1% to about 8%, about 2% to about 7%, about 3% to about 6%, or about 4% to about 5%. There may be permanent deformation.

[0257] Unless otherwise specified, permanent set values ​​are measured by the following method: Dogbone The tensile specimen material is cut and the original length of the specimen is measured. The specimen is approximately 110 mm long. It has a dogbone shape with a gauge length of 75-100 mm and a width of 10 mm. The sample is then cut along its length using an INSTRON® machine. Both were stretched to 15% strain and 0% strain at a constant speed of 3 mm per second. This is repeated five times. Then the original specimen length and the load are The distance between the length of the sample and the zero point is measured. The length measured after repeatedly straining the material is measured. The percent difference between the length and the original length is the % permanent set. For purposes of calculating the permanent set value, Three separate samples of the material are evaluated and the average permanent set value is reported as the permanent set value of the material. .

[0258] In some embodiments, the layered materials described herein have a mass of about 75 g / m 2 / hours or more In some embodiments, the layered compositions described herein may have a moisture vapor transmission rate (MVTR). The material contains a partial range of approximately 75 g / m 2 / hour~about 200g / m 2 / MVT of time range For example, the layered material may have a R of about 80 g / m 2 / hour ~ approx. 190g / m 2 / time, Approximately 90g / m 2 / hour ~ approx. 180g / m 2 / hour, about 100g / m 2 / hour ~ approx. 170g / m 2 / hour, approx. 110g / m 2 / hour ~ approx. 160g / m 2 / hour, about 120g / m 2 / Time ~ approx. 150g / m 2 / hour, or approximately 130g / m 2 / hour ~ approx. 140g / m 2 / time Unless otherwise specified, the MVTR values ​​disclosed herein are based on the AS TM E96 ("Standard Test Method for Water Vapor Transmission Testing of Materials") - Procedure B, Water Method, approx. 7 Measured at 4.3°F, approximately 50% relative humidity, and with a 3 / 4 inch air gap.

[0259] Layered materials having water vapor transmission rates as reported herein are preferred when breathability of the material is desired. These materials may be suitable for use in a variety of applications where breathability is a desirable characteristic. Potential applications include, but are not limited to, footwear, clothing, and upholstery. The layered materials described herein have the same number of layers with the same thickness and are made of the same polymeric material. layer(s) but without a protein blended into the polymer material(s). They can have significantly higher water vapor transmission rates compared to fibrous polymeric materials.

[0260] In some embodiments, the layered materials described herein comply with ISO 11640 ("Leather"). - Color fastness test - Fastness to double rubbing cycles (Wet rubbing fastness test) Therefore, when measured, the color fastness may be Class 4 or higher. The layered materials described in the specification are measured according to the wet rub fastness test of ISO 11640 In this case, the colorfastness may be Class 4, Class 4.5, or Class 5. Durability provides the layered materials described herein with desirable abrasion resistance for a variety of applications. It can be provided.

[0261] The layered materials described herein achieve colorfastness of Class 4 or better without the inclusion of pigments in the materials. This can be achieved by blending proteins (or a mixture of proteins) into polyurethane(s). compared to layered polyurethane materials made with the same polyurethane(s) without The proteins in the layered materials described herein impart color to the materials, which is a unique property. To achieve high color fastness, Polyurethane materials usually do not use pigments as dyes generally do not adhere well to polyurethane. Poor adhesion between the dye and polyurethane results in relatively poor color fastness. The dyed layered materials described herein have improved color strength and pigmented color. It may have other aesthetic features that are not achievable with colored polyurethane.

[0262] In some embodiments, the layered materials described herein or the The individual layers of the layered material are treated with the same or similar finishes used to treat natural leather. In some embodiments, the layered materials described herein may be subjected to a finishing process such as is tumbled or staked to adjust the material properties, such as the feel of the material. In such an embodiment, conventional textile tumbling and staking methods are used. The method can 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 upper surface 1774 of the topcoat layer 1770 may have a rough surface, and the basecoat layer 1760 The top surface 1764 of the protein polyurethane alloy layer 1730 may have a rough surface, and the top surface 1764 of the protein polyurethane alloy layer 1730 may have a rough surface. 734 may have a rough surface, and the top surface 1744 of the protein polyurethane alloy layer 1740 may The rough outer surface may have a surface technology similar in appearance and feel to that of natural leather. In some embodiments, the leather can be textured to create a textured look (e.g., natural pebble leather). The top surface 2002 of the sacrificial layer 2000 is not a layer that was placed directly on the top surface 2002 during the method 1900. The surface may have a roughened surface that is transferred onto the surface of the substrate.

[0264] Rough surface is 1 in 2 has a surface area per square inch that is at least about 1% greater than the surface area per square inch of the In other words, in some embodiments, the layered material 1700 includes a layer having a rough outer surface. A 1 inch square sample will have less surface area than a 1 inch square sample of material with a perfectly smooth surface. In some embodiments, the roughened outer surface may have a surface area of ​​about 1 in. 2 Yo At least about 1% larger than 1 in 2 Approximately 10% larger than 1 in 2 Approximately 20% larger than , 1in 2 Approximately 30% larger than 1in 2 Approximately 40% larger than 1in 2 Approximately 50% larger than Kii, 1in 2 Approximately 60% larger than 1in 2 Approximately 70% larger than 1in 2 About 80 % larger, 1in 2 Approximately 90% larger than 1in 2 Approximately 100% larger than 1in 2 twist Approximately 150% larger, 1in 2 Approximately 200% larger than 1in 2 Approximately 250% larger than 1 in 2Approximately 300% larger than 1in 2 Approximately 350% larger than 1in 2 Approximately 400% more Large, 1 in 2 Approximately 450% larger than or 1 in 2 Approximately 500% larger square Surface area per inch, or a range having any two of these values ​​as endpoints, inclusive. In some embodiments, the rough surface may have a surface area per square inch of n 2 Approximately 1% to 1 inch 2 Approximately 500% more than 1 in 2 Approximately 10% more than ~1 inch 2 twist Approximately over 450%, 1in 2 Approximately 20% more than ~1 inch 2 Approximately 400% more than 1in 2 About 3 Over 0%~1in 2 Approximately 350% more than 1 in 2 Approximately 40% more than ~1 inch 2 Approximately 300% more Super, 1in 2 Approximately 50% more than ~1 inch 2 Approximately 250% more than 1 in 2 Approximately 60% more than 1 in 2 Approximately 200% more than 1 in 2 Approximately 70% more than ~1 inch 2 Approximately 150% more than or in 2 Approximately 80% more than ~1 inch 2 may have about 100% more surface area per square inch than Unless otherwise specified, the surface areas of the materials disclosed herein are determined using profilometry. For opaque materials, optical profilometry is used. In embodiments, the layered material, or individual layers of the layered material, may have a smooth outer surface. The surface is 1 in 2It has a surface area per square inch that is less than 1% greater than that of a smooth The surface is 1 in 2 ~1.01in 2 It may have a surface area per square inch of less than In some embodiments, the top surface 2002 of the sacrificial layer 2000 is The adhesive layer may have a smooth surface that is transferred directly onto the surface of the layer disposed thereon.

[0265] In some embodiments, the layered material, or individual layers of the layered material, are textured. In some embodiments, the top surface 2002 of the sacrificial layer 2000 may be formed by the method 1 900, a textured layer is transferred onto the surface of the layer disposed directly on the upper surface 2002. In some embodiments, the textured outer surface may have a roughened surface. As noted above, the surface area per square inch or surface area range per square inch It can be said that:

[0266] In some embodiments, the texture is a macro-scale texture, e.g., Sa SDWarren Company, titled ppi North America Manufactured by ULTRACAST® or Classic Many of the textures used in Sappi / Warren release papers are available under Examples of macro-scale textures include those of about 50 to about 300 microns. The natural leather grain repeats with the characteristic depth of the long. Any other desired macroscale In some embodiments, macro-scale textures may be used. The material may be a "leather grain texture." As used herein, "leather grain texture" The term "leather" refers to a texture that mimics the look and feel of natural leather. For the "leather grain texture," we have Sappi Matte Freeport 189, S Sappi Freeport 123 or Sappi Expresso 904 are recommended. Examples include, but are not limited to:

[0267] In some embodiments, the texture may be a microscale texture. In some embodiments, the texture is less than 50 microns, for example 1000 nanometers. Microscale textures with surface features having feature sizes less than 50 microns An example of a micro-scale texture is known in the art as "sharkle". Sharklet texture is a surface structured to prevent bacterial growth. The micro-scale texture of the surface can be applied to provide a product with a surface. Repeating shark skin projections arranged in a diamond pattern with millions of tiny ridges. Klett materials are described, for example, in U.S. Pat. Nos. 7,650,848 and 8,997,672. No. 6,239,593, the disclosure of which is incorporated herein by reference.

[0268] In some embodiments, the texture is less than 1000 nanometers, for example 10 nanometers. Nanoscale, with surface features having feature sizes from meters to less than 1000 nanometers An example of a nanoscale texture can be a texture of about 400 nanometers wide. It has a series of ridges, spaced approximately 800 nanometers apart and approximately 100 nanometers deep. It is a diffraction grating having a thickness.

[0269] The embodiments discussed herein will be further clarified by the following examples. It should be understood that the examples are not limited to the above embodiments. [Example 1]

[0270] The sample consisted of 5.5 g of Hauthaway waterborne polyurethane dispersion L3360 and 1 Mix with 0 mL of deionized water and stir at 1000 rpm (revolutions per minute) for 30 minutes at 50°C. The solution was then evaporated in a 10 cm diameter Teflon evaporator. The sample was pipetted onto a dish. The dish was dried overnight in an oven at 45°C. The material was conditioned in a standard reference atmosphere (23°C, 50% humidity) for 24 hours, and the polyurethane filter I got the idea.

[0271] The films were tested using a TA Instruments DMA-850. A die was used to cut 1 cm x 2.5 cm strips from each film. The sample was loaded into the film and fiber tension clamp for testing. A preload of 1 N was applied to the cut film sample. The instrument was cooled to -80°C and held for 1 minute. Then increase the temperature 4 °C / min to 200 °C, or the sample may be too weak to hold the tension. During the temperature gradient, the sample was vibrated at a frequency of 1 Hz with a strain of 0.1%. The storage modulus, loss modulus, and tan(δ) were measured for both films at different temperatures. The second storage modulus transition (the starting point of the final decrease in the measured storage modulus) was obtained. The second DMA modulus transition onset temperature (i.e., the onset temperature) was 114°C for the control sample. The temperature was 0.9℃.

[0272] In addition, five tensile specimens (per ASTM D638) were dry and tensile tested using a metal die. The cut film samples were then cut from the prepared sample film. The wire was placed in a 5960 series machine and tensioned at 100 mm / min until it broke. The average Young's modulus, average tensile strength (maximum tensile stress), and average elongation at break were The Young's modulus was 59 MPa, the maximum tensile stress was 12.9 MPa, and the fracture The elongation at break was 402%. [Examples 2 to 8]

[0273] Examples 2 to 8 were prepared in the same manner as 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 extracting 0.825 g (grams) of gelatin from pig skin and dissolving it in 10 mL (milliliters) of water. ) in deionized water and stirred at 50°C for 1 hour with magnetic stirring at 1000 rpm (revolutions per minute). After the gelatin was completely dissolved, the pH of the solution was adjusted to The pH was adjusted to 7.0 with 0.1N sodium hydroxide. Then, 5.5 g of L3360 was added to the solution. The mixture was stirred at 1000 rpm for 30 minutes. The mixture was pipetted into a 10 cm diameter Teflon evaporating dish. The dish was placed in an oven at 45°C. After drying, the dried samples were placed in a standard reference atmosphere (23°C, humidity 50°C). %) for 24 hours to prepare a gelatin polyurethane alloy film.

[0275] When pipetting, the gelatin polyurethane solution appears milky white with no visible particulates. After drying, the gelatin polyurethane solution had a uniform appearance with no optically visible granules. The results of combining Example 33 and Example 34 were: If the protein is miscible with the hard phase, the protein polyurethane alloy will be transparent. , and that the properties can be enhanced.

[0276] DMA testing was performed as outlined in Example 1. For gelatin polyurethane alloys The second storage modulus transition (as the starting point of the final decrease in the measured storage modulus) was obtained. The second DMA modulus transition onset temperature was 180.6°C, as in Example 1. 65.7°C increase over the control sample described in.

[0277] Tensile testing was 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 breaking elongation was 1.0 MPa. For the ethylene alloy, it was 197%.

[0278] The increase in the second DMA modulus transition onset temperature in this example is greater than that of the polyurethane of Example 1 alone. With increased modulus and strength and decreased elongation compared to gelatin polyurethanes. This indicates that the dissolved gelatin in the alloy is miscible with the hard phase of the polyurethane. [Examples 10 to 19]

[0279] Examples 10-19 show polyurethanes from different manufacturers and different proteins. To demonstrate the range of dispersions, the same method as used in Example 9 was used. The resulting properties of these alloys are listed in Tables 3-6. [Example 20]

[0280] The sample was prepared by dissolving 0.825 g (gram) of Sigma-Aldrich bovine serum albumin (BSA) in 10 mL of water. Dissolve in 100 mL of deionized water and heat at 20°C for 1 hour at 1000 rpm (every The mixture was prepared by stirring with a magnetic stir bar at 1000 rpm. Then, 5.5 g of L3 360 was added to the solution and stirred at 1000 rpm for 30 minutes. The BSA solution was pipetted into a 10 cm diameter Teflon evaporating dish. After drying, the dried samples were placed in a standard reference atmosphere (2 The film was conditioned at 3°C ​​and 50% humidity for 24 hours to prepare a BSA polyurethane alloy film. .

[0281] DMA testing was performed as outlined in Example 1. For BSA polyurethane alloys The second storage modulus transition (taken as the starting point of the final decrease in the measured storage modulus) was The second DMA modulus transition onset temperature was 184.9°C, which is the same as in Example 1. This was a 70°C increase over the control sample listed.

[0282] Tensile testing was 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 1.2 times that of the BSA polyurethane. For Tanalloy, it was 123%. [Example 21]

[0283] Soy protein isolate (SPI) was dissolved in 15 mL of sodium hydroxide at a concentration of 0.05 mol / L. The dispersion was dispersed by adding 0.75 g of SPI to the sodium solution. The mixture was stirred with a stir bar at 600 rpm for 3 hours at 80°C. Then, 5 g of L3360 was added to the solution. The SPI polyurethane solution was then added to the liquid and stirred at 600 rpm for 30 minutes. The mixture was pipetted into a 10 cm Teflon evaporating dish. The dish was placed in an oven at 45°C. After drying, the dried samples were stored in a standard atmosphere (23°C, 50% humidity). After conditioning for 24 hours, an SPI polyurethane alloy film was prepared.

[0284] DMA testing was performed as outlined in Example 1. For SPI polyurethane alloys The second storage modulus transition (taken as the starting point of the final decrease in the measured storage modulus) was The second DMA modulus transition onset temperature was 186.6°C, which is the same as that of Example 1. This was an increase of 72°C over the control.

[0285] Tensile testing was 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 1.5 times that of SPI polyurethane. For the alloy it was 151%.

[0286] An increase in the onset temperature of the second DMA modulus transition is associated with an increase in modulus and strength and a decrease in elongation. The dissolved SPI in the SPI polyurethane alloy is miscible with the hard phase of the polyurethane. Indicates that there is something. [Examples 22 and 23]

[0287] Examples 22-23 were preformed using the same method as Example 21. The resulting properties of the proteins and these protein polymer alloys are listed in Tables 3 to 6. do. [Examples 24 to 29]

[0288] The samples were prepared in the same manner as in Example 9. The amounts of gelatin and L3360 were varied. Various mass ratios of the two components in the alloy samples were achieved. The masses 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. Resulting properties of the alloys are listed in Tables 3 to 6. [Example 30]

[0291] Soy protein isolate (SPI) was prepared by adding 0.25 g of SPI to 15 mL of deionized water. The dispersion was stirred at 600 rpm for 3 hours with a magnetic stir bar. The mixture was stirred at 0°C. Then, 6.42 g of L3360 was added to the solution and stirred at 600 rpm for 30 minutes. The SPI polyurethane solution was then poured into a 10 cm diameter Teflon (registered trademark) The mixture was pipetted into an evaporating dish. The dish was dried overnight in an oven at 45°C. The sample was conditioned in a standard reference atmosphere (23°C, 50% humidity) for 24 hours to A styrene alloy film was prepared.

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

[0293] Soy protein isolate (SPI) was dissolved in 15 mL of sodium hydroxide at a concentration of 0.05 mol / L. The SPI was dispersed by adding 0.5 g of SPI to the sodium solution. The mixture was stirred with a stir bar at 600 rpm for 3 hours at 80°C. was added to the solution and stirred at 600 rpm for 30 minutes. The mixture was transferred to a 10 cm diameter Teflon evaporating dish using a pipette. The dish was placed in an oven at 45°C. After drying, the dried samples were placed 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. Resulting properties of the alloys are listed in Tables 3 to 6. [Example 32]

[0295] Whey protein (Sigma bovine whey W1500) was added at 0.05 mol / L. By adding 0.75 g of whey to 15 mL of sodium hydroxide solution at a concentration of The dispersion was stirred with a magnetic stir bar at 600 rpm for 3 hours at 80°C. Next, 5 g of L3360 was added to the solution and stirred at 600 rpm for 30 minutes. The polyurethane solution was pipetted into a 10 cm diameter Teflon evaporating dish. The dish was dried overnight in an oven at 45°C. After drying, the dried sample was placed in a standard reference atmosphere. The whey polyurethane alloy film was made by adjusting the temperature (23°C, 50% humidity) for 24 hours. Made.

[0296] DMA testing was performed as outlined in Example 1. For whey polyurethane alloys The second storage modulus transition (taken as the starting point of the final decrease in the measured storage modulus) was The second DMA modulus transition onset temperature was 100.9°C, which is the same as that of Example 1. A 14°C decrease compared to the control.

[0297] Tensile testing was 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 breaking elongation was 1.2 times that of whey polyurethane. For the alloy, it was 224%.

[0298] Whey appears to be miscible with the rigid phase of polyurethane, but the protein itself is thermally stabilized. The second DMA modulus transition temperature was not increased due to the poor quality of the material. As such, whey has a denaturation temperature of 158°C and is therefore considered non-thermostable. [Example 33]

[0299] 0.75g casein (from bovine milk, Sigma, C7078) without any other additives Add to 15 mL of deionized water (pH = 7) in a 20 mL glass vial containing no ATP. The mixture was stirred at 600 rpm, heated to 90°C and maintained for 3 hours.

[0300] Then, 5 g of L3360 was added to a 20 mL glass vial. The container was capped and vortexed at maximum speed for 1 minute. The mixture was transferred to a 10 cm Teflon dish. The dish was placed in a 45°C oven overnight (16-24 time) and dried.

[0301] After drying, the casein polyurethane alloy film has many optically distinct structures in the film. The film had an opaque appearance with visible granules. The tensile properties of this film were measured using an INSTRUCTION 300 TEMPERATURE FILM (INSTRUCTION 300 TEMPERATURE FILM). By measuring five tensile specimens using an ON® 5960 series instrument The film was stretched at a tension of 100 mm / min until it broke. The average tensile strength 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. The results show that casein is insoluble and does not disperse in water at pH 7, and therefore L It indicates that it is not soluble in 3360. [Example 34]

[0302] 0.75g of casein (from bovine milk, Sigma, C7078) was added to a 20mL glass Disperse the sample in 15 mL of 0.05 mol / L deionized NaOH solution in a vial. The mixture was stirred at 100 rpm, heated to 90°C and maintained for 3 hours, resulting in a uniform dispersion.

[0303] Then, 5 g of L3360 was added to a 20 mL glass vial. The vial was capped and vortexed at maximum speed for 1 minute. The liquid was transferred to a 10 cm Teflon dish. The dish was placed in a 45°C oven overnight (1 It was dried for 6 to 24 hours.

[0304] After drying, the casein polyurethane alloy film had optically visible granules in the film. The film had a transparent and uniform appearance without any visible impurities. The tensile properties of this film were measured using an INSTRON ( The test was carried out by measuring five tensile specimens using a 5960 series instrument. The sample was pulled at a tension of 100 mm / min until it broke. The tensile strength 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 degree of elongation and stretchability were determined by the fact that the modified casein was dissolved in the polyurethane and mixed with the hard phase of the polyurethane. Indicates harmony. [Example 35]

[0305] 0.375g soy protein isolate (SPI) and 0.375g r-collagen 15 mL of sodium hydroxide solution at 0.05 mol / L concentration in a 20 mL glass vial Soy protein isolate was purchased from MP Medicals (IC9054562). 5) was soy protein isolate purchased from Modern Me. The solution in the vial was stirred for 60 min using a magnetic stir bar. Mixing was carried out at 80°C for 2 hours at 0 rpm.

[0306] Then, 5 g of L3360 was added to a 20 mL glass vial. The container was capped and vortexed at maximum speed for 1 minute. The eluate was transferred to a 10 cm Teflon dish. The dish was dried overnight in an oven at 45°C. After drying, the dried sample was stored in a standard atmosphere (23°C, 50% humidity) for 24 hours. The SPI / r-col polyurethane alloy film was prepared by adjusting the temperature.

[0307] The tensile properties of this film were measured using an INSTRON® 5960 series machine. The test was carried out by measuring five tensile specimens. The specimens were stretched for 100 mm until fracture. The film was stretched at a tension of 15.71 MPa. The average elongation at break of the films was 175.9%. The average Young's modulus of the films was 247. The film was also subjected to TA Instrumentation according to the method described in Example 1. Tests were also conducted using the ents DMA-850. The resulting second storage modulus transition (the onset of the final decrease in the measured storage modulus) The temperature (i.e., the onset temperature of the second DMA modulus transition) was 184.9°C.

[0308] Compared to Examples 1 and 9, these results show an increase in modulus and strength, as well as The second DMA modulus transition temperature increased with a decrease in elongation. The blend of SPI and r-col in the polymer is miscible with the hard phase of polyurethane, and the properties are It is shown that the corresponding enhancement was observed. [Example 37]

[0309] Using the same method as in Example 36, 0.375 g of Bob's Red Mills Egg Pea Protein MTX5232, 0.375g r-Collagen (Modern M Recombinant collagen (Eadow) and 5g of L3360 polyurethane dispersion A room was created.

[0310] The resulting protein polyurethane alloy film was prepared as described for Example 36. The films were tested using the same tensile and DMA test methods. The average tensile strength of the films was 15 The average elongation at break of the film was 183.17%. The average Young's modulus was 231.13 MPa. The onset temperature of the second DMA modulus transition of the ethylene alloy was 189.65°C.

[0311] Compared to Examples 1 and 9, these results show an increase in modulus and strength as well as , showing an increase in the onset temperature of the second DMA modulus transition, and Blends of pea protein and r-col are miscible with the hard phase of polyurethane; It is shown that the resulting cellulose exhibited a corresponding enhancement in properties. [Example 38]

[0312] The gelatin solution was prepared by dissolving 0.825 g (grams) of gelatin in pig skin (Sigma Al Dissolve in 10 mL (milliliters) of deionized water (from 500 mL of deionized water) and by stirring with a magnetic stir bar at 1000 rpm (revolutions per minute) for 1 hour at 0°C. After the gelatin was completely dissolved, the pH of the solution was adjusted to 7.0 with 0.1N sodium hydroxide. Navy Black #1684 fiber reactive dye was added to 100% gelatin. The mixture was added to the gelatin solution at 4.05 parts per part and mixed for 15 minutes at 45°C. 0.5g of L3360 was added to the solution and stirred at 1000 rpm for 30 minutes. Pipette the urethane and gelatin solutions into a 10 cm diameter Teflon (registered trademark) 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 across the samples. A comparable film of the acrylic dispersion could not be dyed uniformly. Example 39A

[0313] Chemically modified soy protein solution (chemically modified SUPRO® XT55 soy protein) Soy Protein Isolate, and Chemically Modified SUPRO® XT221D Soy Protein Isolate Prepare two 5 mL 0.1 mol / L sodium hydroxide solutions: Once prepared, 40 milligrams (mg) of DABCO (1,4-diazabicyclo[2. 2.2 Octane) was added to each solution and dissolved. Once the DABCO was dissolved, 300 mg of poly(ethylene glycol) monoglycidyl ether-550Mn was added to each solution. followed by 0.75 g of SUPRO® XT55 soy protein isolate. 0.75 g of SUPRO® XT221D soy protein monohydrate was added to the solution. The solution was stirred at 600 rpm at 65°C for 45 minutes to obtain the modified solution. Compared to individual soy proteins in 0.1 mol / L sodium hydroxide alone without decoration, We have created a chemically modified soy protein that has much higher solubility in aqueous solution. Poly(ethylene glycol) monoglycidyl ether modified protein solution The results were significantly clearer than those of the same protein solution without monoglycidyl ether (glycidyl ether). In addition, size exclusion chromatography (SEC) data showed increased solubility. The soluble modified protein solution exhibits minimal hydrolysis, and the solubility of the protein is This is due to the modification of the substrate and not to hydrolysis due to the basic conditions used. This shows that Example 39B

[0314] Chemically modified soy protein solution (chemically modified SUPRO® XT55 soy protein) Soy Protein Isolate, and Chemically Modified SUPRO® XT221D Soy Protein Isolate Prepare two 5 mL 0.1 mol / L sodium hydroxide solutions: Once prepared, 40 mg of DABCO (1,4-diazabicyclo[2.2.2]octadecanoate) was added to Once the DABCO was dissolved, 300 mg of poly(ethylene glycol) ethylene glycol) diglycidyl ether-550Mn was added to the solution, followed by 0.7 5 g of SUPRO® XT55 soy protein isolate was added to one of the solutions; 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, and 0.1 mo 1 / L sodium hydroxide alone in aqueous solution compared to individual soy proteins Highly soluble soy protein was prepared. The diglycidyl ether modified protein solution was prepared by adding poly(ethylene glycol) diglycidyl ether. The solution was significantly clearer than the same protein solution without the addition of PEG, indicating increased solubility. Additionally, SEC data showed that the soluble modified soy protein solution exhibited minimal hydrolysis, The solubility of the protein is due to protein modification and not to the basic conditions used. This indicates that the reaction was not due to hydrolysis. [Example 40]

[0315] SUPRO® XT55 soy protein isolate (SPI) was added at 0.1 mol / by adding 0.75 g of SPI to 5 mL of sodium hydroxide solution at a concentration of 1 L. The dispersion was stirred with a magnetic stir bar at 600 rpm for 2 hours at 65°C. eiQ Chemtex 2317 (anionic surfactant) to 100 parts by weight of protein 5 g of L3360 was then added to the solution and the mixture was stirred at 600 rpm. The mixture was stirred for 30 minutes. The SPI polyurethane solution was then poured into a 10 cm diameter Teflon (registered trademark) The mixture was pipetted into an evaporating dish. The dish was dried overnight in an oven at 45°C. After drying, The dried sample was conditioned in a standard reference atmosphere (23°C, 50% humidity) for 24 hours to measure the SPI performance. A polyurethane alloy film was prepared. [Example 41]

[0316] The gelatin solution was prepared by dissolving 3.885 g of gelatin in pig skin (Sigma Aldrich G2500) in 22 mL of deionized water and simmered at 50°C for 1 hour in an overhead oven. The gelatin was mixed at 450 rpm using an impeller mixer. After dissolving in 1N sodium hydroxide, the pH of the solution was adjusted to 7.0. Antimicrobial Ultra-Fresh DW-56 was added at 1:1 per 100 parts by weight of gelatin solution. The solution was then mixed at 50°C for 10 minutes to ensure good mixing of all components. Dispersion was ensured. After 10 minutes, 15 mL of the solution was aliquoted and A mixture of organic polyether dispersions (manufactured by Igma Aldrich) was added to the estimated final solution. The solution was mixed at 50°C for 10 minutes, and the resulting mixture was added at 0.5 parts per 100 parts of liquid weight. A good dispersion of all components was ensured. Then, 25.885 g of L3360 was added to the solution. After the addition of L3360, the solution was mixed until it reached a temperature of 43°C to 45°C.

[0317] To the other aliquot of solution, add 5.5 parts of HeiQ Ch per 100 parts of solution weight. emtex 2216-T (a stabilized blend of nonionic and anionic surfactants), and 2.2 parts per 100 parts of HeiQ Chemtex 2317 (nonionic and ionic). A stabilized blend of anionic surfactants was added to HeiQ Chemtex 2243 (non-ionic surfactant). The solution was then added with 0.1 parts per 100 parts of a soluble silicone dispersion. Mechanically foam at a temperature of 43°C to 45°C until a wet density of 650g / L to 850g / L is reached. The mixture was then frozen in an upright position, thereby forming a foamed blended mixture.

[0318] A surface finish including a top coat and a base coat is prepared using a protein polyurethane A press skin of the alloy was prepared. The topcoat blend consisted of 9.74 parts Stahl M elio WF-5227.A LIQ, 100 copies of Stahl WT-42-511, 30 copies of Stahl DI-17-701, 30 copies of Stahl XR-13-820, and 25 parts water. The basecoat blend was made by blending 45 0 parts Stahl RC-43-023, 50 parts Stahl RU-3901, 150 50 parts Stahl RA-30, 50 parts Stahl FI-1208, 30 parts Stahl l XR-13-820 and 100 parts Stahl RA-22-063 blended together It was produced by

[0319] The blended non-foaming solution was applied to a drawdown device at a target wet thickness of 200 gsm. Deposited on a dry press skin and coated in a Mathis LTE-S Labcoater The temperature was set at 75°C, the air speed was 2000 rpm, and 70% air was blown in from below the sample. This was dried for 15 minutes to form a protein polyurethane alloy layer. After allowing to stand, a second layer of the blended foam solution was applied onto the first layer to a target wet thickness of 350 gs. Deposited at 75°C for 5 minutes in a Mathis LTE-S Labcoater. , then 100°C for 5 minutes, and finally 120°C for 5 minutes at 700 rpm air speed. The first batch was dried for 15 minutes in a gradient drying procedure with 0% air blown from below. A foam protein polyurethane alloy layer was formed. After the foam layer was dried, the blended foam A third layer of foam solution was deposited onto the first foam layer at a target wet thickness of 350 gsm. in his LTE-S Labcoater at 75°C for 5 minutes, then at 100°C 5 minutes, and finally at 120°C, 70% air was blown in from below at an air speed of 700 rpm. Dry the second foam protein polyurethane for 15 minutes using a gradient drying procedure while watching. An alloy layer was formed.

[0320] The samples were allowed to dry completely and stored in a conditioning chamber at 23°C and 50% humidity for 24 hours. After conditioning at room temperature for 24 hours, samples were cut and subjected to the DMA and tensile mechanical property tests described herein. The second storage modulus transition (the final decrease in the measured storage modulus) was measured. The starting point of the second DMA modulus transition (i.e., the onset temperature) was 190°C. The Young's modulus is 88.9 MPa, the tensile stress is 5.4 MPa, and the elongation at break is 1 It was 10%. [Example 42]

[0321] The sample was prepared by dissolving 1 g of 50 kDa rCol in 5 mL of deionized water and storing at 20°C for 1 The solution was prepared by stirring with a magnetic stir bar at 1000 rpm for 1 hour. The rCol protein is a Modern Polyclonal Antibody comprising the amino acid sequence listed as SEQ ID NO: 1. After stirring for 1 hour, 6.7 g of collagen fragments were obtained. L3360 was added to the solution and stirred at 1000 rpm for 30 minutes. Pipet the 50KDa rCol solution into a 10cm diameter Teflon evaporating dish. The dish was dried overnight in an oven at 45°C. After drying, the dried sample was transferred to a standard After adjusting for 24 hours in a standard atmosphere (23°C, 50% humidity), 50KDa rCol polyurethane was A styrene alloy film was prepared.

[0322] DMA testing was performed as outlined in Example 1. 50KDa rCol polyurethane The second storage modulus transition (the final decrease in the measured storage modulus) obtained for the Zn alloy The starting point (i.e., the second DMA modulus transition onset temperature) was 177.8 °C. This was an increase of 62.9°C over the control sample described in Example 1.

[0323] Tensile testing was 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 50 KDa. For the polyurethane alloy, it was 173%. [Example 43]

[0324] The sample was natural trichoderma available from CREATIVE ENZYMES®. 1 g of Trichoderma cellulase (Cellulase-RG) was dissolved in 5 ml of deionized water. The solution was dissolved in 1000 rpm and stirred with a magnetic stir bar at 20°C for 1 hour. After stirring for 1 hour, 11.4 g of L3360 was added to the solution and 1000 rp The polyurethane and cellulase solution were then poured into a 10 cm diameter Teflon tube and stirred at 400 rpm for 30 minutes. The mixture was pipetted into a Ron® evaporating dish. The dish was dried overnight in an oven at 45°C. After drying, the dried samples were conditioned in a standard reference atmosphere (23°C, 50% humidity) for 24 hours. A cellulase-polyurethane alloy film was produced using this method.

[0325] DMA testing was performed as outlined in Example 1. Celluase-RG Polyurethane The second storage modulus transition (the final decrease in the measured storage modulus) obtained for Tan alloy The starting point of the second DMA modulus transition (i.e., the onset temperature) was 153.1 °C. , an increase of 38.2°C over the control sample described in Example 1.

[0326] Tensile testing was 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 breaking elongation was 1.0 For the urethane alloy, it was 252%. [Example 44]

[0327] Samples were purchased from Carolina Biological Supply Company. 1 g of laboratory-grade cellulase (Cellulase-IG) available from Dissolve in deionized water and stir with a magnetic stir bar at 1000 rpm for 1 hour at 20°C. After stirring for 1 hour, 11.4 g of L3360 was added to the solution, and 10 The polyurethane and cellulase solution was then stirred at 100 rpm for 30 minutes. The mixture was pipetted into a 1000 ml Teflon evaporating dish. The dish was dried in an oven at 45°C overnight. After drying, the dried sample was stored in a standard atmosphere (23°C, 50% humidity) for 24 hours. The time was adjusted to prepare a cellulase polyurethane alloy film.

[0328] DMA testing was performed as outlined in Example 1. Cellulase-IG Poly The second storage modulus transition (the final decrease in the measured storage modulus) obtained for the polyethylene alloy The starting point of the second DMA modulus transition (onset temperature) was 122.1°C. , an increase of 7.2°C over the control sample described in Example 1.

[0329] Tensile testing was 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 breaking elongation was 1.0 MPa. For the ethylene alloy, it was 286%. [Example 45]

[0330] Two control samples (Example 45a and Example 45b) were prepared by the following process: 0.4 g of AF-715 (a soluble fiber available from Quaker Color) was used. Foaming agent) was added to 38g of CL Hauthaway & Sons Corporation. The mixture was mixed into a water-borne polyurethane dispersion, Hauthane HD-2001. The mixture was mixed using an impeller at a speed of 500 rpm and stirred at room temperature for 5 minutes. After mixing, 0.6 g of BORCHI® Gel L 75 N was added and mixed. The mixture was allowed to thicken and the mixture was mixed for 5 minutes. The mixture was then added to a Mathis The coating was performed on release paper using an LTE-S Labcoater coater at 75°C for 1 The coating was then removed from the release paper and dried at 100°C for 10 minutes. A protein-free polyurethane film was prepared using the method described above.

[0331] After drying, the thickness of the sample of Example 45a was 0.4 mm and the thickness of the sample of Example 45b was As reported in Table 7, the polyurethane film of Example 45a had a thickness of 0.4 mm. 30g / m 2 / 24 hour water vapor transmission rate, and the polyurethane film of Example 45b 38g / m 2 It had a water vapor transmission rate of 1 / 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 pig skin was mixed with 2 g of antimicrobial Ultra-F resh DW-56, 0.8g of AF-715 (available from Quaker Color The gelatin was dissolved in a solution of 75 mL of water at 50°C. The solution was stirred with an impeller at 500 rpm until the pH of the solution reached 8. The pH was increased with 1 M NaOH until a pH of 9 was achieved. After adjusting the pH, C. 77g waterborne polyurethane from L. Hauthaway & Sons Corporation Add the gelatin dispersion, Hauthane HD-2001, to the gelatin solution and stir for 15 minutes. After the gelatin and polyurethane solution were properly mixed, 1 g of RM from Stahl was added. -4410 was added to increase the viscosity of the solution, and the solution was mixed for 5 minutes. The surface was covered with a thin IMPRANIL® DLS coating layer (0.03 mm thick). Coated on a 0.35mm thick micro suede textile The gelatin polyurethane solution was applied to a thin IMPRANIL® DLS coating. The coating was applied onto the coating layer using a handheld drawdown device and placed in a standard reference atmosphere ( Drying at 23°C and 50% humidity yielded gelatin-polyurethane sheets with textile backings. A thin IMPRANIL® DLS coating was used to prepare the film. This allows the gelatin polyurethane coating to penetrate deeply into the microsuede textile. This prevented the

[0333] After drying, the thickness of the sample of Example 46a was 0.77 mm (this is due to the gelatin-poly polyurethane film, a thin IMPRANIL® DLS coating, and The thickness of the sample in Example 46b was 0.8 2 mm (this was a gelatin-polyurethane film, a thin Impranil ( The thickness of the DLS coating and the microsuede textile was ).

[0334] As reported in Table 7, the sample of Example No. 46a was 180 g / m 2 / 24-hour steaming air permeability of 150 g / m compared to the sample of Example No. 45a 2 / 24 hours 142 g / m compared to the sample of Example No. 45b. 2 / 24 hour increase Also, as reported in Table 7, the sample of Example 46b had a thickness of 138 g / m 2 / 24 hours The water vapor transmission rate is 108 / m compared to the sample of Example No. 45a. 2 / 2 4 hours, an increase of 100 g / m compared to the sample of Example No. 45b 2 / 24 hour increase It was added.

[0335] Thin IMPRANIL® DLS coating or microsuede textile None of the solutions had a significant effect on the water vapor transmission rate of the samples of Example No. 46a or No. 46b. In other words, the water vapor transmission rates reported in Table 7 were comparable to those of gelatin-polyurethane. Reflects the water vapor transmission rate of the tan film only. [Example 47]

[0336] Two control samples (Example 47a and Example 47b) were prepared by the following process: 0.4 g of AF-715 (a soluble fiber available from Quaker Color) was used. Foaming agent) was mixed into 38g of waterborne polyurethane dispersion L3360 manufactured by Hauthaway. 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 7 5 N was added to increase the viscosity of the mixture, and the mixture was mixed for 5 minutes. The resulting mixture was coated onto release paper using a Mathis LTE-S Labcoater coater. The coating was then dried at 75°C for 10 minutes and at 100°C for 10 minutes. The film was removed from the release paper to produce a protein-free polyurethane film.

[0337] After drying, the thickness of the sample of Example 47a was 0.32 mm and the thickness of the sample of Example 47b was 0.32 mm. As reported in Table 7, the polyurethane filler of Example 47a had a thickness of 0.36 mm. The weight is 23g / m 2 / 24-hour water vapor transmission rate, and the polyurethane filler of Example 47b The weight is 27g / m 2 It had a water vapor transmission rate of 1 / 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 pig skin was mixed with 2 g of antimicrobial Ultra-F resh DW-56, 0.8g of AF-715 (available from Quaker Color The gelatin was dissolved in a solution of 75 mL of water at 50°C. The solution was stirred with an impeller at 500 rpm until the pH of the solution reached 8. The pH was increased with 1 M NaOH until a pH of 9 was achieved. After adjusting the pH, 77g of waterborne polyurethane dispersion L3360 from Uthaway was added to the gelatin solution. After the gelatin and polyurethane solution were properly mixed, Sta 1 g of RM-4410 manufactured by hl was added to increase the viscosity of the solution, and the solution was mixed for 5 minutes. This solution was then applied to a thin IMPRANIL® DLS coating layer (thickness 0.03mm) coated micro suede textile with a thickness of 0.35mm The gelatin and polyurethane solution was coated onto a thin layer of IMPRANIL ( A handheld drawdown device was used to coat the DLS coating layer. The test pieces were then dried in a standard atmosphere (23°C and 50% humidity) to obtain a test piece with a textile backing. A thin IMPRANIL® DL gelatin-polyurethane film was prepared. Using S coating, gelatin polyurethane coating is applied to the micro suede texture It prevented the style from penetrating too deeply.

[0339] After drying, the thickness of the sample of Example 48a was 0.77 mm (this is due to the gelatin-poly polyurethane film, a thin IMPRANIL® DLS coating, and The thickness of the sample in Example 48b was 0.8 4 mm (this was a gelatin-polyurethane film, a thin Impranil ( The thickness of the DLS coating and the microsuede textile was ).

[0340] As reported in Table 7, the sample of Example No. 48a had a viscosity of 117 g / m 2 / 24-hour steaming air permeability of 94 g / m compared to the sample of Example No. 47a 2 / 24 hours An increase of 90 g / m compared to the sample of Example No. 47b 2 / 24-hour increase Also, as reported in Table 7, the sample of Example 48b had a density of 74 g / m 2 / 24-hour water vapor The permeability was 51 g / m compared to the sample of Example No. 47a. 2 / 24 hour increase 47 g / m compared to the sample of Example 47b. 2 / 24 hour increase.

[0341] Thin IMPRANIL® DLS coating or microsuede textile None of the solutions had a significant effect on the water vapor transmission rate of the samples of Example No. 46a or No. 46b. In other words, the water vapor transmission rates reported in Table 7 were comparable to those of gelatin-polyurethane. Reflects the water vapor transmission rate of the tan film only. [Example 49]

[0342] Two control samples (Example 49a and Example 49b) were prepared by the following process: 0.2 g of AF-715 (a soluble fiber available from Quaker Color) was used. Foaming agent) was mixed into 38g of waterborne polyurethane dispersion L3360 manufactured by Hauthaway. The mixture was mixed with an impeller at a speed of 500 rpm for 5 minutes. After thorough mixing, 0.6 g of BORCHI® Gel L 75 N was added. The mixture was allowed to thicken and the mixture was mixed again for 5 minutes. The mixture was coated onto release paper using a Mathis LTE-S Labcoater. The mixture was dried at 75°C for 10 minutes and at 100°C for 10 minutes.

[0343] The foaming solution was then diluted with HeiQ Chemtex 2216-T (based on solution weight) 3%), HeiQ Chemtex 2317 (3% by weight of solution), HeiQ Chemtex 2241-A (1% by weight of solution), and HeiQ Chemt Ex 2243 (0.1% by weight of solution) waterborne The polyurethane dispersion L3360 was prepared by mixing the mixture with The mixture was then stirred with an impeller at 500 rpm for 5 minutes. Foamed mixtures with wet densities ranging from 0 g / L to 900 g / L were prepared. This LTE-S Labcoater is used to coat pre-coated polypropylene. The coating was then coated onto the retentate layer and dried at 75°C for 10 minutes and at 100°C for 10 minutes. After this first foam coating has dried, a second foam coating made from the same foam mixture is applied. A coating layer was coated onto the first foam coating using the same conditions. After the second foam layer dried, the three-layer sample was removed from the release paper.

[0344] The thickness of the three-layer sample of Example 49a was 0.23 mm, and that of Example 49b was 0.23 mm. The thickness of the three-layer sample was 0.24 mm. As reported in Table 7, Example 49a The three-layer sample is 83 g / m 2 / 24-hour water vapor transmission rate, three-layer sample of Example No. 49b is 87g / m 2 It had a water vapor transmission rate of 1 / 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 added to 3 The pH of the mixture was then adjusted with 1M NaCl until a pH of 8-9 was achieved. After adjusting the pH, the water was added with Ultra-Fresh DW-56 ( 15% by weight based on the amount of soy protein isolate and AF-715 antifoam agent (based on the solution weight) 1% by weight based on the soy protein isolate was added to the mixture and the mixture was stirred until the soy protein isolate was completely dissolved. The mixture was stirred at 500 rpm with an impeller until the soy protein isolate was completely dissolved. To dissolve the solution, 32 g of waterborne polyurethane dispersion L3360 from Hauthaway was added to the tank. The solution was stirred with an impeller at 500 rpm for 10 minutes at room temperature. The protein solution was then added to Mathis LTE-S Labcoat The coating was applied to a release paper using a r and dried at 75°C for 10 minutes and at 100°C for 10 minutes. made him do so.

[0346] Then, 5.3 g of SUPRO® XT221D soy protein isolate was added to 30 A foaming solution was prepared by mixing 100 ml of water with 100 ml of water. The pH of the mixture was adjusted to a pH of 8-9. Adjust the pH using 1M NaOH until the pH is reached. Once the ingredients are completely dissolved, add Ultra-Fresh DW-56 (based on soy protein mass). 15% by weight based on solution weight), HeiQ Chemtex 2216-T (3% by weight based on solution weight) % by weight), HeiQ Chemtex 2317 (3% based on solution weight), HeiQ Chemtex 2241-A (1% by weight of solution), HeiQ Chemte x 2243 (0.1% by weight of solution), 32 g water-based solution from Hauthaway Polyurethane Dispersion L3360 was added to the solution and the solution was stirred for 5 minutes at room temperature using an impeller. The solution was then stirred at 500 rpm. A foam solution with a wet density of 1 L was prepared. The foam solution was prepared using Mathis LTE-S L Using the abcoater, coat the pre-coated protein solution layer. The first foam solution coat was then dried at 75°C for 10 minutes and at 100°C for 10 minutes. After the coating had dried, a second foam layer was applied over the first foam coating using the same conditions. After the second foam solution layer was dried, the three-layer sample was removed from the release paper. .

[0347] The thickness of the three-layer sample of Example 50a was 0.24 mm, and the thickness of the three-layer sample of Example 50b was 0.24 mm. The thickness of the sample was 0.25 mm. As reported in Table 7, the sample of Example No. 50a 268g / m 2 1 / 24 hour water vapor transmission rate, which is comparable to that of the sample of Example No. 49a. Compared to 185g / m 2 / 24 hours increase of 18% compared to the sample of Example No. 49b 1g / m 2 As also reported in Table 7, Example 50b The sample is 277 g / m 2 / 24 hour water vapor transmission rate, which is the same as Example No. 49a Compared to the sample, 194 g / m 2 / 24 hour increase compared to sample No. 49b 190g / m 2 / 24 hour increase. [Example 51]

[0348] The control sample was 0.4 g of AF-715 (an antifoaming agent available from Quaker Color agent) was added to 38g of waterborne polyurethane dispersion IMPRAPERM ( The mixture was prepared by mixing into DL5249. The mixture was mixed at a speed of 500 rpm and stirred at room temperature for 5 minutes. 0.6 g of BORCHI® Gel L 75 N was added to increase the viscosity of the mixture. The mixture was then mixed for 5 minutes using a Mathis LTE-S L Coat onto release paper using an Abcoater coater at 75°C for 10 minutes and 1 The coating was then removed from the release paper and the protein A polyurethane film containing no

[0349] After drying, the thickness of the sample was 0.08 mm. As reported in Table 7, the polyurethane The film is 338 g / m 2 It had a water vapor transmission rate of 1 / 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 added to 3 The pH of the mixture was then adjusted with 1M NaCl until a pH of 8-9 was achieved. After adjusting the pH, the water was added with Ultra-Fresh DW-56 ( 15% by weight based on the amount of soy protein isolate and AF-715 antifoam agent (based on the solution weight) 1% by weight based on the soy protein isolate was added to the mixture and the mixture was stirred until the soy protein isolate was completely dissolved. The mixture was stirred at 500 rpm with an impeller until the soy protein isolate was completely dissolved. To dissolve the solution, 32g of waterborne polyurethane dispersion IMPRAPERM manufactured by Covestro was used. DL 5249® was added to the protein solution and the solution was stirred with an impeller for 500 min. The protein solution was then stirred at 200 rpm for 10 minutes at room temperature. s Coating onto release paper using LTE-S Labcoater and heating at 75°C for 10 minutes. The mixture was dried at 100°C for 10 minutes.

[0351] Then, 5.3 g of SUPRO® XT221D soy protein isolate was added to 30 A foaming solution was prepared by mixing 100 ml of water with 100 ml of water. The pH of the mixture was adjusted to a pH of 8-9. Adjust the pH using 1M NaOH until the pH is reached. Once the ingredients are completely dissolved, add Ultra-Fresh DW-56 (based on soy protein mass). 15% by weight based on solution weight), HeiQ Chemtex 2216-T (3% by weight based on solution weight) % by weight), HeiQ Chemtex 2317 (3% based on solution weight), HeiQ Chemtex 2241-A (1% by weight of solution), HeiQ Chemte x 2243 (0.1% by weight of solution), 32g of waterborne polypropylene glycol ether from Covestro Urethane dispersion IMPRAPERM® DL 5249 was added to the solution and dissolved. The solution was stirred at 500 rpm with an impeller at room temperature for 5 minutes. This resulted in a foaming solution with a wet density of 700 g / L to 900 g / L. Pre-coated with a Mathis LTE-S Labcoater The resulting protein solution was coated on the coated film and dried at 75°C for 10 minutes and at 100°C for 10 minutes. After this first foam coating was dried, a second foam layer was applied using the same conditions. After the second foam solution layer was dried, The three-ply sample was removed from the release paper.

[0352] The thickness of the three-layer sample of Example 52a was 0.22 mm, and that of Example 52b was 0.22 mm. The thickness of the three-layer sample was 0.23 mm. As reported in Table 7, Example No. 52a The sample is 626 g / m 2 / 24 hour water vapor transmission rate, and the sample of Example No. 52b was 64 4g / m 2 All three samples had a water vapor transmission rate of 1 / 24 hours. The non-foamed layer has substantially the same thickness as that of the non-foamed layer made with DL5249. Therefore, in order to evaluate the change in water vapor transmission rate, the water vapor transmission rate of Examples 52a and 52b was The vapor transmission rate can be compared to the water vapor transmission rate of Example No. 51. Example No. 52a The foam layers of Nos. 52a and 52b have high porosity, which resulted in a high water vapor transmission rate of these samples. Compared to the sample of Example 51, the sample of Example 52a The sample has a water vapor permeability of 288 g / m 2 / 24 hour increase, and the sample of Example No. 52b Water vapor transmission rate of 306g / m 2 / 24-hour increase. [Example 53]

[0353] The control sample was 0.2 g of AF-715 (an antifoaming agent available from Quaker Color) agent) was added to 38g of waterborne polyurethane dispersion IMPRAPERM ( The mixture was prepared by mixing into DL5249. The mixture was mixed at a speed of 500 rpm for 5 minutes. After the mixture was properly mixed, 0.6 g of BOR CHI® Gel L 75 N was added to increase the viscosity of the mixture, and the mixture was The polyurethane mixture was then mixed again for 5 minutes. The mixture was coated onto release paper using a S Labcoater and heated at 75°C for 10 minutes and 1 It was dried at 00°C for 10 minutes.

[0354] The foaming solution was then diluted with HeiQ Chemtex 2216-T (based on solution weight) 3%), HeiQ Chemtex 2317 (3% by weight of solution), HeiQ Chemtex 2241-A (1% by weight of solution), and HeiQ Chemt Ex 2243 (0.1% by weight of solution) waterborne The polyurethane dispersion L3360 was prepared by mixing the mixture at room temperature. The mixture was then stirred with an impeller at 500 rpm for 5 minutes. Foamed mixtures with wet densities ranging from 0 g / L to 900 g / L were prepared. This LTE-S Labcoater is used to coat pre-coated polypropylene. It was coated onto the retentate layer and dried at 75°C for 10 minutes and at 100°C for 10 minutes. After this first foam coating had dried, a foam coating made from the same L3360 foam mix was applied. A second foam coating layer was coated onto the first foam coating using the same conditions. After the second foam layer was dried, the three-layer sample was removed from the release paper.

[0355] The thickness of the three-layer sample of Example No. 53 was 0.32 mm. The three-layer sample of Example No. 53 has a water vapor transmission rate of 84 g / m 2 / 24 hours. [Example 54]

[0356] 5.3g of SUPRO® XT221D soy protein isolate with 30g of water The sample was prepared by mixing the mixture. The pH of the mixture was adjusted until a pH of 8-9 was achieved. After adjusting the pH, the concentration was increased with 1M NaOH. W-56 (15% by weight based on the amount of soy protein isolate) and AF-715 antifoam agent ( 1% by weight based on the weight of the solution was added to the mixture, and the mixture was stirred until the soy protein isolate The soy protein isolate was stirred at 500 rpm with an impeller until completely dissolved. Once completely dissolved, 53.7 g of waterborne polyurethane dispersion IM from Covestro was added. PRAPERM® DL 5249 was added to the protein solution and the solution was impregnated. The protein solution was then stirred at 500 rpm for 10 minutes at room temperature. was coated onto release paper using a Mathis LTE-S Labcoater. , 75°C for 10 minutes, and 100°C for 10 minutes.

[0357] Then, 5.3 g of SUPRO® XT221D soy protein isolate was added to 30 A foaming solution was prepared by mixing 100 ml of water with 100 ml of water. The pH of the mixture was adjusted to a pH of 8-9. Adjust the pH using 1M NaOH until the pH is reached. Once the ingredients are completely dissolved, add Ultra-Fresh DW-56 (based on soy protein mass). 15% by weight based on solution weight), HeiQ Chemtex 2216-T (3% by weight based on solution weight) % by weight), HeiQ Chemtex 2317 (3% based on solution weight), HeiQ Chemtex 2241-A (1% by weight of solution), HeiQ Chemte x 2243 (0.1% based on solution weight), Hauthaway, 53.7g water The carrier polyurethane dispersion L3360 was added to the solution, and the solution was stirred for 5 minutes at room temperature using an impeller. The solution was then bubbled to a concentration of 700 g / L to 900 g / L. The foam solution was prepared using a Mathis LTE-S Using a Labcoater, coat the pre-coated protein solution layer. The first foaming solution was then dried at 75°C for 10 minutes and at 100°C for 10 minutes. After the coating had dried, a second layer of foamed L3360 was applied using the same conditions as the first. After the second foaming solution layer dried, the three-layer sample was peeled off. Removed from the paper.

[0358] The thickness of the three-layer sample of Example No. 54 was 0.32 mm. The sample of Example No. 54 is 166 g / m 2 / 24 hour water vapor transmission rate, which is Compared with sample No. 53, 82 g / m 2 The graph in Figure 23 shows an increase of 1 / 24 hours. This shows that the breathability of the sample of Example No. 54 is consistent over time. The amount of water absorbed increased linearly with time during the breathability test. Proteins in the poly(urethane) alloy do not significantly affect the breathability of the alloy over time. This shows that it does not cause any fluctuations. [Example 55]

[0359] The control sample was prepared by adding 0.4 g of AF-715 (a defoamer manufactured by Quaker Color) to the 25% by weight of IMPRAPERM® DL5249 and Ha 38g of waterborne polyurethane consisting of 75% by weight of L3360 manufactured by Uthaway The mixture was mixed into a dispersion at a speed of 500 rpm using an impeller. After the mixture was properly mixed, 0.6 g of BORC was added. HI® Gel L 75 N was added to increase the viscosity of the mixture, and the mixture was stirred for 5 minutes. The mixture was then mixed in a Mathis LTE-S Labcoater The coating was applied to a release paper using a dryer and dried at 75°C for 10 minutes and at 100°C for 10 minutes. The coating was then removed from the release paper and coated with a protein-free polyurethane. A retro film was prepared.

[0360] After drying, the thickness of the sample was 0.07 mm. As reported in Table 7, the polyurethane The film is 168 g / m 2 It had a water vapor transmission rate of 1 / 24 hours. [Example 56]

[0361] 5.3g of SUPRO® XT221D soy protein isolate with 30g of water The sample was prepared by mixing the mixture. The pH of the mixture was adjusted until a pH of 8-9 was achieved. After adjusting the pH, the concentration was increased with 1M NaOH. W-56 (15% by weight based on the amount of soy protein isolate) and AF-715 antifoam agent ( 1% by weight based on the weight of the solution was added to the mixture, and the mixture was stirred until the soy protein isolate The soy protein isolate was stirred at 500 rpm with an impeller until completely dissolved. Once completely dissolved, 25% by weight of IMPRAPERM® (manufactured by Covestro) 53.7 g of a waterborne polyurethane dispersion composed of DL 5249 and Hauth 75% by weight of L3360 manufactured by Away was added to the protein solution, and the solution was stirred by an impeller. The protein solution was then stirred at 500 rpm for 10 minutes at room temperature. This was coated onto release paper using a LTE-S Labcoater and then dried at 75°C. The film was dried at 100°C for 10 minutes and at 100°C for 10 minutes.

[0362] After drying, the thickness of the sample was 0.05 mm. As reported in Table 7, the sample weighed 266 g. / m 2 1 / 24 hour water vapor transmission rate, which is 98% higher than that of the sample of Example No. 55. g / m 2 / 24 hour increase.

[0363] Example Table Tables 3 to 6 below report the DMA and mechanical property test results for Examples 1 to 31. The "Sancure" polyurethane in the table is a 47% solid in water product made by Lubrizol. SANCURE™ 2002, a shaped aliphatic polyester polyurethane dispersion 5F. "Impranil DLS" polyurethane is a water-repellent polyurethane manufactured by Covestro. IMPRANIL (IMPRANIL), an aliphatic polyester polyurethane with a 50% solids content "L2996" polyurethane is a water-based polyurethane manufactured by Hauthaway. It is an aliphatic polycarbonate polyurethane dispersion with 35% solids in gelatin. The "SPI" protein is Sigma-Aldrich Type A pig skin gelatin G2500. Protein is MP Medicals Soy Protein Isolate IC905456 25. "Collagen" protein is a protein found in Wuxi BIOT bio It is bovine collagen from logy technology. "BSA" protein is Bovine serum albumin 5470 from Sigma. "rCol" protein recombinant bovine collagen prepared from mother "albumin" protein The protein is Sigma-Aldrich chicken egg albumin A5253. It is a pea protein powder MTX5232 manufactured by Bobs Red Mills. "Peanut" protein is peanut protein powder manufactured by Tru-Nut. Table 7 reports the water vapor transmission rate test results 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 by way of example and not limitation. Adaptations and modifications are readily apparent to those skilled in the art based on the teachings and guidance presented herein. It is clear that the meaning and range of equivalents of the embodiments are intended to be included in the present invention. Therefore, modifications may be made to the embodiments disclosed herein without departing from the spirit and scope of the present disclosure. It will be apparent to those skilled in the art that various changes in form and detail can be made to the present invention. Elements of the embodiments presented herein are not necessarily mutually exclusive, but may be readily apparent to those skilled in the art. As will be appreciated, these may be interchanged to suit various circumstances.

[0370] Embodiments of the present disclosure are herein described with reference to embodiments thereof as illustrated in the accompanying drawings. Throughout the detailed description, like reference numbers may be used to indicate identical or functionally similar elements. "One embodiment," "an embodiment," "some embodiments," "a particular implementation" References such as "configuration" and "particulars" may be used to indicate that the described embodiment may include a particular feature, structure, or characteristic. , indicates that not all embodiments necessarily include a particular feature, structure, or characteristic. Moreover, such phrases are not necessarily referring to the same embodiment. When a feature, structure, or characteristic is described in connection with an embodiment, it is expressly stated. Regardless of whether such features, structures, or characteristics are related to other embodiments, The effects are within the knowledge of one skilled in the art.

[0371] The examples are illustrative, but not limiting, of the present disclosure. , and other suitable modifications and adaptations of a variety of conditions and parameters normally encountered in the art are contemplated herein. It is within the spirit and scope of the

[0372] The phraseology or terminology employed herein is for the purpose of description and not of limitation. It should be understood that the breadth and scope of the present disclosure does not necessarily encompass any of the above exemplary embodiments. but should not be limited by the following claims and their equivalents. should be defined as follows:

[0373] array SEQ ID NO: 1: Human collagen alpha-1(III) chain DVKSGVAVGGLAGYPGPAGPPGPPGPPGTSGHPGSPGSP GYQGPPGEPGQAGPSGPPGPPGAIGPSGPAGKDGESGRPG RPGERGLPGPPGIKGPAGIPGFPGMKGHRGFDGRNGEKGE TGAPGLKGENGLPGENGAPGPMGPRGAPGERGRPGLPGAA GARGNDGARGSDGQPGPPGPPGTAGFPGSPGAKGEVGPAG SPGSNGAPGQRGEPGPQGHAGAQGPPGPPGINGSPGGKGE MGPAGIPGAPGLMGARGPPGPAGANGAPGLRGGAGEPGKN GAKGEPGPRGERGEAGIPGVPGAKGEDGKDGSPGEPGANG LPGAAGERGAPGFRGPAGPNGIPGEKGPAGERGAPGPAGP RGAAGEPGRDGVPGGPGMRGMPGSPGGPGSDGKPGPPGSQ GESGRPGPPGPSGPRGQPGVMGFPGPKGNDGAPGKNGERG GPGGPGPQGPPGKNGETGPQGPPGPTGPGGGDKGDTGPPGP QGLQGLPGTGGPPGENGKPGEPGPKGDAGAPGAPGGKGDA GAPGERGPP

Claims

1. 1. A protein polyurethane alloy comprising a protein dissolved in polyurethane, The protein polyurethane a is a protein other than soy protein. Roy.

2. The protein polyurethane alloy comprises: Dynamic Mechanical Analysis (DMA) at temperatures ranging from about -60°C to about 30°C lysis:DMA) tan(δ) peak, a second DMA modulus transition onset temperature ranging from about 120°C to about 200°C; 2. The protein polyurethane alloy of claim 1, having

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

4. The polyurethane has a Young's modulus in the absence of protein, The polyurethane alloy has a Young's modulus of 100% or less in the absence of protein.

4. The method according to claim 1, wherein the Young's modulus is greater than that of the sintered body by about 10% to about 600%. The protein polyurethane alloy according to any one of claims 1 to 4.

5. The polyurethane has a Young's modulus in the absence of protein, The polyurethane alloy has a Young's modulus of 100% or less in the absence of protein.

4. The method according to claim 1, wherein the Young's modulus is greater than that of the sintered body by about 40% to about 600%. The protein polyurethane alloy according to any one of claims 1 to 4.

6. The polyurethane has a Young's modulus in the absence of protein, The polyurethane alloy has a Young's modulus of 100% or less in the absence of protein. 10 MPa to 350 MPa greater than 6. A protein polyurethane alloy according to any one of claims 1 to 5.

7. The polyurethane has a Young's modulus in the absence of protein, The polyurethane alloy has a Young's modulus of 100% or less in the absence of protein.

10. The method of claim 1, wherein the Young's modulus is greater than that of the method of claim 1, in a range of about 25 MPa to about 350 MPa.

6. A protein polyurethane alloy according to any one of claims 1 to 5.

8. The polyurethane has a Young's modulus in the absence of protein, The polyurethane alloy has a Young's modulus of 100% or less in the absence of protein. and a Young's modulus greater than about 100 MPa to about 350 MPa.

6. The protein polyurethane alloy according to any one of 1 to 5.

9. The protein polyurethane alloy has a modulus ranging from about 50 MPa to about 450 MPa. The protein polyurethane alloy according to any one of claims 1 to 8, having a Young's modulus 。

10. The protein polyurethane alloy has a modulus ranging from about 75 MPa to about 450 MPa. The protein polyurethane alloy according to any one of claims 1 to 8, having a Young's modulus 。

11. The polyurethane has a second DMA modulus transition onset temperature in the absence of protein. and the protein polyurethane alloy is a mixture of the poly(urethane) and the poly(urethane) in the absence of protein. the second DMA modulus transition onset temperature of the urethane in a range of about 5% to about 70%; 11. The method of claim 1, having a second DMA modulus transition onset temperature over a large range of degrees Celsius. The protein polyurethane alloy according to any one of claims 1 to 4.

12. The polyurethane has a second DMA modulus transition onset temperature in the absence of protein. and the protein polyurethane alloy is a mixture of the poly(urethane) and the poly(urethane) in the absence of protein. The second DMA modulus transition temperature of the urethane is about 15% to about 70% higher than the second DMA modulus transition temperature.

10. The method of claim 1, wherein the second DMA modulus transition onset temperature is greater than 100°C. The protein polyurethane alloy according to any one of claims 1 to 4.

13. The polyurethane has a second DMA modulus transition onset temperature in the absence of protein. and the protein polyurethane alloy is a mixture of the poly(urethane) and the poly(urethane) in the absence of protein. The temperature range is from about 5°C to about 100°C above the second DMA modulus transition onset temperature of the urethane.

13. The method according to claim 1, wherein the second DMA modulus transition onset temperature is in a range greater than Item 1. The protein polyurethane alloy according to item 1.

14. The polyurethane has a second DMA modulus transition onset temperature in the absence of protein. and the protein polyurethane alloy is a mixture of the poly(urethane) and the poly(urethane) in the absence of protein. The temperature range is from about 20°C to about 80°C above the second DMA modulus transition onset temperature of the urethane.

13. The method according to claim 1, wherein the second DMA modulus transition onset temperature is in a range greater than Item 1. The protein polyurethane alloy according to item 1.

15. The polyurethane has a second DMA modulus transition onset temperature in the absence of protein. and the protein polyurethane alloy is a mixture of the poly(urethane) and the poly(urethane) in the absence of protein. The temperature range is from about 40°C to about 80°C above the second DMA modulus transition onset temperature of the urethane.

13. The method according to claim 1, wherein the second DMA modulus transition onset temperature is in a range greater than Item 1. The protein polyurethane alloy according to item 1.

16. The protein polyurethane alloy is heated to a second temperature ranging from about 130°C to about 200°C. The protein according to any one of claims 1 to 15, having a DMA elastic modulus transition onset temperature. Polyurethane alloy.

17. The protein polyurethane alloy is heated to a second temperature ranging from about 165°C to about 200°C. The protein according to any one of claims 1 to 15, having a DMA elastic modulus transition onset temperature. Polyurethane alloy.

18. The protein is: (a) an isoelectric point ranging from about 4 to about 5; (b) a lysine weight percentage ranging from about 1% to about 100% by weight; The protein polyurethane alloy according to any one of claims 1 to 17, having

19. The polyurethane has a tensile strength in the absence of protein, and The tensile strength of the polyurethane in the absence of protein is Claims 1 to 18: The tensile strength is in the range of about 5% to about 55% greater than the strength of The protein polyurethane alloy according to any one of claims 1 to 4.

20. The polyurethane has a tensile strength in the absence of protein, and The tensile strength of the polyurethane in the absence of protein is tensile strength in the range of about 15% to about 55% greater than that of the 9. A protein polyurethane alloy according to any one of claims 8 to 8.

21. The polyurethane has a tensile strength in the absence of protein, and The tensile strength of the polyurethane in the absence of protein is 10. The method of claim 1, wherein the tensile strength is greater than the tensile strength by about 2 MPa to about 8 MPa.

21. A protein polyurethane alloy according to any one of claims 1 to 20.

22. The polyurethane has a tensile strength in the absence of protein, and The tensile strength of the polyurethane in the absence of protein is 10. The method of claim 1, wherein the tensile strength is greater than the tensile strength by about 5 MPa to about 8 MPa.

21. A protein polyurethane alloy according to any one of claims 1 to 20.

23. The protein polyurethane alloy has a tensile strength ranging from about 7 MPa to about 21 MPa. The protein polyurethane alloy according to any one of claims 1 to 22, which has high strength. 。

24. about 10% to about 50% by weight of said protein and about 50% to about 90% by weight of said The protein polyurethane according to any one of claims 1 to 23, Nalloy.

25. about 20% to about 35% by weight of said protein and about 65% to about 80% by weight of said The protein polyurethane according to any one of claims 1 to 23, Nalloy.

26. 26. The method according to claim 1, wherein the protein is a protein other than collagen. Item 1. The protein polyurethane alloy according to item 1.

27. The polyurethane has a water vapor transmission rate in the absence of protein, and The polyurethane alloy is formed by the steam treatment of the polyurethane in the absence of protein. a water vapor transmission rate that is greater than the air transmission rate by about 20% to about 600%. Item 27. The protein polyurethane alloy according to any one of items 1 to 26.

28. The polyurethane has a water vapor transmission rate in the absence of protein, and The polyurethane alloy is formed by the steam treatment of the polyurethane in the absence of protein. Air permeability is approximately 30 g / m ２ / 24 hours ~ approx. 500g / m ２ / Over a 24-hour period The protein polyethylene according to any one of claims 1 to 27, which has a high water vapor transmission rate. Lethanalloy.

29. The protein polyurethane alloy has a density of about 30 g / m ２ / 24 hours ~ approx. 1000g / m ２ 29. The method according to claim 1, wherein the water vapor transmission rate is in the range of 1 / 24 hours. Protein polyurethane alloy.

30. Soy protein polyurethane alloy containing soy protein dissolved in polyurethane. The soy protein polyurethane alloy has a temperature range of about -60°C to about 30°C. Dynamic mechanical analysis (DMA) tan(δ) peaks at temperatures between about 130°C and about 200°C. and a second DMA modulus transition onset temperature ranging from 0.1 to 1.

0. Alloy.

31. 31. The soy protein polyurethane alloy of claim 30, wherein the soy protein polyurethane alloy is transparent. High quality polyurethane alloy.

32. The polyurethane has a Young's modulus in the absence of soy protein, The protein polyurethane alloy exhibits the properties of the polyurethane in the absence of soy protein. a Young's modulus greater than said Young's modulus by about 60% to about 570%; Item 32. The soy protein polyurethane alloy according to item 30 or 31.

33. The polyurethane has a Young's modulus in the absence of soy protein, The protein polyurethane alloy exhibits the properties of the polyurethane in the absence of soy protein. Having a Young's modulus greater than the Young's modulus in the range of about 35 MPa to about 340 MPa. The soy protein polyurethane alloy according to any one of claims 30 to 32.

34. The soy protein polyurethane alloy has a modulus in the range of about 90 MPa to about 400 MPa. The soy protein polyester according to any one of claims 30 to 33, having a Young's modulus Lethanalloy.

35. The polyurethane exhibits a second DMA modulus transition in the absence of soy protein. a temperature at which the second DMA modulus transition of the soy protein polyurethane alloy begins; the temperature is such that the second DMA modulus of the polyurethane in the absence of soy protein is Any one of claims 30 to 34, wherein the temperature is in the range of about 15°C to about 100°C higher than the transition onset temperature. A soy protein polyurethane alloy according to claim 1.

36. The polyurethane has a tensile strength in the absence of soy protein, The protein polyurethane alloy is prepared by subjecting said polyurethane to the absence of soy protein. having a tensile strength in the range of about 10% to about 45% greater than the tensile strength of The soy protein polyurethane alloy according to any one of claims 30 to 35.

37. The polyurethane has a tensile strength in the absence of soy protein, The protein polyurethane alloy is prepared by subjecting said polyurethane to the absence of soy protein. A tensile strength greater than the tensile strength of the above in the range of about 1.5 MPa to about 5.5 MPa. The soy protein polyurethane alloy according to any one of claims 30 to 36, stomach.

38. The soy protein polyurethane alloy has a modulus in the range of about 14 MPa to about 19 MPa. The soy protein polyester according to any one of claims 30 to 37, having a tensile strength Lethanalloy.

39. About 10% to about 50% by weight of the soy protein and about 50% to about 90% by weight of The soy protein according to any one of claims 30 to 38, comprising: Polyurethane alloy.

40. about 20% to about 35% by weight of said soy protein and about 65% to about 80% by weight of The soy protein according to any one of claims 30 to 38, comprising: Polyurethane alloy.

41. The polyurethane has a water vapor transmission rate in the absence of protein, and the soybean ta The protein polyurethane alloy is characterized by the fact that the polyurethane is having a water vapor transmission rate that is greater than the water vapor transmission rate by about 20% to about 600%; The soy protein polyurethane alloy according to any one of claims 30 to 40.

42. The polyurethane has a water vapor transmission rate in the absence of protein, and the soybean ta The protein polyurethane alloy is characterized by the fact that the polyurethane is Water vapor permeability is approximately 30 g / m ２ / 24 hours ~ approx. 500g / m ２ / 24 hour range The soy protein according to any one of claims 30 to 41, having a water vapor transmission rate greater than High quality polyurethane alloy.

43. The soy protein polyurethane alloy has a density of about 30 g / m ２ / 24 hours to about 1000g / m ２ 43. The method according to claim 30, wherein the water vapor transmission rate is in the range of 1 / 24 hours. Item 1. The soy protein polyurethane alloy according to item 1.

44. 44. Any one of claims 30 to 43, wherein the soy protein is a soy protein isolate. Item 1. The soy protein polyurethane alloy according to item 1.

45. 30 to 4, wherein the soy protein is a chemically modified soy protein isolate.

4. The soy protein polyurethane alloy according to any one of claims 3 to 3.

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